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| Names | |||
|---|---|---|---|
| Systematic IUPAC name Perchlorate[1] | |||
| Identifiers | |||
3D model (JSmol) | |||
| ChEBI | |||
| ChEMBL | |||
| ChemSpider |
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| DrugBank |
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| ECHA InfoCard | 100.152.366 | ||
| 2136 | |||
| MeSH | 180053 | ||
| UNII | |||
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| Properties | |||
| ClO−4 | |||
| Molar mass | 99.45 g·mol−1 | ||
| Conjugate acid | Perchloric acid | ||
Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa). | |||
Aperchlorate is achemical compound containing the perchlorateion,ClO−4, theconjugate base ofperchloric acid (ionic perchlorate). As counterions, there can bemetalcations,quaternary ammonium cations or other ions, for example,nitronium cation (NO+2).
The termperchlorate can also describeperchlorate esters orcovalent perchlorates.[2] These are organic compounds that arealkyl orarylesters ofperchloric acid. They are characterized by acovalent bond between anoxygen atom of the ClO4moiety and anorganyl group.
In most ionic perchlorates, the cation isnon-coordinating. The majority of ionic perchlorates are commercially produced salts commonly used as oxidizers for pyrotechnic devices and for their ability to controlstatic electricity infood packaging.[3] Additionally, they have been used inrocket propellants,fertilizers, and asbleaching agents in thepaper andtextile industries.
Perchlorate contamination of food andwater endangers human health, primarily affecting thethyroid gland.
Ionic perchlorates are typically colorless solids that exhibit goodsolubility in water. The perchlorate ion forms when they dissolve in water,dissociating into ions. Many perchlorate salts also exhibit good solubility in non-aqueoussolvents.[4] Four perchlorates are of primary commercial interest:ammonium perchlorate(NH4)ClO4,perchloric acidHClO4,potassium perchlorateKClO4 andsodium perchlorateNaClO4.
Very few chemical oxidants are strong enough to convert chlorate to perchlorate.Persulfate,ozone, orlead dioxide are all known to do so, but the reactions are too delicate and low-yielding for commercial viability.[5]
Perchlorate salts are typically manufactured through the process ofelectrolysis, which involves oxidizing aqueous solutions of correspondingchlorates. This technique is commonly employed in the production ofsodium perchlorate, which finds widespread use as a key ingredient inrocket fuel.[5] Perchlorate salts are also commonly produced by reactingperchloric acid with bases, such asammonium hydroxide orsodium hydroxide.Ammonium perchlorate, which is highly valued,[why?] can also be produced via anelectrochemical process.[6]
Perchlorate esters are formed in the presence of a nucleophiliccatalyst via a perchlorate salt'snucleophilic substitution onto analkylating agent.[7]
The perchlorate ion is the leastredox reactive of the generalizedchlorates. Perchlorate containschlorine in its highestoxidation number (+7). A table ofreduction potentials of the fourchlorates shows that, contrary to expectation, perchlorate inaqueous solution is the weakestoxidant among the four.[12]
| Ion | Acidic reaction | E° (V) | Neutral/basic reaction | E° (V) |
|---|---|---|---|---|
| Hypochlorite | 2 H+ + 2 HOCl + 2 e− → Cl2 (g) + 2 H2O | 1.63 | ClO− + H2O + 2 e− → Cl− + 2 OH− | 0.89 |
| Chlorite | 6 H+ + 2 HOClO + 6 e− → Cl2 (g) + 4 H2O | 1.64 | ClO−2 + 2 H2O + 4 e− → Cl− + 4 OH− | 0.78 |
| Chlorate | 12 H+ + 2 ClO−3 + 10 e− → Cl2 (g) + 6 H2O | 1.47 | ClO−3 + 3 H2O + 6 e− → Cl− + 6 OH− | 0.63 |
| Perchlorate | 16 H+ + 2 ClO−4 + 14 e− → Cl2 (g) + 8 H2O | 1.42 | ClO−4 + 4 H2O + 8 e− → Cl− + 8 OH− | 0.56 |
These data show that the perchlorate and chlorate are stronger oxidizers in acidic conditions than in basic conditions.
Gas phase measurements of heats of reaction (which allow computation of ΔfH°) of various chlorine oxides do follow the expected trend whereinCl2O7 exhibits the largest endothermic value of ΔfH° (238.1 kJ/mol) whileCl2O exhibits the lowest endothermic value of ΔfH° (80.3 kJ/mol).[13]
Asperchloric acid is one of the strongest mineral acids, perchlorate is a very weakbase in the sense ofBrønsted–Lowry acid–base theory. As it is also generally aweakly coordinating anion, perchlorate is commonly used as abackground, orsupporting, electrolyte.
Perchlorate compounds oxidize organic compounds, especially when the mixture is heated. The explosive decomposition ofammonium perchlorate is catalyzed by metals and heat.[14]
As perchlorate is a weakLewis base (i.e., a weak electron pair donor) and a weaknucleophilic anion, it is also a very weaklycoordinatinganion.[14] This is why it is often used as asupporting electrolyte to study thecomplexation and thechemical speciation of manycations inaqueous solution or inelectroanalytical methods (voltammetry,electrophoresis…).[14] Although the perchlorate reduction isthermodynamically favorable(∆G < 0;E° > 0), and thatClO−4 is expected to be a strongoxidant, most often in aqueous solution, it is practically an inert species behaving as an extremely slowoxidant because of severekinetics limitations.[15][16] Themetastable character of perchlorate in the presence ofreducing cations such asFe2+ in solution is due to the difficulty to form anactivated complex facilitating theelectron transfer and the exchange of oxo groups in the opposite direction. These strongly hydrated cations cannot form a sufficiently stable coordination bridge with one of the four oxo groups of the perchlorate anion. Although thermodynamically a mild reductant,Fe2+ ion exhibits a stronger trend to remain coordinated by water molecules to form the corresponding hexa-aquo complex in solution. The highactivation energy of the cation binding with perchlorate to form a transientinner sphere complex more favourable toelectron transfer considerably hinders theredox reaction.[17] The redox reaction rate is limited by the formation of a favorableactivated complex involving an oxo-bridge between the perchlorate anion and the metallic cation.[18] It depends on themolecular orbital rearrangement (HOMO and LUMOorbitals) necessary for a fastoxygen atom transfer (OAT)[19] and the associated electron transfer as studied experimentally byHenry Taube (1983 Nobel Prize in Chemistry)[20][21] and theoretically byRudolph A. Marcus (1992 Nobel Prize in Chemistry),[22] both awarded for their respective works on the mechanisms of electron-transfer reactions with metal complexes and in chemical systems.
In contrast to theFe2+ cations which remain unoxidized in deaerated perchlorate aqueous solutions free of dissolved oxygen, other cations such as Ru(II) and Ti(III) can form a more stable bridge between the metal centre and one of the oxo groups ofClO−4. In theinner sphere electron transfer mechanism to observe the perchlorate reduction, theClO−4 anion must quickly transfer an oxygen atom to the reducing cation.[23][24] When it is the case, metallic cations can readily reduce perchlorate in solution.[20] Ru(II) can reduceClO−4 toClO−3, while V(II), V(III), Mo(III), Cr(II) and Ti(III) can reduceClO−4 toCl−.[25]
Some metal complexes, especially those ofrhenium, and some metalloenzymes cancatalyze the reduction of perchlorate under mild conditions.[26]Perchlorate reductase (see below), amolybdoenzyme, also catalyzes the reduction of perchlorate.[27] Both the Re- and Mo-basedcatalysts operate via metal-oxo intermediates.
Over 40 phylogenetically and metabolically diverse microorganisms capable of growth using perchlorate as an electron acceptor[28] have been isolated since 1996. Most originate from thePseudomonadota, but others include theBacillota,Moorella perchloratireducens andSporomusa sp., and thearchaeonArchaeoglobus fulgidus.[29][30] With the exception ofA. fulgidus, microbes that grow via perchlorate reduction utilize the enzymesperchlorate reductase andchlorite dismutase, which collectively take perchlorate to chloride.[29] In the process, freeoxygen (O2) is generated.[29]
Perchlorate is created by lightning discharges in the presence of chloride. Perchlorate has been detected in rain and snow samples fromFlorida andLubbock, Texas.[31] It is also present inMartian soil.
Naturally occurring perchlorate at its most abundant can be found commingled with deposits of sodium nitrate in theAtacama Desert of northern Chile. These deposits have been heavily mined as sources for nitrate-based fertilizers. Chilean nitrate is in fact estimated to be the source of around 81,000 tonnes (89,000 tons) of perchlorate imported to the U.S. (1909–1997). Results from surveys of ground water, ice, and relatively unperturbed deserts have been used to estimate a 100,000 to 3,000,000 tonnes (110,000 to 3,310,000 tons) "global inventory" of natural perchlorate presently on Earth.[32]
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Perchlorate was detected in Martian soil at the level of ~0.6% by weight.[33][34] It was shown that at the Phoenix landing site it was present as a mixture of 60%Ca(ClO4)2 and 40%Mg(ClO4)2.[35] These salts, formed from perchlorates, act asantifreeze and substantially lower thefreezing point of water. Based on the temperature and pressure conditions on present-day Mars at thePhoenix lander site, conditions would allow a perchlorate salt solution to be stable in liquid form for a few hours each day during the summer.[36]
The possibility that the perchlorate was a contaminant brought from Earth was eliminated by several lines of evidence. ThePhoenix retro-rockets used ultra purehydrazine and launch propellants consisting ofammonium perchlorate orammonium nitrate. Sensors on boardPhoenix found no traces ofammonium nitrate, and thus the nitrate in the quantities present in all three soil samples is indigenous to the Martian soil. Perchlorate is widespread in Martian soils at concentrations between 0.5 and 1%. At such concentrations, perchlorate could be an important source of oxygen, but it could also become a critical chemical hazard to astronauts.[37]
In 2006, a mechanism was proposed for the formation of perchlorates that is particularly relevant to the discovery of perchlorate at thePhoenix lander site. It was shown that soils with high concentrations ofchloride converted to perchlorate in the presence of titanium dioxide and sunlight/ultraviolet light. The conversion was reproduced in the lab using chloride-rich soils fromDeath Valley.[38] Other experiments have demonstrated that the formation of perchlorate is associated with wide band gap semiconducting oxides.[39] In 2014, it was shown that perchlorate and chlorate can be produced from chloride minerals under Martian conditions via UV using only NaCl and silicate.[40]
Further findings of perchlorate and chlorate in theMartian meteorite EETA79001[41] and by the MarsCuriosity rover in 2012-2013 support the notion that perchlorates are globally distributed throughout the Martian surface.[42][43][44] With concentrations approaching 0.5% and exceeding toxic levels on Martian soil, Martian perchlorates would present a serious challenge tohuman settlement,[45] as well as microorganisms.[46] On the other hand, the perchlorate would provide a convenient source ofoxygen for the settlements.
On September 28, 2015, NASA announced that analyses of spectral data from the Compact Reconnaissance Imaging Spectrometer for Mars instrument (CRISM) on board the Mars Reconnaissance Orbiter from four different locations whererecurring slope lineae (RSL) are present found evidence for hydrated salts. The hydrated salts most consistent with the spectral absorption features are magnesium perchlorate, magnesium chlorate and sodium perchlorate. The findings strongly support the hypothesis that RSL form as a result of contemporary water activity on Mars.[47][48][49][50][51]
Perchlorates are of concern because of uncertainties about toxicity and health effects at low levels in drinking water, impact on ecosystems, and indirect exposure pathways for humans due to accumulation in vegetables.[11] They are water-soluble, exceedingly mobile in aqueous systems, and can persist for many decades under typical groundwater and surface water conditions.[52]
Perchlorates are used mostly inrocket propellants but also in disinfectants, bleaching agents, and herbicides. Perchlorate contamination is caused during both the manufacture and ignition of rockets and fireworks.[4] Fireworks are also a source of perchlorate in lakes.[53] Removal and recovery methods of these compounds from explosives and rocket propellants include high-pressure water washout, which generates aqueous ammonium perchlorate.
In 2000, perchlorate contamination beneath the former flare manufacturing plantOlin Corporation Flare Facility,Morgan Hill, California was first discovered 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 theSanta Clara Valley Water District had confirmed a groundwater plume currently extending over nine miles through residential and agricultural communities.[citation needed]The California Regional Water Quality Control Board and theSanta Clara Valley Water District have engaged[when?] in a major outreach effort, awater well testing program has been underway for about 1,200 residential, municipal, and agricultural wells. Large ion exchange treatment units are operating in three public water supply systems which include seven municipal wells with perchlorate detection. Thepotentially responsible parties, Olin Corporation and Standard Fuse Incorporated, have been supplying bottled water to nearly 800 households with private wells,[when?] and the Regional Water Quality Control Board has been overseeing cleanup efforts.[54]
The source of perchlorate in California was mainly attributed to two manufacturers in the southeast portion of the Las Vegas Valley in Nevada, where perchlorate has been produced for industrial use.[55] This led to perchlorate release intoLake Mead in Nevada and theColorado River which affected regions of Nevada, California andArizona, where water from this reservoir is used for consumption, irrigation and recreation for approximately half the population of these states.[4] Lake Mead has been attributed[when?] as the source of 90% of the perchlorate in Southern Nevada's drinking water. Based on sampling, perchlorate has been affecting 20 million people, with highest detection inTexas, southern California,New Jersey, and Massachusetts, but intensive sampling of theGreat Plains and other middle state regions may lead to revised estimates with additional affected regions.[4] An action level of 18 μg/L has been adopted[when?] by several affected states.[52]
In 2001, the chemical was detected at levels as high as 5 μg/L atJoint Base Cape Cod (formerlyMassachusetts Military Reservation), over theMassachusetts then state regulation of 2 μg/L.[56][57]
As of 2009, low levels of perchlorate had been detected in both drinking water andgroundwater in 26 states in the U.S., according to theEnvironmental Protection Agency (EPA).[58]
In 2004, the chemical was found in cow's milk in California at an average level of 1.3parts per billion (ppb, or μg/L), which may have entered the cows through feeding on crops exposed to water containing perchlorates.[59]A 2005 study suggestedhuman breast milk had an average of 10.5 μg/L of perchlorate.[60]
In some places, there is no clear source of perchlorate, and it may be naturally occurring. Natural perchlorate on Earth was first identified in terrestrial nitrate deposits /fertilizers of theAtacama Desert in Chile as early as the 1880s[61] and for a long time considered a unique perchlorate source. The perchlorate released from historic use of Chilean nitrate based fertilizer which the U.S.imported by the hundreds of tons in the early 19th century can still be found in some groundwater sources of the United States, for example Long Island, New York.[62] 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,[63] salt evaporites in California and Nevada,[64] Pleistocene groundwater in New Mexico,[65] and even present in extremely remote places such asAntarctica.[66] 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 remain poorly understood. Laboratory experiments in conjunction with isotopic studies[67] have implied that perchlorate may be produced on earth by oxidation of chlorine species through pathways involving ozone or its photochemical products.[68][69] Other studies have suggested that perchlorate can also be formed by lightning activated oxidation of chloride aerosols (e.g., chloride in sea salt sprays),[70] and ultraviolet or thermal oxidation of chlorine (e.g., bleach solutions used in swimming pools) in water.[71][72][73]
Although perchlorate as an environmental contaminant is usually associated with the manufacture, storage, and testing ofsolid rocket motors,[74] contamination of perchlorate has been focused as a side effect of the use of natural nitratefertilizer and its release into ground water. The use of naturally contaminated nitrate fertilizer contributes to the infiltration of perchlorate anions into the ground water and threaten the water supplies of many regions in the US.[74]
One of the main sources of perchlorate contamination from natural nitrate fertilizer use was found to come from the fertilizer derived from Chileancaliche (calcium carbonate), because Chile has rich source of naturally occurring perchlorate anion.[75] Perchlorate concentration was the highest in Chilean nitrate, ranging from 3.3 to 3.98%.[52] Perchlorate in the solid fertilizer ranged from 0.7 to 2.0 mg g−1, variation of less than a factor of 3 and it is estimated that sodium nitrate fertilizers derived from Chilean caliche contain approximately 0.5–2 mg g−1 of perchlorate anion.[75] The direct ecological effect of perchlorate is not well known; its impact can be influenced by factors including rainfall and irrigation, dilution, natural attenuation, soil adsorption, and bioavailability.[75] Quantification of perchlorate concentrations in nitrate fertilizer components viaion chromatography revealed that in horticultural fertilizer components contained perchlorate ranging between 0.1 and 0.46%.[52]
There have been many attempts to eliminate perchlorate contamination. Currentremediation technologies for perchlorate have downsides of high costs and difficulty in operation.[76] Thus, there have been interests in developing systems that would offer economic and green alternatives.[76]
Several technologies can remove perchlorate, via treatmentsex situ (away from the location) andin situ (at the location).
Ex situ treatments include ion exchange using perchlorate-selective or nitrite-specific resins,bioremediation using packed-bed or fluidized-bedbioreactors, and membrane technologies viaelectrodialysis andreverse osmosis.[77] In ex situ treatment via ion exchange, contaminants are attracted and adhere to the ion exchange resin because such resins and ions of contaminants have opposite charge.[78] As the ion of the contaminant adheres to the resin, another charged ion is expelled into the water being treated, in which then ion is exchanged for the contaminant.[78] Ion exchange technology has advantages of being well-suitable for perchlorate treatment and high volume throughput but has a downside that it does not treatchlorinated solvents. In addition, ex situ technology of liquid phase carbon adsorption is employed, where granular activated carbon (GAC) is used to eliminate low levels of perchlorate and pretreatment may be required in arranging GAC for perchlorate elimination.[77]
In situ treatments, such as bioremediation via perchlorate-selective microbes and permeable reactive barrier, are also being used to treat perchlorate.[77] In situ bioremediation has advantages of minimal above-groundinfrastructure and its ability to treat chlorinated solvents, perchlorate,nitrate, andRDX simultaneously. However, it has a downside that it may negatively affect secondary water quality. In situ technology ofphytoremediation could also be utilized, even though perchlorate phytoremediation mechanism is not fully founded yet.[77]
Bioremediation using perchlorate-reducing bacteria, which reduce perchlorate ions to harmless chloride, has also been proposed.[79]
Perchlorate is a potentcompetitive inhibitor of the thyroidsodium-iodide symporter.[80] Thus, it has been used to treathyperthyroidism since the 1950s.[81] 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 large amounts perchlorate interferes withiodine uptake into thethyroid gland. In adults, the thyroid gland helps regulate themetabolism by releasing hormones, while in children, the thyroid helps in proper development. TheNAS, in its 2005 report,Health Implications of Perchlorate Ingestion, emphasized that this effect, also known as Iodide Uptake Inhibition (IUI) is not an adverse health effect. However, in January 2008, California's Department of Toxic Substances Control stated that perchlorate is becoming a serious threat to human health and water resources.[82] In 2010, the EPA's Office of the Inspector General determined that the agency's own perchloratereference dose (RfD) of 24.5 parts per billion protects against all human biological effects from exposure, as the federal government is responsible for all US military base groundwater contamination. 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.[83]
Because of ammonium perchlorate's adverse effects upon children, Massachusetts set its maximum allowed limit ofammonium perchlorate in drinking water at 2 parts per billion (2 ppb = 2 micrograms per liter).[84]
Perchlorate affects only thyroid hormone. Because it is neither stored normetabolized, effects of perchlorate on the thyroid gland are reversible, though effects on brain development from lack of thyroid hormone infetuses,newborns, and children are not.[85]
Toxic effects of perchlorate have been studied in a survey of industrial plant workers who had been exposed to perchlorate, compared to a control group of other industrial plant workers who had no known exposure to perchlorate. After undergoing multiple tests, workers exposed to perchlorate were found to have a significant systolic blood pressure rise compared to the workers who were not exposed to perchlorate, as well as a significant decreased thyroid function compared to the control workers.[86]
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 thethyroid gland's ability to absorb iodine from thebloodstream ("iodide uptake inhibition", thus perchlorate is a knowngoitrogen).[87] The EPA converted this dose into areference 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 kg (150 lb) and consumes 2 L (0.44 imp gal; 0.53 US gal) of drinking water per day over a lifetime.[88][needs update]
In 2006, a study 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. The authors also indicated that they did not originally normalize their findings forcreatinine, which would have essentially accounted for fluctuations in the concentrations of one-time urine samples like those used in this study.[89] 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, any remaining association between the results and perchlorate intake disappeared.[90] Soon after the revised Blount Study was released, Robert Utiger, a doctor with the Harvard Institute of Medicine, testified before the US 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."[91]
In 2014, a study was published, showing that environmental exposure to perchlorate in pregnant women with hypothyroidism is associated with a significant risk of low IQ in their children.[92]
Some studies suggest that perchlorate has pulmonary toxic effects as well. Studies have been performed on rabbits where perchlorate has been injected into the trachea. The lung tissue was removed and analyzed, and it was found that perchlorate injected lung tissue showed several adverse effects when compared to the control group that had been intratracheally injected with saline. Adverse effects included inflammatory infiltrates, alveolar collapse, subpleural thickening, and lymphocyte proliferation.[93]
In the early 1960s,potassium perchlorate used to treatGraves' disease was implicated in the development ofaplastic anemia—a condition where thebone marrow fails to produce newblood cells in sufficient quantity—in thirteen patients, seven of whom died.[94] 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.[95]
In 1998, perchlorate was included in the U.S. EPAContaminant Candidate List, primarily due to its detection in California drinking water.[96][4]
In 2002, the EPA completed its draft toxicological review of perchlorate and proposed anreference dose of 0.00003 milligrams per kilogram per day (mg/kg/day) based primarily on studies that identified neurodevelopmental deficits in rat pups. These deficits were linked to maternal exposure to perchlorate.[97]
In 2003, afederal district court in California found that theComprehensive Environmental Response, Compensation and Liability Act applied, because perchlorate is ignitable, and therefore was a "characteristic" hazardous waste.[98]
Subsequently, the U.S. National Research Council of theNational Academy of Sciences (NAS) reviewed the health implications of perchlorate, and in 2005 proposed a much higher reference dose of 0.0007 mg/kg/day based primarily on a 2002 study by Greeret al.[97] During that study, 37 adult human subjects were split into four exposure groups exposed to 0.007 (7 subjects), 0.02 (10 subjects), 0.1 (10 subjects), and 0.5 (10 subjects) mg/kg/day. Significant decreases in iodide uptake were found in the three highest exposure groups. Iodide uptake was not significantly reduced in the lowest exposed group, but four of the seven subjects in this group experienced inhibited iodide uptake. In 2005, theRfD proposed by NAS was accepted by EPA and added to its integrated risk information system (IRIS).
Although there has generally been consensus with the Greeret al. study, there has been no consensus with regard to developing a perchlorate RfD. One of the key differences results from how the point of departure is viewed (i.e., NOEL or "lowest-observed-adverse-effect level",LOAEL), or whether a benchmark dose should be used to derive the RfD. Defining the point of departure as a NOEL or LOAEL has implications when it comes to applying appropriate safety factors to the point of departure to derive the RfD.[99]
In early 2006, EPA issued a "Cleanup Guidance" and recommended aDrinking Water Equivalent Level (DWEL) for perchlorate of 24.5 μg/L.[citation needed] Both DWEL and Cleanup Guidance were based on a 2005 review of the existing research by theNational Academy of Sciences (NAS).[100]
Lacking a federal drinking water standard, several states subsequently published their own standards for perchlorate including Massachusetts in 2006[citation needed] and California in 2007. Other states, including Arizona, Maryland, Nevada, New Mexico, New York, and Texas have established non-enforceable, advisory levels for perchlorate.[citation needed]
In 2008, EPA issued an interimdrinking water health advisory for perchlorate and with it a guidance and analysis concerning the impacts on the environment and drinking water.[101] California also issued guidance[when?] regarding perchlorate use.[102] Both theDepartment of Defense and some environmental groups voiced questions about the NAS report,[citation needed] but no credible science has emerged to challenge the NAS findings.[citation needed]
In February 2008, the U.S.Food and Drug Administration (FDA) reported that U.S. toddlers on average were being exposed to more than half of EPA's safe dose from food alone.[103] In March 2009, aCenters for Disease Control study found 15 brands of infant formula contaminated with perchlorate and that combined with existing perchlorate drinking water contamination, infants could be at risk for perchlorate exposure above the levels considered safe by EPA.
In 2010, theMassachusetts Department of Environmental Protection set a 10 fold lower RfD (0.07 μg/kg/day) than the NAS RfD using a much higher uncertainty factor of 100. They also calculated an Infant drinking water value, which neither US EPA norCalEPA had done.[104]
On February 11, 2011, EPA determined that perchlorate meets theSafe Drinking Water Act criteria for regulation as a contaminant.[101][105] The agency found that perchlorate may have an adverse effect on the health of persons and is known to occur inpublic water systems with a frequency and at levels that it presents a public health concern. Since then EPA has continued to determine what level of contamination is appropriate. EPA prepared extensive responses to submitted public comments.[106][better source needed]
In 2016, theNatural Resources Defense Council (NRDC) filed a lawsuit to accelerate EPA's regulation of perchlorate.[107]
In 2019, EPA proposed aMaximum Contaminant Level of 0.056 mg/L for public water systems.[108]
On June 18, 2020, EPA announced that it was withdrawing its 2011 regulatory determination and its 2019 proposal, stating that it had taken "proactive steps" with state and local governments to address perchlorate contamination.[109] In September 2020 NRDC filed suit against EPA for its failure to regulate perchlorate, and stated that 26 million people may be affected by perchlorate in their drinking water.[110] On March 31, 2022, the EPA announced that a review confirmed its 2020 decision.[111] Following the NRDC lawsuit, in 2023 theUS Court of Appeals for the DC Circuit ordered EPA to develop a perchlorate standard for public water systems.[112] EPA stated that it will publish a proposed standard for perchlorate in 2025, and issue a final rule in 2027.[113]
Although typically found as a non-coordinating anion, a fewmetal complexes are known.Hexaperchloratoaluminate andtetraperchloratoaluminate are strongoxidising agents.
Several perchlorate esters are known.[2] For example,methyl perchlorate is a high energy material that is a strongalkylating agent.Chlorine perchlorate is a covalent inorganic analog.
As discussed above, iodide is competitor in the thyroid glands. In the presence of reductants, perchlorate forms potentially explosive mixtures. ThePEPCON disaster destroyed a production plant forammonium perchlorate when a fire caused the ammonium perchlorate stored on site to react with the aluminum that the storage tanks were constructed with and explode.
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