Perchlorates are the salts derived from perchloric acid—in particular when referencing the polyatomic anions found in solution, perchlorate is often written with the formula ClO4−. Perchlorates are often produced by natural processes but can also be produced artificially. They have been used for more than fifty years to treat thyroid disorders. They are used extensively within the pyrotechnics industry, and ammonium perchlorate is also a component of solid rocket fuel. Lithium perchlorate, which decomposes exothermically to produce oxygen, is used in oxygen “candles” on spacecraft, submarines, and in other situations where a reliable backup oxygen supply is needed. Most perchlorates are soluble in water, except for potassium perchlorate which has the lowest solubility of any alkali metal perchlorate (1.5 g in 100 mL of water at 25 °C).
Production and use
Perchlorate salts are produced industrially by the oxidation of solutions of sodium chlorate by electrolysis. This method is used to prepare sodium perchlorate. Four perchlorates are of primary commercial interest: ammonium perchlorate (NH4ClO4), perchloric acid (HClO4), potassium perchlorate (KClO4), and sodium perchlorate (NaClO4). The main application is for rocket fuel.
Low levels of perchlorate have been detected in both drinking water and groundwater in 26 states in the U.S., according to the Environmental Protection Agency. In 2004, the chemical was also found in cow’s milk in California with an average level of 1.3 parts per billion (“ppb” or µg/L), which may have entered the cows through feeding on crops that had exposure to water containing perchlorates. According to the Impact Area Groundwater Study Program, the chemical has been detected as high as 5 µg/L in Massachusetts, well over the state regulation of 2 µg/L. Fireworks are also a source of perchlorate in lakes.
Natural perchlorate on Earth
In some places, perchlorate is detected because of contamination from industrial sites that use or manufacture it. In other places, there is no clear source of perchlorate. In those areas it may be naturally occurring. Natural perchlorate on Earth was first identified in terrestrial nitrate deposits of the Atacama Desert in Chile as early as in the 1880s and for a long time considered a unique perchlorate source. Interestingly, the perchlorate released from the historic use of Chilean nitrate based fertilizer which were imported to the U.S. by the hundreds of tons in the early 19th century can still be found in some groundwater sources of the United States. Recent improvements in analytical sensitivity using ion chromatography based techniques have revealed a more widespread presence of natural perchlorate, particularly in subsoils of Southwest USA, salt evaporites in California and Nevada, Pleistocene groundwater in New Mexico, and even present in extremely remote places such as Antarctica. The data from these studies and others indicate that natural perchlorate is globally deposited on Earth with the subsequent accumulation and transport governed by the local hydrologic conditions.
Despite its importance to environmental contamination, the specific source and processes involved in natural perchlorate production still remain poorly understood. Recent laboratory experiments in conjunction with isotopic studies have implied that perchlorate may be produced on Earth by the oxidation of chlorine species through pathways involving ozone or its photochemical products. Other studies have suggested that perchlorate can also be created by lightnining activated oxidation of chloride aerosols (e.g., chloride in sea salt sprays), and ultraviolet or thermal oxidation of chlorine (e.g., bleach solutions used in swimming pools) in water.
Regulatory issues in the U.S.
On February 11, 2011, the U.S. Environmental Protection Agency (EPA) issued a “regulatory determination” that perchlorate meets the Safe Drinking Water Act criteria for regulation as a contaminant. The agency found that perchlorate may have an adverse effect on the health of persons and is known to occur in public water systems with a frequency and at levels that it presents a public health concern. As a result of EPA’s regulatory determination, it begins a process to determine what level of contamination is the appropriate level for regulation. The EPA prepared, as part of its regulatory determination, extensive responses to submitted public comments. The “docket ID” for EPA’s regulatory action is EPA-HQ-OW-2009-0297 and can be found on regulations.gov.
Prior to issuance of its regulatory determination, the U.S. EPA issued a recommended Drinking Water Equivalent Level (DWEL) for perchlorate of 24.5 µg/L. In early 2006, EPA issued a “Cleanup Guidance” for this same amount. Both the DWEL and the Cleanup Guidance were based on a thorough review of the existing research by the National Academy of Science (NAS). This followed numerous other studies, including one that suggested human breast milk had an average of 10.5 µg/L of perchlorate. Both the Pentagon and some environmental groups have voiced questions about the NAS report, but no credible science has emerged to challenge the NAS findings. In February 2008, U.S. Food and Drug Administration said that U.S. toddlers on average are being exposed to more than half of the U.S. EPA’s safe dose from food alone. In March 2009, a Centers for Disease Control study found 15 brands of infant formula contaminated with perchlorate. Combined with existing perchlorate drinking water contamination, infants could be at risk for exposure to perchlorate above the levels considered safe by E.P.A.
The US Environmental Protection Agency has issued substantial guidance and analysis concerning the impacts of perchlorate on the environment as well as drinking water. California has also issued guidance regarding perchlorate use.
Several states in the U.S. have enacted drinking water standard for perchlorate including Massachusetts in 2006. California’s legislature enacted AB 826, the Perchlorate Contamination Prevention Act of 2003, requiring California’s Department of Toxic Substance Control (DTSC) to adopt regulations specifying best management practices for perchlorate and perchlorate-containing substances. The Perchlorate Best Management Practices were adopted on December 31, 2005, and became operative on July 1, 2006.  California issued drinking water standards in 2007. Several other states, including Arizona, Maryland, Nevada, New Mexico, New York, and Texas have established non-enforceable, advisory levels for perchlorate.
In 2003, a federal district court in California found that the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) applied because perchlorate is ignitable and therefore a “characteristic” hazardous waste. (see Castaic Lake Water Agency v. Whittaker, 272 F. Supp. 2d 1053, 1059–61 (C.D. Cal. 2003)).
One example of perchlorate related problems was found at the Olin Flare Facility, Morgan Hill, California—Perchlorate contamination beneath a former flare manufacturing plant in California was first discovered in 2000, several years after the plant had closed. The plant had used potassium perchlorate as one of the ingredients during its 40 years of operation. By late 2003, the state of California and the Santa Clara Valley Water District had confirmed a groundwater plume currently extending over nine miles through residential and agricultural communities.
The Regional Water Quality Control Board and the Santa Clara Valley Water District have engaged in a major outreach effort that has received extensive press and community response. A well testing program is underway for approximately 1,200 residential, municipal, and agricultural wells in the area. Large ion exchange treatment units are operating in three public water supply systems that include seven municipal wells where perchlorate has been detected. The potentially responsible parties, Olin Corporation and Standard Fuse Incorporated, are supplying bottled water to nearly 800 households with private wells. The Regional Water Quality Control Board is overseeing potentially responsible party (PRP) cleanup efforts.