Zusammenfassung
Bei der Untersuchung von belasteten Standorten stellt sich häufig die Frage, ob unterschiedliche Schadstoffquellen zu einer Grundwasserbelastung beitragen. Chlorierte Kohlenwasserstoffe (CKWs) von verschiedenen Produzenten können unterschiedliche Kohlenstoff- und Chlor-Isotopensignaturen (C-Cl-Isotopensignaturen) aufweisen, was eine Differenzierung von CKW-Quellen ermöglicht. Dazu muss aber die Variabilität der Isotopensignatur bekannt sein. Da die ursprünglich verwendeten Lösungsmittel meist nicht mehr zugänglich sind, werden in dieser Studie die Perchlorethen (PCE) C-Cl-Isotopensignaturen an belasteten Standorten in der Schweiz untersucht. Zehn Standorte wurden ausgewählt, die verschiedene Branchen und Landesregionen abdecken. Eine Variabilität der C-Cl-Isotopensignaturen zwischen einigen Standorten bestätigt die Anwendbarkeit dieser Methode zur Quellendifferenzierung. Gewisse Standorte zeigen jedoch ähnliche Isotopensignaturen. Deswegen ist der Erfolg dieser Identifikationsmethode standortspezifisch. Außerdem ist die Variabilität geringer als publizierte Isotopensignaturen von nordamerikanischen Herstellern. Es hat sich außerdem bestätigt, dass der biologische Abbau von PCE durch reduktive Dechlorierung bei der Identifikation der Kontaminationsquellen berücksichtigt werden muss.
Abstract
When dealing with contaminated sites, identifying the source of contamination is critical for regulatory purposes. For chlorinated ethenes, previous studies have shown that dual carbon-chlorine (C-Cl) stable isotope analysis could be a key to address this issue as isotopic signatures vary between manufacturers and therefore, supposedly between sources. A successful application of this method relies on the assumption that different sources in the field will also show different signatures. Since the solvents used in the past are no longer available, this study aimed at investigating the extent of applicability of C-Cl stable isotope measurements for source identification based on field investigations. Ten sites which covered all of Switzerland and various sectors employing perchloroethene (PCE) were chosen. Differences were observed between some sites, suggesting that this method could be successfully applied. Other sites showed very similar isotopic signatures, indicating that this method applicability is site-specific. Additionally, the isotopic signature variability between sites was less significant than between the values previously reported for solvents from various manufacturers from North America. It was also confirmed that PCE reductive dechlorination should be considered when applying C-Cl isotope analysis for source identification.
This is a preview of subscription content, log in via an institution to check access.
Notes
Zur Vereinfachung des Leseflusses sind die Isotopensignaturen im Text als (δ13C (‰); δ37Cl (‰)) angegeben.
Literatur
Aeppli, C., Holmstrand, H., Andersson, P., Gustafsson, O.: Direct compound-specific stable chlorine isotope analysis of organic compounds with quadrupole GC/MS Using standard isotope bracketing. Anal. Chem. 82(1), 420–426 (2010)
Amaral, H.I., Aeppli, C., Kipfer, R., Berg, M.: Assessing the transformation of chlorinated ethenes in aquifers with limited potential for natural attenuation: added values of compound-specific carbon isotope analysis and groundwater dating. Chemosphere. 85(5), 774–781 (2011)
Badin, A., Buttet, G., Maillard, J., Holliger, C., Hunkeler, D.: Multiple dual C–Cl isotope patterns associated with reductive dechlorination of tetrachloroethene. Environ. Sci. Technol. 48(16), 9179–9186 (2014)
Bernstein, A., Shouakar-Stash, O., Ebert, K., Laskov, C., Hunkeler, D., Jeannottat, S., Sakaguchi-Söder, K., Laaks, J., Jochmann, M.A., Cretnik, S., Jager, J., Haderlein, S.B., Schmidt, T.C., Aravena, R., Elsner, M.: Compound-specific chlorine isotope analysis: a comparison of gas chromatography/isotope ratio mass spectrometry and gas chromatography/quadrupole mass spectrometry methods in an interlaboratory study. Anal. Chem. 83(20), 7624–7634 (2011)
BIPM, I., IFCC, ISO, IUPAC, IUPAP, OIML: Guide to the expression of uncertainty in measurement. International Organization for Standardization, Geneva, (1993)
Blessing, M., Schmidt, T.C., Dinkel, R., Haderlein, S.B.: Delineation of multiple chlorinated ethene sources in an industrialized area – a forensic field study using compound-specific isotope analysis. Environ. Sci. Technol. 43(8), 2701–2707 (2009)
Bloom, Y., Aravena, R., Hunkeler, D., Edwards, E., Frape, S.K.: Carbon isotope fractionation during microbial dechlorination of trichloroethene, cis –1,2-dichloroethene, and vinyl chloride: Implications for assessment of natural attenuation. Environ. Sci. Technol. 34(13), 2768–2772 (2000)
Clark, I.D., Fritz, P.: Environmental isotopes in hydrogeology, S 328. Lewis Publishers, Boca Raton (1997)
Doherty, R.E.: A history of the production and use of carbon tetrachloride, tetrachloroethylene, trichloroethylene and 1,1,1-trichloroethane in the United States: Part 1– Historical background; Carbon tetrachloride and tetrachloroethylene. Environ. Forens. 1(2), 69–81 (2000)
Eberts, S.M., Braun, C., Jones, S.: Compound-specific isotope analysis: questioning the origins of a trichloroethene plume. Environ. Forens. 9(1), 85–95 (2008)
Eisenmann, H., Fischer, A.: Isotopenuntersuchungen in der Altlastenbewertung. In: Franzius, V., Altenbockum, M., Gerhold, T. (Hrsg.) Handbuch der Altlastensanierung und Flächenmanagement, S 47. Hüthig Jehle Rehm, München (2010)
Hitzfeld, K.L., Gehre, M., Richnow, H.-H.: A novel online approach to the determination of isotopic ratios for organically bound chlorine, bromine and sulphur. Rapid. Commun. Mass. Spectrom. 25(20), 3114–3122 (2011)
Holt, B.D., Sturchio, N.C., Abrajano, T.A., Heraty L.J.: Conversion of chlorinated volatile organic compounds to carbon dioxide and methyl chloride for isotopic analysis of carbon and chlorine. Anal. Chem. 69(14), 2727–2733 (1997)
Hunkeler, D., Aravena, R., Butler, B.J.: Monitoring microbial dechlorination of tetrachloroethene (PCE) in groundwater using compound-specific stable carbon isotope ratios: Microcosm and field studies. Environ. Sci. Technol. 33(16), 2733–2738 (1999)
Hunkeler, D., Chollet, N., Pittet, X., Aravena, R., Cherry, J.A., Parker, B.L.: Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers. J. Contam. Hydrol. 74(1–4), 265–282 (2004)
Hunkeler, D., Meckenstock, R.U., Lollar Sherwood, B., Schmidt, T.C., Wilson, J.T.: A Guide for Assessing Biodegradation and Source Identification of Organic Groundwater Contaminants Using Compound Specific Isotope Analysis (CSIA), Environmental Protection Agency. EPA/600/R -08/148 (2008)
Jeannottat, S., Hunkeler, D.: Chlorine and carbon isotopes fractionation during volatilization and diffusive transport of trichloroethene in the unsaturated zone. Environ. Sci. Technol. 46(6), 3169–3176 (2012)
Jeannottat, S., Hunkeler, D.: Can soil gas VOCs be related to groundwater plumes based on their isotope signature? Environ. Sci. Technol. 47(21), 12115–12122 (2013)
Jendrzejewski, N., Eggenkamp, H.G.M., Coleman, M.L.: Characterisation of chlorinated hydrocarbons from chlorine and carbon isotopic compositions: scope of application to environmental problems. Appl. Geochem. 16(9–10), 1021–1031 (2001)
Jin, B.A., Laskov, C., Rolle, M., Haderlein, S.B.: Chlorine isotope analysis of organic contaminants using GC-qMS: method optimization and comparison of different evaluation schemes. Environ. Sci. Technol. 45(12), 5279–5286 (2011)
Kaown, D., Shouakar-Stash, O., Yang, J., Hyun, Y., Lee, K.-K.: Identification of multiple sources of groundwater contamination by dual isotopes. Ground. Water. 52(6), 875–885 (2014)
Lojkasek-Lima, P., Aravena R., Parker, B.L., Cherry, J.A.: Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis. Ground. Water. 50(5), 754–764 (2012)
Lollar, B.S., Slater, G.F., Ahad, J., Sleep, B., Spivack, J., Brennan, M., MacKenzie, P.: Contrasting carbon isotope fractionation during biodegradation of trichloroethylene and toluene: Implications for intrinsic bioremediation. Org. Geochem. 30(8A), 813–820 (1999)
McHugh, T., Kuder, T., Fiorenza, S., Gorder, K., Dettenmaier, E., Philp, P.: Application of CSIA to distinguish between vapor intrusion and indoor sources of VOCs. Environ. Sci. Technol. 45(14), 5952–5958 (2011)
Moran, M.J., Zogorski, J.S., Squillace, P.J.: Chlorinated solvents in groundwater of the United States. Environ. Sci. Technol. 41(1), 74–81 (2007)
Nijenhuis, I., Schmidt, M., Pellegatti, E., Paramatti, E., Richnow, H.H., Gargini, A.: A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site. J. Contam. Hydrol. 153, 92–105 (2013)
Palau, J., Marchesi, M., Chambon, J.C.C., Aravena, R., Canals, À., Binning, P.J., Bjerg, P.L., Otero, N., Soler, A.: Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes. Sci. Total Environ. 475, 61–70 (2014)
Pankow, J. F., Cherry, J.A.: Dense chlorinated solvents and other DNAPLs in groundwater: history, behavior, and remediation. Waterloo Press, Portland (1996)
Sakaguchi-Söder, K., Jager, J., Grund, H., Matthäus, F., Schüth, C.: Monitoring and evaluation of dechlorination processes using compound-specific chlorine isotope analysis. Rapid. Commun. Mass. Spectrom. 21(18), 3077–3084 (2007)
Slater, G.F., Dempster, H.S., Lollar, B.S., Ahad, J.: Headspace analysis: a new application for isotopic characterization of dissolved organic contaminants. Environ. Sci. Technol. 33(1), 190–194 (1999)
vanWarmerdam, E.M., Frape, S.K., Aravena, R., Drimmie, R.J., Flatt, H., Cherry, J.A.: Stable chlorine and carbon isotope measurements of selected chlorinated organic solvents. Appl. Geochem. 10(5), 547–552 (1995)
Wiegert, C., Aeppli, C., Knowles, T., Holmstrand, H., Evershed, R., Pancost, R.D., Macháčková, J., Gustafsson, Ö.: Dual carbon–chlorine stable isotope investigation of sources and fate of chlorinated ethenes in contaminated groundwater. Environ. Sci. Technol. 46(20), 10918–10925 (2012)
Danksagung
Diese Studie wurde im Rahmen des Marie Curie Initial Training Network „ADVOCATE – Advancing sustainable in situ remediation for contaminated land and groundwater“ durchgeführt, und von der Europäische Kommission, Marie Curie Actions Project No. 265063 finanziert. Den Standorteigentümern, die die Probennahmen ermöglicht haben, den Mitarbeitern von Ingenieurbüros sowie den Kollegen von Ämtern, die die Daten von den Standorten zur Verfügung gestellt und den Zustand der Standorte mit Geduld erklärt haben, wird herzlichst gedankt. Weiter gebührt ein herzlicher Dank Jordi Palau und Dimitri Boulaz für ihre wertvolle Hilfe während der Feldarbeit und Daniel Bouchard, Jordi Palau und Simon Jeannottat für Ihre Hilfe bei den Isotopenmessungen. Weiter wird Vivien Hakoun und Radu Slobodeanu für die konstruktiven Diskussionen bezüglich der Datenauswertung gedankt.
Author information
Authors and Affiliations
Corresponding author
Elektronisches zusätzliches Material
Rights and permissions
About this article
Cite this article
Badin, A., Schirmer, M., Wermeille, C. et al. Perchlorethen-Quellendifferenzierung mittels Kohlenstoff-Chlor-Isotopenanalyse: Felduntersuchungen zur Beurteilung der Variabilität der Isotopensignatur. Grundwasser 20, 263–270 (2015). https://doi.org/10.1007/s00767-015-0301-0
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00767-015-0301-0