COMPOUND-SPECIFIC STABLE ISOTOPE ANALYSIS TO DEMONSTRATE IN-SITU MTBE BIOTRANSFORMATION

EPA Science Inventory

Change of stable isotope composition of organic contaminants (isotopic fractionation) is a useful indicator of biotransformation. Most of applications to date are in the area of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (biotic- and abiotic transfor...

Investigating chloroperoxidase-catalyzed formation of chloroform from humic substances using stable chlorine isotope analysis.

PubMed

Breider, Florian; Hunkeler, Daniel

2014-01-01

Chloroperoxidase (CPO) is suspected to play an important role in the biosynthesis of natural chloroform. The aims of the present study are to evaluate the variability of the δ(37)Cl value of naturally produced chloroform and to better understand the reaction steps that control the chlorine isotope signature of chloroform. The isotope analyses have shown that the chlorination of the humic substances (HS) in the presence of high H3O(+) and Cl(-) concentrations induces a large apparent kinetic isotope effect (AKIE = 1.010-1.018) likely associated with the transfer of chlorine between two heavy atoms, whereas in the presence of low H3O(+) and Cl(-) concentrations, the formation of chloroform induces a smaller AKIE (1.005-1.006) likely associated with the formation of an HOCl-ferriprotoporphyrin IX intermediate. As the concentration of H3O(+) and Cl(-) in soils are generally at submillimolar levels, the formation of the HOCl-ferriprotoporphyrin IX intermediate is likely rate-limiting in a terrestrial environment. Given that the δ(37)Cl values of naturally occurring chloride tend to range between -1 and +1‰, the δ(37)Cl value of natural chloroform should vary between -5‰ and -8‰. As the median δ(37)Cl value of industrial chloroform is -3.0‰, the present study suggests that chlorine isotopic composition of chloroform might be used to discriminate industrial and natural sources in the environment.

Analysis of nitrosamines in water by automated SPE and isotope dilution GC/HRMS Occurrence in the different steps of a drinking water treatment plant, and in chlorinated samples from a reservoir and a sewage treatment plant effluent.

PubMed

Planas, Carles; Palacios, Oscar; Ventura, Francesc; Rivera, Josep; Caixach, Josep

2008-08-15

A method based on automated solid-phase extraction (SPE) and isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS) has been developed for the analysis of nine nitrosamines in water samples. The combination of automated SPE and GC/HRMS for the analysis of nitrosamines has not been reported previously. The method shows as advantages the selectivity and sensitivity of GC/HRMS analysis and the high efficiency of automated SPE with coconut charcoal EPA 521 cartridges. Low method detection limits (MDLs) were achieved, along with a greater facility of the procedure and less dependence on the operator with regard to the methods based on manual SPE. Quality requirements for isotope dilution-based methods were accomplished for most analysed nitrosamines, regarding to trueness (80-120%), method precision (<15%) and MDLs (0.08-1.7 ng/L). Nineteen water samples (16 samples from a drinking water treatment plant {DWTP}, 2 chlorinated samples from a sewage treatment plant {STP} effluent, and 1 chlorinated sample from a reservoir) were analysed. Concentrations of nitrosamines in the STP effluent were 309.4 and 730.2 ng/L, being higher when higher doses of chlorine were applied. N-Nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) were the main compounds identified in the STP effluent, and NDEA was detected above 200 ng/L, regulatory level for NDMA in effluents stated in Ontario (Canada). Lower concentrations of nitrosamines were found in the reservoir (20.3 ng/L) and in the DWTP samples (n.d. -28.6 ng/L). NDMA and NDEA were respectively found in the reservoir and in treated and highly chlorinated DWTP samples at concentrations above 10 ng/L (guide value established in different countries). The highest concentrations of nitrosamines were found after chlorination and ozonation processes (ozonated, treated and highly chlorinated water) in DWTP samples.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

High-precision measurement of chlorine stable isotope ratios

USGS Publications Warehouse

Long, A.; Eastoe, C.J.; Kaufmann, R.S.; Martin, J.G.; Wirt, L.; Finley, J.B.

1993-01-01

We present an analysis procedure that allows stable isotopes of chlorine to be analyzed with precision sufficient for geological and hydrological studies. The total analytical precision is ?????0.09%., and the present known range of chloride in the surface and near-surface environment is 3.5???. As Cl- is essentially nonreactive in natural aquatic environments, it is a conservative tracer and its ??37Cl is also conservative. Thus, the ??37Cl parameter is valuable for quantitative evaluation of mixing of different sources of chloride in brines and aquifers. ?? 1993.

Vitamin B12 effects on chlorinated methanes-degrading microcosms: Dual isotope and metabolically active microbial populations assessment.

PubMed

Rodríguez-Fernández, Diana; Torrentó, Clara; Guivernau, Miriam; Viñas, Marc; Hunkeler, Daniel; Soler, Albert; Domènech, Cristina; Rosell, Mònica

2018-04-15

Field-derived anoxic microcosms were used to characterize chloroform (CF) and carbon tetrachloride (CT) natural attenuation to compare it with biostimulation scenarios in which vitamin B 12 was added (B 12 /pollutant ratio of 0.01 and 0.1) by means of by-products, carbon and chlorine compound-specific stable-isotope analysis, and the active microbial community through 16S rRNA MiSeq high-throughput sequencing. Autoclaved slurry controls discarded abiotic degradation processes. B 12 catalyzed CF and CT biodegradation without the accumulation of dichloromethane, carbon disulphide, or CF. The carbon isotopic fractionation value of CF (ƐC CF ) with B 12 was -14±4‰, and the value for chlorine (ƐCl CF ) was -2.4±0.4‰. The carbon isotopic fractionation values of CT (ƐC CT ) were -16±6 with B 12 , and -13±2‰ without B 12 ; and the chlorine isotopic fractionation values of CT (ƐCl CT ) were -6±3 and -4±2‰, respectively. Acidovorax, Ancylobacter, and Pseudomonas were the most metabolically active genera, whereas Dehalobacter and Desulfitobacterium were below 0.1% of relative abundance. The dual C-Cl element isotope slope (Λ=Δδ 13 C/Δδ 37 Cl) for CF biodegradation (only detected with B 12 , 7±1) was similar to that reported for CF reduction by Fe(0) (8±2). Several reductive pathways might be competing in the tested CT scenarios, as evidenced by the lack of CF accumulation when B 12 was added, which might be linked to a major activity of Pseudomonas stutzeri; by different chlorine apparent kinetic isotope effect values and Λ which was statistically different with and without B 12 (5±1 vs 6.1±0.5), respectively. Thus, positive B 12 effects such as CT and CF degradation catalyst were quantified for the first time in isotopic terms, and confirmed with the major activity of species potentially capable of their degradation. Moreover, the indirect benefits of B 12 on the degradation of chlorinated ethenes were proved, creating a basis for remediation strategies in multi-contaminant polluted sites. Copyright © 2017 Elsevier B.V. All rights reserved.

Use of dual carbon-chlorine isotope analysis to assess the degradation pathways of 1,1,1-trichloroethane in groundwater.

PubMed

Palau, Jordi; Jamin, Pierre; Badin, Alice; Vanhecke, Nicolas; Haerens, Bruno; Brouyère, Serge; Hunkeler, Daniel

2016-04-01

Compound-specific isotope analysis (CSIA) is a powerful tool to track contaminant fate in groundwater. However, the application of CSIA to chlorinated ethanes has received little attention so far. These compounds are toxic and prevalent groundwater contaminants of environmental concern. The high susceptibility of chlorinated ethanes like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in the subsurface. In this study, the use of a dual C-Cl isotope approach to identify the active degradation pathways of 1,1,1-TCA is evaluated for the first time in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. The reaction-specific dual carbon-chlorine (C-Cl) isotope trends determined in a recent laboratory study illustrated the potential of a dual isotope approach to identify contaminant degradation pathways of 1,1,1-TCA. Compared to the dual isotope slopes (Δδ(13)C/Δδ(37)Cl) previously determined in the laboratory for dehydrohalogenation/hydrolysis (DH/HY, 0.33 ± 0.04) and oxidation by persulfate (∞), the slope determined from field samples (0.6 ± 0.2, r(2) = 0.75) is closer to the one observed for DH/HY, pointing to DH/HY as the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA is the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C-Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field. Copyright © 2016 Elsevier Ltd. All rights reserved.

Stabile Chlorine Isotope Study of Martian Shergottites and Nakhlites; Whole Rock and Acid Leachates and Residues

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C-Y; Fujitani, T.; Okano, O.

2011-01-01

We have established a precise analytical technique for stable chlorine isotope measurements of tiny planetary materials by TIMS (Thermal Ionization Mass Spectrometry) [1], for which the results are basically consistent with the IRMS tech-nique (gas source mass spectrometry) [2,3,4]. We present here results for Martian shergottites and nakhlites; whole rocks, HNO3-leachates and residues, and discuss the chlorine isotope evolution of planetary Mars.

The chlorine isotope fingerprint of the lunar magma ocean

PubMed Central

Boyce, Jeremy W.; Treiman, Allan H.; Guan, Yunbin; Ma, Chi; Eiler, John M.; Gross, Juliane; Greenwood, James P.; Stolper, Edward M.

2015-01-01

The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free (“dry”) Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because 37Cl/35Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, 37Cl/35Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high 37Cl/35Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon’s history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets. PMID:26601265

The chlorine isotope fingerprint of the lunar magma ocean.

PubMed

Boyce, Jeremy W; Treiman, Allan H; Guan, Yunbin; Ma, Chi; Eiler, John M; Gross, Juliane; Greenwood, James P; Stolper, Edward M

2015-09-01

The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free ("dry") Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because (37)Cl/(35)Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, (37)Cl/(35)Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high (37)Cl/(35)Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon's history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets.

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

NASA Astrophysics Data System (ADS)

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

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50 years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in 13C (<-60‰) suggesting production lines which have used depleted methane for synthesis. The other source had typical carbon isotope compositions of >-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, 13C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas.

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

PubMed

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

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in ¹³C (<-60‰) suggesting production lines which have used depleted methane for synthesis. The other source had typical carbon isotope compositions of >-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, ¹³C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas. © 2013 Elsevier B.V. All rights reserved.

Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes.

PubMed

Palau, Jordi; Marchesi, Massimo; Chambon, Julie C C; Aravena, Ramon; Canals, Àngels; Binning, Philip J; Bjerg, Poul L; Otero, Neus; Soler, Albert

2014-03-15

The use of compound specific multi-isotope approach (C and Cl) in the characterization of a chlorinated ethenes contaminated fractured aquifer allows the identification of several sources and contaminant plumes, as well as the occurrence of biodegradation and mixing processes. The study site is located in Spain with contamination resulting in groundwater concentrations of up to 50mg/L of trichloroethene (TCE), the most abundant chlorinated ethene, and 7 mg/L of tetrachloroethene (PCE). The potential sources of contamination including abandoned barrels, an underground tank, and a disposal lagoon, showed a wide range in δ(13)C values from -15.6 to -40.5‰ for TCE and from -18.5 to -32.4‰ for PCE, allowing the use of isotope fingerprinting for tracing of the origin and migration of these contaminants in the aquifer. In contrast, there is no difference between the δ(37)Cl values for TCE in the contaminant sources, ranging from +0.53 to +0.66‰. Variations of δ(37)Cl and δ(13)C in the different contaminant plumes were used to investigate the role of biodegradation in groundwater. Moreover, the isotopic data were incorporated into a reactive transport model for determination of whether the isotope pattern observed downstream from the tank's source could be explained by the simultaneous effect of mixing and biodegradation. The results demonstrate that a multi-isotope approach is a valuable tool for characterization of complex sites such as fractured bedrock aquifer contaminated by multiple sources, providing important information which can be used by consultants and site managers to prioritize and design more successful remediation strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

Congener-specific determination of ultratrace levels of chlorinated and brominated polycyclic aromatic hydrocarbons in atmosphere and industrial stack gas by isotopic dilution gas chromatography/high resolution mass spectrometry method.

PubMed

Jin, Rong; Liu, Guorui; Zheng, Minghui; Fiedler, Heidelore; Jiang, Xiaoxu; Yang, Lili; Wu, Xiaolin; Xu, Yang

2017-08-04

Isotopic dilution gas chromatography combined with high resolution mass spectrometry (GC/HRMS) has overwhelming advantages with respect to the accuracy of congener-specific ultratrace analysis of complex persistent organic pollutants (POPs) in environmental matrices. However, an isotopic dilution GC/HRMS method for analysis of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) using 13 C-labelled congeners as internal standards has not been established. In this study, a method for identification and quantification of 38 congeners of Cl-PAHs and Br-PAHs in atmosphere and stack gas samples from waste incinerators was developed using the isotopic dilution GC/HRMS technique. The instrumental detection limits of the GC/HRMS method ranged from 0.2pg to 1.8pg for Cl-PAH congeners, and 0.7pg to 2.7pg for Br-PAH congeners, which were about three orders of magnitude lower than those of the GC/quadrupole MS method. This new method developed was also the first to enable determination of Cl-PAH and Br-PAH homologs comprising congeners with the same molecular skeleton and chlorine or bromine substitution numbers. Among the detected congeners, seven Cl-PAH congeners and thirteen Br-PAH congeners that were abundant in the atmosphere and stack gases released from waste incinerators were firstly detected in real samples and reported using the established isotopic dilution GC/HRMS method. The developed isotopic dilution GC/HRMS is significant and needed for better studying the environmental behavior and health risk of Cl-PAHs and Br-PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.

Chlorine isotope geochemistry of Icelandic thermal fluids: Implications for geothermal system behavior at divergent plate boundaries

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Barnes, Jaime D.

2016-09-01

The chlorine isotope composition of thermal fluids from Iceland were measured in order to evaluate the source of chlorine and possible chlorine isotope fractionation in geothermal systems at divergent plate boundaries. The geothermal systems studied have a wide range of reservoir temperatures from 40 to 437 °C and in-situ pH of 6.15 to 7.15. Chlorine concentrations range from 5.2 to 171 ppm and δ37 Cl values are -0.3 to + 2.1 ‰ (n = 38). The δ37 Cl values of the thermal fluids are interpreted to reflect the source of the chlorine in the fluids. Geothermal processes such as secondary mineral formation, aqueous and vapor speciation and boiling were found to have minimal effects on the δ37 Cl values. However, further work is needed on incorporation of Cl into secondary minerals and its effect on Cl isotope fractionation. Results of isotope geochemical modeling demonstrate that the range of δ37 Cl values documented in the natural thermal fluids can be explained by leaching of the basaltic rocks by meteoric source water under geothermal conditions. Magmatic gas partitioning may also contribute to the source of Cl in some cases. The range of δ37 Cl values of the fluids result mainly from the large range of δ37 Cl values observed for Icelandic basalts, which range from -0.6 to + 1.2 ‰.

Monitoring of the aerobe biodegradation of chlorinated organic solvents by stable isotope analysis

NASA Astrophysics Data System (ADS)

Horváth, Anikó; Futó, István; Palcsu, László

2014-05-01

Our chemical-biological basic research aims to eliminate chlorinated environmental contaminants from aquifers around industrial areas in the frame of research program supported by the European Social Fund (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). The most careful and simplest way includes the in situ biodegradation with the help of cultured and compound specific strains. Numerous members of Pseudomonas bacteria are famous about function of bioremediation. They can metabolism the environmental hazardous chemicals like gas oils, dyes, and organic solvents. Our research based on the Pseudomonas putida F1 strain, because its ability to degrade halogenated hydrocarbons such as trichloroethylene. Several methods were investigated to estimate the rate of biodegradation, such as the measurement of the concentration of the pollutant along the contamination pathway, the microcosm's studies or the compound specific stable isotope analysis. In this area in the Transcarpathian basin we are pioneers in the stable isotope monitoring of biodegradation. The main goal is to find stable isotope fractionation factors by stable isotope analysis, which can help us to estimate the rate and effectiveness of the biodegradation. The subsequent research period includes the investigation of the method, testing its feasibility and adaptation in the environment. Last but not least, the research gives an opportunity to identify the producer of the contaminant based on the stable isotope composition of the contaminant.

Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

PubMed

Wu, Langping; Kümmel, Steffen; Richnow, Hans H

2017-04-01

Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

Assessment of In-Situ Reductive Dechlorination Using Compound-Specific Stable Isotopes, Functional-Gene Pcr, and Geochemical Data

PubMed Central

Carreón-Diazconti, Concepción; Santamaría, Johanna; Berkompas, Justin; Field, James A.; Brusseau, Mark L.

2010-01-01

Isotopic analysis and molecular-based bioassay methods were used in conjunction with geochemical data to assess intrinsic reductive dechlorination processes for a chlorinated-solvent contaminated site in Tucson, Arizona. Groundwater samples were obtained from monitoring wells within a contaminant plume comprising tetrachloroethene and its metabolites trichloroethene, cis-1,2-dichloroethene, vinyl chloride, and ethene, as well as compounds associated with free-phase diesel present at the site. Compound specific isotope (CSI) analysis was performed to characterize biotransformation processes influencing the transport and fate of the chlorinated contaminants. PCR analysis was used to assess the presence of indigenous reductive dechlorinators. The target regions employed were the 16s rRNA gene sequences of Dehalococcoides sp. and Desulfuromonas sp., and DNA sequences of genes pceA, tceA, bvcA, and vcrA, which encode reductive dehalogenases. The results of the analyses indicate that relevant microbial populations are present and that reductive dechlorination is presently occurring at the site. The results further show that potential degrader populations as well as biotransformation activity is non-uniformly distributed within the site. The results of laboratory microcosm studies conducted using groundwater collected from the field site confirmed the reductive dechlorination of tetrachloroethene to dichloroethene. This study illustrates the use of an integrated, multiple-method approach for assessing natural attenuation at a complex chlorinated-solvent contaminated site. PMID:19603638

Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene.

PubMed

Van Breukelen, Boris M; Thouement, Héloïse A A; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz

2017-09-01

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ 37 Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ 2 H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

NASA Astrophysics Data System (ADS)

Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

2014-05-01

Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems to catalyse PCE reductive dechlorination according to a different mechanism. In another study, an m value of 2.5±0.8 was found for PCE anaerobic dechlorination by a bacterial consortium dominated by species closely related to Desulfitobacterium aromaticivorans strain UKTL (consortia A) [2]. This value is indistinguishable from the one found for PceATCE within a 95% confidence interval although the reductive dehalogenase protein sequence of consortia A is distinctly different from the sequences of our two cultures. This suggests that the reaction mechanism is not related to the similarities between reductive dehalogenases. References 1. Abe, Y., et al., Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride and cis-1,2-Dichloroethene. Environmental Science & Technology, 2009. 43(1): p. 101-107. 2. Wiegert, C., et al., Carbon and Chlorine Isotope Fractionation During Microbial Degradation of Tetra- and Trichloroethene. Environmental Science & Technology, 2013. 47(12): p. 6449-6456.

Stable Carbon Isotope Evidence and Quantification of Reductive Dechlorination of Chlorinated Ethenes at Kelly AFB, TX

NASA Astrophysics Data System (ADS)

Morrill, P.; Lacrampe-Couloume, G.; Slater, G.; Sleep, B.; Edwards, E.; McMaster, M.; Major, D.; Sherwood Lollar, B.

2002-12-01

Cis-1, 2-dichloroethene (cDCE) was the primary volatile organic compound (VOC) after biostimulation of a perchloroethene (PCE) plume in a pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. A stable natural microbial consortium, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene was added in a pilot test area (PTA). After the addition of KB-1 stable carbon isotope values were measured for each chlorinated ethene to verify the occurrence of reductive dechlorination and quantify the extent of cDCE degradation. After bioaugmentation with KB-1, PCE, TCE and cDCE concentrations declined, while VC concentrations increased and subsequently decreased, as ethene became the dominant transformation product measured. Shifts in carbon isotopic values up to 2.7 permil, 6.4 permil, 10.9 permil and 10.6 permil were observed for PCE, TCE, cDCE and VC respectively. These isotopic shifts are consistent with the effects of biodegradation observed during laboratory and field studies. Most notably, isotopic enrichment trends characteristic of reductive dechlorination were detectable in the parent compounds before measurable concentrations of daughter products VC and ethene were produced. These results illustrate the advantage of using the more sensitive compound specific isotope analysis to confirm degradation in addition to the traditional method of monitoring the appearance of degradation products. Fractionation factors obtained from laboratory studies were used in conjunction with isotope data measured in the field to estimate the extent of cDCE degraded. It is estimated that within a 44 day period, 37 to 48 percent of the cDCE was reductively dechlorinated. Independent biodegradation estimates using data from a bromide tracer test, a groundwater flow model, and concentration analyses were all in good agreement with the isotope degradation estimate.

Carbon Isotopic Composition of CO2, Evolved During Perchlorate-Induced Reactions in Mars Analog Materials: Interpreting SAM/MSL Rocknest Data

NASA Technical Reports Server (NTRS)

Stern, J. C.; McAdam, A. C.; Archer, P. D., Jr.; Bower, H.; Buch, A.; Eigenbrode, J.; Freissinet, C.; Franz, H. B.; Glavin, D.; Jones, J. H.;

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, 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 (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, 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. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

STABLE CHLORINE ISOTOPIC COMPOSITIONS OF AROCLORS AND ARCLOR-CONTAMINATED SEDIMENT

EPA Science Inventory

An exploratory investigation was conducted to evaluate if stable chlorine isotopic ratios of polychlorinated biphenyls (PCBs) could be useful in studying the processes that determine their transport and fate in the environment. First, we determined the variability of 37Cl in the...

Integrated Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation

DTIC Science & Technology

2016-05-01

Certification Program ETH Ethene GC Gas Chromatography GC-IRMS Gas Chromatography Isotope Ratio Mass Spectroscopy H Hydrogen IRMS Isotope...tool for attenuation of chlorinated solvents. The Demonstration Site was Operable Unit 10 at Hill AFB, Utah , a site where groundwater is impacted...techniques. The method involves extraction of the target compounds from environmental sample matrix, followed by separation of the compounds using gas

Identification of abiotic and biotic reductive dechlorination in a chlorinated ethene plume after thermal source remediation by means of isotopic and molecular biology tools

NASA Astrophysics Data System (ADS)

Badin, Alice; Broholm, Mette M.; Jacobsen, Carsten S.; Palau, Jordi; Dennis, Philip; Hunkeler, Daniel

2016-09-01

Thermal tetrachloroethene (PCE) remediation by steam injection in a sandy aquifer led to the release of dissolved organic carbon (DOC) from aquifer sediments resulting in more reduced redox conditions, accelerated PCE biodegradation, and changes in microbial populations. These changes were documented by comparing data collected prior to the remediation event and eight years later. Based on the premise that dual C-Cl isotope slopes reflect ongoing degradation pathways, the slopes associated with PCE and TCE suggest the predominance of biotic reductive dechlorination near the source area. PCE was the predominant chlorinated ethene near the source area prior to thermal treatment. After thermal treatment, cDCE became predominant. The biotic contribution to these changes was supported by the presence of Dehalococcoides sp. DNA (Dhc) and Dhc targeted rRNA close to the source area. In contrast, dual C-Cl isotope analysis together with the almost absent VC 13C depletion in comparison to cDCE 13C depletion suggested that cDCE was subject to abiotic degradation due to the presence of pyrite, possible surface-bound iron (II) or reduced iron sulphides in the downgradient part of the plume. This interpretation is supported by the relative lack of Dhc in the downgradient part of the plume. The results of this study show that thermal remediation can enhance the biodegradation of chlorinated ethenes, and that this effect can be traced to the mobilisation of DOC due to steam injection. This, in turn, results in more reduced redox conditions which favor active reductive dechlorination and/or may lead to a series of redox reactions which may consecutively trigger biotically induced abiotic degradation. Finally, this study illustrates the valuable complementary application of compound-specific isotopic analysis combined with molecular biology tools to evaluate which biogeochemical processes are taking place in an aquifer contaminated with chlorinated ethenes.

[Changes of chlorine isotope composition characterize bacterial dehalogenation of dichloromethane].

PubMed

Ziakun, A M; Firsova, Iu E; Torgonskaia, M L; Doronina, N V; Trotsenko, Iu A

2007-01-01

Fractionation of dichloromethane (DCM) molecules with different chlorine isotopes by aerobic methylobacteria Methylobacterium dichloromethanicum DM4 and Albibacter nethylovorans DM10; cell-free extract of strain DM4; and transconjugant Methylobacterium evtorquens Al1/pME 8220, expressing the dcmA gene for DCM dehalogenase but unable to grow on DCM, was studied. Kinetic indices of DCM isotopomers for chlorine during bacterial dehalogenation and diffusion were compared. A two-step model is proposed, which suggests diffusional DCM transport to bacterial cells.

Monitoring biodegradation of ethene and bioremediation of chlorinated ethenes at a contaminated site using compound-specific isotope analysis (CSIA)

USGS Publications Warehouse

Mundle, S.O.C.; Johnson, T.; Lacrampe-Couloume, G.; Perez-De-Mora, A.; Duhamel, M.; Edwards, E.A.; McMaster, M.L.; Cox, E.; Revesz, K.; Lollar, B. Sherwood

2012-01-01

Chlorinated ethenes are commonly found in contaminated groundwater. Remediation strategies focus on transformation processes that will ultimately lead to nontoxic products. A major concern with these strategies is the possibility of incomplete dechlorination and accumulation of toxic daughter products (cis-1,2-dichloroethene (cDCE), vinyl chloride (VC)). Ethene mass balance can be used as a direct indicator to assess the effectiveness of dechlorination. However, the microbial processes that affect ethene are not well characterized and poor mass balance may reflect biotransformation of ethene rather than incomplete dechlorination. Microbial degradation of ethene is commonly observed in aerobic systems but fewer cases have been reported in anaerobic systems. Limited information is available on the isotope enrichment factors associated with these processes. Using compound-specific isotope analysis (CSIA) we determined the enrichment factors associated with microbial degradation of ethene in anaerobic microcosms (ε = −6.7‰ ± 0.4‰, and −4.0‰ ± 0.8‰) from cultures collected from the Twin Lakes wetland area at the Savannah River site in Georgia (United States), and in aerobic microcosms (ε = −3.0‰ ± 0.3‰) from Mycobacterium sp. strain JS60. Under anaerobic and aerobic conditions, CSIA can be used to determine whether biotransformation of ethene is occurring in addition to biodegradation of the chlorinated ethenes. Using δ13C values determined for ethene and for chlorinated ethenes at a contaminated field site undergoing bioremediation, this study demonstrates how CSIA of ethene can be used to reduce uncertainty and risk at a site by distinguishing between actual mass balance deficits during reductive dechlorination and apparent lack of mass balance that is related to biotransformation of ethene.

Monitoring biodegradation of ethene and bioremediation of chlorinated ethenes at a contaminated site using compound-specific isotope analysis (CSIA).

PubMed

Mundle, Scott O C; Johnson, Tiffany; Lacrampe-Couloume, Georges; Pérez-de-Mora, Alfredo; Duhamel, Melanie; Edwards, Elizabeth A; McMaster, Michaye L; Cox, Evan; Révész, Kinga; Sherwood Lollar, Barbara

2012-02-07

Chlorinated ethenes are commonly found in contaminated groundwater. Remediation strategies focus on transformation processes that will ultimately lead to nontoxic products. A major concern with these strategies is the possibility of incomplete dechlorination and accumulation of toxic daughter products (cis-1,2-dichloroethene (cDCE), vinyl chloride (VC)). Ethene mass balance can be used as a direct indicator to assess the effectiveness of dechlorination. However, the microbial processes that affect ethene are not well characterized and poor mass balance may reflect biotransformation of ethene rather than incomplete dechlorination. Microbial degradation of ethene is commonly observed in aerobic systems but fewer cases have been reported in anaerobic systems. Limited information is available on the isotope enrichment factors associated with these processes. Using compound-specific isotope analysis (CSIA) we determined the enrichment factors associated with microbial degradation of ethene in anaerobic microcosms (ε = -6.7‰ ± 0.4‰, and -4.0‰ ± 0.8‰) from cultures collected from the Twin Lakes wetland area at the Savannah River site in Georgia (United States), and in aerobic microcosms (ε = -3.0‰ ± 0.3‰) from Mycobacterium sp. strain JS60. Under anaerobic and aerobic conditions, CSIA can be used to determine whether biotransformation of ethene is occurring in addition to biodegradation of the chlorinated ethenes. Using δ(13)C values determined for ethene and for chlorinated ethenes at a contaminated field site undergoing bioremediation, this study demonstrates how CSIA of ethene can be used to reduce uncertainty and risk at a site by distinguishing between actual mass balance deficits during reductive dechlorination and apparent lack of mass balance that is related to biotransformation of ethene.

The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.

ERIC Educational Resources Information Center

O'Malley, Rebecca M.

1982-01-01

Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

What's New in the Site Characterization Tool Box: Molecular Biological Tools to Identify Microorganisms that Degrade Contaminants and Contaminant-Specific Isotope Analysis to Identify Sources and Document Degradation

EPA Science Inventory

In the past, it was necessary to conduct intensive sampling and monitoring of concentrations of contaminants in ground water to trace plumes back to their true source. Now it is possible to determine the ratio of stable isotopes of carbon, hydrogen or chlorine in the contaminan...

The Chlorine Isotope Composition of the Solar Nebula & Implications to the Sources of Volatiles to the Terrestrial Planets

NASA Astrophysics Data System (ADS)

Gargano, A. M.; Sharp, Z. D.

2017-12-01

It was originally proposed by Sharp et al., 2016 that the solar nebula was isotopically light based on limited sampling of the Ol-phyric shergottites and two ordinary chondrites (Parnallee LL3.00, and NWA 8276 L3.00). Iron meteorites are remnants of early planetesimals which segregated cores <1Ma after CAI's and have δ37Cl values as low as -7‰, consistent with a light nebular source. Chondrules are relatively younger than iron meteorite parent bodies (2-3Ma after CAI's) and exhibit evidence for mixing with & recycling numerous isotopically distinct precursors as observed by Cl rich chondrules in Semarkona, and Qingzhen. The average δ37Cl values of chondrites are around 0‰, independent of petrologic type or [Cl], suggesting that chondrule forming regions have similar chlorine isotope sources. The average δ37Cl values of chondrites are consistent with a +3 to +6‰ isotopic fractionation of HCl clathrate from HCl gas, which occurred beyond the snow-line at 150K. The recycling of chondritic precursors mixed with HCl clathrate can account for pristine type 3.00 chondrites with δ37Cl values at approximately 0‰ independent of [Cl], or petrologic type. The source of volatiles to the terrestrial planets is commonly assumed to be chondritic in origin. These preliminary chlorine isotope data suggest that early planetesimals and planetary embryos had a solar Cl component at -7‰ or less, and secondary processes has since increased the δ37Cl values of Earth, Mars, and most chondrites. The chlorine isotope system therefore provides a new constraint regarding the sources of volatiles to the terrestrial planets. The δ37Cl value of the bulk Earth is around 0‰, inconsistent with a nebular source as measured in the Martian mantle but similar to that of chondrites with HCl clathrate precursors. The prolonged accretion of heavy chondritic material to Earth can account for the chlorine isotope discrepancy between the Earth and Mars, but is unconstrained by HSE abundances before complete core-mantle differentiation. Here, we examine the amount of chondritic chlorine and water that can added to the Earth allowable by HSE abundances and explore other potential sources of volatiles to the terrestrial planets to account for isotopic and elemental discrepancies.

Chlorine isotope fractionation between chloride (Cl-) and dichlorine (Cl2)

NASA Astrophysics Data System (ADS)

Giunta, Thomas; Labidi, Jabrane; Eggenkamp, Hans G. M.

2017-09-01

The use of chlorine stable isotopes (35Cl and 37Cl) can help to constrain natural processes that involve chlorine species with different oxidation states. Theoretical studies based on thermodynamic and quantum mechanical approaches predict large isotope fractionation during redox reactions but to date, these reactions have not been studied experimentally. Here, we explore the chlorine isotope fractionation during the oxidation of hydrated Cl- (redox state of -I) to Cl2 (redox state of 0) at 25 °C and at 0 °C. Our apparatus consists of a sealed glass reactor where liquid HCl is mixed with liquid H2O2, a strong oxidant. Following complex reaction pathways, this mixture ultimately leads to the oxidation of Cl- and to the formation of Cl2 gas. As long as it is degassing, the Cl2 gas is flushed out of solution using N2 as a vector-gas from the glass-reactor to a potassium hydroxide (KOH) solution (pH 14) where it disproportionates into soluble species: Cl- and ClO-. After each experiment, the chlorine isotopic composition was measured in the recovered KOH-trap solution, as well as in the residual HCl solution. Consistent with theoretical predictions, the produced Cl2 gas is always enriched in the heavier 37Cl as compared to the initial Cl-reservoir. The following isotope fractionation factors are obtained: At 0 °C the isotopic fractionation 1000ln α(Cl2-Cl-) is 4.51 (+1.65/-0.49)‰ At 25 °C the isotopic fractionation 1000ln α(Cl2-Cl-) is 3.94 (+0.69/-0.18)‰. From the obtained data it is suggested that the production of Cl2 gas in our experiments is best described by a closed-system distillation. Our results are in agreement with published theoretical ab-initio calculations.

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.

A Method for Analyzing A+2 Isotope Patterns for Use in Undergraduate Organic Courses

ERIC Educational Resources Information Center

Gross, Ray A.

2007-01-01

A novel ratio method is developed and automated for finding the bromine-chlorine-sulfur stoichiometry in the molecular formula of an unknown. This method is also useful in spectrometric analysis or beginning organic chemistry.

Anaerobic microbial dehalogenation and its key players in the contaminated Bitterfeld-Wolfen megasite.

PubMed

Nijenhuis, Ivonne; Stollberg, Reiner; Lechner, Ute

2018-04-01

The megasite Bitterfeld-Wolfen is highly contaminated as a result of accidents and because of dumping of wastes from local chemical industries in the last century. A variety of contaminants including chlorinated ethenes and benzenes, hexachlorohexanes and chlorinated dioxins can still be found in the groundwater and (river) sediments. Investigations of the in situ microbial transformation of organohalides have been performed only over the last two decades at this megasite. In this review, we summarise the research on the activity of anaerobic dehalogenating bacteria at the field site in Bitterfeld-Wolfen, focusing on chlorinated ethenes, monochlorobenzene and chlorinated dioxins. Various methods and concepts were applied including ex situ cultivation and isolation, and in situ analysis of hydrochemical parameters, compound-specific stable isotope analysis of contaminants, 13C-tracer studies and molecular markers. Overall, biotransformation of organohalides is ongoing at the field site and Dehalococcoides mccartyi species play an important role in the detoxification process in the Bitterfeld-Wolfen region.

Compound-Specific Chlorine Isotope Analysis of Tetrachloromethane and Trichloromethane by Gas Chromatography-Isotope Ratio Mass Spectrometry vs Gas Chromatography-Quadrupole Mass Spectrometry: Method Development and Evaluation of Precision and Trueness.

PubMed

Heckel, Benjamin; Rodríguez-Fernández, Diana; Torrentó, Clara; Meyer, Armin; Palau, Jordi; Domènech, Cristina; Rosell, Mònica; Soler, Albert; Hunkeler, Daniel; Elsner, Martin

2017-03-21

Compound-specific chlorine isotope analysis of tetrachloromethane (CCl 4 ) and trichloromethane (CHCl 3 ) was explored by both, gas chromatography-isotope ratio mass spectrometry (GC-IRMS) and GC-quadrupole MS (GC-qMS), where GC-qMS was validated in an interlaboratory comparison between Munich and Neuchâtel with the same type of commercial GC-qMS instrument. GC-IRMS measurements analyzed CCl isotopologue ions, whereas GC-qMS analyzed the isotopologue ions CCl 3 , CCl 2 , CCl (of CCl 4 ) and CHCl 3 , CHCl 2 , CHCl (of CHCl 3 ), respectively. Lowest amount dependence (good linearity) was obtained (i) in H-containing fragment ions where interference of 35 Cl- to 37 Cl-containing ions was avoided; (ii) with tuning parameters favoring one predominant rather than multiple fragment ions in the mass spectra. Optimized GC-qMS parameters (dwell time 70 ms, 2 most abundant ions) resulted in standard deviations of 0.2‰ (CHCl 3 ) and 0.4‰ (CCl 4 ), which are only about twice as large as 0.1‰ and 0.2‰ for GC-IRMS. To compare also the trueness of both methods and laboratories, samples from CCl 4 and CHCl 3 degradation experiments were analyzed and calibrated against isotopically different reference standards for both CCl 4 and CHCl 3 (two of each). Excellent agreement confirms that true results can be obtained by both methods provided that a consistent set of isotopically characterized reference materials is used.

A Chlorine-Centric Perspective on Fluid-Mediated Processes at Convergent Plate Boundaries

NASA Astrophysics Data System (ADS)

Selverstone, J.

2014-12-01

The release and migration of metamorphic fluids from subducting slabs into overlying mantle is widely recognized as a major mechanism in producing arc geochemical signatures and returning fluid-mobile elements to earth's crust and surface environments. Although the magnitudes of many geochemical fluxes are well constrained, the processes whereby mass transfer occurs in different portions of the subduction system are less well known. Chlorine stable isotopes provide a new perspective on some of these processes: Cl is hydrophilic, but decarbonation reactions favor Cl retention in minerals. Cl also shows less isotopic fractionation than other fluid-sensitive systems and may thus preserve evidence of specific fluid sources and/or fluid mixing events. Detailed studies of sedimentary sequences show that individual beds are isotopically homogeneous but large heterogeneities in δ37Cl exist across beds on a cm to m scale and vary as a function of depositional environment. Compositionally correlative medium-, high-, and ultrahigh-pressure metamorphic sequences in the Alps record decreases of 30-50% in Cl contents in the earliest stages of metamorphism, but little change thereafter. No statistically significant change in isotopic composition occurs during prograde metamorphism of individual horizons, and the same large degree of isotopic heterogeneity (up to 6‰) persists throughout the prograde devolatilization history of the rocks. Likewise, analysis of HP/UHP serpentinites and altered oceanic crust show that heterogeneous protolith compositions are preserved during transport to sub-arc depths, despite large-scale devolatilization. However, upward transport of rocks within the subduction channel results in highly localized interaction with isotopically distinct, Cl-bearing fluid packets. Overlying forearc wedge rocks also record heterogeneous and channelized interaction with distinct fluid components with different δ37Cl. Within-layer fluid compartmentalization during continuous devolatilization reactions must thus be reconciled with discontinuous, cross-layer fluid percolation out of the slab and into the wedge. The resulting implications of the chlorine data for recent mechanical models of slab-to-wedge fluid transport will be discussed.

Evaluating the fate of chlorinated ethenes in streambed sediments by combining stable isotope, geochemical and microbial methods

NASA Astrophysics Data System (ADS)

Abe, Yumiko; Aravena, Ramon; Zopfi, Jakob; Parker, Beth; Hunkeler, Daniel

2009-06-01

The occurrence of chlorinated ethene transformation in a streambed was investigated using concentration and carbon isotope data from water samples taken at different locations and depths within a 15 × 25 m study area across which a tetrachloroethene (PCE) plume discharges. Furthermore, it was evaluated how the degree of transformation is related to groundwater discharge rates, redox conditions, solid organic matter content (SOM) and microbial factors. Groundwater discharge rates were quantified based on streambed temperatures, and redox conditions using concentrations of dissolved redox-sensitive species. The degree of chlorinated ethene transformation was highly variable in space from no transformation to transformation beyond ethene. Complete reductive dechlorination to ethane and ethene occurred at locations with at least sulfate-reducing conditions and with a residence time in the samples streambed zone (80 cm depth) of at least 10 days. Among these locations, Dehalococcoides was detected using a PCR method where SOM contents were > 2% w/w and where transformation proceeded beyond ethene. However, it was not detected at locations with low SOM, which may cause an insufficient H 2 supply to sustain a detectably dense Dehalococcoides population. Additionally, it is possible that other organisms are responsible for the biodegradation. A microcosm study with streambed sediments demonstrated the potential of VC oxidation throughout the site even at locations without a pre-exposure to VC, consistent with the detection of the epoxyalkane:coenzyme M transferase (EaCoMT) gene involved in the degradation of chlorinated ethenes via epoxidation. In contrast, no aerobic transformation of cDCE in microcosms over a period of 1.5 years was observed. In summary, the study demonstrated that carbon isotope analysis is a sensitive tool to identify the degree of chlorinated ethene transformation even in hydrologically and geochemically complex streambed systems. In addition, it was observed that the degree of transformation is related to redox conditions, which in turn depend on groundwater discharge rates.

Origin of PCDDs in ball clay assessed with compound-specific chlorine isotope analysis and radiocarbon dating.

PubMed

Holmstrand, Henry; Gadomski, Damien; Mandalakis, Manolis; Tysklind, Mats; Irvine, Robert; Andersson, Per; Gustafsson, Orjan

2006-06-15

Polychlorinated dibenzo-p-dioxins (PCDDs) of high concentrations in a ball clay deposit from the Mississippi Embayment were found to be consistent with a natural abiotic and non-pyrogenic origin by investigation with bulk radiocarbon analysis, compound-specific chlorine isotope analysis (CSIA-delta37Cl) of octachlorodibenzo-p-dioxin (OCDD), and black carbon (BC) analysis. The conventional radiocarbon date of total organic carbon from a depth of approximately 10 m in three parallel cores ranged from 14 700 years to >48 000 years, indicating that the strata with elevated levels of PCDDs have remained isolated from recent anthropogenic input in these >40 Ma old clay sediments. The CSIA-delta37Cl of OCDD yielded a delta37Cl of -0.2 per thousandth, which is significantly higher than the postulated range for biotic chlorination by chloroperoxidase enzymes, -11 to -10 per thousandth, and falls within the known range for abiotic organochlorines, -6 to +3 per thousandth. The absence of correlations between concentrations of PCDDs and corresponding pyrogenic black carbon (BC), together with estimations of BC sorptive loadings and the absence of polychlorinated dibenzofurans (PCDFs), suggest that vegetation fires did not form these ball-clay PCDDs. Results from this study indicate that the high levels of the toxic and carcinogenic PCDDs found in kaolinite-bearing clays may result from natural abiotic formation via in situ surface-promoted reactions on the clay mineral, including a so-far unknown organic precursor, rather than being the result of anthropogenic contamination.

Application of Stable Isotope Analysis to Understand Behavior of Chlorinated Solvents

EPA Science Inventory

The traditional approach of monitoring a reduction in the concentrations of contaminants at sites does not always offer compelling documentation that the contaminants are actually being degraded. When data on concentrations are the only data available, it is may be difficult or i...

Stable Isotope Systematics of Martian Perchlorate

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

DTIC Science & Technology

2011-12-01

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

Approaches for the Analysis of Chlorinated Lipids

PubMed Central

Wang, Wen-yi; Albert, Carolyn J.; Ford, David A.

2013-01-01

Leukocytes are key cellular mediators of human diseases through their role in inflammation. Identifying unique molecules produced by leukocytes may provide new biomarkers and mechanistic insights into the role of leukocytes in disease. Chlorinated lipids are generated as a result of myeloperoxidase-containing leukocyte-derived hypochlorous acid targeting the vinyl ether bond of plasmalogens. The initial product of this reaction is α-chlorofatty aldehyde. α -Chlorofatty aldehyde is both oxidized to α-chlorofatty acid and reduced to α-chlorofatty alcohol by cellular metabolism. This review focuses on the separation techniques and quantitative analysis for these chlorinated lipids. For α-chlorofatty acid the negative charge of carboxylic acids is exploited to detect the chlorinated lipid species of these acids by electrospray ionization mass spectrometry in the negative ion mode. In contrast, α-chlorofatty aldehyde and α-chlorofatty alcohol are converted to pentafluorobenzyl oxime and pentafluorobenzoyl ester derivatives, which are detected by negative ion-chemical ionization mass spectrometry. These two detection methods coupled with the use of stable isotope internal standards and either liquid chromatography or gas chromatography provide highly sensitive analytical approaches to measure these novel lipids. PMID:24056259

Complementing approaches to demonstrate chlorinated solvent biodegradation in a complex pollution plume: Mass balance, PCR and compound-specific stable isotope analysis

NASA Astrophysics Data System (ADS)

Courbet, Christelle; Rivière, Agnès; Jeannottat, Simon; Rinaldi, Sandro; Hunkeler, Daniel; Bendjoudi, Hocine; de Marsily, Ghislain

2011-11-01

This work describes the use of different complementing methods (mass balance, polymerase chain reaction assays and compound-specific stable isotope analysis) to demonstrate the existence and effectiveness of biodegradation of chlorinated solvents in an alluvial aquifer. The solvent-contaminated site is an old chemical factory located in an alluvial plain in France. As most of the chlorinated contaminants currently found in the groundwater at this site were produced by local industries at various times in the past, it is not enough to analyze chlorinated solvent concentrations along a flow path to convincingly demonstrate biodegradation. Moreover, only a few data were initially available to characterize the geochemical conditions at this site, which were apparently complex at the source zone due to (i) the presence of a steady oxygen supply to the groundwater by irrigation canal losses and river infiltration and (ii) an alkaline pH higher than 10 due to former underground lime disposal. A demonstration of the existence of biodegradation processes was however required by the regulatory authority within a timeframe that did not allow a full geochemical characterization of such a complex site. Thus a combination of different fast methods was used to obtain a proof of the biodegradation occurrence. First, a mass balance analysis was performed which revealed the existence of a strong natural attenuation process (biodegradation, volatilization or dilution), despite the huge uncertainty on these calculations. Second, a good agreement was found between carbon isotopic measurements and PCR assays (based on 16S RNA gene sequences and functional genes), which clearly indicated reductive dechlorination of different hydrocarbons (Tetrachloroethene—PCE-, Trichloroethene—TCE-, 1,2- cisDichloroethene— cis-1,2-DCE-, 1,2- transDichloroethene— trans-1,2-DCE-, 1,1-Dichloroethene—1,1-DCE-, and Vinyl Chloride—VC) to ethene. According to these carbon isotope measurements, although TCE biodegradation seems to occur only in the upgradient part of the studied zone, DCE and VC dechlorination (originating from the initial TCE dechlorination) occurs along the entire flowpath. TCE reductase was not detected among the Dehalococcoides bacteria identified by quantitative PCR (qPCR), while DCE and VC reductases were present in the majority of the population. Reverse transcriptase PCR assays (rt-PCR) also indicated that bacteria and their DCE and VC reductases were active. Mass balance calculations showed moreover that 1,1-DCE was the predominant DCE isomer produced by TCE dechlorination in the upgradient part of the site. Consequently, coupling rt-PCR assays with isotope measurements removes the uncertainties inherent in a simple mass balance approach, so that when the three methods are used jointly, they allow the identification and quantification of natural biodegradation, even under apparently complex geochemical and hydraulic conditions.

Improvements in Precise and Accurate Isotope Ratio Determination via LA-MC-ICP-MS by Application of an Alternative Data Reduction Protocol

NASA Astrophysics Data System (ADS)

Fietzke, J.; Liebetrau, V.; Guenther, D.; Frische, M.; Zumholz, K.; Hansteen, T. H.; Eisenhauer, A.

2008-12-01

An alternative approach for the evaluation of isotope ratio data using LA-MC-ICP-MS will be presented. In contrast to previously applied methods it is based on the simultaneous responses of all analyte isotopes of interest and the relevant interferences without performing a conventional background correction. Significant improvements in precision and accuracy can be achieved when applying this new method and will be discussed based on the results of two first methodical applications: a) radiogenic and stable Sr isotopes in carbonates b) stable chlorine isotopes of pyrohydrolytic extracts. In carbonates an external reproducibility of the 87Sr/86Sr ratios of about 19 ppm (RSD) was achieved, an improvement of about a factor of 5. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170±0.000007 (2SE) was determined, which agrees well with the value of 0.7091741±0.0000024 (2SE) reported for modern sea water [1,2]. Stable chlorine isotope ratios were determined ablating pyrohydrolytic extracts with a reproducibility of about 0.05‰ (RSD). For basaltic reference material JB1a and JB2 chlorine isotope ratios were determined relative to SMOC (standard mean ocean chlorinity) δ37ClJB-1a = (-0.99±0.06) ‰ and δ37ClJB-1a = (-0.60±0.03) ‰ (SD), respectively, in accordance with published data [3]. The described strategies for data reduction are considered to be generally applicable for all isotope ratio measurements using LA-MC-ICP-MS. [1] J.M. McArthur, D. Rio, F. Massari, D. Castradori, T.R. Bailey, M. Thirlwall, S. Houghton, Palaeogeo. Palaeoclim. Palaeoeco., 2006, 242 (126), doi: 10.1016/j.palaeo.2006.06.004 [2] J. Fietzke, V. Liebetrau, D. Guenther, K. Guers, K. Hametner, K. Zumholz, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 955-961, doi:10.1039/B717706B [3] J. Fietzke, M. Frische, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 769-772, doi:10.1039/B718597A

Analysis of solid uranium samples using a small mass spectrometer

NASA Astrophysics Data System (ADS)

Kahr, Michael S.; Abney, Kent D.; Olivares, José A.

2001-07-01

A mass spectrometer for isotopic analysis of solid uranium samples has been constructed and evaluated. This system employs the fluorinating agent chlorine trifluoride (ClF 3) to convert solid uranium samples into their volatile uranium hexafluorides (UF 6). The majority of unwanted gaseous byproducts and remaining ClF 3 are removed from the sample vessel by condensing the UF 6 and then pumping away the unwanted gases. The UF 6 gas is then introduced into a quadrupole mass spectrometer and ionized by electron impact ionization. The doubly charged bare metal uranium ion (U 2+) is used to determine the U 235/U 238 isotopic ratio. Precision and accuracy for several isotopic standards were found to be better than 12%, without further calibration of the system. The analysis can be completed in 25 min from sample loading, to UF 6 reaction, to mass spectral analysis. The method is amenable to uranium solid matrices, and other actinides.

The Chlorine Isotope Composition of Earth’s Mantle

NASA Astrophysics Data System (ADS)

Bonifacie, M.; Jendrzejewski, N.; Agrinier, P.; Humler, E.; Coleman, M.; Javoy, M.

2008-03-01

Chlorine stable isotope compositions (δ37Cl) of 22 mid-ocean ridge basalts (MORBs) correlate with Cl content. The high-δ37Cl, Cl-rich basalts are highly contaminated by Cl-rich materials (seawater, brines, or altered rocks). The low-δ37Cl, Cl-poor basalts approach the composition of uncontaminated, mantle-derived magmas. Thus, most or all oceanic lavas are contaminated to some extent during their emplacement. MORB-source mantle has δ37Cl ≤ 1.6 per mil (‰), which is significantly lower than that of surface reservoirs (~ 0‰). This isotopic difference between the surface and deep Earth results from net Cl isotopic fractionation (associated with removal of Cl from the mantle and its return by subduction over Earth history) and/or the addition (to external reservoirs) of a late volatile supply that is 37Cl-enriched.

The chlorine isotope composition of the moon and implications for an anhydrous mantle.

PubMed

Sharp, Z D; Shearer, C K; McKeegan, K D; Barnes, J D; Wang, Y Q

2010-08-27

Arguably, the most striking geochemical distinction between Earth and the Moon has been the virtual lack of water (hydrogen) in the latter. This conclusion was recently challenged on the basis of geochemical data from lunar materials that suggest that the Moon's water content might be far higher than previously believed. We measured the chlorine isotope composition of Apollo basalts and glasses and found that the range of isotopic values [from -1 to +24 per mil (per thousand) versus standard mean ocean chloride] is 25 times the range for Earth. The huge isotopic spread is explained by volatilization of metal halides during basalt eruption--a process that could only occur if the Moon had hydrogen concentrations lower than those of Earth by a factor of approximately 10(4) to 10(5), implying that the lunar interior is essentially anhydrous.

Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

NASA Astrophysics Data System (ADS)

Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

2013-04-01

Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation. The method was developed for the multi-element isotope analysis (carbon and hydrogen) of priority volatile organic groundwater pollutants (methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene and o-xylene (BTEX)), and for carbon isotope analysis of chlorinated benzenes and ethenes. The extraction and injection conditions were optimized in terms of maximum sensitivity and minimum isotope effects. During the injection of the headspace sample, the liner is maintained at a low temperature, such that the compounds are retained in a hydrophobic insert packing while the water vapor is eliminated through the split line. With the optimized conditions, it was possible to inject up to 5mL headspace sample with no significant carbon or hydrogen isotopic effects except for the most hydrophobic substance (MTBE), which was subject to a small and reproducible isotope fractionation for hydrogen. The increment on method sensitivity was at least 20 fold in comparison with conventional static headspace analysis. The environmental applicability of the HS-PTV-GC-IRMS method was evaluated by the analysis of groundwater samples from different contaminated field sites, containing BTEX and chlorinated volatile organic contaminants in the low µg/L range. The results obtained demonstrate that this pre-concentration technique is highly promising to enhance the limits of detection of current CSIA methods and broaden its possibilities.

Stable carbon isotope fractionation of chlorinated ethenes by a microbial consortium containing multiple dechlorinating genes.

PubMed

Liu, Na; Ding, Longzhen; Li, Haijun; Zhang, Pengpeng; Zheng, Jixing; Weng, Chih-Huang

2018-08-01

The study aimed to determine the possible contribution of specific growth conditions and community structures to variable carbon enrichment factors (Ɛ- carbon ) values for the degradation of chlorinated ethenes (CEs) by a bacterial consortium with multiple dechlorinating genes. Ɛ- carbon values for trichloroethylene, cis-1,2-dichloroethylene, and vinyl chloride were -7.24% ± 0.59%, -14.6% ± 1.71%, and -21.1% ± 1.14%, respectively, during their degradation by a microbial consortium containing multiple dechlorinating genes including tceA and vcrA. The Ɛ- carbon values of all CEs were not greatly affected by changes in growth conditions and community structures, which directly or indirectly affected reductive dechlorination of CEs by this consortium. Stability analysis provided evidence that the presence of multiple dechlorinating genes within a microbial consortium had little effect on carbon isotope fractionation, as long as the genes have definite, non-overlapping functions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

NASA Astrophysics Data System (ADS)

Boulyga, Sergei F.; Heumann, Klaus G.

2005-04-01

Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark(TM)-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3-3 was observed when changing the nebulizer gas flow rate in the range of 0.84-1.0 L min-1 and the laser power density in the range of 2-10 GW cm-2, respectively. When using an internal standard for halogen quantification in LA-ICP-MS, this inter-element fractionation can cause systematic errors, which can be avoided by applying the isotope dilution technique. However, at high laser power densities (>5.7 GW cm-2 for iodine and >4.0 GW cm-2 for bromine and chlorine) the corresponding measured isotope ratio of the isotope-diluted sample deviates significantly from the target value. Under optimised conditions concentrations in the range of 30 [mu]g g-1-16 × 103 [mu]g g-1 for chlorine, <2-140 [mu]g g-1 for bromine, and <0.1-31 [mu]g g-1 for iodine were determined by LA-ICP-IDMS in two sediment reference materials (SRM 1646, SRM 2704) and three rock reference samples (GS-N, Granite; BX-N, Bauxite; DT-N, Disthene), which have not been certified for these halogens. The sediment results agree well within the given uncertainties with indicative values by different methods and the results of the rock samples with those obtained by negative thermal ionisation isotope dilution mass spectrometry. The detection limits of LA-ICP-IDMS are 8 [mu]g g-1 for chlorine, 1.7 [mu]g g-1 for bromine, and 0.1 [mu]g g-1 for iodine.

Chlorine isotope fractionation during supergene enrichment of copper

NASA Astrophysics Data System (ADS)

Reich, M.; Barnes, J.; Barra, F.; Milojevic, C.; Drew, D.

2017-12-01

Supergene enrichment of Cu deposits in the Atacama Desert has played a critical role in making this the prime Cu-producing province of the world. The Cu-hydroxychloride atacamite is a major component of supergene zones in this region whereas in similar deposits elsewhere it is rare. Atacamite requires saline water to form and dissolves rapidly when exposed to fresh, meteoric water. Previous chlorine stable isotope data [1] for atacamite mineralization at the Radomiro Tomic, Chuquicamata and Mina Sur Cu deposits show δ37Cl values that range from -0.1 to +0.2‰, indicating a similar nonmagmatic source for the introduction of chloride. However, distal atacamite mineralization on the periphery of these orebodies show more fractionated and lighter δ37Cl values (-3.2 to -0.1‰). Although little disagreement currently exists about the involvement of saline groundwater during the formation of atacamite [2], no δ37Cl data are currently available for atacamite within a single deposit and/or supergene enrichment profile that allow explaining the aforementioned differences in the observed δ37Cl values. Furthermore, no experimental data for chlorine isotope fractionation between Cu-hydroxychloride minerals and water exist that help evaluate possible mechanisms of fractionation along the groundwater flow path. Here we present a new database that combines detailed mineralogical observations with δ37Cl data of atacamite along a thick ( 100 m) supergene enrichment profile at the Barreal Seco IOCG deposit in the Atacama Desert of northern Chile. Chlorine stable isotope data of atacamite vary between -0.62 and +2.1 ‰ and show a well-defined trend where δ37Cl values progressively decrease (become lighter) with depth. These data, when combined with new experimental determinations of chlorine isotope fractionation between atacamite and water, point to changes triggered by the progressive deepening of groundwater tables during Andean uplift and the extreme desiccation of Atacama. References [1] Arcuri T, Brimhall G (2003) The chloride source for atacamite mineralization at the Radomiro Tomic porphyry copper deposit, Northern Chile. Econ Geol 98:1667-1681 [2] Reich M et al. (2009) Supergene enrichment of copper deposits since the onset of modern hyperaridity in the Atacama Desert, Chile. Miner Deposita 44: 497-504

Tracing chlorine sources of thermal and mineral springs along and across the Cascade Range using halogen and chlorine isotope compositions

USGS Publications Warehouse

Cullen, Jeffrey T.; Barnes, Jaime D.; Hurwitz, Shaul; Leeman, William P.

2015-01-01

In order to provide constraints on the sources of chlorine in spring waters associated with arc volcanism, the major/minor element concentrations and stable isotope compositions of chlorine, oxygen, and hydrogen were measured in 28 thermal and mineral springs along the Cascade Range in northwestern USA. Chloride concentrations in the springs range from 64 to 19,000 mg/L and View the MathML source values range from +0.2‰ to +1.9‰ (average=+1.0±0.4‰), with no systematic variation along or across the arc, nor correlations with their presumed underlying basement lithologies. Additionally, nine geochemically well-characterized lavas from across the Mt. St. Helens/Mt. Adams region of the Cascade Range (Leeman et al., 2004 and Leeman et al., 2005) were analyzed for their halogen concentrations and Cl isotope compositions. In the arc lavas, Cl and Br concentrations from the volcanic front are higher than in lavas from the forearc and backarc. F and I concentrations progressively decrease from forearc to backarc, similar to the trend documented for B in most arcs. View the MathML source values of the lavas range from −0.1 to +0.8‰ (average = +0.4±0.3‰). Our results suggest that the predominantly positive View the MathML source values observed in the springs are consistent with water interaction with underlying 37Cl-enriched basalt and/or altered oceanic crust, thereby making thermal spring waters a reasonable proxy for the Cl isotope compositions of associated volcanic rocks in the Cascades. However, waters with View the MathML source values >+1.0‰ also suggest additional contributions of chlorine degassed from cooling magmas due to subsurface vapor–liquid HCl fractionation in which Cl is lost to the aqueous fluid phase and 37Cl is concentrated in the ascending magmatic HCl vapor. Future work is necessary to better constrain Cl isotope behavior during volcanic degassing and fluid–rock interaction in order to improve volatile flux estimates through subduction zones.

Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

NASA Astrophysics Data System (ADS)

Jin, Biao; Rolle, Massimo

2016-04-01

Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M., 2013. Integrated carbon and chlorine isotope modeling: Applications to chlorinated aliphatic hydrocarbons dechlorination. Environ. Sci. Technol. 47, 1443-1451. doi:10.1021/es304053h. [3] Jin, B., Rolle, M., 2014. Mechanistic approach to multi-element isotope modeling of organic contaminant degradation. Chemosphere 95, 131-139. doi:10.1016/j.chemosphere.2013.08.050.

ω-Oxidation of α-Chlorinated Fatty Acids

PubMed Central

Brahmbhatt, Viral V.; Albert, Carolyn J.; Anbukumar, Dhanalakshmi S.; Cunningham, Bryce A.; Neumann, William L.; Ford, David A.

2010-01-01

Myeloperoxidase-derived HOCl targets tissue- and lipoprotein-associated plasmalogens to generate α-chlorinated fatty aldehydes, including 2-chlorohexadecanal. Under physiological conditions, 2-chlorohexadecanal is oxidized to 2-chlorohexadecanoic acid (2-ClHA). This study demonstrates the catabolism of 2-ClHA by ω-oxidation and subsequent β-oxidation from the ω-end. Mass spectrometric analyses revealed that 2-ClHA is ω-oxidized in the presence of liver microsomes with initial ω-hydroxylation of 2-ClHA. Subsequent oxidation steps were examined in a human hepatocellular cell line (HepG2). Three different α-chlorinated dicarboxylic acids, 2-chlorohexadecane-(1,16)-dioic acid, 2-chlorotetradecane-(1,14)-dioic acid, and 2-chloroadipic acid (2-ClAdA), were identified. Levels of 2-chlorohexadecane-(1,16)-dioic acid, 2-chlorotetradecane-(1,14)-dioic acid, and 2-ClAdA produced by HepG2 cells were dependent on the concentration of 2-ClHA and the incubation time. Synthetic stable isotope-labeled 2-ClHA was used to demonstrate a precursor-product relationship between 2-ClHA and the α-chlorinated dicarboxylic acids. We also report the identification of endogenous 2-ClAdA in human and rat urine and elevations in stable isotope-labeled urinary 2-ClAdA in rats subjected to intraperitoneal administration of stable isotope-labeled 2-ClHA. Furthermore, urinary 2-ClAdA and plasma 2-ClHA levels are increased in LPS-treated rats. Taken together, these data show that 2-ClHA is ω-oxidized to generate α-chlorinated dicarboxylic acids, which include α-chloroadipic acid that is excreted in the urine. PMID:20956542

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

DTIC Science & Technology

2013-05-31

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

The Chlorine Isotope Composition of Martian Meteorites

NASA Astrophysics Data System (ADS)

Sharp, Z. D.; Shearer, C. K.; Agee, C.; Burger, P. V.; McKeegan, K. D.

2014-11-01

The Cl isotope composition of martian meteorites range from -3.8 to +8.6 per mil. Ol-phyric shergottites are lightest; crustally contaminated samples are heaviest, basaltic shergottites are in-between. The system is explained as two component mixing.

Data Validation Standard Operating Procedure for EPA Method 1613 Revision B, Tetra-through Octa-chlorinated Dioxins and Furans by Isotope Dillution (High Resolution Gas Chromatography/High Resolution Mass Spectrometry)

EPA Pesticide Factsheets

Method used for isomer specific determination todetect the Tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans associatedwith the CWA, RCRA, Comprehensive Environmental Response, Compensation and Liability Act and the SDWA

Performance and limits of liquid chromatography isotope ratio mass spectrometry system for halogenated compounds

NASA Astrophysics Data System (ADS)

Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans

2014-05-01

Compound Specific Isotope Analysis (CSIA) has been an important step for the assessment of the origin and fate of compounds in environmental science.[1] Biologically or pharmaceutically important compounds often are not amenable for gas chromatographic separation because of high polarity and lacking volatility, thermostability. In 2004 liquid chromatography isotope ratio mass spectrometry (LC-IRMS) became commercially available. LC-IRMS system intent a quantitative conversion of analytes separation into CO2 via wet oxidation with sodium persulfate in the presence of phosphoric acid while analytes are still dissolved in the aqueous liquid phase.[2] The aim of this study is to analyze the oxidation capacity of the interface of the LC-IRMS system and determine which parameters could improve oxidation of compounds which are resistant to persulfate oxidation. Oxidation capacity of the liquid chromatography isotope ratio mass spectrometry system was tested with halogenated acetic acid and a set of aromatic compounds with different substitutes. Acetic acid (AA) was taken as a model compound for complete oxidation and compared to the oxidation of other analytes on a molar basis. Correct values were obtained for di- and mono chlorinated and fluorinated and also for tribrominated acetic acid and for all studied aromatic compounds. Incomplete oxidation for trichloroacetic (TCAA) and trifluoroacetic (TFAA) acid was revealed with lower recovery compared to acetic acid and isotope fractionation leading to depleted carbon isotope composition compared to values obtained with an elementary analyzer connected to an isotope mass spectrometer Several optimization steps were tried in order to improve the oxidation of TCAA and TFAA: (i) increasing the concentration of the oxidizing agent, (ii) variation of flow rate of the oxidizing and acid solution, (iii) variation of flow rate of liquid chromatography pump (iv) addition of a catalyzer. These modifications lead to longer reaction time in the coil and increase in the concentration of radical but complete combustion of highly chlorinated or fluorinated compounds was not achieved. Due to these findings the limit for a LC-IRMS system for similar structure compounds can be predicted. 1. Elsner, M., et al., Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Analytical and Bioanalytical Chemistry, 2012. 403(9): p. 2471-2491. 2. Krummen, M., et al., A new concept for isotope ratio monitoring liquid chromatography/mass spectrometry. Rapid Communications in Mass Spectrometry, 2004. 18(19): p. 2260-2266.

METHOD OF PURIFYING CATALYSTS

DOEpatents

Joris, G.G.

1958-09-01

It has been fuund that the presence of chlorine as an impurity adversely affects the performance of finely divided platinum catalysts such as are used in the isotopic exchange process for the production of beavy water. This chlorine impurity may be removed from these catalysts by treating the catalyst at an elevated temperature with dry hydrogen and then with wet hydrogen, having a hydrogen-water vapor volume of about 8: 1. This alternate treatment by dry hydrogen and wet hydrogen is continued until the chlorine is largely removed from the catalyst.

Stable isotope sales: Mound Facility customer and shipment summaries, FY 1981

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

Ruwe, Jr, A H

1982-10-01

A listing is given of Mound Facility's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, chlorine, and sulfur for Fiscal Year 1981. Purchasers are listed alphabetically and are divided into domestic and foreign groups. A cross-reference index by location is included for domestic customers. Cross-reference listings by isotope purchased are included for all customers.

Compound-specific isotope analysis: Questioning the origins of a trichloroethene plume

USGS Publications Warehouse

Eberts, S.M.; Braun, C.; Jones, S.

2008-01-01

Stable carbon isotope ratios of trichloroethene (TCE), cis-1,2- dichloroethene, and trans-1,2-dichloroethene were determined by use of gas chromatography-combustion-isotope ratio mass spectroscopy to determine whether compound-specific stable carbon isotopes could be used to help understand the origin and history of a TCE groundwater plume in Fort Worth, TX. Calculated ??13C values for total chlorinated ethenes in groundwater samples, which can approximate the ??13C of a spilled solvent if all degradation products are accounted for, were useful for determining whether separate lobes of the plume resulted from different sources. Most notably, values for one lobe, where tetrachloroethene (PCE) has been detected periodically, were outside the range for manufactured TCE but within the range for manufactured PCE, whereas values for a separate lobe, which is downgradient of reported TCE spills, were within the range for manufactured TCE. Copyright ?? Taylor & Francis Group, LLC.

Evaluating potential chlorinated methanes degradation mechanisms and treatments in interception trenches filled with concrete-based construction wastes

NASA Astrophysics Data System (ADS)

Rodríguez-Fernandez, Diana; Torrentó, Clara; Rosell, Mònica; Audí-Miró, Carme; Soler, Albert

2014-05-01

A complex mixture of chlorinated organic compounds is located in an unconfined carbonated bedrock aquifer with low permeability in a former industrial area next to Barcelona (NE Spain). The site exhibited an especially high complexity due to the presence of multiple contaminant sources, wide variety of pollutants (mainly chlorinated ethenes but also chlorinated methanes) and unknown system of fractures (Palau et al., 2014). Interception trenches were installed in the place of the removed pollution sources and were filled with construction wastes with the aim of retaining and treating the accumulated contaminated recharge water before reaching the aquifer. Recycled concrete-based aggregates from a construction and demolition waste recycling plant were used to maintain alkaline conditions in the water accumulated in the trenches (pH 11.6±0.3) and thus induce chloroform (CF) degradation by alkaline hydrolysis. An efficacy of around 30-40% CF degradation in the interception trenches was calculated from the significant and reproducible CF carbon isotopic fractionation (-53±3o obtained in batch experiments (Torrentó et al., 2014). Surprisingly, although hydrolysis of carbon tetrachloride (CT) is extremely slow, a significant CT carbon isotopic enrichment was also observed in the trenches. The laboratory experiments verified the low capability of concrete to hydrolyze the CT and showed the high adsorption of CT on the concrete particles (73% after 50 days) with invariability in its δ13C values. Therefore, the significant CT isotopic fractionation observed in the interception trenches could point out the occurrence of other degradation processes distinct than alkaline hydrolysis. Geochemical speciation modelling using the code PHREEQC showed that water collected at the trenches is supersaturated with respect to several iron oxy-hydroxides and therefore, CT degradation processes related to these iron minerals cannot be discarded. In addition, the combination of alkaline conditions in the trenches with in situ chemical oxidation (ISCO), which would be able to remove the rest of the accompanying pollutants, is proposed and merits evaluation. Preliminary batch experiments were performed to evaluate the feasibility of different chemical oxidation reactions (permanganate, persulphate, hydrogen peroxide and Fenton) on the complex contaminated recharge water which were, in general, more effective for degrading the chlorinated ethenes than for the chlorinated methanes (Torrentó et al. EGU 2012). Therefore, this study seeks to improve the understanding of CF and CT degradation mechanisms/processes that are going on in the interception trenches as well as to select between the two most effective chemical oxidation remediation treatments (persulphate and permanganate) taking into account their efficiency respect the chlorinated methanes removal, the generated acute toxicity and the applicability of the carbon isotopic fractionation as an indicator of the effectiveness of the future in situ remediation. Additionally, ongoing batch experiments are expected to elucidate if CT is undergoing abiotic reductive dechlorination by Fe-bearing minerals such as hydrophobic green rust (Ayala-Luis et al., 2012) which transform CT into non-chlorinated substances such as formic acid and carbon monoxide. This unstable iron compound might be formed in the interception trenches during chloride induced corrosion of iron mineral phases present in the concrete-based construction wastes (Sagoe-Crentsil and Glasser, 1993). The role of other minerals like iron oxy-hydroxides, carbonates or sulphides cannot be discarded at all. The potential of δ13C values to assess the efficiency of this abiotic CT degradation reaction will be also evaluated. References Ayala-Luis, K.; Cooper, N.; Bender C. and Hansen. H. (2012) Efficient dechlorination of carbon tetrachloride by hydrophobic green rust intercaled with dodecanoate anions. Environmental Science & Technology 46, 3390-3397. Palau, J.; Marchesi, M.: Chambon, J.: Aravena, R.; Canals, A.; Binning, P. J., Bjerg P. L.; Otero, N.; Soler, A. (2014) Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes. Science of the Total Environment 475, 61-70. Sagoe-Crentsil, K.K.; Glasser, F.P. (1993) 'Green Rust', Iron Solubility and the Role of Chloride in the Corrosion of Steel at High pH,' Cement and Concrete Research, 23(4), 785-91. Torrentó, C., Audí-Miró, C., Marchesi, M., Otero, N. and Soler, A. (2012) Comparison of four oxidation processes for the treatment of water contaminated with a mixture of chlorinated volatile organic compounds. EGU General Assembly 2012. Vienna. Geophysical Research Abstracts, 14: EGU2012-11310. Torrentó, C.; Audí-Miró, C.; Bordeleau, G.; Marchesi, M.; Rosell, M.; Otero, N.; Soler, A. (2014) The use of alkaline hydrolysis as a novel strategy for chloroform remediation: the feasibility of using construction wastes and evaluation of carbon isotopic fractionation. Environmental Science & Technology, Just Accepted Manuscript (DOI: 10.1021/es403838t)

Experimental investigation of concentration and stable isotopes signals during organic contaminants back diffusion

NASA Astrophysics Data System (ADS)

Jin, Biao; Nika, Chrysanthi-Elisabeth; Rolle, Massimo

2017-04-01

Back diffusion of organic contaminants is often the cause of groundwater plumes' persistence and can significantly hinder cleanup interventions [1, 2]. In this study we perform a high-resolution investigation of back diffusion in a well-controlled flow-through laboratory setup. We considered cis-dichloroethene (cis-DCE) as model contaminant and we investigated its back diffusion from an impermeable source into a permeable saturated layer, in which advection-dominated flow conditions were established. We used concentration and stable chlorine isotope measurements to investigate the plumes originated by cis-DCE back diffusion in a series of flow-through experiments, performed in porous media with different hydraulic conductivity and at different seepage velocities (i.e., 0.4, 0.8 and 1.2 m/day). A two-centimeter thick agarose gel layer was placed at the bottom of the setup to simulate the source of cis-DCE back diffusion from an impervious layer. Intensive sampling (>1000 measurements) was carried out, including the withdrawal of aqueous samples at closely spaced (1 cm) outlet ports, as well as the high-resolution sampling of the source zone (agarose gel) at the end of each experiment. The transient behavior of the plumes originated by back diffusion was investigated by sampling the outlet ports at regular intervals in the experiments, each run for a total time corresponding to 15 pore volumes. The high-resolution sampling allowed us to resolve the spatial and temporal evolution of concentration and stable isotope gradients in the flow-through setup. In particular, steep concentration and stable isotope gradients were observed at the outlet. Lateral isotope gradients corresponding to chlorine isotope fractionation up to 20‰ were induced by cis-DCE back diffusion and subsequent advection-dominated transport in all flow-through experiments. A numerical modeling approach, tracking individually all chlorine isotopologues, based on the accurate parameterization of local dispersion, as well as on the values of aqueous diffusion coefficients and diffusion-induced isotope fractionation from a previous study [3], provided a good agreement with the experimental data. References [1] Mackay, D. M.; Cherry, J. A. Groundwater contamination: Pumpand-treat remediation. Environ. Sci. Technol. 1989, 23, 630-636. [2] Parker, B. L.; Chapman, S. W.; Guilbeault, M. A. Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation. J. Contam. Hydrol. 2008, 102, 19-19. [3] Jin, B., Rolle, M., Li, T., Haderlein, S.B., 2014. Diffusive fractionation of BTEX and chlorinated ethenes in aqueous solution: quantification of spatial isotope gradients. Environ. Sci. Technol. 48, 6141-6150.

Isotopic tracing of perchlorate in the environment

USGS Publications Warehouse

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

2012-01-01

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

Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

NASA Astrophysics Data System (ADS)

Blum, P.; Sültenfuß, J.; Martus, P.

2014-12-01

Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

Evaluation of perchlorate sources in the Rialto-Colton and Chino California subbasins using chlorine and oxygen isotope ratio analysis

USGS Publications Warehouse

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

2015-01-01

Perchlorate (ClO4-) in groundwater can be from synthetic or natural sources, the latter of which include both historical application of imported nitrate fertilizers from the Atacama Desert of Chile and naturally deposited ClO4- that forms atmospherically and accumulates in arid regions such as the southwestern US. The objective of this study was to evaluate the use of isotopic data to distinguish sources of ClO4- in groundwater in a specific region of the Rialto-Colton and Chino, CA groundwater subbasins (Study Area). This region includes two groundwater ClO4- plumes emanating from known military/industrial source areas, and a larger area outside of these plumes having measurable ClO4-. Perchlorate extracted from wells in this region was analyzed for chlorine and oxygen stable isotope ratios (δ37Cl, δ18O, δ17O) and radioactive chlorine-36 (36Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotope data indicate synthetic, Atacama, and indigenous natural ClO4- were present in the Study Area. Stable isotope data from nearly all sampled wells within the contours of the two characterized plumes, including those located in a perched zone and within the regional groundwater aquifer, were consistent with a dominant synthetic ClO4- source. In wells downgradient from the synthetic plumes and in the Chino subbasin to the southwest, isotopic data indicate the dominant source of ClO4- largely was Atacama, presumably from historical application of nitrate fertilizer in this region. Past agricultural land use and historical records are consistent with this source being present in groundwater. The 36Cl and δ18O data indicate that wells having predominantly synthetic or Atacama ClO4- also commonly contained small fractions of indigenous natural ClO4-. The indigenous ClO4- was most evident isotopically in wells having the lowest overall ClO4- concentrations (< 1 μg/L), consistent with its occurrence as a low-level background constituent in the region. A small subset of wells outside the contours of the two synthetic plumes, including an upgradient well, had characteristics indicating small amounts of synthetic ClO4- mixed with one or both of the natural source types. Hydrogeologic data indicate synthetic ClO4- in the upgradient well may be from a source other than the identified plume sources, but it is not known whether this source might also be present in other wells at low concentrations. The stable isotope and 36Cl data provided relatively unambiguous discrimination of synthetic and Atacama ClO4- sources in most wells having relatively high concentrations, providing regional perspective on anthropogenic ClO4- contamination in the Rialto-Colton and Chino subbasins. Where indigenous natural ClO4- was indicated as a substantial component, total ClO4- concentrations were low and concentrations of anthropogenic components were near background levels.

Liquid chromatography/electrospray ionization/isotopic dilution mass spectrometry analysis of n-(phosphonomethyl) glycine and mass spectrometry analysis of aminomethyl phosphonic acid in environmental water and vegetation matrixes.

PubMed

Grey, L; Nguyen, B; Yang, P

2001-01-01

A liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) method was developed for the analysis of glyphosate (n-phosphonomethyl glycine) and its metabolite, aminomethyl phosphonic acid (AMPA) using isotope-labelled glyphosate as a method surrogate. Optimized parameters were achieved to derivatize glyphosate and AMPA using 9-fluorenylmethyl chloroformate (FMOC-Cl) in borate buffer prior to a reversed-phase LC analysis. Method spike recovery data obtained using laboratory and real world sample matrixes indicated an excellent correlation between the recovery of the native and isotope-labelled glyphosate. Hence, the first performance-based, isotope dilution MS method with superior precision, accuracy, and data quality was developed for the analysis of glyphosate. There was, however, no observable correlation between the isotope-labelled glyphosate and AMPA. Thus, the use of this procedure for the accurate analysis of AMPA was not supported. Method detection limits established using standard U.S. Environmental Protection Agency protocol were 0.06 and 0.30 microg/L, respectively, for glyphosate and AMPA in water matrixes and 0.11 and 0.53 microg/g, respectively, in vegetation matrixes. Problems, solutions, and the method performance data related to the analysis of chlorine-treated drinking water samples are discussed. Applying this method to other environmental matrixes, e.g., soil, with minimum modifications is possible, assuring accurate, multimedia studies of glyphosate concentration in the environment and the delivery of useful multimedia information for regulatory applications.

Chlorine isotopic composition of perchlorate in human urine as a means of distinguishing among exposure sources.

PubMed

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

2016-01-01

Perchlorate (ClO4(-)) is a ubiquitous environmental contaminant with high human exposure potential. Natural perchlorate forms in the atmosphere from where it deposits onto the surface of Earth, whereas synthetic perchlorate is manufactured as an oxidant for industrial, aerospace, and military applications. Perchlorate exposure can potentially cause adverse health effects in humans by interfering with the production of thyroid hormones through competitively blocking iodide uptake. To control and reduce perchlorate exposure, the contributions of different sources of perchlorate exposure need to be quantified. Thus, we demonstrate a novel approach for determining the contribution of different perchlorate exposure sources by quantifying stable and radioactive chlorine isotopes of perchlorate extracted from composite urine samples from two distinct populations: one in Atlanta, USA and one in Taltal, Chile (Atacama region). Urinary perchlorate from the Atlanta region resembles indigenous natural perchlorate from the western USA (δ(37)Cl=+4.1±1.0‰; (36)Cl/Cl=1 811 (±136) × 10(-15)), and urinary perchlorate from the Taltal, Chile region is similar to natural perchlorate in nitrate salt deposits from the Atacama Desert of northern Chile (δ(37)Cl=-11.0±1.0‰; (36)Cl/Cl=254 (±40) × 10(-15)). Neither urinary perchlorate resembled the isotopic pattern found in synthetic perchlorate. These results indicate that natural perchlorate of regional provenance is the dominant exposure source for the two sample populations, and that chlorine isotope ratios provide a robust tool for elucidating perchlorate exposure pathways.

Use of Compound-Specific Stable Isotope Analysis to Distinguish Between Vapor Intrusion and Indoor Sources of VOCs - CSIA Protocol for Vapor Intrusion Investigations

DTIC Science & Technology

2014-07-01

Analyzer TCE Trichloroethene USEPA U.S. Environmental Protection Agency V- PDB Vienna - Pee Dee Belemnite V-SMOW Vienna – Standard Mean Ocean Water ... PDB ) for carbon, Standard Mean Ocean Chloride (SMOC) for chlorine, and Vienna-Standard Mean Ocean Water (V-SMOW) for hydrogen. CSIA Protocol for...7 3.3 INDOOR AIR SAMPLING LOCATIONS ............................................................ 8 3.4 COLLECTION OF WATER SAMPLES

Insights into dechlorination of PCE and TCE from carbon isotope fractionation by vitamin B12

NASA Astrophysics Data System (ADS)

Slater, G.; Sherwood Lollar, B.; Lesage, S.; Brown, S.

2003-04-01

Reductive dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) by vitamin B12 is both a potential remediation technique and an analogue of the microbial reductive dechlorination reaction. Stable carbon isotopic analysis, an effective and powerful tool for the investigation and monitoring of contaminant remediation, was used to characterize the isotopic effects of reductive dechlorination of PCE and TCE by vitamin B12 in laboratory microcosms. 10 mg/L vitamin B12 degraded greater than 90% of an initial concentration of PCE of 20 mg/L. TCE, the primary product of PCE degradation, accounted for between 64 - 72% of the PCE degraded. In experiments with TCE, 147 mg/L vitamin B12 degraded greater than 90% of an initial concentration of TCE of 20 mg/L. Cis-dichloroethene (cDCE), the primary product of TCE degradation, accounted for between 30 - 35% of the TCE degraded. Degradation of both PCE and TCE exhibited first order kinetics. Strong isotopic fractionation of the reactant PCE and of the reactant TCE was observed over the course of degradation. This fractionation could be described by a Rayleigh model with enrichment factors between -16.5 ppm and -15.8 ppm for PCE, and -17.2 ppm and -16.6 ppm for TCE. Fractionation was similar in all four experiments, with a mean enrichment factor of -16.5 +/- 0.6 ppm. These large enrichment factors indicate that isotopic analysis can be used to assess the occurrence of dechlorination of PCE and TCE by vitamin B12 in remediation situations. Significantly, the Rayleigh model could be used to predict the isotopic compositions of the major products of the reaction as well as the reactant, notwithstanding the lack of complete mass balance observed between product and reactant. This evidence suggests that isotopic fractionation is taking place during complexation of the chlorinated ethenes to vitamin B12, as has been suggested for reductive dechlorination by zero valent iron. The differences between e for this reaction and those observed for microbial biodegradation of the chlorinated ethenes suggest that there may be differences in the rate determining step for these two processes. Determining which steps are rate determining during degradation may allow optimization of contaminant remediation.

Integrated Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation

DTIC Science & Technology

2016-06-16

immediate electron donor. In the microcosm, H2 was produced by fermentation of lactate. It was previously reported that H2 and water undergo fast...being tied to the H isotope composition of the fermentation substrate (see Kuder et al., 2013 for more information). ESTCP Final Report

Chlorine Diffusion in Uranium Dioxide: Thermal Effects versus Radiation Enhanced Effects

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

Pipon, Yves; Moncoffre, Nathalie; Bererd, Nicolas

2007-07-01

Chlorine is present as an impurity in the UO{sub 2} nuclear fuel. {sup 35}Cl is activated into {sup 36}Cl by thermal neutron capture. In case of interim storage or deep geological disposal of the spent fuel, this isotope is known to be able to contribute significantly to the instant release fraction because of its mobile behavior and its long half life (around 300000 years). It is therefore important to understand its migration behavior within the fuel rod. During reactor operation, chlorine diffusion can be due to thermally activated processes or can be favoured by irradiation defects induced by fission fragmentsmore » or alpha decay. In order to decouple both phenomena, we performed two distinct experiments to study the effects of thermal annealing on the behaviour of chlorine on one hand and the effects of the irradiation with fission products on the other hand. During in reactor processes, part of the {sup 36}Cl may be displaced from its original position, due to recoil or to collisions with fission products. In order to study the behavior of the displaced chlorine, {sup 37}Cl has been implanted into sintered depleted UO{sub 2} pellets (mean grain size around 18 {mu}m). The spatial distribution of the implanted and pristine chlorine has been analyzed by SIMS before and after treatment. Thermal annealing of {sup 37}Cl implanted UO{sub 2} pellets (implantation fluence of 10{sup 13} ions.cm{sup -2}) show that it is mobile from temperatures as low as 1273 K (E{sub a}=4.3 eV). The irradiation with fission products (Iodine, E=63.5 MeV) performed at 300 and 510 K, shows that the diffusion of chlorine is enhanced and that a thermally activated contribution is preserved (E{sub a}=0.1 eV). The diffusion coefficients measured at 1473 K and under fission product irradiation at 510 K are similar (D = 3.10{sup -14} cm{sup 2}.s{sup -1}). Considering in first approximation that the diffusion length L can be expressed as a function of the diffusion coefficient D and time t by : L=(Dt)1/2, the diffusion distance after 3 years is L=17 {mu}m. It results that there is a great probability for the chlorine contained in the UO{sub 2} grains to have reached the grain boundaries after 3 years, in the core of the fuel rod as well as at its periphery. Moreover, diffusion and concentration of chlorine at grain boundaries has been evidenced using SIMS mapping. Our results indicate therefore, that, during reactor operation and after, the majority of {sup 36}Cl is likely to have moved to grain boundaries, rim and gap. This fraction might then significantly contribute to the rapid or instant release of chlorine. This could have important consequences for safety assessment. During reactor operation, chlorine ({sup 35}Cl), an impurity of the nuclear fuel, is activated into {sup 36}Cl, a long lived mobile isotope. Because of its long half life and its mobility, this isotope may contribute significantly to the instant release fraction under disposal conditions. Thermal annealing of Cl implanted UO{sub 2} sintered pellets show that it is mobile from temperatures as low as 1273 K (E{sub a} = 4.3 eV). Chlorine diffusion induced by irradiation with fission products preserves a thermally activated contribution. The radiation induced defects significantly enhance chlorine migration. (authors)« less

Integrating Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation

DTIC Science & Technology

2016-06-01

Dehalococcoides species require molecular hydrogen as the immediate electron donor. In the microcosm, H2 was produced by fermentation of lactate. It was...superimposed depletion upon H2/H2O equilibrium rather than being tied to the H isotope composition of the fermentation substrate (see Kuder et al., 2013 for more

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Messenger, S.; Sharp, Z. D.; Burger, P. V.; Nguyen, N.; McCubbin, F. M.

2017-01-01

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

Investigating the Transport and Fate of Polychlorinated Biphenyls with Stable Chlorine Isotopes

DTIC Science & Technology

2001-09-30

recently accepted in the journal Organic Geochemistry. We published another manuscript in Environmental Science and Pollution Research on the...Chlorine in the Environment a book written by Ruth Stringer and Paul Johnson. This review will soon appear in the journal Environmental Science and...Heraty, L.J., Holt, B.D., Sturchio, N.C., Eglinton, T.I., Drenzek, N.J., Xu, L., Lake, J.L., Maruya, K.A., 2000. Environmental Science and

Variation of brine compositions resulting from flow from matrix or fracture permeability, investigated by high pressure laboratory experiments

NASA Astrophysics Data System (ADS)

Poszwa, A. C.; Coleman, M. L.; Pouya, A.; Ader, M.; Bounenni, A.

2003-04-01

Planning oil production from a chalk reservoir oilfield is difficult because the matrix usually has low permeability despite its high porosity. Most oil is thought to come from fracture porosity but the matrix contribution should increase as compaction occurs during production. To better understand the respective contributions from matrix and fracture, we studied the geochemical characteristics of fluids using high-pressure brine flow experiments on chalk cores. During the experiment axial load was changed relative to confining pressure to induce fractures and to close them again. We used chlorine stable isotope variations to study fluid pathway, because chlorine is a chemically conservative element in sedimentary systems and its isotopes fractionate only with physical processes like diffusion or adsorption that could occur mainly in the chalk matrix. A first experiment was performed on a very porous chalk from Henley (on-shore UK) and using a low-salinity brine. Large variations of brine Cl isotope composition were observed (from -0.56 to +0.08 per mil). The variations were correlated positively with the brine flux through the chalk and the permeability of the rock, both parameters controlled by the rock fracturing. A second experiment used brine with salinity similar to that of seawater. In this case, chemical and isotopic variations were not significant. From the beginning, the chalk structure seems to have been destroyed very quickly (induced fracture porosity collapsed) possibly because of the fluid nature, so that whatever pressure was applied, the permeability did not change significantly. Using Valhall reservoir chalk (offshore Norwegian North Sea) and fluid half the salinity of seawater in a third experiment, we obtained a large range of permeabilities. Brine isotopic trends were very similar on average to those of the first experiment even though variations were smaller (Cl isotopes from -0.09 to +0.29 per mil) and not significantly correlated simply to permeability values. The highest isotopic values were in brine flowed through chalk when the permeability was high and fractures opened; the lowest values were in brine flowed through the chalk when its permeability was reduced by closing fractures and increasing the relative contribution from matrix flow where diffusion processes fractionated chlorine isotopes. From this work it seems that the relative contributions from fracture and matrix permeability in reservoirs can be estimated from the geochemical compositions of brines that flowed from them.

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

DTIC Science & Technology

2015-03-01

MRGB Middle Rio Grande Basin MVSL Mid-Valley Sanitary Landfill m/z mass to charge ratio N nitrogen or normal or number of entities N2... Sanitary Landfill (MVSL) operated by San Bernardino County, including the Rialto Ammunition Backup Storage Point, a site of several World War II era...SAIC, 2004). This site is known as the “Mid Valley Sanitary Landfill/Bunker Site” (Geologic Associates, 2003; SARWQCB, 2005; Woolfenden, 2007) or

Stable Cl isotope composition of the Changjiang River water

NASA Astrophysics Data System (ADS)

Lang, Y.; Liu, C. Q.; LI, S. L.; Aravena, R.; Ding, H.; WANG, B.; Benjamin, C.

2017-12-01

To understand chemical wreathing, nutrient cycling, and the impact of human activities on eco-environments of the Changjiang River (Yangtze River) Basin, we carried out a geochemical study on water chemistry and multiple isotopes (C, N, S, Sr…...) of Changjiang River water in the summer season. Some of the research results about the water chemistry, boron isotope geochemistry and suspended matter have been published (Chetelat et al., 2008; Li et al., 2010). Ten samples were selected for the measurement of δ37Cl values, among which 7 samples were collected from main stream and 3 samples from tributaries. The range of δ37Cl values varies between 0.02‰ and 0.33‰ in the main stream and between 0.16‰ and 0.71‰ in the tributary waters. The δ37Cl values in general are negatively correlated with Cl- concentrations for both main stream and tributary waters. δ37Cl value of Wujiang, which is one of the large tributaries in the upper reach of Changjiang and dominated by carbonate rocks in lithology of the watershed, has the maximum value but minimum value of Cl- concentration in this study. The lowest δ37Cl value was measured for the water collected from the estuary of Changjiang River. The variation of δ37Cl values in the waters would be attributed to mixing of different sources of chlorine, which most likely include rain water, ground water, seawater, and pollutants. Systematic characterization of different Cl sources in terms of their chlorine isotope composition is imperative for better understanding of sources and processes of chlorine cycling. Acknowledgements: This work was financially supported by NSFC through project 41073099. (Omit references)

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

PubMed Central

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

2015-01-01

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

Variable dual carbon-bromine stable isotope fractionation during enzyme-catalyzed reductive dehalogenation of brominated ethenes.

PubMed

Woods, Angela; Kuntze, Kevin; Gelman, Faina; Halicz, Ludwik; Nijenhuis, Ivonne

2018-01-01

The potential of compound-specific stable isotope analysis (CSIA) to characterize biotransformation of brominated organic compounds (BOCs) was assessed and compared to chlorinated analogues. Sulfurospirillum multivorans and Desulfitobacterium hafniense PCE-S catalyzed the dehalogenation of tribromoethene (TBE) to either vinyl bromide (VB) or ethene, respectively. Significantly lower isotope fractionation was observed for TBE dehalogenation by S. multivorans (ε C  = -1.3 ± 0.2‰) compared to D. hafniense (ε C  = -7.7 ± 1.5‰). However, higher fractionation was observed for dibromoethene (DBE) dehalogenation by S. multivorans (ε C  = -16.8 ± 1.8‰ and -21.2 ± 1.6‰ for trans- and cis-1,2- (DBE) respectively), compared to D. hafniense PCE-S (ε C  = -9.5 ± 1.2‰ and -14.5 ± 0.7‰ for trans-1,2-DBE and cis-1,2-DBE, respectively). Significant, but similar, bromine fractionation was observed for for S. multivorans (ε Br  = -0.53 ± 0.15‰, -1.03 ± 0.26‰, and -1.18 ± 0.13‰ for trans-1,2-DBE, cis-1,2-DBE and TBE, respectively) and D. hafniense PCE-S (ε Br  = -0.97 ± 0.28‰, -1.16 ± 0.36‰, and -1.34 ± 0.32‰ for cis-1,2-DBE, TBE and trans-1,2-DBE, respectively). Variable CBr dual-element slopes were estimated at Λ (ε C /ε Br ) = 1.03 ± 0.2, 17.9 ± 5.8, and 29.9 ± 11.0 for S. multivorans debrominating TBE, cis-1,2-DBE and trans-1,2-DBE, respectively, and at 7.14 ± 1.6, 8.27 ± 3.7, and 8.92 ± 2.4 for D. hafniense PCE-S debrominating trans-1,2-DBE, TBE and cis-1,2-DBE, respectively. A high variability in isotope fractionation, which was substrate property related, was observed for S. multivorans but not D. hafniense, similar as observed for chlorinated ethenes, and may be due to rate-limiting steps preceding the bond-cleavage or differences in the reaction mechanism. Overall, significant isotope fractionation was observed and, therefore, CSIA can be applied to monitor the fate of brominated ethenes in the environment. Isotope effects differences, however, are not systematically comparable to chlorinated ethenes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Using chloride and chlorine-36 as soil-water tracers to estimate deep percolation at selected locations on the U.S. Department of Energy Hanford Site, Washington

USGS Publications Warehouse

Prych, Edmund A.

1998-01-01

A chloride mass-balance method and a chlorine-36 isotope bomb-pulse method were used to estimate long-term average rates of deep percolation at at the U.S. Department of Energy Hanford Site. Because the bomb-pulse method typically gives an upper limit and the mass-balance method may underestimate, estimates from both methods probably bracket actual rates.

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one-dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 x 10(exp 7) molecules/sq cm/s sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

Screening of Chlorinated Paraffins and Unsaturated Analogues in Commercial Mixtures: Confirmation of Their Occurrences in the Atmosphere.

PubMed

Li, Tong; Gao, Shixiong; Ben, Yujie; Zhang, Hong; Kang, Qiyue; Wan, Yi

2018-02-20

Characterizing the detailed compositions of chlorinated paraffins (CPs) commercial mixtures is crucial to understand their environmental sources, fates, and potential risks. In this study, dichloromethane (DCM)-enhanced UPLC-ESI-QTOFMS analysis combined with characteristic isotope chlorine peaks is applied to screen all CPs and their structural analogues in the three most commonly produced CP commercial mixtures (CP-42, CP-52, and CP-70). Mass fractions of total short-chain CPs (SCCPs), medium-chain CPs (MCCPs) and long-chain CPs (LCCPs) ranged from 0.64 to 31.9%, 0.64 to 21.8%, and 0.04 to 43.9%, respectively, in the three commercial mixtures. 113 unsaturated SCCPs, MCCPs, and LCCPs were identified in the commercial mixtures. The detailed mass percentages of saturated and unsaturated CPs with carbon numbers of 10-30, chlorine numbers of 5-28, and unsaturated degrees of 0-7 were characterized in all commercial mixtures. Occurrences of the predominant saturated and unsaturated CPs were further confirmed in air samples collected in Guangdong Province, one of the major CP production areas in China, over one year. The profiles of the detected compounds indicated that LCCPs in air samples might come mainly from the production and usage of CP-52, and unsaturated C 24-29 -LCCPs were specifically originated from CP-70 used in the area.

Evaluation of carbon isotope fractionation during anaerobic reductive dehalogenation of chlorinated and brominated benzenes.

PubMed

Sohn, Seo Yean; Kuntze, Kevin; Nijenhuis, Ivonne; Häggblom, Max M

2018-02-01

Compound specific stable isotope analysis (CSIA) has been established as a useful tool to evaluate in situ biodegradation. Here, CSIA was used to determine microbial dehalogenation of chloro- and bromobenzenes in microcosms derived from Hackensack River sediments. Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) was used to measure carbon isotope fractionation during reductive dehalogenation of hexachlorobenzene (HCB), pentachlorobenzene (PeCB), 1,2,3,5-tetrachlorobenzene (TeCB), 1,2,3,5-tetrabromobenzene (TeBB), and 1,3,5-tribromobenzene (TriBB). Strong evidence of isotope fractionation coupled to dehalogenation was not observed in the substrate, possibly due to the low solubilities of the highly halogenated benzene substrates and a dilution of the isotope signal. Nonetheless, we could measure a depletion of the δ 13 C value in the dichlorobenzene product during dechlorination of HCB, the sequential depletion and enrichment of δ 13 C value for trichlorobenzene in TeCB dechlorinating cultures, and the enrichment of δ 13 C during debromination of TriBB. This indicates that a measurable isotope fractionation occurred during reductive dehalogenation of highly halogenated chloro- and bromobenzenes in aquatic sediments. Thus, although more quantitative measurements will be needed, the data suggests that CSIA may have application for monitoring in situ microbial reductive dehalogenation of highly halogenated benzenes. Copyright © 2017. Published by Elsevier Ltd.

Reanalysis of the Viking results suggests perchlorate and organics at mid-latitudes on Mars

NASA Astrophysics Data System (ADS)

Navarro-Gonzalez, R.; Vargas, E.; de La Rosa, J.; Raga, A. C.; McKay, C.

2010-12-01

The most comprehensive search for organics in the Martian soil was performed by the Viking Landers. Martian soil was subjected to a thermal volatilization process in order to vaporize and break organic molecules, and the resultant gases and volatiles were analyzed by gas chromatography-mass spectrometry. Only water at 0.1-1.0 wt% was detected with traces of chloromethane at 15 ppb in the Viking Landing site 1, and water at 0.05-1.0 wt% and carbon dioxide at 50-700 ppm with traces of dichloromethane at 0.04-40 ppb in the Viking Landing site 2. The abundance ratio of the 35Cl and 37Cl isotopes in these chlorohydrocarbons was 3:1, corresponding to the terrestrial isotopic abundance. Therefore, these chlorohydrocarbons were considered to be terrestrial contaminants although they had not been detected at those levels in the blank runs. Recently, perchlorate was discovered in the Martian Arctic soil by the Phoenix Lander. Here we show that when Mars-like soils from the Atacama Desert with 32±6 ppm of organic carbon are mixed with 1 wt% magnesium perchlorate and heated nearly all the organics present are decomposed to water and carbon dioxide, but a small amount are chlorinated forming 1.6 ppm of chloromethane and 0.02 ppm of dichloromethane at 500○C. A chemical kinetics model was developed to predict the degree of oxidation and chlorination of organics in the Viking oven. The isotopic distribution of 35Cl and 37Cl for Mars is not known. Studies on Earth indicate that there is no isotopic fractionation of chlorine in the mantle or crust, despite the fact that it is significantly depleted on the planet as compare to solar abundances. The 37Cl/35Cl isotopic ratio in carbonaceous chondrites is similar to the Earth’s value, which suggests that the terrestrial planets, including Mars, were all formed from a similar reservoir of chlorine species in the presolar nebulae and that there was no further isotopic fractionation during the Earth’s differentiation or late accretion of volatiles. Consequently, 37Cl/35Cl ratio should be the same on Mars as well as on the Earth. Re-interpretation of the Viking results therefore suggests ≤0.1% perchlorate and 1.5-6.5 ppm organic carbon at the landing site 1, and ≤0.1% perchlorate and 0.7-2.6 ppm organic carbon at the landing site 2. The detection of organics on Mars is important to assess locations for future experiments to detect life itself. We suggest that future missions to Mars should include life detection experiments.

Compound specific isotope analysis to investigate pesticide degradation in lysimeter experiments at field conditions

NASA Astrophysics Data System (ADS)

Ryabenko, Evgenia; Elsner, Martin; Bakkour, Rani; Hofstetter, Thomas; Torrento, Clara; Hunkeler, Daniel

2015-04-01

The frequent detection of organic micropollutants such as pesticides, consumer care products or pharmaceuticals in water is an increasing concern for human and ecosystem health. Degradation analysis of these compounds can be challenging in complex systems due to the fact that metabolites are not always found and mass balances frequently cannot be closed. Many abiotic and biotic degradation pathways cause, however, distinct isotope fractionation, where light isotopes are transferred preferentially from the reactant to the product pool (normal isotope fractionation). Compound-specific isotope analysis (CSIA) of multiple elements is a particularly powerful method to evaluate organic micropollutant transformation, because it can even give pathway-specific isotope fractionation (1,2). Available CSIA field studies, however, have focused almost exclusively on volatile petroleum and chlorinated hydrocarbons, which are present in high concentrations in the environment and can be extracted easily from water for GC-IRMS analysis. In the case of micropollutants, such as pesticides, CSIA in more challenging since it needs to be conducted at lower concentrations and requires pre-concentration, purification and high chromatographic performance (3). In this study we used lysimeters experiments to analyze transformation of atrazine, acetochlor, metolachlor and chloridazone by studying associated isotope fractionation. The project combines a) analytical method development for CSIA, b) identification of pathways of micropollutant degradation and c) quantification of transformation processes under field condition. The pesticides were applied both, at the soil surface and below the top soil under field-relevant concentrations in May 2014. After typical irrigation of the lysimeters, seepage water was collected in 50L bottles and stored for further SPE and CSIA. Here we present the very first result of a) analytical method development, b) improvement of SPE methods for complex pesticide mixtures and c) transformation of pesticides in lysimeters during the year 2014. 1 Elsner, M. Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations. J. Environ. Monit. 12, 2005-2031 (2010). 2 Hofstetter, T. B. & Berg, M. Assessing transformation processes of organic contaminants by compound-specific stable isotope analysis. TrAC Trends in Analytical Chemistry 30, 618-627 (2011). 3 Elsner, M. et al. Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Anal. Bioanal. Chem. 403, 2471-2491, doi:10.1007/s00216-011-5683-y (2012).

Investigation of the mechanism of chlorination of glyphosate and glycine in water.

PubMed

Mehrsheikh, Akbar; Bleeke, Marian; Brosillon, Stephan; Laplanche, Alain; Roche, Pascal

2006-09-01

The chlorination reactions of glyphosate and glycine in water were thoroughly studied. Utilizing isotopically enriched (13C and 15N) samples of glycine and glyphosate and 1H, 13C, 31P, and 15N NMR spectroscopy we were able to identify all significant terminal chlorination products of glycine and glyphosate, and show that glyphosate degradation closely parallels that of glycine. We have determined that the C1 carboxylic acid carbon of glycine/glyphosate is quantitatively converted to CO2 upon chlorination. The C2 methylene carbon of glycine/glyphosate is converted to CO2 and methanediol. The relative abundance of these two products is a function of the pH of the chlorination reactions. Under near neutral to basic reaction conditions (pH 6-9), CO2 is the predominant product, whereas, under acidic reaction conditions (pH < 6) the formation of methanediol is favored. The C3 phosphonomethylene carbon of glyphosate is quantitatively converted to methanediol under all conditions tested. The nitrogen atom of glycine/glyphosate is transformed into nitrogen gas and nitrate, and the phosphorus moiety of glyphosate produces phosphoric acid upon chlorination. In addition to these terminal chlorination products, a number of labile intermediates were also identified including N-chloromethanimine, N-chloroaminomethanol, and cyanogen chloride. The chlorination products identified in this study are not unique to glyphosate and are similar to those expected from chlorination of amino acids, proteins, peptides, and many other natural organic matters present in drinking water.

Natural Organochlorines as Precursors of 3-Monochloropropanediol Esters in Vegetable Oils.

PubMed

Tiong, Soon Huat; Saparin, Norliza; Teh, Huey Fang; Ng, Theresa Lee Mei; Md Zain, Mohd Zairey Bin; Neoh, Bee Keat; Md Noor, Ahmadilfitri; Tan, Chin Ping; Lai, Oi Ming; Appleton, David Ross

2018-01-31

During high-temperature refining of vegetable oils, 3-monochloropropanediol (3-MCPD) esters, possible carcinogens, are formed from acylglycerol in the presence of a chlorine source. To investigate organochlorine compounds in vegetable oils as possible precursors for 3-MCPD esters, we tested crude palm, soybean, rapeseed, sunflower, corn, coconut, and olive oils for the presence of organochlorine compounds. Having found them in all vegetable oils tested, we focused subsequent study on oil palm products. Analysis of the chlorine isotope mass pattern exhibited in high-resolution mass spectrometry enabled organochlorine compound identification in crude palm oils as constituents of wax esters, fatty acid, diacylglycerols, and sphingolipids, which are produced endogenously in oil palm mesocarp throughout ripening. Analysis of thermal decomposition and changes during refining suggested that these naturally present organochlorine compounds in palm oils and perhaps in other vegetable oils are precursors of 3-MCPD esters. Enrichment and dose-response showed a linear relationship to 3-MCPD ester formation and indicated that the sphingolipid-based organochlorine compounds are the most active precursors of 3-MCPD esters.

Mass Spectrometry Identification of N-Chlorinated Dipeptides in Drinking Water.

PubMed

Huang, Guang; Jiang, Ping; Li, Xing-Fang

2017-04-04

We report the identification of N-chlorinated dipeptides as chlorination products in drinking water using complementary high-resolution quadrupole time-of-flight (QTOF) and quadrupole ion-trap mass spectrometry techniques. First, three model dipeptides, tyrosylglycine (Tyr-Gly), tyrosylalanine (Tyr-Ala), and phenylalanylglycine (Phe-Gly), reacted with sodium hypochlorite, and these reaction solutions were analyzed by QTOF. N-Cl-Tyr-Gly, N,N-di-Cl-Tyr-Gly, N-Cl-Phe-Gly, N,N-di-Cl-Phe-Gly, N-Cl-Tyr-Ala, and N,N-di-Cl-Tyr-Ala were identified as the major products based on accurate masses, 35 Cl/ 37 Cl isotopic patterns, and MS/MS spectra. These identified N-chlorinated dipeptides were synthesized and found to be stable in water over 10 days except N,N-di-Cl-Phe-Gly. To enable sensitive detection of N-chlorinated dipeptides in authentic water, we developed a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method with multiple reaction monitoring (MRM) mode. N-Cl-Tyr-Gly, N,N-di-Cl-Tyr-Gly, N-Cl-Phe-Gly, N-Cl-Tyr-Ala, and N,N-di-Cl-Tyr-Ala along with their corresponding dipeptides were detected in authentic tap water samples. The dipeptides were clearly detected in the raw water, but the N-chlorinated dipeptides were at background levels. These results suggest that the N-chlorinated dipeptides are produced by chlorination. This study has identified N-chlorinated dipeptides as new disinfection byproducts in drinking water. The strategy developed in this study can be used to identify chlorination products of other peptides in drinking water.

Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer

PubMed Central

Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

2014-01-01

Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ13CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed (34ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. PMID:25039851

Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer.

PubMed

Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

2014-11-01

Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ(13) CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed ((34) ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. © 2014 The Authors. Geobiology Published by John Wiley & Sons Ltd.

Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

PubMed

Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

2016-04-22

Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%. Copyright © 2016 Elsevier B.V. All rights reserved.

Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis

PubMed Central

Larsen, K.K.; Wielandt, D.; Schiller, M.; Bizzarro, M.

2016-01-01

Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr3+, CrCl2+ and CrCl2+) with equilibrium mass-dependent isotope fractionation spanning a range of ~1‰/amu and consistent with theory. The heaviest isotopes partition into Cr3+, intermediates in CrCl2+ and the lightest in CrCl2+/CrCl3°. Thus, for a typical reported loss of ~25% Cr (in the form of Cr3+) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected 53Cr/52Cr (μ53 Cr* of 5.2 ppm) and 54Cr/52Cr (μ54Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr3+ by >5 days exposure to HNO3 —H2O2 solutions at room temperature, resulting in >~98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%. PMID:27036208

Chlorine Isotope Ratios in M Giants and S Stars

NASA Astrophysics Data System (ADS)

Maas, Zachary; Pilachowski, C. A.

2018-01-01

Chlorine is an odd-Z, light element that has been poorly studied in stars. Recently, the first stellar abundance measurements of the isotopologue 35Cl were made and the 35Cl/37Cl ratio was derived in RZ Ari (Maas et al. 2016). Additional abundance measurements are necessary to understand the Galactic chemical evolution and complex nucleosynthesis of Cl. The Cl isotope ratio in particular is important in distinguishing contributions from different nucleosynthesis sites to the surface abundances of stars. For example, current nucloesynthesis models predict that both isotopes of Cl are produced primarily during core collapse supernovae (CCSNe) with the energy and progenitor mass impacting the isotopic ratio of the ejected material. In addition to CCSNe, 37Cl is formed by the s-process both in massive stars and in AGB stars, and 35Cl may be produced from neutrino spallation. Understanding the formation of the Cl isotopes is also important to studies of the interstellar medium (ISM). A range of Cl isotope ratios mainly between 2 - 3.5 have been measured in star forming regions, in the circumstellar envelopes of evolved stars, and in proto-stellar cores using Cl bearing molecules. Additional measurements of the Cl isotope ratio in nearby stars will test nucleosynthesis models and allow comparisons with the range of isotope ratios observed in the ISM.We build on the results of Maas et al. (2016) by measuring the Cl isotope ratio in six M giants and four S stars using R~50,000 resolution spectra from Phoenix on Gemini South. We find no significant difference between the average Cl isotope ratios in the M stars and S stars and our measurements are consistent with the range of values seen in the ISM. We also find the average Cl ratio to be larger than the predicted isotope ratio of 1.8 for the solar neighborhood. Finally, two S stars, GG Pup and WY Pyx, show anomalously strong HCl features with equivalent widths ~3-5 times larger than the HCl features of other stars of similar temperature.

Chlorinated paraffin analysis by gas chromatography Orbitrap high-resolution mass spectrometry: Method performance, investigation of possible interferences and analysis of fish samples.

PubMed

Krätschmer, Kerstin; Cojocariu, Cristian; Schächtele, Alexander; Malisch, Rainer; Vetter, Walter

2018-03-02

For decades, high quantities of short-chain chlorinated paraffins (SCCP) and medium-chain chlorinated paraffins (MCCP) have been widely used, for instance as plasticizers or flame retardants, leading to global pollution due to unintentional emissions from products or waste. Due to the high complexity of chlorinated paraffins with several thousand congeners there is no consensus on an analytical procedure for SCCPs and MCCPs in food samples. Amongst the multitude of methods currently in use, high-resolution mass spectrometry is particularly valuable for in-depth studies of homologue patterns. Here we analyse SCCPs and MCCPs with gas chromatography coupled to high-resolution Orbitrap mass spectrometry (GC-Orbitrap-HRMS) operated in full-scan acquisition in electron capture negative ion (ECNI) mode at 60,000 and 120,000 resolution (FWHM, m/z 200, equals roughly 30,000 and 60,000 at 5% peak height). Linear dynamic range, selectivity and sensitivity tests confirmed an excellent linearity in a concentration range of 25-15,000 pg/μL with very low limits of detection (LODs) in the low pg/μL range. Spiking experiments with high levels of native mono- and di-ortho-polychlorinated biphenyls (PCBs) and mixtures of MCCP and SCCP standards did not have a negative impact on isotope ratios of the examined homologues. Besides the [M-Cl] - fragment ions used for quantification, the mass spectra of homologues also featured [M-HCl] - ions whose abundance increased with decreasing chlorination degree. In addition, [M-HCl-Cl] - ions were detected with a relative abundance of 5-10%. Three salmon (Salmo salar) samples farmed in Norway showed a consistent CP homologue pattern which differed both from the CP pattern in a sample from Scottish aquaculture and a wild salmon sample. These measurements produce evidence that discretely different CP patterns may exist in different areas of origin. Our results demonstrate that GC/ECNI-Orbitrap-HRMS is well-suited for the analysis of CPs by overcoming a range of mass interference problems and due to its thus far unmatched sensitivity. Copyright © 2018 Elsevier B.V. All rights reserved.

Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California

USGS Publications Warehouse

Leenheer, J.A.; Rostad, C.E.; Barber, L.B.; Schroeder, R.A.; Anders, R.; Davisson, M.L.

2001-01-01

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.

Fast and Simple Analytical Method for Direct Determination of Total Chlorine Content in Polyglycerol by ICP-MS.

PubMed

Jakóbik-Kolon, Agata; Milewski, Andrzej; Dydo, Piotr; Witczak, Magdalena; Bok-Badura, Joanna

2018-02-23

The fast and simple method for total chlorine determination in polyglycerols using low resolution inductively coupled plasma mass spectrometry (ICP-MS) without the need for additional equipment and time-consuming sample decomposition was evaluated. Linear calibration curve for 35 Cl isotope in the concentration range 20-800 µg/L was observed. Limits of detection and quantification equaled to 15 µg/L and 44 µg/L, respectively. This corresponds to possibility of detection 3 µg/g and determination 9 µg/g of chlorine in polyglycerol using studied conditions (0.5% matrix-polyglycerol samples diluted or dissolved with water to an overall concentration of 0.5%). Matrix effects as well as the effect of chlorine origin have been evaluated. The presence of 0.5% (m/m) of matrix species similar to polyglycerol (polyethylene glycol-PEG) did not influence the chlorine determination for PEGs with average molecular weights (MW) up to 2000 Da. Good precision and accuracy of the chlorine content determination was achieved regardless on its origin (inorganic/organic). High analyte recovery level and low relative standard deviation values were observed for real polyglycerol samples spiked with chloride. Additionally, the Combustion Ion Chromatography System was used as a reference method. The results confirmed high accuracy and precision of the tested method.

Hydrogeochemistry and quality of surface water and groundwater in the vicinity of Lake Monoun, West Cameroon: approach from multivariate statistical analysis and stable isotopic characterization.

PubMed

Kamtchueng, Brice T; Fantong, Wilson Y; Wirmvem, Mengnjo J; Tiodjio, Rosine E; Takounjou, Alain F; Ndam Ngoupayou, Jules R; Kusakabe, Minoru; Zhang, Jing; Ohba, Takeshi; Tanyileke, Gregory; Hell, Joseph V; Ueda, Akira

2016-09-01

With the use of conventional hydrogeochemical techniques, multivariate statistical analysis, and stable isotope approaches, this paper investigates for the first time surface water and groundwater from the surrounding areas of Lake Monoun (LM), West Cameroon. The results reveal that waters are generally slightly acidic to neutral. The relative abundance of major dissolved species are Ca(2+) > Mg(2+) > Na(+) > K(+) for cations and HCO3 (-) ≫ NO3 (-) > Cl(-) > SO4 (2-) for anions. The main water type is Ca-Mg-HCO3. Observed salinity is related to water-rock interaction, ion exchange process, and anthropogenic activities. Nitrate and chloride have been identified as the most common pollutants. These pollutants are attributed to the chlorination of wells and leaching from pit latrines and refuse dumps. The stable isotopic compositions in the investigated water sources suggest evidence of evaporation before recharge. Four major groups of waters were identified by salinity and NO3 concentrations using the Q-mode hierarchical cluster analysis (HCA). Consistent with the isotopic results, group 1 represents fresh unpolluted water occurring near the recharge zone in the general flow regime; groups 2 and 3 are mixed water whose composition is controlled by both weathering of rock-forming minerals and anthropogenic activities; group 4 represents water under high vulnerability of anthropogenic pollution. Moreover, the isotopic results and the HCA showed that the CO2-rich bottom water of LM belongs to an isolated hydrological system within the Foumbot plain. Except for some springs, groundwater water in the area is inappropriate for drinking and domestic purposes but good to excellent for irrigation.

Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction.

PubMed

Davis, William E; Li, Yongtao

2008-07-15

A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-(15)N2 used as the surrogate standard formed acetone azine and acetone azine-(15)N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine-(15)N2. The extracted acetone azine was quantified against the extracted acetone azine-(15)N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine-(15)N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.

Short-, Medium-, and Long-Chain Chlorinated Paraffins in Wildlife from Paddy Fields in the Yangtze River Delta.

PubMed

Du, Xinyu; Yuan, Bo; Zhou, Yihui; Benskin, Jonathan P; Qiu, Yanling; Yin, Ge; Zhao, Jianfu

2018-02-06

Short-chain chlorinated paraffins (SCCPs) were added to Annex A of the Stockholm Convention on Persistent Organic Pollutants in April, 2017. As a consequence of this regulation, increasing production and usage of alternatives, such as medium- and long-chain chlorinated paraffins (MCCPs and LCCPs, respectively), is expected. Little is known about the environmental fate and behavior of MCCPs and LCCPs. In the present study, SCCPs, MCCPs, and LCCPs were analyzed in nine wildlife species from paddy fields in the Yangtze River Delta, China, using atmospheric pressure chemical ionization-quadrupole time-of-flight mass spectrometry. SCCPs, MCCPs, and LCCPs were detected in all samples at concentrations ranging from <91-43 000, 96-33 000, and 14-10 000 ng/g lipid, respectively. Most species contained primarily MCCPs (on average 44%), with the exception of collared scops owl and common cuckoo, in which SCCPs (43%) accumulated to a significantly (i.e., p < 0.05) greater extent than MCCPs (40%). Cl 6 groups were dominant in most species except for yellow weasel and short-tailed mamushi, which contained primarily Cl 7 groups. Principal components analysis, together with CP concentrations and carbon stable isotope analysis showed that habitat and feeding habits were key factors driving CP accumulation and congener group patterns in wildlife. This is the first report of LCCP exposure in wildlife and highlights the need for data on risks associated with CP usage.

The geochemistry of fluids from an active shallow submarine hydrothermal system: Milos island, Hellenic Volcanic Arc

NASA Astrophysics Data System (ADS)

Valsami-Jones, E.; Baltatzis, E.; Bailey, E. H.; Boyce, A. J.; Alexander, J. L.; Magganas, A.; Anderson, L.; Waldron, S.; Ragnarsdottir, K. V.

2005-10-01

Geothermal activity in the Aegean island of Milos (Greece), associated with island-arc volcanism, is abundant both on-and off-shore. Hydrothermal fluids venting from several sites, mainly shallow submarine (up to 10 m), but also just above seawater level in one locality, were sampled over four summer field seasons. Some of the discharging fluids are associated with the formation of hydrothermal edifices. Overall, the main characteristics of the hydrothermal fluids are low pH and variable chlorinity. The lowest recorded pH was 1.7, and chlorinity ranged from 0.1 to 2.5 times that of seawater. The highest fluid temperatures recorded on site were 115 °C. Two main types of fluids were identified: low-chlorinity fluids containing low concentrations of alkalis (potassium, lithium, sodium) and calcium, and high concentrations of silica and sulphate; and high-chlorinity fluids containing high concentrations of alkalis and calcium, and lower concentrations of silica and sulphate. The type locality of the high-chlorinity fluids is shallow submarine in Palaeochori, near the east end of the south coast of the island, whereas the type locality of the low-chlorinity fluids is a cave to the west of Palaeochori. The two fluid types are therefore often referred to as "submarine" and "cave" fluids respectively. Both fluid types had low magnesium and high metal concentrations but were otherwise consistently different from each other. The low-chlorinity fluids had the highest cobalt, nickel, aluminium, iron and chromium (up to 1.6 μM, 3.6 μM, 1586 μM, 936 μM and 3.0 μM, respectively) and the high-chlorinity fluids had the highest zinc, cadmium, manganese and lead (up to 4.1 μM, 1.0 μM, 230 μM and 32 μM, respectively). Geochemical modelling suggests that metals in the former are likely to have been transported as sulphate species or free ions and in the latter as chloride species or free ions. Isotopic values for both water types range between δD -12 to 33‰ and δ 18O 1.2 to 4.6‰. The range of fluid compositions and isotopic contents indicates a complex history of evolution for the system. Both types of fluids appear to be derived from seawater and thus are likely to represent end members of a single fluid phase that underwent phase separation at depth.

STABLE CHLORINE INTRAMOLECULAR KINETIC ISOTOPE EFFECTS FROM THE ABIOTIC DEHYDROCHLORINATION OF DDT. (R828161)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

STABLE CHLORINE AND CARBON ISOTOPIC COMPOSITIONS OF SELECTED SEMI-VOLATILE ORGANOCHLORINE COMPOUNDS. (R828161)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

NASA Astrophysics Data System (ADS)

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. > 9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and δ13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched δ13C values compared to the upgradient mean. In addition, δ13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis.

PubMed

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Chlorine isotope constraints on fluid-rock interactions during subduction and exhumation of the Zermatt-Saas ophiolite

NASA Astrophysics Data System (ADS)

Selverstone, J.; Sharp, Z. D.

2013-10-01

Chlorine isotope compositions of high-pressure (˜2.3 GPa) serpentinite, rodingite, and hydrothermally altered oceanic crust (AOC) differ significantly from high- and ultrahigh-pressure (> 3.2 GPa) metasedimentary rocks in the Aosta region, Italy. Texturally early serpentinites, rodingites, and AOC have bulk δ37Cl values indistinguishable from those of modern seafloor analogues (δ37Cl = -1.0 to +1.0‰). In contrast, serpentinites and AOC samples that recrystallized during exhumation have low δ37Cl values (-2.7 to -0.5‰); 37Cl depletion correlates with progressive changes in bulk chemistry. HP/UHP metasediments have low δ37Cl values (median = -2.5‰) that differ statistically from modern marine sediments (median = -0.6‰). Cl in metasedimentary rocks is concentrated in texturally early minerals, indicating modification of seafloor compositions early in the subduction history. The data constrain fluid sources during both subduction and exhumation-related phases of fluid-rock interaction: (1) marine sediments at the top of the downgoing plate likely interacted with isotopically light pore fluids from the accretionary wedge in the early stages of subduction. (2) No pervasive interaction with externally derived fluid occurred during subsequent subduction to the maximum depths of burial. (3) Localized mixing between serpentinites and fluids released by previously isotopically modified metasediments occurred during exhumation in the subduction channel. Most samples, however, preserved protolith signatures during subduction to near-arc depths.

Cytotoxic acyl amides from the soil fungus Gymnascella dankaliensis.

PubMed

Hammerschmidt, Lena; Aly, Amal H; Abdel-Aziz, Mohammed; Müller, Werner E G; Lin, Wenhan; Daletos, Georgios; Proksch, Peter

2015-02-15

The soil fungus Gymnascella dankaliensis was collected in the vicinity of the Giza pyramids, Egypt. When grown on solid rice medium the fungus yielded four new compounds including 11'-carboxygymnastatin N (1), gymnastatin S (2), dankamide (3), and aranorosin-2-methylether (4), the latter having been reported previously only as a semisynthetic compound. In addition, six known metabolites (5-10) were isolated. Addition of NaCl or KBr to the rice medium resulted in the accumulation of chlorinated or brominated compounds as indicated by LC-MS analysis due to the characteristic isotope patterns observed. From the rice medium spiked with 3.5% NaCl the known chlorinated compounds gymnastatin A (11) and gymnastatin B (12) were obtained. All isolated compounds were unambiguously structurally elucidated on the basis of comprehensive spectral analysis (1D and 2D NMR, and mass spectrometry), as well as by comparison with the literature. Compounds 4, 7 and 11 showed potent cytotoxicity against the murine lymphoma cell line L5178Y (IC50 values 0.44, 0.58 and 0.64μM, respectively), whereas 12 exhibited moderate activity with an IC50 value of 5.80μM. Copyright © 2015 Elsevier Ltd. All rights reserved.

Transport, biodegradation and isotopic fractionation of chlorinated ethenes: modeling and parameter estimation methods

NASA Astrophysics Data System (ADS)

Béranger, Sandra C.; Sleep, Brent E.; Lollar, Barbara Sherwood; Monteagudo, Fernando Perez

2005-01-01

An analytical, one-dimensional, multi-species, reactive transport model for simulating the concentrations and isotopic signatures of tetrachloroethylene (PCE) and its daughter products was developed. The simulation model was coupled to a genetic algorithm (GA) combined with a gradient-based (GB) method to estimate the first order decay coefficients and enrichment factors. In testing with synthetic data, the hybrid GA-GB method reduced the computational requirements for parameter estimation by a factor as great as 300. The isotopic signature profiles were observed to be more sensitive than the concentration profiles to estimates of both the first order decay constants and enrichment factors. Including isotopic data for parameter estimation significantly increased the GA convergence rate and slightly improved the accuracy of estimation of first order decay constants.

Isotopic Tracers for Delineating Non-Point Source Pollutants in Surface Water

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

Davisson, M L

2001-03-01

This study tested whether isotope measurements of surface water and dissolved constituents in surface water could be used as tracers of non-point source pollution. Oxygen-18 was used as a water tracer, while carbon-14, carbon-13, and deuterium were tested as tracers of DOC. Carbon-14 and carbon-13 were also used as tracers of dissolved inorganic carbon, and chlorine-36 and uranium isotopes were tested as tracers of other dissolved salts. In addition, large databases of water quality measurements were assembled for the Missouri River at St. Louis and the Sacramento-San Joaquin Delta in California to enhance interpretive results of the isotope measurements. Muchmore » of the water quality data has been under-interpreted and provides a valuable resource to investigative research, for which this report exploits and integrates with the isotope measurements.« less

Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Shrestha, Yesha

2016-01-01

There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

NASA Astrophysics Data System (ADS)

Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

2018-02-01

Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in highly acidic brines is controlled by the distribution of dissolved chlorine species, which changes from Cl- to HClo dominance with the progressive pH decline. The Kawah Ijen lake acquired its extreme composition through influx of sulphur and halogen-rich magmatic gas components and extensive rock dissolution. If hyperacid brines with comparable chemical composition existed on Mars, evaporation processes up to the extent reported here (aH2O = 0.85), were likely accompanied by losses of gaseous HCl. The resulting changes in Cl isotope compositions, Br/Cl, S/Cl and other ratios in the residual brine might be potentially recorded in assemblages of halogen-bearing secondary evaporation minerals. Also, volcanic-hydrothermal brines as these would extend the stability of liquid water on the Martian surface down to a temperature of -90 °C.

Compound-specific nitrogen and carbon isotope analysis of nitroaromatic compounds in aqueous samples using solid-phase microextraction coupled to GC/IRMS.

PubMed

Berg, Michael; Bolotin, Jakov; Hofstetter, Thomas B

2007-03-15

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry was used to determine the delta15N and delta13C signatures of selected nitroaromatic contaminants such as the explosive 2,4,6-trinitrotoluene (TNT) for derivation of isotopic enrichment factors of contaminant transformation. Parameters for efficient extraction of nitroaromatic compounds (NACs) and substituted anilines from water samples were evaluated by SPME-GC/MS. delta13C signatures determined by SPME-GC/IRMS and elemental analyzer IRMS (EA-IRMS) were in good agreement, generally within +/-0.7 per thousand, except for 2,4-dinitrotoluene (2,4-DNT) and TNT, which showed slight deviations (<1.3 per thousand). Limits of detection (LODs) for delta13C analysis by SPME-GC/IRMS were between 73 and 780 microg L-1 and correlated with the extraction efficiencies of the compounds determined by SPME-GC/MS. Nitrogen isotope measurements by SPME-GC/IRMS were of similar precision (standard deviations <0.8 per thousand) for all NACs except for TNT. delta15N signatures matched the reference values obtained by EA-IRMS within +/-1.3 per thousand (+2.5 per thousand for TNT), but no systematic trend was found for the deviations. LODs of delta15N measurements ranged from 1.6 to 9.6 mg L-1 for nitrotoluenes, chlorinated NACs and DNTs (22 mg L-1 for TNT). The SPME-GC/IRMS method is well suited for the determination of isotopic enrichment factors of various NAC transformation processes and provides so far unexplored possibilities to elucidate behavior and degradation mechanisms of nitroaromatic contaminants in soils and groundwaters.

Chlorine-36 and chlorine concentrations within several compartments of a deciduous forest ecosystem in Meuse/Haute-Marne (France)

NASA Astrophysics Data System (ADS)

Pupier, Julie; Benedetti, Lucilla; Bourles, Didier; Leclerc, Elisabeth; Thiry, Yves

2013-04-01

Chlorine-36 is a cosmogenic nuclide mainly produced in the atmosphere by interactions between energetic particles originating from the cosmic radiations and 40Ar. Because of its long half-life (T1-2 = 3.01 105 yr) and its high mobility, chlorine-36 is a critical radionuclide concerning radioactive waste repository sites. Moreover, it has been shown that inorganic chlorine could be enriched along the trophic chain due to its high solubility and bioavailability (Ashworth and Shaw, 2006). Additionally, many studies during the last decades have established that due to chlorination process, organic chlorine may account for a large proportion of the total soil chlorine pool (more than 80 % in surface soils of temperate ecosystems. Redon et al., 2012). The aim of this study is thus to measure chlorine-36 in all the compartments of the biogeochemical cycle, to better understand its recycling in the biosphere. The study site is the experimental beech forest site of the Andra long-term monitoring and testing system (OPE*). It is located at Montiers-sur-Saulx, North-East of France and is associated to the future radioactive waste repository site of Bure. Since March 2012, rainwater above (rainfall collected from a 45 m high tower built on purpose) and below (throughfall and stemflow) the canopy, has been collected monthly, as well as soil solutions (gravitational and bound waters) at four depths (0, 10, 30, 60 cm deep). Chlorine-36 and chlorine have been measured in the rainfall samples between March and July 2012 and in water solutions collected from all compartments of the biosphere using isotope dilution mass spectrometry at the french AMS national facility ASTER located at CEREGE. The results yielded from the rainfall samples allow to study the temporal fluctuations of chlorine-36 in the atmosphere, which represents the main inflow of chlorine-36 in its biogeochemical cycle. The first results indicate a flow increase during the late spring-early summer. Santos et al., 2004 have also observed a similar pattern in southern Spain. This increase might be due to a tropopause break, a natural process which occurs in spring and in fall. This break implies an increase of the air masses exchange between the tropopause and the stratosphere and therefore could cause high chlorine-36 inflow. All together, those results allow to draw a profile of the evolution of chlorine-36 concentrations in the various pools of the biogeochemical cycle (from the upper rainfall through stemflow and throughfall to the lower soil). Both 36Cl and Cl concentrations in stemflow samples are 25-50% higher than in the rainfall and throughfall samples. In water solutions collected from the soil, chlorine-36 concentrations vary between 3 to 8 10 3 at/ml, with an increase in the concentration at 30 cm depth. To understand the chlorine-36 recycling in soil, the next step will be to isolate and measure the 36Cl concentrations in the inorganic and organic fractions of chlorine in a soil profile. * : OPE : Observatoire Pérenne de l'Environnement (SOERE), French national long-term monitoring and experimental system for research in environment, www.andra-ope.fr Ashworth, D. J. and Shaw, G. (2006). A comparison of the soil migration and plant uptake of radioactive chlorine and iodine from contaminated groundwater. Journal of environmental radioactivity, 89(1) :61-80. Redon, P.-O., Jolivet, C., Saby, N. P. a., Abdelouas, A., and Thiry, Y. (2012). Occurrence of natural organic chlorine in soils for different land uses. Biogeochemistry (In press), doi : 10.1007/s10533- 012-9771-7. Santos, F., Lopez-Gutierrez, J., Garcia-Leon, M., Schnabel, C., Synal, H., and Suter, M. (2004). Analysis of 36Cl in atmospheric samples from Seville (Spain) by AMS. Nuclear Instruments and Methods in Physics Research Section B : Beam Interactions with Materials and Atoms, 223-224 :501-506.

Reconstruction of the Earthquake History of Limestone Fault Scarps in Knidos Fault Zone Using in-situ Chlorine-36 Exposure Dating and "R" Programming Language

NASA Astrophysics Data System (ADS)

Sahin, Sefa; Yildirim, Cengiz; Akif Sarikaya, Mehmet; Tuysuz, Okan; Genc, S. Can; Ersen Aksoy, Murat; Ertekin Doksanalti, Mustafa

2016-04-01

Cosmogenic surface exposure dating is based on the production of rare nuclides in exposed rocks, which interact with cosmic rays. Through modelling of measured 36Cl concentrations, we might obtain information of the history of the earthquake activity. Yet, there are several factors which may impact production of rare nuclides such as geometry of the fault, topography, geographic location of the study area, temporal variations of the Earth's magnetic field, self-cover and denudation rate on the scarp. Recently developed models provides a method to infer timing of earthquakes and slip rates on limited scales by taking into account these parameters. Our study area, the Knidos Fault Zone, is located on the Datça Peninsula in Southwestern Anatolia and contains several normal fault scarps formed within the limestone, which are appropriate to generate cosmogenic chlorine-36 (36Cl) dating models. Since it has a well-preserved scarp, we have focused on the Mezarlık Segment of the fault zone, which has an average length of 300 m and height 12-15 m. 128 continuous samples from top to bottom of the fault scarp were collected to carry out analysis of cosmic 36Cl isotopes concentrations. The main purpose of this study is to analyze factors affecting the production rates and amount of cosmogenic 36Cl nuclides concentration. Concentration of Cl36 isotopes are measured by AMS laboratories. Through the local production rates and concentration of the cosmic isotopes, we can calculate exposure ages of the samples. Recent research elucidated each step of the application of this method by the Matlab programming language (e.g. Schlagenhauf et al., 2010). It is vitally helpful to generate models of Quaternary activity of the normal faults. We, however, wanted to build a user-friendly program through an open source programing language "R" (GNU Project) that might be able to help those without knowledge of complex math programming, making calculations as easy and understandable as possible. Through our codes, physical parameters, statistical analysis and graphics production of the fault models can be generated for each platform. This project is supported by the Scientific and Technological Research Council of Turkey (TUBITAK, Grant number: 113Y436) This study was conducted with the Decision of the Council of Ministers with No. 2013/5387 on the date 30.09.2013 and was done with the permission of Knidos Presidency of excavation in accordance with the scope of Knidos Excavation and Research carried out on behalf of Selcuk University and Ministry of Culture and Tourism. Keywords: Knidos, geomorphology, modelling, cosmogenic surface exposure dating, chlorine36

Combined C and Cl isotope effects indicate differences between corrinoids and enzyme (Sulfurospirillum multivorans PceA) in reductive dehalogenation of tetrachloroethene, but not trichloroethene.

PubMed

Renpenning, Julian; Keller, Sebastian; Cretnik, Stefan; Shouakar-Stash, Orfan; Elsner, Martin; Schubert, Torsten; Nijenhuis, Ivonne

2014-10-21

The role of the corrinoid cofactor in reductive dehalogenation catalysis by tetrachloroethene reductive dehalogenase (PceA) of Sulfurospirillum multivorans was investigated using isotope analysis of carbon and chlorine. Crude extracts containing PceA--harboring either a native norpseudo-B12 or the alternative nor-B12 cofactor--were applied for dehalogenation of tetrachloroethene (PCE) or trichloroethene (TCE), and compared to abiotic dehalogenation with the respective purified corrinoids (norpseudovitamin B12 and norvitamin B12), as well as several commercially available cobalamins and cobinamide. Dehalogenation of TCE resulted in a similar extent of C and Cl isotope fractionation, and in similar dual-element isotope slopes (εC/εCl) of 5.0-5.3 for PceA enzyme and 3.7-4.5 for the corrinoids. Both observations support an identical reaction mechanism. For PCE, in contrast, observed C and Cl isotope fractionation was smaller in enzymatic dehalogenation, and dual-element isotope slopes (2.2-2.8) were distinctly different compared to dehalogenation mediated by corrinoids (4.6-7.0). Remarkably, εC/εCl of PCE depended in addition on the corrinoid type: εC/εCl values of 4.6 and 5.0 for vitamin B12 and norvitamin B12 were significantly different compared to values of 6.9 and 7.0 for norpseudovitamin B12 and dicyanocobinamide. Our results therefore suggest mechanistic and/or kinetic differences in catalytic PCE dehalogenation by enzymes and different corrinoids, whereas such differences were not observed for TCE.

Elucidating Turnover Pathways of Bioactive Small Molecules by Isotopomer Analysis: The Persistent Organic Pollutant DDT

PubMed Central

Ehlers, Ina; Betson, Tatiana R.; Vetter, Walter; Schleucher, Jürgen

2014-01-01

The persistent organic pollutant DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) is still indispensable in the fight against malaria, although DDT and related compounds pose toxicological hazards. Technical DDT contains the dichloro congener DDD (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethyl]benzene) as by-product, but DDD is also formed by reductive degradation of DDT in the environment. To differentiate between DDD formation pathways, we applied deuterium NMR spectroscopy to measure intramolecular deuterium distributions (2H isotopomer abundances) of DDT and DDD. DDD formed in the technical DDT synthesis was strongly deuterium-enriched at one intramolecular position, which we traced back to 2H/1H fractionation of a chlorination step in the technical synthesis. In contrast, DDD formed by reductive degradation was strongly depleted at the same position, which was due to the incorporation of 2H-depleted hydride equivalents during reductive degradation. Thus, intramolecular isotope distributions give mechanistic information on reaction pathways, and explain a puzzling difference in the whole-molecule 2H/1H ratio between DDT and DDD. In general, our results highlight that intramolecular isotope distributions are essential to interpret whole-molecule isotope ratios. Intramolecular isotope information allows distinguishing pathways of DDD formation, which is important to identify polluters or to assess DDT turnover in the environment. Because intramolecular isotope data directly reflect isotope fractionation of individual chemical reactions, they are broadly applicable to elucidate transformation pathways of small bioactive molecules in chemistry, physiology and environmental science. PMID:25350380

Using the nuclear activation AMS method for determining chlorine in solids at ppb-levels and below

NASA Astrophysics Data System (ADS)

Winkler, Stephan R.; Eigl, Rosmarie; Forstner, Oliver; Martschini, Martin; Steier, Peter; Sterba, Johannes H.; Golser, Robin

2015-10-01

Neutron activation analysis using decay counting of the activated element is a well-established method in elemental analysis. However, for chlorine there is a better alternative to measuring decay of the short-lived activation product chlorine-38 (t1/2 = 37.24 min) - accelerator mass spectrometry (AMS) of 36Cl: the relatively high neutron capture cross section of chlorine-35 for thermal neutrons (43.7 b) and combined the AMS technique for chlorine-36 (t1/2 = 301 ka) allow for determination of chlorine down to ppb-levels using practical sample sizes and common exposure durations. The combination of neutron activation and AMS can be employed for a few other elements (nitrogen, thorium, and uranium) as well. For bulk solid samples an advantage of the method is that lab contamination can be rendered irrelevant. The chlorine-35 in the sample is activated to chlorine-36, and surface chlorine can be removed after the irradiation. Subsequent laboratory contamination, however, will not carry a prominent chlorine-36 signature. After sample dissolution and addition of sufficient amounts of stable chlorine carrier the produced chlorine-36 and thus the original chlorine-35 of the sample can be determined using AMS. We have developed and applied the method for analysis of chlorine in steel samples. The chlorine content of steel is of interest to nuclear industry, precisely because of above mentioned high neutron capture cross section for chlorine-35, which leads to accumulation of chlorine-36 as long-term nuclear waste. The samples were irradiated at the TRIGA Mark II reactor of the Atominstitut in Vienna and the 36Cl-AMS setup at the Vienna Environmental Research Accelerator (VERA) was used for 36Cl/Cl analysis.

The Abundance and Isotopic Signature of Chlorine in UrKREEP: Implications for the Early Degassing of the Moon

NASA Technical Reports Server (NTRS)

Boyce, J. W.; Kanee, S.; McCubbin, F. M.; Barnes, J. J.; Bricker, H.; Treiman. A. H.

2017-01-01

Initally, the elevated delta-37 Cl values of lunar materials were attributed to volcanic degassing[1]. However, chlorine isotope ratios of apatite in lunarmare basalts appear to reflect mixing between two reservoirs.One component, with elevated delta-37 Cl is greater than or equal to + (25%) ([2] may represent the urKREEP--the final product of the crystallization of the lunar magma ocean. The second component, with delta-37 Cl is approximately (0%), is inferred to represent either a mare basalt reservoir or meteoritic materials. The idea that high delta-37 Cl is related to urKREEP suggest a global enrichment that occurred earlier in the lunar history [2,3]. Here we test this urKREEP-mixing hypothesis more rigorously, and report the observed limits of the model. We then use the results to calculate the Cl content of the urKREEP component and use those results to update estimates of the bulk Cl content of the Moon. This allows us to speculate on the mechanisms of loss of Cl from the lunar magma ocean.

Constraining the global bromomethane budget from carbon stable isotopes

NASA Astrophysics Data System (ADS)

Bahlmann, Enno; Wittmer, Julian; Greule, Markus; Zetzsch, Cornelius; Seifert, Richard; Keppler, Frank

2016-04-01

Despite intense research in the last two decades, the global bromomethane (CH3Br) budget remains unbalanced with the known sinks exceeding the known sources by about 25%. The reaction with OH is the largest sink for CH3Br. We have determined the kinetic isotope effects for the reactions of CH3Br with the OH and Cl radical in order to better constrain the global CH3Br budget from an isotopic perspective. The isotope fractionation experiments were performed at 20±1°C in a 3500 L Teflon smog-chamber with initial CH3Br mixing ratios of about 2 and 10 ppm and perflourohexane (25 ppb) as internal standard. Atomic chlorine (Cl) was generated via photolysis of molecular chlorine (Cl2) using a solar simulator with an actinic flux comparable to that of the sun in mid-summer in Germany. OH radicals were generated via the photolysis of ozone (O3) at 253.7 nm in the presence of water vapor (RH = 70%).The mixing ratios of CH3Br, and perflourohexane were monitored by GC-MS with a time resolution of 15 minutes throughout the experiments. From each experiment 10 to 15 sub samples were taken in regular time intervals for subsequent carbon isotope ratio determinations by GC-IRMS performed at two independent laboratories in parallel. We found a kinetic isotope effect (KIE) of 17.6±3.3‰ for the reaction of CH3Br with OH and a KIE of 9.8±1.4 ‰ for the reaction with Cl*. We used these fractionation factors along with new data on the isotopic composition of CH3Br in the troposphere (-34±7‰) and the surface ocean (-26±7‰) along with reported source signatures, to constrain the unknown source from an isotopic perspective. The largest uncertainty in estimating the isotopic composition of the unknown source arises from the soil sink. Microbial degradation in soils is the second largest sink and assigned with a large fractionation factors of about 50‰. However, field experiments revealed substantially smaller apparent fractionation factors ranging from 11 to 22‰. In addition, simple model studies suggest that the soil uptake of CH3Br and hence its isotopic effect is largely controlled by diffusion resulting in an even smaller apparent isotopic fractionation. As a consequence, the estimated source signature for the unknown source is discussed with respect to the assumptions made for the soil sink.

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

USGS Publications Warehouse

Sturchio, N.C.; Böhlke, J.K.; Beloso, Abelardo D.; Streger, S.H.; Heraty, L.J.; Hatzinger, P.B.

2007-01-01

Perchlorate is a widespread environmental contaminant having both anthropogenic and natural sources. Stable isotope ratios of O and Cl in a given sample of perchlorate may be used to distinguish its source(s). Isotopic ratios may also be useful for identifying the extent of biodegradation of perchlorate, which is critical for assessing natural attenuation of this contaminant in groundwater. For this approach to be useful, however, the kinetic isotopic fractionations of O and Cl during perchlorate biodegradation must first be determined as a function of environmental variables such as temperature and bacterial species. A laboratory study was performed in which the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial strains (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10??C and 22??C with acetate as the electron donor. Perchlorate was completely reduced by both strains within 280 h at 22??C and 615 h at 10??C. Measured values of isotopic fractionation factors were ??18O = -36.6 to -29.0??? and ??37Cl = -14.5 to -11.5???, and these showed no apparent systematic variation with either temperature or bacterial strain. An experiment using 18O-enriched water (??18O = +198???) gave results indistinguishable from those observed in the isotopically normal water (??18O = -8.1???) used in the other experiments, indicating negligible isotope exchange between perchlorate and water during biodegradation. The fractionation factor ratio ??18O/??37Cl was nearly invariant in all experiments at 2.50 ?? 0.04. These data indicate that isotope ratio analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (??18O/??37Cl) also has significant implications for forensic studies. ?? 2007 American Chemical Society.

Compound-specific stable isotopes of organic compounds from lake sediments track recent environmental changes in an alpine ecosystem, Rocky Mountain National Park, Colorado

USGS Publications Warehouse

Enders, S.K.; Pagani, M.; Pantoja, S.; Baron, Jill S.; Wolfe, A.P.; Pedentchouk, N.; Nunez, L.

2008-01-01

Compound-specific nitrogen, carbon, and hydrogen isotope records from sediments of Sky Pond, an alpine lake in Rocky Mountain National Park (Colorado, United States of America), were used to evaluate factors contributing to changes in diatom assemblages and bulk organic nitrogen isotope records identified in lake sediments across Colorado, Wyoming, and southern Montana. Nitrogen isotopic records of purified algal chlorins indicate a substantial shift in nitrogen cycling in the region over the past ???60 yr. Temporal changes in the growth characteristics of algae, captured in carbon isotope records in and around Sky Pond, as well as a -60??? excursion in the hydrogen isotope composition of algal-derived palmitic acid, are coincident with changes in nitrogen cycling. The confluence of these trends is attributed to an increase in biologically available nitrogenous compounds caused by an expansion of anthropogenic influences and temporal changes in catchment hydrology and nutrient delivery associated with meltwater dynamics. ?? 2008, by the American Society of Limnology and Oceanography, Inc.

Use of a multi-isotope and multi-tracer approach including organic matter isotopes for quantifying nutrient contributions from agricultural vs wastewater sources

NASA Astrophysics Data System (ADS)

Kendall, C.; Silva, S. R.; Young, M. B.

2013-12-01

While nutrient isotopes are a well-established tool for quantifying nutrients inputs from agricultural vs wastewater treatment plant (WWTP) sources, we have found that combining nutrient isotopes with the C, N, and S isotopic compositions of dissolved and particulate organic matter, as part of a comprehensive multi-isotope and multi-tracer approach, is a much more diagnostic approach. The main reasons why organic matter C-N-S isotopes are a useful adjunct to studies of nutrient sources and biogeochemical processes are that the dissolved and particulate organic matter associated with (1) different kinds of animals (e.g., humans vs cows) often have distinctive isotopic compositions reflecting the different diets of the animals, and (2) the different processes associated with the different land uses (e.g., in the WWTP or associated with different crop types) often result in significant differences in the isotopic compositions of the organics. The analysis of the δ34S of particulate organic matter (POM) and dissolved organic matter (DOM) has been found to be especially useful for distinguishing and quantifying water, nutrient, and organic contributions from different land uses in aquatic systems where much of the organic matter is aquatic in origin. In such environments, the bacteria and algae incorporate S from sulfate and sulfide that is isotopically labeled by the different processes associated with different land uses. We have found that there is ~35 permil range in δ34S of POM along the river-estuary continuum in the San Joaquin/Sacramento River basin, with low values associated with sulfate reduction in the upstream wetlands and high values associated with tidal inputs of marine water into the estuary. Furthermore, rice agriculture results in relatively low δ34S values whereas WWTP effluent in the Sacramento River produces distinctly higher values than upstream of the WWTP, presumably because SO2 is used to treat chlorinated effluent. The fish living downstream of these different land uses become isotopically labeled by the environments, making δ34S a useful tracer of fish derived from these different environments. This presentation will use examples from several large-scale river and wetlands studies to demonstrate useful applications of POM and DOM isotopes for environmental monitoring studies, and will discuss the relative merits of different methods for the collection and analysis of POM and DOM samples for C, N, and S isotopes.

MNA of Chlorinated Solvents and Fuel Oxygenates: Why it occurs, how it evolved, and using stable carbon isotopes to predict plume behavior

EPA Science Inventory

The organisms that degrade MTBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

Pharmacokinetics of Chlorin e6-Cobalt Bis(Dicarbollide) Conjugate in Balb/c Mice with Engrafted Carcinoma

PubMed Central

Volovetsky, Arthur B.; Balalaeva, Irina V.; Dudenkova, Varvara V.; Shilyagina, Natalia Yu.; Feofanov, Аlexey V.; Efremenko, Anastasija V.; Grin, Mikhail A.; Mironov, Andrey F.; Bregadze, Vladimir I.; Maslennikova, Anna V.

2017-01-01

The necessary precondition for efficient boron neutron capture therapy (BNCT) is control over the content of isotope 10B in the tumor and normal tissues. In the case of boron-containing porphyrins, the fluorescent part of molecule can be used for quantitative assessment of the boron content. Study Objective: We performed a study of the biodistribution of the chlorin e6-Cobalt bis(dicarbollide) conjugate in carcinoma-bearing Balb/c mice using ex vivo fluorescence imaging, and developed a mathematical model describing boron accumulation and release based on the obtained experimental data. Materials and Methods: The study was performed on Balb/c tumor-bearing mice (CT-26 tumor model). A solution of the chlorin e6-Cobalt bis(dicarbollide) conjugate (CCDC) was injected into the blood at a dose of 10 mg/kg of the animal’s weight. Analysis of the fluorescence signal intensity was performed at several time points by spectrofluorimetry in blood and by laser scanning microscopy in muscle, liver, and tumor tissues. The boron content in the same samples was determined by mass spectroscopy with inductively coupled plasma. Results: Analysis of a linear approximation between the fluorescence intensity and boron content in the tissues demonstrated a satisfactory value of approximation reliability with a Spearman’s rank correlation coefficient of r = 0.938, p < 0.01. The dynamics of the boron concentration change in various organs, calculated on the basis of the fluorescence intensity, enabled the development of a model describing the accumulation of the studied compound and its distribution in tissues. The obtained results reveal a high level of correspondence between the model and experimental data. PMID:29182594

Pharmacokinetics of Chlorin e₆-Cobalt Bis(Dicarbollide) Conjugate in Balb/c Mice with Engrafted Carcinoma.

PubMed

Volovetsky, Arthur B; Sukhov, Vladimir S; Balalaeva, Irina V; Dudenkova, Varvara V; Shilyagina, Natalia Yu; Feofanov, Аlexey V; Efremenko, Anastasija V; Grin, Mikhail A; Mironov, Andrey F; Sivaev, Igor B; Bregadze, Vladimir I; Maslennikova, Anna V

2017-11-28

The necessary precondition for efficient boron neutron capture therapy (BNCT) is control over the content of isotope 10 B in the tumor and normal tissues. In the case of boron-containing porphyrins, the fluorescent part of molecule can be used for quantitative assessment of the boron content. Study Objective: We performed a study of the biodistribution of the chlorin e ₆-Cobalt bis(dicarbollide) conjugate in carcinoma-bearing Balb/c mice using ex vivo fluorescence imaging, and developed a mathematical model describing boron accumulation and release based on the obtained experimental data. Materials and Methods: The study was performed on Balb/c tumor-bearing mice (CT-26 tumor model). A solution of the chlorin e ₆-Cobalt bis(dicarbollide) conjugate (CCDC) was injected into the blood at a dose of 10 mg/kg of the animal's weight. Analysis of the fluorescence signal intensity was performed at several time points by spectrofluorimetry in blood and by laser scanning microscopy in muscle, liver, and tumor tissues. The boron content in the same samples was determined by mass spectroscopy with inductively coupled plasma. Results: Analysis of a linear approximation between the fluorescence intensity and boron content in the tissues demonstrated a satisfactory value of approximation reliability with a Spearman's rank correlation coefficient of r = 0.938, p < 0.01. The dynamics of the boron concentration change in various organs, calculated on the basis of the fluorescence intensity, enabled the development of a model describing the accumulation of the studied compound and its distribution in tissues. The obtained results reveal a high level of correspondence between the model and experimental data.

The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

NASA Astrophysics Data System (ADS)

Gleeson, S. A.; Smith, M. P.

2009-10-01

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

Compound-Specific Carbon and Hydrogen Isotope Analysis - Field Evidence of MTBE Bioremediation

NASA Astrophysics Data System (ADS)

Kuder, T.; Kolhatkar, R. V.; Philp, P.; Wilson, J. T.; Landmeyer, J. E.; Allen, J.

2002-12-01

Compound-specific stable isotope analysis allows opportunity to determine the isotopic ratios of individual contaminants. The technique has been applied to confirm biodegradation in studies of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (including bio- and inorganic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting with enrichment of the unreacted substrate in the heavier isotopic species (13C, D), referred to as kinetic isotopic fractionation, so that the extent of fractionation may be used as a proxy for biodegradation. Processes such as volatilization, sorption etc., result in minimal degree of fractionation and do not interfere with the isotopic signal due to biodegradation. The results presented here show the first successful applications of compound-specific isotope analysis to understanding MTBE biodegradation in the field, at both aerobic and anaerobic sites. Observed fractionations suggest that two different biodegradation pathways may be involved. At a number of anaerobic locations major fractionation effects were observed for both C and H; enrichment factors Ÿnfor both elements were approaching or exceeding -10. A laboratory microcosm study using an enrichment culture yielded similar results (C data only). A characteristic feature of these sites was the presence of high concentrations of TBA. Conversely, at a number of sites, the C composition remained stable with little fractionation and stayed within the analytical precision range or changed minimally, while H displayed significant fractionation in excess of 60 per mil. Moderate agreement of the data with Rayleigh fractionation model was observed, suggesting that biodegradation effect was distorted by variability at the source or the plume was not homogeneous. The enrichment factor calculated for these data is similar to the one Ÿnpublished for aerobic microcosm of MTBE-degrading culture from Vandenberg AFB by Gray et al. (Env. Sci. Tech., 2002, 36, 1931-1938) and appears to be in excess of -60 for H and under -2 for C. The high H fractionation observed under aerobic conditions may be attributed to the initial, monooxygenase transformation of MTBE (cf., Deeb et al., Biodegradation, 2000, 11, 171-186). The anaerobic enzymatic reactions were not characterized yet, but a hydrolytic process may be responsible. Interestingly, isotopic fractionation at an anaerobic site, which was treated by oxygen injection, did not show differences between aerobic and anaerobic parts of the plume. Despite oxygen addition, there was no evidence for monooxygenase activity.

MNA for Chlorinated Solvents and Fuel Oxygenates: Why It Occurs, How It Evolved, and Using Stable Carbon Isotopes to Predict Plume Behavior

EPA Science Inventory

The organisms that degrade MtBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

Delta 37Cl and Characterisation of Petroleum-gas Reservoirs

NASA Astrophysics Data System (ADS)

Woulé Ebongué, V.; Jendrzejewski, N.; Walgenwitz, F.; Pineau, F.; Javoy, M.

2003-04-01

The geochemical characterisation of formation waters from oil/gas fields is used to detect fluid-flow barriers in reservoirs and to reconstruct the system dynamic. During the progression of the reservoir filling, the aquifer waters are pushed by hydrocarbons toward the reservoir bottom and their compositions evolve due to several parameters such as water-rock interactions, mixing with oil-associated waters, physical processes etc. The chemical and isotopic evolution of these waters is recorded in irreducible waters that have been progressively "fossilised" in the oil/gas column. Residual salts precipitated from these waters were recovered. Chloride being the most important dissolved anion in these waters and not involved in diagenetic reactions, its investigation should give insights into the different transport or mixing processes taking place in the sedimentary basin and point out to the formation waters origins. The first aim of our study was to test the Cl-RSA technique (Chlorine Residual Salts Analysis) based on the well-established Sr-RSA technique. The main studied area is a turbiditic sandstone reservoir located in the Lower Congo basin in Angola. Present-day aquifer waters, irreducible waters from sandstone and shale layers as well as drilling mud and salt dome samples were analysed. Formation waters (aquifer and irreducible trapped in shale) show an overall increase of chlorinity with depth. Their δ37Cl values range from -1.11 ppm to +2.30 ppm ± 0.05 ppm/ SMOC. Most Cl-RSA data as well as the δ37Cl obtained on a set of water samples (from different aquifers in the same area) are lower than -0.13 ppm with lower δ37Cl values at shallower depths. In a δ37Cl versus chlorinity diagram, they are distributed along a large range of chlorinity: 21 to 139 g/l, in two distinct groups. (1) Irreducible waters from one of the wells display a positive correlation between chlorinity and the δ37Cl values. (2) In contrary, the majority of δ37Cl measured on aquifers and on residual salts from a second well are anti-correlated with chlorinity. The preliminary determinations of δ37Cl values of sandstone irreducible waters seem to match the values obtained on irreducible waters trapped in the shale porosity. δ37Cl values and chlorinities are used to identify the contributions of physico-chemical processes such as ion filtration, diffusion or mixing. The chronology of the events and their relative importance are discussed.

Systematic screening and identification of the chlorinated transformation products of aromatic pharmaceuticals and personal care products using high-resolution mass spectrometry.

PubMed

Chen, Wen-Ling; Cheng, Jiun-Yi; Lin, Xiao-Qian

2018-05-08

Pharmaceuticals and personal care products (PPCPs) are an emerging concern because of the large amount of PPCPs that is discharged and its potential ecological effects on the aquatic environment. Chlorination has proven efficient for removing some aromatic PPCPs from wastewater, but the formation of by-products has not been thoroughly investigated partly because of analytical difficulties. This study developed a method for systematically screening and identifying the transformation products (TPs) of multiple aromatic PPCPs through high-resolution mass spectrometry (HRMS). We spiked an environmentally relevant concentration (5000 ng/L) of three anti-inflammatory drugs, four parabens, bisphenol A, oxybenzone, and triclosan in the Milli-Q water and water containing natural organic matter (NOM). Low-dose chlorination (0.2-0.7 mg/L) was performed. We compared the chemical profiles of the chlorinated and untreated water and selected the ions to be identified based on the results of t-test and the ratio of signal intensities. Compound matching and isotopic pattern comparison were applied to characterising the molecular formulae of TPs. The fragmentation of the PPCPs and TPs was used in elucidating the structures of the TPs. The confirmation of TPs was achieved by comparing the retention time and fragment patterns of TPs with the isomer standards. In the chlorinated water, the aromatic PPCPs were substantially removed, except for the anti-inflammatory drugs (removal rates -5.2%-26%). Even with moderate chlorine dosages, all of the aromatic PPCPs, except for acetylsalicylic acid, were transformed into chlorinated derivatives in the Milli-Q water, and so were some PPCPs in the NOM-added water. The results of structure elucidation and compound confirmation as well as the increases in log K ow suggested that chlorination could transform aromatic PPCPs into more persistent, bioaccumulative, and toxic TPs. The presence of these TPs in the effluents where the PPCPs are removed through chlorination may pose increased risks to aquatic organisms. Copyright © 2018 Elsevier B.V. All rights reserved.

Preliminary lead isotope investigations of brine from the Red Sea, Galena from the Kingdom of Saudi Arabia, and galena from United Arab Republic (Egypt)

USGS Publications Warehouse

Delevaux, M.H.; Doe, B.R.; Brown, G.F.

1967-01-01

The isotopic composition of lead in Red Sea chloride brine containing 0.5 ppm Pb is found to be similar to that of some Cenozoic ore leads such as galena at Rabigh in Saudi Arabia that may have formed during mineralization accompanying Tertiary rifting. Bir Ranga galena in Miocene sediments from United Arab Republic (Egypt) is also isotopically similar to lead in Red Sea brine. The chlorine brine must be considered a possible mineralizing fluid. Lead isotopes show promise for use in mineral prospect evaluation in that galena from Samrah is isotopically similar to that from Mahd adh Dhahab, which has been the only ore producer in Saudi Arabia since 1945. Drilling at Samrah does indicate a possible economic mineralization. The lead isotope data coupled with available geologic knowledge and geochronometry are used to tentatively divide the ore prospects of the Kingdom of Saudi Arabia into relative categories of mineralization age. Two Mesozoic and Cenozoic mineralizations are distinguished on the basis of a 207Pb/204Pb difference; an early Paleozoic mineralization grouping is outlined; and a late Precambrian mineralization period is suggested. ?? 1967.

CHEMICAL ANALYSIS OF REVERSE OSMOSIS MEMBRANE AND XAD RESIN ADSORPTION CONCENTRATES OF WATER DISINFECTED BY CHLORINATION OR OZONATION/CHLORINATION PROCESSES

EPA Science Inventory

Chemical Analysis of Reverse Osmosis Membrane and XAD Resin Adsorption Concentrates of Water Disinfected by Chlorination or Ozonation/Chlorination Processes.

J. E. Simmons1, S.D. Richardson2, K.M. Schenck3, T. F. Speth3, R. J. Miltner3 and A. D. Thruston2

1 NHEE...

Chlorine isotopic compositions of apatite in Apollo 14 rocks: Evidence for widespread vapor-phase metasomatism on the lunar nearside ∼4 billion years ago

NASA Astrophysics Data System (ADS)

Potts, Nicola J.; Barnes, Jessica J.; Tartèse, Romain; Franchi, Ian A.; Anand, Mahesh

2018-06-01

Compared to most other planetary materials in the Solar System, some lunar rocks display high δ37Cl signatures. Loss of Cl in a H ≪ Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with δ37Cl values ranging from +14.6 ± 1.6‰ to +40.0 ± 2.9‰. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and δ37Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of δ37Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ∼4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

Vibrational Spectroscopy of the CCI[subscript 4]?[subscript 1] Mode: Effect of Thermally Populated Vibrational States

ERIC Educational Resources Information Center

Gaynor, James D.; Wetterer, Anna M.; Cochran, Rea M.; Valente, Edward J.; Mayer, Steven G.

2015-01-01

In our previous article on CCl[subscript 4] in this "Journal," we presented an investigation of the fine structure of the symmetric stretch of carbon tetrachloride (CCl[subscript 4]) due to isotopic variations of chlorine in C[superscript 35]Cl[subscript x][superscript 37]Cl[subscript 4-x]. In this paper, we present an investigation of…

The volatile content of Vesta: Clues from apatite in eucrites

NASA Astrophysics Data System (ADS)

Sarafian, Adam Robert; Roden, Michael F.; PatiñO-Douce, Alberto E.

2013-11-01

Apatite was analyzed by electron microprobe in 3 cumulate and 10 basaltic eucrites. Eucritic apatite is fluorine-rich with minor chlorine and hydroxyl (calculated by difference). We confirmed the hydroxyl content by measuring hydroxyl directly in apatites from three representative eucrites using secondary ionization mass spectroscopy. Overall, most eucritic apatites resemble fluorine-rich lunar mare apatites, but intriguing OH- and Cl-rich apatites suggest a role for water and/or hydrothermal fluids in the Vestan interior or on other related differentiated asteroids. Most late-stage apatite found in mesostasis has little hydroxyl or chlorine and is thought to have crystallized from a degassed magma; however, several apatites exhibit atypical compositions and/or textural characteristics. For example, the isotopically anomalous basaltic eucrite Pasamonte has apatite in the mesostasis with significant OH. Apatites in Juvinas also have significant OH and occur as veinlets crosscutting silicates. Euhedral apatites in the Moore County cumulate eucrite occur as inclusions in pyroxene and are also hydroxyl-rich (0.62 wt% OH). The OH was confirmed by SIMS analysis and this apatite clearly points to the presence of water, at least locally, in the Vestan interior. Portions of Elephant Moraine (EET) 90020 have large and abundant apatites, which may be the product of apatite accumulation in a zone of melt-rock reaction. Relatively chlorine-rich apatites occur in basaltic eucrite Graves Nunataks (GRA) 98098 (approximately 1 wt% Cl). Particularly striking is the compositional similarity between apatite in GRA 98098 and apatites in lunar KREEP, which may indicate the presence of residual magmas from an asteroid-wide magma ocean on Vesta.

Gas hydrates (clathrates) causing pore-water freshening and oxygen isotope fractionation in deep-water sedimentary sections of terrigenous continental margins

USGS Publications Warehouse

Hesse, R.; Harrison, W.E.

1981-01-01

The occurrence of gas hydrates in deep-water sections of the continental margins predicted from anomalous acoustic reflectors on seismic profiles has been confirmed by recent deep-sea drilling results. On the Pacific continental slope off Guatemala gas hydrates were brought up for the first time from two holes (497, 498A) drilled during Leg 67 of the DSDP in water depths of 2360 and 5500 m, respectively. The hydrates occur in organic matter-rich Pleistocene to Miocene terrigenous sediments. In the hydrate-bearing zone a marked decrease in interstitial water chlorinities was observed starting at about 10-20 m subbottom depth. Pore waters at the bottom of the holes (near 400 m subbottom) have as little as half the chlorinity of seawater (i.e. 9???). Similar, but less pronounced, trends were observed during previous legs of the DSDP in other hydrate-prone segments of the continental margins where recharge of fresh water from the continent can be excluded (e.g. Leg 11). The crystallization of hydrates, like ice, excludes salt ions from the crystal structure. During burial the dissolved salts are separated from the solids. Subsidence results in a downward motion of the solids (including hydrates) relative to the pore fluids. Thawing of hydrates during recovery releases fresh water which is remixed with the pore fluid not involved in hydrate formation. The volume of the latter decreases downhole thus causing downward decreasing salinity (chlorinity). Hydrate formation is responsible for oxygen isotope fractionation with 18O-enrichment in the hydrate explaining increasingly more positive ??18O values in the pore fluids recovered (after hydrate dissociation) with depth. ?? 1981.

Chlorine Analysis - Water. Training Module 5.260.2.77.

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 the procedures for chlorine residual analysis. It includes objectives, an instructor guide, and student handouts. The module addresses the determination of combined and free residual chlorine in water supply samples using three…

Chloromethane release from carbonaceous meteorite affords new insight into Mars lander findings

NASA Astrophysics Data System (ADS)

Keppler, Frank; Harper, David B.; Greule, Markus; Ott, Ulrich; Sattler, Tobias; Schöler, Heinz F.; Hamilton, John T. G.

2014-11-01

Controversy continues as to whether chloromethane (CH3Cl) detected during pyrolysis of Martian soils by the Viking and Curiosity Mars landers is indicative of organic matter indigenous to Mars. Here we demonstrate CH3Cl release (up to 8 μg/g) during low temperature (150-400°C) pyrolysis of the carbonaceous chondrite Murchison with chloride or perchlorate as chlorine source and confirm unequivocally by stable isotope analysis the extraterrestrial origin of the methyl group (δ2H +800 to +1100‰, δ13C -19.2 to +10‰,). In the terrestrial environment CH3Cl released during pyrolysis of organic matter derives from the methoxyl pool. The methoxyl pool in Murchison is consistent both in magnitude (0.044%) and isotope signature (δ2H +1054 +/- 626‰, δ13C +43.2 +/- 38.8‰,) with that of the CH3Cl released on pyrolysis. Thus CH3Cl emissions recorded by Mars lander experiments may be attributed to methoxyl groups in undegraded organic matter in meteoritic debris reaching the Martian surface being converted to CH3Cl with perchlorate or chloride in Martian soil. However we cannot discount emissions arising additionally from organic matter of indigenous origin. The stable isotope signatures of CH3Cl detected on Mars could potentially be utilized to determine its origin by distinguishing between terrestrial contamination, meteoritic infall and indigenous Martian sources.

Chloromethane release from carbonaceous meteorite affords new insight into Mars lander findings.

PubMed

Keppler, Frank; Harper, David B; Greule, Markus; Ott, Ulrich; Sattler, Tobias; Schöler, Heinz F; Hamilton, John T G

2014-11-13

Controversy continues as to whether chloromethane (CH3Cl) detected during pyrolysis of Martian soils by the Viking and Curiosity Mars landers is indicative of organic matter indigenous to Mars. Here we demonstrate CH3Cl release (up to 8 μg/g) during low temperature (150-400°C) pyrolysis of the carbonaceous chondrite Murchison with chloride or perchlorate as chlorine source and confirm unequivocally by stable isotope analysis the extraterrestrial origin of the methyl group (δ(2)H +800 to +1100‰, δ(13)C -19.2 to +10‰,). In the terrestrial environment CH3Cl released during pyrolysis of organic matter derives from the methoxyl pool. The methoxyl pool in Murchison is consistent both in magnitude (0.044%) and isotope signature (δ(2)H +1054 ± 626‰, δ(13)C +43.2 ± 38.8‰,) with that of the CH3Cl released on pyrolysis. Thus CH3Cl emissions recorded by Mars lander experiments may be attributed to methoxyl groups in undegraded organic matter in meteoritic debris reaching the Martian surface being converted to CH3Cl with perchlorate or chloride in Martian soil. However we cannot discount emissions arising additionally from organic matter of indigenous origin. The stable isotope signatures of CH3Cl detected on Mars could potentially be utilized to determine its origin by distinguishing between terrestrial contamination, meteoritic infall and indigenous Martian sources.

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

Beyond C, H, O, and N! Analysis of the elemental composition of U.S. FDA approved drug architectures.

PubMed

Smith, Brandon R; Eastman, Candice M; Njardarson, Jon T

2014-12-11

The diversity of elements among U.S. Food and Drug Administration (FDA) approved pharmaceuticals is analyzed and reported, with a focus on atoms other than carbon, hydrogen, oxygen, and nitrogen. Our analysis reveals that sulfur, chlorine, fluorine, and phosphorous represent about 90% of elemental substitutions, with sulfur being the fifth most used element followed closely by chlorine, then fluorine and finally phosphorous in the eighth place. The remaining 10% of substitutions are represented by 16 other elements of which bromine, iodine, and iron occur most frequently. The most detailed parts of our analysis are focused on chlorinated drugs as a function of approval date, disease condition, chlorine attachment, and structure. To better aid our chlorine drug analyses, a new poster showcasing the structures of chlorinated pharmaceuticals was created specifically for this study. Phosphorus, bromine, and iodine containing drugs are analyzed closely as well, followed by a discussion about other elements.

Stable carbon isotope fractionation of trans-1,2-dichloroethylene during co-metabolic degradation by methanotrophic bacteria

USGS Publications Warehouse

Brungard, Karen L.; Munakata-Marr, Junko; Johnson, Craig A.; Mandernack, Kevin W.

2003-01-01

Changes in the carbon isotope ratio (δ13C) of trans-1,2-dichloroethylene (t-DCE) were measured during its co-metabolic degradation by Methylomonas methanica, a type I methanotroph, and Methylosinus trichosporium OB3b, a type II methanotroph. In closed-vessel incubation experiments with each bacterium, the residual t-DCE became progressively enriched in 13C, indicating isotopic fractionation. From these experiments, the biological fractionation during t-DCE co-metabolism, expressed as ε, was measured to be -3.50/00 for the type I culture and -6.70/00 for the type II culture. This fractionation effect and subsequent enrichment in the δ13C of the residual t-DCE can thus be applied to determine the extent of biodegradation of DCE by these organisms. Based on these results, isotopic fractionation clearly warrants further study, as measured changes in the δ13C values of chlorinated solvents could ultimately be used to monitor the extent of biodegradation in laboratory or field settings where co-metabolism by methanotrophs occurs.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Analysis of residual chlorine in simple drinking water distribution system with intermittent water supply

NASA Astrophysics Data System (ADS)

Goyal, Roopali V.; Patel, H. M.

2015-09-01

Knowledge of residual chlorine concentration at various locations in drinking water distribution system is essential final check to the quality of water supplied to the consumers. This paper presents a methodology to find out the residual chlorine concentration at various locations in simple branch network by integrating the hydraulic and water quality model using first-order chlorine decay equation with booster chlorination nodes for intermittent water supply. The explicit equations are developed to compute the residual chlorine in network with a long distribution pipe line at critical nodes. These equations are applicable to Indian conditions where intermittent water supply is the most common system of water supply. It is observed that in intermittent water supply, the residual chlorine at farthest node is sensitive to water supply hours and travelling time of chlorine. Thus, the travelling time of chlorine can be considered to justify the requirement of booster chlorination for intermittent water supply.

Transformation of acesulfame in chlorination: Kinetics study, identification of byproducts, and toxicity assessment.

PubMed

Li, Adela Jing; Wu, Pengran; Law, Japhet Cheuk-Fung; Chow, Chi-Hang; Postigo, Cristina; Guo, Ying; Leung, Kelvin Sze-Yin

2017-06-15

Acesulfame (ACE) is one of the most commonly used artificial sweeteners. Because it is not metabolized in the human gut, it reaches the aquatic environment unchanged. In the present study, the reactivity of ACE in free chlorine-containing water was investigated for the first time. The degradation of ACE was found to follow pseudo-first-order kinetics. The first-order rate increased with decreasing pH from 9.4 to 4.8 with estimated half-lives from 693 min to 2 min. Structural elucidation of the detected transformation products (TPs) was performed by ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Integration of MS/MS fragments, isotopic pattern and exact mass allowed the characterization of up to 5 different TPs in the ultrapure water extracts analyzed, including two proposed new chlorinated compounds reported for the first time. Unexpectedly, several known and regulated disinfection by-products (DBPs) were present in the ACE chlorinated solution. In addition, two of the six DBPs are proposed as N-DBPs. Time-course profiles of ACE and the identified by-products in tap water and wastewater samples were followed in order to simulate the actual disinfection process. Tap water did not significantly affect degradation, but wastewater did; it reacted with the ACE to produce several brominated-DBPs. A preliminary assessment of chlorinated mixtures by luminescence inhibition of Vibrio fischeri showed that these by-products were up to 1.8-fold more toxic than the parent compound. The generation of these DBPs, both regulated and not, representing enhanced toxicity, make chlorine disinfection a controversial treatment for ACE. Further efforts are urgently needed to both assess the consequences of current water treatment processes on ACE and to develop new processes that will safely treat ACE. Human health and the health of our aquatic ecosystems are at stake. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isotope-abundance variations of selected elements (IUPAC technical report)

USGS Publications Warehouse

Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples.

PubMed

Boulyga, Sergei F; Heilmann, Jens; Prohaska, Thomas; Heumann, Klaus G

2007-10-01

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for (35)Cl+ to more than 6 x 10(5) cps for (238)U+ for 1 microg of trace element per gram of coal sample. Detection limits vary from 450 ng g(-1) for chlorine and 18 ng g(-1) for sulfur to 9.5 pg g(-1) for mercury and 0.3 pg g(-1) for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis.

Carbon isotopic constraints on the contribution of plant material to the natural precursors of trihalomethanes

USGS Publications Warehouse

Bergamaschi, B.A.; Fram, M.S.; Kendall, C.; Silva, S.R.; Aiken, G.R.; Fujii, R.

1999-01-01

The ??13C values of individual trihalomethanes (THM) formed on reaction of chlorine with dissolved organic carbon (DOC) leached from maize (corn, Zea maize L) and Scirpus acutus (an aquatic bulrush), and with DOC extracted from agricultural drainage waters were determined using purge and trap introduction into a gas chromatograph-combustion-isotope ratio monitoring mass spectrometer. We observed a 1-6.8??? difference between the ??13C values of THM produced from the maize and Scirpus leachates, similar to the isotopic difference between the whole plant materials. Both maize and Scirpus formed THM 12??? lower in 13C than whole plant material. We suggest that the low value of the THM relative to the whole plant material is evidence of distinct pools of THM-forming DOC, representing different biochemical types or chemical structures, and possessing different environmental reactivity Humic extracts of waters draining an agricultural field containing Scirpus peat soils and planted with maize formed THM with isotopic values intermediate between those of maize and Scirpus leachates, indicating maize may contribute significantly to the THM-forming DOC. The difference between the ??13C values of the whole isolate and that of the THM it yielded was 3 9???, however, suggesting diagenesis plays a role in determining the ??13C value of THM-forming DOC in the drainage waters, and precluding the direct use of isotopic mixing models to quantitatively attribute sources.The ??13C values of individual trihalomethanes (THM) formed on reaction of chlorine with dissolved organic carbon (DOC) leached from maize (corn; Zea maize L.) and Scirpus acutus (an aquatic bulrush), and with DOC extracted from agricultural drainage waters were determined using purge and trap introduction into a gas chromatograph-combustion-isotope ratio monitoring mass spectrometer. We observed a 16.8qq difference between the ??13C values of THM produced from the maize and Scirpus leachates, similar to the isotopic difference between the whole plant materials. Both maize and Scirpus formed THM 12qq lower in 13C than whole plant material. We suggest that the low value of the THM relative to the whole plant material is evidence of distinct pools of THM-forming DOC, representing different biochemical types or chemical structures, and possessing different environmental reactivity. Humic extracts of waters draining an agricultural field containing Scirpus peat soils and planted with maize formed THM with isotopic values intermediate between those of maize and Scirpus leachates, indicating maize may contribute significantly to the THM-forming DOC. The difference between the ??13C values of the whole isolate and that of the THM it yielded was 3.9qq, however, suggesting diagenesis plays a role in determining the ??13C value of THM-forming DOC in the drainage waters, and precluding the direct use of isotopic mixing models to quantitatively attribute sources.

Chlorine-36 investigations of groundwater infiltration in the Exploratory Studies Facility at Yucca Mountain, Nevada

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

Levy, S.S.; Fabryka-Martin, J.T.; Dixon, P.R.

1997-12-01

Chlorine-36, including the natural cosmogenic component and the component produced during atmospheric nuclear testing in the 1950`s and 1960`s (bomb pulse), is being used as an isotopic tracer for groundwater infiltration studies at Yucca Mountain, a potential nuclear waste repository. Rock samples have been collected systematically in the Exploratory Studies Facility (ESF), and samples were also collected from fractures, faults, and breccia zones. Isotopic ratios indicative of bomb-pulse components in the water ({sup 36}Cl/Cl values > 1,250 x 10{sup {minus}15}), signifying less than 40-yr travel times from the surface, have been detected at a few locations within the Topopah Springmore » Tuff, the candidate host rock for the repository. The specific features associated with the high {sup 36}Cl/Cl values are predominantly cooling joints and syngenetic breccias, but most of the sites are in the general vicinity of faults. The non-bomb pulse samples have {sup 36}Cl/Cl values interpreted to indicate groundwater travel times of at least a few thousand to possibly several hundred thousand years. Preliminary numerical solute-travel experiments using the FEHM (Finite Element Heat and Mass transfer) code demonstrate consistency between these interpreted ages and the observed {sup 36}Cl/Cl values but do not validate the interpretations.« less

Terrestrial Scavenging of Marine Mammals: Cross-Ecosystem Contaminant Transfer and Potential Risks to Endangered California Condors (Gymnogyps californianus).

PubMed

Kurle, Carolyn M; Bakker, Victoria J; Copeland, Holly; Burnett, Joe; Jones Scherbinski, Jennie; Brandt, Joseph; Finkelstein, Myra E

2016-09-06

The critically endangered California condor (Gymnogyps californianus) has relied intermittently on dead-stranded marine mammals since the Pleistocene, and this food source is considered important for their current recovery. However, contemporary marine mammals contain persistent organic pollutants that could threaten condor health. We used stable carbon and nitrogen isotope, contaminant, and behavioral data in coastal versus noncoastal condors to quantify contaminant transfer from marine mammals and created simulation models to predict the risk of reproductive impairment for condors from exposure to DDE (p,p'-DDE), a major metabolite of the chlorinated pesticide DDT. Coastal condors had higher whole blood isotope values and mean concentrations of contaminants associated with marine mammals, including mercury (whole blood), sum chlorinated pesticides (comprised of ∼95% DDE) (plasma), sum polychlorinated biphenyls (PCBs) (plasma), and sum polybrominated diphenyl ethers (PBDEs) (plasma), 12-100-fold greater than those of noncoastal condors. The mean plasma DDE concentration for coastal condors was 500 ± 670 (standard deviation) (n = 22) versus 24 ± 24 (standard deviation) (n = 8) ng/g of wet weight for noncoastal condors, and simulations predicted ∼40% of breeding-age coastal condors have DDE levels associated with eggshell thinning in other avian species. Our analyses demonstrate potentially harmful levels of marine contaminant transfer to California condors, which could hinder the recovery of this terrestrial species.

Constraints on the composition of the ancient terrestrial atmosphere and hydrosphere from fluid inclusion analysis

NASA Astrophysics Data System (ADS)

Marty, B.; Avice, G.; Burgess, R.

2016-12-01

The evolution of the hydrosphere and atmosphere during the first half of Earth's history is still largely unknown. We are currently investigating the compositions of these reservoirs from the analysis of fluid inclusions trapped in 3.5-2.7 Ga-old hydrothermal quartz. We specifically analyze noble gases and nitrogen which are conservative enough to have survived the long history of their host phases. The samples come from Archean terranes situated in North Pole, the Pilbara, NW Australia, and in the Barberton greenstone belt, South Africa. Their morphologies suggest that the quartz deposition was contemporary with terrane formation. They were selected on the basis of their ages determined by the Ar-Ar method. The results published by our group show that the noble gas isotopic composition of the Archean atmosphere was similar to the modern one, with the outstanding exception of xenon. This heavy noble gas experienced gradual isotopic fractionation through time, as a result of its preferential escape to space, which mechanism remains to be elucidated. In contrast, the isotope composition of atmospheric N was similar to the modern one, suggesting little, if any, loss of this element from the terrestrial atmosphere from 3.5 Ga to Present. The atmospheric partial pressure of N2 was likely to be comparable to, or lower than, the modern one, casting doubt on the possibility of enhanced pN2 as a mean to counterbalance the faint Sun energy flux. Here we shall newly report data on chlorine and potassium in fluid inclusions with, together with noble gases, suggest that the salinity of the Archean oceans was not very different from that of the modern seawater.

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis.

PubMed

Lojkasek-Lima, Paulo; Aravena, Ramon; Parker, Beth L; Cherry, John A

2012-01-01

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation. © 2012, The Author(s). Ground Water © 2012, National Ground Water Association.

The tumor affinity of chlorin e6 and its sonodynamic effects on non-small cell lung cancer.

PubMed

Chen, Bei; Zheng, Ruinian; Liu, Duan; Li, Baofeng; Lin, Jinrong; Zhang, Weimin

2013-03-01

Sonodynamic therapy (SDT) is a promising new approach for cancer therapy. The aim of this study was to investigate the tumor affinity of chlorin e6, a photosensitizer, and its sonodynamic effects on NSCLC. Human lung adenocarcinoma cells SPCA-1 and mice bearing SPCA-1 tumor xenograft were exposed to ultrasound in the presence or absence of chlorin e6. Chlorin e6 distribution was detected by laser scan confocal microscope. Cell apoptosis and necrosis were studied by flow cytometry analysis. Tumor size and weight were measured after different treatments. The concentration of chlorin e6 in tumor tissue was remarkably higher than that in normal muscle near tumor, and the difference was greatest at 18h (the fluorescence intensity was 5.38-fold higher in tumor than in muscle, P<0.05). In vivo, ultrasound (0.4-1.6W/cm(2)) or chlorin e6 (10-40mg/kg) alone had no remarkable anti-tumor effects, but the combination of ultrasound (1.6W/cm(2)) with chlorin e6 (SDT) hampered tumor growth significantly (P<0.05). Intraperitoneal injection of 40mg/kg chlorin e6 exerted no notable side effect on blood, liver and kidney function. Flow cytometry analysis showed that chlorin e6-mediated sonodynamic effect was mainly through the induction of cell necrosis. Chlorin e6 is a promising sonosensitizer and chlorin e6-mediated SDT may provide a new approach for NSCLC therapy. Copyright © 2012 Elsevier B.V. All rights reserved.

Chloromethane release from carbonaceous meteorite affords new insight into Mars lander findings

PubMed Central

Keppler, Frank; Harper, David B.; Greule, Markus; Ott, Ulrich; Sattler, Tobias; Schöler, Heinz F.; Hamilton, John T. G.

2014-01-01

Controversy continues as to whether chloromethane (CH3Cl) detected during pyrolysis of Martian soils by the Viking and Curiosity Mars landers is indicative of organic matter indigenous to Mars. Here we demonstrate CH3Cl release (up to 8 μg/g) during low temperature (150–400°C) pyrolysis of the carbonaceous chondrite Murchison with chloride or perchlorate as chlorine source and confirm unequivocally by stable isotope analysis the extraterrestrial origin of the methyl group (δ2H +800 to +1100‰, δ13C −19.2 to +10‰,). In the terrestrial environment CH3Cl released during pyrolysis of organic matter derives from the methoxyl pool. The methoxyl pool in Murchison is consistent both in magnitude (0.044%) and isotope signature (δ2H +1054 ± 626‰, δ13C +43.2 ± 38.8‰,) with that of the CH3Cl released on pyrolysis. Thus CH3Cl emissions recorded by Mars lander experiments may be attributed to methoxyl groups in undegraded organic matter in meteoritic debris reaching the Martian surface being converted to CH3Cl with perchlorate or chloride in Martian soil. However we cannot discount emissions arising additionally from organic matter of indigenous origin. The stable isotope signatures of CH3Cl detected on Mars could potentially be utilized to determine its origin by distinguishing between terrestrial contamination, meteoritic infall and indigenous Martian sources. PMID:25394222

Geothermal investigation of spring and well waters of the Los Alamos Region, New Mexico

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

Goff, F.E.; Sayer, S.

1980-04-01

The chemical and isotopic characters of 20 springs and wells in the Los Alamos area were investigated for indications of geothermal potential. These waters were compared with known hot and mineral springs from adjacent Valles Caldera and San Ysidro. All waters in the Los Alamos area are composed of meteoric water. Isotopic data show that the two primary aquifers beneath the Los Alamos region have different recharge areas. Relatively high concentrations of lithium, arsenic, chlorine, boron, and fluorine in some of the Los Alamos wells suggest these waters may contain a small fraction of thermal/mineral water of deep origin. Thermalmore » water probably rises up high-angle faults associated with a graben of the Rio Grande rift now buried by the Pajarito Plateau.« less

Calcium isotope systematics at hydrothermal conditions: Mid-ocean ridge vent fluids and experiments in the CaSO4-NaCl-H2O system

NASA Astrophysics Data System (ADS)

Scheuermann, Peter P.; Syverson, Drew D.; Higgins, John A.; Pester, Nicholas J.; Seyfried, William E.

2018-04-01

Two sets of hydrothermal experiments were performed to explore Ca isotope fractionation and exchange rates at hydrothermal conditions (410-450 °C, 31.0-50.0 MPa). The first set of experiments determined the magnitude of vapor-liquid Ca isotope fractionation and anhydrite solubility in the CaSO4-NaCl-H2O system. The data indicate no statistical difference between the Ca isotopic composition of coexisting vapor and liquid. The second set of experiments utilized an anomalous 43Ca spike to determine the rate of Ca exchange between fluid and anhydrite as a function of total dissolved Ca concentration. Results show that the rate of exchange increases with dissolved Ca concentrations (12-23 mM/kg), but no change in exchange rate is observed when the Ca concentration increases from 23 to 44 mM/kg Ca. 74-142 days are required to achieve 90% anhydrite-fluid Ca isotope exchange at the conditions investigated, while only several hours are necessary for vapor-liquid isotopic equilibrium. The lack of vapor-liquid Ca isotope fractionation in our experiments is consistent with δ44Ca of mid-ocean ridge hydrothermal vent fluids that remain constant, regardless of chlorinity. Moreover, the narrow range of end member fluid δ44Ca, -0.98 to -1.13‰ (SW), is largely indistinguishable from MORB δ44Ca, suggesting that neither phase separation nor fluid-rock interactions at depth significantly fractionate Ca isotopes in modern high-temperature mid-ocean ridge hydrothermal systems.

Water in the Lunar Interior and the Apparent KREEP-Mare Dichotomy

NASA Astrophysics Data System (ADS)

McCubbin, F. M.; Nekvasil, H.

2010-12-01

Recent SIMS analysis of lunar apatite has shown that hydroxyl is structurally bound within lunar apatite from a number of different lunar lithologic types (McCubbin et al., 2010a, 2010b; Boyce et al., 2010; Greenwood et al., 2010). These studies along with previous SIMS analyses of lunar fire fountain glasses (Saal et al., 2008) confirm that there is at least some water in the lunar interior, with abundance estimates in magmatic source regions ranging from 64 ppb to 5 ppm water (McCubbin et al., 2010a). Surprisingly, apatite from rocks with KREEP-rich incompatible trace element signatures are depleted in hydroxyl in comparison to apatite from typical mare basalts. This result is counter-intuitive to the lunar magma ocean model, which predicts that incompatible constituents (e.g., water) would have been concentrated in the last dregs of liquid referred to as “urKREEP”. The mare basalts, which formed by partial melting of earlier LMO cumulates, are typically depleted in these incompatible constituents. Complicating the issue further, chlorine, another incompatible magmatic volatile element in apatite, follows the predicted trend with apatite from KREEP-rich rocks containing significant chlorine concentrations in comparison to apatite from mare basalts (McCubbin et al., 2009). The preceding results imply one of two scenarios 1) Water did not behave incompatibly during LMO crystallization and was preferentially stored within the LMO cumulate minerals 2) A secondary process such as degassing has perturbed the initial volatile contents of the urKREEP liquid or of the secondary magmas that have KREEP-rich incompatible trace element signatures. In regards to the first scenario, the mineral melt partition coefficients for water would need to have exceeded unity at the very low water concentrations of the LMO liquid. This scenario is consistent with the behavior of chlorine, as chlorine is not typically stored in nominally anhydrous phases like pyroxene or olivine, likely due to its large ionic radius. However, there is no empirical or experimental evidence to support the elevated D values for water. Regarding the second scenario, if significant degassing of the urKREEP liquid or KREEP-rich secondary magmas occurred, water would have certainly been lost preferentially to the other volatile constituents in apatite (fluorine and chlorine); however chlorine isotopes analyzed in lunar apatites are highly fractionated (Sharp et al., 2010), indicating degassing of chlorine in the absence of water. Therefore, this scenario only works if degassing on the Moon was a multi-stage and complex process where water and chlorine degassing are decoupled, which is not typically the case for terrestrial systems (Aiuppa et al., 2009, Webster and De Vivo, 2002; Webster et al., 1999). Solving this apparent KREEP-mare dichotomy regarding magmatic volatiles in the lunar interior is the next important step in figuring out the importance, relevance, and implications of water in the lunar interior. Moreover, it will lend insight into the roles of the other magmatic volatiles during the thermal and magmatic evolution of the Moon.

Microbial chlorination of organic matter in forest soil: investigation using 36Cl-chloride and its methodology.

PubMed

Rohlenová, J; Gryndler, M; Forczek, S T; Fuksová, K; Handova, V; Matucha, M

2009-05-15

Chloride, which comes into the forest ecosystem largely from the sea as aerosol (and has been in the past assumed to be inert), causes chlorination of soil organic matter. Studies of the chlorination showed that the content of organically bound chlorine in temperate forest soils is higher than that of chloride, and various chlorinated compounds are produced. Our study of chlorination of organic matter in the fermentation horizon of forest soil using radioisotope 36Cl and tracer techniques shows that microbial chlorination clearly prevails over abiotic, chlorination of soil organic matter being enzymatically mediated and proportional to chloride content and time. Long-term (>100 days) chlorination leads to more stable chlorinated substances contained in the organic layer of forest soil (overtime; chlorine is bound progressively more firmly in humic acids) and volatile organochlorines are formed. Penetration of chloride into microorganisms can be documented by the freezing/thawing technique. Chloride absorption in microorganisms in soil and in litter residues in the fermentation horizon complicates the analysis of 36Cl-chlorinated soil. The results show that the analytical procedure used should be tested for every soil type under study.

Isotopic fractionation of volatile species during bubble growth in magmas

NASA Astrophysics Data System (ADS)

Watson, E. B.

2016-12-01

Bubbles grow in decompressing magmas by simple expansion and also by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate isotopes, raising the possibility that the isotopic character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the complete absence of equilibrium vapor/melt isotopic fractionation. None of the foregoing is conceptually new, but recent experimental studies have established the existence of isotope mass effects on diffusion in silicate melts for several elements (Li, Mg, Ca, Fe), and this finding has now been extended to the volatile (anionic) element chlorine (Fortin et al. 2016; this meeting). Knowledge of isotope mass effects on diffusion of volatile species opens the way for quantitative models of diffusive fractionation during bubble growth. Significantly different effects are anticipated for "passive" volatiles (e.g., noble gases and Cl) that are partitioned into existing bubbles but play little role in nucleation and growth, as opposed to "active" volatiles whose limited solubilities lead to bubble nucleation during magma decompression. Numerical solution of the appropriate diffusion/mass-conservation equations reveals that the isotope effect on passive volatiles partitioned into bubbles growing at a constant rate in a static system depends (predictably) upon R/D, Kd and D1/D2 (R = growth rate; D = diffusivity; Kd = bubble/melt partition coefficient; D1/D2 = diffusivity ratio of the isotopes of interest). Constant R is unrealistic, but other scenarios can be explored by including the solubility and EOS of an "active" volatile (e.g., CO2) in numerical simulations of bubble growth. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble.

Contrasting dual (C, Cl) isotope fractionation offers potential to distinguish reductive chloroethene transformation from breakdown by permanganate.

PubMed

Doğan-Subaşı, Eylem; Elsner, Martin; Qiu, Shiran; Cretnik, Stefan; Atashgahi, Siavash; Shouakar-Stash, Orfan; Boon, Nico; Dejonghe, Winnie; Bastiaens, Leen

2017-10-15

cis-1,2-Dichloroethene (cis-DCE) and trichloroethene (TCE) are persistent, toxic and mobile pollutants in groundwater systems. They are both conducive to reductive dehalogenation and to oxidation by permanganate. In this study, the potential of dual element (C, Cl) compound specific isotope analyses (CSIA) for distinguishing between chemical oxidation and anaerobic reductive dechlorination of cis-DCE and TCE was investigated. Well-controlled cis-DCE degradation batch tests gave similar carbon isotope enrichment factors ε C (‰), but starkly contrasting dual element isotope slopes Δδ 13 C/Δδ 37 Cl for permanganate oxidation (ε C =-26‰±6‰, Δδ 13 C/Δδ 37 Cl≈-125±47) compared to reductive dechlorination (ε C =-18‰±4‰, Δδ 13 C/Δδ 37 Cl≈4.5±3.4). The difference can be tracked down to distinctly different chlorine isotope fractionation: an inverse isotope effect during chemical oxidation (ε Cl =+0.2‰±0.1‰) compared to a large normal isotope effect in reductive dechlorination (ε Cl =-3.3‰±0.9‰) (p≪0.05). A similar trend was observed for TCE. The dual isotope approach was evaluated in the field before and up to 443days after a pilot scale permanganate injection in the subsurface. Our study indicates, for the first time, the potential of the dual element isotope approach for distinguishing cis-DCE (and TCE) concentration drops caused by dilution, oxidation by permanganate and reductive dechlorination both at laboratory and field scale. Copyright © 2017. Published by Elsevier B.V.

PINS Spectrum Identification Guide

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

A.J. Caffrey

2012-03-01

The Portable Isotopic Neutron Spectroscopy—PINS, for short—system identifies the chemicals inside munitions and containers without opening them, a decided safety advantage if the fill chemical is a hazardous substance like a chemical warfare agent or an explosive. The PINS Spectrum Identification Guide is intended as a reference for technical professionals responsible for the interpretation of PINS gamma-ray spectra. The guide is divided into two parts. The three chapters that constitute Part I cover the science and technology of PINS. Neutron activation analysis is the focus of Chapter 1. Chapter 2 explores PINS hardware, software, and related operational issues. Gamma-ray spectralmore » analysis basics are introduced in Chapter 3. The six chapters of Part II cover the identification of PINS spectra in detail. Like the PINS decision tree logic, these chapters are organized by chemical element: phosphorus-based chemicals, chlorine-based chemicals, etc. These descriptions of hazardous, toxic, and/or explosive chemicals conclude with a chapter on the identification of the inert chemicals, e.g. sand, used to fill practice munitions.« less

Correction for isotopic interferences between analyte and internal standard in quantitative mass spectrometry by a nonlinear calibration function.

PubMed

Rule, Geoffrey S; Clark, Zlatuse D; Yue, Bingfang; Rockwood, Alan L

2013-04-16

Stable isotope-labeled internal standards are of great utility in providing accurate quantitation in mass spectrometry (MS). An implicit assumption has been that there is no "cross talk" between signals of the internal standard and the target analyte. In some cases, however, naturally occurring isotopes of the analyte do contribute to the signal of the internal standard. This phenomenon becomes more pronounced for isotopically rich compounds, such as those containing sulfur, chlorine, or bromine, higher molecular weight compounds, and those at high analyte/internal standard concentration ratio. This can create nonlinear calibration behavior that may bias quantitative results. Here, we propose the use of a nonlinear but more accurate fitting of data for these situations that incorporates one or two constants determined experimentally for each analyte/internal standard combination and an adjustable calibration parameter. This fitting provides more accurate quantitation in MS-based assays where contributions from analyte to stable labeled internal standard signal exist. It can also correct for the reverse situation where an analyte is present in the internal standard as an impurity. The practical utility of this approach is described, and by using experimental data, the approach is compared to alternative fits.

Characterization and identification of a chlorine-resistant bacterium, Sphingomonas TS001, from a model drinking water distribution system.

PubMed

Sun, Wenjun; Liu, Wenjun; Cui, Lifeng; Zhang, Minglu; Wang, Bei

2013-08-01

This study describes the identification and characterization of a new chlorine resistant bacterium, Sphingomonas TS001, isolated from a model drinking water distribution system. The isolate was identified by 16s rRNA gene analysis and morphological and physiological characteristics. Phylogenetic analysis indicates that TS001 belongs to the genus Sphingomonas. The model distribution system HPC results showed that, when the chlorine residual was greater than 0.7 mg L(-1), 100% of detected heterotrophic bacteria (HPC) was TS001. The bench-scale inactivation efficiency testing showed that this strain was very resistant to chlorine, and 4 mg L(-1) of chlorine with 240 min retention time provided only approximately 5% viability reduction of TS001. In contrast, a 3-log inactivation (99.9%) was obtained for UV fluencies of 40 mJ cm(-2). A high chlorine-resistant and UV sensitive bacterium, Sphingomonas TS001, was documented for the first time. Copyright © 2013 Elsevier B.V. All rights reserved.

Characterizing chlorine oxidation of dissolved organic matter and disinfection by-product formation with fluorescence spectroscopy and parallel factor analysis

NASA Astrophysics Data System (ADS)

Beggs, Katherine M. H.; Summers, R. Scott; McKnight, Diane M.

2009-12-01

Relationships between chlorine demand and disinfection by-product (DBP) formation during chlorination and fluorescence of dissolved organic matter (DOM) were developed. Fluorescence excitation and emission (EEM) spectroscopy was employed, and parameters including fluorescence index, redox index, and overall fluorescence intensity (OFI) were correlated to chlorine demand and DBP formation. The EEMs were also analyzed using a well established global parallel factor analysis (PARAFAC) model which resolves the fluorescence signal into 13 components, including quinone-like and protein-like components. Over an 8-day chlorination period the OFI and sum of the 13 PARAFAC loadings decreased by more than 70%. The remaining identified quinone-like compounds within the DOM were shifted to a more oxidized state. Quinone fluorescence was strongly correlated to both reduced fluorescence intensity and to chlorine demand which indicates that fluorescence may be used to track the chlorine oxidation of DOM. Quinone fluorescence was also correlated strongly with both classes of regulated DBPs: total trihalomethanes and haloacetic acids. Quinone-like components were found to be strongly correlated to overall, short-term, and long-term specific DBP formation. The results of this study show that fluorescence is a useful tool in tracking both DOM oxidation and DBP formation during chlorination.

Biosynthesis and Total Synthesis of Pyrronazol B: a Secondary Metabolite from Nannocystis pusilla.

PubMed

Witte, Swjatoslaw N R; Hug, Joachim J; Géraldy, Magalie N E; Müller, Rolf; Kalesse, Markus

2017-11-13

The first stereoselective total synthesis of the natural product pyrronazol B, which contains a chlorinated pyrrole-oxazole-pyrone framework, has been achieved. Genome sequencing of the myxobacterial producer strain Nannocystis pusilla Ari7 led to the identification of the putative biosynthetic gene cluster. The proposed biosynthetic pathway was supported by feeding experiments with stable isotopes of three biosynthetic building blocks, namely l-proline, l-serine, and l-methionine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Inactivation of Mycobacteria mucogenicum in drinking water: chlorine resistance and mechanism analysis].

PubMed

Zheng, Qi; Chen, Chao; Zhang, Xiao-Jian; Lu, Pin-Pin; Liu, Yuan-Yuan; Chen, Yu-Qiao

2013-02-01

In recent years, chlorine-resistant bacteria were detected in drinking water distribution systems which threatened the drinking water safety. Our group detected one strain named Mycobacteria mucogenicum from the drinking water distribution system of a city in south China. This paper studied chlorine resistance and mechanism of Mycobacteria mucogenicum. Inactivation experiments of one strain Mycobacteria mucogenicum were conducted with free chlorine, monochloramind and chlorine dioxide. The CT values of 99.9% inactivation by free chlorine, monochloramine and chlorine dioxide were detected as (76.25 +/- 47.55)mg.min.L-1, (1396 +/-382)mg.min.L-1, (13.5 +/- 4.9) mg.min L-1. Using transmission electronmicroscopy (TEM) observed the inactivation process of Mycobacteria mucogenicum. The bacteria surface hydrophobic of Mycobacteria mucogenicum was 37.2%. Mycobacteria mucogenicum has a higher hydrophobicity than other bacteria which prevented the diffusion of chlorine into cells. Mycobacteria mucogenicum is more resistant to chorine than other bacteria.

Biogeochemial modeling of biodegradation and stable isotope fractionation of DCE in a small-scale wetland

NASA Astrophysics Data System (ADS)

Alvarez-Zaldívar, Pablo; Imfeld, Gwenaël; Maier, Uli; Centler, Florian; Thullner, Martin

2013-04-01

In recent years, the use of (constructed) wetlands has gained significant attention for the in situ remediation of groundwater contaminated with (chlorinated) organic hydrocarbons. Although many sophisticated experimental methods exist for the assessment of contaminant removal in such wetlands the understanding how changes in wetland hydrochemistry affect the removal processes is still limited. This knowledge gap might be reduced by the use of biogeochemical reactive transport models. This study presents the reactive transport simulation of a small-scale constructed wetland treated with groundwater containing cis-1,2-dichloroethene (cDCE). Simulated processes consider different cDCE biodegradation pathways and the associated carbon isotope fractionation, a set of further (bio)geochemical processes as well as the activity of the plant roots. Spatio-temporal hydrochemical and isotope data from a long-term constructed wetland experiment [1] are used to constrain the model. Simulation results for the initial oxic phase of the wetland experiment indicate carbon isotope enrichment factors typical for cometabolic DCE oxidation, which suggests that aerobic treatment of cDCE is not an optimal remediation strategy. For the later anoxic phase of the experiment model derived enrichment factors indicate reductive dechlorination pathways. This degradation is promoted at all wetland depths by a sufficient availability of electron donor and carbon sources from root exudates, which makes the anoxic treatment of groundwater in such wetlands an effective remediation strategy. In combination with the previous experimental data results from this study suggest that constructed wetlands are viable remediation means for the treatment of cDCE contaminated groundwater. Reactive transport models can improve the understanding of the factors controlling chlorinated ethenes removal, and the used model approach would also allow for an optimization of the wetland operation needed for a complete degradation of these contaminants. [1] Imfeld, G., Aragonés, C., Zeiger, S., von Eckstädt, C., Paschke, H., Trabitzsch, R., Weiss, H., and Richnow, H. (2008). Tracking in situ biodegradation of 1,2-dicholoroethenes in a model wetland. Environ. Sci. Technol., 42: 7924-7930.

Fluids on differentiated asteroids: Evidence from phosphates in differentiated meteorites GRA 06128 and GRA 06129

NASA Astrophysics Data System (ADS)

Shearer, Charles K.; Burger, Paul V.; Papike, James J.; Sharp, Zachary D.; McKeegan, Kevin D.

2011-09-01

Abstract- Paired meteorites Graves Nunatak 06128 and 06129 (GRA) represent an ancient cumulate lithology (4565.9 Ma ± 0.3) containing high abundances of sodic plagioclase. Textures and stable isotope compositions of GRA indicate that superimposed on the igneous lithology is a complex history of subsolidus reequilibration and low-temperature alteration that may have extended over a period of 150 Myr. In GRA, apatite is halogen-rich with Cl between 4.5 and 5.5 wt% and F between 0.3 and 0.9 wt%. The Cl/(Cl+F+OH) ratio of the apatite is between 0.65 and 0.82. The Cl and F are negatively correlated and are heterogeneously distributed in the apatite. Merrillite is low in halogens with substantial Na in the 6-fold coordinated Na-site (≈2.5%) and Mg in the smaller octahedral site. The merrillite has a negative Eu anomaly, whereas the apatite has a positive Eu anomaly. The chlorine isotope composition of the bulk GRA leachate is +1.2‰ relative to standard mean ocean chloride (SMOC). Ion microprobe chlorine isotope analyses of the apatite range between -0.5 and +1.2‰. Textural relationships between the merrillite and apatite, and the high-Cl content of the apatite, suggest that the merrillite is magmatic in origin, whereas the apatite is a product of the interaction between merrillite and a Cl-rich fluid. If the replacement of merrillite by apatite occurred at approximately 800 °C, the fluid composition is f(HCl)/f(H2O) = 0.0383 and a HCl molality of 2.13 and f(HCl)/f(HF) = 50-100. It is anticipated that the calculated f(HCl)/f(H2O) and a HCl molality are minimum values due to assumptions made on the OH component in apatite and basing the calculations on the apatite with the lowest XCl. The bulk δ37Cl of GRA is a >2σ outlier from chondritic meteorites and suggests that parent body processes resulted in fractionation of the Cl isotopes.

Iridoid glucosides from the aerial parts of Globularia alypum L. (Globulariaceae).

PubMed

Es-Safi, Nour-Eddine; Khlifi, Samira; Kollmann, Albert; Kerhoas, Lucien; El Abbouyi, Ahmed; Ducrot, Paul-Henri

2006-01-01

From the hydromethanolic extract of the aerial parts of Globularia alypum grown in Morocco, a new chlorinated iridoid glucoside, globularioside has been isolated beside 5 known iridoid glycosides, globularin, globularicisin, globularidin, globularinin and globularimin. This is the first report of a chlorinated iridoid in G. alypum and in the Globulareaceae. Unlike all other known 7-chlorinated iridoid glucosides where the chlorine atom exhibits an alpha configuration, globularioside incorporate the chlorine atom as a 7beta substituent. The structures of the isolated compounds were established on the basis of ESI-MS, MS-MS, 1D and 2D NMR spectral analysis.

Kinetic modelling of chlorination of nitrided ilmenite using MATLAB

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

Ramakrishnan, Sivakumar, E-mail: srsivakumar@usm.my; Kwok, Teong Chen, E-mail: ctck@live.com; Hamid, Sheikh Abdul Rezan Sheikh Abdul, E-mail: rezanshk@gmail.com

In the present study, chlorination of nitride ilmenite using 2{sup k} factorial design was investigated. The reduction experiments were carried out in a temperature range of 400°C to 500°C, chlorination duration from 1 hour to 3 hours and using different type of carbon reactant. Phases of raw materials and reduced samples were analyzed by X-ray diffraction (XRD). Ilmenite was reduced to TiO{sub x}C{sub y}N{sub z} through carbothermal and nitridation for further chlorination into titanium tetrachloride. The Design of Experiment analysis suggested that the types of carbon reactant contribute most influence to the extent of chlorination of nitride ilmenite. The extentmore » of chlorination was highest at 500°C with 3 hours chlorination time and carbon nanotube as carbon reactant.« less

Thermodynamic analysis of the selective chlorination of electric arc furnace dust.

PubMed

Pickles, C A

2009-07-30

The remelting of automobile scrap in an electric arc furnace (EAF) results in the production of a dust, which contains high concentrations of the oxides of zinc, iron, calcium and other metals. Typically, the lead and zinc are of commercial value, while the other metals are not worth recovering. At the present time, EAF dusts are treated in high temperature Waelz rotary kiln-type processes, where the lead and zinc oxides are selectively reduced and simultaneously reoxidized and a crude zinc oxide is produced. Another alternative processing route is selective chlorination, in which the non-ferrous metals are preferentially chlorinated to their gaseous chlorides and in this manner separated from the iron. In the present research, a detailed thermodynamic analysis of this chlorination process has been performed and the following factors were investigated; temperature, amount of chlorine, lime content, silica content, presence of an inert gas and the oxygen potential. High lead and zinc recoveries as gaseous chlorides could be achieved but some of the iron oxide was also chlorinated. Additionally, the calcium oxide in the dust consumes chlorine, but this can be minimized by adding silica, which results in the formation of stable calcium silicates. The optimum conditions were determined for a typical dust composition. The selectivities achieved with chlorination were lower than those for reduction, as reported in the literature, but there are other advantages such as the potential recovery of copper.

Impact of vegetation and ecosystems on chlorine(-36) cycling and its modeling: from simplified approaches towards more complex biogeochemical tools

NASA Astrophysics Data System (ADS)

Thiry, Yves; Redon, Paul-Olivier; Gustafsson, Malin; Marang, Laura; Bastviken, David

2013-04-01

Chlorine is very soluble at a global scale with chloride (Cl-), the dominating form. Because of its high mobility, chlorine is usually perceived as a good conservative tracer in hydrological studies and by analogy as little reactive in biosphere. Since 36Cl can be considered to have the same behaviour than stable Cl, a good knowledge of chlorine distribution between compartments of terrestrial ecosystems is sufficient to calibrate a specific activity model which supposes rapid dilution of 36Cl within the large pool of stable Cl and isotopic equilibrium between compartments. By assuming 36Cl redistribution similar to that of stable Cl at steady-state, specific activity models are simplified interesting tools for regulatory purposes in environmental safety assessment, especially in case of potential long term chronic contamination of agricultural food chain (IAEA, 2010). In many other more complex scenarios (accidental acute release, intermediate time frame, and contrasted natural ecosystems), new information and tools are necessary for improving (radio-)ecological realism, which entails a non-conservative behavior of chlorine. Indeed observed dynamics of chlorine in terrestrial ecosystems is far from a simple equilibrium notably because of natural processes of organic matter (SOM) chlorination mainly occurring in surface soils (Öberg, 1998) and mediated by microbial activities on a large extent (Bastviken et al. 2007). Our recent studies have strengthened the view that an organic cycle for chlorine should now be recognized, in addition to its inorganic cycle. Major results showed that: organochlorine (Clorg) formation occurs in all type of soils and ecosystems (culture, pasture, forest), leading to an average fraction of the total Cl pool in soil of about 80 % (Redon et al., 2012), chlorination in more organic soils over time leads to a larger Clorg pool and in turn to a possible high internal supply of inorganic chlorine (Clin) upon dechlorination. (Gustafsson et al., 2012), average Cl residence time in forest soils calculated for Clin and Clorg together was 5-fold higher that the residence time estimated for Clin alone (Redon et al., 2011), locally, Cl amount taken up by certain vegetation types can be larger than annual atmospheric deposits, the Cl in excess being recycled mainly by throughfall (Thiry, 2010), root uptake and chlorine transformation rates in soils are essential to calibrate dynamic compartment models since those processes control the persistence of chlorine in the whole system but data are still deficient for different land uses (Van den Hoof & Thiry, 2012). References: Bastviken, D., Thomsen, F., Svensson, T., Karlsson, S., Sandén, P., Shaw, G., Matucha, M., and Öberg, G. (2007). Chloride retention in forest soil by microbial uptake and by natural chlorination of organic matter. Geochim. Cosmochim. Acta, 71: 3182-3192. Gustavsson, M., Karlsson, S.,Öberg, G.,Sandén, P.,Svensson, T.,Valinia, S.,Thiry, Y. and Bastviken, D. (2012). Organic matter chlorination rates in different boreal soils: the role of soil organic matter content. Environmental Science & Technology, 46 (3): 1504-1510 Thiry, Y., 2010. Contribution à l'étude du cycle biogéochimique du chlore en écosystème forestier: cas d'un peuplement de pin sylvestre. Rapport Andra n° ENV.NT.ASTR.10.0068. IAEA (2010). Handbook of parameter values for the prediction of radionuclide transfer to humans in terrestrial and freshwater environments. Technical Report Series n° 472, Vienna, Austria. Öberg, G. (1998). Chloride and organic chlorine in soil. Acta hydrochimica et hydrobiologica, 26 (3): 137-144. Redon, P-O., Abdelouas, A., Bastviken, D., Cecchini, S. Nicolas, M. and Thiry, Y. (2011). Chloride and organic chlorine in forest soils: storage, residence times, and influence of ecological conditions. Environmental Science & Technology, 45: 7202-7208. Redon, P-O., Jolivet, C., Saby, N., Abdelouas, A.and Thiry, Y. (2012). Occurrence of natural organic chlorine in soils for different land uses. Biogeochemistry (In press), doi: 10.1007/s10533-012-9771-7. Van den Hoof, C. and Thiry, Y. (2012). Modelling of the natural chlorine cycling in a coniferous stand: implications for chlorine-36 behaviour in a contaminated forest environment. Journal of Environmental Radioactivity., 107: 56-67.

Chlorine-Resistant Polyamide Reverse Osmosis Membrane with Monitorable and Regenerative Sacrificial Layers.

PubMed

Huang, Hai; Lin, Saisai; Zhang, Lin; Hou, Li'an

2017-03-22

Improving chlorine stability is a high priority for aromatic polyamide (PA) reverse osmosis (RO) membranes especially in long-term desalination. In this Research Article, PA RO membranes of sustainable chlorine resistance was synthesized. Glycylglycine (Gly) was grafted onto the membrane surface as a regenerative chlorine sacrificial layer, and the zeta-potential was used to monitor the membrane performance and to conduct timely regeneration operations for chlorinated Gly. The Gly-grafted PA membrane exhibited ameliorative chlorine resistance in which the N-H moiety of glycylglycine served as sacrificial pendants against chlorine attacks. Cyclic chlorination experiments, combined with FT-IR and XPS analysis, were carried out to characterize the membrane. Results indicated that the resulting N-halamines could be fast regenerated by a simple alkaline reduction step (pH 10). A synchronous relationship between the zeta-potential and the chlorination extent of the sacrificial layer was observed. This indicated that the zeta-potential can be used as an on-site sensor to conduct a timely regeneration operation. The intrinsic mechanism of the surface sacrificial process was also studied.

ENHANCED CONCENTRATION AND ANALYSIS METHOD FOR MEASURING WATER SOLUABLE ENDOGENOUS COMPOUNDS IN HUMAN BREATH

EPA Science Inventory

Exhaled human breath analysis has become a standard technique for assessing exposure to exogenous volatile organic compounds (VOCs) such as trihalomethanes from water chlorination; aromatics, hydrocarbons, and oxygenates from fuels usage; and various chlorinated solvents from i...

Industrial metabolism of chlorine: a case study of a chlor-alkali industrial chain.

PubMed

Han, Feng; Li, Wenfeng; Yu, Fei; Cui, Zhaojie

2014-05-01

Substance flow analysis (SFA) is applied to a case study of chlorine metabolism in a chlor-alkali industrial chain. A chain-level SFA model is constructed, and eight indices are proposed to analyze and evaluate the metabolic status of elemental chlorine. The primary objectives of this study are to identify low-efficiency links in production processes and to find ways to improve the operational performance of the industrial chain. Five-year in-depth data collection and analysis revealed that system production efficiency and source efficiency continued increasing since 2008, i.e., when the chain was first formed, at average annual growth rates of 21.01 % and 1.01 %, respectively. In 2011, 64.15 % of the total chlorine input was transformed into final products. That is, as high as 98.50 % of the chlorine inputs were utilized when other by-products were counted. Chlorine loss occurred mostly in the form of chloride ions in wastewater, and the system loss rate was 0.54 %. The metabolic efficiency of chlorine in this case was high, and the chain system had minimal impact on the environment. However, from the perspectives of processing depth and economic output, the case study of a chlor-alkali industrial chain still requires expansion.

Metagenomic insights into chlorination effects on microbial antibiotic resistance in drinking water.

PubMed

Shi, Peng; Jia, Shuyu; Zhang, Xu-Xiang; Zhang, Tong; Cheng, Shupei; Li, Aimin

2013-01-01

This study aimed to investigate the chlorination effects on microbial antibiotic resistance in a drinking water treatment plant. Biochemical identification, 16S rRNA gene cloning and metagenomic analysis consistently indicated that Proteobacteria were the main antibiotic resistant bacteria (ARB) dominating in the drinking water and chlorine disinfection greatly affected microbial community structure. After chlorination, higher proportion of the surviving bacteria was resistant to chloramphenicol, trimethoprim and cephalothin. Quantitative real-time PCRs revealed that sulI had the highest abundance among the antibiotic resistance genes (ARGs) detected in the drinking water, followed by tetA and tetG. Chlorination caused enrichment of ampC, aphA2, bla(TEM-1), tetA, tetG, ermA and ermB, but sulI was considerably removed (p < 0.05). Metagenomic analysis confirmed that drinking water chlorination could concentrate various ARGs, as well as of plasmids, insertion sequences and integrons involved in horizontal transfer of the ARGs. Water pipeline transportation tended to reduce the abundance of most ARGs, but various ARB and ARGs were still present in the tap water, which deserves more public health concerns. The results highlighted prevalence of ARB and ARGs in chlorinated drinking water and this study might be technologically useful for detecting the ARGs in water environments. Copyright © 2012 Elsevier Ltd. All rights reserved.

δ37Cl of Mid-Ocean Ridge Vent Fluids Determined by a new SIMS Method for Stable Chlorine Isotope Ratio Measurements

NASA Astrophysics Data System (ADS)

Bach, W.; Layne, G. L.; von Damm, K. L.

2002-12-01

A method has been developed for the direct determination of δ37Cl in natural fluid samples or rock leachates (pyrohydrolysis products) using Secondary Ion Mass Spectrometry (SIMS). Samples as small as 1 μl (<2 μg Cl) are simply dried by evaporation and the residual salts are then admixed with 1 mg of graphite powder and pressed into a small (1mm diameter) pellet amenable to SIMS analysis. Analyses are performed with a large format high-transmission, high-resolution ion microprobe -- the IMS 1270. Mass resolving powers of greater than 5000 are used to exclude isobaric interferences on 35Cl and 37Cl, producing an accurate and reproducible measurement of δ37Cl. Nine analyses of NIST Cl isotope standard 975a yield an external reproducibility of 0.5 ‰ (2σ ). Repeat analyses of samples are reproducible within 1 ‰ . First δ37Cl data for mid-ocean ridge hydrothermal vent fluids from three sites at EPR 9°N and the Logatchev site (MAR 15°N) have been collected. End member δ37Cl compositions for the EPR fluids are between +6.5 and +7.1 ‰ , whereas that of the Logatchev fluid is +4.6 ‰ . Together with pore waters from accretionary prisms, which are depleted in 37Cl (-2.0 to -7.7 ‰ ; Ransom et al., Geology, 23, 715-718, 1995), seawater-derived fluids in the marine environment span range in δ37Cl of 15 ‰ . This variability is remarkably large when compared to >100 analyses of continental waters (formation and oil-field waters, fresh waters, brines, etc.) that cluster around 0 ‰ with a maximum variation of only 5 ‰ . Two observations suggest that the 37Cl enriched nature of the vent fluids is not related to phase separation. (1) Laboratory experiments indicate that the Δ37Cl(vapor-brine) associated with super-critical phase separation of seawater between 420 and 450°C is small (-0.6 to 0.2 ‰ ; Magenheim, PhD Thesis, UCSD, 1995). (2) Conjugate vapor-brine pairs of boiling sampled in 1991 and 1994 at F vent (Von Damm et al. EPSL, 149, 101-111, 1997) have basically identical δ37Cl values indicating that phase separation (sub- or super-critical) does not significantly fractionate chlorine isotopes. We suggest, therefore, that the heavy Cl isotope signature of the fluids is a result of seawater-rock interaction and/or mineral precipitation rather than phase separation of seawater. However, the specific mechanisms responsible for this enrichment are not yet understood. The Cl isotope signatures of hydrothermally altered gabbros and sheeted dike rocks (δ37Cl: 0.4-3.4 ‰ ) tend to be heavier than seawater and it has been suggested that this indicates preferential uptake of 37Cl by amphibole (Magenheim et al., EPSL 131, 427-432, 1995). Amphibolitization can therefore not account for the development of the 37Cl enrichment of the fluids. Although the exact mechanisms of Cl isotope fractionation are not yet defined, our data suggest that Cl may not be a strictly conservative component in MOR hydrothermal systems.

INTERACTION OF AQUEOUS SOLUTIONS OF CHLORINE WITH MALIC ACID, TARTARIC ACID, AND VARIOUS FRUIT JUICES, A SOURCE OF MUTAGENS

EPA Science Inventory

The interactions of aqueous solutions of chlorine with some fruit acids (citric acid, DL-malic acid, and L-tartaric acid) at different pH values were studied. iethyl ether extraction followed by GC/MS analysis indicated that a number of mutagens (certain chlorinated propanones an...

Solar neutrino production of technetium-97 and technetium-98.

PubMed

Cowan, G A; Haxton, W C

1982-04-02

It may be possible to determine the boron-8 solar neutrino flux, averaged over the past several million years, from the concentration of technetium-98 in molybdenite. The mass spectrometry of this system is greatly simplified by the absence of stable technetium isotopes, and the presence of the fission product technetium-99 provides a monitor of uiranium-induced backgrounds. This geochemical experiment could provide the first test of nonstandard solar models that suggest a relation between the chlorine-37 solar neutrino puzzle and the recent ice age.

METHOD OF OPERATING A CALUTRON

DOEpatents

Davidson, P.H.

1960-01-12

A method of operating an electromagnetic isotope separator of the calutron class is reported whereby uranium tetrachloride is produced at a controlled rate within the source rather than betng introduced therein as was formerly practiced. This is accomplished by placing a uranium-bearing material, such as uranium metal, uranium trichloride, or uranium carbide in the charge receptacle of the calutron, heating this material to about to produce uranium tetrachloride vapor at a rate controlled by the chlorine gas flow into the source. The vapor is subsequently ionized by an electric arc and mass separated by conventional calutron methods.

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/H 2 O 2 /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. Copyright © 2016 Elsevier B.V. All rights reserved.

Short-term organic carbon migration from polymeric materials in contact with chlorinated drinking water.

PubMed

Mao, Guannan; Wang, Yingying; Hammes, Frederik

2018-02-01

Polymeric materials are widely used in drinking water distribution systems. These materials could release organic carbon that supports bacterial growth. To date, the available migration assays for polymeric materials have not included the potential influence of chlorination on organic carbon migration behavior. Hence, we established a migration and growth potential protocol specifically for analysis of carbon migration from materials in contact with chlorinated drinking water. Four different materials were tested, including ethylene propylene dienemethylene (EPDM), poly-ethylene (PEX b and PEX c) and poly-butylene (PB). Chlorine consumption rates decreased gradually over time for EPDM, PEXc and PB. In contrast, no free chlorine was detected for PEXb at any time during the 7 migration cycles. Total organic carbon (TOC) and assimilable organic carbon (AOC) was evaluated in both chlorinated and non-chlorinated migrations. TOC concentrations for EPDM and PEXb in chlorinated migrations were significantly higher than non-chlorinated migrations. The AOC results showed pronounced differences among tested materials. AOC concentrations from chlorinated migration waters of EPDM and PB were higher compared to non-chlorinated migrations, whereas the opposite trend was observed for PEXb and PEXc. There was also a considerable difference between tested materials with regards to bacterial growth potential. The results revealed that the materials exposed to chlorine-influenced migration still exhibited a strong biofilm formation potential. The overall results suggested that the choice in material would make a considerable difference in chlorine consumption and carbon migration behavior in drinking water distribution systems. Copyright © 2017 Elsevier B.V. All rights reserved.

ENHANCED RETENTION AND SENSITIVITY IN THE ANALYSIS OF CYANURIC ACID IN WATER USING POROUS GRAPHITIC CARBON AND UV DETECTION IN HIGH PRESSURE LIQUID CHROMATOGRAPHY

EPA Science Inventory

Cyanuric acid (CA) has found application as a chlorine stabilizer in pool waters. The National Swimming Pool Foundation recommends CA levels between 30-50 ppm and a chlorine residual of 1.0-3.0 ppm. These chlorine levels are needed to destroy harmful pathogenic organisms. Develo...

Behavior of Al2O3 and SiO2 with heating in a Cl2 + CO stream

NASA Technical Reports Server (NTRS)

Shchetinin, L. K.

1984-01-01

Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA) were used to study the chlorination of alpha-Al2O3, gamma-Al2O3 and amorphous SiO2 in a Cl + CO stream, for the preparation of AlCl3 and SiCl4. The chlorination starting temperatures were 235 deg for Al2O3 and 680 deg for SiO2. The chlorination of alpha- and gamma-Al2O3 takes place via the formation of AlOCl as an intermediate product, and its subsequent dissociation at 480 to 560 deg, according to 3AlOCl yields AlCl3 + Al2O3. The chlorination activation energies are given for the three oxides.

Selective recovery of uranium from Ca-Mg uranates by chlorination

NASA Astrophysics Data System (ADS)

Pomiro, Federico J.; Gaviría, Juan P.; Quinteros, Raúl D.; Bohé, Ana E.

2017-07-01

A chlorination process is proposed for the uranium extraction and separation using Calciumsbnd Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO4) as reaction product. The formation of U3O8 and MgU3O10 was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h-1 of chlorine and 10 hs of reaction at 700 °C being U3O8 the single uranium product obtained.

Monitoring Natural Biodegradation of TCE in Fractured Sedimentary Rocks Using delta 13C of TCE and its Degradation Products: Estimating Isotopic Fractionation Factor under Field Conditions

NASA Astrophysics Data System (ADS)

Revesz, K.; Shapiro, A. M.; Tiedeman, C.; Goode, D. J.; Lacombe, P. J.; Imbrigiotta, T. E.

2008-12-01

The isotopic ratio of 13C/12C, expressed in delta13CVPDB per mill for trichloroethene (TCE), can differentiate between microbial degradation and other processes (dilution, dispersion, and sorption) that can also affect the concentration of TCE and its degradation products. The delta13C of TCE isotopically fractionates during microbial degradation; however, it remains practically unchanged during other processes. The isotope fractionation factor (alpha) estimated under laboratory conditions, however, may not be representative of microbial degradation in natural ground waters. Estimating alpha under field conditions provides evidence of the presence or absence of in situ microbial degradation and provides valuable information on the in situ processes that affect the fate and transport of chlorinated hydrocarbons. Our modified analytical method of analyzing for the isotopic ratio proved to be comparable to previously published methods. Isotope values were stable within analytical uncertainty in sample sizes ranging from 22 to 2200 nanomoles. Prepared standard mixtures of TCE and DCEs (trans- and cis- dichloroethene) were analyzed after every five field samples, and were stable during the time period that field samples were processed (a year). Water samples were collected from multiple boreholes completed in the fractured mudstone underlying the former Naval Air Warfare Center, West Trenton, NJ, and analyzed for delta13C of the chlorinated hydrocarbons. The results showed an ongoing natural microbial degradation following the typical dehalogenation pathway: TCE to DCE (trans- and cis-dichloroethene) to VC (vinyl chloride). The carbon isotope enrichment due to fractionation was smaller between TCE to DCE degradation than the enrichment between DCE to VC degradation, which is consistent with previous investigations. Results also showed a correlation between delta13C of TCE and the transmissivity of the boreholes where water samples were collected. We assumed that boreholes with extremely low transmissivity behaved analogously to microbial batch reactors. The value of alpha obtained from the borehole interval with the lowest transmissivity was 0.99345, which is in the range of published values: 0.9862 to 0.9934. We consider this value to represent the "field alpha" for microbial degradation in the absence of other processes. Values of alpha in other boreholes that differ from the field alpha could point to other processes affecting the delta13C and concentration of TCE. The value of alpha from the various monitored intervals is referred to as the "apparent alpha". The apparent alpha is characteristic of the borehole and the time at which the concentrations and the isotope values were measured. The difference between the apparent alpha and the field alpha provides insight into hydrologic conditions around the well. Results from one well showed fluctuation in the TCE concentrations, which were correlated with the calculated apparent alpha, and pointed to the recent introduction of TCE into the ground water that had not been significantly degraded. Recent drilling in the vicinity of this well may have remobilized free-phase TCE.

Atmospheric Production of Perchlorate on Earth and Mars

NASA Astrophysics Data System (ADS)

Claire, M.; Catling, D. C.; Zahnle, K. J.

2009-12-01

Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

Total synthesis of isotopically enriched Si-29 silica NPs as potential spikes for isotope dilution quantification of natural silica NPs.

PubMed

Pálmai, Marcell; Szalay, Roland; Bartczak, Dorota; Varga, Zoltán; Nagy, Lívia Naszályi; Gollwitzer, Christian; Krumrey, Michael; Goenaga-Infante, Heidi

2015-05-01

A new method was developed for the preparation of highly monodisperse isotopically enriched Si-29 silica nanoparticles ((29)Si-silica NPs) with the purpose of using them as spikes for isotope dilution mass spectrometry (IDMS) quantification of silica NPs with natural isotopic distribution. Si-29 tetraethyl orthosilicate ((29)Si-TEOS), the silica precursor was prepared in two steps starting from elementary silicon-29 pellets. In the first step Si-29 silicon tetrachloride ((29)SiCl4) was prepared by heating elementary silicon-29 in chlorine gas stream. By using a multistep cooling system and the dilution of the volatile and moisture-sensitive (29)SiCl4 in carbon tetrachloride as inert medium we managed to reduce product loss caused by evaporation. (29)Si-TEOS was obtained by treating (29)SiCl4 with absolute ethanol. Structural characterisation of (29)Si-TEOS was performed by using (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopy and Fourier-transform infrared (FTIR) spectroscopy. For the NP preparation, a basic amino acid catalysis route was used and the resulting NPs were analysed using transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential measurements. Finally, the feasibility of using enriched NPs for on-line field-flow fractionation coupled with multi-angle light scattering and inductively coupled plasma mass spectrometry (FFF/MALS/ICP-MS) has been demonstrated. Copyright © 2015 Elsevier Inc. All rights reserved.

Degradation of chloramphenicol by UV/chlorine treatment: Kinetics, mechanism and enhanced formation of halonitromethanes.

PubMed

Dong, Huiyu; Qiang, Zhimin; Hu, Jun; Qu, Jiuhui

2017-09-15

Ultraviolet (UV)/chlorine process is considered as an emerging advanced oxidation process for the degradation of micropollutants. This study investigated the degradation of chloramphenicol (CAP) and formation of disinfection by-products (DBPs) during the UV/chlorine treatment. It was found that CAP degradation was enhanced by combined UV/chlorine treatment compared to that of UV and chlorination treatment alone. The pseudo-first-order rate constant of the UV/chlorine process at pH 7.0 reached 0.016 s -1 , which was 10.0 and 2.0 folds that observed from UV and chlorination alone, respectively. The enhancement can be attributed to the formation of diverse radicals (HO and reactive chlorine species (RCSs)), and the contribution of RCSs maintained more stable than that of HO at pH 5.5-8.5. Meanwhile, enhanced DBPs formation during the UV/chlorine treatment was observed. Both the simultaneous formation and 24-h halonitromethanes formation potential (HNMsFP) were positively correlated with the UV/chlorine treatment time. Although the simultaneous trichloronitromethane (TCNM) formation decreased with the prolonged UV irradiation, TCNM dominated the formation of HNMs after 24 h (>97.0%). According to structural analysis of transformation by-products, both the accelerated CAP degradation and enhanced HNMs formation steps were proposed. Overall, the formation of diverse radicals during the UV/chlorine treatment accelerated the degradation of CAP, while also enhanced the formation of DBPs simultaneously, indicating the need for DBPs evaluation before the application of combined UV/chlorine process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chlorine levels and species in fine and size resolved atmospheric particles by X-ray absorption near-edge structure spectroscopy analysis in Beijing, China.

PubMed

Ouyang, Jie; Yang, Guo-Sheng; Ma, Ling-Ling; Luo, Min; Zheng, Lei; Huo, Qing; Zhao, Yi-Dong; Hu, Tian-Dou; Cai, Zhen-Feng; Xu, Dian-Dou

2018-04-01

An understanding of the species of chlorine is crucial in the metropolis-Beijing, which is suffering serious haze pollution with high frequency. Particulate Matters (PMs) with five different sizes were collected in Beijing from July 2009 to March 2016, and characterized non-destructively by X-ray absorption near edge structure spectroscopy. PM <0.2 , PM 0.2-0.5 and PM >2.5 contributed for the major PMs mass in spring and summer, PM 0.5-1.0 and PM 1.0-2.5 contributed for the major PMs mass in autumn and winter. The concentrations of the three chlorine species were in the order of inorganic chlorine (Cl inorg ) > aliphatic chlorine (Cl ali ) > aromatic chlorine (Cl aro ), indicating that Cl inorg constituted the primary chlorine fraction and less toxic Cl ali constituted the primary total organic chlorine (Cl ali  + Cl aro , abbreviated as Cl org ) in the PMs in Beijing. In addition, these three chlorine species exhibited identical seasonal variation in PM 2.5 : winter > autumn > spring > summer. Wet precipitation is an important factor to result in the lower mass concentrations of these three chlorine species in summer. The temporal variations of both size resolved PM mass concentrations and chlorine species concentrations suggested that the air pollution prevention and control in Beijing has just won initial success. Copyright © 2017 Elsevier Ltd. All rights reserved.

Environmental legacy of an underground gas well blowout: long-term effects of gas and brine leakage on groundwater quality

NASA Astrophysics Data System (ADS)

Schout, Gilian; Hartog, Niels; Majid Hassanizadeh, S.; Griffioen, Jasper

2017-04-01

In 1965, a catastrophic underground blowout occurred during the drilling of a gas well in the village of Sleen, the Netherlands. The blowout led to the uncontrolled release of large amounts of natural gas and saline groundwater. Now, 50 years later, a number of nearby groundwater monitoring have been sampled to study the long term effects of this event on the groundwater composition of the overlying freshwater aquifers. The findings are used as an analogue for studying the potential adverse effects of hydraulic fracturing on groundwater quality. In total, 27 samples were taken and analysed for dissolved gas molecular and isotopic composition, major ion chemistry, water isotopes and stable chlorine isotope ratios. The resulting data show that concentrations of dissolved methane are still strongly elevated compared to background samples in a plume downstream of the blowout location. Isotopic data reveals the thermogenic nature of this plume; all samples with methane concentrations greater than 10 mg/l (n=12) had δC-CH4 values greater than -30‰ (VPDB), characteristic of thermogenic methane. The maximum distance at which thermogenic methane is observed is at approximately 500 meter downstream of the centre of the blowout. The progressive enrichment of both δ13C-CH4 and δ2D-CH4, that is observed with distance from the well and decreasing methane concentrations, presents strong evidence for the role of anaerobic methane oxidation (AOM) in limiting the spread of the dissolved methane plume. Low sulphate and increased Fe(II) and Mn(II) concentrations indeed suggest that multiple AOM pathways are involved in the natural attenuation of the dissolved methane plume. Chlorine concentrations were only elevated in a subset of wells in close proximity to the blowout location, indicating that the present-day effects of brine migration are minimal. Nevertheless, elevated Na/Cl ratio's in multiple wells reveal that freshening of the aquifer is still on-going. In summary, this research sheds new light on the long-term effects of natural gas and brine leakage on groundwater quality, which is considered one of the main environmental hazards related to hydraulic fracturing and unconventional gas production in general. Notably, it shows that the anaerobic oxidation of methane may play a major role in containing the effects of uncontrolled gas migration from reservoirs to shallow aquifers.

Atomically precise edge chlorination of nanographenes and its application in graphene nanoribbons

PubMed Central

Tan, Yuan-Zhi; Yang, Bo; Parvez, Khaled; Narita, Akimitsu; Osella, Silvio; Beljonne, David; Feng, Xinliang; Müllen, Klaus

2013-01-01

Chemical functionalization is one of the most powerful and widely used strategies to control the properties of nanomaterials, particularly in the field of graphene. However, the ill-defined structure of the present functionalized graphene inhibits atomically precise structural characterization and structure-correlated property modulation. Here we present a general edge chlorination protocol for atomically precise functionalization of nanographenes at different scales from 1.2 to 3.4 nm and its application in graphene nanoribbons. The well-defined edge chlorination is unambiguously confirmed by X-ray single-crystal analysis, which also discloses the characteristic non-planar molecular shape and detailed bond lengths of chlorinated nanographenes. Chlorinated nanographenes and graphene nanoribbons manifest enhanced solution processability associated with decreases in the optical band gap and frontier molecular orbital energy levels, exemplifying the structure-correlated property modulation by precise edge chlorination. PMID:24212200

Two-dimensional fuzzy fault tree analysis for chlorine release from a chlor-alkali industry using expert elicitation.

PubMed

Renjith, V R; Madhu, G; Nayagam, V Lakshmana Gomathi; Bhasi, A B

2010-11-15

The hazards associated with major accident hazard (MAH) industries are fire, explosion and toxic gas releases. Of these, toxic gas release is the worst as it has the potential to cause extensive fatalities. Qualitative and quantitative hazard analyses are essential for the identification and quantification of these hazards related to chemical industries. Fault tree analysis (FTA) is an established technique in hazard identification. This technique has the advantage of being both qualitative and quantitative, if the probabilities and frequencies of the basic events are known. This paper outlines the estimation of the probability of release of chlorine from storage and filling facility of chlor-alkali industry using FTA. An attempt has also been made to arrive at the probability of chlorine release using expert elicitation and proven fuzzy logic technique for Indian conditions. Sensitivity analysis has been done to evaluate the percentage contribution of each basic event that could lead to chlorine release. Two-dimensional fuzzy fault tree analysis (TDFFTA) has been proposed for balancing the hesitation factor involved in expert elicitation. Copyright © 2010 Elsevier B.V. All rights reserved.

A temperature-programmed X-ray photoelectron spectroscopy (TPXPS) study of chlorine adsorption and diffusion on Ag(1 1 1)

NASA Astrophysics Data System (ADS)

Piao, H.; Adib, K.; Barteau, Mark A.

2004-05-01

Synchrotron-based temperature programmed X-ray photoelectron spectroscopy (TPXPS) has been used to investigate the surface chloridation of Ag(1 1 1) to monolayer coverages. At 100 K both atomic and molecular chlorine species are present on the surface; adsorption at 300 K or annealing the adlayer at 100 K to this temperature generates adsorbed Cl atoms. As the surface is heated from 300 to 600 K, chlorine atoms diffuse below the surface, as demonstrated by attenuation of the Cl2p signals in TPXPS experiments. Quantitative analysis of the extent of attenuation is consistent with chlorine diffusion below the topmost silver layer. For coverages in the monolayer and sub-monolayer regime, chlorine diffusion to and from the bulk appears not to be significant, in contrast to previous results obtained at higher chlorine loadings. Chlorine is removed from the surface at 650-780 K by desorption as AgCl. These results demonstrate that chlorine diffusion beneath the surface does occur at coverages and temperatures relevant to olefin epoxidation processes carried out on silver catalysts with chlorine promoters. The surface sensitivity advantages of synchrotron-based XPS experiments were critical to observing Cl diffusion to the sub-surface at low coverages.

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.

Application of direct thermometric analysis in iodometry.

PubMed

Marik-Korda, P; Erdey, L

1970-12-01

Elementary chlorine was determined by a thermometric method using potassium iodide as reagent. The temperature rise corresponding to the heat of reaction was proportional to the chlorine content. Iodine formed in the reaction was also determined with sodium thiosulphate. The heat of the chlorine-iodide reaction is about five times that of the iodine-thiosulphate reaction. Direct determination with potassium iodide is simpler and more rapid than the indirect one.

Analysis of iodinated haloacetic acids in drinking water by reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry with large volume direct aqueous injection.

PubMed

Li, Yongtao; Whitaker, Joshua S; McCarty, Christina L

2012-07-06

A large volume direct aqueous injection method was developed for the analysis of iodinated haloacetic acids in drinking water by using reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry in the negative ion mode. Both the external and internal standard calibration methods were studied for the analysis of monoiodoacetic acid, chloroiodoacetic acid, bromoiodoacetic acid, and diiodoacetic acid in drinking water. The use of a divert valve technique for the mobile phase solvent delay, along with isotopically labeled analogs used as internal standards, effectively reduced and compensated for the ionization suppression typically caused by coexisting common inorganic anions. Under the optimized method conditions, the mean absolute and relative recoveries resulting from the replicate fortified deionized water and chlorinated drinking water analyses were 83-107% with a relative standard deviation of 0.7-11.7% and 84-111% with a relative standard deviation of 0.8-12.1%, respectively. The method detection limits resulting from the external and internal standard calibrations, based on seven fortified deionized water replicates, were 0.7-2.3 ng/L and 0.5-1.9 ng/L, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Analysis of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues in chlorine-treated water by gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS).

PubMed

Planas, Carles; Ventura, Francesc; Caixach, Josep; Martín, Jordi; Boleda, M Rosa; Paraira, Miquel

2015-11-01

A simple, selective and sensitive method for the analysis of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues (BMXs) in chlorine-treated water has been developed. The method is based on gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS), previous liquid-liquid extraction (LLE) of a smaller sample volume compared to other methods and on-line derivatization with a silylation reactive. GC-QqQ-MS/MS has been raised as an alternative easier to perform than gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) for the analysis of MX and BMXs, and it allows to achieve low LODs (0.3 ng/L for MX and 0.4-0.9 ng/L for BMXs). This technique had not been previously described for the analysis of MX and BMXs. Quality parameters were calculated and real samples related to 3 drinking water treatment plants (DWTPs), tap water and both untreated and chlorinated groundwater were analyzed. Concentrations of 0.3-6.6 ng/L for MX and 1.0-7.3 ng/L for BMXs were detected. Results were discussed according to five of the main factors affecting MX and BMXs formation in chlorine-treated water (organic precursors, influence of bromide ions, evolution of MX and BMXs in the drinking water distribution system, groundwater chlorination and infiltration of water coming from chlorination processes in groundwater). Copyright © 2015 Elsevier B.V. All rights reserved.

How unique is the Udachnaya-East kimberlite? Comparison with kimberlites from the Slave Craton (Canada) and SW Greenland

NASA Astrophysics Data System (ADS)

Kamenetsky, Vadim S.; Kamenetsky, Maya B.; Weiss, Yakov; Navon, Oded; Nielsen, Troels F. D.; Mernagh, Terrence P.

2009-11-01

The origin of alkali carbonates and chlorides in the groundmass of unaltered Udachnaya-East kimberlites in Siberia is still controversial. Contrary to existing dogma that the Udachnaya-East kimberlite was either contaminated by the crustal sediments or platform brines, magmatic origin of the groundmass assemblage has been proposed on the basis of melt immiscibility textures, melt inclusion studies, and strontium and neon isotope compositions. We further tested the idea of alkali- and chlorine enrichment of the kimberlite parental melt by studying olivine-hosted melt inclusions and secondary serpentine in kimberlites from the Slave Craton, Canada (Gahcho Kué, Jericho, Aaron and Leslie pipes) and southern West Greenland (Majuagaa dyke). Host olivine phenocrysts closely resemble groundmass olivine from the Udachnaya-East kimberlite in morphology, compositions (high-Fo, low-Ca), complex zoning with cores of varying shapes and compositions and rims of constant Fo. Melt inclusions in olivine consist of several translucent and opaque daughter phases and vapour bubble(s). The daughter crystals studied in unexposed inclusions by laser Raman spectroscopy and in carefully exposed inclusions by WDS-EDS are represented by Na-K chlorides, calcite, dolomite, magnesite, Ca-Na, Ca-Na-K and Ca-Mg-Ba carbonates, bradleyite Na 3 Mg(CO 3)(PO 4), K-bearing nahpoite Na 2(HPO 4), apatite, phlogopite and tetraferriphlogopite, unidentified sulphates, Fe sulphides, djerfisherite, pyrochlore (Na,Ca) 2Nb 2O 6(OH,F), monticellite, Cr-spinel and Fe-Ti oxides. High abundances of Na, K (e.g., (Na + K)/Ca = 0.15-0.85) and incompatible trace elements in the melt inclusions are confirmed by LA-ICPMS analysis of individual inclusions. Heating experiments show that melting of daughter minerals starts and completes at low temperatures (~ 100 °C and 600 °C, respectively), further reinforcing the similarity with the Udachnaya-East kimberlite. Serpentine minerals replacing olivine in some of the studied kimberlites demonstrate elevated abundances of chlorine (up to 3-4 wt.%), especially in the early generation. Despite heterogeneous distribution of chlorine such abundances are significantly higher than in the serpentine in abyssal and ophiolitic peridotites (< 0.5 wt.%). The groundmass of most kimberlites, including those studied here and altered kimberlites from the Udachnaya pipe, contain no alkali carbonates and chlorides and have low Na 2O (< 0.2 wt.%). We believe that alteration disturbs original melt compositions, with the alkaline elements and chlorine being mostly affected. However, the compositions of melt inclusions and serpentine are indicative of the chemical signature of a parental kimberlite melt. It appears that enrichment in alkalies and chlorine, as seen in unaltered Udachnaya-East kimberlites, is shared by other kimberlites, and thus can be assigned to deep mantle origin.

Characteristics of salt taste and free chlorine or chloramine in drinking water.

PubMed

Wiesenthal, K E; McGuire, M J; Suffet, I H

2007-01-01

Salty taste with or without chlorine or chloramine flavour is one of the major consumer complaints to water utilities. The flavour profile analysis (FPA) taste panel method determined the average taste threshold concentration for salt (NaCl) in Milli-Q water to be 640 +/- 3 mg/L at pH 8. Chlorine and chloramine disinfectants have no antagonistic or synergistic effects on the taste of NaCl, salt, in Milli-Q water. The flavour threshold concentrations for chlorine or chloramine in Milli-Q water alone or in the presence of NaCl could not be estimated by the Weber-Fechner curves due to the chlorine or chloramine flavour outliers in the 0.2-0.8 mg/L concentration range. Apparently, NaCl is not equilibrated with the concentration of ions in the saliva in the mouth and the concentration of free chlorine or chloramines cannot be tasted correctly. Therefore, dechlorinated tap water may be the best background water to use for a particular drinking water evaluation of chlorine and chloramine thresholds. Laboratory FPA studies of free chlorine found that a 67% dilution of Central Arizona Project (CAP) (Tucson, AZ) water with Milli-O water was required to reduce the free chlorine flavour to a threshold value instead of a theoretical value of 80% (Krasner and Barrett, 1980). No synergistic effect was found for chlorine flavour on the dilution of CAP water with Milli-Q water. When Central Avra Valley (AVRA) groundwater was used for the dilution of CAP water, a synergistic effect of the TDS present was observed for the chlorine flavour. Apparently, the actual mineral content of drinking water, and not just NaCl in Milli-Q water, is needed for comparative flavour tests for chlorine and chloramines.

Shifts of live bacterial community in secondary effluent by chlorine disinfection revealed by Miseq high-throughput sequencing combined with propidium monoazide treatment.

PubMed

Pang, Yu-Chen; Xi, Jin-Ying; Xu, Yang; Huo, Zheng-Yang; Hu, Hong-Ying

2016-07-01

Chlorine disinfection is a commonly used disinfection process in wastewater treatment, but its effects on the indigenous bacterial community in treated wastewater have not been fully elucidated. In this study, secondary effluent samples collected in four wastewater treatment plants (WWTPs) were selected for chlorine disinfection. Shifts in the bacterial community compositions in secondary effluent samples upon chlorine disinfection, both immediately and after 24 h of storage, were investigated using Illumina MiSeq sequencing combined with propidium monoazide (PMA) treatment. The results showed that the phylum Proteobacteria was sensitive to chlorine, with the relative proportions of Proteobacteria decreased from 39.2 to 75.9 % in secondary effluent samples to 7.5 to 62.2 % immediately after chlorine disinfection. The phylogenetic analysis indicated that the most dominant genera belonging to Proteobacteria were sensitive to chlorine. In contrast, the phyla Firmicutes and Planctomycetes showed a certain resistance to chlorine, with their relative proportions increasing from 5.1 to 23.1 % and 0.8 to 9.3 % to 11.3 to 44.6 % and 1.5 to 13.3 %, respectively. Most dominant genera belonging to Firmicutes showed resistance to chlorine. A significant reduction in the richness and diversity of the bacterial community was observed after 24 h of storage of chlorinated secondary effluent. During the 24-h storage process, the relative proportions of most dominant phyla shifted in reverse from the changes induced by chlorine disinfection. Overall, chlorine disinfection not only changes the bacterial community compositions immediately after the disinfection process but also exerts further impacts over a longer period (24 h).

Phenotypic and genetic diversity of chlorine-resistant Methylobacterium strains isolated from various environments.

PubMed Central

Hiraishi, A; Furuhata, K; Matsumoto, A; Koike, K A; Fukuyama, M; Tabuchi, K

1995-01-01

Strains of pink-pigmented facultative methylotrophs which were isolated previously from various environments and assigned tentatively to the genus Methylobacterium were characterized in comparison with authentic strains of previously known species of this genus. Most of the isolates derived from chlorinated water supplies exhibited resistance to chlorine, whereas 29 to 40% of the isolates from air, natural aquatic environments, and clinical materials were chlorine resistant. None of the tested authentic strains of Methylobacterium species obtained from culture collections exhibited chlorine resistance. Numerical analysis of phenotypic profiles showed that the test organisms tested were separated from each other except M. organophilum and M. rhodesianum. The chlorine-resistant isolates were randomly distributed among all clusters. The 16S ribosomal DNA (rDNA) sequence-based phylogenetic analyses showed that representatives of the isolates together with known Methylobacterium species formed a line of descent distinct from that of members of related genera in the alpha-2 subclass of the Proteobacteria and were divided into three subclusters within the Methylobacterium group. These results demonstrate that there is phenotypic and genetic diversity among chlorine-resistant Methylobacterium strains within the genus. PMID:7793931

Phenotypic and genetic diversity of chlorine-resistant Methylobacterium strains isolated from various environments.

PubMed

Hiraishi, A; Furuhata, K; Matsumoto, A; Koike, K A; Fukuyama, M; Tabuchi, K

1995-06-01

Strains of pink-pigmented facultative methylotrophs which were isolated previously from various environments and assigned tentatively to the genus Methylobacterium were characterized in comparison with authentic strains of previously known species of this genus. Most of the isolates derived from chlorinated water supplies exhibited resistance to chlorine, whereas 29 to 40% of the isolates from air, natural aquatic environments, and clinical materials were chlorine resistant. None of the tested authentic strains of Methylobacterium species obtained from culture collections exhibited chlorine resistance. Numerical analysis of phenotypic profiles showed that the test organisms tested were separated from each other except M. organophilum and M. rhodesianum. The chlorine-resistant isolates were randomly distributed among all clusters. The 16S ribosomal DNA (rDNA) sequence-based phylogenetic analyses showed that representatives of the isolates together with known Methylobacterium species formed a line of descent distinct from that of members of related genera in the alpha-2 subclass of the Proteobacteria and were divided into three subclusters within the Methylobacterium group. These results demonstrate that there is phenotypic and genetic diversity among chlorine-resistant Methylobacterium strains within the genus.

Atomic weights of the elements 1999

USGS Publications Warehouse

Coplen, T.B.

2001-01-01

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: from to nitrogen 14.006 74??0.000 07 14.0067??0.0002 sulfur 32.066??0.006 32.065??0.005 chlorine 35.4527??0.0009 35.453??0.002 germanium 72.61??0.02 72.64??0.01 xenon 131.29??0.02 131.293??0.006 erbium 167.26??0.03 167.259??0.003 uranium 238.0289??0.0001 238.028 91??0.000 03 Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community. ?? 2001 American Institute of Physics.

Chlorine Isotope Evidence for Syn-Subduction Modification of Serpentinites by Interaction with Sediment-Derived Fluid

NASA Astrophysics Data System (ADS)

Selverstone, J.; Sharp, Z. D.

2012-12-01

High-pressure serpentinites and rodingites and high- to ultrahigh-pressure metasedimentary rocks from the Aosta region, Italy, preserve strikingly different chlorine isotope compositions that can be used to constrain the nature of fluid-rock interactions during subduction. Serpentinites and rodingitized gabbroic dikes subducted to 70-80 km have bulk δ37Cl values between -1.6 and +0.9‰ (median= -0.5‰, n=26 plus 5 replicates; one amphibole-vein outlier at -2.9‰). Serpentinite δ37Cl values are positively correlated with Cr ± Cl contents (r2= 0.97 and 0.58) and negatively correlated with CaO (r2=0.72). BSE imaging and X-ray mapping reveal up to three generations of compositionally distinct serpentine and chlorite in single samples. The youngest generation, which is most abundant, has the lowest chlorine content. Three rodingite samples contain abundant texturally early fluid inclusions. These samples were finely crushed and leached in 18 MΩ H2O to extract water-soluble chlorides. The leachates, which are assumed to record the compositions of the fluid inclusions, have δ37Cl values that are 0.7-1.5‰ lower than the corresponding bulk rock values. Leachate from the outlier amph-magnesite vein is indistinguishable from the bulk value at -2.7‰. There is almost no overlap between the Cl isotope compositions of HP serp/rod samples and associated HP/UHP metasedimentary rocks. Calcmica schists, diamond-bearing Mn nodules, and impure marbles subducted to >130 km and calcmica schists and Mn crusts transported to 70-80 km have δ37Cl values between -4.5 and -1.5‰ (median= -2.7‰, n=25 plus 7 replicates; two outlier points at -0.5‰). Primary fluid inclusions in the diamondiferous samples contain carbonate- and silicate-bearing aqueous fluids with very low chloride contents (Frezzotti et al., 2011, Nature Geosci). Taken together, these data record a history of progressive modification of serpentinites and rodingites by mixing with low-δ37Cl, low-Cl, high-Ca fluids during subduction and metamorphism. Serpentinites with the highest Cr contents have Cl isotopic compositions identical to those of modern seafloor serpentinites (δ37Cl=0.2-0.6‰), consistent with primary serpentinization by seawater (e.g., Barnes et al. 2009, Lithos). Low-Cr serpentinites record significant interaction with a Ca-rich fluid that shifted the rocks to lower δ37Cl values and diluted the original Cr and Cl contents. The fluid was likely derived from continuous devolatilization reactions in associated low-δ37Cl, calcareous metasedimentary rocks. These data have important implications for models of subduction mass transfer associated with antigorite breakdown. If serpentinites are commonly modified by interaction with metasedimentary fluids prior to antigorite dehydration, chemical signatures imparted during deserpentinization will reflect the integrated history of fluid-rock interaction in the subduction channel rather than an endmember "serpentinite signature". The data further suggest that Cl may be hydrophobic in HP/UHP carbonate-bearing aqueous fluids, resulting in generation of low-Cl fluid during metamorphic devolatilization.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2007-08-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2003-09-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Identification of α-Chloro-2,2',4,4',6,6'-Hexanitrobibenzyl as an Impurity in Hexanitrostilbene

NASA Astrophysics Data System (ADS)

Bellamy, A. J.

2010-01-01

The final intermediate in the Shipp synthesis of 2,2‧,4,4‧,6,6‧-hexanitrostilbene (HNS) from TNT, α-chloro-2,2‧,4,4‧,6,6‧-hexanitrobibenzyl, has been extracted and characterized by nuclear magnetic resonance (NMR) spectroscopy, chlorine elemental analysis, and high-performance liquid chromatography (HPLC). It has also been shown that digestion in NMP of HNS containing α-chlorohexanitrobibenzyl generates another chlorine-containing by-product, 2-chloro-2‧,4,4‧,6,6‧-pentanitrostilbene. This too has been characterized by NMR spectroscopy, chlorine elemental analysis, and HPLC.

Perchlorate in the Great Lakes: isotopic composition and origin.

PubMed

Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

2014-10-07

Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.

[Preliminary investigation on emission of PCDD/Fs and DL-PCBs through flue gas from coke plants in China].

PubMed

Sun, Peng-Cheng; Li, Xiao-Lu; Cheng, Gang; Lu, Yong; Wu, Chang-Min; Wu, Chang-Min; Luo, Jin-Hong

2014-07-01

According to the Stockholm Convention, polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) are classified into unintentionally produced persistent organic pollutants (UP-POPs), and named dioxins. Coke production as a thermal process contains organic matters, metal and chlorine, is considered to be a potential source of dioxins. Intensive studies on the emission of dioxins from coking industry are still very scarce. In order to estimate the emission properties of dioxins through coke production, isotope dilution HRGC/HRMS technique was used to determine the concentration of dioxins through flue gas during heating of coal. Three results were obtained. First, total toxic equivalents at each stationary emission source were in the range of 3.9-30.0 pg x m(-3) (at WHO-TEQ) for dioxins which was lower than other thermal processes such as municipal solid waste incineration. Second, higher chlorinated PCDD/Fs were the dominant congeners. Third, emissions of dioxins were dependent on coking pattern. Stamping coking and higher coking chamber may lead to lower emission.

Atmospheric origins of perchlorate on Mars and in the Atacama

NASA Astrophysics Data System (ADS)

Catling, D. C.; Claire, M. W.; Zahnle, K. J.; Quinn, R. C.; Clark, B. C.; Hecht, M. H.; Kounaves, S.

2010-01-01

Isotopic studies indicate that natural perchlorate is produced on Earth in arid environments by the oxidation of chlorine species through pathways involving ozone or its photochemical products. With this analogy, we propose that the arid environment on Mars may have given rise to perchlorate through the action of atmospheric oxidants. A variety of hypothetical pathways can be proposed including photochemical reactions, electrostatic discharge, and gas-solid reactions. Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we made a preliminary study of the means to produce Atacama perchlorate to help shed light on the origin of Martian perchlorate. We investigated gas phase pathways using a 1-D photochemical model. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. The feasibility of gas phase production for the Atacama provides justification for future investigations of gas phase photochemistry as a possible source for Martian perchlorate.

Salinity of the Archaean oceans from analysis of fluid inclusions in quartz

NASA Astrophysics Data System (ADS)

Marty, Bernard; Avice, Guillaume; Bekaert, David V.; Broadley, Michael W.

2018-05-01

Fluids trapped in inclusions in well-characterized Archaean hydrothermal quartz crystals were analyzed by the extended argon-argon method, which permits the simultaneous measurement of chlorine and potassium concentrations. Argon and nitrogen isotopic compositions of the trapped fluids were also determined by static mass spectrometry. Fluids were extracted by stepwise crushing of quartz samples from North Pole (NW Australia) and Barberton (South Africa) 3.5-3.0-Ga-old greenstone belts. The data indicate that fluids are a mixture of a low salinity end-member, regarded as the Archaean oceanic water, and several hydrothermal end-members rich in Cl, K, N, and radiogenic parentless 40Ar. The low Cl-K end-member suggests that the salinity of the Archaean oceans was comparable to the modern one, and that the potassium content of the Archaean oceans was lower than at present by about 40%. A constant salinity of the oceans through time has important implications for the stabilization of the continental crust and for the habitability of the ancient Earth.

The quantification of short-chain chlorinated paraffins in sediment samples using comprehensive two-dimensional gas chromatography with μECD detection.

PubMed

Muscalu, Alina M; Morse, Dave; Reiner, Eric J; Górecki, Tadeusz

2017-03-01

The analysis of persistent organic pollutants in environmental samples is a challenge due to the very large number of compounds with varying chemical and physical properties. Chlorinated paraffins (CPs) are complex mixtures of chlorinated n-alkanes with varying chain lengths (C 10 to C 30 ) and degree of chlorination (30 to 70% by weight). Their physical-chemical properties make these compounds persistent in the environment and able to bioaccumulate in living organisms. Comprehensive two-dimensional gas chromatography (GC × GC) coupled with micro-electron capture detection (μECD) was used to separate and quantify short-chain chlorinated paraffins (SCCP) in sediment samples. Distinct ordered bands were observed in the GC × GC chromatograms pointing to group separation. Using the Classification function of the ChromaTOF software, summary tables were generated to determine total area counts to set up multilevel-calibration curves for different technical mixes. Fortified sediment samples were analyzed by GC × GC-μECD with minimal extraction and cleanup. Recoveries ranged from 120 to 130%. To further validate the proposed method for the analysis of SCCPs, the laboratory participated in interlaboratory studies for the analysis of standards and sediment samples. The results showed recoveries between 75 and 95% and z-score values <2, demonstrating that the method is suitable for the analysis of SCCPs in soil/sediment samples. Graphical abstract Quantification of SCCPs by 2D-GC-μECD.

Functional genomics of chlorine-induced acute lung injury in mice.

PubMed

Leikauf, George D; Pope-Varsalona, Hannah; Concel, Vincent J; Liu, Pengyuan; Bein, Kiflai; Brant, Kelly A; Dopico, Richard A; Di, Y Peter; Jang, An-Soo; Dietsch, Maggie; Medvedovic, Mario; Li, Qian; Vuga, Louis J; Kaminski, Naftali; You, Ming; Prows, Daniel R

2010-07-01

Acute lung injury can be induced indirectly (e.g., sepsis) or directly (e.g., chlorine inhalation). Because treatment is still limited to supportive measures, mortality remains high ( approximately 74,500 deaths/yr). In the past, accidental (railroad derailments) and intentional (Iraq terrorism) chlorine exposures have led to deaths and hospitalizations from acute lung injury. To better understand the molecular events controlling chlorine-induced acute lung injury, we have developed a functional genomics approach using inbred mice strains. Various mouse strains were exposed to chlorine (45 ppm x 24 h) and survival was monitored. The most divergent strains varied by more than threefold in mean survival time, supporting the likelihood of an underlying genetic basis of susceptibility. These divergent strains are excellent models for additional genetic analysis to identify critical candidate genes controlling chlorine-induced acute lung injury. Gene-targeted mice then could be used to test the functional significance of susceptibility candidate genes, which could be valuable in revealing novel insights into the biology of acute lung injury.

Integrated chemical and toxicological investigation of UV-chlorine/chloramine drinking water treatment.

PubMed

Lyon, Bonnie A; Milsk, Rebecca Y; DeAngelo, Anthony B; Simmons, Jane Ellen; Moyer, Mary P; Weinberg, Howard S

2014-06-17

As the use of alternative drinking water treatment increases, it is important to understand potential public health implications associated with these processes. The objective of this study was to evaluate the formation of disinfection byproducts (DBPs) and cytotoxicity of natural organic matter (NOM) concentrates treated with chlorine, chloramine, and medium pressure ultraviolet (UV) irradiation followed by chlorine or chloramine, with and without nitrate or iodide spiking. The use of concentrated NOM conserved volatile DBPs and allowed for direct analysis of the treated water. Treatment with UV prior to chlorine in ambient (unspiked) samples did not affect cytotoxicity as measured using an in vitro normal human colon cell (NCM460) assay, compared to chlorination alone when toxicity is expressed on the basis of dissolved organic carbon (DOC). Nitrate-spiked UV+chlorine treatment produced greater cytotoxicity than nitrate-spiked chlorine alone or ambient UV+chlorine samples, on both a DOC and total organic halogen basis. Samples treated with UV+chloramine were more cytotoxic than those treated with only chloramine using either dose metric. This study demonstrated the combination of cytotoxicity and DBP measurements for process evaluation in drinking water treatment. The results highlight the importance of dose metric when considering the relative toxicity of complex DBP mixtures formed under different disinfection scenarios.

Extraction of titanium from low-iron nitrided Malaysian ilmenite by chlorination

NASA Astrophysics Data System (ADS)

Ibrahim, Najwa; Ahmadi, Eltefat; Rahman, Shaik Abdul; Fauzi, M. N. Ahmad; Rezan, Sheikh Abdul

2017-01-01

In this paper, production of TiCl4 from low-iron nitrided ilmenite samples at relatively low temperature using chlorine gas generated from the reaction between KMnO4 and HCl has been investigated. The effects of chlorination soaking time, potassium permanganate (KMnO4) to hydrochloric acid (HCl) molar ratio and aluminium powder catalyst in chlorine gas generation on titanium extraction from nitrided Malaysian ilmenite were examined. The low-iron nitrided Malaysian ilmenite contained titanium oxycarbonitride (TiOxCyNz) after carbothermal reduction and nitridation with subsequent leaching. Chlorination process was performed at 500°C for 30 - 60 minutes. Statistical analysis of the data was done by Design of Experiment (DOE) to identify the significant variables and their interactions. The results achieved in this study showed that the highest extent of chlorination was about 98.34% at 500°C for 60 minutes. The lowest extent of chlorination was about 68.51% obtained in KMnO4 to HCl molar ratio of 2.0 and 0.35 g of aluminium powder. The chlorinated titanium oxycarbonitride powders and TiCl4 solutions were analyzed by X-ray diffraction (XRD) and inductively coupled plasma-optical emission spectroscopy (ICP-OES), respectively. The purpose of this study was to explore the relationship between the processing parameters on extracting titanium via pyrometallurgical technique.

Effects of Chlorine Promoted Oxidation on Arsenic Release from Sulfide Minerals

NASA Astrophysics Data System (ADS)

West, N.; Schreiber, M.; Gotkowitz, M.

2007-12-01

High arsenic concentrations (>100 ppb) have been measured in wells completed in the Ordovician St. Peter sandstone aquifer of eastern Wisconsin. The primary source of arsenic is As-bearing sulfide minerals within the aquifer. Periodic disinfection of wells by chlorination may facilitate arsenic release to groundwater by increasing the rate of sulfide mineral oxidation. During typical well disinfection procedures, aquifer solids exposed along uncased portions of wells remain in direct contact with chlorine disinfection solutions for up to twenty-four hours. Due to the redox sensitivity of arsenic mobility in groundwater, it is important to evaluate the effect of repeatedly adding oxidizers to an arsenic impacted aquifer system. This study focuses on abiotic processes that mobilize arsenic from the solid phase during controlled exposure to chlorinated solutions. Two St. Peter samples with As concentrations of 21 and 674 ppm were selected for the experiments. Before reaction, the aquifer mineralogy is characterized using scanning electron microscopy (SEM) and electron microprobe analysis (EMPA). The samples are then reacted with solutions of 60 mg/L free chlorine, 1200 mg/L free chlorine, or nanopure water (control) at pH 7.0 and pH 8.5. These parameters represent typical solution chemistries present within the wells after disinfection. Solutions are sampled periodically during the experiments and analyzed for As, Fe, other trace metals such as Co, Mo, Cr, and Ni, and sulfate. Analysis of the post-reaction solids using SEM, EMPA, laser ablation ICP-MS and Raman techniques are used to document the changes in mineralogy due to chlorination and to document which solid phases contain As.

Assessment of chloroethene biodegradation in the subsurface by microbiological, molecular and isotopic tools

NASA Astrophysics Data System (ADS)

Schmidt, K. R.; Kranzioch, I.; Heidinger, M.; Ertl, S.; Tiehm, A.

2012-04-01

A multiple lines of evidence approach to assess the biodegradation potential of contaminated sites includes - site investigation analysing pollutant distribution (compounds, concentrations, isotopic composition) and hydrochemical conditions (redox conditions) - determination of the presence of pollutant degrading bacteria in the field by microbiological (most probable number, MPN) and molecular (polymerase chain reaction, PCR) methods - analysis of degradation processes in the laboratory by microcosms with determination of site specific isotopic enrichment factors enabling the quantification of biodegradation processes in the field. Results will be shown of the application of such a multiple lines of evidence approach at a chloroethene-contaminated site in Frankenthal, Germany. In anaerobic groundwater microcosms, reductive transformation of perchloroethene (PCE) and trichloroethene (TCE) was observed to mainly proceed to cis-1,2-dichloroethene (cDCE). 16S-PCR analysis showed a wide distribution of halorespiring bacteria capable of PCE degradation to cDCE, whereas Dehalococcoides - the only organisms described so far being able of complete reductive dechlorination down to ethene - was only found in one groundwater sample. Aerobic microcosms showed metabolic degradation of the lower chlorinated compounds cDCE and vinyl chloride (VC). Co-metabolic degradation of cDCE with VC as auxiliary substrate occurred, too. Significant stable carbon isotope fractionation was observed during anaerobic degradation of PCE and TCE as well as during aerobic degradation of cDCE and VC. Compiling the results of the different assessment methods, sequential dechlorination - PCE/TCE to cDCE anaerobically and cDCE to CO2 aerobically - was demonstrated to occur at the Frankenthal site. The extent of biodegradation in the field was calculated based on the enrichment factors determined in microcosms and the 13C-isotopic composition of the contaminants on site. The application of molecular methods is continuously increasing. For example, microbiological and molecular tools showed the presence and activity of halorespiring bacteria in sediment samples of the Yangtze river, China. PCR-detection demonstrated the presence of five different halorespiring bacterial groups as well as of four different dechlorinating enzymes of Dehalococcoides. In conclusion, our study demonstrates that (i) multiple lines of evidence approaches result in a profound understanding of the biodegradation processes occurring in the field, (ii) stable isotope fractionation is suitable for assessing and quantifying anaerobic and aerobic chloroethene degradation and (iii) detection and quantification of dechlorinating bacteria and enzymes by PCR methods provide more insight into biodegradation processes. Acknowledgement The authors gratefully acknowledge financial support by the German Ministry of Education and Research (BMBF, grant no 02WN0446, 02WN0447 and 02WT1130), the German Ministry of Economics and Technology (BMWi, grant no KF2265705AK9 and KF2285302AK9) and the federal state of Rhineland-Palatinate. We thank all project partners for fruitful cooperation.

Oxidation of formic acid by oxyanions of chlorine and its implications to the Viking Labeled Release experiment

NASA Astrophysics Data System (ADS)

Martinez, P.; Navarro-gonzalez, R.

2013-05-01

The Viking Landers that arrived on Mars in 1976 carried out three biological experiments designed to investigate if there was microbial life. These were the Gas-Exchange, Pyrolitic Release and Labeled Release experiments. The three experiments yielded positive responses but the Labeled Release experiment had a kinetic response indicative of microbial activity. The experiment consisted of adding a broth of nutrients (formic acid, glycolic acid, glycine, D- and L-alanine and D- and L-lactic acid uniformly marked with 14C) to martian soil samples. The results were surprising; the nutrients were consumed releasing radioactive gases in a manner that is compatible by terrestrial microorganisms. The existence of Martian life was contradicted by soil chemical analysis that indicated the absence of organic compounds above the detection limits of parts per billion (ppb). Instead the positive response of the Labeled Release Experiment was attributed to the existence of peroxides and/or superoxides in the Martian soils that destroyed the nutrients upon contact. Recently, the Phoenix mission that landed in the Martian Arctic in 2008 revealed the presence of a highly oxidized form of the element chlorine in the soil: perchlorate. Perchlorate is thought to have formed in the Martian atmosphere by the oxidation of chloride from volcanic sources with ozone. Therefore perchlorate is formed by the stepwise oxidation of hypochlorite, chlorite and chlorate. These oxyanions of chlorine are powerful oxidizers that may exist in the Martian soil and may have reacted with the nutrients of the Labeled Release Experiment. This paper aims to better understand these results by designing experiments to determine the kinetics of decomposition of formic acid to carbon dioxide with different oxidized forms of chlorine by headspace technique in gas chromatography coupled to mass spectrometry (GC / MS). Previous studies done in the laboratory showed that only hypochlorite quantitatively reacted with the formate, this is why we conducted experiments at 20 ° C, 30 ° C and 40 ° C at times 0, 0.1, 0.5, 1, 3 , 5, 10, 20, 30, 40 and 60 min. The resulting kinetics were similar to those obtained by the LR experiment, however the speeds at which reacted in the laboratory were very rapid, almost instantaneous, a comparison of the acquired by the Viking was kinetics days. This may be because in the laboratory we do not used soil samples, Viking used Mars regolith Martian, like a complex matrix that may affect the reaction rate. We conclude that the response obtained by the LR experiment is possibly due to the presence of oxyanions of chlorine, hypochlorite specific which is increased by the dismutations chlorine species in solution, all in combination with other components very likely soil nutrients reacted with isotopically labeled. This project is still ongoing, open a new hypothesis of whether there is microbial life on Mars, since, if the Labeled Release experiment found no biological activity, may have been a chemical oxidation of organic nutrients for sodium hypochlorite .

Dual element (CCl) isotope approach to distinguish abiotic reactions of chlorinated methanes by Fe(0) and by Fe(II) on iron minerals at neutral and alkaline pH.

PubMed

Rodríguez-Fernández, Diana; Heckel, Benjamin; Torrentó, Clara; Meyer, Armin; Elsner, Martin; Hunkeler, Daniel; Soler, Albert; Rosell, Mònica; Domènech, Cristina

2018-05-07

A dual element CCl isotopic study was performed for assessing chlorinated methanes (CMs) abiotic transformation reactions mediated by iron minerals and Fe(0) to further distinguish them in natural attenuation monitoring or when applying remediation strategies in polluted sites. Isotope fractionation was investigated during carbon tetrachloride (CT) and chloroform (CF) degradation in anoxic batch experiments with Fe(0), with FeCl 2 (aq), and with Fe-bearing minerals (magnetite, Mag and pyrite, Py) amended with FeCl 2 (aq), at two different pH values (7 and 12) representative of field and remediation conditions. At pH 7, only CT batches with Fe(0) and Py underwent degradation and CF accumulation evidenced hydrogenolysis. With Py, thiolytic reduction was revealed by CS 2 yield and is a likely reason for different Λ value (Δδ 13 C/Δδ 37 Cl) comparing with Fe(0) experiments at pH 7 (2.9 ± 0.5 and 6.1 ± 0.5, respectively). At pH 12, all CT experiments showed degradation to CF, again with significant differences in Λ values between Fe(0) (5.8 ± 0.4) and Fe-bearing minerals (Mag, 2 ± 1, and Py, 3.7 ± 0.9), probably evidencing other parallel pathways (hydrolytic and thiolytic reduction). Variation of pH did not significantly affect the Λ values of CT degradation by Fe(0) nor Py. CF degradation by Fe(0) at pH 12 showed a Λ (8 ± 1) similar to that reported at pH 7 (8 ± 2), suggesting CF hydrogenolysis as the main reaction and that CF alkaline hydrolysis (13.0 ± 0.8) was negligible. Our data establish a base for discerning the predominant or combined pathways of CMs natural attenuation or for assessing the effectiveness of remediation strategies using recycled minerals or Fe(0). Copyright © 2018 Elsevier Ltd. All rights reserved.

Determination of fluorine, chlorine and bromine in household products by means of oxygen bomb combustion and ion chromatography.

PubMed

Zhang, Shuai; Zhao, Tianbo; Wang, Jia; Qu, Xiaoling; Chen, Wei; Han, Yin

2013-01-01

A method for routine determination of fluorine, chlorine and bromine in household products was developed and validated. In this work, halogen analyses were made based on oxygen bomb combustion followed by ion chromatography (IC). The chromatographic analysis was performed by an IonPac AS19 hydroxide-selective anion-exchange column, a reagent free ion chromatograph eluent generator and an anion self-regenerating suppressor in 10 min. The response was linear (r ≥ 0.9995) in the entire investigated domain. The limit of detection for the halogens was in the range of 2 to 9 × 10(-3) mg/L and the limit of quantification was lower than 8 mg/Kg with 20 µL of injection volume. The certified reference material of ERM-EC 681k was pretreated using an oxygen bomb combustion procedure to demonstrate the precision of the proposed method. The quantitative analysis results obtained by IC for the target elements were 797 ± 9 mg/Kg chlorine and 786 ± 25 mg/Kg bromine, which were in good agreement with the certified values of 800 ± 4 mg/Kg chlorine, 770 ± 5 mg/Kg bromine for ERM-EC 681k, respectively. This validated method was successfully applied for the analysis of fluorine, chlorine and bromine in household product samples, and the variation of halogen contained among the tested samples was remarkable.

A COMPREHENSIVE ANALYSIS OF CHLORINE TRANSPORT AND FATE FOLLOWING A LARGE ENVIRONMENTAL RELEASE

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

Buckley, R.; Hunter, C.; Werth, D.

2011-05-10

A train derailment occurred in Graniteville, South Carolina during the early morning of January 6, 2005, and resulted in the release of a large amount of cryogenic pressurized liquid chlorine to the environment in a short time period. A comprehensive evaluation of the transport and fate of the released chlorine was performed, accounting for dilution, diffusion, transport and deposition into the local environment. This involved the characterization of a three-phased chlorine release, a detailed determination of local atmospheric mechanisms acting on the released chlorine, the establishment of atmospheric-hydrological physical exchange mechanisms, and aquatic dilution and mixing. This presentation will providemore » an overview of the models used in determining the total air-to-water mass transfer estimated to have occurred as a result of the roughly 60 tons of chlorine released into the atmosphere from the train derailment. The assumptions used in the modeling effort will be addressed, along with a comparison with available observational data to validate the model results. Overall, model-estimated chlorine concentrations in the airborne plume compare well with human and animal exposure data collected in the days after the derailment.« less

Two-chamber configuration of Bio-Nano electron cyclotron resonance ion source for fullerene modification.

PubMed

Uchida, T; Rácz, R; Muramatsu, M; Kato, Y; Kitagawa, A; Biri, S; Yoshida, Y

2016-02-01

We report on the modification of fullerenes with iron and chlorine using two individually controllable plasmas in the Bio-Nano electron cyclotron resonance ion source (ECRIS). One of the plasmas is composed of fullerene and the other one is composed of iron and chlorine. The online ion beam analysis allows one to investigate the rate of the vapor-phase collisional modification process in the ECRIS, while the offline analyses (e.g., liquid chromatography-mass spectrometry) of the materials deposited on the plasma chamber can give information on the surface-type process. Both analytical methods show the presence of modified fullerenes such as fullerene-chlorine, fullerene-iron, and fullerene-chlorine-iron.

XAFS Study on Chlorination of Y2O3 in LiCl-KCl-ZrCl4 Melt

NASA Astrophysics Data System (ADS)

Okamoto, Yoshihiro; Yaita, Tsuyoshi; Shiwaku, Hideaki; Suzuki, Shinichi

2008-11-01

The chlorination reaction of Y2O3 with ZrCl4 in LiCl-KCl eutectic melt was investigated by X-ray absorption fine structure (XAFS) technique. The chlorination reaction was observed between 773 K and 823 K as the 1st peak shift of the Fourier transform magnitude function |FT(k3χ(k))|. The peak corresponding to the nearest Y3+-Cl- correlation was observed in the XAFS analysis at 823 K as the result of the chlorination. It was confirmed that the mixture melts after the reaction is almost equivalent to a molten 5% YCl3-(LiCl-KCl eutectic) mixture.

Chlorination processing of local planetary ores for oxygen and metallurgically important metals

NASA Technical Reports Server (NTRS)

Lynch, D. C.

1989-01-01

The use of chlorine to extract, reclaim, and purify metals has attractive possibilities for extraterrestrial processing of local planetary resources. While a complete cyclic process has been proposed for the recovery of metallurgically significant metals and oxygen, herein the chlorination step of the cycle is examined. An experimental apparatus for reacting refractory materials, such as ilmenite, in a microwave induced plasma is being built. Complex equilibria calculations reveal that stable refractory materials can, under the influence of a plasma, undergo chlorination and yield oxygen as a by-product. These issues and the potential advantages for plasma processing in space are reviewed. Also presented is a discussion of the complex equilibria program used in the analysis.

The Market Responses to the Government Regulation of Chlorinated Solvents: A Policy Analysis

DTIC Science & Technology

1988-10-01

in the process of statistical estimation of model parameters. The results of the estimation process applied to chlorinated solvent markets show the...93 C.5. Marginal Feedstock Cost Series Estimates for Process Share of Total Production .................................. 94 F.I...poliay context for this research. Section III provides analysis necessary to understand the chemicals involved, their production processes and costs, and

Revealing hidden spectral information of chlorine and sulfur in data of a mobile Laser-induced Breakdown Spectroscopy system using chemometrics

NASA Astrophysics Data System (ADS)

Gottlieb, C.; Millar, S.; Günther, T.; Wilsch, G.

2017-06-01

For the damage assessment of reinforced concrete structures the quantified ingress profiles of harmful species like chlorides, sulfates and alkali need to be determined. In order to provide on-site analysis of concrete a fast and reliable method is necessary. Low transition probabilities as well as the high ionization energies for chlorine and sulfur in the near-infrared range makes the detection of Cl I and S I in low concentrations a difficult task. For the on-site analysis a mobile LIBS-system (λ = 1064 nm, Epulse ≤ 3 mJ, τ = 1.5 ns) with an automated scanner has been developed at BAM. Weak chlorine and sulfur signal intensities do not allow classical univariate analysis for process data derived from the mobile system. In order to improve the analytical performance multivariate analysis like PLS-R will be presented in this work. A comparison to standard univariate analysis will be carried out and results covering important parameters like detection and quantification limits (LOD, LOQ) as well as processing variances will be discussed (Allegrini and Olivieri, 2014 [1]; Ostra et al., 2008 [2]). It will be shown that for the first time a low cost mobile system is capable of providing reproducible chlorine and sulfur analysis on concrete by using a low sensitive system in combination with multivariate evaluation.

Factors affecting THMs, HAAs and HNMs formation of Jin Lan Reservoir water exposed to chlorine and monochloramine.

PubMed

Hong, Huachang; Xiong, Yujing; Ruan, Mengyong; Liao, Fanglei; Lin, Hongjun; Liang, Yan

2013-02-01

The formations of THMs, HAAs, and HNMs from chlorination and chloramination of water from Jinlan Reservoir were investigated in this study. Results showed that monochloramine rather than chlorine generally resulted in lower concentration of DBPs, and the DBPs formation varied greatly as the treatment conditions changed. Specifically, the yields of THMs, HAAs and HNMs all increased with the high bromide level and high disinfectant dose both during chlorination and chloramination. The longer reaction time had a positive effect on the formation of THMs, HAAs and HNMs during chlorination and HNMs during chloramination. However, no time effect was observed on the formation of THMs and HAAs during chloramination. An increase in pH enhanced the levels of THMs and HNMs upon chlorination but reduced levels of HNMs upon chloramination. As for the THMs in chloramination and HAAs in chlorination and chloramination, no obvious pH effect was observed. The elevated temperature significantly increased the yields of THMs during chlorination and HNMs during chloramination, but has no effect on THMs and HAAs yields during chloramination. In the same temperature range, the formation of HAAs and HNMs in chlorination showed a first increasing and then a decreasing trend. In chloramination study, addition of nitrite markedly increased the formation of HNMs but had little impact on the formation of THMs and HAAs. While in chlorination study, the presence of high nitrite levels significantly reduced the yields of THMs, HAAs and HNMs. Range analysis revealed that the bromide and disinfectant levels were the major factors affecting THMs, HAAs and HNMs formation, in both chlorination and chloramination. Finally, comparisons of the speciation of mono-halogenated, di-halogenated, tri-halogenated HAAs and HNMs between chlorination and monochloramination were also conducted, and factors influencing the speciation pattern were identified. Copyright © 2012 Elsevier B.V. All rights reserved.

Preparation, structure and luminescent characterization of a series of metal-organic frameworks based on flexible ligands with nitrogen heterocycles and carboxyl

NASA Astrophysics Data System (ADS)

Dai, Hai-yu; Tang, Yu-yuan; Wang, Cui-juan; Chen, Shuang; Tong, Yan; Zhang, Zhi-Bing

2017-12-01

Seven new compounds, [Zn(pypymba)2]n(1), [Co(pypymba)2]n(2), [Cd(pypymba)2]n(3), [Cd(Hpypymba)Cl2]n(4), {[Cd(pypymba)Cl]·C2H5OH·H2O}n(5), [Cd(pypyaa)Cl]n(6), {[Cd2(pyznpy)2Cl2H2O]·H2O}n(7) [Hpypymba = 4-((3-(pyrazin-2-yl)-1H-pyrazol-1-yl)methyl)benzoic acid, Hpyznpy = 4-((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzoic acid, Hpypyaa = 2-(3-pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid], were hydrothermally synthesized by tuning the metal ion's species, counter anions, solvents and pH values and characterized by routine methods: XRD, elemental analysis, fluorescence properties analysis, TGA and crystal structure analysis and single-crystal X-ray crystallography. The main structures of the compounds 1, 2, and 3 are extended to similar 3D structures by C-H…N, C-H…O hydrogen bonds and π…π stacking under the same synthesis method. Each Cd(II) node of compound 4 has four chlorine bridges (two pairs of double chlorine); Each Cd(II) node of compounds 5, 6 has two chlorine bridges (a pair of double chlorine bridges), while their spatial structures are expanded in different ways. Compound 7 also contains chlorine atoms, but does not contain chlorine bridged structures. The luminescent properties of compound 7 and the ones immersed in various kinds of organic compounds and nitrate@EtOH solutions have been investigated. Importantly, 7 shows highly sensitive response to nitrobenzene and Fe3+ through luminescence quenching effects, making it a promising luminescent sensor for nitrobenzene and Fe3+.

Chemical Loss of Ozone in the Arctic Polar Vortex in the Winter of 1991-1992

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; Gottlieb, E. W.; Lait, L. R.; Newman, P. A.; Schoeberl, M. R.; Strahan, S. E.; Loewenstein, M.; Podolske, J. R.; Chan, K. R.;

Analysis of Organohalogen Products From Chlorination of Natural Waters Under Simulated Biofouling Control Conditions

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

Bean, R. M.; Mann, D. C.; Riley, R. G.

1980-06-01

The products of low-level chlorination of natural waters from ten locations across the continental United States have been studied, with emphasis on volatile and lipophilic organohalogen components. A specially designed apparatus permitted continuous sampling and chlorination of water in a manner analogous to some types of cooling water treatments. Volatile components were analyzed using headspace, purge-and-trap, and resin adsorption methods. The less-volatile components were collected by passing large volumes of the chlorinated water over XAD-2 columns. Total organic halogen collected on XAD resins was compared with the halogen contribution of haloform compounds. The XAD samples were further separated into fractionsmore » according to molecular weight and polarity using liquid chrOmatography. These studies indicate that haloforms are the most abundant lipophilic halogenated products formed from low-level chlorination of natural waters, but that other halogenated lipophilic material is also formed.« less

AN HPLC METHOD WITH UVDETECTION, PH CONTROL, AND REDUCTIVE ASCORBIC ACID FOR CYANURIC ACID ANALYSIS IN WATER

EPA Science Inventory

Every year over 250 million pounds of cyanuric acid (CA) and chlorinated isocyanurates are produced industrially. These compounds are standard ingredients in formulations for household bleaches, industrial cleansers, dishwasher compounds, general sanitizers, and chlorine stabiliz...

Investigating the management performance of disinfection analysis of water distribution networks using data mining approaches.

PubMed

Zounemat-Kermani, Mohammad; Ramezani-Charmahineh, Abdollah; Adamowski, Jan; Kisi, Ozgur

2018-06-13

Chlorination, the basic treatment utilized for drinking water sources, is widely used for water disinfection and pathogen elimination in water distribution networks. Thereafter, the proper prediction of chlorine consumption is of great importance in water distribution network performance. In this respect, data mining techniques-which have the ability to discover the relationship between dependent variable(s) and independent variables-can be considered as alternative approaches in comparison to conventional methods (e.g., numerical methods). This study examines the applicability of three key methods, based on the data mining approach, for predicting chlorine levels in four water distribution networks. ANNs (artificial neural networks, including the multi-layer perceptron neural network, MLPNN, and radial basis function neural network, RBFNN), SVM (support vector machine), and CART (classification and regression tree) methods were used to estimate the concentration of residual chlorine in distribution networks for three villages in Kerman Province, Iran. Produced water (flow), chlorine consumption, and residual chlorine were collected daily for 3 years. An assessment of the studied models using several statistical criteria (NSC, RMSE, R 2 , and SEP) indicated that, in general, MLPNN has the greatest capability for predicting chlorine levels followed by CART, SVM, and RBF-ANN. Weaker performance of the data-driven methods in the water distribution networks, in some cases, could be attributed to improper chlorination management rather than the methods' capability.

Assessing the Impact of Chlorinated-Solvent Sites on Metropolitan Groundwater Resources

PubMed Central

Brusseau, Mark L.; Narter, Matthew

2014-01-01

Chlorinated-solvent compounds are among the most common groundwater contaminants in the U.S.A. The majority of the many sites contaminated by chlorinated-solvent compounds are located in metropolitan areas, and most such areas have one or more chlorinated-solvent contaminated sites. Thus, contamination of groundwater by chlorinated-solvent compounds may pose a potential risk to the sustainability of potable water supplies for many metropolitan areas. The impact of chlorinated-solvent sites on metropolitan water resources was assessed for Tucson, AZ, by comparing the aggregate volume of extracted groundwater for all pump-and-treat systems associated with contaminated sites in the region to the total regional groundwater withdrawal. The analysis revealed that the aggregate volume of groundwater withdrawn for the pump-and-treat systems operating in Tucson, all of which are located at chlorinated-solvent contaminated sites, was 20% of the total groundwater withdrawal in the city for the study period. The treated groundwater was used primarily for direct delivery to local water supply systems or for reinjection as part of the pump-and-treat system. The volume of the treated groundwater used for potable water represented approximately 13% of the total potable water supply sourced from groundwater, and approximately 6% of the total potable water supply. This case study illustrates the significant impact chlorinated-solvent contaminated sites can have on groundwater resources and regional potable-water supplies. PMID:24116872

Identification of reaction products from reactions of free chlorine with the lipid-regulator gemfibrozil.

PubMed

Krkošek, Wendy H; Koziar, Stephen A; White, Robert L; Gagnon, Graham A

2011-01-01

High global consumption rates have led to the occurrence of pharmaceutically active compounds (PhACs) in wastewater. The use of chlorine to disinfect wastewater prior to release into the environment may convert PhACs into uncharacterized chlorinated by-products. In this investigation, chlorination of a common pharmaceutical, the antihyperlipidemic agent gemfibrozil, was documented. Gemfibrozil (2,2-dimethyl-5-(2,5-dimethylphenoxy)pentanoic acid) was reacted with sodium hypochlorite and product formation was monitored by gas chromatography-mass spectrometry (GC-MS). The incorporation of one, two or three chlorine atoms into the aromatic region of gemfibrozil was demonstrated using negative-ion electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS). Further analysis using (1)H nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as 4'-ClGem (5-(4-chloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid) 4',6'-diClGem (5-(4,6-dichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), and 3',4',6'-triClGem (5-(3,4,6-trichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), products consistent with electrophilic aromatic substitution reactions. The rapid reaction of gemfibrozil with free chlorine at pH conditions relevant to water treatment indicates that a mixture of chlorinated gemfibrozils is likely to be found in wastewater disinfected with chlorine. Copyright © 2010 Elsevier Ltd. All rights reserved.

Behavior and stability of adenosine triphosphate (ATP) during chlorine disinfection.

PubMed

Nescerecka, Alina; Juhna, Talis; Hammes, Frederik

2016-09-15

Adenosine triphosphate (ATP) analysis is a cultivation-independent alternative method for the determination of bacterial viability in both chlorinated and non-chlorinated water. Here we investigated the behavior and stability of ATP during chlorination in detail. Different sodium hypochlorite doses (0-22.4 mg-Cl2 L(-1); 5 min exposure) were applied to an Escherichia coli pure culture suspended in filtered river water. We observed decreasing intracellular ATP with increasing chlorine concentrations, but extracellular ATP concentrations only increased when the chlorine dose exceeded 0.35 mg L(-1). The release of ATP from chlorine-damaged bacteria coincided with severe membrane damage detected with flow cytometry (FCM). The stability of extracellular ATP was subsequently studied in different water matrixes, and we found that extracellular ATP was stable in sterile deionized water and also in chlorinated water until extremely high chlorine doses (≤11.2 mg-Cl2 L(-1); 5 min exposure). In contrast, ATP decreased relatively slowly (k = 0.145 h(-1)) in 0.1 μm filtered river water, presumably due to degradation by either extracellular enzymes or the fraction of bacteria that were able to pass through the filter. Extracellular ATP decreased considerably faster (k = 0.368 h(-1)) during batch growth of a river water bacterial community. A series of growth potential tests showed that extracellular ATP molecules were utilized as a phosphorus source during bacteria proliferation. From the combined data we conclude that ATP released from bacteria at high chlorine doses could promote bacteria regrowth, contributing to biological instability in drinking water distribution systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of saponification for determination of polychlorinated biphenyls in marine sediments.

PubMed

Numata, Masahiko; Yarita, Takashi; Aoyagi, Yoshie; Yamazaki, Misako; Takatsu, Akiko

2005-02-01

The effects of saponification conditions (temperature and water content of saponifying solution) on the determination of chlorinated biphenyls (CBs) in marine sediments were investigated. Although highly chlorinated biphenyls (nona- to deca-CBs) decomposed during high-temperature saponification, the degree of degradation was reduced by adding water to the ethanolic potassium hydroxide saponifying solution. Room-temperature saponification yielded quantitative recovery of highly chlorinated biphenyl surrogates but low extraction efficiencies of lightly chlorinated biphenyls (mono- to di-CBs). The same samples were analyzed by other extraction techniques, for example, pressurized liquid extraction, and analytical results were compared. The mono- and di-CB concentrations were correlated with the extraction temperatures of various extraction techniques. In particular, the concentrations of some CB congeners (CB11, CB14) were higher with saponification. The low degree of degradation of highly chlorinated biphenyls and the high recovery of lightly chlorinated biphenyls were compatible when room-temperature and high-temperature saponification were combined. Except for the anomalies of CB11 and CB14, the combined method gave satisfactory results for analysis of PCBs.

Mechanism of chlorine inactivation of DNA-containing parvovirus H-1.

PubMed Central

Churn, C C; Bates, R C; Boardman, G D

1983-01-01

An investigation was undertaken to determine the effect of chlorine on a small DNA-containing enteric virus. Parvovirus H-1 was exposed to sodium hypochlorite in a phosphate-buffered saline solution at pH 7. Then, the whole virion, the protein capsid, or the nucleic acid was subjected to analysis. The sedimentation rate of the chlorine-treated whole virus decreased from 110S to 43S. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis of the virus demonstrated the formation of higher-molecular-weight aggregates resulting from covalent cross-linking of the capsid proteins. Electron microscopic examination revealed that the DNA was extruded as a taillike structure which remained attached to the virus particle. Furthermore, the DNA was intact and still capable of in vitro replication. The adsorption of the chlorine-treated virions to host cells was inhibited, presumably due to the effect of chlorine on the particular spatial arrangement of the capsid proteins required for adsorption. Specific sites on these proteins had become highly reactive, indicating that the initial action of chlorine on parvovirus H-1 was on the viral capsid. Images PMID:6660876

Luminescent ZnO quantum dots as an efficient sensor for free chlorine detection in water.

PubMed

Singh, Kulvinder; Mehta, S K

2016-04-21

Highly luminescent ZnO quantum dots (QDs) synthesized via a simple and facile route are used for the preparation of an optical sensor for the detection of free chlorine. The concentration of free chlorine greatly affects the PL emission of the ZnO QDs at 525 nm. Since hypochlorite gains electrons with high efficiency, it takes electrons from the oxygen vacancies of ZnO QDs, which gives rise to defect emission in ZnO QDs. UV-vis data analysis shows that free chlorine does not affect the optical absorption spectra of ZnO QDs. The optical sensing of free chlorine using ZnO QDs has several advantages, like quick response time, good selectivity and of course high sensitivity. The pH has very little effect on the PL emission of ZnO QDs. It does not interfere in the sensing mechanism for free chlorine. After 60 s, the response of the ZnO QDs remains stable. The present sensor shows high selectivity with respect to various common cations, as well as anions.

ANALYSIS OF NASAL TISSUE FOR BIOMARKERS OF CHLORINE EXPOSURE

EPA Science Inventory

Both 3-chloro-tyrosine (CT) and 3,5-dichloro-tyrosine (dCT) are sensitive and specific biomarkers for evaluating exposure to chlorine gas (Cl2) and hypochlorous acid (HOCl). Previous investigations have focused on the formation of CT and dCT resulting from biochemical responses ...

MEMBRANE EXTRACTION GC/MS FOR THE ANALYSIS OF DISINFECTION BY-PRODUCTS

EPA Science Inventory

For many years, public water supplies in the U.S.have been treated with a variety of chemicals aimed at reducing or eliminating infectious diseases. Chlorine is the most common disinfectant used to combat waterborne microbial diseases; however, the use of ozone, chlorine dioxid...

ANALYSIS OF IN VIVO AND IN VITRO DNA STRAND BREAKS FROM TRIHALOMETHANE EXPOSURE

EPA Science Inventory

Abstract
Background: Epidemiological studies have linked the consumption of chlorinated surface waters to an increased risk of two major causes of human mortality, colorectal and bladder cancer. Trihalomethanes (THMs) are by-products formed when chlorine is used to disinfect d...

Stable Carbon Isotope Fractionation in Chlorinated Ethene Degradation by Bacteria Expressing Three Toluene Oxygenases

PubMed Central

Clingenpeel, Scott R.; Moan, Jaina L.; McGrath, Danielle M.; Hungate, Bruce A.; Watwood, Mary E.

2012-01-01

One difficulty in using bioremediation at a contaminated site is demonstrating that biodegradation is actually occurring in situ. The stable isotope composition of contaminants may help with this, since they can serve as an indicator of biological activity. To use this approach it is necessary to establish how a particular biodegradation pathway affects the isotopic composition of a contaminant. This study examined bacterial strains expressing three aerobic enzymes for their effect on the 13C/12C ratio when degrading both trichloroethene (TCE) and cis-1,2-dichloroethene (c-DCE): toluene 3-monoxygenase, toluene 4-monooxygenase, and toluene 2,3-dioxygenase. We found no significant differences in fractionation among the three enzymes for either compound. Aerobic degradation of c-DCE occurred with low fractionation producing δ13C enrichment factors of −0.9 ± 0.5 to −1.2 ± 0.5, in contrast to reported anaerobic degradation δ13C enrichment factors of −14.1 to −20.4‰. Aerobic degradation of TCE resulted in δ13C enrichment factors of −11.6 ± 4.1 to −14.7 ± 3.0‰ which overlap reported δ13C enrichment factors for anaerobic TCE degradation of −2.5 to −13.8‰. The data from this study suggest that stable isotopes could serve as a diagnostic for detecting aerobic biodegradation of TCE by toluene oxygenases at contaminated sites. PMID:22363335

Oxidation-chlorination of binary Ni-Cr alloys in flowing Ar-O2-Cl2 gas mixtures at 1200 K

NASA Technical Reports Server (NTRS)

Mcnallan, M. J.; Lee, Y. Y.; Chang, Y. W.; Jacobson, N. S.; Doychak, J.

1991-01-01

Nickel-chromium alloys are resistant to oxidation because of the selective oxidation of chromium to form a protective Cr2O3 scale. In chlorine-containing environments, volatile corrosion products can also be formed. The mixed oxidation-chlorination of Ni-4.5Cr, Ni-13.8Cr, and Ni-26.5Cr (by weight) alloys in Ar-O2-Cl2 gas mixtures is investigated using thermogravimetric analysis and atmospheric-pressure-sampling mass spectrometry, followed by examination of the corrosion products using scanning electron microscopy and X-ray diffraction analysis. The overall kinetics of the corrosion are affected by the relative amounts of oxides and chlorides formed and the composition of the oxide corrosion products.

Method of Analysis by the U.S. Geological Survey California District Sacramento Laboratory?Determination of Trihalomethane Formation Potential, Method Validation, and Quality-Control Practices

USGS Publications Warehouse

Crepeau, Kathryn L.; Fram, Miranda S.; Bush, Noel

2004-01-01

An analytical method for the determination of the trihalomethane formation potential of water samples has been developed. The trihalomethane formation potential is measured by dosing samples with chlorine under specified conditions of pH, temperature, incubation time, darkness, and residual-free chlorine, and then analyzing the resulting trihalomethanes by purge and trap/gas chromatography equipped with an electron capture detector. Detailed explanations of the method and quality-control practices are provided. Method validation experiments showed that the trihalomethane formation potential varies as a function of time between sample collection and analysis, residual-free chlorine concentration, method of sample dilution, and the concentration of bromide in the sample.

Two-chamber configuration of Bio-Nano electron cyclotron resonance ion source for fullerene modification

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

Uchida, T., E-mail: uchida-t@toyo.jp; Graduate School of Interdisciplinary New Science, Toyo University, Kawagoe 350-8585; Rácz, R.

2016-02-15

We report on the modification of fullerenes with iron and chlorine using two individually controllable plasmas in the Bio-Nano electron cyclotron resonance ion source (ECRIS). One of the plasmas is composed of fullerene and the other one is composed of iron and chlorine. The online ion beam analysis allows one to investigate the rate of the vapor-phase collisional modification process in the ECRIS, while the offline analyses (e.g., liquid chromatography-mass spectrometry) of the materials deposited on the plasma chamber can give information on the surface-type process. Both analytical methods show the presence of modified fullerenes such as fullerene-chlorine, fullerene-iron, andmore » fullerene-chlorine-iron.« less

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

Atomic Weights of the Elements 1999

NASA Astrophysics Data System (ADS)

Coplen, T. B.

2001-05-01

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: from to nitrogen 14.006 74±0.000 07¯r 14.0067±0.0002¯ sulfur 32.066±0.006 32.065±0.005 chlorine 35.4527±0.0009 35.453±0.002 germanium 72.61±0.02 72.64±0.01 xenon 131.29±0.02 131.293±0.006 erbium 167.26±0.03 167.259±0.003 uranium 238.0289±0.0001 238.028 91±0.000 03 Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community.

Effect of Chlorine Exposure on the Survival and Antibiotic Gene Expression of Multidrug Resistant Acinetobacter baumannii in Water

PubMed Central

Karumathil, Deepti Prasad; Yin, Hsin-Bai; Kollanoor-Johny, Anup; Venkitanarayanan, Kumar

2014-01-01

Acinetobacter baumannii is a multidrug resistant pathogen capable of causing a wide spectrum of clinical conditions in humans. Acinetobacter spp. is ubiquitously found in different water sources. Chlorine being the most commonly used disinfectant in water, the study investigated the effect of chlorine on the survival of A. baumannii in water and transcription of genes conferring antibiotic resistance. Eight clinical isolates of A. baumannii, including a fatal meningitis isolate (ATCC 17978) (~108 CFU/mL) were separately exposed to free chlorine concentrations (0.2, 1, 2, 3 and 4 ppm) with a contact time of 30, 60, 90 and 120 second. The surviving pathogen counts at each specified contact time were determined using broth dilution assay. In addition, real-time quantitative PCR (RT-qPCR) analysis of the antibiotic resistance genes (efflux pump genes and those encoding resistance to specific antibiotics) of three selected A. baumannii strains following exposure to chlorine was performed. Results revealed that all eight A. baumannii isolates survived the tested chlorine levels during all exposure times (p > 0.05). Additionally, there was an up-regulation of all or some of the antibiotic resistance genes in A. baumannii, indicating a chlorine-associated induction of antibiotic resistance in the pathogen. PMID:24514427

STATISTICAL ANALYSIS OF GROUNDWATER GEOCHEMISTRY DATA FROM AREA 6, DOVER AIR FORCE BASE, DOVER, DELAWARE

EPA Science Inventory

The work described in this report is part of a project undertaken by the Bioremediation of Chlorinated Solvents Action Team of the Remediation Technologies Development Forum, a joint U.S. Federal agency-industry collaboration, to study the natural attenuation of chlorinated ethen...

Chlorine Analysis - Wastewater. Training Module 5.125.2.77.

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 the laboratory procedures for determining the combined chlorine residual of a wastewater sample. Included are objectives, instructor guides, student handouts, and transparency masters. This module considers the amperometric, DPD,…

JOURNAL ARTICLE: ANALYSIS OF IN VIVO AND IN VITRO DNA STRAND BREAKS FROM TRIHALOMETHANE EXPOSURE

EPA Science Inventory

Epidemiological studies have linked the consumption of chlorinated surface waters to an increased risk of two major causes of human mortality, colorectal and bladder cancer. Trihalomethanes (THMs) are by-products formed when chlorine is used to disinfect drinking water. The pur...

Immunocytochemistry and Image Analysis of Beta-Catenin Redistribution in Normal Human Colon Cell Cultures Treated with Disinfection By-Products.

EPA Science Inventory

Epidemiological studies have shown an association between the consumption of chlorinated drinking water and increased risk for colon cancer. In vivo studies proved that rodents exposed to chlorination disinfection byproducts (DBPs) developed aberrant crypt foci (ACF) in t...

Diffusion related isotopic fractionation effects with one-dimensional advective-dispersive transport.

PubMed

Xu, Bruce S; Lollar, Barbara Sherwood; Passeport, Elodie; Sleep, Brent E

2016-04-15

Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining "observable" DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C0), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (Dmech/Deff). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective-dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C0/MDL ratios of 50 or higher. Much larger C0/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1m) for a relatively young diffusive plume (<100years), and DRIF will not easily be detected by using the conventional sampling approach with "typical" well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where Dmech/Deff is larger than 10, DRIF effects will likely not be observable for common groundwater contaminants. Importantly, under most field conditions, Dmech/Deff≥10 is usually satisfied in the longitudinal direction, suggesting that DRIF is not likely to be observable in most groundwater systems in which contaminant transport is predominantly one-dimensional. Given the importance in the MDL it is recommended that MDL should always be explicitly reported in both modeling and field studies. Copyright © 2016. Published by Elsevier B.V.

Primary retention following nuclear recoil in β-decay: Proposed synthesis of a metastable rare gas oxide ((38)ArO4) from ((38)ClO4(-)) and the evolution of chemical bonding over the nuclear transmutation reaction path.

PubMed

Timm, Matthew J; Matta, Chérif F

2014-12-01

Argon tetroxide (ArO4) is the last member of the N=50 e(-) isoelectronic and isosteric series of ions: SiO4(4-), PO4(3-), SO4(2-), and ClO4(-). A high level computational study demonstrated that while ArO4 is kinetically stable it has a considerable positive enthalpy of formation (of ~298kcal/mol) (Lindh et al., 1999. J. Phys. Chem. A 103, pp. 8295-8302) confirming earlier predictions by Pyykkö (1990. Phys. Scr. 33, pp. 52-53). ArO4 can be expected to be difficult to synthesize by traditional chemistry due to its metastability and has not yet been synthesized at the time of writing. A computational investigation of the changes in the chemical bonding of chlorate (ClO4(-)) when the central chlorine atom undergoes a nuclear transmutation from the unstable artificial chlorine isotope (38)Cl to the stable rare argon isotope (38)Ar through β-decay, hence potentially leading to the formation of ArO4, is reported. A mathematical model is presented that allows for the prediction of yields following the recoil of a nucleus upon ejecting a β-electron. It is demonstrated that below a critical angle between the ejected β-electron and that of the accompanying antineutrino their respective linear momentums can cancel to such an extent as imparting a recoil to the daughter atom insufficient for breaking the Ar-O bond. As a result, a primary retention yield of ~1% of ArO4 is predicted following the nuclear disintegration. The study is conducted at the quadratic configuration interaction with single and double excitations [QCISD/6-311+G(3df)] level of theory followed by an analysis of the electron density by the quantum theory of atoms in molecules (QTAIM). Crossed potential energy surfaces (PES) were used to construct a PES from the metastable ArO4 ground singlet state to the Ar-O bond dissociation product ArO3+O((3)P) from which the predicted barrier to dissociation is ca. 22kcal/mol and the exothermic reaction energy is ca. 28kcal/mol [(U)MP2/6-311+G(d)]. Copyright © 2014 Elsevier Ltd. All rights reserved.

Environmental applications for the analysis of chlorinated dibenzo-p-dioxins and dibenzofurans using mass spectrometry/mass spectrometry

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

Reiner, E.J.; Schellenberg, D.H.; Taguchi, V.Y.

1991-01-01

A mass spectrometry/mass spectrometry-multiple reaction monitoring (MS/MS-MRM) technique for the analysis of all tetra- through octachlorinated dibenzo-p-dioxins (Cl{sub x}DD, x = 4-8) and dibenzofurans (Cl{sub x}DF, x = 4-8) has been developed at the Ministry of the Environment (MOE) utilizing a triple quadrupole mass spectrometer. Optimization of instrumental parameters using the analyte of interest in a direct insertion probe (DIP) resulted in sensitivities approaching those obtainable by high-resolution mass spectrometric (HRMS) methods. All congeners of dioxins and furans were detected in the femtogram range. Results on selected samples indicated that for some matrices, fewer chemical interferences were observed by MS/MSmore » than by HRMS. The technique used to optimize the instrument for chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs) analysis is adaptable to other analytes.« less

Structures and Nuclear Quadrupole Coupling Tensors of a Series of Chlorine-Containing Hydrocarbons

NASA Astrophysics Data System (ADS)

Dikkumbura, Asela S.; Webster, Erica R.; Dorris, Rachel E.; Peebles, Rebecca A.; Peebles, Sean A.; Seifert, Nathan A.; Pate, Brooks

2016-06-01

Rotational spectra for gauche-1,2-dichloroethane (12DCE), gauche-1-chloro-2-fluoroethane (1C2FE) and both anti- and gauche-2,3-dichloropropene (23DCP) have been observed using chirped-pulse Fourier-transform microwave (FTMW) spectroscopy in the 6-18 GHz region. Although the anti conformers for all three species are predicted to be more stable than the gauche forms, they are nonpolar (12DCE) or nearly nonpolar (predicted dipole components for anti-1C2FE: μ_a = 0.11 D, μ_b = 0.02 D and for anti-23DCP: μ_a = 0.25 D, μ_b = 0.02 D); nevertheless, it was also possible to observe and assign the spectrum of anti-23DCP. Assignments of parent spectra and 37Cl and 13C substituted isotopologues utilized predictions at the MP2/6-311++G(2d,2p) level and Pickett's SPCAT/SPFIT programs. For the weak anti-23DCP spectra, additional measurements also utilized a resonant-cavity FTMW spectrometer. Full chlorine nuclear quadrupole coupling tensors for gauche-12DCE and both anti- and gauche-23DCP have been diagonalized to allow comparison of coupling constants. Kraitchman's equations were used to determine r_s coordinates of isotopically substituted atoms and r_0 structures were also deduced for gauche conformers of 12DCE and 1C2FE. Structural details and chlorine nuclear quadrupole coupling constants of all three molecules will be compared, and effects of differing halogen substitution and carbon chain length on molecular properties will be evaluated.

Health Effects from Swimming Training in Chlorinated Pools and the Corresponding Metabolic Stress Pathways

PubMed Central

Li, Jiang-Hua; Wang, Zhi-Hui; Zhu, Xiao-Juan; Deng, Zhao-Hui; Cai, Can-Xin; Qiu, Li-Qiang; Chen, Wei; Lin, Ya-Jun

2015-01-01

Chlorination is the most popular method for disinfecting swimming pool water; however, although pathogens are being killed, many toxic compounds, called disinfection by-products (DBPs), are formed. Numerous epidemiological publications have associated the chlorination of pools with dysfunctions of the respiratory system and with some other diseases. However, the findings concerning these associations are not always consistent and have not been confirmed by toxicological studies. Therefore, the health effects from swimming in chlorinated pools and the corresponding stress reactions in organisms are unclear. In this study, we show that although the growth and behaviors of experimental rats were not affected, their health, training effects and metabolic profiles were significantly affected by a 12-week swimming training program in chlorinated water identical to that of public pools. Interestingly, the eyes and skin are the organs that are more directly affected than the lungs by the irritants in chlorinated water; instead of chlorination, training intensity, training frequency and choking on water may be the primary factors for lung damage induced by swimming. Among the five major organs (the heart, liver, spleen, lungs and kidneys), the liver is the most likely target of DBPs. Through metabolomics analysis, the corresponding metabolic stress pathways and a defensive system focusing on taurine were presented, based on which the corresponding countermeasures can be developed for swimming athletes and for others who spend a lot of time in chlorinated swimming pools. PMID:25742134

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Time-dependent imidazole-catalyzed HPA chlorination by NH2Cl was also demonstrated by product analyses. Quantitative assessment of the data suggests that physiological levels of histidyl groups will react with primary chloramines to generate a flux of imidazole chloramine sufficient to catalyze biological chlorination via HImCl+, particularly in environments that generate high concentrations of HOCl such as the neutrophil phagosome. PMID:25660996

Chlorination of lignin by ubiquitous fungi has a likely role in global organochlorine production

PubMed Central

Ortiz-Bermúdez, Patricia; Hirth, Kolby C.; Srebotnik, Ewald; Hammel, Kenneth E.

2007-01-01

Soils and decayed plant litter contain significant quantities of chlorinated aromatic polymers that have a natural but largely unknown origin. We used cupric oxide ligninolysis coupled with gas chromatography/mass spectrometry to show that Curvularia inaequalis, a widely distributed litter ascomycete, chlorinated the aromatic rings of lignin in wood that it was degrading. In aspen wood decayed for 24 weeks, two chlorolignin fragments, 5-chlorovanillin and 2-chlorosyringaldehyde, were each found at ≈10 μg/g of wood (dry weight). These levels resemble those of similar structures generally found in unpolluted environmental samples. Fractionation of the extractable proteins followed by tandem mass spectrometric analysis showed that the colonized wood contained a previously described C. inaequalis chloroperoxidase that very likely catalyzed lignin chlorination. Chlorolignin produced by this route and humus derived from it are probably significant components of the global chlorine cycle because chloroperoxidase-producing fungi are ubiquitous in decaying lignocellulose and lignin is the earth's most abundant aromatic substance. PMID:17360449

Microbial community dynamics of an urban drinking water distribution system subjected to phases of chloramination and chlorination treatments.

PubMed

Hwang, Chiachi; Ling, Fangqiong; Andersen, Gary L; LeChevallier, Mark W; Liu, Wen-Tso

2012-11-01

Water utilities in parts of the U.S. control microbial regrowth in drinking water distribution systems (DWDS) by alternating postdisinfection methods between chlorination and chloramination. To examine how this strategy influences drinking water microbial communities, an urban DWDS (population ≅ 40,000) with groundwater as the source water was studied for approximately 2 years. Water samples were collected at five locations in the network at different seasons and analyzed for their chemical and physical characteristics and for their microbial community composition and structure by examining the 16S rRNA gene via terminal restriction fragment length polymorphism and DNA pyrosequencing technology. Nonmetric multidimension scaling and canonical correspondence analysis of microbial community profiles could explain >57% of the variation. Clustering of samples based on disinfection types (free chlorine versus combined chlorine) and sampling time was observed to correlate to the shifts in microbial communities. Sampling location and water age (<21.2 h) had no apparent effects on the microbial compositions of samples from most time points. Microbial community analysis revealed that among major core populations, Cyanobacteria, Methylobacteriaceae, Sphingomonadaceae, and Xanthomonadaceae were more abundant in chlorinated water, and Methylophilaceae, Methylococcaceae, and Pseudomonadaceae were more abundant in chloraminated water. No correlation was observed with minor populations that were detected frequently (<0.1% of total pyrosequences), which were likely present in source water and survived through the treatment process. Transient microbial populations including Flavobacteriaceae and Clostridiaceae were also observed. Overall, reversible shifts in microbial communities were especially pronounced with chloramination, suggesting stronger selection of microbial populations from chloramines than chlorine.

Microbial Community Dynamics of an Urban Drinking Water Distribution System Subjected to Phases of Chloramination and Chlorination Treatments

PubMed Central

Hwang, Chiachi; Ling, Fangqiong; Andersen, Gary L.; LeChevallier, Mark W.

2012-01-01

Water utilities in parts of the U.S. control microbial regrowth in drinking water distribution systems (DWDS) by alternating postdisinfection methods between chlorination and chloramination. To examine how this strategy influences drinking water microbial communities, an urban DWDS (population ≅ 40,000) with groundwater as the source water was studied for approximately 2 years. Water samples were collected at five locations in the network at different seasons and analyzed for their chemical and physical characteristics and for their microbial community composition and structure by examining the 16S rRNA gene via terminal restriction fragment length polymorphism and DNA pyrosequencing technology. Nonmetric multidimension scaling and canonical correspondence analysis of microbial community profiles could explain >57% of the variation. Clustering of samples based on disinfection types (free chlorine versus combined chlorine) and sampling time was observed to correlate to the shifts in microbial communities. Sampling location and water age (<21.2 h) had no apparent effects on the microbial compositions of samples from most time points. Microbial community analysis revealed that among major core populations, Cyanobacteria, Methylobacteriaceae, Sphingomonadaceae, and Xanthomonadaceae were more abundant in chlorinated water, and Methylophilaceae, Methylococcaceae, and Pseudomonadaceae were more abundant in chloraminated water. No correlation was observed with minor populations that were detected frequently (<0.1% of total pyrosequences), which were likely present in source water and survived through the treatment process. Transient microbial populations including Flavobacteriaceae and Clostridiaceae were also observed. Overall, reversible shifts in microbial communities were especially pronounced with chloramination, suggesting stronger selection of microbial populations from chloramines than chlorine. PMID:22941076

Dendrochemistry of multiple releases of chlorinated solvents at a former industrial site

USGS Publications Warehouse

Balouet, Jean Christophe; Burken, Joel G.; Karg, Frank; Vroblesky, Don; Smith, Kevin T.; Grudd, Hakan; Rindby, Anders; Beaujard, Francois; Chalot, Michel

2012-01-01

Trees can take up and assimilate contaminants from the soil, subsurface, and groundwater. Contaminants in the transpiration stream can become bound or incorporated into the annual rings formed in trees of the temperate zones. The chemical analysis of precisely dated tree rings, called dendrochemistry, can be used to interpret past plant interactions with contaminants. This investigation demonstrates that dendrochemistry can be used to generate historical scenarios of past contamination of groundwater by chlorinated solvents at a site in Verl, Germany. Increment cores from trees at the Verl site were collected and analyzed by energy-dispersive X-ray fluorescence (EDXRF) line scanning. The EDXRF profiles showed four to six time periods where tree rings had anomalously high concentrations of chlorine (Cl) as an indicator of potential contamination by chlorinated solvents.

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 European Commission Joint Research Centre [fish oils (cod and mackerel) and mussel tissue].

High Temperature Chemistry of Chlorinated Acenaphthylene. 3C Bay Acetylene Additions and Annealing by Five-Membered Ring Shifts.

PubMed

McIntosh, Grant J; Russell, Douglas K

2015-12-24

Experimental and theoretical results concerning the growth and isomerization of chlorinated acenaphthylene, C12H8, during the pyrolysis of chlorohydrocarbons are presented here. A fullerene subunit, C12H8, is a useful system to investigate regarding C60 formation. However, direct experimental observation of isomerization and annealing processes in particular are difficult to confirm due to the high symmetry of the parent molecule. Chlorination lowers the symmetry, essentially labeling carbon atoms, allowing growth and isomerization to be followed directly. Pyrolysis of dichloro- and trichloroethylene, and their copyrolyses with trichlorobenzenes, provides an efficient and general source of chlorinated acenaphthylenes in a range of degrees of chlorination and over a number of unique congeners. Analysis of congener yields as a function of reagents employed, guided by DFT/B3LYP/6-311G(d,p) level calculations, strongly suggests that C2 addition across three-carbon bays in naphthalene is a major driver of growth. Additionally, extremely facile five-membered ring shifts are operative, with chlorine promoting isomerization. Theoretical study of C16H10- and C18H10-based congeners indicate that this is a general phenomenon, and with chlorine also favoring internal cyclopentafused rings in addition to increased isomerization rates, this suggests halogen moieties may be an important feature for efficient fullerene growth.

Long-term persistence of a single Legionella pneumophila strain possessing the mip gene in a municipal shower despite repeated cycles of chlorination.

PubMed

Cooper, I R; White, J; Mahenthiralingam, E; Hanlon, G W

2008-10-01

The ability of Legionella pneumophila to colonise domestic water systems is a primary cause of outbreaks of Legionnaire's disease in humans. World Health Organization guidelines recommend that drinking water is chlorinated to between 0.2 and 1mg/L [Chlorine in drinking-water. Guidelines for drinking-water quality, 2nd edn. Geneva: World Health Organization; 1996], but L. pneumophila is repeatedly isolated from chlorinated water systems, indicating that this treatment is not effective at preventing colonisation. Current UK guidelines recommend a one-off treatment of 20-50mg/L of free chlorine to remove the bacteria. In this study we report on the persistence of L. pneumophila serogroup 1 in a domestic shower system despite repeated cycles of chlorination at 50mg/L for 1h exposure time, over the course of two and a half years. Persisting isolates were subjected to in-vitro phenotypic analyses and polymerase chain reaction analysis for the toxin-encoding mip gene. Random amplified polymorphic DNA typing was also performed to determine whether the isolates recovered on different occasions were the same strain. We found that seven isolates of L. pneumophila recovered over a two-and-a-half year period are the same genetically defined strain, indicating that the bacteria can persist despite repeated cycles of chlorination after each successive isolation.

Modeling and optimization of trihalomethanes formation potential of surface water (a drinking water source) using Box-Behnken design.

PubMed

Singh, Kunwar P; Rai, Premanjali; Pandey, Priyanka; Sinha, Sarita

2012-01-01

The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control. A five-factor Box-Behnken experimental design combined with response surface and optimization modeling was used for predicting the THMs levels in chlorinated water. The adequacy of the selected model and statistical significance of the regression coefficients, independent variables, and their interactions were tested by the analysis of variance and t test statistics. The THMs levels predicted by the model were very close to the experimental values (R(2) = 0.95). Optimization modeling predicted maximum (192 μg/l) TMHs formation (highest risk) level in water during chlorination was very close to the experimental value (186.8 ± 1.72 μg/l) determined in laboratory experiments. The pH of water followed by reaction time and temperature were the most significant factors that affect the THMs formation during chlorination. The developed model can be used to determine the optimum characteristics of raw water and chlorination conditions for maintaining the THMs levels within the safe limit.

Validation Study for Crediting Chlorine in Criticality Analyses for US Spent Nuclear Fuel Disposition

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

Sobes, Vladimir; Scaglione, John M.; Wagner, John C.

2015-01-01

Spent nuclear fuel (SNF) management practices in the United States rely on dry storage systems that include both canister- and cask-based systems. The United States Department of Energy Used Fuel Disposition Campaign is examining the feasibility of direct disposal of dual-purpose (storage and transportation) canisters (DPCs) in a geological repository. One of the major technical challenges for direct disposal is the ability to demonstrate the subcriticality of the DPCs loaded with SNF for the repository performance period (e.g., 10,000 years or more) as the DPCs may undergo degradation over time. Specifically, groundwater ingress into the DPC (i.e., flooding) could allowmore » the system to achieve criticality in scenarios where the neutron absorber plates in the DPC basket have degraded. However, as was shown by Banerjee et al., some aqueous species in the groundwater provide noticeable reactivity reduction for these systems. For certain amounts of particular aqueous species (e.g., chlorine, lithium) in the groundwater, subcriticality can be demonstrated even for DPCs with complete degradation of the neutron absorber plates or a degraded fuel basket configuration. It has been demonstrated that chlorine is the leading impurity, as indicated by significant neutron absorption in the water that is available in reasonable quantities for the deep geological repository media under consideration. This paper presents the results of an investigation of the available integral experiments worldwide that could be used to validate DPC disposal criticality evaluations, including credit for chlorine. Due to the small number of applicable critical configurations, validation through traditional trending analysis was not possible. The bias in the eigenvalue of the application systems due only to the chlorine was calculated using TSURFER analysis and found to be on the order of 100 percent mille (1 pcm = 10 -5 k eff). This study investigated the design of a series of critical configurations with varying amounts of chlorine to address validation gaps. Such integral experiments would support the crediting of the chlorine neutron-absorption properties in groundwater and the demonstration of subcriticality for DPCs in deep geologic repositories with sufficient chlorine availability.« less

Chlorine dioxide water disinfection: a prospective epidemiology study

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

Michael, G.E.; Miday, R.K.; Bercz, J.P.

An epidemiologic study of 198 persons exposed for 3 months to drinking water disinfected with chlorine dioxide was conducted in a rural village. A control population of 118 nonexposed persons was also studied. Pre-exposure hematologic and serum chemical parameters were compared with test results after 115 days of exposure. Chlorite ion levels in the water averaged approximately 5 ppM during the study period. Statistical analysis (ANOVA) of the data failed to identify any significant exposure-related effects. This study suggests that future evaluations of chlorine dioxide disinfection should be directed toward populations with potentially increased sensitivity to hemolytic agents.

Microbial community response to chlorine conversion in a chloraminated drinking water distribution system.

PubMed

Wang, Hong; Proctor, Caitlin R; Edwards, Marc A; Pryor, Marsha; Santo Domingo, Jorge W; Ryu, Hodon; Camper, Anne K; Olson, Andrew; Pruden, Amy

2014-09-16

Temporary conversion to chlorine (i.e., "chlorine burn") is a common approach to controlling nitrification in chloraminated drinking water distribution systems, yet its effectiveness and mode(s) of action are not fully understood. This study characterized occurrence of nitrifying populations before, during and after a chlorine burn at 46 sites in a chloraminated distribution system with varying pipe materials and levels of observed nitrification. Quantitative polymerase chain reaction analysis of gene markers present in nitrifying populations indicated higher frequency of detection of ammonia oxidizing bacteria (AOB) (72% of samples) relative to ammonia oxidizing archaea (AOA) (28% of samples). Nitrospira nitrite oxidizing bacteria (NOB) were detected at 45% of samples, while presence of Nitrobacter NOB could not be confirmed at any of the samples. During the chlorine burn, the numbers of AOA, AOB, and Nitrospira greatly reduced (i.e., 0.8-2.4 log). However, rapid and continued regrowth of AOB and Nitrospira were observed along with nitrite production in the bulk water within four months after the chlorine burn, and nitrification outbreaks appeared to worsen 6-12 months later, even after adopting a twice annual burn program. Although high throughput sequencing of 16S rRNA genes revealed a distinct community shift and higher diversity index during the chlorine burn, it steadily returned towards a condition more similar to pre-burn than burn stage. Significant factors associated with nitrifier and microbial community composition included water age and sampling location type, but not pipe material. Overall, these results indicate that there is limited long-term effect of chlorine burns on nitrifying populations and the broader microbial community.

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.;

Dichloromethane biodegradation in multi-contaminated groundwater: Insights from biomolecular and compound-specific isotope analyses.

PubMed

Hermon, L; Denonfoux, J; Hellal, J; Joulian, C; Ferreira, S; Vuilleumier, S; Imfeld, G

2018-05-31

Dichloromethane (DCM) is a widespread and toxic industrial solvent which often co-occurs with chlorinated ethenes at polluted sites. Biodegradation of DCM occurs under both oxic and anoxic conditions in soils and aquifers. Here we investigated in situ and ex situ biodegradation of DCM in groundwater sampled from the industrial site of Themeroil (France), where DCM occurs as a major co-contaminant of chloroethenes. Carbon isotopic fractionation (ε C ) for DCM ranging from -46 to -22‰ were obtained under oxic or denitrifying conditions, in mineral medium or contaminated groundwater, and for laboratory cultures of Hyphomicrobium sp. strain GJ21 and two new DCM-degrading strains isolated from the contaminated groundwater. The extent of DCM biodegradation (B%) in the aquifer, as evaluated by compound-specific isotope analysis (δ 13 C), ranged from 1% to 85% applying DCM-specific ε C derived from reference strains and those determined in this study. Laboratory groundwater microcosms under oxic conditions showed DCM biodegradation rates of up to 0.1 mM·day -1 , with concomitant chloride release. Dehalogenase genes dcmA and dhlA involved in DCM biodegradation ranged from below 4 × 10 2 (boundary) to 1 × 10 7 (source zone) copies L -1 across the contamination plume. High-throughput sequencing on the 16S rrnA gene in groundwater samples showed that both contaminant level and terminal electron acceptor processes (TEAPs) influenced the distribution of genus-level taxa associated with DCM biodegradation. Taken together, our results demonstrate the potential of DCM biodegradation in multi-contaminated groundwater. This integrative approach may be applied to contaminated aquifers in the future, in order to identify microbial taxa and pathways associated with DCM biodegradation in relation to redox conditions and co-contamination levels. Copyright © 2018 Elsevier Ltd. All rights reserved.

Assessing TNT and DNT groundwater contamination by compound-specific isotope analysis and 3H-3He groundwater dating: a case study in Portugal.

PubMed

Amaral, Helena I F; Fernandes, Judite; Berg, Michael; Schwarzenbach, René P; Kipfer, Rolf

2009-10-01

Trinitrotoluene (TNT) and dinitrotoluene (DNT) originating from 50 years of explosives production have heavily contaminated two stacked aquifers in the vicinity of Lisboa, Portugal. To assess if these poly-nitroaromatic compounds (P-NACs) are being degraded in the subsurface, tracer-based groundwater dating techniques combined with compound-specific isotope analyses (CSIA) were applied. The groundwater residence times were distinctly different in the two aerobic aquifers, as determined by the tritium ((3)H)-(3)He method. In the contaminated zones, the upper aquifer exhibited groundwater ages of 25 years, whereas the lower (presumably confined) aquifer contained hardly any tritium which indicates water ages >55 years. P-NACs-containing waste waters are known to have leaked into the upper, unconfined aquifer. However, P-NACs were present in both aquifers in high concentrations (up to 33000 microg L(-1) TNT), which implies a hydraulic connection, although tritium concentrations and chemical data suggest two separated aquifers. Based on the (3)H-(3)He groundwater dating and the presence of very high P-NAC concentrations, the contamination of the lower aquifer must have happened during the early stage of the explosive production, i.e. >50 years ago. Despite this 'old' contamination, TNT and DNT have not been transformed until to date as is demonstrated by the negligible changes in their carbon isotopic signatures (delta(13)C). Thus, P-NACs are very recalcitrant to degradation at the investigated site. If the aquifers remain aerobic, TNT and DNT are expected to persist in the subsurface for many decades to centuries. The presented approach of assessing time scales of natural attenuation at the field scale by the combination of CSIA and (3)H-(3)He water dating has the potential to be applied to any other groundwater contaminants, such as chlorinated hydrocarbons, gasoline components, heterocyclic carbenes, or polyaromatic hydrocarbons.

Cold plasma processing of local planetary ores for oxygen and metallurgically important metals

NASA Technical Reports Server (NTRS)

Lynch, D. C.; Bullard, D.; Ortega, R.

1990-01-01

The utilization of a cold plasma in chlorination processing is described. Essential equipment and instruments were received, the experimental apparatus assembled and tested, and preliminary experiments conducted. The results of the latter lend support to the original hypothesis: a cold plasma can both significantly enhance and bias chemical reactions. In two separate experiments, a cold plasma was used to reduce TiCl4 vapor and chlorinate ilmenite. The latter, reacted in an argon-chlorine plasma, yielded oxygen. The former experiment reveals that chlorine can be recovered as HCl vapor from metal chlorides in a hydrogen plasma. Furthermore, the success of the hydrogen experiments has lead to an analysis of the feasibility of direct hydrogen reduction of metal oxides in a cold plasma. That process would produce water vapor and numerous metal by-products.

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

PubMed

Groom, Carl A; Hawari, Jalal

2007-02-01

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

Regional contamination versus regional dietary differences: Understanding geographic variation in brominated and chlorinated contaminant levels in polar bears

USGS Publications Warehouse

McKinney, M.A.; Letcher, R.J.; Aars, Jon; Born, E.W.; Branigan, M.; Dietz, R.; Evans, T.J.; Gabrielsen, G.W.; Muir, D.C.G.; Peacock, E.; Sonne, C.

2011-01-01

The relative contribution of regional contamination versus dietary differences to geographic variation in polar bear (Ursus maritimus) contaminant levels is unknown. Dietary variation between Alaska Canada, East Greenland, and Svalbard subpopulations was assessed by muscle nitrogen and carbon stable isotope (?? 15N, ?? 13C) and adipose fatty acid (FA) signatures relative to their main prey (ringed seals). Western and southern Hudson Bay signatures were characterized by depleted ?? 15N and ??13C, lower proportions of C20 and C22 monounsaturated FAs and higher proportions of C18 and longer chain polyunsaturated FAs. East Greenland and Svalbard signatures were reversed relative to Hudson Bay. Alaskan ?? 2011 American Chemical Society.

Monte Carlo analysis of uncertainty propagation in a stratospheric model. 2: Uncertainties due to reaction rates

NASA Technical Reports Server (NTRS)

Stolarski, R. S.; Butler, D. M.; Rundel, R. D.

1977-01-01

A concise stratospheric model was used in a Monte-Carlo analysis of the propagation of reaction rate uncertainties through the calculation of an ozone perturbation due to the addition of chlorine. Two thousand Monte-Carlo cases were run with 55 reaction rates being varied. Excellent convergence was obtained in the output distributions because the model is sensitive to the uncertainties in only about 10 reactions. For a 1 ppby chlorine perturbation added to a 1.5 ppby chlorine background, the resultant 1 sigma uncertainty on the ozone perturbation is a factor of 1.69 on the high side and 1.80 on the low side. The corresponding 2 sigma factors are 2.86 and 3.23. Results are also given for the uncertainties, due to reaction rates, in the ambient concentrations of stratospheric species.

Chlorine-36 and 14C chronology support a limited last glacial maximum across central Chukotka, northeastern Siberia, and no Beringian ice sheet

USGS Publications Warehouse

Brigham-Grette, J.; Gualtieri, L.M.; Glushkova, O.Y.; Hamilton, T.D.; Mostoller, D.; Kotov, A.

2003-01-01

The Pekulney Mountains and adjacent Tanyurer River valley are key regions for examining the nature of glaciation across much of northeast Russia. Twelve new cosmogenic isotope ages and 14 new radiocarbon ages in concert with morphometric analyses and terrace stratigraphy constrain the timing of glaciation in this region of central Chukotka. The Sartan Glaciation (Last Glacial Maximum) was limited in extent in the Pekulney Mountains and dates to ???20,000 yr ago. Cosmogenic isotope ages > 30,000 yr as well as non-finite radiocarbon ages imply an estimated age no younger than the Zyryan Glaciation (early Wisconsinan) for large sets of moraines found in the central Tanyurer Valley. Slope angles on these loess-mantled ridges are less than a few degrees and crest widths are an order of magnitude greater than those found on the younger Sartan moraines. The most extensive moraines in the lower Tanyurer Valley are most subdued implying an even older, probable middle Pleistocene age. This research provides direct field evidence against Grosswald's Beringian ice-sheet hypothesis. ?? 2003 Elsevier Science (USA). All rights reserved.

Degradation of Perchloroethene by zero-valent iron evaluated by carbon isotope fractionation

NASA Astrophysics Data System (ADS)

Leitner, Simon; Watzinger, Andrea; Reichenauer, Thomas G.

2014-05-01

Perchloroethene (PCE) is a widely spread groundwater contaminant in formally used industrial sites. Zero valent iron (ZVI) is used for in situ chemical reduction (ISCR) of PCE contaminants in the groundwater. A key factor in the application of in situ remediation technologies is a proper monitoring of contaminant reduction. The measurement of the stable isotope ratio is a promising method that is already used for quantifying microbial degradation of chlorinated contaminants. The carbon isotope ratio of PCE, measured by - isotope ratio mass spectrometry coupled to a gas chromatograph via a combustion interface (GC-C-IRMS), increases during degradation of PCE and can be directly related to the degree of degradation. It can be used to directly quantify chemical degradation and thus serves as a useful monitoring tool for groundwater remediation. An experiment to determine the carbon isotopic fractionation factor was performed as a lab experiment using Nanofer Star (NANOIRON). Two different PCE concentrations (c1: 220mgL-1, c2: 110mgL-1) mixed with 0.5 g of ZVI were sealed under deoxygenated conditions in 250 ml glas bottles locked with mininert caps. The bottles were incubated on a shaker for 865 h. Samples were taken weekly to measure the change in the carbon isotopic ratio of PCE as well as its concentration. Results showed a strong increase in the carbon isotope ratio (δ-value) of PCE (start: -27 o end: -4 ), which indicates a significant dechlorination process of PCE. Beside PCE also one degradation product (Trichloroethylene - TCE) was measured. TCE was further dechlorinated as indicated by the δ-value change of TCE from -26 o to -4 oȦn unexpected intermediate value of -45 o for TCE was observed in the experiment. This fluctuation could be induced by the time depending concentration due to degradation and conversation processes. Furthermore, it seems that the progress of the δ-value is affected by the starting concentration of PCE (δ-value of c1 < c2) as there is a higher ratio of PCE to ZVI.

From Gene Expression to the Earth System: Isotopic Constraints on Nitrogen Cycling Across Scales

NASA Astrophysics Data System (ADS)

Houlton, B. Z.

2015-12-01

A central motivation of the Biogeosciences is to understand the cycling of biologically essential elements over multiple scales of space and time. This charge is vital to basic knowledge of Earth system functioning. It is also relevant to many of the global challenges we face, such as climate change, biodiversity conservation, and the multifaceted role of global fertilizer use in maximizing human health and well-being. Nitrogen is connected to all of these; yet it has been one of the more vexing elements to quantitatively appraise across systems and scales. Here I discuss how research in my group has been exploring the use of natural nitrogen isotope abundance (15N/14N) as a biogeochemical tracer - from the level of gene expression to nitrogen's role in global climate change. First, I present evidence for a positive correlation between the bacterial genes that encode for gaseous nitrogen production (i.e., nirS) and the 15N/14N of soil extractable nitrate pools across an array of terrestrial ecosystems. Second, I demonstrate how these local-scale results fit with our work on ecosystem-scale nitrogen isotope budgets, where we quantify a uniformly small isotope effect (i.e., < 1 per mil) of nitrogen leaching losses from tropical rainforest to highly disturbed arid sites. Third, I present results from our global isotope model, which is based on results from our field investigations, providing a new nitrogen "benchmarking" scheme for global computational models and climate change forecasts. Finally, I move to a new research frontier where we have been developing a technique to measure the nitrogen isotope composition of ancient terrestrial plant compounds (i.e., chlorins) buried in the soil. This research aims to address the response of the nitrogen cycle to glacial-interglacial transitions over millennia, which is beyond the window of experimental testing. Together, this research highlights the utility of nitrogen isotope composition in addressing the myriad scales of this element's interaction with Earth's environment, and supports the working hypothesis that bacterial denitrification is the major fractionating pathway of nitrogen loss from the terrestrial biosphere, much like the global ocean.

Bacterial communities in the collection and chlorinated distribution sections of a drinking water system in Budapest, Hungary.

PubMed

Homonnay, Zalán G; Török, György; Makk, Judit; Brumbauer, Anikó; Major, Eva; Márialigeti, Károly; Tóth, Erika

2014-07-01

Bacterial communities of a bank-filtered drinking water system were investigated by aerobic cultivation and clone library analysis. Moreover, bacterial communities were compared using sequence-aided terminal restriction fragment length polymorphism (T-RFLP) fingerprinting at ten characteristic points located at both the collecting and the distributing part of the water supply system. Chemical characteristics of the samples were similar, except for the presence of chlorine residuals in the distribution system and increased total iron concentration in two of the samples. Assimilable organic carbon (AOC) concentration increased within the collection system, it was reduced by chlorination and it increased again in the distribution system. Neither fecal indicators nor pathogens were detected by standard cultivation techniques. Chlorination reduced bacterial diversity and heterotrophic plate counts. Community structures were found to be significantly different before and after chlorination: the diverse communities in wells and the collection system were dominated by chemolithotrophic (e.g., Gallionella and Nitrospira) and oligocarbophilic-heterotrophic bacteria (e.g., Sphingomonas, Sphingopyxis, and Bradyrhizobium). After chlorination in the distribution system, the most characteristic bacterium was related to the facultative methylotrophic Methylocella spp. Communities changed within the distribution system too, Mycobacterium spp. or Sphingopyxis spp. became predominant in certain samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chlorinated Phospholipids and Fatty Acids: (Patho)physiological Relevance, Potential Toxicity, and Analysis of Lipid Chlorohydrins

PubMed Central

2016-01-01

Chlorinated phospholipids are formed by the reaction of hypochlorous acid (HOCl), generated by the enzyme myeloperoxidase under inflammatory conditions, and the unsaturated fatty acyl residues or the head group. In the first case the generated chlorohydrins are both proinflammatory and cytotoxic, thus having a significant impact on the structures of biomembranes. The latter case leads to chloramines, the properties of which are by far less well understood. Since HOCl is also widely used as a disinfecting and antibacterial agent in medicinal, industrial, and domestic applications, it may represent an additional source of danger in the case of abuse or mishandling. This review discusses the reaction behavior of in vivo generated HOCl and biomolecules like DNA, proteins, and carbohydrates but will focus on phospholipids. Not only the beneficial and pathological (toxic) effects of chlorinated lipids but also the importance of these chlorinated species is discussed. Some selected cleavage products of (chlorinated) phospholipids and plasmalogens such as lysophospholipids, (chlorinated) free fatty acids and α-chloro fatty aldehydes, which are all well known to massively contribute to inflammatory diseases associated with oxidative stress, will be also discussed. Finally, common analytical methods to study these compounds will be reviewed with focus on mass spectrometric techniques. PMID:28090245

Heterogeneity of Chlorinity distribution within gas hydrate reservoir at Daini-Atsumi knoll, based on logging data analysis

NASA Astrophysics Data System (ADS)

Suzuki, K.; Takayama, T.; Fujii, T.

2016-12-01

We will present possible heterogeneity of pore-water salinity within methane hydrate reservoir of Daini-Atsumi knoll, on the basis of Logging-while-drilling (LWD) data and several kind of wire-line logging dataset. The LWD and the wire-line logging had been carried out during 2012 to 2013, before/after the first offshore gas-production-test from marine-methane-hydrate reservoir at Daini-Atsumi Knoll along the northeast Nankai trough. Several data from the logging, especially data from the reservoir saturation tool; RST, gave us some possible interpretation for heterogeneity distribution of chlorinity within the methane-hydrate reservoir. The computed pore-water chlorinity could be interpreted as condense of chlorinity at gas-hydrate formation. This year, we drilled several number of wells at Daini-Atsumi Knoll, again for next gas production test, and we have also found out possibility of chlorinity heterogeneity from LWD data of Neutron-capture cross section; i.e. Sigma. The distribution of chlorinity within gas-hydrate reservoir may help our understanding of gas hydrate-crystallization and/or dissociation in turbidite reservoir at Daini-Atsumi Knoll. This research is conducted as a part of the Research Consortium for Methane Hydrate Resource in Japan (MH21 Research consortium).

Synthesis of magnesium aluminate spinel by periclase and alumina chlorination

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

Orosco, Pablo, E-mail: porosco@unsl.edu.ar; Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis Chacabuco y Pedernera, San Luis; Barbosa, Lucía

2014-11-15

Highlights: • Use of chlorination for the synthesis of magnesium aluminate spinel. • The reagents used were alumina, periclase and chlorine. • Isothermal and non-isothermal assays were performed in air and Cl{sub 2}–N{sub 2} flows. • The chlorination produced magnesium aluminate spinel at 700 °C. • Selectivity of the chlorination reaction to obtain spinel is very high. - Abstract: A pyrometallurgical route for the synthesis of magnesium aluminate spinel by thermal treatment of a mechanical mixture containing 29 wt% MgO (periclase) and 71 wt% Al{sub 2}O{sub 3} (alumina) in chlorine atmosphere was developed and the results were compared with thosemore » obtained by calcining the same mixture of oxides in air atmosphere. Isothermal and non-isothermal assays were performed in an experimental piece of equipment adapted to work in corrosive atmospheres. Both reagents and products were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF). Thermal treatment in Cl{sub 2} atmosphere of the MgO–Al{sub 2}O{sub 3} mixture produces magnesium aluminate spinel at 700 °C, while in air, magnesium spinel is generated at 930 °C. The synthesis reaction of magnesium aluminate spinel was complete at 800 °C.« less

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. © 2011 Society for Risk Analysis.

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Different profiles of anthropogenic and naturally produced organohalogen compounds in serum from residents living near a coastal area and e-waste recycling workers in India.

PubMed

Eguchi, Akifumi; Nomiyama, Kei; Devanathan, Gnanasekaran; Subramanian, Annamalai; Bulbule, Kesav A; Parthasarathy, Peethambaram; Takahashi, Shin; Tanabe, Shinsuke

2012-10-15

We determined the contamination status and accumulation profiles of polychlorinated biphenyls (PCBs), hydroxylated PCB congeners (OH-PCBs), polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs), methoxylated PBDEs (MeO-PBDEs), and bromophenols (BPhs) in serum from e-waste recycling workers and residents near a coastal area in India. Residue levels of penta- to octa-chlorinated PCBs, penta- to octa-chlorinated OH-PCBs, 6MeO-BDE47, 6OH-BDE47, and 2,4,6-tri-BPh in serum from residents living near the coastal area were significantly higher than those in serum from e-waste recycling workers. Residue levels of tri- to tetra-chlorinated PCBs, tri- to tetra-chlorinated OH-PCBs, PBDEs, octa-brominated OH-PBDEs, and tetra-BPhs in serum from e-waste recycling workers were higher than those in serum from residents living near the coastal area. Principal component analysis revealed that residents living near the coastal area and e-waste recycling workers had different serum profiles of chlorinated and brominated compounds. Copyright © 2012 Elsevier Ltd. All rights reserved.

Type of disinfectant in drinking water and patterns of mortality in Massachusetts.

PubMed Central

Zierler, S; Danley, R A; Feingold, L

1986-01-01

Chlorination has been the major strategy for disinfection of drinking water in the United States. Concern about the potential health effects of the reaction by-products of chlorine has prompted use of alternative strategies. One such method is chloramination, a treatment process that does not appear to have carcinogenic by-products, but may have less potent biocidal activity than chlorination. We examined the patterns of mortality of residents in Massachusetts who died between 1969 and 1983 and lived in communities using drinking water that was disinfected either by chlorine or chloramine. Comparison of type of disinfectant among 51,645 cases of deaths due to selected cancer sites and 214,988 controls who died from cardiovascular, cerebrovascular, or pulmonary disease, or from lymphatic cancer showed small variation in the patterns of mortality. Bladder cancer was moderately associated with residence at death in a chlorinated community (mortality odds ratio = 1.7, 95% confidence interval = 1.3-2.2) in a logistic regression analysis using controls who died from lymphatic cancer. A slight excess of deaths from pneumonia and influenza was observed in communities whose residents drank chloraminated water compared to residents from chlorinated communities, as well as to all Massachusetts residents (standardized mortality ratio = 118, 95% confidence interval = 116-120 for chloraminated communities, and standardized mortality ratio = 98, 95% confidence interval = 95-100 for chlorinated communities). These results are intended to be preliminary and crude descriptions of the relationship under study.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3816730

Evaluation of the fate and transport of chlorinated ethenes in a complex groundwater system discharging to a stream in Wonju, Korea

NASA Astrophysics Data System (ADS)

Lee, Seong-Sun; Kaown, Dugin; Lee, Kang-Kun

2015-11-01

Chlorinated ethenes such as trichloroethylene (TCE) are common and persistent groundwater contaminants. If contaminated groundwater discharges to a stream, then stream water pollution near the contamination site also becomes a problem. In this respect, the fate and transport of chlorinated ethenes around a stream in an industrial complex were evaluated using the concentration of each component, and hydrogeochemical, microbial, and compound-specific carbon isotope data. Temporal and spatial monitoring reveal that a TCE plume originating from main and local source zones continues to be discharged to a stream. Groundwater geochemical data indicate that aerobic conditions prevail in the upgradient area of the studied aquifer, whereas conditions become anaerobic in the downgradient. The TCE molar fraction is high at the main and local source zones, ranging from 87.4 to 99.2% of the total volatile organic compounds (VOCs). An increasing trend in the molar fraction of cis-1, 2-Dichloroethene (cis-DCE) and vinyl chloride (VC) was observed in the downgradient zone of the study area. The enriched δ13C values of TCE and depleted values of cis-DCE in the stream zone, compared to those of the source zone, also suggest biodegradation of VOCs. Microbial community structures in monitoring wells adjacent to the stream zone in the downgradient area were analyzed using 16S rRNA gene-based pyrosequencing to identify the microorganisms responsible for biodegradation. This was attributed to the high relative abundance of dechlorinating bacteria in monitoring wells under anaerobic conditions farthest from the stream in the downgradient area. The multilateral approaches adopted in this study, combining hydrogeochemical and biomolecular methods with compound-specific analyses, indicate that contaminants around the stream were naturally attenuated by active anaerobic biotransformation processes.

Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production.

PubMed

Sinkkonen, Seija; Lahtiperä, Mirja; Vattulainen, Antero; Takhistov, Viatcheslav V; Viktorovskii, Igor V; Utsal, Viktor A; Paasivirta, Jaakko

2003-07-01

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000ng g(-1) in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5ng g(-1) indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450ng g(-1)) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5ng g(-1)). Fraction of the most polar compounds (from reversed toluene elution of carbon column ("dioxin fraction") contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205ng g(-1)) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388ng g(-1). In addition, 12 novel brominated and chlorinated compounds were found as abundant (8-441ng g(-1) in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.

Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Ren, Shuoyi; Yu, Jianwei; Ji, Feng; Luo, Wenbin; Yang, Min

2012-10-15

Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH(4) against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water. Copyright © 2012 Elsevier Ltd. All rights reserved.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of chlorinated pesticides in aquatic tissue by capillary-column gas chromatography with electron-capture detection

USGS Publications Warehouse

Leiker, Thomas J.; Madsen, J.E.; Deacon, J.R.; Foreman, W.T.

1995-01-01

A method for the determination of chlorinated organic compounds in aquatic tissue by dual capillary-column gas chromatography with electron-capture detection is described. Whole-body-fish or corbicula tissue is homogenized, Soxhlet extracted, lipid removed by gel permeation chromatography, and fractionated using alumina/silica adsorption chromatography. The extracts are analyzed by dissimilar capillary-column gas chromatography with electron-capture detection. The method reporting limits are 5 micrograms per kilogram (μg/kg) for chlorinated compounds, 50 μg/kg for polychlorinated biphenyls, and 200 μg/kg for toxaphene.

Trace analysis of trimethoprim and sulfonamide, macrolide, quinolone, and tetracycline antibiotics in chlorinated drinking water using liquid chromatography electrospray tandem mass spectrometry

USGS Publications Warehouse

Ye, Z.; Weinberg, H.S.; Meyer, M.T.

2007-01-01

A multirun analytical method has been developed and validated for trace determination of 24 antibiotics including 7 sulfonamides, 3 macrolides, 7 quinolones, 6 tetracyclines, and trimethoprim in chlorine-disinfected drinking water using a single solid-phase extraction method coupled to liquid chromatography with positive electrospray tandem mass spectrometry detection. The analytes were extracted by a hydrophilic-lipophilic balanced resin and eluted with acidified methanol (0.1% formic acid), resulting in analyte recoveries generally above 90%. The limits of quantitation were mostly below 10 ng/L in drinking water. Since the concentrated sample matrix typically caused ion suppression during electrospray ionization, the method of standard addition was used for quantitation. Chlorine residuals in drinking water can react with some antibiotics, but ascorbic acid was found to be an effective chlorine quenching agent without affecting the analysis and stability of the antibiotics in water. A preliminary occurrence study using this method revealed the presence of some antibiotics in drinking waters, including sulfamethoxazole (3.0-3.4 ng/L), macrolides (1.4-4.9 ng/L), and quinolones (1.2-4.0 ng/L). ?? 2007 American Chemical Society.

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.

Depletion of chlorine into HCl ice in a protostellar core. The CHESS spectral survey of OMC-2 FIR 4

NASA Astrophysics Data System (ADS)

Kama, M.; Caux, E.; López-Sepulcre, A.; Wakelam, V.; Dominik, C.; Ceccarelli, C.; Lanza, M.; Lique, F.; Ochsendorf, B. B.; Lis, D. C.; Caballero, R. N.; Tielens, A. G. G. M.

2015-02-01

Context. The freezeout of gas-phase species onto cold dust grains can drastically alter the chemistry and the heating-cooling balance of protostellar material. In contrast to well-known species such as carbon monoxide (CO), the freezeout of various carriers of elements with abundances <10-5 has not yet been well studied. Aims: Our aim here is to study the depletion of chlorine in the protostellar core, OMC-2 FIR 4. Methods: We observed transitions of HCl and H2Cl+ towards OMC-2 FIR 4 using the Herschel Space Observatory and Caltech Submillimeter Observatory facilities. Our analysis makes use of state of the art chlorine gas-grain chemical models and newly calculated HCl-H2 hyperfine collisional excitation rate coefficients. Results: A narrow emission component in the HCl lines traces the extended envelope, and a broad one traces a more compact central region. The gas-phase HCl abundance in FIR 4 is 9 × 10-11, a factor of only 10-3 that of volatile elemental chlorine. The H2Cl+ lines are detected in absorption and trace a tenuous foreground cloud, where we find no depletion of volatile chlorine. Conclusions: Gas-phase HCl is the tip of the chlorine iceberg in protostellar cores. Using a gas-grain chemical model, we show that the hydrogenation of atomic chlorine on grain surfaces in the dark cloud stage sequesters at least 90% of the volatile chlorine into HCl ice, where it remains in the protostellar stage. About 10% of chlorine is in gaseous atomic form. Gas-phase HCl is a minor, but diagnostically key reservoir, with an abundance of ≲10-10 in most of the protostellar core. We find the [35Cl]/[37Cl] ratio in OMC-2 FIR 4 to be 3.2 ± 0.1, consistent with the solar system value. Appendices are available in electronic form at http://www.aanda.org

Degradation kinetics of organic chloramines and formation of disinfection by-products during chlorination of creatinine.

PubMed

Zhang, Tianyang; Xu, Bin; Wang, Anqi; Cui, Changzheng

2018-03-01

Organic chloramines can interfere with the measurement of effective combined chlorine in chlorinated water and are potential intermediate products of highly toxic disinfection by-products (DBPs). In order to know more about the degradation and transformation of organic chloramines, a typical organic chloramine precursor creatinine was selected for investigation and a corresponding individual organic chloramine chlorocreatinine was prepared in this study. The preparation condition of chlorocreatinine by chlorination was established as chlorine/creatinine = 1 M/M, reaction time = 2 h and pH = 7.0. Then the degradation kinetics of chlorocreatinine during further chlorination was studied, and a second-order rate constant of 1.16 (±0.14) M -1 s -1 was obtained at pH 7.0. Solution pH significantly influenced the degradation rate, and the elementary rate constants of chlorocreatinine with HOCl+H + , HOCl, OCl - and chlorocreatinine - with OCl - were calculated as 2.43 (±1.55) × 10 4  M -2  s -1 , 1.05 (±0.09) M -1 s -1 , 2.86 (±0.30) M -1 s -1 and 3.09 (±0.24) M -1 s -1 , respectively. Besides, it was found that chlorocreatinine could be further converted into several C-DBPs (chloroform and trichloroacetone) and N-DBPs (dichloroacetonitrile (DCAN) and trichloronitromethane (TCNM)) during chlorination. The total yield of DBPs increased obviously with increasing pH, especially for TCNM. In addition, the presence of humic acid in creatinine solution could increase the formation of DCAN obviously during chlorination. Based on the UPLC-Q-TOF-MS analysis, the conversion pathways of chlorocreatinine were proposed. Several kinds of intermediate products were also identified as organic chloramines and some of them could even exist stably during the further chlorination. Copyright © 2017 Elsevier Ltd. All rights reserved.

Urea degradation by electrochemically generated reactive chlorine species: products and reaction pathways.

PubMed

Cho, Kangwoo; Hoffmann, Michael R

2014-10-07

This study investigated the transformation of urea by electrochemically generated reactive chlorine species (RCS). Solutions of urea with chloride ions were electrolyzed using a bismuth doped TiO2 (BiOx/TiO2) anode coupled with a stainless steel cathode at applied anodic potentials (Ea) of either +2.2 V or +3.0 V versus the normal hydrogen electrode. In NaCl solution, the current efficiency of RCS generation was near 30% at both potentials. In divided cell experiments, the pseudo-first-order rate of total nitrogen decay was an order of magnitude higher at Ea of +3.0 V than at +2.2 V, presumably because dichlorine radical (Cl2(-)·) ions facilitate the urea transformation primary driven by free chlorine. Quadrupole mass spectrometer analysis of the reactor headspace revealed that N2 and CO2 are the primary gaseous products of the oxidation of urea, whose urea-N was completely transformed into N2 (91%) and NO3(-) (9%). The higher reaction selectivity with respect to N2 production can be ascribed to a low operational ratio of free available chlorine to N. The mass-balance analysis recovered urea-C as CO2 at 77%, while CO generation most likely accounts for the residual carbon. In light of these results, we propose a reaction mechanism involving chloramines and chloramides as reaction intermediates, where the initial chlorination is the rate-determining step in the overall sequence of reactions.

Temporal variations in natural attenuation of chlorinated aliphatic hydrocarbons in eutrophic river sediments impacted by a contaminated groundwater plume.

PubMed

Hamonts, Kelly; Kuhn, Thomas; Vos, Johan; Maesen, Miranda; Kalka, Harald; Smidt, Hauke; Springael, Dirk; Meckenstock, Rainer U; Dejonghe, Winnie

2012-04-15

Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater baseflow. Biotransformation, sorption and dilution of CAHs in the impacted river sediments have been reported to reduce discharge, but the effect of temporal variations in environmental conditions on the occurrence and extent of those processes in river sediments is largely unknown. We monitored the reduction of CAH discharge into the Zenne River during a 21-month period. Despite a relatively stable influx of CAHs from the groundwater, the total reduction in CAH discharge from 120 to 20 cm depth in the river sediments, on average 74 ± 21%, showed moderate to large temporal variations, depending on the riverbed location. High organic carbon and anaerobic conditions in the river sediments allowed microbial reductive dechlorination of both chlorinated ethenes and chlorinated ethanes. δ(13)C values of the CAHs showed that this biotransformation was remarkably stable over time, despite fluctuating pore water temperatures. Daughter products of the CAHs, however, were not detected in stoichiometric amounts and suggested the co-occurrence of a physical process reducing the concentrations of CAHs in the riverbed. This process was the main process causing temporal variations in natural attenuation of the CAHs and was most likely dilution by surface water-mixing. However, higher spatial resolution monitoring of flow transients in the riverbed is required to prove dilution contributions due to dynamic surface water-groundwater flow exchanges. δ(13)C values and a site-specific isotope enrichment factor for reductive dechlorination of the main groundwater pollutant vinyl chloride (VC) allowed assessment of changes over time in the extent of both biotransformation and dilution of VC for different scenarios in which those processes either occurred consecutively or simultaneously between 120 and 20 cm depth in the riverbed. The extent of reductive dechlorination of VC ranged from 27 to 89% and differed spatially but was remarkably stable over time, whereas the extent of VC reduction by dilution ranged from 6 to 94%, showed large temporal variations, and was often the main process contributing to the reduction of VC discharge into the river. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of receiving-water quality and wastewater treatment on injury, survival, and regrowth of fecal-indicator bacteria and implications for assessment of recreational water quality

USGS Publications Warehouse

Francy, D.S.; Hart, T.L.; Virosteck, C.M.

1996-01-01

Bacterial injury, survival, and regrowth were investigated by use of replicate flow-through incubation chambers placed in the Cuyahoga River or Lake Erie in the greater Cleveland metropolitan area during seven 4-day field studies. The chambers contained wastewater or combined-sewer-overflow (CSO) effluents treated three ways-unchlorinated, chlorinated, and dechlorinated. At timestep intervals, the chamber contents were analyzed for concentrations of injured and healthy fecal coliforms by use of standard selective and enhanced-recovery membrane-filtration methods. Mean percent injuries and survivals were calculated from the fecal-coliform concentration data for each field study. The results of analysis of variance (ANOVA) indicated that treatment affected mean percent injury and survival, whereas site did not. In the warm-weather Lake Erie field study, but not in the warm-weather Cuyahoga River studies, the results of ANOVA indicated that dechlorination enhanced the repair of injuries and regrowth of chlorine-injured fecal coliforms on culture media over chlorination alone. The results of ANOVA on the percent injury from CSO effluent field studies indicated that dechlorination reduced the ability of organisms to recover and regrow on culture media over chlorination alone. However, because of atypical patterns of concentration increases and decreases in some CSO effluent samples, more work needs to be done before the effect of dechlorination and chlorination on reducing fecal-coliform concentrations in CSO effluents can be confirmed. The results of ANOVA on percent survivals found statistically significant differences among the three treatment methods for all but one study. Dechlorination was found to be less effective than chlorination alone in reducing the survival of fecal coliforms in wastewater effluent, but not in CSO effluent. If the concentration of fecal coliforms determined by use of the enhanced-recovery method can be predicted accurately from the concentration found by use of the standard method, then increased monitoring and expense to detect chlorine-injured organisms would be unnecessary. The results of linear regression analysis, however, indicated that the relation between enhanced-recovery and standard-method concentrations was best represented when the data were grouped by treatment. The model generated from linear regression of the unchlorinated data set provided an accurate estimate of enhanced-recovery concentrations from standard-method concentrations, whereas the models generated from the chlorinated and dechlorinated data sets did not. In addition, evaluation of fecal-coliform concentrations found in field studies in terms of Ohio recreational water-quality standards showed that concentrations obtained by standard and enhanced-recovery methods were not comparable. Sample treatment and analysis methods were found to affect the percentage of samples meeting and exceeding Ohio's bathing-water, primary-contact, and secondary-contact standards. Therefore, determining the health risk of swimming in receiving waters was often difficult without information on enhanced-recovery method concentrations and was especially difficult in waters receiving high proportions of chlorinated or dechlorinated effluents.

The study of interrelationship between raw water quality parameters, chlorine demand and the formation of disinfection by-products

NASA Astrophysics Data System (ADS)

Abdullah, Md. Pauzi; Yee, Lim Fang; Ata, Sadia; Abdullah, Abass; Ishak, Basar; Abidin, Khairul Nidzham Zainal

Disinfection is the most crucial process in the treatment of drinking water supply and is the final barrier against bacteriological impurities in drinking water. Chlorine is the primary disinfectant used in the drinking water treatment process throughout Malaysia. However, the occurrence of various disinfection by-products such as trihalomethanes (THM) and haloacetic acids created a major issue on the potential health hazards which may pose adverse health effects in both human and animals. To simulate real water treatment conditions and to represent the conditions inherent in a tropical country, this study was performed at an urbanized water treatment plant with a daily production of about 549,000 m 3 of treated water. The purpose of this work is to examine the relationship between the water quality parameters in the raw water with chlorine demand and the formation of disinfection by-products. This study also investigated the possibility of the statistical model applications for the prediction of chlorine demand and the THM formation. Two models were developed to estimate the chlorine demand and the THM formation. For the statistical evaluation, correlation and simple linear regression analysis were conducted using SPSS. The results of Kolmogorov-Smirnov test for the estimation of goodness-of-fit of the dependent variables of the models to the normal distribution showed that all the dependent variables followed the normal distribution at significance level of 0.05. Good linear correlations were observed between the independent parameters and formation of THM and the chlorine demand. This study also revealed that ammonia and the specific ultraviolet absorbent (SUVA) were the function of chlorine consumption in the treatment process. Chlorine dosage and SUVA increase the yield of THM. Chlorine demand and THM formation was moderately sensitive, but significant to the pH. The level of significance ( α) for the statistical tests and the inclusion of a variable in the model was 0.05. A better understanding of these relationships will help the water utilities or plant operators to minimize the THM formation, providing a healthier and better drinking water quality as well as optimizing the chlorine dosage in the disinfection process.

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

USGS Publications Warehouse

Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

2007-01-01

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

NASA Astrophysics Data System (ADS)

Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

2004-12-01

In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater nearby (+0.9 - +1.2 ‰ ) cannot be explained by a simple reductive dissolution process, which would be expected to favour the lighter Fe isotopes. Removal of iron in the WTP is followed by a strong decrease of δ 57Fe, probably due to formation of heavier Fe(III) phases. High δ 57Fe values are found in both aquifers and correspond to high concentrations of iron in the groundwater. We hypothesize that the iron isotopic variations observed so far are an indication for iron sources and transformation processes that could not be detected by only measuring dissolved iron concentrations. Current investigations will further explore this hypothesis.

Use of On-Site GC/MS Analysis to Distinguish Between Vapor Intrusion and Indoor Sources of VOCs

DTIC Science & Technology

2013-11-01

Toxaphene, Volatile Organics, Acid Extractables, Benzidines, Phthalates, Nitrosamines, Nitroaromatics & Cyclic Ketones , PAHs, Haloethers, Chlorinated...SW 8270), Nitrosamines (SW 8270), Nitroaromatics & Cyclic Ketones (SW 8270), PAHs (SW 8270), Haloethers (SW 8270), Chlorinated Hydrocarbons (SW 8270...alpha-BHC, beta-BHC, gamma-BHC, delta-BHC, Dieldrin, DDD, DDE, DDT,Endosulfan I, Endosulfan II, Endosulfan sulfate, Endrin, Endrin Aldehyde

Monsoon Circulations and Tropical Heterogeneous Chlorine Chemistry in the Stratosphere

NASA Astrophysics Data System (ADS)

Kinnison, Doug; Solomon, Susan; Garcia, Rolando; Bandoro, Justin; Wilka, Catherine; Neeley, Ryan, III; Schmidt, Anja; Barnes, John; Vernier, Jean-Paul; Höpfner, Michael; Mills, Michael

2017-04-01

Heterogeneous chlorine chemistry on and in liquid polar stratospheric particles is thought to play a significant role in polar and subpolar ozone depletion. Previous studies have not provided evidence for heterogeneous chlorine chemistry occurring in the tropical stratosphere. Using the current best understanding of liquid stratospheric particle chemistry in a state-of-the-art numerical model, we examine whether such processes should be expected to affect tropical composition, particularly at and slightly above the cold tropical tropopause, in association with the Asian and North American summer (June-July-August) monsoons. The Specified Dynamics version of the Community Earth System Model version 1 (CESM1) Whole Atmosphere Community Climate Model (WACCM) is used in this study. This model is nudged to externally specified dynamical fields for temperature, zonal and meridional winds, and surface pressure fields from the NASA Modern Era Retrospective Analysis for Research and Applications (MERRA). Model simulations suggest that transport processes associated with the summer monsoons bring increased abundances of hydrochloric acid (HCl) into contact with liquid sulfate aerosols in the cold tropical lowermost stratosphere, leading to heterogeneous chemical activation of chlorine species. The calculations indicate that the spatial and seasonal distributions of chlorine monoxide (ClO) and chlorine nitrate (ClONO2) near the monsoon regions of the northern hemisphere tropical and subtropical lowermost stratosphere could provide indicators of heterogeneous chlorine processing. In the model, these processes impact the local ozone budget and decrease ozone abundances, implying a chemical contribution to longer-term northern tropical ozone profile changes at 16-19 km.

Mobilization of lead and other trace elements following shock chlorination of wells

USGS Publications Warehouse

Seiler, R.L.

2006-01-01

Many owners of domestic wells shock chlorinate their wells to treat for bacterial contamination or control bad odors from sulfides. Analysis of well water with four wells from Fallon, Nevada, showed that following recommended procedures for shock chlorinating wells can cause large, short-lasting increases in trace-element concentrations in ground water, particularly for Cu, Fe, Pb, and Zn. Lead concentrations increased up to 745 fold between samples collected just before the well was shock chlorinated and the first sample collected 22-24??h later; Zn concentrations increased up to 252 fold, Fe concentrations increased up to 114 fold, and Cu concentrations increased up to 29 fold. Lead concentrations returned to near background levels following pumping of about one casing volume, however, in one well an estimated 120??mg of excess Pb were pumped before concentrations returned to prechlorination levels. Total Pb concentrations were much greater than filtered (0.45????m) concentrations, indicating the excess Pb is principally particulate. Recommended procedures for purging treated wells following shock chlorination may be ineffective because a strong NaOCl solution can remain in the casing above the pump even following extended pumping. Only small changes in gross alpha and beta radioactivity occurred following shock chlorination. USEPA has not promulgated drinking-water standards for 210Pb, however, measured 210Pb activities in the study area typically were less than the Canadian Maximum Acceptable Concentration of 100??mBq/L. By consuming well water shortly after shock chlorination the public may inadvertently be exposed to levels of Pb, and possibly 210Pb, that exceed drinking-water standards.

Determination of levels of polychlorinated biphenyl in transformers oil from some selected transformers in parts of the Greater Accra Region of Ghana.

PubMed

Buah-Kwofie, Archibold; Yeboah, Philip O; Pwamang, John

2011-01-01

Although polychlorinated biphenyls have never been manufactured in Ghana, it has been used extensively as dielectric fluid in electric transformers and capacitors. However, very little is known of its health and environmental impacts by both managers of these transformers and capacitors and also the general public. This work therefore seeks to explore INAA as a possible alternative to screening transformer oils for PCBs by determining the total chlorine content. The total chlorine content of transformer oil samples from Ghana that tested positive and some randomly selected samples that tested negative from screening using CLOR-N-OIL test kits, have had their total chlorine estimated. INAA using the Research Reactor located at the Ghana Atomic Energy Commission was used to estimate the total chlorine content of the oil samples. Neutron Activation and gamma ray spectroscopy using HPGe detector coupled to MAESTRO 32 software was used to determine the total chlorine content by integrating the peak area of the spectrum into a simplified program that was developed from the activation equation. Instrumental Neutron Activation Analysis was able to validate the result obtained from the test kits screening with accuracy 7.5%. The minimum total chlorine content of the positive samples determined by NAA was 71.34 μg g⁻¹. Copyright © 2010 Elsevier Ltd. All rights reserved.

Environmental behaviour of short-chain chlorinated paraffins in aquatic and terrestrial ecosystems of Ny-Ålesund and London Island, Svalbard, in the Arctic.

PubMed

Li, Huijuan; Fu, Jianjie; Pan, Wenxiao; Wang, Pu; Li, Yingming; Zhang, Qinghua; Wang, Yawei; Zhang, Aiqian; Liang, Yong; Jiang, Guibin

2017-07-15

The environmental behaviour of short-chain chlorinated paraffins (SCCPs) was investigated in both aquatic and terrestrial ecosystems in the Arctic. The mean concentrations of SCCPs in the aquatic and terrestrial samples were 178.9ng/g dry weight (dw) and 157.2ng/g dw, respectively. Short carbon chain (C 10 ) and less-chlorinated (Cl 6 ) congener groups were predominant in the Arctic samples, accounting for 48.6% and 34.8% of the total SCCPs, respectively. The enrichment of lighter SCCP congener groups (i.e., fewer chlorine atoms with shorter carbon chain lengths) indicated that the fractionation process occurred during long-range transport. The biomagnification factor (BMF) was 0.46 from gammarid to cod, which indicated that the SCCPs did not biomagnify between these two species. The soil-vegetation bioaccumulation factor (BAF) of SCCPs was 29.9, and C 13 and Cl 7, 8 congener groups tended to accumulate in the terrestrial vegetation. Regression analysis (BAFs=10.9×#C+5.6×#Cl-125.2, R=0.53, P<0.01) showed that the number of carbon and chlorine atoms influenced the bioaccumulative behaviour of SCCPs and suggested that the number of carbon atoms had a greater influence on the BAFs of SCCPs in the terrestrial ecosystem than did the number of chlorine atoms. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Sobes, Vladimir; Scaglione, John M; Wagner, John C

Spent nuclear fuel (SNF) management practices in the United States rely on dry storage systems that include both canister- and cask-based systems. The United States Department of Energy Used Fuel Disposition Campaign is examining the feasibility of direct disposal of dual-purpose (storage and transportation) canisters (DPCs) in a geological repository. One of the major technical challenges for direct disposal is the ability to demonstrate the subcriticality of the DPCs loaded with SNF for the repository performance period (e.g., 10,000 years or more) as the DPCs may undergo degradation over time. Specifically, groundwater ingress into the DPC (i.e., flooding) could allowmore » the system to achieve criticality in scenarios where the neutron absorber plates in the DPC basket have degraded. However, as was shown by Banerjee et al., some aqueous species in the groundwater provide noticeable reactivity reduction for these systems. For certain amounts of particular aqueous species (e.g., chlorine, lithium) in the groundwater, subcriticality can be demonstrated even for DPCs with complete degradation of the neutron absorber plates or a degraded fuel basket configuration. It has been demonstrated that chlorine is the leading impurity, as indicated by significant neutron absorption in the water that is available in reasonable quantities for the deep geological repository media under consideration. This paper presents the results of an investigation of the available integral experiments worldwide that could be used to validate DPC disposal criticality evaluations, including credit for chlorine. Due to the small number of applicable critical configurations, validation through traditional trending analysis was not possible. The bias in the eigenvalue of the application systems due only to the chlorine was calculated using TSURFER analysis and found to be on the order of 100 percent mille (1 pcm = 10 -5 k eff). This study investigated the design of a series of critical configurations with varying amounts of chlorine to address validation gaps. Such integral experiments would support the crediting of the chlorine neutron-absorption properties in groundwater and the demonstration of subcriticality for DPCs in deep geologic repositories with sufficient chlorine availability.« less

Concentrations and Loads of Organic Compounds and Trace Elements in Tributaries to Newark and Raritan Bays, New Jersey

USGS Publications Warehouse

Wilson, Timothy P.; Bonin, Jennifer L.

2007-01-01

A study was undertaken to determine the concentrations and loads of sediment and chemicals delivered to Newark and Raritan Bays by five major tributaries: the Raritan, Passaic, Rahway, Elizabeth, and Hackensack Rivers. This study was initiated by the State of New Jersey as Study I-C of the New Jersey Toxics Reduction Workplan for the New York-New Jersey Harbor, working under the NY-NJ Harbor Estuary Program (HEP) Contaminant Assessment and Reduction Program (CARP). The CARP is a comprehensive effort to evaluate the levels and sources of toxic contaminants to the tributaries and estuarine areas of the NY-NJ Harbor, including Newark and Raritan Bays. The Raritan and Passaic Rivers are large rivers (mean daily discharges of 1,189 and 1,132 cubic feet per second (ft3/s), respectively), that drain large, mixed rural/urban basins. The Elizabeth and Rahway Rivers are small rivers (mean daily discharges of 25.9 and 49.1 ft3/s, respectively) that drain small, highly urbanized and industrialized basins. The Hackensack River drains a small, mixed rural/urban basin, and its flow is highly controlled by an upstream reservoir (mean daily discharge of 90.4 ft3/s). These rivers flow into urbanized estuaries and ultimately, to the Atlantic Ocean. Each of these tributaries were sampled during two to four storm events, and twice each during low-flow discharge conditions. Samples were collected using automated equipment installed at stations adjacent to U.S. Geological Survey streamflow-gaging stations near the heads-of-tide of these rivers. Large-volume (greater than 50 liters of water and a target of 1 gram of sediment), flow-weighted composite samples were collected for chemical analysis using filtration to collect suspended particulates and exchange resin (XAD-2) to sequester dissolved contaminants. Composite whole-water samples were collected for dissolved polycyclic aromatic hydrocarbons (PAH) and for trace element analysis. Additional discrete grab samples were collected throughout each event for trace-element analysis, and multiple samples were collected for suspended sediment (SS), particulate carbon (POC), and dissolved organic carbon (DOC) analysis. The suspended sediment and exchange resin were analyzed for 114 polychlorinated biphenyls (PCBs, by US EPA method 1668A, modified), seven 2,3,7,8-substituted chlorinated dibenzo-p-dioxins (CDD) and 10 dibenzo-p-difurans (CDF) (by US EPA method 1613), 24 PAHs (by low-resolution isotope dilution/mass-spectral methods), 27 organo-chlorine pesticides (OCPs) (by high resolution isotope dilution/mass-spectral methods), and the trace elements mercury (Hg), methyl-mercury (MeHg), lead (Pb), and cadmium (Cd). Isotope dilution methods using gas chromatography and high-and low-resolution mass spectral (GC/MS) detection were used to accurately identify and quantify organic compounds in the sediment and water phases. Trace elements were measured using inductively coupled plasma-mass spectrometry and cold-vapor atomic fluorescence spectrometry methods. The loads of sediment, carbon, and chemicals were calculated for each storm and low-flow event sampled. Because only a few storm events were sampled, yearly loads of sediment were calculated from rating curves developed using historical SS and POC data. The average annual loads of sediment and carbon were calculated for the period 1975-2000, along with the loads for the selected water years being modeled as part of the New York New Jersey Harbor Estuary Program CARP. Comparison of loads calculated using the rating curve method to loads measured during the sampled storm events indicated that the rating curve method likely underpredicts annual loads. Average annual loads of suspended sediment in the tributaries were estimated to be 395,000 kilograms per year (kg/yr) in the Hackensack River, 417,000 kg/yr in the Elizabeth River, 882,000 kg/yr in the Rahway River, 22,700,000 kg/yr in the Passaic River, and 93,100,000 kg/yr in the Raritan River. Averag

Decontamination of PCBs-containing soil using subcritical water extraction process.

PubMed

Islam, Mohammad Nazrul; Park, Jeong-Hun; Shin, Moon-Su; Park, Ha-Seung

2014-08-01

Polychlorinated biphenyls (PCBs) are one of the excision compounds listed at the Stockholm convention in 2001. Although their use has been heavily restricted, PCBs can be found in some specific site-contaminated soils. Either removal or destruction is required prior to disposal. The subcritical water extraction (SCWE) of organic hazardous compounds from contaminated soils is a promising technique for hazardous waste contaminated-site cleanup. In this study, the removal of PCBs by the SCWE process was investigated. The effects of temperature and treatment time on removal efficiency have been determined. In the SCWE experiments, a removal percentage of 99.7% was obtained after 1h of treatment at 250°C. The mass removal efficiency of low-chlorinated species was higher than high-chlorinated congeners at lower temperatures, but it was oppositely observed at higher temperatures because the lower chlorinated congeners are formed by dechlorination of higher chlorinated congeners. Gas chromatography/mass spectrometry analysis confirmed that the PCBs underwent partial degradation. Several degradation products including mono- and di-chlorinated biphenyls, oxygen-containing aromatic compounds, and small-size hydrocarbons were identified in the effluent water, which were not initially present in the contaminated soil. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Determinants of Caregivers' Use and Adoption of Household Water Chlorination: A Qualitative Study with Peri-Urban Communities in the Peruvian Amazon.

PubMed

Rothstein, Jessica D; Leontsini, Elli; Olortegui, Maribel Paredes; Yori, Pablo Peñataro; Surkan, Pamela J; Kosek, Margaret

2015-09-01

The gap between the efficacy and the effectiveness of household water treatment in reducing diarrhea-related morbidity indicates the need for a better understanding of the determinants of long-term behavior change. To explore the barriers to drinking water chlorination in the Peruvian Amazon, where diarrhea is endemic among under-5 children, we conducted qualitative research with 23 caregivers from peri-urban communities of Iquitos, Peru. Our inquiry drew on the Transtheoretical Model of behavior change and the Integrated Behavioral Model for Water, Sanitation, and Hygiene to identify the most relevant contextual, psychosocial, and technological determinants of initial action and long-term adoption of chlorination. Our findings suggest that the decision to try out this practice resulted from the combined effect of knowledge of chlorination benefits and product availability and affordability. Progress from action to adoption was influenced by caretakers' understanding of dosage, the packaging of chlorine products, knowledge and skills for multipurpose laundry bleach, the taste of treated water, and reinforcement. This analysis suggests that a focus on these determinants and the household domain may help to improve the sustainability of future intervention efforts. © The American Society of Tropical Medicine and Hygiene.

Determinants of Caregivers' Use and Adoption of Household Water Chlorination: A Qualitative Study with Peri-urban Communities in the Peruvian Amazon

PubMed Central

Rothstein, Jessica D.; Leontsini, Elli; Olortegui, Maribel Paredes; Yori, Pablo Peñataro; Surkan, Pamela J.; Kosek, Margaret

2015-01-01

The gap between the efficacy and the effectiveness of household water treatment in reducing diarrhea-related morbidity indicates the need for a better understanding of the determinants of long-term behavior change. To explore the barriers to drinking water chlorination in the Peruvian Amazon, where diarrhea is endemic among under-5 children, we conducted qualitative research with 23 caregivers from peri-urban communities of Iquitos, Peru. Our inquiry drew on the Transtheoretical Model of behavior change and the Integrated Behavioral Model for Water, Sanitation, and Hygiene to identify the most relevant contextual, psychosocial, and technological determinants of initial action and long-term adoption of chlorination. Our findings suggest that the decision to try out this practice resulted from the combined effect of knowledge of chlorination benefits and product availability and affordability. Progress from action to adoption was influenced by caretakers' understanding of dosage, the packaging of chlorine products, knowledge and skills for multipurpose laundry bleach, the taste of treated water, and reinforcement. This analysis suggests that a focus on these determinants and the household domain may help to improve the sustainability of future intervention efforts. PMID:26175028

Genotyping and chlorine-resistance of Methylobacterium aquaticum isolated from water samples in Japan.

PubMed

Furuhata, Katsunori; Banzai, Azusa U; Kawakami, Yasushi; Ishizaki, Naoto; Yoshida, Yoshihiro; Goto, Keiichi; Fukuyama, Masafumi

2011-09-01

For microbial ecological analysis, 14 strains of Methylobacterium aquaticum isolated from water samples were subjected to clustering analysis on the basis of ribotyping and RAPD-PCR tests. The ribopatterns after digestion with EcoRI obtained from 14 strains of M. aquaticum were used to divide the strains into two groups (Groups I and II) with a similarity of 55%. From the analysis of RAPD patterns using primer 208, the 14 strains were divided into 3 groups (A-C) based on a homology of 45% or greater, and from that using primer 272, there were 4 groups (A-D) based on a homology of 50% or greater. The chlorine resistance (99.9% CT values) of these isolates was also experimentally confirmed, and we attempted to define the connection between chlorine resistance and the geno-cluster. The average CT value of group I was 0.89 mg•min/l and the average of group II was 0.69 mg•min/l. No remarkable differences in the CT values for the groups were found.

Chemical tagging of chlorinated phenols for their facile detection and analysis by NMR spectroscopy

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

Valdez, Carlos A.; Leif, Roald N.

2015-03-22

A derivatization method that employs diethyl (bromodifluoromethyl) phosphonate (DBDFP) to efficiently tag the endocrine disruptor pentachlorophenol (PCP) and other chlorinated phenols (CPs) along with their reliable detection and analysis by NMR is presented. The method accomplishes the efficient alkylation of the hydroxyl group in CPs with the difluoromethyl (CF 2H) moiety in extremely rapid fashion (5 min), at room temperature and in an environmentally benign manner. The approach proved successful in difluoromethylating a panel of 18 chlorinated phenols, yielding derivatives that displayed unique 1H, 19F NMR spectra allowing for the clear discrimination between isomerically related CPs. Due to its biphasicmore » nature, the derivatization can be applied to both aqueous and organic mixtures where the analysis of CPs is required. Furthermore, the methodology demonstrates that PCP along with other CPs can be selectively derivatized in the presence of other various aliphatic alcohols, underscoring the superiority of the approach over other general derivatization methods that indiscriminately modify all analytes in a given sample. The present work demonstrates the first application of NMR on the qualitative analysis of these highly toxic and environmentally persistent species.« less

Factorial analysis of the trihalomethane formation in the reaction of colloidal, hydrophobic, and transphilic fractions of DOM with free chlorine.

PubMed

Platikanov, Stefan; Tauler, Roma; Rodrigues, Pedro M S M; Antunes, Maria Cristina G; Pereira, Dilson; Esteves da Silva, Joaquim C G

2010-09-01

This study focuses on the factors that affect trihalomethane (THMs) formation when dissolved organic matter (DOM) fractions (colloidal, hydrophobic, and transphilic fractions) in aqueous solutions were disinfected with chlorine. DOM fractions were isolated and fractionated from filtered lake water and were characterized by elemental analysis. The investigation involved a screening Placket-Burman factorial analysis design of five factors (DOM concentration, chlorine dose, temperature, pH, and bromide concentration) and a Box-Behnken design for a detailed assessment of the three most important factor effects (DOM concentration, chlorine dose, and temperature). The results showed that colloidal fraction has a relatively low contribution to THM formation; transphilic fraction was responsible for about 50% of the chloroform generation, and the hydrophobic fraction was the most important to the brominated THM formation. When colloidal and hydrophobic fraction solutions were disinfected, the most significant factors were the following: higher DOM fraction concentration led to higher THM concentration, an increase of pH corresponded to higher concentration levels of chloroform and reduced bromoform, higher levels of chlorine dose and temperature produced a rise in the total THM formation, especially of the chlorinated THMs; higher bromide concentration generates higher concentrations of brominated THMs. Moreover, linear models were implemented and response surface plots were obtained for the four THM concentrations and their total sum in the disinfection solution as a function of the DOM concentration, chlorine dose, and temperature. Overall, results indicated that THM formation models were very complex due to individual factor effects and significant interactions among the factors. In order to reduce the concentration of THMs in drinking water, DOM concentrations must be reduced in the water prior to the disinfection. Fractionation of DOM, together with an elemental analysis of the fractions, is important issue in the revealing of the quality and quantity characteristics of DOM. Systematic study composed from DOM fraction investigation and factorial analysis of the responsible parameters in the THM formation reaction can, after an evaluation of the adjustment of the models with the reality, serves well for the evaluation of the spatial and temporal variability in the THM formation in dependence of DOM. However, taking into consideration the natural complexity of DOM, different operations and a strict control of them (like coagulation/flocculation and filtration) has to be used to quantitatively remove DOM from the raw water. Assuming that this study represents a local case study, similar experiments can be easily applied and will supply with relevant information every local water treatment plant meeting problems with THM formation. The coagulation/flocculation and the filtration stages are the main mechanisms to remove DOM, particularly the colloidal DOM fraction. With the objective to minimize THMs generation, different unit operation designed to quantitatively remove DOM from water must be optimized.

Inducamides A–C, Chlorinated Alkaloids from an RNA Polymerase Mutant Strain of Streptomyces sp.

PubMed Central

2015-01-01

Inducamides A–C (1–3), three new chlorinated alkaloids featuring an amide skeleton generated by a tryptophan fragment and a 6-methylsalicylic acid unit, were isolated from a chemically induced mutant strain of Streptomyces sp. with the inducamides only being produced in the mutant strain. Their structures, including stereochemistry, were determined by spectroscopic analysis, Marfey’s method, and CD spectroscopy. PMID:25338006

Lithium isotope as a proxy for water/rock interaction between hydrothermal fluids and oceanic crust at Milos, Greece

NASA Astrophysics Data System (ADS)

Lou, U.-Lat; You, Chen-Feng; Wu, Shein-Fu; Chung, Chuan-Hsiung

2014-05-01

Hydrothermal activity at Milos in the Aegean island (Greece) is mainly located at rather shallow depth (about 5 m). It is interesting to compare these chemical compositions and the evolution processes of the hydrothermal fluids at deep sea hydrothermal vents in Mid-ocean Ridge (MOR). Lithium (Li) is a highly mobile element and its isotopic composition varies at different geological settings. Therefore, Li and its isotope could be used as an indicator for many geochemical processes. Since 6Li preferential retained in the mineral phase where 7Li is leached into fluid phase during basalt alteration, the Li isotopic fractionation between the rocks and the fluids reflect sensitively the degree of water-rock interaction. In this study, Bio-Rad AG-50W X8 cation exchange resin was used for purifying the hydrothermal fluids to separate Li from other matrix elements. The Li isotopic composition (δ7Li) was determined by Multi-collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) with precision better than 0.2‰ (2σ, n=20). The Li concentration in the hydrothermal fluids falls between 0.02 to 10.31 mM. The δ7Li values vary from +1.9 to +29.7‰, indicating significant seawater contamination have occurred. These hydrothermal fluids fit well with seawater and brine two end-member binary mixing model. During phase separation, lithium, boron, chlorine, iodine, bromine, sodium and potassium were enriched in the brine phase. On the other hand, aluminum, sulphur and iron were enriched in the vapor phase. There is no significant isotope fractionation between the two phases. The water/rock ratio (W/R) calculated is low (about 1.5 to 1.8) for the Milos fluids, restricted seawater recharge into the oceanic crust. Moreover, the oceanic crust in the region becomes less altered since the W/R is low. The δ7Li value of the hydrothermal fluids can be used as a sensitive tool for studying water-rock interaction.

The Performance of Four Different Mineral Liners on the Transportation of Chlorinated Phenolic Compounds to Groundwater in Landfills

PubMed Central

Adar, Elanur; Bilgili, Mehmet Sinan

2015-01-01

The aim of this study was to investigate the efficiency of four different mineral liners (clay, bentonite, kaoline, and zeolite) which could be utilized to prevent the transport of phenolic compounds to groundwater through alternative liner systems. Four laboratory-scale HDPE reactors with 80 cm height and 40 cm inner diameter were operated for a period of 180 days. Results indicated that the transport of mono- or dichlorophenols is significantly prevented by the liner systems used, while the transport of highly chlorinated phenolic compounds cannot be prevented by the landfill liner system effectively. Highly chlorinated phenolic compounds in groundwater can be found in higher concentrations than the leachate, as a result of the degradation and transformation of these compounds. Thus, the analysis of highly chlorinated phenolic compounds such as 2,4,6-TCP, 2,3,6-TCP, 3,4,5-TCP, and PCP is of great significance for the studies to be conducted on the contamination of groundwater around landfills. PMID:26759828

Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

PubMed

Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

2014-07-01

Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

Effect of disinfectant residual on the interaction between bacterial growth and assimilable organic carbon in a drinking water distribution system.

PubMed

Li, Weiying; Zhang, Junpeng; Wang, Feng; Qian, Lin; Zhou, Yanyan; Qi, Wanqi; Chen, Jiping

2018-07-01

Public health is threatened by deteriorated water quality due to bacterial regrowth and uncontrolled growth-related problems in drinking water distribution systems (DWDSs). To investigate the scope of this problem, a two-year field study was conducted in south China. The amount of assimilable organic carbon (AOC), total cell concentrations (TCC), and intact cell concentrations (ICC) of water samples were determined by flow cytometry. The results indicated that ICC was significantly correlated to AOC concentration when the chlorine concentration was less than 0.15 mg/L, and ICC was lower at chlorine concentrations greater than 0.15 mg/L, suggesting that free chlorine level had effect on AOC and ICC. To further analyze the effect of disinfectant on AOC and bacterial growth, we designed an orthogonal experiment with different dosages of two commonly used disinfectants, chlorine and chloramine. The results demonstrated that high concentrations of free chlorine (＞0.15 mg/L) and chloramine (＞0.4 mg/L) were associated with relatively low proportions of intact cells and cultivable bacteria. Compared with chlorine, chloramine tended to cause lower AOC level and intact cells, likely because the chlorinated disinfection byproducts (DBPs) were more easily absorbed by bacteria than the chloraminated DBPs. Based on the statistical analysis of 240 water samples, ICC was limited when AOC concentration was less than 135 μg/L, while temperature and the number of small-size particles showed positive effects on ICC (P＜0.05). We conclude that the use of chloramine and controlling particle numbers should be suitable strategies to limit bacterial regrowth. Copyright © 2018 Elsevier Ltd. All rights reserved.

Inhibitory effect of chlorine and ultraviolet radiation on growth of Listeria monocytogenes in chicken breast and development of predictive growth models.

PubMed

Oh, S R; Kang, I; Oh, M H; Ha, S D

2014-01-01

The inhibitory effect of chlorine (50, 100, and 200 mg/kg) was investigated with and without UV radiation (300 mW·s/cm(2)) for the growth of Listeria monocytogenes in chicken breast meat. Using a polynomial model, predictive growth models were also developed as a function of chlorine concentration, UV exposure, and storage temperature (4, 10, and 15°C). A maximum L. monocytogenes reduction (0.8 log cfu, cfu/g) was obtained when combining chlorine at 200 mg/kg and UV at 300 mW·s/cm(2), and a maximum synergistic effect (0.4 log cfu/g) was observed when using chlorine at 100 mg/kg and UV at 300 mW·s/cm(2). Primary models developed for specific growth rate and lag time showed a good fitness (R(2) > 0.91), as determined by the reparameterized Gompertz equation. Secondary polynomial models were obtained using nonlinear regression analysis. The developed models were validated with mean square error, bias factor, and accuracy factor, which were 0.0003, 0.96, and 1.11, respectively, for specific growth rate and 7.69, 0.99, and 1.04, respectively, for lag time. The treatment of chlorine and UV did not change the color and texture of chicken breast after 7 d of storage at 4°C. As a result, the combination of chlorine at 100 mg/kg and UV at 300 mW·s/cm(2) appears to an effective method into inhibit L. monocytogenes growth in broiler carcasses with no negative effects on color and textural quality. Based on the validation results, the predictive models can be used to accurately predict L. monocytogenes growth in chicken breast.

Simultaneous control of microorganisms and disinfection by-products by sequential chlorination.

PubMed

Chen, Chao; Zhang, Xiao-Jian; He, Wen-Jie; Han, Hong-Da

2007-04-01

To introduce a new sequential chlorination disinfection process in which short-term free chlorine and chloramine are sequentially added. Pilot tests of this sequential chlorination were carried out in a drinking water plant. The sequential chlorination disinfection process had the same or better efficiency on microbe (including virus) inactivation compared with the free chlorine disinfection process. There seemed to be some synergetic disinfection effect between free chlorine and monochloramine because they attacked different targets. The sequential chlorination disinfection process resulted in 35.7%-77.0% TTHM formation and 36.6%-54.8% THAA5 formation less than the free chlorination process. The poorer the water quality was, the more advantage the sequential chlorination disinfection had over the free chlorination. This process takes advantages of free chlorine's quick inactivation of microorganisms and chloramine's low disinfection by-product (DBP) yield and long-term residual effect, allowing simultaneous control of microbes and DBPs in an effective and economic way.

[Analysis of UV-visible absorption spectrum on the decolorization of industrial wastewater by disinfection].

PubMed

Huang, Xin; Wang, Long-Yong; Gao, Nai-Yun; Li, Wei-Guo

2012-10-01

The UV-Visible absorption spectrum of industrial wastewater was explored to introduce a substituting method determining the color of water, and to compare the decolorization efficacy of different disinfectants. The results show that the visible absorption spectrum(350-600 nm), instead of ultraviolet absorption spectrum, should be applied to characterize the color of wastewater. There is a good correlation between the features of visible absorption spectrum and the true color of wastewater. Both ozone and chlorine dioxide has a better decolorization performance than chlorine. However, the color of chlorine dioxide itself has a negative effect on decolorization. The changes in the features of visible absorption spectrum effectively reflect the variations in the color of wastewater after disinfection.

The study on the extraction and recovery of Au from scrap of the used computer using chloride solvent

NASA Astrophysics Data System (ADS)

Oh, Su-ji; Choi, Eunju; Choi, Nagchoul; Park, Cheonyoung

2013-04-01

Recently, due to the realization of environmental problems of cyanide, it is a worldwide quest to find viable alternatives. One of the alternatives is a chloride solvent(chlorine-hypochlorite acid) with an appropriate oxidizing agent. The rate of dissolution of Au by chloride solvent is much faster than that by cyanide. Also, due to presence of chloride ions, there is no passivation of gold surfaces during chlorination. The objective of this work was to investigate the effect of Au extraction efficiency under various experimental conditions(pulp density, chlorine-hypochlorite ratio and concentration of NaCl) from scrap of the used computer by chloride solvent. In addition, the recovery experiment was conducted to examine of the precipitation efficiency of Au under various metabisulfite concentration from extracted solution. In an EDS analysis, valuable metals such as Cu, Sn, Sb, Al, Ni, Pb and Au were observed in scrap of the used computer. The result of extraction experiment showed that the highest extraction rate was obtained under 1% of pulp density with a chlorine-hypochlorite ratio of 2:1, and a concentration of NaCl at 2M. The highest Au recovery(precipitation) rate was observed the addition of sodium metabisulfite at 2M concentration. Under these conditions, chlorine-hypochlorite could effectively Au extraction from scrap of the used computer sections and the additive reagent using sodium metabisulfite could easily precipitate the Au from the chlorine-hypochlorite solution.

Improvement of the air quality in student health centers with chlorine dioxide.

PubMed

Hsu, Ching-Shan; Huang, Da-Ji; Lu, Ming-Chun

2010-04-01

This study aims to monitor bioaerosol levels of a local campus of a student health center in Taiwan and then to perform disinfection by applying chlorine dioxide. First, air samples were taken and evaluated in the six areas of the center. The average background bioaerosol levels were 714 +/- 1706 CFU/m(3) for bacterium and 802 +/- 633 CFU/m(3) for fungi. Then, chlorine dioxide was applied through three different procedures: single, multiple and regular disinfections. The results indicated that both multiple and regular disinfections can achieve efficiency levels higher than 59.0%. The regression analysis on bioaerosol levels showed that the number of people present correlating to the number of persons entering the room per door-opening, had a correlation of p < 0.05. Utilizing this analysis result, an empirical model was developed to predict indoor bioaerosol concentrations. It can be inferred that for indoor human activity of health centers, regular disinfection is a very effective process.

Thermodynamic Analysis for the Refining Ability of Salt Flux for Aluminum Recycling

PubMed Central

Hiraki, Takehito; Miki, Takahiro; Nakajima, Kenichi; Matsubae, Kazuyo; Nakamura, Shinichiro; Nagasaka, Tetsuya

2014-01-01

The removability of impurities during the aluminum remelting process by oxidation was previously investigated by our research group. In the present work, alternative impurity removal with chlorination has been evaluated by thermodynamic analysis. For 43 different elements, equilibrium distribution ratios among metal, chloride flux and oxide slag phases in the aluminum remelting process were calculated by assuming the binary systems of aluminum and an impurity element. It was found that the removability of impurities isn’t significantly affected by process parameters such as chloride partial pressure, temperature and flux composition. It was shown that Ho, Dy, Li, La, Mg, Gd, Ce, Yb, Ca and Sr can be potentially eliminated into flux by chlorination from the remelted aluminum. Chlorination and oxidation are not effective to remove other impurities from the melting aluminum, due to the limited parameters which can be controlled during the remelting process. It follows that a proper management of aluminum scrap such as sorting based on the composition of the products is important for sustainable aluminum recycling. PMID:28788144

Two-step chlorination: A new approach to disinfection of a primary sewage effluent.

PubMed

Li, Yu; Yang, Mengting; Zhang, Xiangru; Jiang, Jingyi; Liu, Jiaqi; Yau, Cie Fu; Graham, Nigel J D; Li, Xiaoyan

2017-01-01

Sewage disinfection aims at inactivating pathogenic microorganisms and preventing the transmission of waterborne diseases. Chlorination is extensively applied for disinfecting sewage effluents. The objective of achieving a disinfection goal and reducing disinfectant consumption and operational costs remains a challenge in sewage treatment. In this study, we have demonstrated that, for the same chlorine dosage, a two-step addition of chlorine (two-step chlorination) was significantly more efficient in disinfecting a primary sewage effluent than a one-step addition of chlorine (one-step chlorination), and shown how the two-step chlorination was optimized with respect to time interval and dosage ratio. Two-step chlorination of the sewage effluent attained its highest disinfection efficiency at a time interval of 19 s and a dosage ratio of 5:1. Compared to one-step chlorination, two-step chlorination enhanced the disinfection efficiency by up to 0.81- or even 1.02-log for two different chlorine doses and contact times. An empirical relationship involving disinfection efficiency, time interval and dosage ratio was obtained by best fitting. Mechanisms (including a higher overall Ct value, an intensive synergistic effect, and a shorter recovery time) were proposed for the higher disinfection efficiency of two-step chlorination in the sewage effluent disinfection. Annual chlorine consumption costs in one-step and two-step chlorination of the primary sewage effluent were estimated. Compared to one-step chlorination, two-step chlorination reduced the cost by up to 16.7%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigations on the effect of chlorine in lubricating oil and the presence of a diesel oxidation catalyst on PCDD/F releases from an internal combustion engine.

PubMed

Dyke, Patrick H; Sutton, Mike; Wood, David; Marshall, Jonathan

2007-04-01

This paper reports on an intensive study into releases of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated furans (PCDF) and polychlorinated biphenyls (PCB) from a diesel engine and the analysis of PCDD/F and PCB in crankcase lubricating oil. Experimental conditions were set and carefully controlled in order to maximize the possible impact of, and our ability to measure the effect of, changes in the levels of chlorine in the lubricant. Emissions to air were measured using modified EPA methods following the principles of the European EN 1948 standards. A series of 40 experimental runs were completed using three reference lubricants formulated to have three levels of chlorine present as a residual component (at levels of 12, 131 and 259 mg kg(-1) or ppm). The engine was run with and without the diesel oxidation catalyst. All lubricants were realistic oils and the use of unrealistic additives or doping of components - particularly chlorine - in the fuel and lubricant was carefully avoided. Analysis of fuel and lubricant (before and after testing) samples required strenuous attention to achieve acceptable recoveries and showed non-detectable levels of PCB and PCDD/F at a detection limit of around 1.5 ng I-TEQ kg(-1) (ppt), indistinguishable from the laboratory blank. The testing demonstrated the need for extreme care to be taken in developing measurement methods that are sufficiently sensitive for measuring chlorine content of fluids and PCDD/F in oils, the latter being particularly challenging. Mean emissions of PCDD/F with the diesel oxidation catalyst in place were 23 pg I-TEQ l(-1) of fuel and with the diesel oxidation catalyst removed 97 pg I-TEQ l(-1) of fuel. The results of this testing showed that the emissions of PCDD/F were greatly reduced by the presence of a diesel oxidation catalyst in the exhaust, a finding that has not been explicitly tested in previous work. They also show that emissions from the engine were not controlled by the level of chlorine in the lubricant and that emissions did not change in response to a much greater step change in the total chlorine entering the combustion chamber due to a change in the level of chlorine in the fuel. Emissions when the engine was configured with a diesel oxidation catalyst showed a consistent pattern that appears to be unique in the experience of the authors.

Hydrochemical and isotopic characterization of groundwater in the Ghis-Nekor plain (northern Morocco)

NASA Astrophysics Data System (ADS)

Chafouq, D.; El Mandour, A.; Elgettafi, M.; Himi, M.; Chouikri, I.; Casas, A.

2018-03-01

The coastal aquifer of Ghis-Nekor (Morocco) was studied to identify the major processes causing salinization of groundwater. In fact, a geochemical approach multi tracer (general chemistry and isotopes - δ2H, δ18O-H2O, δ34S, δ18O-SO4) was utilized, with the hydrodynamics to explain the processes responsible for the salinization of groundwater, and for identttifying areas most vulnerable to seawater intrusion. The recharge of the aquifer is mainly by the Al-Khattabi dam, the Nekor River and the Ghis River, on the eastern border of the plain. The water that feeds the aquifer shows a relatively high level of salinity and for this reason, the majority of sampled wells indicate high values of electric conductivity and total salinity which arrives at 7.5 g L-1. The plot of the geochemical results analyzes of groundwater in the Piper diagram shows two distinct chemical facies; sodium chloride-facies and chlorinated calcium and magnesium sulfated facies. The concentrations of 18O range between -4.15‰ and -5.73‰, while the values of 2H range between -28.4‰ and -41.7‰. The Nekor river water is depleted in heavy isotopes, and the isotopic compositions are in the order on -6‰ for 18O and -40.5‰ for deuterium. Most of the wells have a slope <8 indicating a slight evaporation before infiltration. The data show low and variable d-excess values (range from -0.02‰ to 11.6‰), reflect recharge during different climatic conditions. The isotopic concentrations of 18O-SO4 vary between 4.35‰ and 8.60‰, while the 34S isotope values range from -4.3‰ to 9.9‰. For Ghis River, these values are between -4.4‰ and 4.95‰, respectively, for sulfur and oxygen. The interpretation of the chemical and isotopic results suggesting the intrusion of seawater to increase salinity of groundwater in the region is low. However, only the NE area shows probable contamination of seawater. In contrast, wells are saline independent of seawater intrusion, the origin of the high salinity can be related to: 1- the accumulation of rivers fluid intake and water dam rich dissolved salts and sulphates, 2- the anthropogenic pollution (domestic sewage, agricultural inputs, septic uses).

Chlorination Revisited: Does Cl- Serve as a Catalyst in the Chlorination of Phenols?

PubMed

Lau, Stephanie S; Abraham, Sonali M; Roberts, A Lynn

2016-12-20

The aqueous chlorination of (chloro)phenols is one of the best-studied reactions in the environmental literature. Previous researchers have attributed these reactions to two chlorine species: HOCl (at circum-neutral and high pH) and H 2 OCl + (at low pH). In this study, we seek to examine the roles that two largely overlooked chlorine species, Cl 2 and Cl 2 O, may play in the chlorination of (chloro)phenols. Solution pH, chloride concentration, and chlorine dose were systematically varied in order to assess the importance of different chlorine species as chlorinating agents. Our findings indicate that chlorination rates at pH < 6 increase substantially when chloride is present, attributed to the formation of Cl 2 . At pH 6.0 and a chlorine dose representative of drinking water treatment, Cl 2 O is predicted to have at best a minor impact on chlorination reactions, whereas Cl 2 may contribute more than 80% to the overall chlorination rate depending on the (chloro)phenol identity and chloride concentration. While it is not possible to preclude H 2 OCl + as a chlorinating agent, we were able to model our low-pH data by considering Cl 2 only. Even traces of chloride can generate sufficient Cl 2 to influence chlorination kinetics, highlighting the role of chloride as a catalyst in chlorination reactions.

Analysis of chlorophenoxy acid herbicides in water by large-volume on-line derivatization and gas chromatography-mass spectrometry.

PubMed

Ding, W H; Liu, C H; Yeh, S P

2000-10-27

This work presents a modified method to analyze chlorophenoxy acid herbicides in water samples. The herbicides 2,4-D (2,4-dichlorophenoxyacetic acid). Silvex (2,4,5-trichlorophenoxypropionic acid) and 2,4,5-T (2,4,5-trichlorophenoxyacetic acid) were used to evaluate the method. The method involves extraction of samples by a graphitized carbon black cartridge, and on-line derivatization in the GC injection port using a large-volume (10-20 microl) direct sample introduction (DSI) device with tetraalkylammonium salts. The analytes were then identified and quantitated by ion-trap gas chromatography-mass spectrometry. The large-volume DSI injection-port derivatization technique provides sensitivity, fast and reproducible results for chlorophenoxy acid herbicides residues, to quantitation at 0.1 to 0.2 microg/l in 500-ml water samples. An enhanced characteristic mass chromatogram of molecular ions of butylated chlorophenoxy acid herbicides with a significant chlorine isotope pattern by electron impact ionization MS allows us to determine herbicides residues at trace levels in aqueous samples. Recovery of the herbicide residues in spiked various water samples ranged from 70 to 99% while RSDs ranged from 1 to 13%.

40 CFR 704.45 - Chlorinated terphenyl.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Chlorinated terphenyl. 704.45 Section....45 Chlorinated terphenyl. (a) Definitions. (1) Chlorinated terphenyl means a chemical substance, CAS No. 61788-33-6, comprised of chlorinated ortho-, meta-, and paraterphenyl. (2) Extent of chlorination...

Temperature Dependence of Gas Properties in Polynomial Form

DTIC Science & Technology

1981-01-01

Carbonyl Sulfide Chlorine Chlorine (Monatomic) Chlorine Dioxide Chlorine Fluoride Chlorine Monoxide Chlorine Oxide Chlorine Trifluoride ...dis- cussed in Section 5 and the following eqn: 100-1500K~ Cp(T)= 515.3754 + 0.426933T -2.91036E-04T 2 -+ 6.836113E-08Ti CHLORINE TRIFLUORIDE C1F 3...3 Trimeric Boron Tribromide BBr3 250.538 33.186 A-3 Boron Trichloride BC1 3 117.170 70.959 A-4 Boron Trifluoride BF3 67.806 122.619 A-4 Bromine Br2

Non-targeted analysis of electronics waste by comprehensive two-dimensional gas chromatography combined with high-resolution mass spectrometry: Using accurate mass information and mass defect analysis to explore the data.

PubMed

Ubukata, Masaaki; Jobst, Karl J; Reiner, Eric J; Reichenbach, Stephen E; Tao, Qingping; Hang, Jiliang; Wu, Zhanpin; Dane, A John; Cody, Robert B

2015-05-22

Comprehensive two-dimensional gas chromatography (GC×GC) and high-resolution mass spectrometry (HRMS) offer the best possible separation of their respective techniques. Recent commercialization of combined GC×GC-HRMS systems offers new possibilities for the analysis of complex mixtures. However, such experiments yield enormous data sets that require new informatics tools to facilitate the interpretation of the rich information content. This study reports on the analysis of dust obtained from an electronics recycling facility by using GC×GC in combination with a new high-resolution time-of-flight (TOF) mass spectrometer. New software tools for (non-traditional) Kendrick mass defect analysis were developed in this research and greatly aided in the identification of compounds containing chlorine and bromine, elements that feature in most persistent organic pollutants (POPs). In essence, the mass defect plot serves as a visual aid from which halogenated compounds are recognizable on the basis of their mass defect and isotope patterns. Mass chromatograms were generated based on specific ions identified in the plots as well as region of the plot predominantly occupied by halogenated contaminants. Tentative identification was aided by database searches, complementary electron-capture negative ionization experiments and elemental composition determinations from the exact mass data. These included known and emerging flame retardants, such as polybrominated diphenyl ethers (PBDEs), hexabromobenzene, tetrabromo bisphenol A and tris (1-chloro-2-propyl) phosphate (TCPP), as well as other legacy contaminants such as polychlorinated biphenyls (PCBs) and polychlorinated terphenyls (PCTs). Copyright © 2015 Elsevier B.V. All rights reserved.

Intramolecular carbon and nitrogen isotope analysis by quantitative dry fragmentation of the phenylurea herbicide isoproturon in a combined injector/capillary reactor prior to GC separation.

PubMed

Penning, Holger; Elsner, Martin

2007-11-01

Potentially, compound-specific isotope analysis may provide unique information on source and fate of pesticides in natural systems. Yet for isotope analysis, LC-based methods that are based on the use of organic solvents often cannot be used and GC-based analysis is frequently not possible due to thermolability of the analyte. A typical example of a compound with such properties is isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), belonging to the worldwide extensively used phenylurea herbicides. To make isoproturon accessible to carbon and nitrogen isotope analysis, we developed a GC-based method during which isoproturon was quantitatively fragmented to dimethylamine and 4-isopropylphenylisocyanate. Fragmentation occurred only partially in the injector but was mainly achieved on a heated capillary column. The fragments were then chromatographically separated and individually measured by isotope ratio mass spectrometry. The reliability of the method was tested in hydrolysis experiments with three isotopically different batches of isoproturon. For all three products, the same isotope fractionation factors were observed during conversion and the difference in isotope composition between the batches was preserved. This study demonstrates that fragmentation of phenylurea herbicides does not only make them accessible to isotope analysis but even enables determination of intramolecular isotope fractionation.

Using digital flow cytometry to assess the degradation of three cyanobacteria species after oxidation processes.

PubMed

Wert, Eric C; Dong, Mei Mei; Rosario-Ortiz, Fernando L

2013-07-01

Depending on drinking water treatment conditions, oxidation processes may result in the degradation of cyanobacteria cells causing the release of toxic metabolites (microcystin), odorous metabolites (MIB, geosmin), or disinfection byproduct precursors. In this study, a digital flow cytometer (FlowCAM(®)) in combination with chlorophyll-a analysis was used to evaluate the ability of ozone, chlorine, chlorine dioxide, and chloramine to damage or lyse cyanobacteria cells added to Colorado River water. Microcystis aeruginosa (MA), Oscillatoria sp. (OSC) and Lyngbya sp. (LYN) were selected for the study due to their occurrence in surface water supplies, metabolite production, and morphology. Results showed that cell damage was observed without complete lysis or fragmentation of the cell membrane under many of the conditions tested. During ozone and chlorine experiments, the unicellular MA was more susceptible to oxidation than the filamentous OSC and LYN. Rate constants were developed based on the loss of chlorophyll-a and oxidant exposure, which showed the oxidants degraded MA, OSC, and LYN according to the order of ozone > chlorine ~ chlorine dioxide > chloramine. Digital and binary images taken by the digital flow cytometer provided qualitative insight regarding cell damage. When applying this information, drinking water utilities can better understand the risk of cell damage or lysis during oxidation processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

An in vitro evaluation of the antibacterial efficacy of chlorine dioxide on E. faecalis in bovine incisors.

PubMed

Eddy, Russell S; Joyce, Anthony P; Roberts, Steven; Buxton, Thomas B; Liewehr, Frederick

2005-09-01

This study investigated the ability of chlorine dioxide to eliminate Enterococcus faecalis from dentinal tubules of bovine incisors. Thirty-seven extracted bovine incisor roots were sectioned into seventy-four 5 mm disks. Standardized lumens were filled with either sterile Brain Heart Infusion Broth (contamination controls, n = 10) or BHI containing E. faecalis (1.0 x 10 cfu/ml). Disks were incubated in 5% CO2 at 37 degrees C for 72 h. To simulate endodontic instrumentation the lumens were again enlarged. Sixty disks were randomly divided into four experimental groups and filled with one of the following irrigants: 10% Clidox-S (chlorine dioxide), 13.8% BioClenz (chlorine dioxide), 5.25% Clorox, or saline. The disks were incubated for 30 min and were then frozen, pulverized, serially diluted in phosphate buffered saline, and plated on BHI plates in triplicate. Total colony forming units were counted macroscopically. Statistical analysis of the data was performed with a Kruskal-Wallis one-way ANOVA on ranks (p < 0.05, n = 60). Bacterial counts, expressed in log10 cfu/disk were as follows (">" denotes significant differences): Saline > Clidox-S = BioClenz > Clorox. All negative controls were sterile. Chlorine dioxide and NaOCL were both effective in eliminating E. faecalis from the dentinal disks within 30 min.

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and 2HH2O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks

USGS Publications Warehouse

Révész, Kinga M.; Lollar, Barbara Sherwood; Kirshtein, Julie D.; Tiedeman, Claire; Imbrigiotta, Thomas E.; Goode, Daniel J.; Shapiro, Allen M.; Voytek, Mary A.; Lancombe, Pierre J.; Busenberg, Eurybiades

2014-01-01

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in 2H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ13C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ2H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H2 gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE + VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average 13C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor.

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and ²HH₂O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks.

PubMed

Révész, Kinga M; Lollar, Barbara Sherwood; Kirshtein, Julie D; Tiedeman, Claire R; Imbrigiotta, Thomas E; Goode, Daniel J; Shapiro, Allen M; Voytek, Mary A; Lacombe, Pierre J; Busenberg, Eurybiades

2014-01-01

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in ²H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ¹³C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ²H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H₂ gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE+VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average ¹³C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor. © 2013. Published by Elsevier B.V. All rights reserved.

Fate of free chlorine in drinking water during distribution in premise plumbing.

PubMed

Zheng, Muzi; He, Chunguang; He, Qiang

2015-12-01

Free chlorine is a potent oxidizing agent and has been used extensively as a disinfectant in processes including water treatment. The presence of free chlorine residual is essential for the prevention of microbial regrowth in water distribution systems. However, excessive levels of free chlorine can cause adverse health effects. It is a major challenge to maintain appropriate levels of free chlorine residual in premise plumbing. As the first effort to assessing the fate of chlorine in premise plumbing using actual premise plumbing pipe sections, three piping materials frequently used in premise plumbing, i.e. copper, galvanized iron, and polyvinyl chloride (PVC), were investigated for their performance in maintaining free chlorine residual. Free chlorine decay was shown to follow first-order kinetics for all three pipe materials tested. The most rapid chlorine decay was observed in copper pipes, suggesting the need for higher chlorine dosage to maintain appropriate levels of free chlorine residual if copper piping is used. PVC pipes exhibited the least reactivity with free chlorine, indicative of the advantage of PVC as a premise plumbing material for maintaining free chlorine residual. The reactivity of copper piping with free chlorine was significantly hindered by the accumulation of pipe deposits. In contrast, the impact on chlorine decay by pipe deposits was not significant in galvanized iron and PVC pipes. Findings in this study are of great importance for the development of effective strategies for the control of free chlorine residual and prevention of microbiological contamination in premise plumbing.

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.;

Biodegradation of polychlorinated biphenyls (PCBs) by the novel identified cyanobacterium Anabaena PD-1

PubMed Central

Zhang, Hangjun; Jiang, Xiaojun; Lu, Liping; Xiao, Wenfeng

2015-01-01

Polychlorinated biphenyls (PCBs), a class of hazardous pollutants, are difficult to dissipate in the natural environment. In this study, a cyanobacterial strain Anabaena PD-1 showed good resistance against PCB congeners. Compared to a control group, chlorophyll a content decreased 3.7% and 11.7% when Anabaena PD-1 was exposed to 2 and 5 mg/L PCBs for 7 d. This cyanobacterial strain was capable of decomposing PCB congeners which was conclusively proved by determination of chloride ion concentrations in chlorine-free medium. After 7 d, the chloride ion concentrations in PCB-treated groups (1, 2, 5 mg/L) were 3.55, 3.05, and 2.25 mg/L, respectively. The genetic information of strain PD-1 was obtained through 16S rRNA sequencing analysis. The GenBank accession number of 16S rRNA of Anabaena PD-1 was KF201693.1. Phylogenetic tree analysis clearly indicated that Anabaena PD-1 belonged to the genus Anabaena. The degradation half-life of Aroclor 1254 by Anabaena PD-1 was 11.36 d; the total degradation rate for Aroclor 1254 was 84.4% after 25 d. Less chlorinated PCB congeners were more likely to be degraded by Anabaena PD-1 in comparison with highly chlorinated congeners. Meta- and para-chlorines in trichlorodiphenyls and tetrachlorobiphenyls were more susceptible to dechlorination than ortho-chlorines during the PCB-degradation process by Anabaena PD-1. Furthermore, Anabaena PD-1 can decompose dioxin-like PCBs. The percent biodegradation of 12 dioxin-like PCBs by strain PD-1 ranged from 37.4% to 68.4% after 25 days. Results above demonstrate that Anabaena PD-1 is a PCB-degrader with great potential for the in situ bioremediation of PCB-contaminated paddy soils. PMID:26177203

Optimal design and management of chlorination in drinking water networks: a multi-objective approach using Genetic Algorithms and the Pareto optimality concept

NASA Astrophysics Data System (ADS)

Nouiri, Issam

2017-11-01

This paper presents the development of multi-objective Genetic Algorithms to optimize chlorination design and management in drinking water networks (DWN). Three objectives have been considered: the improvement of the chlorination uniformity (healthy objective), the minimization of chlorine booster stations number, and the injected chlorine mass (economic objectives). The problem has been dissociated in medium and short terms ones. The proposed methodology was tested on hypothetical and real DWN. Results proved the ability of the developed optimization tool to identify relationships between the healthy and economic objectives as Pareto fronts. The proposed approach was efficient in computing solutions ensuring better chlorination uniformity while requiring the weakest injected chlorine mass when compared to other approaches. For the real DWN studied, chlorination optimization has been crowned by great improvement of free-chlorine-dosing uniformity and by a meaningful chlorine mass reduction, in comparison with the conventional chlorination.

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.

Meteoritic Sulfur Isotopic Analysis

NASA Technical Reports Server (NTRS)

Thiemens, Mark H.

1996-01-01

Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

Importance of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

PubMed

Wikström, Evalena; Ryan, Shawn; Touati, Abderrahmane; Telfer, Marnie; Tabor, Dennis; Gullett, Brian K

2003-03-15

The role of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) has been studied thoroughly in an entrained flow reactor during simulated waste combustion. The effects of gas-phase chlorine species such as chlorine (Cl2), hydrogen chloride (HCl), and chlorine radicals (Cl*), as well as ash-bound chlorine, on PCDD/F de novo formation were isolated for investigation. The ash-bound chlorine alone was observed to be a sufficient chlorine source for PCDD/F formation. The addition of HCl to the system did not influence the yields of the PCDDs/Fs nor the degree of chlorination due to its poor chlorinating ability. Addition of 200 ppm of Cl2 to the ash-feed system resulted in increased PCDD/F yields, especially for the octa- and hepta-chlorinated congeners. Altering the reaction temperature to enable the presence of only Cl2 to the system did not change the yields of PCDD/F compared to those when both Cl2/Cl* were present. However, comparison between ash-bound and gas-phase chlorine, the latter at a concentration typical of a realistic combustion process, revealed ash-bound chlorine to be the more important chlorine source for de novo formation of PCDD/F in a full-scale incinerator.

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

Barden, Holly E.; Behnsen, Julia; Bergmann, Uwe

Solenopora jurassica is a fossil calcareous alga that functioned as an important reef-building organism during the Palaeozoic. It is of significant palaeobiological interest due to its distinctive but poorly understood pink and white banding. Though widely accepted as an alga there is still debate over its taxonomic affinity, with recent work arguing that it should be reclassified as a chaetetid sponge. The banding is thought to be seasonal, but there is no conclusive evidence for this. Other recent work has, however demonstrated the presence of a unique organic boron-containing pink/red pigment in the pink bands of S. jurassica. We presentmore » new geochemical evidence concerning the seasonality and pigmentation of S. jurassica. Seasonal growth cycles are demonstrated by X-ray radiography, which shows differences in calcite density, and by varying δ 13C composition of the bands. Temperature variation in the bands is difficult to constrain accurately due to conflicting patterns arising from Mg/Ca molar ratios and δ 18O data. Fluctuating chlorine levels indicate increased salinity in the white bands, when combined with the isotope data this suggests more suggestive of marine conditions during formation of the white band and a greater freshwater component (lower chlorinity) during pink band precipitation (δ 18O). Increased photosynthesis is inferred within the pink bands in comparison to the white, based on δ 13C. Pyrolysis Gas Chromatography Mass Spectrometry (Py-GCMS) and Fourier Transform Infrared Spectroscopy (FTIR) show the presence of tetramethyl pyrrole, protein moieties and carboxylic acid groups, suggestive of the presence of the red algal pigment phycoerythrin. This is consistent with the pink colour of S. jurassica. As phycoerythrin is only known to occur in algae and cyanobacteria, and no biomarker evidence of bacteria or sponges was detected we conclude S. jurassica is most likely an alga. Pigment analysis may be a reliable classification method for fossil algae.« less

Geochemical Evidence of the Seasonality, Affinity and Pigmenation of Solenopora jurassica

DOE PAGES

Barden, Holly E.; Behnsen, Julia; Bergmann, Uwe; ...

2015-09-14

Solenopora jurassica is a fossil calcareous alga that functioned as an important reef-building organism during the Palaeozoic. It is of significant palaeobiological interest due to its distinctive but poorly understood pink and white banding. Though widely accepted as an alga there is still debate over its taxonomic affinity, with recent work arguing that it should be reclassified as a chaetetid sponge. The banding is thought to be seasonal, but there is no conclusive evidence for this. Other recent work has, however demonstrated the presence of a unique organic boron-containing pink/red pigment in the pink bands of S. jurassica. We presentmore » new geochemical evidence concerning the seasonality and pigmentation of S. jurassica. Seasonal growth cycles are demonstrated by X-ray radiography, which shows differences in calcite density, and by varying δ 13C composition of the bands. Temperature variation in the bands is difficult to constrain accurately due to conflicting patterns arising from Mg/Ca molar ratios and δ 18O data. Fluctuating chlorine levels indicate increased salinity in the white bands, when combined with the isotope data this suggests more suggestive of marine conditions during formation of the white band and a greater freshwater component (lower chlorinity) during pink band precipitation (δ 18O). Increased photosynthesis is inferred within the pink bands in comparison to the white, based on δ 13C. Pyrolysis Gas Chromatography Mass Spectrometry (Py-GCMS) and Fourier Transform Infrared Spectroscopy (FTIR) show the presence of tetramethyl pyrrole, protein moieties and carboxylic acid groups, suggestive of the presence of the red algal pigment phycoerythrin. This is consistent with the pink colour of S. jurassica. As phycoerythrin is only known to occur in algae and cyanobacteria, and no biomarker evidence of bacteria or sponges was detected we conclude S. jurassica is most likely an alga. Pigment analysis may be a reliable classification method for fossil algae.« less

Geochemical Evidence of the Seasonality, Affinity and Pigmenation of Solenopora jurassica

PubMed Central

Barden, Holly E.; Behnsen, Julia; Bergmann, Uwe; Leng, Melanie J.; Manning, Phillip L.; Withers, Philip J.; Wogelius, Roy A.; van Dongen, Bart E.

2015-01-01

Solenopora jurassica is a fossil calcareous alga that functioned as an important reef-building organism during the Palaeozoic. It is of significant palaeobiological interest due to its distinctive but poorly understood pink and white banding. Though widely accepted as an alga there is still debate over its taxonomic affinity, with recent work arguing that it should be reclassified as a chaetetid sponge. The banding is thought to be seasonal, but there is no conclusive evidence for this. Other recent work has, however demonstrated the presence of a unique organic boron-containing pink/red pigment in the pink bands of S. jurassica. We present new geochemical evidence concerning the seasonality and pigmentation of S. jurassica. Seasonal growth cycles are demonstrated by X-ray radiography, which shows differences in calcite density, and by varying δ13C composition of the bands. Temperature variation in the bands is difficult to constrain accurately due to conflicting patterns arising from Mg/Ca molar ratios and δ18O data. Fluctuating chlorine levels indicate increased salinity in the white bands, when combined with the isotope data this suggests more suggestive of marine conditions during formation of the white band and a greater freshwater component (lower chlorinity) during pink band precipitation (δ18O). Increased photosynthesis is inferred within the pink bands in comparison to the white, based on δ13C. Pyrolysis Gas Chromatography Mass Spectrometry (Py-GCMS) and Fourier Transform Infrared Spectroscopy (FTIR) show the presence of tetramethyl pyrrole, protein moieties and carboxylic acid groups, suggestive of the presence of the red algal pigment phycoerythrin. This is consistent with the pink colour of S. jurassica. As phycoerythrin is only known to occur in algae and cyanobacteria, and no biomarker evidence of bacteria or sponges was detected we conclude S. jurassica is most likely an alga. Pigment analysis may be a reliable classification method for fossil algae. PMID:26367117

Three-step effluent chlorination increases disinfection efficiency and reduces DBP formation and toxicity.

PubMed

Li, Yu; Zhang, Xiangru; Yang, Mengting; Liu, Jiaqi; Li, Wanxin; Graham, Nigel J D; Li, Xiaoyan; Yang, Bo

2017-02-01

Chlorination is extensively applied for disinfecting sewage effluents, but it unintentionally generates disinfection byproducts (DBPs). Using seawater for toilet flushing introduces a high level of bromide into domestic sewage. Chlorination of sewage effluent rich in bromide causes the formation of brominated DBPs. The objectives of achieving a disinfection goal, reducing disinfectant consumption and operational costs, as well as diminishing adverse effects to aquatic organisms in receiving water body remain a challenge in sewage treatment. In this study, we have demonstrated that, with the same total chlorine dosage, a three-step chlorination (dosing chlorine by splitting it into three equal portions with a 5-min time interval for each portion) was significantly more efficient in disinfecting a primary saline sewage effluent than a one-step chlorination (dosing chlorine at one time). Compared to one-step chlorination, three-step chlorination enhanced the disinfection efficiency by up to 0.73-log reduction of Escherichia coli. The overall DBP formation resulting from one-step and three-step chlorination was quantified by total organic halogen measurement. Compared to one-step chlorination, the DBP formation in three-step chlorination was decreased by up to 23.4%. The comparative toxicity of one-step and three-step chlorination was evaluated in terms of the development of embryo-larva of a marine polychaete Platynereis dumerilii. The results revealed that the primary sewage effluent with three-step chlorination was less toxic than that with one-step chlorination, indicating that three-step chlorination could reduce the potential adverse effects of disinfected sewage effluents to aquatic organisms in the receiving marine water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of a Chlorine Dosing Strategy for Fresh Produce Washing Process to Maintain Microbial Food Safety and Minimize Residual Chlorine.

PubMed

Chen, Xi; Hung, Yen-Con

2018-06-01

The residual free chlorine level in fresh produce wash solution is closely correlated to the chemical and microbial safety of produce. Excess amount of free chlorine can quickly react with organic matters to form hazardous disinfection by-products (DBPs) above EPA-permitted levels, whereas deficiency of residual chlorine in produce wash solution may result in incompletely removing pathogens on produce. The purpose of this study was to develop a chlorine dosing strategy to optimize the chlorine dosage during produce washing process without impacting the microbial safety of fresh produce. Prediction equations were developed to estimate free chlorine needed to reach targeted residual chlorine at various sanitizer pH and organic loads, and then validated using fresh-cut iceberg lettuce and whole strawberries in an automated produce washer. Validation results showed that equations successfully predicted the initial chlorine concentration needed to achieve residual chlorine at 10, 30, 60, and 90 mg/L for both lettuce and strawberry washing processes, with the root mean squared error at 4.45 mg/L. The Escherichia coli O157:H7 reductions only slightly increased on iceberg lettuce and strawberries with residual chlorine increasing from 10 to 90 mg/L, indicating that lowering residual chlorine to 10 mg/L would not compromise the antimicrobial efficacy of chlorine-based sanitizer. Based on the prediction equations and E. coli O157:H7 reduction results, a chlorine dosing strategy was developed to help the produce industry to maintain microbial inactivation efficacy without adding excess amount of free chlorine. The chlorine dosing strategy can be used for fresh produce washing process to enhance the microbial food safety and minimize the DBPs formation potential. © 2018 Institute of Food Technologists®.

Use of 0.1% chlorine dioxide to inhibit the formation of morning volatile sulphur compounds (VSC).

PubMed

Peruzzo, Daiane Cristina; Jandiroba, Priscila Fontoura Castelo Branco; Nogueira Filho, Getulio da Rocha

2007-01-01

The aim of this study was to evaluate the VSC-inhibiting effect of a commercially available mouthrinse (0.1% chlorine dioxide) when compared to its placebo. A 2-step double blind, crossover, randomised study was conducted with 14 dental students with healthy periodontium, who refrained from any mechanical plaque and tongue coating control during two 4-day experimental periods. The subjects were instructed to rinse 3 times daily with the assigned product during each period. A 7-day washout interval was established. VSCs levels were measured by a sulphide monitor at the beginning (baseline) and at the end of each experimental period. Statistical analyses were performed using Wilcoxon's and Mann-Whitney's non-parametric tests. At baseline, intragroup analysis revealed that VSCs levels did not differ between groups (p > 0.05); at day 5, the use of the chlorine dioxide mouthrinse did not change the baseline VSCs scores in the control group (p > 0.05), while a 2-fold increase was observed with the use of the placebo mouthrinse (p < 0.05). Intergroup analysis showed a significant difference between the VSCs levels of the test and control groups (40.2 +/- 30.72 and 82.3 +/- 75.63 ppb, p < 0.001) at day 5. Within the limits of this study, the findings suggest that a mouthrinse containing chlorine dioxide can maintain VSCs at lower levels in the morning breath.

Short-chain chlorinated paraffins (SCCPs) in surface soil from a background area in China: occurrence, distribution, and congener profiles.

PubMed

Wang, Xue-Tong; Zhang, Yuan; Miao, Yi; Ma, Ling-Ling; Li, Yuan-Cheng; Chang, Yue-Ya; Wu, Ming-Hong

2013-07-01

Short-chain chlorinated paraffins (SCCPs) are extremely complex technical mixtures of polychlorinated n-alkanes with carbon chain lengths from C10 to C13 and chlorine content between 49 and 70%. SCCPs are under consideration for inclusion in the Stockholm Convention on persistent organic pollutants. SCCPs have been used extensively in industrial production, but little is known about the pollution level in soil environment in China. In this study, levels and distribution of SCCPs in soil samples from Chongming Island were analyzed. Concentrations of total SCCPs in soil samples ranged from 0.42 to 420 ng g(-1), with a median of 9.6 ng g(-1). The ubiquitous occurrence of SCCPs in Chongming Island implied that long-range atmospheric transport and soil-air exchange may be the most important pathways for SCCP contamination in the background area. The localized SCCP contamination could be derived from an unidentified source. Hierarchical cluster analysis indicated that C13- and C11-congeners were predominant in most soils and C10- and C12-congeners dominated in the remaining soils. Cl7- and Cl8-congeners were on the average the most dominant chlorine congeners in nearly all soils. Principal component analysis suggested that the separation of even and odd carbon chain congeners occurred during long-range atmospheric transport and aging in soil in the study area.

Enduracidin Analogues with Altered Halogenation Patterns Produced by Genetically Engineered Strains of Streptomyces fungicidicus

PubMed Central

Yin, Xihou; Chen, Ying; Zhang, Ling; Wang, Yang; Zabriskie, T. Mark

2010-01-01

Enduracidins (1, 2) and ramoplanin (3) are structurally and functionally closely related lipodepsipeptide antibiotics. They are active against multidrug resistant Gram-positive pathogens, including MRSA. Each peptide contains one chlorinated non-proteinogenic amino acid residue, Cl2-Hpg or Cl-Hpg. To investigate the timing of halogenation, the importance of chlorination on bioactivity and bioavailability of enduracidin, and to probe the substrate specificity and portability of the ramoplanin halogenase, we constructed the mutant strain SfΔ30 in which the enduracidin halogenase gene orf30 had been deleted and complemented it with the ramoplanin counterpart orf20. We also expressed orf20 in the enduracidin wild type producer. Metabolite analysis revealed SfΔ30 produced the novel analogues dideschloroenduracidins A (4) and B (5), while the recombinant strains SfΔ30R20 and SfR20 produced monodeschloroenduracidins A (6) and B (7), and a trichlorinated enduracidin (8), respectively. In addition, orf30 self-complementation yielded the strain SfΔ30E30 which is capable of producing six peptides including 6 and 7. MS/MS analysis positioned the single chlorine atom in 6 at Hpg13 and localized the third chlorine atom in 8 to Hpg11. Biological evaluation of these enduracidin analogues indicated that all retained activity against Staphylococcus aureus. Our findings lay the foundation for further utilization of enduracidin and ramoplanin halogenases in combinatorial biosynthesis. PMID:20353165

Chlorine in mid-ocean ridge magmas: Evidence for assimilation of seawater-influenced components

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

Michael, P.J.; Schilling, J.G.

1989-12-01

Suites of depleted MORB glasses from the fast-spreading Pacific-Nazca Ridge at 28{degree}S and 32{degree}S and the slow-spreading eastern boundary of the Juan Fernandez microplate were analyzed for chlorine by electron microprobe. The Cl concentrations in FeTi basalts exceed by a factor of 5 to 10 the amounts that can be generated by fractional crystallization of the primitive magmas. Selective melting or breakdown of amphibole and incorporation of Cl-rich brine contained in the wall rocks may be important processes. A magmatic source for the additional Cl and H{sub 2}O cannot be ruled out on geochemical grounds but is physically unrealistic becausemore » it requires that large volumes of magma have crystallized and exsolved a Cl-rich vapor phase that has somehow migrated to a small magma chamber. Excess Cl in evolved magmas is best developed in evolved MORB from propagating or overlapping spreading centers such as the Galapagos Spreading Center at 85{degree}W and 95{degree}W and the west ridge of the Juan Fernandez microplate. Cl overenrichment has not been observed on slow-spreading ridges including the eastern ridge of the Juan Fernandez microplate, the Southwest Indian Ridge, and the mid-Atlantic Ridge. The assimilation of hydrothermally altered material could influence the concentration and isotopic ratios of other elements which have low abundances in MORB relative to seawater.« less

Formation of halogenated organics during waste-water disinfection

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

Singer, P.C.; Brown, R.A.; Wiseman, J.F.

The research examined the formation of trihalomethanes (THMs) and total organic halides (TOX) during wastewater chlorination at three wastewater treatment plants in the central Piedmont of North Carolina. Secondary effluent samples were collected before and after the addition of chlorine at each of the three treatment facilities; chlorinated samples were taken from various locations within the chlorine contact chambers and at the plant discharge. Water samples were also collected upstream and downstream from two of the plant outfalls to determine the increase and persistence of THMs and TOX below each plant. TOX and THM formation was evaluated in terms ofmore » effluent wastewater quality (e.g., residual chemical oxygen demand, total organic carbon and ammonia concentration), chlorine dose, chlorine contacting system, methods of chlorine addition, and chlorine-to-ammonia ratio. The results showed that TOX was present in the unchlorinated wastewater and that additional TOX was formed immediately after chlorine addition. Small to insignificant amounts of THMS were detected. TOX formation did not increase with increasing contact time, due to the rapid depletion of free chlorine and the formation of combined chlorine in the chlorine contact chamber.« less

Influence of increasing chlorine content on the accumulation and metabolism of polychlorinated biphenyls (PCBs) by Paul's Scarlet rose cells

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

Groeger, A.G.; Fletcher, J.S.

1988-01-01

Four radiolabeled congeners of biphenyls with increasing chlorine content (biphenyl; 1-monochlorobiphenyl; 2,2',4,4'-tetrachlorobiphenyl; and 2,2',4,4',5,5'-hexachlorobiphenyl) were provided to suspension cultures of rose (Rosa sp. vc. Paul's Scarlet) for four days. Both the kinetics of (14)C exchange between the cells and medium, and the metabolism of the parent compounds depended on the chlorine content of the congeners. Analysis of both the cells and their medium showed that of the recovered radioactivity 88%, 86%, and 3% of the biphenyl, 1-PCB, and 2,2',4,4'-PCB were metabolized respectively to polar and insoluble residue products. The 2,2',4,4',5,5'-PCB did not appear to be metabolized.

[Analysis of short-chain chlorinated paraffins in sediment samples from the mouth of the Daliao River by HRGC/ECNI-LRMS].

PubMed

Gao, Yuan; Wang, Cheng; Zhang, Hai-jun; Zou, Li-li; Tian, Yu-zeng; Chen, Ji-ping

2010-08-01

An analytical method for quantifying short-chain chlorinated paraffins (SCCPs) by high-resolution gas chromatography/electron capture negative ion low-resolution mass spectrometry (HRGC/ECNI-LRMS) was presented. The cleanup procedure with an acid silica gel column and activated neutral alumina column was optimized to remove the interferences. As illustration of the application of the method to environmental samples, it is found that lower chlorinated C10 and C11 compounds were the main SCCPs compounds in six sediment samples from the mouth of the Daliao River. The concentrations of SCCPs in sediments were determined to be in the range of 64.9-407.0 ng/g and showed a decreasing tendency from the shore to the remote location.

Is it really organic?--multi-isotopic analysis as a tool to discriminate between organic and conventional plants.

PubMed

Laursen, K H; Mihailova, A; Kelly, S D; Epov, V N; Bérail, S; Schjoerring, J K; Donard, O F X; Larsen, E H; Pedentchouk, N; Marca-Bell, A D; Halekoh, U; Olesen, J E; Husted, S

2013-12-01

Novel procedures for analytical authentication of organic plant products are urgently needed. Here we present the first study encompassing stable isotopes of hydrogen, carbon, nitrogen, oxygen, magnesium and sulphur as well as compound-specific nitrogen and oxygen isotope analysis of nitrate for discrimination of organically and conventionally grown plants. The study was based on wheat, barley, faba bean and potato produced in rigorously controlled long-term field trials comprising 144 experimental plots. Nitrogen isotope analysis revealed the use of animal manure, but was unable to discriminate between plants that were fertilised with synthetic nitrogen fertilisers or green manures from atmospheric nitrogen fixing legumes. This limitation was bypassed using oxygen isotope analysis of nitrate in potato tubers, while hydrogen isotope analysis allowed complete discrimination of organic and conventional wheat and barley grains. It is concluded, that multi-isotopic analysis has the potential to disclose fraudulent substitutions of organic with conventionally cultivated plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

How effective is intermittent chlorination to control adult mussel fouling in cooling water systems?

PubMed

Rajagopal, Sanjeevi; Van der Velde, Gerard; Van der Gaag, Marinus; Jenner, Henk A

2003-01-01

Mussel control in cooling water systems is generally achieved by means of chlorination. Chlorine is applied continuously or intermittently, depending on cost and discharge criteria. In this paper, we examined whether mussels will be able to survive intermittent chlorination because of their ability to close their valves during periods of chlorination. Experiments were carried out using three common species of mussels: a freshwater mussel, Dreissena polymorpha, a brackish water mussel, Mytilopsis leucophaeata and a marine mussel, Mytilus edulis. The mussels were subjected to continuous or intermittent (4 h chlorination followed by 4 h no chlorination) chlorination at concentrations varying from 1 to 3 mg l(-1) and their responses (lethal and sublethal) were compared to those of control mussels. In addition, shell valve activity of mussels was monitored using a Mussel-monitor. Data clearly indicate that mussels shut their valves as soon as chlorine is detected in the environment and open only after chlorine dosing is stopped. However, under continuous chlorination mussels are constrained to keep the shell valves shut continuously. The mussels subjected to continuous chlorination at 1 mg l(-1) showed 100% mortality after 588 h (D. polymorpha), 966 h (Mytilus edulis) and 1104 h (Mytilopsis leucophaeata), while those subjected to intermittent chlorination at 1 mg l(-1) showed very little or no mortality during the same periods. Filtration rate, foot activity index and shell valve movement of D. polymorpha, Mytilopsis leucophaeata and Mytilus edulis decreased more than 90% at 1 mg l(-1) chlorine residual when compared to control. However, mussels subjected to intermittent chlorination showed a similar reduction (about 90%) in filtration rate, foot activity index and shell valve movement during chlorination and 3% during breaks in chlorination. The data indicate that intermittent chlorination between 1 and 3 mg l(-1) applied at 4 h on and 4 h off cycle is unlikely to control biofouling if mussels are the dominant fouling organisms.

In-situ Ar isotope, 40Ar/39Ar analysis and mineral chemistry of nosean in the phonolite from Olbrück volcano, East Eifel volcanic field, Germany: Implication for the source of excess 40Ar

NASA Astrophysics Data System (ADS)

Sudo, Masafumi; Altenberger, Uwe; Günter, Christina

2014-05-01

Since the report by Lippolt et al. (1990), hauyne and nosean phenocrysts in certain phonolites from the northwest in the Quaternary East Eifel volcanic field in Germany were known to contain significant amounts of excess 40Ar, thus, show apparent older ages than the other minerals. However, its petrographic meaning have not been well known. Meanwhile, Sumino et al. (2008) has identified the source of the excess 40Ar in the plagioclase phenocrysts from the historic Unzen dacite lava as the melt inclusions in the zones parallely developed to the plagioclase rim by in-situ laser Ar isotope analysis. In order to obtain eruption ages of very young volcanoes as like Quaternary Eifel volcanic field by the K-Ar system, it is quite essential to know about the location of excess 40Ar in volcanic rocks. We have collected phonolites from the Olbrück volcano in East Eifel and investigated its petrography and mineral chemistry and also performed in-situ Ar isotope analyses of unirradiated rock section sample and also in-situ 40Ar/39Ar analysis of neutron irradiated section sample with the UV pulse laser (wavelength 266 nm) and 40Ar/39Ar analytical system of the University of Potsdam. Petrographically, nosean contained fine melt and/or gas inclusions of less than 5 micrometer, which mostly distribute linearly and are relatively enriched in chlorine than the areas without inclusions. Solid inclusions of similar sizes contain CaO and fluorine. In nosean, typically around 5 wt% of sulfur is contained. The 40Ar/39Ar dating was also performed to leucite, sanidine and groundmass in the same section for comparison of those ages with that of nosean. In each analysis, 200 micrometer of beam size was used for making a pit with depth of up to 300 micrometer by laser ablation. As our 40Ar/39Ar analyses were conducted one and half year after the neutron irradiation, thus, short lived 37Ar derived from Ca had decayed very much, we measured Ca and K contents in nosean by SEM-EDS then applied their Ca/K ratios to the Ar analytical results. The in-situ Ar isotopic analysis of nosean and leucite show clearly the different slope of isochron and implied apparent older age for the nosean. The in-situ 40Ar/39Ar analysis of nosean yields three various ages, from 6.86 ± 2.77 Ma to 41.57 ± 11.58 Ma, but clearly older than those of the other minerals and groundmass. However, it was difficult to analyze and compare the 40Ar/39Ar ages between different areas with or without inclusions by the UV-laser because of its less spatial resolution, therefore, was difficult to understand the correlation between ages and the presence of inclusions. Considering the enriched contents of S and Cl in nosean, the excess 40Ar could be derived from the common volatile component separated from the magma which provided S and Cl then be trapped in nosean during or after the formation of nosean. References: Lippolt, H. J., M. Troesch and J. C. Hess (1990) Earth Planet. Sci. Lett., 101, 19-33 Sumino, H., K. Ikehata, A. Shimizu, K. Nagao and S. Nakada (2008) J. Volcanol. Geotherm. Res., 175, 189-207

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

Matzel, J P; Jacobsen, B; Hutcheon, I D

The abundance of short-lived radionuclides (SLRs) in early solar system materials provide key information about their nucleosynthetic origin and can constrain the timing of early solar system events. Excesses of {sup 36}S ({sup 36}S*) correlated with {sup 35}Cl/{sup 34}S ratios provide direct evidence for in situ decay of {sup 36}Cl ({tau}{sub 1/2} {approx} 0.3 Ma) and have been reported in sodalite (Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}Cl{sub 2}) and wadalite (Ca{sub 6}Al{sub 5}Si{sub 2}O{sub 16}Cl{sub 3}) in CAIs and chondrules from the Allende and Ningqiang CV carbonaceous chondrites. While previous studies demonstrate unequivocally that {sup 36}Cl was extant in the earlymore » solar system, no consensus on the origin or initial abundance of {sup 36}Cl has emerged. Understanding the origin of {sup 36}Cl, as well as the reported variation in the initial {sup 36}Cl/{sup 35}Cl ratio, requires addressing when, where and how chlorine was incorporated into CAIs and chondrules. These factors are key to distinguishing between stellar nucleosynthesis or energetic particle irradiation for the origin of {sup 36}Cl. Wadalite is a chlorine-rich secondary mineral with structural and chemical affinities to grossular. The high chlorine ({approx}12 wt%) and very low sulfur content (<<0.01 wt%) make wadalite ideal for studies of the {sup 36}Cl-{sup 36}S system. Wadalite is present in Allende CAIs exclusively in the interior regions either in veins crosscutting melilite or in zones between melilite and anorthite associated with intergrowths of grossular, monticellite, and wollastonite. Wadalite and sodalite most likely resulted from open-system alteration of primary minerals with a chlorine-rich fluid phase. We recently reported large {sup 36}S* correlated with {sup 35}Cl/{sup 34}S in wadalite in Allende Type B CAI AJEF, yielding a ({sup 36}Cl/{sup 35}Cl){sub 0} ratio of (1.7 {+-} 0.3) x 10{sup -5}. This value is the highest reported {sup 36}Cl/{sup 35}Cl ratio and is {approx}5 times greater than values for sodalite in some CAIs and chondrules. We report here new {sup 36}Cl-{sup 36}S isotope measurements of wadalite in two Type B CAIs (TS34 and Egg-6) and sodalite in a fine-grained CAI (Pink Angel) from Allende.« less

Influence of Plants on Chlorine Cycling in Terrestrial Environments

NASA Astrophysics Data System (ADS)

Montelius, Malin; Thiry, Yves; Marang, Laura; Ranger, Jacques; Cornelis, Jean-Thomas; Svensson, Teresia; Bastviken, David

2016-04-01

Chlorine (Cl), one of the 20 most abundant elements on Earth, is crucial for life as a regulator of cellular ionic strength and an essential co-factor in photosynthesis. Chlorinated organic compounds (Clorg) molecules are surprisingly abundant in soils, in fact many studies during the last decades show that Clorg typically account for more than 60% of the total soil Cl pool in boreal and temperate forest soils and frequently exceed chloride (Cl-) levels. The natural and primarily biotic formation of this Clorg pool has been confirmed experimentally but the detailed content of the Clorg pool and the reasons for its high abundance remains puzzling and there is a lack of Cl budgets for different ecosystems. Recently, the radioisotope 36Cl has caused concerns because of presence in radioactive waste, a long half-life (301 000 years), potential high mobility, and limited knowledge about Cl residence times, speciation and uptake by organisms in terrestrial environments. The chlorination of organic molecules may influence the pool of available Cl- to organisms and thereby the Cl cycling dynamics. This will prolong residence times of total Cl in the soil-vegetation system, which affects exposure times in radioactive 36Cl isotope risk assessments. We tested to what extent the dominating tree species influences the overall terrestrial Cl cycling and the balance between Cl- and Clorg. Total Cl and Clorg were measured in different tree compartments and soil horizons in the Breuil experimental forest, Bourgogne, established in 1976 and located at Breuil-Chenue in Eastern France. The results from this field experiment show how the dominating tree species affected Cl cycling and accumulation over a time period of 30 years. Cl uptake by trees as well as content of both total Cl and Clorg in soil humus was much higher in experimental plots with coniferous forests compared to deciduous forests. The amounts of Clorg found in plant tissue indicate significant Clorg production inside trees in addition to substantial soil production of Clorg. A large and tree species dependent "luxury" Cl uptake, rapidly released through the leaves and returned to the soil as throughfall, was indicated for some tree species. The physiology of dominating tree species, along with tree-related soil microbial communities, thus appears more important for the local Cl levels and cycling than atmospheric Cl deposition.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

PubMed

Sun, Peizhe; Lee, Wan-Ning; Zhang, Ruochun; Huang, Ching-Hua

2016-12-20

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br - and Cl - may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

40 CFR 268.40 - Applicability of treatment standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... chlorinated aliphatic hydrocarbons by free radical catalyzed processes. These chlorinated aliphatic... chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic... production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These...

40 CFR 268.40 - Applicability of treatment standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... chlorinated aliphatic hydrocarbons by free radical catalyzed processes. These chlorinated aliphatic... chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic... production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These...

Biometrics from the carbon isotope ratio analysis of amino acids in human hair.

PubMed

Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

2015-01-01

This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

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.

Evaluating the Sustained Health Impact of Household Chlorination of Drinking Water in Rural Haiti

PubMed Central

Harshfield, Eric; Lantagne, Daniele; Turbes, Anna; Null, Clair

2012-01-01

The Jolivert Safe Water for Families program has sold sodium hypochlorite solution (chlorine) and conducted household visits in rural Haiti since 2002. To assess the impact of the program on diarrheal disease, in 2010 we conducted a survey and water quality testing in 201 program participants and 425 control households selected at random. Fifty-six percent of participants (versus 10% of controls) had free chlorine residuals between 0.2 and 2.0 mg/L, indicating correct water treatment. Using intention-to-treat analysis, we found that significantly fewer children < 5 in participant households had an episode of diarrhea in the previous 48 hours (32% versus 52%; P < 0.001) with 59% reduced odds (odds ratio = 0.41, 95% confidence interval = 0.21–0.79). Treatment-on-treated estimates of the odds of diarrhea indicated larger program effects for participants who met more stringent verifications of participation. Diarrheal disease reduction in this long-term program was comparable with that seen in short-term randomized, controlled interventions, suggesting that household chlorination can be an effective long-term water treatment strategy. PMID:22987657

Effect of sodium hypochlorite on typical biofilms formed in drinking water distribution systems.

PubMed

Lin, Huirong; Zhu, Xuan; Wang, Yuxin; Yu, Xin

2017-04-01

Human health and biological safety problems resulting from urban drinking water pipe network biofilms pollution have attracted wide concern. Despite the inclusion of residual chlorine in drinking water distribution systems supplies, the bacterium is a recalcitrant human pathogen capable of forming biofilms on pipe walls and causing health risks. Typical drinking water bacterial biofilms and their response to different concentrations of chlorination was monitored. The results showed that the four bacteria all formed single biofilms susceptible to sodium hypochlorite. After 30 min disinfection, biomass and cultivability decreased with increasing concentration of disinfectant but then increased in high disinfectant doses. PMA-qPCR results indicated that it resulted in little cellular damage. Flow cytometry analysis showed that with increasing doses of disinfectant, the numbers of clusters increased and the sizes of clusters decreased. Under high disinfectant treatment, EPS was depleted by disinfectant and about 0.5-1 mg/L of residual chlorine seemed to be appropriate for drinking water treatment. This research provides an insight into the EPS protection to biofilms. Resistance of biofilms against high levels of chlorine has implications for the delivery of drinking water.

Evaluating the sustained health impact of household chlorination of drinking water in rural Haiti.

PubMed

Harshfield, Eric; Lantagne, Daniele; Turbes, Anna; Null, Clair

2012-11-01

The Jolivert Safe Water for Families program has sold sodium hypochlorite solution (chlorine) and conducted household visits in rural Haiti since 2002. To assess the impact of the program on diarrheal disease, in 2010 we conducted a survey and water quality testing in 201 program participants and 425 control households selected at random. Fifty-six percent of participants (versus 10% of controls) had free chlorine residuals between 0.2 and 2.0 mg/L, indicating correct water treatment. Using intention-to-treat analysis, we found that significantly fewer children < 5 in participant households had an episode of diarrhea in the previous 48 hours (32% versus 52%; P < 0.001) with 59% reduced odds (odds ratio = 0.41, 95% confidence interval = 0.21-0.79). Treatment-on-treated estimates of the odds of diarrhea indicated larger program effects for participants who met more stringent verifications of participation. Diarrheal disease reduction in this long-term program was comparable with that seen in short-term randomized, controlled interventions, suggesting that household chlorination can be an effective long-term water treatment strategy.

Genotoxicity of drinking water treated with different disinfectants and effects of disinfection conditions detected by umu-test.

PubMed

Nie, Xuebiao; Liu, Wenjun; Zhang, Liping; Liu, Qing

2017-06-01

The genotoxicity of drinking water treated with 6 disinfection methods and the effects of disinfection conditions were investigated using the umu-test. The pretreatment procedure of samples for the umu-test was optimized for drinking water analysis. The results of the umu-test were in good correlation with those of the Ames-test. The genotoxicity and production of haloacetic acids (HAAs) were the highest for chlorinated samples. UV+chloramination is the safest disinfection method from the aspects of genotoxicity, HAA production and inactivation effects. For chloramination, the effects of the mass ratio of Cl 2 to N of chloramine on genotoxicity were also studied. The changes of genotoxicity were different from those of HAA production, which implied that HAA production cannot represent the genotoxic potential of water. The genotoxicity per chlorine decay of chlorination and chloramination had similar trends, indicating that the reaction of organic matters and chlorine made a great contribution to the genotoxicity. The results of this study are of engineering significance for optimizing the operation of waterworks. Copyright © 2016. Published by Elsevier B.V.

Decline in Antarctic Ozone Depletion and Lower Stratospheric Chlorine Determined From Aura Microwave Limb Sounder Observations

NASA Astrophysics Data System (ADS)

Strahan, Susan E.; Douglass, Anne R.

2018-01-01

Attribution of Antarctic ozone recovery to the Montreal protocol requires evidence that (1) Antarctic chlorine levels are declining and (2) there is a reduction in ozone depletion in response to a chlorine decline. We use Aura Microwave Limb Sounder measurements of O3, HCl, and N2O to demonstrate that inorganic chlorine (Cly) from 2013 to 2016 was 223 ± 93 parts per trillion lower in the Antarctic lower stratosphere than from 2004 to 2007 and that column ozone depletion declined in response. The mean Cly decline rate, 0.8%/yr, agrees with the expected rate based on chlorofluorocarbon lifetimes. N2O measurements are crucial for identifying changes in stratospheric Cly loading independent of dynamical variability. From 2005 to 2016, the ozone depletion and Cly time series show matching periods of decline, stability, and increase. The observed sensitivity of O3 depletion to changing Cly agrees with the sensitivity simulated by the Global Modeling Initiative chemistry transport model integrated with Modern Era Retrospective Analysis for Research and Applications 2 meteorology.

Kraft pulp bleaching and delignification by dikaryons and monokaryons of trametes versicolor

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

Addleman, K.; Archibald, F.

1993-01-01

To reduce the levels of chlorinated lignin residues in effluents from the pulp and paper industry, interest has focused on the white rot basidiomycete fungi. The kraft process, the most common commercial delignification method, produces a dark pulp which is bleached by use of chlorine, chlorine dioxide, and caustic extraction. A dikaryon of Trametes (Coriolus) versicolor has been shown to bleach and delignify kraft pulp, offering a possible alternative to chlorine. A monokaryon strain, if comparable to the effect of the dikaryon, would be a much simpler system for study of mechanisms and genetic munipulation. The researchers compared strains ofmore » both and conclude that the following characteristics justify replacing the parent dikaryon with monokaryon 52J in future work on biobleaching and biological delignification: (1) reduced biomass and slower growth rate; (2)no dark pigment production; (3) superior biological bleaching ability; (4) a simpler system for genetic manipulation and biochemical analysis. The involvement of MnP, but not LP, in pulp bleaching, delignification is strongly suggested. 40 refs., 3 figs., 4 tabs.« less

Chlorine hazard evaluation for the zinc-chlorine electric vehicle battery. Final technical report

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

Zalosh, R.G.; Bajpai, S.N.; Short, T.P.

1980-04-01

An evaluation of the hazards associated with conceivable accidental chlorine releases from zinc-chlorine electric vehicle batteries is presented. Since commercial batteries are not yet available, this hazard assessment is based both on theoretical chlorine dispersion models and small-scale and large-scale spill tests with chlorine hydrate. Six spill tests involving chlorine hydrate indicate that the danger zone in which chlorine vapor concentrations intermittently exceed 100 ppM extends at least 23 m directly downwind of a spill onto a warm road surface. Chlorine concentration data from the hydrate spill tests compare favorably with calculations based on a quasi-steady area source dispersion modelmore » and empirical estimates of the hydrate decomposition rate. The theoretical dispersion model has been combined with assumed hydrate spill probabilities and current motor vehicle accident statistics in order to project expected chlorine-induced fatality rates. These calculations indicate that expected chlorine fatality rates are several times higher in a city with a warm and calm climate than in a colder and windier city. Calculated chlorine-induced fatality rate projections for various climates are presented as a function of hydrate spill probability in order to illustrate the degree of vehicle/battery crashworthiness required to maintain chlorine-induced fatality rates below current vehicle fatility rates due to fires and asphyxiations.« less

Chlorination kinetics of glyphosate and its by-products: modeling approach.

PubMed

Brosillon, Stephan; Wolbert, Dominique; Lemasle, Marguerite; Roche, Pascal; Mehrsheikh, Akbar

2006-06-01

Chlorination reactions of glyphosate, glycine, and sodium cyanate were conducted in well-agitated reactors to generate experimental kinetic measurements for the simulation of chlorination kinetics under the conditions of industrial water purification plants. The contribution of different by-products to the overall degradation of glyphosate during chlorination has been identified. The kinetic rate constants for the chlorination of glyphosate and its main degradation products were either obtained by calculation according to experimental data or taken from published literature. The fit of the kinetic constants with experimental data allowed us to predict consistently the concentration of the majority of the transitory and terminal chlorination products identified in the course of the glyphosate chlorination process. The simulation results conducted at varying aqueous chlorine/glyphosate molar ratios have shown that glyphosate is expected to degrade in fraction of a second under industrial aqueous chlorination conditions. Glyphosate chlorination products are not stable under the conditions of drinking water chlorination and are degraded to small molecules common to the degradation of amino acids and other naturally occurring substances in raw water. The kinetic studies of the chlorination reaction of glyphosate, together with calculations based on kinetic modeling in conditions close to those at real water treatment plants, confirm the reaction mechanism that we have previously suggested for glyphosate chlorination.

40 CFR 401.15 - Toxic pollutants.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (technical mixture and metabolites) 14. Chlorinated benzenes (other than di-chlorobenzenes) 15. Chlorinated... ethers (chloroethyl and mixed ethers) 17. Chlorinated naphthalene 18. Chlorinated phenols (other than those listed elsewhere; includes trichlorophenols and chlorinated cresols) 19. Chloroform 20. 2...

Design and synthesis of chlorinated benzothiadiazole-based polymers for efficient solar energy conversion

DOE PAGES

Hu, Zhiming; Chen, Hui; Qu, Jianfei; ...

2017-03-10

Here, chlorinated benzothiadiazide based polymers with multiple chlorine atoms has been designed and synthesized for polymer solar cells with enhanced open circuit voltage up to 0.85 V. The chlorine substitution is found to significantly adjust the band gap of the polymers, and change polymer’s orientation from random morphology of chlorine free PBT4T-2OD, to mixed face-on packing of one chlorine substituted PCBT4T-2OD, and finally to edge-on of two chlorine substituted PCCBT4T-2OD. The optimized chlorinated polymer, PCBT4T-2OD with only one chlorine atom substituted on BT moiety, has been founded to achieve the highest power conversion efficiency up to 8.20% with PC 71BM,more » which is about 68% higher than that of its non-chlorine analogues.« less

Evaluation of the fate and transport of chlorinated ethenes in a complex groundwater system discharging to a stream in Wonju, Korea.

PubMed

Lee, Seong-Sun; Kaown, Dugin; Lee, Kang-Kun

2015-11-01

Chlorinated ethenes such as trichloroethylene (TCE) are common and persistent groundwater contaminants. If contaminated groundwater discharges to a stream, then stream water pollution near the contamination site also becomes a problem. In this respect, the fate and transport of chlorinated ethenes around a stream in an industrial complex were evaluated using the concentration of each component, and hydrogeochemical, microbial, and compound-specific carbon isotope data. Temporal and spatial monitoring reveal that a TCE plume originating from main and local source zones continues to be discharged to a stream. Groundwater geochemical data indicate that aerobic conditions prevail in the upgradient area of the studied aquifer, whereas conditions become anaerobic in the downgradient. The TCE molar fraction is high at the main and local source zones, ranging from 87.4 to 99.2% of the total volatile organic compounds (VOCs). An increasing trend in the molar fraction of cis-1, 2-Dichloroethene (cis-DCE) and vinyl chloride (VC) was observed in the downgradient zone of the study area. The enriched δ(13)C values of TCE and depleted values of cis-DCE in the stream zone, compared to those of the source zone, also suggest biodegradation of VOCs. Microbial community structures in monitoring wells adjacent to the stream zone in the downgradient area were analyzed using 16S rRNA gene-based pyrosequencing to identify the microorganisms responsible for biodegradation. This was attributed to the high relative abundance of dechlorinating bacteria in monitoring wells under anaerobic conditions farthest from the stream in the downgradient area. The multilateral approaches adopted in this study, combining hydrogeochemical and biomolecular methods with compound-specific analyses, indicate that contaminants around the stream were naturally attenuated by active anaerobic biotransformation processes. Copyright © 2015 Elsevier B.V. All rights reserved.

Brine/Rock Interaction in Deep Oceanic Layered Gabbros: Petrological Evidence from Cl-Rich Amphibole, High-Temperature Hydrothermal Veins, and Experiments

NASA Astrophysics Data System (ADS)

Currin Sala, A. M.; Koepke, J.; Almeev, R. R.; Teagle, D. A. H.; Zihlmann, B.; Wolff, P. E.

2017-12-01

Evidence of high temperature brine/rock interaction is found in hydrothermal veins and dykelets that cross-cut layered olivine gabbros in the deep palaeocrust of the Sumail Ophiolite, Sultanate of Oman. Here we present petrological and geochemical data from these samples, and an experimental attempt to simulate brine/gabbro interaction using externally heated cold seal pressure vessels. The studied natural veins and dykelets contain pargasite, hornblende, actinolite, and Cl-rich pargasite with up to 5 wt% Cl, showing a range of formation conditions from magmatic to metamorphic (hydrothermal) and thus a complex history of brine/rock interaction. In addition, the isotopic study of the radiogenic 87/86Sr and stable 18O in different amphibole types provide an estimate for the extent of seawater influence as alteration agent in the veins of the studied samples. Experiments performed at 750 °C and 200 MPa with different starting materials (chlorine-free amphibole, olivine gabbro powder) and 20 wt% NaCl aqueous brine, illustrate the process by which gabbro-hosted amphibole-rich veins evolve at subsolidus temperatures in the presence of a seawater-derived fluid. Our results demonstrate a decrease in olivine, plagioclase and magnetite content in favour of hastingsite, pargasite and magnesiohornblende, a decrease of IVAl and Ti in the starting amphibole, and an increase in Cl in amphibole, up to 0.2 Cl wt%. Our experiments show the change of magmatic pargasite towards more magnesium and silica-rich end members with results comparable to mildly chlorine-rich pargasites and hornblendes found in the natural samples studied. However, the experimental setup also presents limitations in the attainment of very high-chlorine amphibole (up to 5 wt%). Our analytical and experimental results provide further evidence for the existence of a hydrothermal cooling system in the deep oceanic crust.

Reactive Minerals and Dechlorinating Communities: Mechanisms Governing the Degradation of Chlorinated Ethenes during Back Diffusion from Low Permeability Zones in Aerobic and Anaerobic Environments

NASA Astrophysics Data System (ADS)

Berns, E. C.; Zeng, R.; Singh, H.; Valocchi, A. J.; Sanford, R. A.; Strathmann, T. J.; Schaefer, C. E.; Werth, C. J.

2017-12-01

Low permeability zones (LPZs) comprised of silts and clays, and contaminated with chlorinated ethenes, can act as a long term source of contaminated groundwater by diffusion into adjacent high permeability zones (HPZs). Following initial remediation efforts, chlorinated ethenes that have diffused into LPZs will back diffuse and recontaminate HPZs. Because chlorinated ethenes are known to cause cancer and damage the liver, kidneys, and central nervous system, it is important to understand how they degrade in natural systems and how to model their fate and transport. Previous work has shown that anaerobic hydrogenolysis reactions are facilitated by both dechlorinating microorganisms and reactive minerals. Abiotic dichloro-elimination reactions with reactive minerals can also degrade chlorinated ethenes to acetylene, albeit at slower rates than biotic processes. More recently, studies have explored aerobic abiotic degradation of chlorinated ethenes to formate, glycolate, and carbon dioxide. This study focuses on these biotic and abiotic reactions and their contributions to chlorinated ethene degradation under aerobic and anaerobic conditions at the LPZ/HPZ interface. A two-dimensional flow cell was constructed to model this interface using clay and sand from Pease Air Force Base. The clay was inoculated with a dechlorinating enrichment culture. Tenax adsorbent beads equilibrated with trichloroethylene (TCE) were used as a chlorinated ethene source zone at the base of the clay. TCE and its degradation products diffused from the clay into the sand, where they were removed from the flow cell by groundwater at a rate of 50 mL/day. Volatile compounds were trapped in a sample loop and removed every 48 hours for analysis by GC-FID. Organic and inorganic ions in the effluent were analyzed on the HPLC and IC. The experiment was terminated by freezing the flow cell, and chemical profiles through the flow cell material were created to show the spatial distribution of degradation products. Chemical profiles through the clay were modeled using a 1D diffusion-reaction model, and the contributions of abiotic and biotic processes to TCE degradation were determined. The model and experimental data lend insights into transformation processes that control the fate and transport of chlorinated ethenes at contaminated sites.

Comparative investigation of X-ray contrast medium degradation by UV/chlorine and UV/H2O2.

PubMed

Kong, Xiujuan; Jiang, Jin; Ma, Jun; Yang, Yi; Pang, Suyan

2018-02-01

The degradation of iopamidol and diatrizoate sodium (DTZ) by UV/chlorine was carried out according to efficiency, mechanism, and oxidation products, and compared to that by UV/H 2 O 2 . The pseudo-first order rate (k') of iopamidol and DTZ was accelerated by UV/chlorine compared to that by UV and chlorine alone. k' of iopamidol and DTZ by UV/chlorine increased with increasing chlorine dosage. Both of iopamidol and DTZ could not be effectively removed by UV/H 2 O 2 compared to that by UV/chlorine. Secondary radicals (Cl 2 - and ClO) rather than primary radicals (HO and Cl) were demonstrated to be mainly responsible for the enhanced removal of iopamidol and DTZ by UV/chlorine. The oxidation products of iopamidol and DTZ resulting from UV/chlorine and UV/H 2 O 2 process were identified, and differences existed in the two systems. IO 3 - (the desired sink of I - ) was the major inorganic product in the UV/chlorine process whereas I - was the predominant inorganic product in the UV/H 2 O 2 process. The formation of chlorine-containing products during the degradation of iopamidol and DTZ by UV/chlorine was also observed. H-abstraction, additions, de-iodination were shared during the degradation of iopamidol by UV/chlorine and UV/H 2 O 2 . Neutral pH condition was preferred for the removal of iopamidol and DTZ by UV/chlorine. UV/chlorine could also be applied in real waters for the removal of iopamidol and DTZ. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

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... chlorine dioxide with respect to all chlorine species as determined by Method 4500-ClO2 E in the “Standard...

Phosgene- and chlorine-induced acute lung injury in rats: comparison of cardiopulmonary function and biomarkers in exhaled breath.

PubMed

Luo, Sa; Trübel, Hubert; Wang, Chen; Pauluhn, Jürgen

2014-12-04

This study compares changes in cardiopulmonary function, selected endpoints in exhaled breath, blood, and bronchoalveolar lavage fluid (BAL) following a single, high-level 30-min nose-only exposure of rats to chlorine and phosgene gas. The time-course of lung injury was systematically examined up to 1-day post-exposure with the objective to identify early diagnostic biomarkers suitable to guide countermeasures to accidental exposures. Chlorine, due to its water solubility, penetrates the lung concentration-dependently whereas the poorly water-soluble phosgene reaches the alveolar region without any appreciable extent of airway injury. Cardiopulmonary endpoints were continually recorded by telemetry and barometric plethysmography for 20h. At several time points blood was collected to evaluate evidence of hemoconcentration, changes in hemostasis, and osteopontin. One day post-exposure, protein, osteopontin, and cytodifferentials were determined in BAL. Nitric oxide (eNO) and eCO2 were non-invasively examined in exhaled breath 5 and 24h post-exposure. Chlorine-exposed rats elaborated a reflexively-induced decreased respiratory rate and bradycardia whereas phosgene-exposed rats developed minimal changes in lung function but a similar magnitude of bradycardia. Despite similar initial changes in cardiac function, the phosgene-exposed rats showed different time-course changes of hemoconcentration and lung weights as compared to chlorine-exposed rats. eNO/eCO2 ratios were most affected in chlorine-exposed rats in the absence of any marked time-related changes. This outcome appears to demonstrate that nociceptive reflexes with changes in cardiopulmonary function resemble typical patterns of mixed airway-alveolar irritation in chlorine-exposed rats and alveolar irritation in phosgene-exposed rats. The degree and time-course of pulmonary injury was reflected best by eNO/eCO2 ratios, hemoconcentration, and protein in BAL. Increased fibrin in blood occurred only in chlorine-exposed rats 1-day post-exposure. Hence, the analysis of NO and CO2 in exhaled breath, including endpoints in blood mirroring changes in the peripheral to pulmonary fluid distribution, seem to be sensitive diagnostic endpoints readily available for early prognostic assessment of severity of injury and efficacy of any chosen countermeasure. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

The behavior of SiC and Si3N4 ceramics in mixed oxidation/chlorination environments

NASA Technical Reports Server (NTRS)

Marra, John E.; Kreidler, Eric R.; Jacobson, Nathan S.; Fox, Dennis S.

1989-01-01

The behavior of silicon-based ceramics in mixed oxidation/chlorination environments was studied. High pressure mass spectrometry was used to quantitatively identify the reaction products. The quantitative identification of the corrosion products was coupled with thermogravimetric analysis and thermodynamic equilibrium calculations run under similar conditions in order to deduce the mechanism of corrosion. Variations in the behavior of the different silicon-based materials are discussed. Direct evidence of the existence of silicon oxychloride compounds is presented.

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

Hu, Zhiming; Chen, Hui; Qu, Jianfei

Here, chlorinated benzothiadiazide based polymers with multiple chlorine atoms has been designed and synthesized for polymer solar cells with enhanced open circuit voltage up to 0.85 V. The chlorine substitution is found to significantly adjust the band gap of the polymers, and change polymer’s orientation from random morphology of chlorine free PBT4T-2OD, to mixed face-on packing of one chlorine substituted PCBT4T-2OD, and finally to edge-on of two chlorine substituted PCCBT4T-2OD. The optimized chlorinated polymer, PCBT4T-2OD with only one chlorine atom substituted on BT moiety, has been founded to achieve the highest power conversion efficiency up to 8.20% with PC 71BM,more » which is about 68% higher than that of its non-chlorine analogues.« less

DBP formation from degradation of DEET and ibuprofen by UV/chlorine process and subsequent post-chlorination.

PubMed

Aghdam, Ehsan; Xiang, Yingying; Sun, Jianliang; Shang, Chii; Yang, Xin; Fang, Jingyun

2017-08-01

The formation of disinfection by-products (DBPs) from the degradation of N,N-diethyl-3-methyl benzoyl amide (DEET) and ibuprofen (IBP) by the ultraviolet irradiation (UV)/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H 2 O 2 process. The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H 2 O 2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species (RCS) and hydroxyl radicals (HO) in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50% after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine (TOCl), respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H 2 O 2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%-63% higher, likely due to the generation of more DBP precursors from the attack of RCS, in addition to HO. Copyright © 2017. Published by Elsevier B.V.

The source and significance of argon isotopes in fluid inclusions from areas of mineralization

NASA Astrophysics Data System (ADS)

Kelley, S.; Turner, G.; Butterfield, A. W.; Shepherd, T. J.

1986-09-01

Argon isotopes in fluid inclusions in quartz veins associated with granite-hosted tungsten mineralization in the southwest and north of England have been investigated in detail by the 40Ar- 39Ar technique. The natural argon is present as a number of discrete components which can be identified through correlations with 39Ar, 38Ar and 37Ar induced by neutron bombardment of potassium, chlorine and calcium. The potassium-correlated component arises principally from in situ decay of potassium in solid phases in the inclusions. In the case of the Hemerdon tungsten deposit of southwest England the phases responsible are small (≈ 25 μm) captive authigenic micas which are shown to have been deposited from a fluid 268 ± 20 Ma ago, shortly after the emplacement of the host granite. The chlorine-correlated component is present in the brines which constitute the fluid phase of the inclusions. The argon in these hydrothermal fluids is made up in part of "parentless" or "excess" 40Ar leached from surrounding crustal rocks, and in part of dissolved ancient atmospheric argon. Absolute concentrations of both atmospheric and excess components in the brine can be estimated from ( 40ArCl ) ratios and independent determinations of the salinity of the inclusions. The absolute concentrations of the atmospheric argon are close to those found in modern meteoric water, while those of the excess component can be interpreted in terms of the degree of interaction betwen the circulating fluids and country rock. A calcium-correlated component, with a much higher ratio of excess to atmospheric argon than that in the brine, was found to be a dominant phase in one sample from the Hemerdon deposit, indicating the presence of a solid phase (probably a CaSO 4 daughter mineral). Inclusions of this composition represent fluids which have had a more prolonged interaction- with crustal rocks. The results obtained from this study provide a systematization and a framework for future multi-component argon studies of fluid inclusions, together with an indication of the wide range of information which can be inferred.

Acute lung injury and persistent small airway disease in a rabbit model of chlorine inhalation

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

Musah, Sadiatu; Schlueter, Connie F.; Humphrey, Da

Chlorine is a pulmonary toxicant to which humans can be exposed through accidents or intentional releases. Acute effects of chlorine inhalation in humans and animal models have been well characterized, but less is known about persistent effects of acute, high-level chlorine exposures. In particular, animal models that reproduce the long-term effects suggested to occur in humans are lacking. Here, we report the development of a rabbit model in which both acute and persistent effects of chlorine inhalation can be assessed. Male New Zealand White rabbits were exposed to chlorine while the lungs were mechanically ventilated. After chlorine exposure, the rabbitsmore » were extubated and were allowed to survive for up to 24 h after exposure to 800 ppm chlorine for 4 min to study acute effects or up to 7 days after exposure to 400 ppm for 8 min to study longer term effects. Acute effects observed 6 or 24 h after inhalation of 800 ppm chlorine for 4 min included hypoxemia, pulmonary edema, airway epithelial injury, inflammation, altered baseline lung mechanics, and airway hyperreactivity to inhaled methacholine. Seven days after recovery from inhalation of 400 ppm chlorine for 8 min, rabbits exhibited mild hypoxemia, increased area of pressure–volume loops, and airway hyperreactivity. Lung histology 7 days after chlorine exposure revealed abnormalities in the small airways, including inflammation and sporadic bronchiolitis obliterans lesions. Immunostaining showed a paucity of club and ciliated cells in the epithelium at these sites. These results suggest that small airway disease may be an important component of persistent respiratory abnormalities that occur following acute chlorine exposure. This non-rodent chlorine exposure model should prove useful for studying persistent effects of acute chlorine exposure and for assessing efficacy of countermeasures for chlorine-induced lung injury. - Highlights: • A novel rabbit model of chlorine-induced lung disease was developed. • Acute effects of chlorine were pulmonary edema, hypoxemia and impaired lung function. • Persistent small airway disease developed following recovery from acute injury. • Small airway disease included inflammation and bronchiolitis obliterans lesions. • The model should be useful for studying chlorine lung injury and testing treatments.« less

Chlorinated ethenes from groundwater in tree trunks

USGS Publications Warehouse

Vroblesky, Don A.; Nietch, C.T.; Morris, J.T.

1999-01-01

The purpose of this investigation was to determine whether tree-core analysis could be used to delineate shallow groundwater contamination by chlorinated ethenes. Analysis of tree cores from bald cypress [Taxodium distichum (L.) Rich], tupelo (Nyssa aquatica L.), sweet gum (Liquidambar stryaciflua L.), oak (Quercus spp.), sycamore (Platanus occidentalis L.), and loblolly pine (Pinus taeda L.) growing over shallow groundwater contaminated with cis-1,2-dichloroethene (cDCE) and trichloroethene (TCE) showed that those compounds also were present in the trees. The cores were collected and analyzed by headspace gas chromatography. Bald cypress, tupelo, and loblolly pine contained the highest concentrations of TCE, with lesser amounts in nearby oak and sweet gum. The concentrations of cDCE and TCE in various trees appeared to reflect the configuration of the chlorinated-solvent groundwater contamination plume. Bald cypress cores collected along 18.6-m vertical transects of the same trunks showed that TCE concentrations decline by 30−70% with trunk height. The ability of the tested trees to take up cDCE and TCE make tree coring a potentially cost-effective and simple approach to optimizing well placement at this site. 

Regression equations for disinfection by-products for the Mississippi, Ohio and Missouri rivers

USGS Publications Warehouse

Rathbun, R.E.

1996-01-01

Trihalomethane and nonpurgeable total organic-halide formation potentials were determined for the chlorination of water samples from the Mississippi, Ohio and Missouri Rivers. Samples were collected during the summer and fall of 1991 and the spring of 1992 at twelve locations on the Mississippi from New Orleans to Minneapolis, and on the Ohio and Missouri 1.6 km upstream from their confluences with the Mississippi. Formation potentials were determined as a function of pH, initial free-chlorine concentration, and reaction time. Multiple linear regression analysis of the data indicated that pH, reaction time, and the dissolved organic carbon concentration and/or the ultraviolet absorbance of the water were the most significant variables. The initial free-chlorine concentration had less significance and bromide concentration had little or no significance. Analysis of combinations of the dissolved organic carbon concentration and the ultraviolet absorbance indicated that use of the ultraviolet absorbance alone provided the best prediction of the experimental data. Regression coefficients for the variables were generally comparable to coefficients previously presented in the literature for waters from other parts of the United States.

8-Chloroadenine: a novel product formed from hypochlorous acid-induced damage to calf thymus DNA.

PubMed

Matthew Whiteman Andrew Jenner Barry Halliwell

1999-01-01

Hypochlorous acid (HOCl) is formed by the action of the enzyme myeloperoxidase on hydrogen peroxide and chloride ions. It has been shown to be highly bactericidal and cytotoxic by a variety of mechanisms, one of which, may be the modification of DNA. Previously we have demonstrated by GC-MS analysis that exposure of calf thymus DNA to HOCl causes extensive pyrimidine modification, including 5-chlorocytosine formation. Using GC-MS analysis, we now demonstrate the formation of an additional chlorinated base product, 8-Cl adenine. The addition of 50 μM HOCl was sufficient to produce a significant increase in this product. The reaction of HOCl with adenine in calf thymus DNA was shown to be rapid with the reaction complete after 1 min. pH-dependence studies suggest HOCl rather than its conjugate base (OCl-) to be responsible for 8-Cl adenine formation. Other commercially available chlorinated base products, 6-Cl guanine or 2-Cl adenine were not detected. Therefore, 8-Cl adenine might prove a useful biomarker for studying the role of reactive chlorine species (RCS) during inflammatory processes.

Congener-specific distribution and bioaccumulation of short-chain chlorinated paraffins in sediments and bivalves of the Bohai Sea, China.

PubMed

Ma, Xindong; Chen, Chen; Zhang, Haijun; Gao, Yuan; Wang, Zhen; Yao, Ziwei; Chen, Jiping; Chen, Jingwen

2014-02-15

Short-chain chlorinated paraffins (SCCPs) are a new type of persistent organic pollutants that are of great environmental concern because of their wide distribution. In this study, surface sediments and bivalve samples were collected from the coastal area of the Bohai Sea in China. Total SCCP (ΣSCCP) concentrations in surface sediments and bivalves ranged from 97.4 ng g(-1) dry weight (dw) to 1756.7 ng g(-1) dw and 476.4-3269.5 ng g(-1) dw, respectively. C10-CPs and C11-CPs were the predominant homologue groups in all sediments and bivalves. Specific congener composition analysis and correspondence analysis indicated that the local SCCP source mainly came from CP-42 and CP-52 products, and riverine input had an important function. The biota-sediment accumulation factors of ΣSCCPs for bivalves ranged from 1.08 to 1.61, and a significant correlation indicated that the SCCP congener with higher chlorination degree was more likely to be accumulated in bivalves. Copyright © 2014. Published by Elsevier Ltd.

A new method for calculation of the chlorine demand of natural and treated waters.

PubMed

Warton, Ben; Heitz, Anna; Joll, Cynthia; Kagi, Robert

2006-08-01

Conventional methods of calculating chlorine demand are dose dependent, making intercomparison of samples difficult, especially in cases where the samples contain substantially different concentrations of dissolved organic carbon (DOC), or other chlorine-consuming species. Using the method presented here, the values obtained for chlorine demand are normalised, allowing valid comparison of chlorine demand between samples, independent of the chlorine dose. Since the method is not dose dependent, samples with substantially differing water quality characteristics can be reliably compared. In our method, we dosed separate aliquots of a water sample with different chlorine concentrations, and periodically measured the residual chlorine concentrations in these subsamples. The chlorine decay data obtained in this way were then fitted to first-order exponential decay functions, corresponding to short-term demand (0-4h) and long-term demand (4-168 h). From the derived decay functions, the residual concentrations at a given time within the experimental time window were calculated and plotted against the corresponding initial chlorine concentrations, giving a linear relationship. From this linear function, it was then possible to determine the residual chlorine concentration for any initial concentration (i.e. dose). Thus, using this method, the initial chlorine dose required to give any residual chlorine concentration can be calculated for any time within the experimental time window, from a single set of experimental data.

40 CFR 704.43 - Chlorinated naphthalenes.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 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...

40 CFR 704.43 - Chlorinated naphthalenes.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

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. ...

Acute Lung Injury and Persistent Small Airway Disease in a Rabbit Model of Chlorine Inhalation

PubMed Central

Musah, Sadiatu; Schlueter, Connie F.; Humphrey, David M.; Powell, Karen S.; Roberts, Andrew M.; Hoyle, Gary W.

2016-01-01

Chlorine is a pulmonary toxicant to which humans can be exposed through accidents or intentional releases. Acute effects of chlorine inhalation in humans and animal models have been well characterized, but less is known about persistent effects of acute, high-level chlorine exposures. In particular, animal models that reproduce the long-term effects suggested to occur in humans are lacking. Here, we report the development of a rabbit model in which both acute and persistent effects of chlorine inhalation can be assessed. Male New Zealand White rabbits were exposed to chlorine while the lungs were mechanically ventilated. After chlorine exposure, the rabbits were extubated and were allowed to survive for up to 24 h after exposure to 800 ppm chlorine for 4 min to study acute effects or up to 7 days after exposure to 400 ppm for 8 min to study longer term effects. Acute effects observed 6 or 24 h after inhalation of 800 ppm chlorine for 4 min included hypoxemia, pulmonary edema, airway epithelial injury, inflammation, altered baseline lung mechanics, and airway hyperreactivity to inhaled methacholine. Seven days after recovery from inhalation of 400 ppm chlorine for 8 min, rabbits exhibited mild hypoxemia, increased area of pressure-volume loops, and airway hyperreactivity. Lung histology 7 days after chlorine exposure revealed abnormalities in the small airways, including inflammation and sporadic bronchiolitis obliterans lesions. Immunostaining showed a paucity of club and ciliated cells in the epithelium at these sites. These results suggest that small airway disease may be an important component of persistent respiratory abnormalities that occur following acute chlorine exposure. This non-rodent chlorine exposure model should prove useful for studying persistent effects of acute chlorine exposure and for assessing efficacy of countermeasures for chlorine-induced lung injury. PMID:27913141

Progress towards synthetic chlorins with graded polarity, conjugatable substituents, and wavelength tunability

DOE PAGES

Ra, Doyoung; Gauger, Kelly A.; Muthukumaran, Kannan; ...

2015-04-01

Advances in chlorin synthetic chemistry now enable the de novo preparation of diverse chlorin-containing molecular architectures. Five distinct molecular designs have been explored here, including hydrophobic bioconjugatable (oxo)chlorins; a hydrophilic bioconjugatable chlorin; a trans-ethynyl/iodochlorin building block; a set of chlorins bearing electron-rich (methoxy, dimethylamino, methylthio) groups at the 3-position; and a set of ten 3,13-disubstituted chlorins chiefly bearing groups with extended π-moieties. Altogether 23 new chlorins (17 targets, 6 intermediates) have been prepared. Lastly, the challenge associated with molecular designs that encompass the combination of “hydrophilic, bioconjugatable and wavelength-tunable” chiefly resides in the nature of the hydrophilic unit.

Linking structure and vibrational mode coupling using high-resolution infrared spectroscopy: A comparison of gauche and trans 1-chloro-2-fluoroethane

NASA Astrophysics Data System (ADS)

Miller, C. Cameron; Stone, Stephen C.; Philips, Laura A.

1995-01-01

The high-resolution infrared spectrum of 1-chloro-2-fluoroethane in a molecular beam was collected over the 2975-2994 cm-1 spectral region. The spectral region of 2975-2981 cm-1 contains a symmetric C-H stretching vibrational band of the gauche conformer containing the 35Cl isotope. The spectral region of 2985-2994 cm-1 contains three vibrational bands of the trans conformer. Two of the three bands are assigned as an antisymmetric C-H stretch of each of the two different chlorine isotopes. The third band is assigned as a symmetric C-H stretch of the 35Cl isotope. The gauche conformer of 1-chloro-2-fluoroethane showed doublet patterns similar to those previously observed in 1,2-difluoroethane. The model for 1,2-difluoroethane is further refined in the present work. These refinements suggest that the coupling dark state in 1,2-difluoroethane is composed of 1 quantum C-H bend, 1 quantum C-C stretch, and 12 quanta of torsion. For 1-chloro-2-fluoroethane the dark state could not be identified due to a small data set. The trans conformer of 1-chloro-2-fluoroethane showed no evidence of mode coupling in the three vibrational bands. Including 2-fluoroethanol in this series of molecules, the extent of vibrational mode coupling did not correlate with the density of states available for coupling. Therefore, density of states alone is insufficient to explain the observed trend. A correlation was observed between the degree of intramolecular interaction and vibrational mode coupling.

Chemical Tracer Methods: Chapter 7

USGS Publications Warehouse

Healy, Richard W.

2017-01-01

Tracers have a wide variety of uses in hydrologic studies: providing quantitative or qualitative estimates of recharge, identifying sources of recharge, providing information on velocities and travel times of water movement, assessing the importance of preferential flow paths, providing information on hydrodynamic dispersion, and providing data for calibration of water flow and solute-transport models (Walker, 1998; Cook and Herczeg, 2000; Scanlon et al., 2002b). Tracers generally are ions, isotopes, or gases that move with water and that can be detected in the atmosphere, in surface waters, and in the subsurface. Heat also is transported by water; therefore, temperatures can be used to trace water movement. This chapter focuses on the use of chemical and isotopic tracers in the subsurface to estimate recharge. Tracer use in surface-water studies to determine groundwater discharge to streams is addressed in Chapter 4; the use of temperature as a tracer is described in Chapter 8.Following the nomenclature of Scanlon et al. (2002b), tracers are grouped into three categories: natural environmental tracers, historical tracers, and applied tracers. Natural environmental tracers are those that are transported to or created within the atmosphere under natural processes; these tracers are carried to the Earth’s surface as wet or dry atmospheric deposition. The most commonly used natural environmental tracer is chloride (Cl) (Allison and Hughes, 1978). Ocean water, through the process of evaporation, is the primary source of atmospheric Cl. Other tracers in this category include chlorine-36 (36Cl) and tritium (3H); these two isotopes are produced naturally in the Earth’s atmosphere; however, there are additional anthropogenic sources of them.

Higher modulus compositions incorporating particulate rubber

DOEpatents

Bauman, B.D.; Williams, M.A.; Bagheri, R.

1997-12-02

Rubber particles, to be used as fillers or extenders for various composite polymer systems, are chlorinated by a gas-solid phase reaction with a chlorine-containing gas. A composite polymer containing the chlorinated rubber fillers or extenders exhibits a higher flexural modulus than if prepared using an unchlorinated rubber filler or extender. Chlorination of the rubber particles is carried out by contacting the finely divided rubber particles with a chlorine-containing gas comprising at least about 5 volume percent chlorine. Advantageously, the chlorine can be diluted with air, nitrogen or other essentially inert gases and may contain minor amounts of fluorine. Improved performance is obtained with nitrogen dilution of the chlorine gas over air dilution. Improved polymer composite systems having higher flexural modulus result from the use of the chlorinated rubber particles as fillers instead of unchlorinated rubber particles. 2 figs.

Higher modulus compositions incorporating particulate rubber

DOEpatents

McInnis, E.L.; Scharff, R.P.; Bauman, B.D.; Williams, M.A.

1995-01-17

Rubber particles, to be used as fillers or extenders for various composite polymer systems, are chlorinated by a gas-solid phase reaction with a chlorine-containing gas. A composite polymer containing the chlorinated rubber fillers or extenders exhibits a higher flexural modulus than if prepared using an unchlorinated rubber filler or extender. Chlorination of the rubber particles is carried out by contacting the finely divided rubber particles with a chlorine-containing gas comprising at least about 5 volume percent chlorine. Advantageously, the chlorine can be diluted with air, nitrogen or other essentially inert gases and may contain minor amounts of fluorine. Improved performance is obtained with nitrogen dilution of the chlorine gas over air dilution. Improved polymer composite systems having higher flexural modulus result from the use of the chlorinated rubber particles as fillers instead of unchlorinated rubber particles. 2 figures.

Higher modulus compositions incorporating particulate rubber

DOEpatents

McInnis, E.L.; Bauman, B.D.; Williams, M.A.

1996-04-09

Rubber particles, to be used as fillers or extenders for various composite polymer systems, are chlorinated by a gas-solid phase reaction with a chlorine-containing gas. A composite polymer containing the chlorinated rubber fillers or extenders exhibits a higher flexural modulus than if prepared using an unchlorinated rubber filler or extender. Chlorination of the rubber particles is carried out by contacting the finely divided rubber particles with a chlorine-containing gas comprising at least about 5 volume percent chlorine. Advantageously, the chlorine can be diluted with air, nitrogen or other essentially inert gases and may contain minor amounts of fluorine. Improved performance is obtained with nitrogen dilution of the chlorine gas over air dilution. Improved polymer composite systems having higher flexural modulus result from the use of the chlorinated rubber particles as fillers instead of unchlorinated rubber particles. 2 figs.

21 CFR 177.2430 - Polyether resins, chlorinated.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyether resins, chlorinated. 177.2430 Section 177... Components of Articles Intended for Repeated Use § 177.2430 Polyether resins, chlorinated. Chlorinated..., in accordance with the following prescribed conditions: (a) The chlorinated polyether resins are...

78 FR 72640 - Countervailing Duty Investigation of Chlorinated Isocyanurates From the People's Republic of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-12-03

... Investigation of Chlorinated Isocyanurates From the People's Republic of China: Postponement of Preliminary... duty investigation of chlorinated isocyanurates (``chlorinated isos'') from the People's Republic of...\\ \\1\\ See Chlorinated Isocyanurates from the People's Republic of China: Initiation of Countervailing...

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 ...

Temperature sensitivity indicates that chlorination of organic matter in forest soil is primarily biotic.

PubMed

Bastviken, David; Svensson, Teresia; Karlsson, Susanne; Sandén, Per; Oberg, Gunilla

2009-05-15

Old assumptions that chloride is inert and that most chlorinated organic matter in soils is anthropogenic have been challenged by findings of naturally formed organochlorines. Such natural chlorination has been recognized for several decades, but there are still very few measurements of chlorination rates or estimates of the quantitative importance of terrestrial chlorine transformations. While much is known about the formation of specific compounds, bulk chlorination remains poorly understood in terms of mechanisms and effects of environmental factors. We quantified bulk chlorination rates in coniferous forest soil using 36Cl-chloride in tracer experiments at different temperatures and with and without molecular oxygen (O2). Chlorination was enhanced by the presence of O2 and had a temperature optimum at 20 degrees C. Minimum rates were found at high temperatures (50 degrees C) or under anoxic conditions. The results indicate (1) that most of the chlorination between 4 and 40 degrees C was biotic and driven by O2 dependent enzymes, and (2) that there is also slower background chlorination occurring under anoxic conditions at 20 degrees C and under oxic conditions at 50 degrees C. Hence, while oxic and biotic chlorination clearly dominated, chlorination by other processes including possible abiotic reactions was also detected.

Chlorine measurements at the 5MV French AMS national facility ASTER: Associated external uncertainties and comparability with the 6MV DREAMS facility

NASA Astrophysics Data System (ADS)

Braucher, R.; Keddadouche, K.; Aumaître, G.; Bourlès, D. L.; Arnold, M.; Pivot, S.; Baroni, M.; Scharf, A.; Rugel, G.; Bard, E.

2018-04-01

After 6 years of 36Cl routine operation, more than 6000 unknown samples have been measured at the 5MV French accelerator mass spectrometry (AMS) national facility ASTER (CEREGE, Aix en Provence). This paper presents the long term behavior of ASTER through the analysis of the measurements of the most used chlorine standards and reference materials, KNSTD1600, SM-Cl-12 and SM-CL-13 over a 46 months' time period. Comparison of measured chlorine concentrations (both 35Cl and 36Cl) from ice samples on two AMS facilities operating at 5MV (ASTER) and 6MV (DREAMS, Helmholtz-Zentrum Dresden-Rossendorf) and normalizing to two different reference materials agree within uncertainties making both reference materials (SM-Cl-12 and KNSTD1600) suitable for 36Cl measurement at ASTER.

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

NASA Astrophysics Data System (ADS)

Kouznetsova, Irina; Mao, Xiaomin; Robinson, Clare; Barry, D. A.; Gerhard, Jason I.; McCarty, Perry L.

2010-09-01

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.

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...

77 FR 19644 - Chlorinated Isocyanurates From the People's Republic of China: Rescission of Antidumping Duty New...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-02

... DEPARTMENT OF COMMERCE International Trade Administration [A-570-898] Chlorinated Isocyanurates... duty order on chlorinated isocyanurates (chlorinated isos) from the People's Republic of China (PRC...; telephone: (202) 482-4261. SUPPLEMENTARY INFORMATION Background The antidumping duty order on chlorinated...

Contrast Between 1992 and 1997 High Latitude Spring Haloe Observations of Lower Stratospheric HCl

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Kawa, S. R.

1998-01-01

HCl measurements from HALOE in the northern hemisphere during mid-May 1997 revealed vortex fragments in which the chlorine reservoir partitioning was strongly pushed toward HCl (approx. 90% HCl, approx. 10% ClONO2), similar to partitioning previously observed in the Antarctic vortex region. In contrast, observations of ClONO2 and HCl in the northern polar spring, 1992, and in other years, show these species established the balance typical for gas phase photochemical reactions in this region (approx. 60% HCl, approx. 40% ClONO2). Annually, chlorine reservoirs in the winter lower stratosphere polar vortex are converted to chlorine radicals via heterogeneous reactions on particle surfaces at very cold temperatures (less than about 200 K). As temperatures warm in spring, the heterogeneous processes become insignificant compared with gas phase reactions, and the chlorine reservoirs are reformed. Measurements through the northern winter/spring in 1992 show rapid formation of ClONO2, followed by steady loss of ClONO2 and increasing HCl. Although ClONO2 measurements are not available for 1997, the HCl increase in 1997 is observed to be much more rapid and the eventual HCl mixing ratio is about 50% greater than that of 1992. The observations are examined through comparison with the Goddard three-dimensional chemistry and transport model. This model utilizes winds and temperatures from the Goddard Earth Observing System Data Assimilation System and a complete integration scheme for stratospheric photochemistry. Analysis of the evolution of HCl and ClONO2 shows that the observed difference in the overall rate of HCl formation is explained by the sensitivity of the gas-phase chemistry to the ozone mixing ratio and the temperature. The results show that the model accurately simulates HCl and ClONO2 evolution during these two winters. Model validity is further supported by comparisons with O3 and reactive nitrogen species NO and NO2. This analysis provides a sensitive test of the lower stratospheric chlorine photochemistry, particularly because the analysis considers constituent evolution at a time when the HCl and ClONO2 are far from a photochemical stationary state.

Alleviation of membrane fouling in a submerged membrane bioreactor with electrochemical oxidation mediated by in-situ free chlorine generation.

PubMed

Chung, Chong Min; Tobino, Tomohiro; Cho, Kangwoo; Yamamoto, Kazuo

2016-06-01

The control of membrane fouling is still the biggest challenge that membrane bioreactor (MBR) for wastewater treatment faces with. In this report, we evince that an in-situ electrochemical free chlorine generation is effective for membrane fouling mitigation. An electrochemical oxidation (EO) apparatus with perforated Ti/IrO2 anodes and Ti/Pt cathodes was integrated into a conventional MBR with microfiltration module (EO-MBR). The membrane fouling characteristics of EO-MBR fed with synthetic wastewater were monitored for about 2 months in comparison to control MBRs. In the EO-MBR at a direct current density of 0.4 mA/cm(2), the frequency of membrane fouling when the trans-membrane pressure (TMP) reached 30 kPa was effectively reduced by 40% under a physical membrane cleaning regime. The evolution patterns of TMP together with hydraulic resistance analysis based on resistance-in-series model indicated that the electrochemically generated active chlorine alleviated the physically irremovable membrane fouling. Further analysis on extracellular polymeric substances (EPS) of sludge cake layer (SCL) revealed significant reductions of protein contents in soluble EPS and fluorescence emission intensities from humic acids and other fluorophores in bound EPS, which in-turn would decrease the hydrophobic accumulation of organic foulants on membrane pores. The chlorine dosage from the EO apparatus was estimated to be 4.7 mg Cl2/g MLVSS/day and the overall physicochemical properties (bio-solids concentration, floc diameter, zeta-potential) as well as the microbial activity in terms of specific oxygen utilization rate and removal efficiency of dissolved organic carbon (>97%) were not affected significantly. A T-RFLP (terminal restriction fragment length polymorphism) analysis suggested noticeable shifts in microbial community both in mixed liquor and sludge cake layer. Consequently, our electrochemical chlorination would be an efficient fouling control strategy in membrane-based water treatment processes where additional electricity consumption and cathodic scale deposition are not of serious concerns. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of halogenated impurities on lifetime of organic light emitting diode

NASA Astrophysics Data System (ADS)

Yamawaki, Hayato; Suzuki, Kunihiko; Kubota, Tomohiro; Watabe, Takeyoshi; Ishigaki, Ayumi; Nakamura, Rina; Inoue, Hideko; Nakashima, Harue; Horikoshi, Nozomi; Nowatari, Hiromi; Kataishi, Riho; Hamada, Toshiki; Sasaki, Toshiki; Suzuki, Tsunenori; Seo, Satoshi

2016-09-01

We investigated a correlation between lifetime and the halogen element concentration in an organic light-emitting diode (OLED) and conducted experiments and simulations to discuss degradation mechanisms due to the halogen. OELD is generally formed of high-purity materials. Since the synthesis of high-purity materials takes time and cost, quantitative understanding of the kind, amount, and influence of impurities in OLED devices is expected. The results of combustion ion chromatography show that, if the chlorine concentration in the host material is more than several parts per million, the lifetime of the device is drastically reduced. The chlorine element, which is derived from the chlorinated by-product of the host material, is found to be transferred from the chloride to other materials (e.g., an emissive dopant) according to the results of LC-MS analysis. In addition, the electron transport layer including such impurities is also found to adversely affect the lifetime. The results of TOF-SIMS analysis suggest that the dissociated chlorine element diffuse to the light-emitting layer side when the device is driven. The results of simulations (Gaussian 09) and electrochemical analyses (cyclic voltammetry and electrolysis) reveal that the halogen element is easy to dissociate from halide by excitation or reduction. The halogen element can repeat reactions with the peripheral materials by excitation or reduction and cause damages, e.g., generate radicals or further reaction products due to the radicals. The results of simulation suggest that, such compounds have low energy level and become quenchers.

A study of chlorinated solvent contamination of the aquifers of an industrial area in central Italy: a possibility of bioremediation

PubMed Central

Matteucci, Federica; Ercole, Claudia; del Gallo, Maddalena

2015-01-01

Perchloroethene, trichloroethene, and other chlorinated solvents are widespread groundwater pollutants. They form dense non-aqueous phase liquids that sink through permeable groundwater aquifers until non-permeable zone is reached. In Italy, there are many situations of serious contamination of groundwater that might compromise their use in industry, agriculture, private, as the critical case of a Central Italy valley located in the province of Teramo (“Val Vibrata”), characterized by a significant chlorinated solvents contamination. Data from the various monitoring campaigns that have taken place over time were collected, and new samplings were carried out, resulting in a complete database. The data matrix was processed with a multivariate statistic analysis (in particular principal component analysis, PCA) and was then imported into geographic information system (GIS), to obtain a model of the contamination. A microcosm anaerobic study was utilized to assess the potential for in situ natural or enhanced bioremediation. Most of the microcosms were positive for dechlorination, particularly those inoculated with a mineral medium. This indicate the presence of an active native dechlorinating population in the subsurface, probably inhibited by co-contaminants in the groundwater, or more likely by the absence or lack of nutritional factors. Among the tested electron donors (i.e., yeast extract, lactate, and butyrate) lactate and butyrate enhanced dechlorination of chlorinated compounds. PCA and GIS studies allowed delimiting the contamination; the microcosm study helped to identify the conditions to promote the bioremediation of the area. PMID:26388862

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,…

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.

78 FR 72633 - Chlorinated Isocyanurates From Spain: Final Results of Antidumping Duty Administrative Review...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-12-03

... DEPARTMENT OF COMMERCE International Trade Administration [A-469-814] Chlorinated Isocyanurates... administrative review of the antidumping duty order on chlorinated isocyanurates (chlorinated isos) from Spain.\\1... below in the ``Final Results of Review'' section of this notice. \\1\\ See Chlorinated Isocyanurates from...

77 FR 4992 - Chlorinated Isocyanurates From the People's Republic of China: Extension of Time Limit for the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-01

... DEPARTMENT OF COMMERCE International Trade Administration [A-570-898] Chlorinated Isocyanurates... duty order on chlorinated isocyanurates (chlorinated isos) from the People's Republic of China (PRC... requires additional time to complete the preliminary results of the administrative review of chlorinated...

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…

Effects of ozone, chlorine dioxide, chlorine, and monochloramine on Cryptosporidium parvum oocyst viability

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

Korich, D.G.; Mead, J.R.; Madore, M.S.

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 timesmore » 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.« less

Applications of stable isotope analysis in mammalian ecology.

PubMed

Walter, W David; Kurle, Carolyn M; Hopkins, John B

2014-01-01

In this editorial, we provide a brief introduction and summarize the 10 research articles included in this Special Issue on Applications of stable isotope analysis in mammalian ecology. The first three articles report correction and discrimination factors that can be used to more accurately estimate the diets of extinct and extant mammals using stable isotope analysis. The remaining seven applied research articles use stable isotope analysis to address a variety of wildlife conservation and management questions from the oceans to the mountains.

Chlorination by-product concentration levels in seawater and fish of an industrialised bay (Gulf of Fos, France) exposed to multiple chlorinated effluents.

PubMed

Boudjellaba, D; Dron, J; Revenko, G; Démelas, C; Boudenne, J-L

2016-01-15

Chlorination is one of the most widely used techniques for biofouling control in large industrial units, leading to the formation of halogenated chlorination by-products (CBPs). This study was carried out to evaluate the distribution and the dispersion of these compounds within an industrialised bay hosting multiple chlorination discharges issued from various industrial processes. The water column was sampled at the surface and at 7 m depth (or bottom) in 24 stations for the analysis of CBPs, and muscle samples from 15 conger eel (Conger conger) were also investigated. Temperature and salinity profiles supported the identification of the chlorination releases, with potentially complex patterns. Chemical analyses showed that bromoform was the most abundant CBP, ranging from 0.5 to 2.2 μg L(-1) away from outlets (up to 10 km distance), and up to 18.6 μg L(-1) in a liquefied natural gas (LNG) regasification plume. However, CBP distributions were not homogeneous, halophenols being prominent in a power station outlet and dibromoacetonitrile in more remote stations. A seasonal effect was identified as fewer stations revealed CBPs in summer, probably due to the air and water temperatures increases favouring volatilisation and reactivity. A simple risk assessment of the 11 identified CBPs showed that 7 compounds concentrations were above the potential risk levels to the local marine environment. Finally, conger eel muscles presented relatively high levels of 2,4,6-tribromophenol, traducing a generalised impregnation of the Gulf of Fos to CBPs and a global bioconcentration factor of 25 was determined for this compound. Copyright © 2015 Elsevier B.V. All rights reserved.

A novel two-dimensional liquid-chromatography method for online prediction of the toxicity of transformation products of benzophenones after water chlorination.

PubMed

Li, Jian; Ma, Li-Yun; Xu, Li; Shi, Zhi-Guo

2015-08-01

Benzophenone-type UV filters (BPs) are ubiquitous in the environment. Transformation products (TPs) of BPs with suspected toxicity are likely to be produced during disinfection of water by chlorination. To quickly predict the toxicity of TPs, in this study, a novel two-dimensional liquid-chromatography (2D-LC) method was established in which the objective of the first dimension was to separate the multiple components of the BPs sample after chlorination, using a reversed-phase liquid-chromatography mode. A biochromatographic system, i.e. bio-partitioning micellar chromatography with the polyoxyethylene (23) lauryl ether aqueous solution as the mobile phase, served as the second dimension to predict the toxicity of the fraction from the first dimension on the basis of the quantitative retention-activity relationships (QRARs) model. Six BPs, namely 2,4-dihydroxybenzophenone, oxybenzone, 4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone, were the target analytes subjected to chlorination. The products of these BPs after chlorination were directly injected to the 2D-LC system for analysis. The results indicated that most TPs may be less toxic than their parent chemicals, but some may be more toxic, and that intestinal toxicity of TPs may be more obvious than blood toxicity. The proposed method is time-saving, high-throughput, and reliable, and has great potential for predicting toxicity or bioactivity of unknown and/or known components in a complex sample. Graphical Abstract The scheme for the 2D-LC online prediction of toxicity of the transformation products of benzophenone-type UV filters after chlorination.

Lung Function before and after a Large Chlorine Gas Release in Graniteville, South Carolina

PubMed Central

Karmaus, Wilfried J. J.; Mohr, Lawrence C.; Cai, Bo; Balte, Pallavi; Gibson, James J.; Ownby, Dennis; Lawson, Andrew B.; Vena, John E.; Svendsen, Erik R.

2016-01-01

Rationale: On January 6, 2005 a train derailment led to an estimated 54,915-kg release of chlorine at a local textile mill in Graniteville, South Carolina. Objectives: We used the employee health spirometry records of the textile to identify enduring effects of chlorine gas exposure resulting from the incident on the lung function of workers employed at the textile mill. Methods: Spirometry records from 1,807 mill workers (7,332 observations) were used from 4 years before and 18 months after the disaster. Longitudinal analysis using marginal regression models produced annual population mean estimates for FEV1, FVC, and FEV1/FVC ratio. Covariate adjustment was made for sex, age, smoking, height, season tested, technician, obesity, season × year interactions, and smoker × year interactions. The increased prevalence of mill workers having accelerated FEV1 decline was also evaluated after the chlorine spill. Measurements and Main Results: In the year of the accident, we observed a significant reduction in mean FEV1 (–4.2% predicted; P = 0.019) when compared with the year before the incident. In the second year, partial recovery in the mean FVC % predicted level was seen, but the cohort’s average FEV1/FVC ratio continued to decrease over time. Severe annual FEV1 decline was most prevalent in the year of the accident, and independent of mill worker smoking status. Conclusions: The Graniteville mill worker cohort revealed significant reductions in lung function immediately after the chlorine incident. Improvement was seen in the second year; but the proportion of mill workers experiencing accelerated FEV1 annual decline significantly increased in the 18 months after the chlorine incident. PMID:26695511

Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

USGS Publications Warehouse

Fiege, Adrian; Holtz, François; Shimizu, Nobumichi; Mandeville, Charles W.; Behrens, Harald; Knipping, Jaayke L.

2014-01-01

Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H2O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities (fO2) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure (P) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate (r) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, tA) at the final P and quenched rapidly from 1030 °C to room temperature (T).The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor αg-m.No detectable effect of r and tA on αg-m was observed. However, SIMS data revealed a remarkable increase of αg-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of fO2 on αg-m (or Δ34Sg–m) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope signatures in natural samples (e.g., melt inclusions or volcanic gases).

Tissue distribution, metabolism and excretion of 3, 3′-dichloro-4′-sulfooxy-biphenyl in the rat

PubMed Central

Grimm, Fabian A.; He, Xianran; Teesch, Lynn M.; Lehmler, Hans-Joachim; Robertson, Larry W.; Duffel, Michael W.

2015-01-01

Polychlorinated biphenyls (PCBs) with lower numbers of chlorine atoms exhibit a greater susceptibility to metabolism than their higher-chlorinated counterparts. Following initial hydroxylation of these lower chlorinated PCBs, metabolic sulfation to form PCB sulfates is increasingly recognized as an important component of their toxicology. Since procedures for the quantitative analysis of PCB sulfates in tissue samples have not been previously available, we have now developed an efficient, LC-ESI-MS/MS based, protocol for the quantitative analysis of 4-PCB 11 sulfate in biological samples. This procedure was used to determine the distribution of 4-PCB 11 sulfate in liver, kidney, lung, and brain, as well as its excretion profile, following its intravenous administration to male Sprague-Dawley rats. Following initial uptake of 4-PCB 11 sulfate, its concentration in these tissues and serum declined within the first hour following injection. Although biliary secretion was detected, analysis of 24 hour collections of urine and feces revealed recovery of less than 4% of the administered 4-PCB 11 sulfate. High-resolution LC-MS analysis of bile, urine, and feces showed metabolic products derived from 4-PCB 11 sulfate. Thus, 4-PCB 11 sulfate at this dose was not directly excreted in the urine, but was, instead, re-distributed to tissues and/or subjected to further metabolism. PMID:26046945

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

Inactivation, reactivation and regrowth of indigenous bacteria in reclaimed water after chlorine disinfection of a municipal wastewater treatment plant.

PubMed

Li, Dan; Zeng, Siyu; Gu, April Z; He, Miao; Shi, Hanchang

2013-07-01

Disinfection of reclaimed water prior to reuse is important to prevent the transmission of pathogens. Chlorine is a widely utilized disinfectant and as such is a leading contender for disinfection of reclaimed water. To understand the risks of chlorination resulting from the potential selection of pathogenic bacteria, the inactivation, reactivation and regrowth rates of indigenous bacteria were investigated in reclaimed water after chlorine disinfection. Inactivation of total coliforms, Enterococcus and Salmonella showed linear correlations, with constants of 0.1384, 0.1624 and 0.057 L/(mg.min) and R2 of 0.7617, 0.8316 and 0.845, respectively. However, inactivation of total viable cells by measurement of metabolic activity typically showed a linear correlation at lower chlorine dose (0-22 (mg-min)/L), and a trailing region with chlorine dose increasing from 22 to 69 (mg.min)/L. Reactivation and regrowth of bacteria were most likely to occur after exposure to lower chlorine doses, and extents of reactivation decreased gradually with increasing chlorine dose. In contrast to total coliforms and Enterococcus, Salmonella had a high level of regrowth and reactivation, and still had 2% regrowth even after chlorination of 69 (mg.min)/L and 24 hr storage. The bacterial compositions were also significantly altered by chlorination and storage of reclaimed water, and the ratio of Salmonella was significantly increased from 0.001% to 0.045% after chlorination of 69 (mg.min)/L and 24 hr storage. These trends indicated that chlorination contributes to the selection of chlorine-resistant pathogenic bacteria, and regrowth of pathogenic bacteria after chlorination in reclaimed water with a long retention time could threaten public health security during wastewater reuse.

Combining non-invasive techniques for delimitation and monitoring of chlorinated solvents in groundwater

NASA Astrophysics Data System (ADS)

Sparrenbom, Charlotte; Åkesson, Sofia; Hagerberg, David; Dahlin, Torleif; Holmstrand, Henry; Johansson, Sara

2016-04-01

Large numbers of polluted areas cause leakage of hazardous pollutants into our groundwater. Remediated actions are needed in a vast number of areas to prevent degradation of the quality of our water resources. As excavation of polluted masses is problematic as it often moves the pollutants from one site to another (in best case off site treatment is carried out), in-situ remediation and monitoring thereof needs further development. In general, we need to further develop and improve how we retrieve information on the status of the underground system. This is needed to avoid costly and hazardous shipments associated with excavations and to avoid unnecessary exposure when handling polluted masses. Easier, cheaper, more comprehensive and nondestructive monitoring techniques are needed for evaluation of remediation degree, degradation status of the contaminants and the remaining groundwater contaminant plume. We investigate the possibility to combine two investigation techniques, which are invasive to a very low degree and can give a very good visualization and evaluation of pollutant status underground and changes therein in time. The two methods we have combined are Direct Current resistivity and time-domain Induced Polarization tomography (DCIP) and Compound Specific Isotope Analysis (CSIA) and their use within the context of DNAPL contaminated sites. DCIP is a non-invasive and non-destructive geoelectrical measurement method with emerging new techniques for 4D mapping for promising visualization of underground hydrogeochemical structures and spatial distribution of contaminants. The strength of CSIA is that inherent degradation-relatable isotopic information of contaminant molecules remains unaffected as opposed to the commonly used concentration-based studies. Our aim is to evaluate the possibilities of gas sampling on the ground surface for this technique to become non-invasive and usable without interfering ground conditions.Drillings together with soil and groundwater sampling provide reference data within the project and for calibrating interpretations. In our studies, we show the results from DCIP measurements from two different areasin sothern Sweden with chlorinated solvent contamination. From one of the areas, a pilot test on stimulation reductive dechlorination has been carried out and the treated area reveals sharp anomalies in the DCIP response. Time lapse measurements show changes within the stimulated area and this could be used to follow remediation changes and i.e. groundwater quality changes. Tests with DCIP time lapse are also carried out in the second area together with multiple CSIA analyses of groundwater samples and ongoing is the planning for the gas samples. Evaluation of the possible uses, benefits and limitations of the technique for monitoring changes and delimit polluted areas to be able to monitor and follow groundwater quality changes is ongoing.

Guidelines for the Selection of Chemical Protective Clothing. Volume 2. Technical and Reference Manual.

DTIC Science & Technology

1987-02-01

Handler’s Suit for Protection from Chlorine Trifluoride and Elemental Fluorine Technical Report AFRPL-TR-71-44 (August 1971) NTIS AD731556 199 Masterman’s...Protective Clothing for Chlorine , Edition 1 Chlorine Institute Pamphlet 65, The Chlorine Institute, Inc. New York, New York, (June 1978) 15 Anon...Chemical Company Selection of Gloves for Use With Chlorinated Solvents Chlorinated Solvents Information Midland, Michigan 48640 101 Duffy, R.M., A.R.Beer

PPCP degradation by chlorine-UV processes in ammoniacal water: new reaction insights, kinetic modeling and DBP formation.

PubMed

Zhang, Ruochun; Meng, Tan; Huang, Ching-Hua; Ben, Weiwei; Yao, Hong; Liu, Ruini; Sun, Peizhe

2018-06-15

The combination of chlorine and UV (i.e. chlorine-UV process) has been attracting more attentions in recent years due to its ready incorporation into existing water treatment facilities to remove PPCPs. However, limited information is available on the impact of total ammonia nitrogen (TAN). This study investigated two model PPCPs, N,N-diethyl-3-toluamide (DEET) and caffeine (CAF), in the two stages of chlorine-UV process (i.e. chlorination and UV/chlor(am)ine) to elucidate the impact of TAN. During chlorination, the degradation of DEET and CAF was positively correlated with the overall consumption of total chlorine by TAN. Reactive nitrogen intermediates, including HNO/NO- and ONOOH/ONOO-, along with OH were identified as major contributors to the removal of DEET and CAF. During UV irradiation, DEET and CAF were degraded under UV/chlorine or UV/NH2Cl conditions. OH and Cl were the major reactive species to degrade DEET and CAF under UV/NH2Cl conditions, whereas OCl played a major role for degrading CAF under UV/chlorine conditions. Numerical models were developed to predict the removal of DEET and CAF under chlorination-UV process. Chlorinated disinfection byproducts were detected. Overall, this study presented kinetic features and mechanistic insights on the degradation of PPCPs under chlorine-UV process in ammoniacal water.

Sarcoendoplasmic reticulum Ca(2+) ATPase. A critical target in chlorine inhalation-induced cardiotoxicity.

PubMed

Ahmad, Shama; Ahmad, Aftab; Hendry-Hofer, Tara B; Loader, Joan E; Claycomb, William C; Mozziconacci, Olivier; Schöneich, Christian; Reisdorph, Nichole; Powell, Roger L; Chandler, Joshua D; Day, Brian J; Veress, Livia A; White, Carl W

2015-04-01

Autopsy specimens from human victims or experimental animals that die due to acute chlorine gas exposure present features of cardiovascular pathology. We demonstrate acute chlorine inhalation-induced reduction in heart rate and oxygen saturation in rats. Chlorine inhalation elevated chlorine reactants, such as chlorotyrosine and chloramine, in blood plasma. Using heart tissue and primary cardiomyocytes, we demonstrated that acute high-concentration chlorine exposure in vivo (500 ppm for 30 min) caused decreased total ATP content and loss of sarcoendoplasmic reticulum calcium ATPase (SERCA) activity. Loss of SERCA activity was attributed to chlorination of tyrosine residues and oxidation of an important cysteine residue, cysteine-674, in SERCA, as demonstrated by immunoblots and mass spectrometry. Using cardiomyocytes, we found that chlorine-induced cell death and damage to SERCA could be decreased by thiocyanate, an important biological antioxidant, and by genetic SERCA2 overexpression. We also investigated a U.S. Food and Drug Administration-approved drug, ranolazine, used in treatment of cardiac diseases, and previously shown to stabilize SERCA in animal models of ischemia-reperfusion. Pretreatment with ranolazine or istaroxime, another SERCA activator, prevented chlorine-induced cardiomyocyte death. Further investigation of responsible mechanisms showed that ranolazine- and istaroxime-treated cells preserved mitochondrial membrane potential and ATP after chlorine exposure. Thus, these studies demonstrate a novel critical target for chlorine in the heart and identify potentially useful therapies to mitigate toxicity of acute chlorine exposure.

Sarcoendoplasmic Reticulum Ca2+ ATPase. A Critical Target in Chlorine Inhalation–Induced Cardiotoxicity

PubMed Central

Ahmad, Aftab; Hendry-Hofer, Tara B.; Loader, Joan E.; Claycomb, William C.; Mozziconacci, Olivier; Schöneich, Christian; Reisdorph, Nichole; Powell, Roger L.; Chandler, Joshua D.; Day, Brian J.; Veress, Livia A.; White, Carl W.

2015-01-01

Autopsy specimens from human victims or experimental animals that die due to acute chlorine gas exposure present features of cardiovascular pathology. We demonstrate acute chlorine inhalation–induced reduction in heart rate and oxygen saturation in rats. Chlorine inhalation elevated chlorine reactants, such as chlorotyrosine and chloramine, in blood plasma. Using heart tissue and primary cardiomyocytes, we demonstrated that acute high-concentration chlorine exposure in vivo (500 ppm for 30 min) caused decreased total ATP content and loss of sarcoendoplasmic reticulum calcium ATPase (SERCA) activity. Loss of SERCA activity was attributed to chlorination of tyrosine residues and oxidation of an important cysteine residue, cysteine-674, in SERCA, as demonstrated by immunoblots and mass spectrometry. Using cardiomyocytes, we found that chlorine-induced cell death and damage to SERCA could be decreased by thiocyanate, an important biological antioxidant, and by genetic SERCA2 overexpression. We also investigated a U.S. Food and Drug Administration–approved drug, ranolazine, used in treatment of cardiac diseases, and previously shown to stabilize SERCA in animal models of ischemia–reperfusion. Pretreatment with ranolazine or istaroxime, another SERCA activator, prevented chlorine-induced cardiomyocyte death. Further investigation of responsible mechanisms showed that ranolazine- and istaroxime-treated cells preserved mitochondrial membrane potential and ATP after chlorine exposure. Thus, these studies demonstrate a novel critical target for chlorine in the heart and identify potentially useful therapies to mitigate toxicity of acute chlorine exposure. PMID:25188881

Toxic effects of chlorinated cake flour in rats.

PubMed

Cunningham, H M; Lawrence, G A; Tryphonas, L

1977-05-01

Four experiments were conducted using weanling Wistar rats to determine whether chlorinated cake flour or its constituents were toxic. Levels of 0.2 and 1.0% chlorine added to unbleached cake flour significantly (p less than 0.01) reduced growth rate by 20.7 and 85.2% and increased liver weight relative to body weight by 16.7 and 25.3%, respectively. Lipids extracted from flour chlorinated at the same levels had similar effects. Rat chow diets containing 0.2 and 0.6% chlorine in the form of chlorinated wheat gluten reduced growth rate and increased liver weight as a percentage of body weight. A rat chow diet containing 0.2% chlorine as chlorinated flour lipids increased absolute liver weight by 40%, kidney by 20%, and heart by 10% compared to pair-fed controls.

Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

PubMed

Chew, Gina; Walczyk, Thomas

2013-04-02

Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

Acute lung injury and persistent small airway disease in a rabbit model of chlorine inhalation.

PubMed

Musah, Sadiatu; Schlueter, Connie F; Humphrey, David M; Powell, Karen S; Roberts, Andrew M; Hoyle, Gary W

2017-01-15

Chlorine is a pulmonary toxicant to which humans can be exposed through accidents or intentional releases. Acute effects of chlorine inhalation in humans and animal models have been well characterized, but less is known about persistent effects of acute, high-level chlorine exposures. In particular, animal models that reproduce the long-term effects suggested to occur in humans are lacking. Here, we report the development of a rabbit model in which both acute and persistent effects of chlorine inhalation can be assessed. Male New Zealand White rabbits were exposed to chlorine while the lungs were mechanically ventilated. After chlorine exposure, the rabbits were extubated and were allowed to survive for up to 24h after exposure to 800ppm chlorine for 4min to study acute effects or up to 7days after exposure to 400ppm for 8min to study longer term effects. Acute effects observed 6 or 24h after inhalation of 800ppm chlorine for 4min included hypoxemia, pulmonary edema, airway epithelial injury, inflammation, altered baseline lung mechanics, and airway hyperreactivity to inhaled methacholine. Seven days after recovery from inhalation of 400ppm chlorine for 8min, rabbits exhibited mild hypoxemia, increased area of pressure-volume loops, and airway hyperreactivity. Lung histology 7days after chlorine exposure revealed abnormalities in the small airways, including inflammation and sporadic bronchiolitis obliterans lesions. Immunostaining showed a paucity of club and ciliated cells in the epithelium at these sites. These results suggest that small airway disease may be an important component of persistent respiratory abnormalities that occur following acute chlorine exposure. This non-rodent chlorine exposure model should prove useful for studying persistent effects of acute chlorine exposure and for assessing efficacy of countermeasures for chlorine-induced lung injury. Copyright © 2016 Elsevier Inc. All rights reserved.

Environmental Survey of the B-3 and Ford’s Farm Ranges,

DTIC Science & Technology

1983-08-01

reported have an estimated analytical error of *35% unless noted otherwise. 14 Isotopic Analysis The isotopic uranium analysis procedure used by UST...sulfate buffer and elec- trodeposited on a stainless steel disc, and isotopes of uranium (234U, 23 5U, and 2 38U) were determined by pulse height analysis ...measurements and some environmental sampling. Several special studies were also conducted, including analyses of the isotopic composition of uranium in

In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

NASA Astrophysics Data System (ADS)

Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

2016-06-01

Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

Degradation of natural organic matter by UV/chlorine oxidation: Molecular decomposition, formation of oxidation byproducts and cytotoxicity.

PubMed

Wang, Wen-Long; Zhang, Xue; Wu, Qian-Yuan; Du, Ye; Hu, Hong-Ying

2017-11-01

The degradation of natural organic matters (NOMs) by the combination of UV and chlorine (UV/chlorine) was investigated in this study. UV/chlorine oxidation can effectively degrade NOMs, with the degradation of chromophores (∼80%) and fluorophores (76.4-80.8%) being more efficient than that of DOC (15.1-18.6%). This effect was attributed to the chromophores and fluorophores (double bonds, aromatic groups and phenolic groups) being preferentially degraded by UV/chlorine oxidation, particularly reactive groups with high electron donating capacity. Radical species •OH and •Cl were generated during UV/chlorine oxidation, with the contribution of •OH 1.4 times as high as that of •Cl. The degradation kinetics of different molecular weight (MW) fractions suggests that UV/chlorine oxidation degrades high MW fractions into low MW fractions, with the degradation rates of high MW fractions (>3000 Da) 4.5 times of those of medium MW fractions (1000-3000 Da). In comparison with chlorination alone, UV/chlorine oxidation did not increase the formation (30 min) and formation potential (24 h) of trihalomethanes, but instead promoted the formation and formation potential of haloacetic acids and chloral hydrate. Adsorbable organic halogen (AOX) formed from UV/chlorine oxidation of NOM were 0.8 times higher than those formed from chlorination. Cytotoxicity studies indicated that the cytotoxicity of NOM increased after both chlorination and UV/chlorine oxidation, which may be due to the formation of AOX. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of chlorinated and chloraminated drinking water microbial communities in a distribution system simulator using pyrosequencing data analysis

EPA Science Inventory

The molecular analysis of drinking water microbial communities has focused primarily on 16S rRNA gene sequence analysis. Since this approach provides limited information on function potential of microbial communities, analysis of whole-metagenome pyrosequencing data was used to...

Stability and effectiveness of chlorine disinfectants in water distribution systems.

PubMed

Olivieri, V P; Snead, M C; Krusé, C W; Kawata, K

1986-11-01

A test system for water distribution was used to evaluate the stability and effectiveness of three residual disinfectants--free chlorine, combined chlorine, and chlorine dioxide--when challenged with a sewage contaminant. The test distribution system consisted of the street main and internal plumbing for two barracks at Fort George G. Meade, MD. To the existing pipe network, 152 m (500 ft) of 13-mm (0.5 in.) copper pipe were added for sampling, and 60 m (200 ft) of 2.54-cm (1.0 in.) plastic pipe were added for circulation. The levels of residual disinfectants tested were 0.2 mg/L and 1.0 mg/L as available chlorine. In the absence of a disinfectant residual, microorganisms in the sewage contaminant were consistently recovered at high levels. The presence of any disinfectant residual reduced the microorganism level and frequency of occurrence at the consumer's tap. Free chlorine was the most effective residual disinfectant and may serve as a marker or flag in the distribution network. Free chlorine and chlorine dioxide were the least stable in the pipe network. The loss of disinfectant in the pipe network followed first-order kinetics. The half-life determined in static tests for free chlorine, chlorine dioxide, and combined chlorine was 140, 93, and 1680 min.

Stability and effectiveness of chlorine disinfectants in water distribution systems.

PubMed Central

Olivieri, V P; Snead, M C; Krusé, C W; Kawata, K

1986-01-01

A test system for water distribution was used to evaluate the stability and effectiveness of three residual disinfectants--free chlorine, combined chlorine, and chlorine dioxide--when challenged with a sewage contaminant. The test distribution system consisted of the street main and internal plumbing for two barracks at Fort George G. Meade, MD. To the existing pipe network, 152 m (500 ft) of 13-mm (0.5 in.) copper pipe were added for sampling, and 60 m (200 ft) of 2.54-cm (1.0 in.) plastic pipe were added for circulation. The levels of residual disinfectants tested were 0.2 mg/L and 1.0 mg/L as available chlorine. In the absence of a disinfectant residual, microorganisms in the sewage contaminant were consistently recovered at high levels. The presence of any disinfectant residual reduced the microorganism level and frequency of occurrence at the consumer's tap. Free chlorine was the most effective residual disinfectant and may serve as a marker or flag in the distribution network. Free chlorine and chlorine dioxide were the least stable in the pipe network. The loss of disinfectant in the pipe network followed first-order kinetics. The half-life determined in static tests for free chlorine, chlorine dioxide, and combined chlorine was 140, 93, and 1680 min. PMID:3028767

Long term impacts of CMC/nZVI amendment injection on organohalide-respiring microbial communities at a chlorinated solvent field site

NASA Astrophysics Data System (ADS)

Kocur, C. M.; Lomheim, L.; Boparai, H. K.; Chowdhury, A. I.; Weber, K.; Austrins, L. M.; Sleep, B.; O'Carroll, D. M.; Edwards, E.

2014-12-01

Injection of carboxymethyl-cellulose stabilized nanoscale Zero Valent Iron (CMC/nZVI) has received significant attention in the last decade as an emerging alternative for in-situ remediation of chlorinated solvents and other recalcitrant compounds. There has also been some indication that injection of nZVI will create conditions that will stimulate in-situ microbial populations, leading to further contaminant degradation. Carboxy-methyl cellulose (CMC) is commonly used for nZVI synthesis as it provides steric stabilization for the nanoparticles, however, the CMC is equally important as a subsurface amendment as it may act as a fermentable substrate for microorganisms in-situ. In this study, microbial communities were monitored over a 2.5 year period following the injection of CMC/nZVI at a chlorinated solvent remediation site. Dehalococcoides spp. genetic markers and vinyl chloride reductase genes (vcrA) were targeted in the 16s RNA using quantitative polymerase chain reaction (qPCR). This analysis was complimented with a suite of aqueous chlorinated ethene, ethane, and methane compounds to monitor degradation. Following the injection of CMC/nZVI a decline of parent chlorinated compound concentrations was observed as well as the emergence of daughter products. A period of abiotic nZVI oxidation is believed to be responsible for a portion of the degradation at the site, however, a prolonged period of contaminant degradation followed and is believed to be the result of organohalide-respiring microorganisms native to the site. Further analysis was performed on the microbial samples using 454 pyrotag sequencing of amplified 16S rRNA genes to obtain the genetic profile of the microbial community. Of particular interest within this large genomic profile is the characterization of the stable population of important organohalide-respiring microorganisms on site. Results suggest that there is a distinctly different response in the organohalide-respiring microbial community in areas of the site where CMC/nZVI amendments were injected compared to a background response.

40 CFR 141.65 - Maximum residual disinfectant levels.

Code of Federal Regulations, 2011 CFR

2011-07-01

... MRDL (mg/L) Chlorine 4.0 (as Cl2). Chloramines 4.0 (as Cl2). Chlorine dioxide 0.8 (as ClO2). (b... chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2002. Subpart H systems serving fewer than 10,000 persons and using chlorine dioxide as a...

Formation of trichloromethane in chlorinated water and fresh-cut produce and as a result of reacting with citric acid

USDA-ARS?s Scientific Manuscript database

Chlorine (sodium hypochlorite) is commonly used by the fresh produce industry to sanitize wash water, fresh and fresh-cut fruits and vegetables. However, possible formation of harmful chlorine by-products is a concern. The objectives of this study were to compare chlorine and chlorine dioxide in t...

75 FR 49464 - Chlorinated Isocyanurates from Spain and the People's Republic of China: Final Results of the...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-13

... DEPARTMENT OF COMMERCE International Trade Administration A-469-814, A-570-898 Chlorinated... sunset reviews of the antidumping duty orders on chlorinated isocyanurates (``chlorinated isos'') from... chlorinated isos from Spain and the PRC, pursuant to section 751(c)(3)(B) of the Act and 19 CFR 351.218(e)(1...

A Calibration to Predict the Concentrations of Impurities in Plutonium Oxide by Prompt Gamma Analysis Revision 2

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

Narlesky, Joshua Edward; Kelly, Elizabeth J.

2015-09-10

This report documents the new PG calibration regression equation. These calibration equations incorporate new data that have become available since revision 1 of “A Calibration to Predict the Concentrations of Impurities in Plutonium Oxide by Prompt Gamma Analysis” was issued [3] The calibration equations are based on a weighted least squares (WLS) approach for the regression. The WLS method gives each data point its proper amount of influence over the parameter estimates. This gives two big advantages, more precise parameter estimates and better and more defensible estimates of uncertainties. The WLS approach makes sense both statistically and experimentally because themore » variances increase with concentration, and there are physical reasons that the higher measurements are less reliable and should be less influential. The new magnesium calibration includes a correction for sodium and separate calibration equation for items with and without chlorine. These additional calibration equations allow for better predictions and smaller uncertainties for sodium in materials with and without chlorine. Chlorine and sodium have separate equations for RICH materials. Again, these equations give better predictions and smaller uncertainties chlorine and sodium for RICH materials.« less

Nanodetection of the disinfection by-products on GC-MS techniques

NASA Astrophysics Data System (ADS)

Ristoiu, Dumitru; Haydee, Melinda; Ristoiu, Tania

2009-01-01

Exposures to disinfection by-products (DBPs) in residential drinking water occur through multiple routes and vary across the population because of differences in the amount and ways people use water. Municipal water in the Romania is disinfected, with chlorine being the most common disinfectant agent. Disinfection of water, in additional to having the benefit of destroying microbes that can transmit diseases, has the drawback of producing a series of compounds known as disinfection by-products (DBPs). Chlorination produces many compounds containing chlorine and/or bromine, some of which have been shown to be carcinogenic, mutagenic, and/or teratogenic in animal studies. The most abundant class of DBPs that result from chlorination of drinking water are trihalomethanes (THMs) - chloroform (CHCl3), dichlorobromomethane (CHCl2Br), dibromochloromethane (CHBr2Cl) and bromoform (CHBr3). The most predominant THM species was CHCl3 and it highest concentration was 85•106 ng/m3. The others THMs compounds concentration were lower, between 65•104 ng/m3 and 12•106 ng/m3. THMs compounds were analyzed on gas chromatography coupled with mass spectrometer detector (GC-MS) and head space technique (HS) was used for all analysis.

Derivatization method of free cyanide including cyanogen chloride for the sensitive analysis of cyanide in chlorinated drinking water by liquid chromatography-tandem mass spectrometry.

PubMed

Kang, Hye-In; Shin, Ho-Sang

2015-01-20

A novel derivatization method of free cyanide (HCN + CN(-)) including cyanogen chloride in chlorinated drinking water was developed with d-cysteine and hypochlorite. The optimum conditions (0.5 mM D-cysteine, 0.5 mM hypochlorite, pH 4.5, and a reaction time of 10 min at room temperature) were established by the variation of parameters. Cyanide (C(13)N(15)) was chosen as an internal standard. The formed β-thiocyanoalanine was directly injected into a liquid chromatography-tandem mass spectrometer without any additional extraction or purification procedures. Under the established conditions, the limits of detection and the limits of quantification were 0.07 and 0.2 μg/L, respectively, and the interday relative standard deviation was less than 4% at concentrations of 4.0, 20.0, and 100.0 μg/L. The method was successfully applied to determine CN(-) in chlorinated water samples. The detected concentration range and detection frequency of CN(-) were 0.20-8.42 μg/L (14/24) in source drinking water and 0.21-1.03 μg/L (18/24) in chlorinated drinking water.

Monte Carlo analysis of uncertainty propagation in a stratospheric model. 1: Development of a concise stratospheric model

NASA Technical Reports Server (NTRS)

Rundel, R. D.; Butler, D. M.; Stolarski, R. S.

1977-01-01

A concise model has been developed to analyze uncertainties in stratospheric perturbations, yet uses a minimum of computer time and is complete enough to represent the results of more complex models. The steady state model applies iteration to achieve coupling between interacting species. The species are determined from diffusion equations with appropriate sources and sinks. Diurnal effects due to chlorine nitrate formation are accounted for by analytic approximation. The model has been used to evaluate steady state perturbations due to injections of chlorine and NO(X).

Ballast Water Treatment, U.S. Great Lakes Bulk Carrier Engineering and Cost Study. Volume 2: Analysis of On-Board Treatment Methods, Alternative Ballast Water Management Practices, and Implementation Costs

DTIC Science & Technology

2013-11-01

flushing filter, disinfection with injected chlorine dioxide (chlorine dioxide is generated onboard from two component chemicals, sulfuric acid...Management System 400 80 250-8000 (10000) Sulfuric Acid and Purate for ClO2 generation Yes 0.005-0.028 8-18 Decreased sediment, potential corrosion...feed chemicals, Purate and sulfuric acid. 5. Operational and Maintenance Cost: Estimated operating and maintenance cost is $80/1000 m3 of ballast

State of the art on cyanotoxins in water and their behaviour towards chlorine.

PubMed

Merel, Sylvain; Clément, Michel; Thomas, Olivier

2010-04-01

The occurrence of cyanobacterial blooms is drastically increasing in temperate countries and drinking water resources are threatened. As a result, cyanotoxins should be considered in water treatment to protect human health. This study presents a state of the art on cyanotoxins in water and their behaviour towards chlorination, a common drinking water disinfection process. Chlorination efficiency on cyanotoxins alteration depends on pH, chlorine dose and oxidant nature. Microcystins and cylindrospermopsin are efficiently transformed by chlorine, with respectively 6 and 2 by-products identified. In addition, chlorination of microcystins and cylindrospermopsin is associated with a loss of acute toxicity. Even though they have been less investigated, saxitoxins and nodularins are also altered by chlorine. For these toxins, no by-products have been identified, but the chlorinated mixture does not show acute toxicity. On the contrary, the fact that anatoxin-a has a very slow reaction kinetics suggests that this toxin resists chlorination. Copyright 2009 Elsevier Ltd. All rights reserved.

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

PubMed

Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

2013-03-01

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.

Effects of UV 254 irradiation on residual chlorine and DBPs in chlorination of model organic-N precursors in swimming pools.

PubMed

Weng, ShihChi; Li, Jing; Blatchley, Ernest R

2012-05-15

Ultraviolet (UV) irradiation is commonly applied as a secondary disinfection process in chlorinated pools. UV-based systems have been reported to yield improvements in swimming pool water and air chemistry, but to date these observations have been largely anecdotal. The objectives of this investigation were to evaluate the effects of UV irradiation on chlorination of important organic-N precursors in swimming pools. Creatinine, L-arginine, L-histidine, glycine, and urea, which comprise the majority of the organic-N in human sweat and urine, were selected as precursors for use in conducting batch experiments to examine the time-course behavior of several DBPs and residual chlorine, with and without UV(254) irradiation. In addition, water samples from two natatoria were subjected to monochromatic UV irradiation at wavelengths of 222 nm and 254 nm to evaluate changes of liquid-phase chemistry. UV(254) irradiation promoted formation and/or decay of several chlorinated N-DBPs and also increased the rate of free chlorine consumption. UV exposure resulted in loss of inorganic chloramines (e.g., NCl(3)) from solution. Dichloromethylamine (CH(3)NCl(2)) formation from creatinine was promoted by UV exposure, when free chlorine was present in solution; however, when free chlorine was depleted, CH(3)NCl(2) photodecay was observed. Dichloroacetonitrile (CNCHCl(2)) formation (from L-histidine and L-arginine) was promoted by UV(254) irradiation, as long as free chlorine was present in solution. Likewise, UV exposure was observed to amplify cyanogen chloride (CNCl) formation from chlorination of L-histidine, L-arginine, and glycine, up to the point of free chlorine depletion. The results from experiments involving UV irradiation of chlorinated swimming pool water were qualitatively consistent with the results of model experiments involving UV/chlorination of precursors in terms of the behavior of residual chlorine and DBPs measured in this study. The results indicate that UV(254) irradiation promotes several reactions that are involved in the formation and/or destruction of chlorinated N-DBPs in pool settings. Enhancement of DBP formation was consistent with a mechanism whereby a rate-limiting step in DBP formation was promoted by UV exposure. Promotion of these reactions also resulted in increases of free chlorine consumption rates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Polychlorinated biphenyl toxicity to Japanese quail as related to degree of chlorination

USGS Publications Warehouse

Hill, E.F.; Heath, R.G.; Spann, J.W.; Williams, J.D.

1974-01-01

To learn if the percentage of chlorine in a mixture of polychlorinated biphenyls (PCB's) alone determines toxicity, Japanese quail were fed diets containing Aroelor 1248, 1254, or 1260 at levels that added equal amounts of chlorine to the feed. The experiment comprised two consecutive 5-day periods; three sublethal concentrations of chlorine were evaluated during the first period and three lethal concentrations during the second period. Evaluations utilized comparisons of mortality, time to death, weight change, and food consumption. Sublethal concentrations produced no detectable effects. Lethal concentrations with equal Chlorine showed Aroelor 1248 to be less toxic at the highest chlorine concentrations, but at lower concentrations Aroelor 1254 was more toxic than Aroclor 1260. Although chlorine percentage of a PCB is positively correlated with its avian toxicity, PCB toxicity is apparently not simply a function of chlorination.

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.

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2016-09-01

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Perform Tests and Document Results and Analysis of Oxide Layer Effects and Comparisons

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

Collins, E. D.; DelCul, G. D.; Spencer, B. B.

2014-08-30

During the initial feasibility test using actual used nuclear fuel (UNF) cladding in FY 2012, an incubation period of 30–45 minutes was observed in the initial dry chlorination. The cladding hull used in the test had been previously oxidized in a dry air oxidation pretreatment prior to removal of the fuel. The cause of this incubation period was attributed to the resistance to chlorination of an oxide layer imparted by the dry oxidation pretreatment on the cladding. Subsequently in 2013, researchers at the Korea Atomic Energy Institute (KAERI) reported on their chlorination study [R1] on ~9-gram samples of unirradiated ZirloTMmore » cladding tubes that had been previously oxidized in air at 500oC for various time periods to impart oxide layers of varying thickness. In early 2014, discussions with Indefinite Delivery, Indefinite Quantity (IDIQ) contracted technical consultants from Westinghouse described their previous development (and patents) [R2] on methods of chemical washing to remove some or all of the hydrous oxide layer imparted on UNF cladding during irradiation in light water reactors (LWRs) . Thus, the Oak Ridge National Laboratory (ORNL) study, described herein, was planned to extend the KAERI study on the effects of anhydrous oxide layers, but on larger ~100-gram samples of unirradiated zirconium alloy cladding tubes, and to investigate the effects of various methods of chemical pretreatment prior to chlorination with 100% chlorine on the average reaction rates and Cl2 usage efficiencies.« less

Use of multiple regression models to evaluate the formation of halonitromethane via chlorination/chloramination of water from Tai Lake and the Qiantang River, China.

PubMed

Hong, Huachang; Qian, Lingya; Xiong, Yujing; Xiao, Zhuoqun; Lin, Hongjun; Yu, Haiying

2015-01-01

The deterioration of water quality, especially organic pollution in Tai Lake and the Qiantang River, have recently received attention in China. The objectives of this study were to evaluate the formation of halonitromethanes (HNMs) using multiple regression models for chlorination and chloramination and to identify the key factors that influence the formation of HNMs in Tai Lake and the Qiantang River. The results showed that the total formation of HNMs (T-HNMs) during chlorination and chloramination could be described using the following models: (1) [Formula: see text] =(10)(5.267)(DON)(6.645)(Br(-))(0.737)(DOC)(-)(5.537)(Cl2)(0.333)(t)(0.165) (R(2)=0.974, p<0.01, n=33), and (2) T-HNMNH2Cl=(10)(-)(2.481)(Cl2)(0.451)(NO2(-))(0.382)(Br(-))(0.630)(t)(0.640)(Temp)(0.581) (R(2)=0.961, p<0.05, n=33), respectively. The key factors that influenced the T-HNM yields during chlorination were dissolved organic nitrogen (DON), bromide and dissolved organic carbon (DOC). The nitrite and bromide concentrations and the reaction time mainly affected the T-HNM yields during chloramination. Additional analysis indicated that the bromine incorporation factors (BIFs) for trihalogenated HNMs generally decreased as the chlorine/chloramine dose, temperature and reaction time decreased and increased as the bromide concentration increased. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chlorine leak on Mumbai Port Trust's Sewri yard: A case study

PubMed Central

Sharma, Rakesh Kumar; Chawla, Raman; Kumar, Surendra

2010-01-01

Chemical emergencies involving hazardous chemicals are not uncommon in India. More than 25 incidents have been identified in National Disaster Management Guidelines – Chemical (Industrial) Disaster Management, released in May 2007. In a recent occurrence on the morning of 14 July 2010, nearly at 3:00 a.m., chlorine leak was reported from a gas cylinder referred as turner, weighing about 650 kg, corroding with time at the Haji Bunder hazardous cargo warehouse in Mumbai Port Trust, Sewri, affecting over 120 people in the neighborhood, including students, laborers, port workers and fire fighters, of whom 70 were reported critical. It has been observed to be a blatant case of ignorance and negligence as well as contraventions to the safety and environmental safeguard requirements under existing statues as well as non-maintenance of failsafe conditions at the site requisite for chlorine storage. The analysis revealed significant gaps in the availability of neutralization mechanism and the chlorine stored in open increased the possibility of formation of ingress mixture due to busting of chlorine filled tankers. The Government of India has institutionalized emergency preparedness framework at national, state and district level as envisaged in Disaster Management Act, 2005, to prepare the nation to mitigate such incidences, if all the preventive safety provisions fail. Ministry of Environment and Forests (MoEF) is preparing National Action Plan-Chemical (Industrial) Disaster Management based on National Guidelines to implement all the mechanisms of capacity development across the country. PMID:21829311

Solid recovered fuel: influence of waste stream composition and processing on chlorine content and fuel quality.

PubMed

Velis, Costas; Wagland, Stuart; Longhurst, Phil; Robson, Bryce; Sinfield, Keith; Wise, Stephen; Pollard, Simon

2012-02-07

Solid recovered fuel (SRF) produced by mechanical-biological treatment (MBT) of municipal waste can replace fossil fuels, being a CO(2)-neutral, affordable, and alternative energy source. SRF application is limited by low confidence in quality. We present results for key SRF properties centered on the issue of chlorine content. A detailed investigation involved sampling, statistical analysis, reconstruction of composition, and modeling of SRF properties. The total chlorine median for a typical plant during summer operation was 0.69% w/w(d), with lower/upper 95% confidence intervals of 0.60% w/w(d) and 0.74% w/w(d) (class 3 of CEN Cl indicator). The average total chlorine can be simulated, using a reconciled SRF composition before shredding to <40 mm. The relative plastics vs paper mass ratios in particular result in an SRF with a 95% upper confidence limit for ash content marginally below the 20% w/w(d) deemed suitable for certain power plants; and a lower 95% confidence limit of net calorific value (NCV) at 14.5 MJ kg(ar)(-1). The data provide, for the first time, a high level of confidence on the effects of SRF composition on its chlorine content, illustrating interrelationships with other fuel properties. The findings presented here allow rational debate on achievable vs desirable MBT-derived SRF quality, informing the development of realistic SRF quality specifications, through modeling exercises, needed for effective thermal recovery.

Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Paull, C.K.; Coston, J.A.

1993-01-01

Distributions of porewater constituents, SO4=, NH4+, Cl-, ???CO2, and H2S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ?? 1.9%. and 2.2 ?? 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ???CO2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite ??34S values ranged from -29%. to + 21%. (CDT). However, only positive ??34S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited ??34S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a ??34S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the "front" of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation. ?? 1993.

Converting isotope ratios to diet composition - the use of mixing models - June 2010

EPA Science Inventory

One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

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

Chlorine-36 dating of saline sediments: Preliminary results from Searles Lake, California

USGS Publications Warehouse

Phillips, F.M.; Smith, G.I.; Bentley, H.W.; Elmore, D.; Gove, H.E.

1983-01-01

Measurements have been made of the ratios of chlorine-36 to chlorine in five halite samples from Searles Lake sediments, previously dated by carbon-14, thorium-230, and magnetostratigraphic techniques. The ages calculated from the chlorine ratios are generally concordant with those from the other methods, implying the constancy of the chlorine input ratio over the last million years.

Role of drinking water biofilms on residual chlorine decay and trihalomethane formation: An experimental and modeling study.

PubMed

Xu, Jianeng; Huang, Conghui; Shi, Xiaoyang; Dong, Shengkun; Yuan, Baoling; Nguyen, Thanh H

2018-06-13

PVC pipe loops were constructed to simulate household premise plumbing. These pipe loops were exposed to water treated by physical processes at three water treatment plants in Xiamen, China from August 2016 to June 2017. After the biofilms were allowed to develop inside the pipes, these pipes were deconstructed and exposed to organic-free chlorine solution buffered at pH 6.8 ± 0.2 for 48 h. The decay of chlorine by these biofilms was higher than by the effluent waters that were used to grow the biofilms. A chlorine consumption mass balance model elucidated the role of both the diffusion of chlorine into the biofilm and the reaction of chlorine with the biofilm matrix. Comparable concentrations of trihalomethanes were quantified from the reaction between chlorine and source water organic matters, and chlorine and the biofilm, further emphasizing the role of biofilms in the safety of disinfected drinking water. These findings imply that when chlorine is used in the drinking water distribution system, the ubiquitous presence of biofilms may cause the depletion of chlorine and the formation of non-negligible levels of toxic disinfection byproducts. Copyright © 2018 Elsevier B.V. All rights reserved.

Influence of Multiple Environmental Factors on Organic Matter Chlorination in Podsol Soil.

PubMed

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

2017-12-19

Natural chlorination of organic matter is common in soils. The abundance of chlorinated organic compounds frequently exceeds chloride in surface soils, and the ability to chlorinate soil organic matter (SOM) appears widespread among microorganisms. Yet, the environmental control of chlorination is unclear. Laboratory incubations with 36 Cl as a Cl tracer were performed to test how combinations of environmental factors, including levels of soil moisture, nitrate, chloride, and labile organic carbon, influenced chlorination of SOM from a boreal forest. Total chlorination was hampered by addition of nitrate or by nitrate in combination with water but enhanced by addition of chloride or most additions including labile organic matter (glucose and maltose). The greatest chlorination was observed after 15 days when nitrate and water were added together with labile organic matter. The effect that labile organic matter strongly stimulated the chlorination rates was confirmed by a second independent experiment showing higher stimulation at increased availability of labile organic matter. Our results highlight cause-effect links between chlorination and the studied environmental variables in podsol soil-with consistent stimulation by labile organic matter that did overrule the negative effects of nitrate.

Evaluating four measures of water quality in clay pots and plastic safe storage containers in Kenya.

PubMed

Murphy, Jennifer L; Ayers, Tracy L; Knee, Jacqueline; Oremo, Jared; Odhiambo, Aloyce; Faith, Sitnah H; Nyagol, Ronald O; Stauber, Christine E; Lantagne, Daniele S; Quick, Robert E

2016-11-01

Household water treatment with chlorine can improve microbiological quality and reduce diarrhea. Chlorination is typically assessed using free chlorine residual (FCR), with a lower acceptable limit of 0.2 mg/L, however, accurate measurement of FCR is challenging with turbid water. To compare potential measures of adherence to treatment and water quality, we chlorinated recently-collected water in rural Kenyan households and measured total chlorine residual (TCR), FCR, oxidation reduction potential (ORP), and E. coli concentration over 72 h in clay and plastic containers. Results showed that 1) ORP served as a useful proxy for chlorination in plastic containers up to 24 h; 2) most stored water samples disinfected by chlorination remained significantly less contaminated than source water for up to 72 h, even in the absence of FCR; 3) TCR may be a useful proxy indicator of microbiologic water quality because it confirms previous chlorination and is associated with a lower risk of E. coli contamination compared to untreated source water; and 4) chlorination is more effective in plastic than clay containers presumably because of lower chlorine demand in plastic. Published by Elsevier Ltd.