Perchlorate

Detection and Site Characterization

Developing a detailed conceptual site model (CSM)1 can help target where to sample for perchlorate and identify the appropriate analytical methods. Development of the initial CSM typically involves site research that may include a review of historical documents and interviews with former and current personnel (or other knowledgeable individuals, including community members) to determine whether: 1) perchlorate was manufactured, used, or disposed of; 2) there was an onsite release, the quantity of a release, when it occurred, and the number of occurrences; and 3) perchlorate was manufactured or used upgradient of the site (ITRC, 2005).

Check the National Environmental Methods Index (NEMI), for a free, searchable clearinghouse of methods and procedures for regulatory and non-regulatory analyses.

Historical information can reveal whether there is a point source2, such as a leaking storage drum or nonpoint source3, such as agricultural crops irrigated with perchlorate-contaminated water.

Testing of groundwater and surface water, and/or soil (particularly in arid environments) may be warranted. Deeper soil samples may indicate the presence of perchlorate even if surface soil samples do not. In cases where a drinking water supply is contaminated, it can be challenging to identify the source of perchlorate, and extensive testing of upstream waterways, aqueducts, or groundwater may be necessary to trace the source (ITRC, 2008.) For example, a source investigation of a public water supply in Tewksbury, Massachusetts, successfully tracked the source of perchlorate contamination to an upstream water intake by sampling area rivers, the influent/effluent and process water of the wastewater treatment plants, and sites, facilities and other potential sources along the Merrimack and Concord Rivers. By working with the Town of Billerica, the Massachusetts Department of Environmental Protection, and the manufacturing plant that discharged the wastewater containing perchlorate, the Town of Tewksbury avoided installing a costly drinking water treatment system (ITRC, 2008).

Resources such as documents and journal articles for further information and approaches to sampling for possible perchlorate contamination are listed below under Site Characterization.

There are several analytical and sampling methods used to detect, measure, or monitor perchlorate in drinking water, other aqueous media, and soil. EPA Method 314, an ion chromatography method, was developed in 1999 to analyze raw and finished drinking water samples collected during the first Unregulated Contaminant Monitoring Rule. The minimum reporting level is 4 µg/L; however, high concentrations of other anions, such as chloride, sulfate, and carbonate can interfere with the analysis by destabilizing the retention time window for perchlorate (EPA, 1999). In other words, Method 314 can be subject to detection of "false positives" when high anion concentrations are present, where peaks of other anions appear with perchlorate's retention window and lead to misidentification (Thorne, 2004).

Method 314 was revised in 2005 (EPA Method 314.1: Inline column concentration/matrix elimination ion chromatography [EPA, 2005] with suppressed conductivity detection) and again in 2008 (EPA Method 314.2: Two-dimensional ion chromatography with suppressed conductivity detection) to help address limitations due to the unspecified nature of the conductivity detector. EPA Method 314.1 achieves the lowest concentration minimal reporting level (0.13-0.14 µg/L).

EPA Methods 331 (Revision 1) and 332 (Revision 1) also measure perchlorate drinking water samples, including those with high total dissolved solids (TDS), and achieve reporting levels of 0.02 and 0.1 µg/L, respectively. Method 331 uses non-suppressed ion chromatography with tandem mass spectrometry, and Method 332 uses ion chromatography coupled with suppressed conductivity and electrospray ionization mass spectrometry.

EPA Validated Test Method 6850 uses high performance liquid chromatography coupled with electrospray ionization mass spectrometry for the analysis of aqueous samples with TDS (groundwater, surface water, wastewater, and saltwater) and soil samples. The method has been validated but not yet incorporated into the SW-846 Compendium of methods.

A colorimetric method for detecting perchlorate was developed and tested for a range of aqueous samples (detection limit of 1 µg/L) and soil extracts (detection limit of 0.3 µg/g in spiked soils) (Thorne, 2004). Comparison of field results to Method 314 laboratory analyses showed a slight positive bias that became more significant at close to the detection level. False positives at this level were 10% for well water and 40% for bioreactor effluent.

Perchlorate can occur both naturally and as a result of an environmental release, though forensic techniques (chlorine or oxygen isotope analysis) have been developed that are capable of differentiating between naturally occurring perchlorate and manufactured perchlorate in water samples (Kumarathilaka, et al., 2016; Hatzinger, et al., 2013). Resources for perchlorate detection methods are listed below in Analytical Methods.

References:

EPA, 2012. Corrective Action 101 Key Terms. Website consulted September 2021.

EPA, 2005. Method Determination of Perchlorate in Drinking Water Using Ion Chromatography. Revision 1.0.

Hatzinger, P.B., et. al, 2013. Validation of Chlorine and Oxygen Isotope Ratio Analysis To Differentiate Perchlorate Sources and To Document Perchlorate Biodegradation. ESTCP Project ER-200509. May.

Interstate Technology & Regulatory Council (ITRC), 2008. Remediation Technologies for Perchlorate Contamination in Water and Soil. Report PERC-2, 218 pp.

Interstate Technology Regulatory Council (ITRC). 2005. Perchlorate: Overview of Issues, Status, and Remedial Options. PERC-1, 152 pp.

Kumarathilaka, P., et. al, 2016. Perchlorate as an Emerging Contaminant in Soil, Water, and Food. Chemosphere. May.

Thorne, P.G., 2004. Field Screening Method for Perchlorate in Water and Soil. ERDC/CCREL TR-04-8. April.

Resources

Analytical Methods

Applying Compound-Specific Isotope Analysis to Document Contaminant Degradation and Distinguish Sources
Hatzinger, P. SERDP & ESTCP Webinar #107, March 2020

Demonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO_4-)
Gu, B., A. Jubb, G. Eres, and P.B. Hatzinger. ESTCP Project ER-201327, 107 pp, 2017

Stable Isotope Analyses of Oxygen (¹⁸O:¹⁷O:¹⁶O) and Chlorine (³⁷Cl:³⁵Cl) in Perchlorate: Reference Materials, Calibrations, Methods, and Interferences
Bohlke, J.K., S.J. Mroczkowski, N.C. Sturchio, L.J. Heraty, K.W. Richman, D.B. Sullivan, K.N. Griffith, B. Gu, and P.B. Hatzinger.
Rapid Communications in Mass Spectrometry 31(1):85-110(2016)

Validation of a Novel Bioassay for Low-Level Perchlorate Determination
Coates, J.D. ESTCP Project ER-201030, 191 pp, 2014

Validation of Chlorine and Oxygen Isotope Ratio Analysis to Differentiate Perchlorate Sources and to Document Perchlorate Biodegradation: Final Report
Hatzinger, P., J.K. Boehlke, N.C. Sturchio, and B. Gu. ESTCP Project ER-200509, 263 pp, 2013

Validation of Chlorine and Oxygen Isotope Ratio Analysis to Differentiate Perchlorate Sources and to Document Perchlorate Biodegradation: Guidance Document
Hatzinger, P., J.K. Boehlke, N.C. Sturchio, and B. Gu. ESTCP Project ER-200509, 107 pp, 2011

An Enzymatic Bioassay for Perchlorate
Coates, J.D., M. Heinnickel, L.A. Achenbach. SERDP Project ER-1530, 81 pp, July 2010

Assessing Perchlorate Origins Using Stable Isotopes
T.K.G. Mohr.
Southwest Hydrology, 6(4):22-23;34(2007)

Determination of Perchlorate in Drinking Water by Ion Chromatography with Suppressed Conductivity and Electrospray Ionization Mass Spectrometry
Hedrick, E., R. Slingsby, and D. Munch. EPA Method 332.0-1, Revision 1, EPA 600/R-05/049, 48 pp 2005

Determination of Perchlorate in Drinking Water by Liquid Chromatography Electrospray Ionization Mass Spectrometry
Wendelken S.C. D.J. Munch, B.V. Pepich, D.W. Later and C. A. Pohl. EPA Method 331.0, Revision 1, EPA 815/R-05/007, 34 pp, 2005

Determination of Perchlorate in Drinking Water Using Inline Column Concentration/Matrix Elimination Ion Chromatography With Suppressed Conductivity Detection
Wagner, H.P., B.V. Pepich, C. Pohl, D. Later, R. Joyce, K. Srinivasan, B. DeBorba, D. Thomas, A. Woodruff, and D.J. Munch. EPA Method 314.1-1, Revision 1, EPA 815-R-05-009, 38 pp, 2005

Rapid Determination of Perchlorate Anion in Foods by Ion Chromatography-Tandem Mass Spectrometry, Revision 2
U.S. Food and Drug Administration, Center for Food Safety and Applied Nutrition, 2005

Current Regulatory Aspect of Perchlorate
Munch, D., 15 minutes, June 2002

Viability of Applying Curie Point Pyrolysis/Gas Chromatography Techniques for Characterization of Ammonium Perchlorate Based Propellants
Barnett, J.L. and B.M. Montoya. Sandia Report SAND2002-1922, 32 pp, 2002

Ion Chromatographic Determination of Perchlorate Ion: Analysis of Fertilizers and Related Materials
Collette, T.W., W.P. Robarge, and E.T. Urbansky. EPA/600/R-01/026, 2001

Perchlorate Screening Study: Low Concentration Method for the Determination of Perchlorate in Aqueous Samples Using Ion Selective Electrodes. Letter Report of Findings for Method Development Studies, Interference Studies, and Split Sample Studies, Including Standard Operating Procedure
U.S. Army Corps of Engineers and EPA Region 9, 172 pp, 2001

An Improved Ion Chromatographic Method for Low Level Perchlorate Analysis
Jackson, P.E. 33 slides, 2000

Determination of Perchlorate at Parts-Per-Billion Levels in Plants by Ion Chromatography
Ellington, J.J. and J.J. Evans.
Journal of Chromatography A 898:193-199(2000)

Determination of Perchlorate at Trace Levels in Drinking Water by Ion-Pair Extraction with Electrospray Ionization Mass Spectrometry
Magnuson, M.L., E.T. Urbansky, and C.A. Kelty.
Analytical Chemistry 72:25-29(2000)

Microscale Extraction of Perchlorate in Drinking Water with Low Level Detection by Electrospray-Mass Spectrometry
Magnuson, M.L., E.T. Urbansky, and C.A. Kelty.
Talanta 52:285-291(2000)

Quantitation of Perchlorate Ion: Practices and Advances Applied to the Analysis of Common Matrices
Urbansky, E.
Critical Reviews in Analytical Chemistry, 30(4):311-343(2000)

Determination of Perchlorate in Drinking Water Using Ion Chromatography
Hautman, D.P., D.J. Munch, A.D. Eaton, and A.W. Haghani. EPA Method 314.0, Rev 1.0, 49 pp, Nov 1999

Quantitation of Perchlorate Ion by Electrospray Ionization Mass Spectrometry (ESI-MS) Using Stable Association Complexes with Organic Cations and Bases to Enhance Selectivity
Urbansky, E., E.T. Urbansky, M.L. Magnuson, D. Freeman and C. Jelks.
Journal of Analytical Atomic Spectrometry 14:1861-1866(1999)

Stability and Concentration Verification of Ammonium Perchlorate Dosing Solutions
Tsui, D.T., D.R. Mattie, and L. Narayanan, Dayton, OH. AFRL-HE-WP-TR-1998-0068, 38 pp, 1998

Test Methods for Evaluating Solid Wastes: Physical/Chemical Methods
EPA Report SW-846, 3rd Edition, 689 pp, 1998

Measurement and Monitoring Technologies for the 21st Century Initiative (21M²) Literature Search
EPA Technology Innovative Program

Site Characterization

Phase II: Identification and Characterization of Natural Sources of Perchlorate
Hatzinger, P.B., G. Harvey, W.A. Jackson, J.K. Boehlke, N.C. Sturchio, B. Gu, D. Grantz, K. Burkey, and M. McGrath. SERDP Project ER-1435, 362 pp, 2017

Evaluation of Perchlorate Sources in the Rialto-Colton and Chino California Subbasins Using Chlorine and Oxygen Isotope Ratio Analysis
Hatzinger , P.B., J.K. Boehlke, J. Izbicki, N. Teague, and N.C. Sturchio. ESTCP Project ER-200942, 89 pp, 2015

Lab-on-a-Chip Sensor for Monitoring Perchlorate in Ground and Surface Water
Gertsch, J.C., I.G. Arcibal, C.S. Henry, and D.M. Cropek. SERDP Project ER-1706, 39 pp, 2012

Probability of Detecting Perchlorate under Natural Conditions in Deep Groundwater in California and the Southwestern United States
Fram, M.S. and K. Belitz.

Environmental Science & Technology 45(4):1271-1277(2011)

Demonstration and Validation of a Regenerated Cellulose Dialysis Membrane Diffusion Sampler for Monitoring Ground-Water Quality and Remediation Progress at DoD Sites
Imbrigiotta, T.E. and J.S. Trotsky. ESTCP Project ER-0313, 88 pp, 2010

Demonstration/Validation of the Snap Sampler Passive Ground Water Sampling Device for Sampling Inorganic Analytes at the Former Pease Air Force Base
Parker, L., N. Mulherin, G. Gooch, W. Major, R. Willey, T. Imbrigiotta, J. Gibs, and D. Gronstal. ESTCP Project ER-0630, ERDC/CRREL TR-09-12, 116 pp, 2009

Comparison of Pumped and Diffusion Sampling Methods to Monitor Concentrations of Perchlorate and Explosive Compounds in Ground Water, Camp Edwards, Cape Cod, Massachusetts, 2004-05
D.R. LeBlanc and D.A. Vroblesky. U.S. Geological Survey Scientific Investigations Report 2008-5109, 26 pp, 2008

DoD Perchlorate Handbook
U.S. Department of Defense (DoD, Environmental Data Quality Workgroup. 73 pp, 2007

Field Demonstration and Validation of a New Device for Measuring Water and Solute Fluxes at IHDIV-NSWC, Indian Head, MD: Final Report (Version 2)
K. Hatfield, M.D. Annable, and P.S.C. Rao.
Environmental Security Technology Certification Program, NTIS: ADA468561, 138 pp, 2006

Department of Army Guidance for Assessing Potential Perchlorate Contamination
DoD Office of the Under Secretary of Defense. 25 pp, 2004

Elaboration on the Prioritization Protocol for Perchlorate Impacts
DoD and CalEPA, 7 pp, Sep 2004
See the original protocol, p 22-30, in ASTSWMO's 2005 Perchlorate Issues Document.

Field Screening Method for Perchlorate in Water and Soil
Thorne, P.G. ERDC/CRREL Technical Report 04-8, 36 pp, 2004

Preliminary Analyses for Perchlorate in Selected Natural Materials and Their Derivative Products
Orris, G.J., G.J. Harvey, D.T. Tsui, and J.E. Eldrige. U.S. Geological Survey
Open-File Report 03-314, 6 pp, 2003

Helpful Definitions

A conceptual site model is a three-dimensional model of site conditions that conveys what is known or suspected about the sources, releases and release mechanisms, contaminant fate and transport, exposure pathways, potential receptors, and risks. The conceptual site model is based on the information available at any given point in time and will evolve as more information becomes available (EPA, 2012). ↩
A conceptual site model is a three-dimensional model of site conditions that conveys what is known or suspected about the sources, releases and release mechanisms, contaminant fate and transport, exposure pathways, potential receptors, and risks. The conceptual site model is based on the information available at any given point in time and will evolve as more information becomes available (EPA, 2012). ↩
A point source is any discernible, confined and discrete conveyance, such as a pipe, ditch, channel, tunnel, conduit, well, discrete fissure, container, rolling stock, concentrated animal feeding operation, or vessel or other floating craft, from which pollutants are or may discharged (EPA). ↩
A point source is any discernible, confined and discrete conveyance, such as a pipe, ditch, channel, tunnel, conduit, well, discrete fissure, container, rolling stock, concentrated animal feeding operation, or vessel or other floating craft, from which pollutants are or may discharged (EPA). ↩
A non point source typically originates from multiple sources, such as land runoff, precipitation, atmospheric deposition, drainage, seepage or hydrologic modification (EPA.) ↩
A non point source typically originates from multiple sources, such as land runoff, precipitation, atmospheric deposition, drainage, seepage or hydrologic modification (EPA.) ↩

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