Free Standard AU & NZ Shipping For All Book Orders Over $80!
Register      Login
Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
Shopping Cart: ( empty )
You are here: Home > Journals > EN > EN09008
RESEARCH FRONT
Contents Vol 6(1)

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

Paul B. Hatzinger A F , John Karl Böhlke B , Neil C. Sturchio C , Baohua Gu D , Linnea J. Heraty C and Robert C. Borden E
+ Author Affiliations
- Author Affiliations

A Shaw Environmental, Inc., Lawrenceville, NJ 08648, USA.

B US Geological Survey, Reston, VA 20192, USA.

C University of Illinois at Chicago, Chicago, IL 60607, USA.

D Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.

E North Carolina State University, Raleigh, NC 27695, USA.

F Corresponding author. Email: paul.hatzinger@shawgrp.com

Environmental Chemistry 6(1) 44-52 https://doi.org/10.1071/EN09008
Submitted: 15 January 2009  Accepted: 2 February 2009   Published: 3 March 2009

Environmental context. Perchlorate (ClO4–) and nitrate (NO3–) are common co-contaminants in groundwater, with both natural and anthropogenic sources. Each of these compounds is biodegradable, so in situ enhanced bioremediation is one alternative for treating them in groundwater. Because bacteria typically fractionate isotopes during biodegradation, stable isotope analysis is increasingly used to distinguish this process from transport or mixing-related decreases in contaminant concentrations. However, for this technique to be useful in the field to monitor bioremediation progress, isotope fractionation must be quantified under relevant environmental conditions. In the present study, we quantify the apparent in situ fractionation effects for stable isotopes in ClO4– (Cl and O) and NO3– (N and O) resulting from biodegradation in an aquifer.

Abstract. An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br– as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (ϵ18O/ϵ37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ~0.8 (ϵ18O/ϵ15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (ϵ18O/ϵ37Cl, ϵ18O/ϵ15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent ϵ values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.


Acknowledgements

The present project was supported by the US Department of Defence Environmental Security Technology Certification Program (Project ER-0509), and the USGS National Research Program in Water Resources. Assistance in the USGS laboratory was provided by Stanley Mroczkowski and Janet Hannon. Helpful reviews were provided by Richard L. Smith, Christopher Green, and several anonymous reviewers. Use of trade, product, or firm names is for descriptive purposes only, and does not imply endorsement by the US Government.


References


[1]   Brandhuber P., Clark S., Perchlorate Occurrence Mapping 2005 (American Water Works Association: Washington, DC).

[2]   P. K. Dasgupta , J. V. Dyke , A. B. Kirk , W. A. Jackson , Perchlorate in the United States: analysis of relative source contributions to the food chain. Environ. Sci. Technol. 2006 , 40,  6608.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  [Verified 13 February 2009]

[8]   Performance monitoring of MNA remedies for VOCs in ground water, EPA/600/R-04/027 2004 (National Risk Management Research Laboratory, Office of Research and Development, US Environmental Protection Agency: Cincinnati, OH).

[9]   N. C. Sturchio , J. K. Böhlke , A. D. Beloso , S. H. Streger , L. Heraty , P. B. Hatzinger , Oxygen and chlorine fractionation during perchlorate biodegradation: laboratory results and implications for forensics and natural attenuation studies. Environ. Sci. Technol. 2007 , 41,  2796.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  [Verified 13 February 2009]

[11]   R. C. Borden , Effective distribution of emulsified edible oil for enhanced in situ anaerobic bioremediation. J. Contam. Hydrol. 2007 , 94,  1.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  [Verified 9 February 2009]

[16]   B. Gu , G. M. Brown , L. Maya , M. J. Lance , B. A. Moyer , Regeneration of perchlorate (ClO4–)-loaded anion exchange resins by novel tetrachloroferrate (FeCl4–) displacement technique. Environ. Sci. Technol. 2001 , 35,  3363.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[17]   H. Bao , B. Gu , Natural perchlorate has a unique oxygen isotope signature. Environ. Sci. Technol. 2004 , 38,  5073.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[18]   Sturchio N. C., Böhlke J. K., Gu B., Horita J., Brown G. M., Beloso A. D.Jr, Patterson L. I., Hatzinger P. B., Jackson W. A., Batista J., Stable isotopic composition of chlorine and oxygen in synthetic and natural perchlorate, in Perchlorate: Environmental Occurrence, Interactions, and Treatment (Eds B. Gu, J. D. Coates) 2006, pp. 93–110 (Springer: New York).

[19]   B. Gu , J. Tio , W. Wang , Y. Ku , S. Dai , Raman spectroscopic detection for perchlorate at low concentrations. Appl. Spectrosc. 2004 , 58,  741.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[20]   D. M. Sigman , K. L. Casciotti , M. Andreani , C. Barford , M. Galanter , J. K. Böhlke , A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater. Anal. Chem. 2001 , 73,  4145.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[21]   K. L. Casciotti , D. M. Sigman , M. Hastings , J. K. Böhlke , A. Hilkert , Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method. Anal. Chem. 2002 , 74,  4905.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[22]   J. K. Böhlke , S. J. Mroczkowski , T. B. Coplen , Oxygen isotopes in nitrate: new reference materials for 18O : 17O : 16O measurements and observations on nitrate–water equilibration. Rapid Com. Mass Spec. 2003 , 17,  1835.
        | Crossref | GoogleScholarGoogle Scholar |  open url image1

[23]   J. D. Coates , L. A. Achenbach , Microbial perchlorate reduction: rocket-fuelled metabolism. Nat. Rev. Microbiol. 2004 , 2,  569.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[24]   S. K. Chaudhuri , S. M. O’Conner , R. L. Gustavson , L. A. Achenbach , J. D. Coates , Environmental factors that control microbial perchlorate reduction. Appl. Environ. Microbiol. 2002 , 68,  4425.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[25]   T. Giblin , D. Herman , M. A. Deshusses , W. T. Frankenberger , Removal of perchlorate in ground water with a flow-through bioreactor. J. Environ. Qual. 2000 , 29,  578.
        |  CAS |  open url image1

[26]   Farhan Y. H., Hatzinger P. B., Modeling the biodegradation kinetics of perchlorate in the presence of oxygen and nitrate as competing electron acceptors. Bioremediat. J. 2009, in press.

[27]   M. L. Coleman , M. Ader , S. Chaudhuri , J. D. Coates , Microbial isotopic fractionation of perchlorate chlorine. Appl. Environ. Microbiol. 2003 , 69,  4997.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[28]   N. C. Sturchio , P. B. Hatzinger , M. D. Arkins , C. Suh , L. J. Heraty , Chlorine isotope fractionation during microbial reduction of perchlorate. Environ. Sci. Technol. 2003 , 37,  3859.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[29]   J. D. Cline , I. R. Kaplan , Isotopic fractionation of dissolved nitrate during denitrification in the eastern tropical North Pacific Ocean. Mar. Chem. 1975 , 3,  271.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[30]   A. Mariotti , J. C. Germon , P. Hubert , P. Kaiser , R. Letolle , A. Tardieux , P. Tardieux , Experimental determination of nitrogen kinetic isotope fractionation: some principles; illustration for the denitrification and nitrification processes. Plant Soil 1981 , 62,  413.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[31]   C. C. Barford , J. P. Montoya , M. A. Altabet , R. Mitchell , Steady-state nitrogen isotope effects of N2 and N2O production in Paracoccus denitrificans. Appl. Environ. Microbiol. 1999 , 65,  989.
        |  CAS | PubMed |  open url image1

[32]   J. Granger , D. M. Sigman , M. F. Lehmann , P. D. Tortell , Nitrogen and oxygen isotope fractionation during dissimilatory nitrate reduction by denitrifying bacteria. Limnol. Oceanogr. 2008 , 53,  2533.
        |  CAS |  open url image1

[33]   T. Kawanishi , Y. Hayashi , N. Kihou , T. Yoneyama , Y. Ozaki , Dispersion effect on the apparent nitrogen isotope fractionation factor associated with denitrification in soil: evaluation by a mathematical model. Soil Biol. Biochem. 1993 , 25,  349.
        | Crossref | GoogleScholarGoogle Scholar |  open url image1

[34]   Y. Abe , D. Hunkeler , Does the Rayleigh equation apply to evaluate field isotope data in contaminant hydrology? Environ. Sci. Technol. 2006 , 40,  1588.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[35]   A. Mariotti , B. Simon , A. Landreau , 15N isotope biogeochemistry and natural denitrification process in groundwater: application to the chalk aquifer of northern France. Geochim. Cosmochim. Acta 1988 , 52,  1869.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[36]   J. A. Brandes , A. H. Devol , Isotopic fractionation of oxygen and nitrogen in coastal marine sediments. Geochim. Cosmochim. Acta 1997 , 61,  1793.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[37]   E. T. Urbansky , Perchlorate as an environmental contaminant. Environ. Sci. Pollut. Res. 2002 , 9,  187.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[38]   Brown G. M., Gu B., The chemistry of perchlorate in the environment, in Perchlorate: Environmental Occurrence, Interactions, and Treatment (Eds B. Gu, J. D. Coates) 2006, pp. 17–48 (Springer: New York).

[39]   Espenson J. H., The problem and perversity of perchlorate, in Perchlorate in the Environment (Ed. E. T. Urbansky) 2000, pp. 1–8 (Springer: New York, NY).

[40]   R. L. Smith , B. L. Howes , J. H. Duff , Denitrification in nitrate-contaminated groundwater: occurrence in steep vertical geochemical gradients. Geochim. Cosmochim. Acta 1991 , 55,  1815.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[41]   J. Granger , D. M. Sigman , J. A. Needoba , P. J. Harrison , Coupled nitrogen and oxygen isotope fractionation of nitrate during assimilation by cultures of marine phytoplankton. Limnol. Oceanogr. 2004 , 49,  1763.
        |  CAS |  open url image1

[42]   M. F. Lehmann , P. Reichert , S. M. Bernasconi , A. Barbieri , J. A. Mckenzie , Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone. Geochim. Cosmochim. Acta 2003 , 67,  2529.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[43]   J. Böttcher , O. Strebel , S. Voerkelius , H. L. Schmidt , Using isotope fractionation of nitrate–nitrogen and nitrate–oxygen for evaluation of microbial denitrification in a sandy aquifer. J. Hydrol. 1990 , 114,  413.
        | Crossref | GoogleScholarGoogle Scholar |  open url image1

[44]   D. M. Sigman , J. Granger , P. J. DiFiore , M. M. Lehmann , R. Ho , G. Cane , A. van Geen , Coupled nitrogen and oxygen isotope measurements of nitrate along the eastern North Pacific margin. Global Biogeochem. Cy. 2005 , 19,  GB4022.
        | Crossref | GoogleScholarGoogle Scholar |  open url image1

[45]   E. D. Young , A. Galy , H. Nagahara , Kinetic and equilibrium mass-dependent isotope fractionation laws in nature and their geochemical and cosmochemical significance. Geochim. Cosmochim. Acta 2002 , 66,  1095.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[46]   B. Morasch , H. H. Richnow , B. Schink , R. U. Meckenstock , Carbon and hydrogen stable isotope fractionation during aerobic bacterial degradation of aromatic hydrocarbons. Appl. Environ. Microbiol. 2002 , 68,  5191.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[47]   R. U. Meckenstock , B. Morasch , C. Griebler , H. H. Richnow , Stable isotope fractionation as a tool to monitor biodegradation in contaminated aquifers. J. Contam. Hydrol. 2004 , 75,  215.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1