Emerging Contaminant - Perchlorate April 2008 FACT SHEET At a Glance Introduction White crystalline solid or colorless liquid. Explosive at high temperatures. Short-term exposure to high doses may cause eye and skin irritation, coughing, nausea, vomiting, and diarrhea. Highly soluble in water; migrates quickly from soil to ground water. Primary pathways for human exposure to perchlorate are ingestion of food and contaminated drinking water. Sampling at current federal sites as well as Formerly Used Defense Sites has detected perchlorate primarily in association with sites historically involved in the manufacture, maintenance, use, and disposal of ammunition and rocket fuel. Perchlorate is both naturally occurring and man-made. Health-based goals or drinking water standards have been developed by various states. The presence of high amounts of other anions, such as chloride, sulfate, or carbonate, may interfere with the analysis of perchlorate. Common treatment technologies include ion exchange, bioreactors, and in situ bioremediation. An "emerging contaminant" is a chemical or material that is characterized by a perceived, potential or real threat to human health or the environment or lack of published health standards. A contaminant may also be "emerging" because a new source or a new pathway to humans has been discovered or a new detection method or treatment technology has been developed. This fact sheet, developed by the U.S. Environmental Protection Agency (EPA) Federal Facilities Restoration and Reuse Office (FFRRO), provides a brief summary for perchlorate, including physical and chemical properties; environmental and health impacts; existing federal and state guidelines; detection and treatment methods; and additional sources of information. Perchlorate is a persistent contaminant of concern that has presented a number of issues to the government, the private sector, and other organizations and interested parties. These issues include health effects and risk, regulatory standards and cleanup levels, degradation processes, and treatment technologies (EPA FFRRO 2005). This fact sheet provides basic information on perchlorate to site managers and other field personnel who are addressing perchlorate contamination at a cleanup site or in a drinking water supply. What is perchlorate? *> Perchlorate is a naturally occurring and man-made anion (C1O4~) that consists of one chlorine atom bonded to four oxygen atoms (EPA FFRRO 2005; ITRC 2005). *> Perchlorate is commonly used as an oxidizer in solid propellants, munitions, fireworks, airbag initiators for vehicles, matches, and signal flares (ITRC 2005; EPA FFRRO 2005). It is also found in some disinfectants and some herbicides (ITRC 2005). *> Perchlorate is found as a natural impurity in nitrate salts from Chile, which are imported used to produce nitrate fertilizers and a number of other products (ITRC 2005; EPA FFRRO 2005). *> Perchlorate may occur naturally, particularly in arid regions such as the southwestern United States. (Rao 2007). *> Manufactured forms of perchlorate include perchloric acid and salts such as ammonium perchlorate, sodium perchlorate, and potassium perchlorate (EPA FFRRO 2005; ITRC 2005). *> Of the domestically produced (high grade) perchlorate, 90 percent of perchlorate is estimated to be used in the defense and aerospace industries in the form of ammonium perchlorate (ITRC 2005; GAO 2005). *> Perchlorate has been used by the U. S. Department of Defense (DoD) as an oxidizer in munitions and missiles since the 1940s (Mendiratta, et al 1996). United States Environmental Protection Agency Solid Waste and Emergency Response (5106P) EPA 505-F-07-003 April 2008 1 ------- What are the environmental impacts of perchlorate? Recent surveys have detected perchlorate in food crops and milk (FDA, 2008). Perchlorate is highly soluble, relatively stable and mobile in water. As a result, perchlorate plumes in ground water can be extensive. For example, the perchlorate plume at a former safety flare site (the Olin Flare Facility) in Morgan Hill, California, extends more than 9 miles (EPA FFRRO 2007). Perchlorate compounds and the perchlorate anion do not volatilize from water to air (ITRC 2005, EPA IRIS 2005). Sampling at current and Formerly Used Defense Sites has detected perchlorate primarily in association with sites historically involved in the manufacture, maintenance, use, and disposal of ammunition and rocket fuel (EPA FFRRO 2007). Perchlorate has been detected at nearly 270 sites; more than 45 of these sites are on the National Priorities List (EPA FFRRO 2007). Exhibit 1: Physical and Chemical Properties of Perchlorate Compounds (EPA FFRRO 2005; NIOSH 2007; ITRC 2005) Pert CAS Numbers Physical Description (Physical state at room temperature) Molecular weight (g/mol) Water solubility (g/L at 25°C) Melting / Boiling point (°C) Vapor pressure at 25°C(mmHg) Specific gravity Octanol-water partition coefficient (log Kow) Ammonium Potassium Perchlorate Sodium Perchlorate Perchlorate Perchloric Acid 7790-98-9 White orthorhombic crystal 117.49 200 Melting Point: 65.6 to 439 Not available 1.95 -5.84 7601-89-0 White orthorhombic deliquescent crystal 122.44 2,096 Melting Point: 482 Not available 2.52 -7.18 7778-74-7 Colorless orthorhombic crystal or white crystalline powder 138.55 15 Melting Point: 400 Not available 2.53 -7.18 7601-90-3 Colorless liquid 100.47 Miscible in cold water Melting Point: -112 Boiling Point: 19 6.8 1.664 -4.63 Notes: g/mol - gram per mole; g/L - grams per liter; mg/L - milligrams per liter; °C - degrees Celsius; mm Hg - millimeters of mercury. ------- What are the health effects of perchlorate? The chronic oral reference dose (RfD) is 0.0007 milligrams per kilogram body weight per day (Note: A reference dose is an estimate (with uncertainty spanning perhaps an order of magnitude) of a daily oral exposure to the human population (including sensitive subgroups) that is likely to be without appreciable risk of deleterious effects over a lifetime.) (EPA IRIS 2005). Short-term exposure to high doses may cause eye and skin irritation, cough, nausea, vomiting, and diarrhea (NIOSH 2007). Primary pathways for human exposure to perchlorate are ingestion of food and contaminated drinking water (EPA FFRRO, 2007). At high enough exposures, perchlorate can interfere with iodide uptake into the thyroid gland, disrupting the functions of the thyroid and potentially leading to a reduction in the production of thyroid hormones. Thyroid hormones play an important role in regulating metabolism. In fetuses, infants, and young children, thyroid hormones are critical for normal growth and development (NAS 2005). Because of its ability to inhibit thyroid iodide uptake, potassium perchlorate was historically used to treat hyperthyroidism and Grave's Disease (NAS 2005) Based on studies conducted on rodents, it was found that perchlorate at levels below those required to alter thyroid hormone equilibrium is unlikely to cause thyroid cancer in human beings (EPA IRIS 2005). Are there any existing federal and state guidelines and health standards for perchlorate? The RfD established by EPA equates to a Drinking Water Equivalent Level (DWEL) of 24.5 micrograms per liter (ug/L), or parts per billion (ppb) (EPA FFRRO 2005). A DWEL is a lifetime exposure concentration protective of adverse, non-cancer health effects that assumes all of the exposure to a contaminant is from drinking water. (Note: The DWEL is calculated based on a 70 kg body weight and a drinking water consumption of 2 liters/day.) Massachusetts (2 ug/L) and California (6 ug/L) have established enforceable standards for perchlorate in drinking water (Massachusetts DEP 2006, California DHS 2007). The Office of Solid Waste and Emergency Response (OSWER) has established a preliminary remediation goal (PRO) at NPL sites of 24.5 ug/L. PRGs are developed based on readily available information and are modified, as necessary, before final cleanup goals are established, based on information that becomes available during the remedial investigation/feasibility study. (EPA FFRRO 2007) Certain states have developed advisory levels or health-based goals ranging from 4 to 51 ug/L (ITRC 2005). What detection and site characterization methods are available for perchlorate? • EPA Method 3 31.0—Liquid Chromatography/Electrospray lonization/ Mass Spectrometry (EPA OGWDW 2007). • EPA Method 6850—High Performance Liquid Chromatography/Electrospray lonization/Mass Spectrometry (EPA 2007). • EPA Method 6860—Ion Chromatography/ Electrospray lonization/Mass Spectrometry (EPA 2007). The following methods can be used to analyze for perchlorate in drinking water, in addition to ground water, surface water, and irrigation water: • EPA Method 314.0—Ion Chromatography (EPA OGWDW 2007). • EPA Method 314.1—Inline Column Concentration/Matrix Elimination Ion Chromatography with Suppressed Conductivity Detection (EPA OGWDW 2007). • EPA Method 332.0—Ion Chromatography with Suppressed Conductivity and Electrospray lonization Mass Spectrometry (EPA FFRRO 2005). The presence of high amounts of other anions, such as chloride, sulfate, or carbonate may interfere with the analysis of perchlorate (EPA 1999). Researchers have demonstrated the ability to distinguish man-made and natural sources of perchlorate using chlorine and oxygen stable isotope analysis (Bohlke, et al. 2005). ------- What technologies are being used to treat perchlorate? Ex Situ Treatment: • Ion exchange using perchlorate-selective or nitrite-specific resins (EPA FFRRO 2005; GWRTAC 2001; Boodoo 2003). • Bioremediation using packed-bed or fluidized- bed bioreactors (EPA FFRRO 2005; GWRTAC 200 l;Hatzinger 2005). • Liquid phase carbon adsorption using granular activated carbon (GAC) to remove low levels of perchlorate; pretreatment may be necessary to make it suitable for perchlorate removal (EPA FFRRO 2005; ITRC 2005; GWRTAC 2001). • Membrane technologies (electrodialysis and reverse osmosis) (EPA FFRRO 2005; ITRC 2005; GWRTAC 2001). In Situ Treatment: • Bioremediation using perchlorate-selective microbes (EPA FFRRO 2005; ITRC 2005; GWRTAC 2001). • Permeable reactive barrier (EPA FFRRO 2005; ITRC 2005; GWRTAC 2001). • Phytoremediation may also be used, although the mechanism of phytoremediation of perchlorate is yet to be established (EPA FFRRO 2005; GWRTAC 2001). Where can I find more information about perchlorate? Boodoo, F. 2003. POU/POE Removal of Perchlorate. Water Conditioning & Purification. Pages 1-4. Bohlke, J. K., N.C. Sturchio, B. Gu, J. Horita, G.M. Brown, W.A. Jackson, J. Batista, and P.B. Hatzinger. 2005. Perchlorate isotope forensics. Anal. Chem., 77, 7838-7842. California DHS (Department of Health Services) 2006 Press Release. http://www.applications.dhs.ca.gov/pressreleases/stor e/pressreleases/06-62.html EPA (Environmental Protection Agency). 1999. Method 314.0 Determination of Perchlorate in Drinking Water Using Ion Chromatography. Revision. EPA. 2007. New Test Methods On-line. www.epa.gov/epaoswer/hazwaste/test/new-meth.htm EPA FFRRO (EPA Federal Facilities Restoration and Reuse Office). 2005. Perchlorate Treatment Technology Update - Federal Facilities Forum Issue Paper. EPA 542-R-05-015. EPA FFRRO. 2007. www.epa.gov/fedfac/documents/perchlorate.htm. EPA IRIS (Integrated Risk Information System). 2005. www.epa.gov/iris/subst/1007.htm. EPA OGWDW (Office of Groundwater and Drinking Water). 2007. www.epa.gov/safewater/ FDA (Food and Drug Administration) 2008. U.S. Food and Drug Administration's Total Diet Study: Dietary intake of Perchlorate and Iodine. http://www.cfsan.fda.gov/~dms/clo4dat2.html. GAO (U.S. Government Accountability Office). 2005. Perchlorate: A System to Track Sampling and Cleanup Results is Needed. GAO-05-462. GWRTAC (Ground Water Remediation Technologies Analysis Center). 2001. Technology Status Report: Perchlorate Treatment Technologies. 1st edition. Hatzinger, P.B. 2005. Perchlorate Biodegradation for Water Treatment. Environmental Science & Technology. Vol. A. Pages 239-247. ITRC (Interstate Technology Regulatory Council). 2005. Perchlorate: Overview of Issues, Status, and Remedial Options. http://www.itrcweb.org/Documents/PERC-l.pdf. Massachusetts DEP (Department of Environmental Protection). 2006. Press Release. http://mass.gov/dep/public/press/pchl0706.htm Mendiratta, S.K., R.L. Dotson, and R.T. Brooker. 1996. Kirk-Othmer Encyclopedia of Chemical Technology. Vol. 18. Pages 157-170. NAS (National Research Council of the National Academies). 2005. "Health Implications of Perchlorate Ingestion." http://www.nap.edu/catalog.php7record id=l 1202 NIOSH (National Institute for Occupational Safety and Health). 2007. http://www.cdc.gov/niosh/ipcs/nicstart.html Rao, B., Anderson, T. A., Orris, et al. 2007. Widespread natural perchlorate in unsaturated zones of the Southwest United States. Environmental Science Technology41 (13), 4522 -4528, 2007. Additional information on perchlorate can be found at EPA's www.cluin.org/perchlorate. Contact Information If you have any questions or comments on this fact sheet, please contact: Mary Cooke, FFRRO, by phone at (703) 603-8712 or by e-mail at cooke.maryt(@,epa.gov. ------- |