Perchlorates are the salts derived from perchloric acid (HClO4). They occur both naturally and through manufacturing. They have been used as a medicine for more than 50 years to treat thyroid gland disorders. They are also used as an oxidizer in rocket fuel and explosives and can be found in airbags and fireworks. Both potassium perchlorate (KClO4) and ammonium perchlorate (NH4ClO4) are used extensively within the pyrotechnics industry, whereas ammonium perchlorate is a component of solid rocket fuel. Lithium perchlorate, which decomposes exothermically to give oxygen, is used in oxygen "candles" on spacecraft, submarines and in other esoteric situations where a reliable backup or supplementary oxygen supply is needed. Most perchlorate salts are soluble in water.
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.
As most perchlorates are readily soluble in water, an accumulation of perchlorates in the environment only occurs in arid areas with little or no rainfall. It is known since the beginning of the 20th century that the Atacama Desert not only contains large amounts of nitrates but also trace amounts of perchlorates. The concentration varies but is in the mg/kg range. The dry south west of the United States also shows accumulation of perchlorates. With the use of nitrates from the Atacama Desert, so called Chile saltpeter as fertilizer the chlorates were also distributed into the environment. As the Chile saltpeter was mostly substituted by nitrates produced by the Haber Bosch process, which contains no perchlorates this source of perchlorates nearly vanished.
In 2006 a mechanism for the formation of perchlorates was proposed which is particularly apropos 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.
The electrolysis involves the following reactions:
For example the industrial scale synthesis for sodium perchlorates starts from sodium chloride. If the electrolysis is not done with the method described at chlorine, but a mixing of the chlorine evolved and the sodium hydroxide is allowed, the reaction mentioned above takes place. The hypochlorite and the chlorate are intermediates in this process.
In a statement issued after the discovery of perchlorate on Mars (see below), NASA declared, among other things, that perchlorates are found naturally on Earth at such places as Chile's hyper-arid Atacama Desert.
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.
Fireworks are also a source of perchlorate in lakes.
As of April 2007, the EPA has not yet determined whether perchlorate is present at sufficient levels in the environment to require a nationwide regulation on how much should be allowed in drinking water. In 2005, 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 which 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.
The two production sites of PEPCON and Kerr McGee in Henderson, Nevada, which were the biggest producers till the explosion of PEPCON in 1988 and the closure of the Kerr McGee plant in 1998, leaked significant amounts of perchlorates into the Las Vegas Wash and from there into Lake Mead and the Colorado River.
The disposal of unused rocket motors and ammunition has led to contamination by perchlorates of several military installations.
The NAS found that perchlorate only affects 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 perchlorates 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.
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. Thus, 25 ppb was set as the recommended drinking water standard (the DWEL). For that reason, most media reports call this the "safe" level of exposure. The NAS report also stated additional research would be helpful, but emphasized that the existing database on perchlorate was sufficient to make its reference dose recommendation and ensure it would be protective for everyone.
Recent research, however, has shown inhibition of iodide uptake in the thyroids of women at much lower levels, levels attainable from normally contaminated water and milk.
Several microorganisms have been identified, which are capable to use perchlorates as electron acceptor. The phylogenetically diverse microorganisms are Proteobacteria.
The source of the perchlorate has not yet been evaluated fully, and may represent possible extra-Martian (Earth-sourced) contamination via the Phoenix lander itself. Nevertheless, the ultrapure hydrazine used in the Phoenix retro rockets make this type of contamination unlikely. In addition, perchlorate found below the surface is more highly concentrated than would be expected from contamination during Earth launch operations.