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ESTCP Project ER-200509 FINAL REPORT Validation of Chlorine and Oxygen Isotope Ratio Analysis To Differentiate Perchlorate Sources and To Document Perchlorate Biodegradation ESTCP Project ER-200509 May 2013 Paul Hatzinger Shaw Environmental, Inc. J.K. Böhlke U.S. Geological Survey Neil Sturchio University of Illinois at Chicago Baohua Gu Oak Ridge National Laboratory ii Table of Contents List of Figures ................................................................................................................... vi List of Tables ..................................................................................................................... x List of Appendices ............................................................................................................. x Acronyms and Abbreviations ......................................................................................... xi Acknowledgements ......................................................................................................... xv Executive Summary ....................................................................................................... xvi 1.0 Introduction ................................................................................................................ 1 1.1 Perchlorate Sources .................................................................................................. 1 1.1.1 Synthetic Perchlorate ........................................................................................ 1 1.1.2 Chilean Nitrate Deposits and Fertilizer ............................................................. 2 1.1.3 Indigenous Natural Perchlorate in the U.S. ...................................................... 3 1.1.4 USEPA Guidance on Perchlorate Occurrence .................................................. 4 2.0 TECHNOLOGY DESCRIPTION ........................................................................... 8 2.1 Stable Isotope Ratio Analysis .................................................................................. 8 2.2 Isotopes of Chlorine and Oxygen in Perchlorate ................................................... 11 2.3 Previous Testing of the Technology ...................................................................... 11 2.4 Advantages and Limitations of the Technology .................................................... 17 3.0 Performance Objectives ........................................................................................... 18 3.1 Performance Metrics .............................................................................................. 19 3.1.1 Development of a Simple Procedure for Sample Collection .......................... 19 - 3.1.2 Refinement of Procedures for ClO4 Extraction, Purification, and Analysis ........................................................................................................... 19 3.1.3 Prepare and Characterize Analytical Reference Materials ............................. 19 3.1.4 Precise Isotopic Analysis of δ37C and δ18O, and Δ17O ................................... 19 3.1.5 Develop Isotopic Database (δ37Cl ,δ18O, and Δ17O) from Known - Synthetic and Natural ClO4 Samples ............................................................. 20 3.1.7 Develop Fractionation Factors for 37Cl and 18O through Laboratory Studies and Apply to Quantify Field Biodegradation ..................................... 20 3.1.8 Transition Isotopic Methodology to DoD End-Users ..................................... 20 4.0 Test Site Descriptions .............................................................................................. 22 4.1 Sites Selected for Sampling: History/Characteristics ............................................ 22 - 4.1.1 Sites with Indigenous Natural ClO4 . .............................................................. 22 4.1.1.1 Southern High Plains, West Texas ........................................................... 22 i 4.1.1.2 Middle Rio Grande Basin, NM ................................................................ 23 4.1.1.3 Death Valley, CA ..................................................................................... 24 - 4.1.2 Forensic Evaluations of ClO4 in Groundwater ............................................... 24 4.1.2.1 Suffolk County, Long Island, NY .............................................................. 24 4.1.2.2 Stringfellow Superfund Site, CA .............................................................. 25 4.1.2.3 Lower Umatilla Basin, OR ....................................................................... 25 4.1.2.4 University of Massachusetts, Dartmouth, MA ......................................... 26 - 4.2 ClO4 Isotope Fractionation Evaluation: Biobarrier Site, Elkton, MD .............. 27 5.0 Test Design ................................................................................................................. 29 5.1 Conceptual Experimental Design .......................................................................... 29 - 5.2 Isotopic Analysis of Cl and O in ClO4 : Technology Application ......................... 30 5.2.1 Sampling Groundwater Using Ion Exchange (IX) Columns .......................... 30 5.2.1.1 Sampling Column Construction ............................................................... 31 5.2.1.2 Collection of Perchlorate Samples from Groundwater ........................... 31 5.2.1.3 Sample Preservation and Shipment ......................................................... 37 5.2.2 Soil Sampling .................................................................................................. 37 5.2.3 Collection and Purification of Perchlorate in Samples with Elevated Chlorate ........................................................................................................... 38 5.2.3.1 Bacterial Degradation of Chlorate ........................................................... 38 5.2.3.2 Degradation of Chlorate using Hydrogen Gas and a Nickel Catalyst .... 39 5.2.4 Extraction and Purification of Perchlorate on IX Columns ............................ 41 5.2.4.1 Resin Removal from IX Columns and Resin Pre-Wash ........................... 41 5.2.4.2 Perchlorate Elution and Analysis ............................................................ 42 - 5.2.4.3 Effluent Clean-up and Concentration of ClO4 ....................................... 43 5.2.4.4 Perchlorate Crystallization and Recovery ............................................... 44 5.2.4.5 Assessing Purity of Recovered Perchlorate Crystals ............................... 44 5.2.4.6 Reprocessing Impure Samples ................................................................. 45 5.2.5 Analysis of Oxygen Isotopes in Perchlorate by IRMS ................................... 45 5.2.5.1 Terminology and Standards for Oxygen Stable Isotopic Analysis ........... 46 18 17 5.2.5.2 Analysis of δ O and δ O by Off-Line Conversion to O2, with Dual-Inlet Isotope-Ratio Mass Spectrometry (O2-DI-IRMS) ................................................ 48 5.2.5.3 Analysis of δ18O by On-Line Conversion to CO, with Continuous-Flow Isotope-Ratio Mass Spectrometry (CO-CF-IRMS) ............................................... 49 5.2.6 Analysis of Chlorine Isotopes in Perchlorate by Isotope-Ratio Mass Spectrometry ................................................................................................... 49 ii 5.2.6.1 Terminology and Standards for Chlorine Stable Isotopic Analysis ......... 50 5.2.6.2 Analysis of δ37Cl by Off-Line Conversion to Methyl Chloride, with Dual- Inlet Isotope-Ratio Mass Spectrometry (CH3Cl-DI-IRMS) .................................. 51 5.2.6.3 Analysis of δ37Cl by On-Line Separation of Methyl Chloride, with Continuous-Flow Isotope-Ratio Mass Spectrometry (CH3Cl-CF-IRMS) ............. 52 5.2.7 Analysis of 36Cl from Perchlorate ................................................................... 52 5.2.8. Development of Isotopic Reference Materials............................................... 53 5.2.9 Summary of Sampling, Purification and Analysis of Chlorine and Oxygen Isotopes in Perchlorate ....................................................................... 54 5.3 Supporting Information for Perchlorate Forensic Studies ..................................... 57 5.3.1 Field Parameters .............................................................................................. 57 5.3.2 Groundwater Dating ........................................................................................ 57 5.3.3 Stable Hydrogen and Oxygen Isotopes in Water ............................................ 58 - 5.3.4 Stable Nitrogen and Oxygen Isotopes in NO3 ............................................... 58 5.3.5 Stable Sulfur and Oxygen Isotopes in Sulfate ................................................ 59 5.3.6 Dissolved Gas Concentrations ........................................................................ 59 5.3.7 Trace Element Concentrations ........................................................................ 59 5.3.8 Anion Concentrations .................................................................................... 60 6.0 Results Part I: Isotopic Characteristics of Synthetic and Natural Perchlorate . 62 6.1 Compilation of an Isotopic Database ..................................................................... 62 6.1.1 Stable Isotope Ratios of Cl and O in Synthetic Perchlorate ........................... 63 6.1.2 Stable Isotopes of Chlorine and Oxygen in Natural Perchlorate ...................
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