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|Molar mass||99.451 g mol-1|
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Perchlorates are the salts derived from perchloric acid (HClO4). 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).
The chemical notation for the perchlorate ion is ClO−
4. The ion has a molecular mass of 99.45 amu.
A perchlorate (compound) is a compound containing this group, with chlorine in oxidation state +7.
- Ammonium perchlorate, NH4ClO4
- Barium perchlorate, Ba(ClO4)2
- Caesium perchlorate, CsClO4
- Fluorine perchlorate, FClO4
- Lithium perchlorate, LiClO4
- Magnesium perchlorate, Mg(ClO4)2
- Perchloric acid, HClO4
- Potassium perchlorate, KClO4
- Rubidium perchlorate, RbClO4
- Silver perchlorate, AgClO4
- Sodium perchlorate, NaClO4
Reactivity as an oxidant
The perchlorate ion is the least reactive oxidizer of the generalized chlorates. This appears to be a paradox, since higher oxidation numbers are expected to be progressively stronger oxidizers, and less stable. A table of reduction potentials of the four chlorates shows that, contrary to expectation, perchlorate is the weakest oxidant among the four in water.
H+ + HOCl + e– → ½Cl2(g) + H2O
3H+ + HOClO + 3e– → ½Cl2(g) + 2H2O
6H+ + ClO3– + 5e– → ½Cl2(g) + 3H2O
8H+ + ClO4– + 7e– → ½Cl2(g) + 4H2O
½Cl2(g) + e– → Cl–
ClO– + H2O + 2e– → Cl– + 2OH–
ClO2– + 2H2O + 4e– → Cl– + 4OH–
ClO3– + 3H2O + 6e– → Cl– + 6OH–
ClO4– + 4H2O + 8e– → Cl– + 8OH–
This shows that the chlorates are stronger oxidizers in acidic conditions than basic conditions, while chlorine is unchanged.
Gas phase measurements of heats of reaction (which allow computation of ΔHf°) of various chlorine oxides do follow the expected trend wherein Cl2O7 exhibits the largest endothermic value of ΔHf° (238.1 kJ/mol) while Cl2O exhibits the lowest endothermic value of ΔHf° (80.3 kJ/mol).
The central chlorine in the perchlorate anion is a closed shell atom and is well protected by the four oxygens. Hence, perchlorate reacts sluggishly. Most perchlorate compounds, especially salts of electropositive metals such as sodium perchlorate or potassium perchlorate, are slow to react unless heated. This property is useful in many applications, such as flares, where the device should not explode, or even catch fire spontaneously.
Mixtures of perchlorates with organic compounds are more reactive. Although they do not usually catch fire or explode unless heated, there are a number of exceptions. Large amounts of improperly stored ammonium perchlorate led to the PEPCON disaster, in which an explosion destroyed one of the two large-scale production plants for ammonium perchlorate in the US.
Using Stock nomenclature, if a Roman numeral in brackets follows the word "chlorate", this indicates the oxyanion contains chlorine in the indicated oxidation state, namely
|Common name||Stock name||Oxidation state||Formula|
Using this convention, "chlorate" means any chlorine oxyanion. Commonly, "chlorate" refers only to the oxyanion where chlorine is in the +5 oxidation state.
Perchlorate is a potent competitive inhibitor of the thyroid sodium-iodide symporter. Thus, it has been used to treat hyperthyroidism since the 1950s. At very high doses (70,000–300,000 ppb) the administration of potassium perchlorate was considered the standard of care in the United States, and remains the approved pharmacologic intervention for many countries.
In the early 1960s, potassium perchlorate was implicated in the development of aplastic anemia—a condition where the bone marrow fails to produce new blood cells in sufficient quantity—in thirteen patients, seven of whom died. Subsequent investigations have indicated the connection between administration of potassium perchlorate and development of aplastic anemia to be "equivocable at best," which means that the benefit of treatment, if it is the only known treatment, outweighs the risk, and it appeared a contaminant poisoned the 13.
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.
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, or could be present because of the use of Chilean fertilizers, which were imported to the U.S. by the hundreds of tons in the early 19th century. One recent area of research has even suggested that perchlorate can be created when lightning strikes a body of water, and perchlorates are created as a byproduct of chlorine generators used in swimming pool chlorination systems. In 2010, perchlorate was found at the 1000ppb levels in a vast section of Antarctica, with implications that it is formed naturally and globally on Earth and, it is presumed, on Mars most likely by photochemical reactions in the atmosphere.
Fireworks are also a source of perchlorate in lakes.
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, 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 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.
Over 40 phylogenetically and metabolically diverse microorganisms capable of perchlorate reduction have been isolated since 1996, including members of the Proteobacteria as well as two recently identified Firmicutes, Moorella perchloratireducens and Sporomusa sp.
Perchlorate, in large amounts, interferes with iodine uptake into the thyroid gland. In adults, the thyroid gland helps regulate the metabolism by releasing hormones, while in children, the thyroid helps in proper development. The NAS, in its 2005 report, Health Implications of Perchlorate Ingestion, emphasized that this effect, also known as IUI is not an adverse health effect. In January 2008, California’s Department of Toxic Substances Control stated that perchlorate is becoming a serious threat to human health and water resources. However, in 2010, the Environmental Protectional Agency's (EPA) Office of the Inspector General determined that the EPA's own perchlorate reference dose of 24.5 parts per billion protects against all human biological effects from exposure. This finding was due to a significant shift in policy at the EPA in basing its risk assessment on non-adverse effects such as IUI instead of adverse effects. The Office of the Inspector General also found that because the EPA’s perchlorate reference dose is conservative and protective of human health further reducing perchlorate exposure below the reference dose does not effectively lower risk.
The NAS found that perchlorate affects only the thyroid gland. It is not stored in the body, it is not metabolized, and any effects of perchlorate on the thyroid gland are fully reversible once exposure stops. There has been some concern on perchlorate's effects on fetuses, newborns and children, but several peer-reviewed studies on children and newborns also provide reason to believe that low levels of perchlorate do not pose a threat to these populations. On October 1, 2004, the American Thyroid Association (ATA) reported that perchlorate may not be as harmful to newborns, pregnant women and other adults as previously thought. This finding was later supported in 2010 and 2011 by research on thousands of pregnant women in Italy, Wales, Argentina, and the United States.
A study involving healthy adult volunteers determined that at levels above 0.007 milligrams per kilogram per day (mg/(kg·d)), perchlorate can temporarily inhibit the thyroid gland’s ability to absorb iodine from the bloodstream ("iodide uptake inhibition," thus perchlorate is a known goitrogen). The EPA converted this dose into a reference dose of 0.0007 mg/(kg·d) by dividing this level by the standard intraspecies uncertainty factor of 10. The agency then calculated a "drinking water equivalent level" of 24.5 ppb by assuming a person weighs 70 kilograms (154 pounds) and consumes 2 liters (68 ounces) of drinking water per day over a lifetime.
In 2006, a study by Blount, et al. reported a statistical association between environmental levels of perchlorate and changes in thyroid hormones of women with low iodine. The study authors were careful to point out that hormone levels in all the study subjects remained within normal ranges. Importantly, the authors also indicated that they did not normalize their findings for creatinine, which essentially accounts for fluctuations in the concentrations of one-time urine samples like those used in this study. When the Blount research was re-analyzed with the creatinine adjustment made, the study population limited to women of reproductive age, and results not shown in the original analysis, the association with perchlorate disappeared. Soon after the Blount Study was released, NAS panelist Dr. Robert Utiger, a physician with the Harvard Institutes of Medicine, testified before Congress and stated: “I continue to believe that that reference dose, 0.007 milligrams per kilo (24.5 ppb,) which includes a factor of 10 to protect those who might be more vulnerable, is quite adequate.”
Discovery of perchlorate on Mars
In June 2008, the Wet Chemistry Laboratory (WCL) on board the 2007 Phoenix Mars Lander performed the first wet chemical analysis of martian soil. The analyses on three samples, two from the surface and one from 5 cm depth, revealed a slightly alkaline soil and low levels of salts typically found on Earth. Most unexpected though was the presence of ~ 0.6 wt % perchlorate (ClO4-), most likely as a Mg(ClO4)2 phase.
The extreme temperatures found on Mars typically lead to either crystallization or evaporation of water, making it difficult to imagine that water could be found in liquid form. The salts formed from perchlorates discovered at the Phoenix landing site act as “anti-freeze” and will substantially lower the freezing point of water. Based on the temperature and pressure conditions on present-day Mars at the Phoenix lander site, conditions would allow a perchlorate salt solution to be present in liquid form for a few hours each day during the summer.
The possibility that the perchlorate was a contaminant brought from Earth has been eliminated by several lines of evidence. The Phoenix retro-rockets used ultra pure hydrazine and launch propellants consisted of ammonium perchlorate. Sensors on board Phoenix found no traces of ammonium, and thus the perchlorate in the quantities present in all three soil samples is indigenous to the martian soil.
In 2006, a mechanism was proposed for the formation of perchlorates that is particularly relevant to the discovery of perchlorate at the Mars Phoenix lander site. It was shown that soils with high concentrations of natural salts could have some of their chloride converted to perchlorate in the presence of sunlight and/or ultraviolet light. The mechanism was reproduced in the lab using chloride-rich soils from Death Valley. In 2010, perchlorate was found at the 1000 ppb levels in a vast section of Antarctica, with implications that it is formed naturally and globally on Earth and probably on Mars. Recent isotopic studies have shown that natural perchlorate is produced on Earth by the oxidation of chlorine species through pathways involving tropospheric ozone or its photochemical products.
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- Associated Press. "Toxic chemical found in California milk". MSNBC. June 22, 2004.
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- D. C. Catling et al. (2010). "Atmospheric origins of perchlorate on Mars and in the Atacama". Journal of Geophysical Research 115: E00E11. Bibcode 2010JGRE..11500E11C. doi:10.1029/2009JE003425.
- Fireworks Displays Linked To Perchlorate Contamination In Lakes
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- McKee, Maggie. "Perchlorate found in breast milk across US". New Scientist. February 23, 2005
- Perchlorate In Food
- "CDC Scientists Find Rocket Fuel Chemical In Infant Formula." Anila Jacob, M.D., M.P.H.. Environmental Working Group. 2 April 2009.
- John D. Coates, Laurie A. Achenbach (2004). "Microbial perchlorate reduction: rocket-fuelled metabolism". Nature Reviews Microbiology 2 (7): 569–580. doi:10.1038/nrmicro926. PMID 15197392.
- California Department of Toxic Substances Control Jan 26, 2008
- Scientific Analysis of Perchlorate (Report). United States Environmental Protection Agency, Office of the Inspector General. 19 April 2010. ""What We Found""
- J. Wolff (1998). "Perchlorate and the Thyroid Gland". Pharmacological Reviews 50 (1): 89–105. PMID 9549759.
- "Various Levels of Perchlorate Exposure Found Not to Be Harmful to Newborns, Pregnant Women, and Other Adults" (Press release). American Thyroid Association. 1 October 2004. http://www.thyroid.org/professionals/publications/news/04_10_01_perchlorate.html.
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- US EPA Memorandum Jan 26, 2006
- Benjamin C. Blount, James L. Pirkle, John D. Osterloh, Liza Valentin-Blasini, and Kathleen L. Caldwell (2006). "Urinary Perchlorate and Thyroid Hormone Levels in Adolescent and Adult Men and Women Living in the United States". Environmental Health Perspectives 114 (12): 1865–71. doi:10.1289/ehp.9466. PMC 1764147. PMID 17185277. //www.ncbi.nlm.nih.gov/pmc/articles/PMC1764147/.
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- Miller, Glen. "Photooxidation of chloride to perchlorate in the presence of desert soils and titanium dioxide". American Chemical Society. March 29, 2006
- NAS Report: The Health Effects of Perchlorate Ingestion
- NRDC's criticism of NAS report
- Environment California report (Executive Summary with link to full text)
- Macho Moms: Perchlorate pollutant masculinizes fish: Science News Online, Aug. 12, 2006
- New Scientist Space Blog: Phoenix discovery may be bad for Mars life
- "State Threatening To Sue Military Over Water Pollution", Associated Press, May 19, 2003.
- "Health Effects Of Perchlorate From Spent Rocket", SpaceDaily.com, July 11, 2002.
- = Dept of Defense, Dept of Energy, and US Environmental Protection Agency's Strategic Environmental Research and Development Program, Elimination of Perchlorate Oxidizers from Pyrotechnic Flare Compositions, 2009
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- Perchlorates are the salts derived from perchloric acid (HClO4). 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 ...
- 21 Dec 2012 ... Besides its potential to cause endocrine system and reproductive problems, perchlorate is considered a “likely human carcinogen” by the EPA.
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