U.S. EPA Contaminated Site Cleanup Information (CLU-IN)


U.S. Environmental Protection Agency
U.S. EPA Technology Innovation and Field Services Division

For more information on Perchlorate, please contact:

Linda Fiedler
Technology Assessment Branch

PH: (703) 603-7194 | Email: fiedler.linda@epa.gov



Perchlorate

Detection and Site Characterization

The purpose of this section is to identify analytical and sampling methods used for detecting, measuring, and/or monitoring perchlorate that are available on line. The intent is not to provide an exhaustive list of analytical methods, but to identify standard methods, particularly those used for environmental samples and approved by EPA. Check the National Environmental Methods Index (NEMI) to identify methods for perchlorate that may not be cited on this page. NEMI is a free, searchable clearinghouse of methods and procedures for regulatory and non-regulatory analyses.

EPA Method 314 uses ion chromatography to determine perchlorate in drinking water, and detection limits are now routinely reported at 0.2 µg/L. Several alternative detection schemes have appeared in the literature that involve capillary electrophoresis, ion selective electrode, ion-pair extraction coupled with electrospray ionization/mass spectrometry, or ion chromatography/tandem mass spectrometry. These alternative approaches are being pursued because Method 314 produces only a non-specific response (conductivity) at a retention time that is compared to a perchlorate standard, with no guarantee that an ionic interference that elutes in a peak at that given time is perchlorate.

Sources:

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


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Laboratory Analysis | Site Characterization | Literature References

Laboratory Analysis

Adobe PDF LogoAssessing Perchlorate Origins Using Stable Isotopes
T.G. Mohr.
Southwest Hydrology, Vol 6 No 4, July/Aug 2007

Describes how isotope ratio analysis of naturally occurring stable isotopes of oxygen and chlorine can be used to distinguish sources of water and probable sources of contaminants, such as perchlorate.

Adobe PDF LogoDetermination of Perchlorate at Parts-Per-Billion Levels in Plants by Ion Chromatography
Ellington, et al.
Journal of Chromatography A, 898 (2000) 193-199

Adobe PDF LogoDetermination of Perchlorate at Trace Levels in Drinking Water by Ion-Pair Extraction with Electrospray Ionization Mass Spectrometry
Magnuson, et al.
Anal. Chem. 2000, 72, 25-29

Adobe PDF LogoAn Improved Ion Chromatographic Method for Low Level Perchlorate Analysis (slide presentation)
Peter E. Jackson, Dionex Corp., Sunnyvale, CA.; 2000

The optimized Dionex perchlorate method, an interference-free method for analysis of low µg/L perchlorate in ground and tap water, is based on 1000 µL injection, AS11 column, 100 mM NaOH eluent and suppressed conductivity detection using ASRS. It has an MDL of 0.25 µg/L, MRL of ~ 1.0 µg/L, a linear calibration range of 2 to 100 µg/L, and recovery of 98-99% at 2.5 µg/L level.

Adobe PDF LogoIon Chromatographic Determination of Perchlorate Ion: Analysis of Fertilizers and Related Materials
T.W. Collette, W.P. Robarge, E.T. Urbansky.
Publication EPA/600/R-01/026, Apr 2001
Contact: Tim Collette, collette.tim@epa.gov

Laboratories Approved for UCMR Perchlorate Analysis
U.S. EPA, Office of Ground Water and Drinking Water (OGWDW).

The listed laboratories have successfully completed and passed the EPA-coordinated Perchlorate Performance Testing Study; however, inclusion on this list does not indicate EPA endorsement or recommendation.

Adobe PDF LogoMethod 314.0-Determination of Perchlorate in Drinking Water Using Ion Chromatography
Daniel P. Hautman (U.S. EPA, Office of Ground Water and Drinking Water), David J. Munch; Andrew D. Eaton (Montgomery Watson Laboratories), Ali W. Haghani.
EPA Method 314.0, Rev 1.0, 49 pp, Nov 1999
Contact: Daniel P. Hautman, hautman.dan@epa.gov

This method covers the determination of perchlorate in reagent water, surface water, ground water, and finished drinking water. It is recommended for use only by or under the supervision of analysts experienced in the use of ion chromatography and in the interpretation of the resulting ion chromatograms.

Adobe PDF LogoMethod 314.1 Determination of Perchlorate in Drinking Water Using Inline Column Concentration/Matrix Elimination Ion Chromatography With Suppressed Conductivity Detection
Herbert P. Wagner (Lakeshore Engineering Services, Inc.) Barry V. Pepich (Shaw Environmental, Inc.) Chris Pohl, Douglas Later, Robert Joyce, Kannan Srinivasan, Brian DeBorba, Dave Thomas, and Andy Woodruff (Dionex, Inc., Sunnyvale, CA) David J. Munch (U.S. EPA, Office of Ground Water and Drinking Water)
EPA Method 314.1-1, Revision 1, EPA 815-R-05-009, 38 pp, May 2005

This is a sample pre-concentration, matrix elimination ion chromatographic (IC) method using suppressed conductivity detection for the determination of perchlorate in raw and finished drinking waters. This method requires the use of a confirmation column to validate all perchlorate concentrations reported at or above the MRL on the primary column.

Adobe PDF LogoMethod 331.0 Determination of Perchlorate in Drinking Water by Liquid Chromatography Electrospray Ionization Mass Spectrometry
S.C. Wendelken and D. J. Munch (U.S. EPA, Office of Ground Water and Drinking Water), B.V. Pepich (Shaw Environmental, Inc.), D. W. Later and C. A. Pohl (Dionex, Inc. Sunnyvale, Ca)
EPA Method 331.0, Revision 1, EPA 815/R-05/007, 34 pp, January 2005

This is a liquid chromatography electrospray ionization mass spectrometry (LC/ESI/MS) method for the determination of perchlorate in raw and finished drinking waters.

Adobe PDF LogoMethod 332.0 Determination of Perchlorate in Drinking Water by Ion Chromatography with Suppressed Conductivity and Electrospray Ionization Mass Spectrometry
Elizabeth Hedrick and Thomas Behymer (U.S. EPA, Office of Research and Development), Rosanne Slingsby (Dionex Corporation), David Munch (U.S. EPA, Office of Ground Water and Drinking Water)
EPA Method 332.0-1, Revision 1, EPA 600/R-05/049, 48 pp March 2005

This method is applicable to the identification and quantitation of perchlorate (ClO4-) in raw and finished drinking waters. The approach used is ion chromatography with suppressed conductivity and electrospray ionization mass spectrometry (IC-ESI/MS).

Method Development for the Determination of Perchlorate in Drinking Water Using Ion Chromatography With Mass Spectrometric Detection
U.S. EPA, National Exposure Research Laboratory: FY04 Research Abstract.
Contact: Elizabeth Hedrick, Hedrick.elizabeth@epa.gov

Adobe PDF LogoMicroscale Extraction of Perchlorate in Drinking Water with Low Level Detection by Electrospray-Mass Spectrometry
Magnuson, et al.
Talanta 52 (2000) 285-291

Navy Environmental Sampling & Testing Programs: Perchlorate

This page offers slide presentations on perchlorate sampling and analysis from several intergovernmental meetings.

Perchlorate Analytical Detection Methods
D. Munch
Office of Ground Water and Drinking Water, Technical Support Center
U. S. Environmental Protection Agency
Contact: David Munch, munch.dave@epa.gov

Adobe PDF LogoPerchlorate 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 & U.S. EPA Region 9. 172 pp, 2001.

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

Adobe PDF LogoQuantitation of Perchlorate Ion by Electrospray Ionization Mass Spectrometry (ESI-MS) Using Stable Association Complexes with Organic Cations and Bases to Enhance Selectivity
E. Urbansky, et al.
J. Anal. At. Spectrom., 1999, 14, 1861-1866

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.
Contact: Alexander J. Krynitsky, Alex.Krynitsky@fda.hhs.gov

Adobe PDF LogoStability and Concentration Verification of Ammonium Perchlorate Dosing Solutions
David T. Tsui, D.R. Mattie, L. Narayanan, ManTech/Geo-Centers Joint Venture, Dayton, OH.
DTIC Publication No: ADA367416, 38 pp, 1998
Contact: David R. Mattie, mattied@falcon.al.wpafb.af.mil

A sensitive and selective ion chromatography (IC) method for the analysis of perchlorate and nitrate, a possible interference anion, was developed to support a series of 90-Day Oral Toxicity Studies. The method development and validation data demonstrated the IC method to be capable of detecting both perchlorate and nitrate at 0.003 µg/mL (5 ppb) in reagent water with excellent accuracy and precision. Ion chromatographic analysis of the stability solutions showed that under controlled room temperature, relative humidity, and light intensity, ammonium perchlorate was stable in reagent water for at least 109 days. The concentrations of the ammonium perchlorate dosing solutions (0.05 to 200 µg/mL) were verified by IC analysis to be within an acceptable range of +/- 10%.

Test Methods for Evaluating Solid Wastes: Physical/Chemical Methods, 3rd Edition
U.S. Environmental Protection Agency, SW-846.

Adobe PDF LogoMethod 6850: Perchlorate in Water, Soils and Solid Wastes Using High Performance Liquid Chromatography/Electrospray Ionization /Mass Spectrometry (HPLC/ESI/MS or HPLC/ESI/MS/MS)
Method 6860: Perchlorate in Water, Soils and Solid Wastes Using Ion Chromatography/Electrospray Ionization/Mass Spectrometry (IC/ESI/MS or IC/ESI/MS/MS)

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

An enzymatic bioassay for determining the amount of perchlorate in an aqueous sample initially was developed under SERDP Project ER-1530. Under ESTCP Project ER-201030, the method was examined further to (1) compare benchtop bioassay results from testing in the primary investigator's lab to results from a reference analytical method performed by a commercial lab; and (2) compare results with a benchtop bioassay kit format tested by site field personnel to the site's routine perchlorate detection method (results varied). Because performance of the bioassay was insufficient to warrant proceeding with its field testing in a kit format, the focus of activities shifted to attempting to identify factors that interfere with the benchtop bioassay in order to determine whether operations and performance could be improved.

Adobe PDF LogoValidation 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

The main approach described in this document, chlorine and oxygen isotopic analysis of perchlorate, yields accurate and precise measurements of the relative abundances of the stable isotopes of chlorine and oxygen in perchlorate using isotope-ratio mass spectrometry (IRMS). These measurements provide four independent quantities (isotope abundance ratios) for distinguishing perchlorate sources and potential transformations in the environment. A case study illustrates the application of IRMS of Cl and O stable isotopes to distinguish sources of perchlorate on Long Island, New York. Additional information: 2013 Final ReportAdobe PDF Logo

Adobe PDF LogoViability of Applying Curie Point Pyrolysis/Gas Chromatography Techniques for Characterization of Ammonium Perchlorate Based Propellants
J.L. Barnett; B.M. Montoya, Sandia National Labs., Albuquerque, NM.
SAND2002-1922, 32 pp, 2002
Contact: James L. Barnett, JLBARNE@sandia.gov

Site Characterization

(see Policy and Guidance section for material on field sampling)

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

Comparison of the concentrations of perchlorate, RDX, and HMX in diffusion samplers placed in wells against concentrations in samples collected by low-flow pumped sampling indicates generally good agreement between the pumped and diffusion samples for concentrations of the subject contaminants. The concentration differences indicate no systematic bias related to contaminant type or concentration level.

Adobe PDF LogoDemonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO4-)
Gu, B., A. Jubb, G. Eres, and P.B. Hatzinger.
ESTCP Project ER-201327, 107 pp, 2017

A portable Raman sensor based on surface-enhanced Raman scattering (SERS) technology and elevated gold nano-ellipse dimer architectures was designed and developed for perchlorate with a detection limit of ~100 µg/L in contaminated water. Large-scale commercial production of SERS substrate sensors via nanoimprinting was successfully demonstrated, a major step toward commercialization of the SERS sensors. Commercially produced SERS sensors were able to detect perchlorate at levels >100 µg/L using a portable Raman analyzer. Tests of the performance of the commercial SERS sensors for perchlorate detection in the presence and absence of interferents showed that sulfate exhibited the greatest interference among the anions tested. In the field tests, results generally were comparable with those from a standard ion chromatography approach, but significant variations were observed due to the presence of interference ions and co-contaminants in the groundwater in some samples.

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

The use of regenerated cellulose dialysis membrane (RCDM) diffusion samplers was validated for collection of groundwater samples for perchlorate and a suite of explosives compounds. Field comparisons were conducted at Aberdeen Proving Ground, MD, and Picatinny Arsenal, NJ. Samples collected with RCDM and low-flow purging sampling techniques were compared graphically and statistically to determine the significance of any differences found. Samples from the RCDM samplers were found to cost significantly less than samples collected with low-flow purging equipment; total costs per sample were calculated to be 71% less with an RCDM sampler, compared to low-flow purging. Additionally, sampling time was reduced by 84%, compared to low-flow purging. Additional information is available, including basic research and cost and performance data.

Adobe PDF LogoDemonstration/Validation of the Snap Sampler Passive Ground Water Sampling Device for Sampling Inorganic Analytes at the Former Pease Air Force Base
L. Parker, 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

Lab studies and a field demonstration were conducted to determine the ability of the Snap Sampler to recover representative concentrations of several types of inorganic analytes (including perchlorate, arsenic, and chromium) from groundwater. Samples taken using a Snap Sampler were compared with samples collected using conventional low-flow purging and sampling and a regenerated cellulose passive diffusion sampler, and analyte concentrations were found to be equivalent to those in the low-flow samples with the exception of unfiltered iron, where concentrations were significantly higher in the Snap Sampler samples.

Environmental Forensics: Contaminant-Specific Guide
Robert D. Morrison and Brian Murphy.
Elsevier Academic Press, Boston. ISBN: 0125077513, 576 pp, 2006

Environmental forensics is the application of scientific techniques for the purpose of identifying the source and age of a contaminant. This book discusses the following contaminants and contaminant groups: mercury, asbestos, lead, chromium, methane, radioactive compounds, pesticides, perchlorate, polychlorinated biphenyls, arsenic, chlorinated solvents, polyaromatic hydrocarbons, crude oil, gasoline, microbes, and compounds found in sewage.

Adobe PDF LogoAn Enzymatic Bioassay for Perchlorate
Coates, J.D. and M. Heinnickel (Univ. of California Berkeley); L.A. Achenbach (Southern Illinois Univ.).
SERDP Project ER-1530, 81 pp, July 2010

This technology offers a rapid, sensitive, specific, and cost-effective solution that can be performed on site with minimal training using ubiquitous laboratory equipment. The developed bioassay uses the partially purified perchlorate reductase enzyme from Dechloromonas agitata to detect perchlorate with the redox-active dye phenazine methosulfate and nicotine adenine dinucleotide. By using a specific addition scheme and covering all reactions with mineral oil, the reaction can be performed on the benchtop with a lower detection limit of 2 ppb when combined with perchlorate purification and concentration by solid phase extraction. The authors have accurately analyzed perchlorate concentrations up to 17,000 ppb using the bioassay in the presence of a range of ions (nitrate, phosphate, sulfate, iron, chloride) at a concentration of 100 ppm. The outlined technology is based on a hand-held spectrophotometer (~$300, reusable SPE columns $250) with consumables of ~$0.13 per sample. The bioassay allows for multiple samples to be assayed simultaneously while achieving a minimum detection limit of 2 ppb.

Adobe PDF LogoEvaluation 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

Researchers evaluated the use of isotopic data to distinguish sources of perchlorate in groundwater in a specific region of the Rialto-Colton and Chino, CA, groundwater subbasins. The region has two groundwater perchlorate plumes emanating from known military/industrial source areas, plus a larger area of measurable perchlorate outside the plumes. Isotope data indicate the presence of synthetic, Atacama (presumably from historical application of nitrate fertilizer in the region), and indigenous natural perchlorate in the study area.

Adobe PDF LogoField 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

The demonstration at IHDIV-NSWC applied passive flux meters (PFMs) to the measurement of water and perchlorate contaminant fluxes. Studies also were conducted to demonstrate the applicability of a new PFM sorbent, SMSI-GAC, for field-scale measurement of ground-water and perchlorate fluxes.

Adobe PDF LogoField Demonstration and Validation of a New Device for Measuring Water and Solute Fluxes, NASA LC-34 Site
Environmental Security Technology Certification Program (ESTCP), 172 pp, 2006

ESTCP passive flux meter (PFM) demonstration and validation projects include MTBE flux measurement at Port Hueneme, perchlorate flux at the Naval Surface Warfare Center at Indianhead, and TCE flux at NASA Launch Complex 34 at Cape Canaveral.

Adobe PDF LogoField Screening Method for Perchlorate in Water and Soil
Philip G. Thorne.
ERDC/CRREL Technical Report 04-8, 36 pp, Apr 2004.

Adobe PDF LogoLab-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

This report describes a fieldable microchip capillary electrophoresis device that is selective for perchlorate at reduced analysis times and reagent consumption. The device employs contact conductivity detection and zwitterionic surfactant chemistry to resolve perchlorate selectively from abundant environmental species such as chloride, nitrate, and sulfate. The prototype system is capable of detection limits of 3.4 +/- 1.8 ppb in standards and 5.6 +/- 1.7 ppb in drinking water.

Mass Flux Toolkit to Evaluate Groundwater Impacts, Attenuation, and Remediation Alternatives
Environmental Security Technology Certification Program (ESTCP), 2006

To help site managers and site consultants estimate mass flux and understand the uncertainty in those estimates, ESTCP has funded the development of a computerized Mass Flux Toolkit, free software that gives site personnel the capability to compare different mass flux approaches, calculate mass flux from transect data, and apply mass flux to manage ground-water plumes. The toolkit spreadsheet and associated documentation are available on the ESTCP contractor's website in a zipped file.

Santa Susana Field Laboratory (aka The Boeing Company), Simi Valley, Ventura County
California Department of Toxic Substances Control.

This website documents extensively the characterization activities undertaken in a RCRA facility investigation of a perchlorate-contaminated facility in California, including an evaluation of the potential for perchlorate migration off site.

Literature References

Measurement and Monitoring Technologies for the 21st Century Initiative (21M2) Literature Search
Literature search conducted under EPA's Office of Solid Waste and Emergency Response Measurement and Monitoring Technologies for the 21st Century Initiative (21M2) for perchlorate analysis to meet rising interest in the low level analysis of perchlorates in ground and drinking water.