Toxaphene: Difference between revisions

| Watchedfields = changed

| verifiedrevid = 432143730

| Name = Toxaphene

| ImageFile = Toxaphen.svg

| =

| IUPACName = 2,2,5,6-tetrachloro-1,7-bis(chloromethyl)-7-(dichloromethyl)bicyclo[2.2.1]heptane

| OtherNames = Chlorocamphene, Octachlorocamphene, Polychlorocamphene, Chlorinated camphene, Camphechlor

| Section1 = {{Chembox Identifiers

| = {{||}}

| CASNo = 8001-35-2

| ChEBI = 77850

| ChEMBL_Ref = {{ebicite|correct|EBI}}

| ChEMBL = 1339089

| ChemSpiderID = 4447533

| EINECS = 232-283-3

| KEGG_Ref = {{keggcite|correct|kegg}}

| PubChem = 5518

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = 9924JQ4D5J

| SMILES = C=C1C(C2(C(C(C1(C2(Cl)Cl)Cl)Cl)Cl)Cl)(CCl)CCl

| StdInChI=1S/C10H10Cl8/c1-7(2)3(6(13)14)8(15)4(11)5(12)9(7,16)10(8,17)18/h3-6H,1-2H3

| StdInChIKey = HRBUJQUHXGOSQW-UHFFFAOYSA-N

| Section2 = {{Chembox Properties

| C=10 | H=10 | Cl=8

| Density = 1.65 g/cm³

| MeltingPtC = 65 to 90

| MeltingPt_notes =

| BoilingPt= decomposition at

| BoilingPtC = 155

| Solubility = 0.0003% (20°C)<ref name=PGCH/>

| VaporPressure = 0.4 mmHg (25°C)<ref name=PGCH/>

}}

| Section3 = {{Chembox Hazards

| PEL = TWA 0.5 mg/m³ [skin]<ref name=PGCH>{{PGCH|0113}}</ref>

| IDLH = 200 mg/m³<ref name=PGCH/>

| REL = Ca [skin]<ref name=PGCH/>

| LD50 = 75 mg/kg (oral, rabbit)<br />112 mg/kg (oral, mouse)<br />250 mg/kg (oral, guinea pig)<br />50 mg/kg (oral, rat)<ref name=IDLH>{{cite web |url = https://www.cdc.gov/niosh/idlh/8001352.html |title = Chlorinated camphene |date = 4 December 2014 |publisher = National Institute for Occupational Safety and Health |access-date = 19 February 2014}}</ref>

| LCLo = 2000 mg/m³ (mouse, 2 hr)<ref name=IDLH/>

| FlashPt = noncombustible

| FlashPt_ref = <ref name=PGCH/>

| GHSPictograms = {{GHS06}}{{GHS08}}{{GHS09}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|301|312|315|335|351|410}}

| PPhrases = {{P-phrases|261|273|280|301+310|501}}

}}

'''Toxaphene''' was an [[insecticide]] used primarily for [[cotton]] in the southern [[United States]] during the late 1960s and the 1970s.<ref name="Toxaphene-ToxFAQs">{{cite web|title= Toxaphene - ToxFAQs|url=https://wwwn.cdc.gov/TSP/ToxFAQs/ToxFAQsLanding.aspx?id=547&tid=99|website=Agency for Toxic Substances and Disease Registry|access-date=16 March 2015}}</ref><ref name="Report on Carcinogens">{{cite journal|title=Toxaphene|journal=Report on Carcinogens|date=October 2, 2014|volume=13|url=http://ntp.niehs.nih.gov/ntp/roc/content/profiles/toxaphene.pdf|access-date=16 March 2015|publisher=National Toxicology Program, Department of Health and Human Services}}</ref> Toxaphene is a mixture of over 670 different chemicals and is produced by reacting [[chlorine|chlorine gas]] with [[camphene]].<ref name="Toxaphene-ToxFAQs">{{cite web|title= Toxaphene - ToxFAQs|url=https://wwwn.cdc.gov/TSP/ToxFAQs/ToxFAQsLanding.aspx?id=547&tid=99|website=Agency for Toxic Substances and Disease Registry|access-date=16 March 2015}}</ref><ref name="Saleh" /> It can be most commonly found as a yellow to amber waxy solid.<ref name="Toxaphene-ToxFAQs" />

Toxaphene was banned in the [[United States]] in 1990 and was banned globally by the [[Stockholm Convention on Persistent Organic Pollutants|2001 Stockholm Convention on Persistent Organic Pollutants]].<ref name="Toxaphene-ToxFAQs" /><ref name = "POPs">{{cite journal|last1=Wen-Tien|first1=Tsai|title=Current Status and Regulatory Aspects of Pesticides Considered to be Persistent Organic Pollutants (POPs) in Taiwan|journal=International Journal of Environmental Research and Public Health|date=October 12, 2010|volume=7|issue=10|doi=10.3390/ijerph7103615|pages=3615–3627|pmid=21139852|pmc=2996183|doi-access=free}}</ref> It is a very persistent chemical that can remain in the environment for 1–14 years without degrading, particularly in the soil.<ref>{{cite web|title=Technical Factsheet on: TOXAPHENE|url=http://www.epa.gov/ogwdw/pdfs/factsheets/soc/tech/toxaphen.pdf|website=National Primary Drinking Water Regulations|publisher=United States Environmental Protection Agency|access-date=17 March 2015}}</ref>

Testing performed on animals, mostly [[rat]]s and [[mouse|mice]], has demonstrated that toxaphene is harmful to animals. Exposure to toxaphene has proven to stimulate the [[central nervous system]], as well as induce morphological changes in the [[thyroid]], [[liver]], and [[kidneys]].<ref name = "EPA Toxaphene">{{cite web|title=Toxaphene|url=http://www.epa.gov/airtoxics/hlthef/toxaphen.html|website=Technology Transfer Network - Air Toxics Web Site|publisher=United States Environmental Protection Agency|access-date=17 March 2015}}</ref>

Toxaphene has been shown to cause adverse health effects in [[humans]]. The main sources of exposure are through food, [[drinking water]], breathing contaminated air, and direct contact with contaminated soil. Exposure to high levels of toxaphene can cause damage to the [[lungs]], [[central nervous system|nervous system]], [[liver]], [[kidneys]], and in extreme cases, may even cause death. It is thought to be a potential [[carcinogen]] in [[humans]], though this has not yet been proven.<ref name="Toxaphene-ToxFAQs" />

==Composition==

Toxaphene is a synthetic [[organic compound|organic]] mixture composed of over 670 chemicals, formed by the [[chlorination reaction|chlorination]] of [[camphene]] (C₁₀H₁₆) to an overall chlorine content of 67–69% by weight.<ref name="Toxaphene-ToxFAQs">{{cite web|title= Toxaphene - ToxFAQs|url=https://wwwn.cdc.gov/TSP/ToxFAQs/ToxFAQsLanding.aspx?id=547&tid=99|website=Agency for Toxic Substances and Disease Registry|access-date=16 March 2015}}</ref><ref name="Saleh">{{cite journal | doi = 10.1021/jf00118a017| title = Capillary gas chromatography-electron impact chemical ionization mass spectrometry of toxaphene| journal = Journal of Agricultural and Food Chemistry| volume = 31| issue = 4| pages = 748–751| year = 1983| last1 = Saleh| first1 = Mahmoud Abbas}}</ref><ref>Buntin, G.A. {{US patent|2565471}}, 1951.</ref> The bulk of the compounds (mostly chlorobornanes, chlorocamphenes, and other [[bicyclic]] chloroorganic compounds) found in toxaphene have [[chemical formula]]s ranging from C₁₀H₁₁Cl₅ to C₁₀H₆Cl₁₂, with a mean formula of C₁₀H₁₀Cl₈.<ref name="pmid10739064">{{cite journal | vauthors = Buser HR, Haglund P, Müller MD, Poiger T, Rappe C | title = Rapid anaerobic degradation of toxaphene in sewage sludge | journal = Chemosphere | volume = 40 | issue = 9–11 | pages = 1213–20 | date = 2000 | pmid = 10739064 | doi = 10.1016/s0045-6535(99)00371-9 | bibcode = 2000Chmsp..40.1213B }}</ref> The [[formula weight]]s of these compounds range from 308 to 551 grams/mole; the theoretical mean formula has a value of 414 grams/mole. Toxaphene is usually seen as a yellow to amber waxy [[solid]] with a piney odor. It is highly insoluble in water but freely soluble in [[aromatic hydrocarbon]]s and readily soluble in [[aliphatic compound|aliphatic organic solvents]]. It is stable at room temperature and pressure.<ref name="Toxaphene-ToxFAQs">{{cite web|title= Toxaphene - ToxFAQs|url=https://wwwn.cdc.gov/TSP/ToxFAQs/ToxFAQsLanding.aspx?id=547&tid=99|website=Agency for Toxic Substances and Disease Registry|access-date=16 March 2015}}</ref> It is volatile enough to be transported for long distances through the atmosphere.<ref name="pmid10448561">{{cite journal | vauthors = Shoeib M, Brice KA, Hoff RM | title = Airborne concentrations of toxaphene congeners at Point Petre (Ontario) using gas-chromatography-electron capture negative ion mass spectrometry (GC-ECNIMS) | journal = Chemosphere | volume = 39 | issue = 5 | pages = 849–71 | date = August 1999 | pmid = 10448561 | doi = 10.1016/s0045-6535(99)00018-1 | bibcode = 1999Chmsp..39..849S }}</ref><ref>{{cite journal | vauthors = Rice CP, Samson PJ, Noguchi GE | journal = Environmental Science and Technology | date = 1986 | volume = 20 | issue = 11 | pages = 1109–1116 | doi = 10.1021/es00153a005 | title=Atmospheric transport of toxaphene to Lake Michigan| bibcode = 1986EnST...20.1109R }}</ref>

Advertisements for Toxaphene were seen in agricultural periodicals such as ''Farm Journal''<ref name="FarmJournal1950">{{cite journal |author=Hercules Powder Company |title=These Facts Now Can Help You Fight Insects in 1950 |journal=Farm Journal |date=February 1950 |page=54}}</ref> as early as 1950.<ref name="FarmJournal1950" />

Toxaphene was primarily used as a [[pesticide]] for [[cotton]] in the southern [[United States]] during the late 1960s and 1970s. It was also used on small grains, [[maize]], [[vegetables]], and [[soybeans]]. Outside of the realm of crops, it was also used to control ectoparasites such as [[lice]], [[flies]], [[ticks]], [[mange]], and [[mite|scam mites]] on [[livestock]]. In some cases it was used to kill undesirable [[fish]] species in [[lake]]s and [[stream]]s. The breakdown of usage can be summarized: 85% on [[cotton]], 7% to control [[insect]] pests on [[livestock]] and [[poultry]], 5% on other field [[crop]]s, 3% on [[soybeans]], and less than 1% on [[sorghum]].<ref name="Report on Carcinogens" />

The first recorded usage of toxaphene was in 1966 in the [[United States]], {{Citation needed|reason=Toxaphene is discussed in Silent Spring extensively and this book was published in 1962|date=October 2019}} and by the early to mid 1970s, toxaphene was the United States' most heavily used [[pesticide]]. Over 34 million pounds of toxaphene were used annually from 1966 to 1976. As a result of [[United States Environmental Protection Agency|Environmental Protection Agency]] restrictions, annual toxaphene usage fell to 6.6 million pounds in 1982. In 1990, the EPA banned all usage of toxaphene in the United States.<ref name="Report on Carcinogens">{{cite journal|title=Toxaphene|journal=Report on Carcinogens|date=October 2, 2014|volume=13|url=http://ntp.niehs.nih.gov/ntp/roc/content/profiles/toxaphene.pdf|access-date=16 March 2015|publisher=National Toxicology Program, Department of Health and Human Services}}</ref> Toxaphene is still used in countries outside the United States but much of this usage has been undocumented.<ref name="Toxaphene-ToxFAQs">{{cite web|title= Toxaphene - ToxFAQs|url=https://wwwn.cdc.gov/TSP/ToxFAQs/ToxFAQsLanding.aspx?id=547&tid=99|website=Agency for Toxic Substances and Disease Registry|access-date=16 March 2015}}</ref> Between 1970 and 1995, global usage of toxaphene was estimated to be 670 million kilograms (1.5 billion pounds).<ref name="Report on Carcinogens">{{cite journal|title=Toxaphene|journal=Report on Carcinogens|date=October 2, 2014|volume=13|url=http://ntp.niehs.nih.gov/ntp/roc/content/profiles/toxaphene.pdf|access-date=16 March 2015|publisher=National Toxicology Program, Department of Health and Human Services}}</ref>

==Production==

Toxaphene was first produced in the [[United States]] in 1947 although it was not heavily used until 1966. By 1975, toxaphene production reached its peak at 59.4 million pounds annually. Production decreased more than 90% from this value by 1982 due to [[United States Environmental Protection Agency|Environmental Protection Agency]] restrictions. Overall, an estimated 234,000 metric tons (over 500 million pounds) have been produced in the United States. Between 25% and 35% of the toxaphene produced in the United States has been exported. There are currently 11 toxaphene suppliers worldwide.<ref name="Report on Carcinogens">{{cite journal|title=Toxaphene|journal=Report on Carcinogens|date=October 2, 2014|volume=13|url=http://ntp.niehs.nih.gov/ntp/roc/content/profiles/toxaphene.pdf|access-date=16 March 2015|publisher=National Toxicology Program, Department of Health and Human Services}}</ref>

==Environmental effects==

When released into the environment, toxaphene can be quite persistent and exists in the [[air]], [[soil]], and [[water]]. In water, it can evaporate easily and is fairly [[solubility|insoluble]].<ref name="Toxaphene-ToxFAQs" /> Its solubility is 3&nbsp;mg/L of water at 22 degrees [[Celsius]].<ref name="EPA Factsheet Toxaphene">{{cite web|title=Technical Factsheet on Toxaphene|url=http://www.epa.gov/ogwdw/pdfs/factsheets/soc/tech/toxaphen.pdf|website=Drinking Water Contaminants|publisher=United States Environmental Protection Agency|access-date=21 April 2015}}</ref> Toxaphene breaks down very slowly and has a [[half-life]] of up to 12 years in the soil.<ref name="POPs" /> It is most commonly found in air, soil, and [[sediment]] found at the bottom of [[lake]]s or [[streams]].<ref name="Toxaphene-ToxFAQs" /> It can also be present in many parts of the world where it was never used because toxaphene is able to evaporate and travel long distances through air currents. Toxaphene can eventually be degraded, through [[reductive dechlorination|dechlorination]], in the air using sunlight to break it down. The degradation of toxaphene usually occurs under [[cellular respiration|aerobic conditions]].<ref name="POPs" /> The levels of toxaphene have decreased since its ban. However, due to its persistence, it can still be found in the environment today.

==Exposure==

The three main paths of exposure to toxaphene are ingestion, inhalation, and absorption. For humans, the main source of toxaphene exposure is through ingested [[seafood]].<ref name="POPs" /> When toxaphene enters the body, it usually accumulates in [[adipose tissue|fatty tissues]]. It is broken down through dechlorination and [[redox|oxidation]] in the [[liver]], and the byproducts are eliminated through [[feces]].<ref name="POPs" />

People that live near an area that has high toxaphene contamination are at high risk to toxaphene exposure through inhalation of contaminated air or direct skin contact with contaminated soil or water. Eating large quantities of fish on a daily basis also increases susceptibility to toxaphene exposure.<ref name="Toxaphene-ToxFAQs" /> Finally, exposure is rare, yet possible through [[drinking water]] when contaminated by toxaphene runoff from the soil.<ref name="Toxaphene-ToxFAQs" /> However, toxaphene has been rarely seen at high levels in drinking water due to toxaphene's nearly complete [[solubility|insolubility]] in water.<ref name = "EPA Toxaphene" />

[[Shellfish]], [[algae]], [[fish]] and [[marine mammals]] have all been shown to exhibit high levels of toxaphene. People in the [[Northern Canada|Canadian Arctic]], where a traditional diet consists of [[fish]] and [[marine biology|marine animals]], have been shown to consume ten times the accepted daily intake of toxaphene.<ref name="POPs" /> Also, [[blubber]] from [[beluga whales]] in the [[Arctic]] were found to have unhealthy and toxic levels of toxaphene.<ref name="POPs" />

==Health effects==

=== In humans ===

When inhaled or ingested, sufficient quantities of toxaphene can damage the [[lungs]], [[nervous system]], and [[kidneys]], and may cause [[Pesticide poisoning|death]]. The major health effects of toxaphene involve [[central nervous system]] stimulation leading to convulsive [[seizures]]. The dose necessary to induce nonfatal convulsions in humans is about 10 milligrams per kilogram body weight per day.<ref name="EPA Toxaphene" /> Several deaths linked to toxaphene have been documented in which an unknown quantity of toxaphene was ingested intentionally or accidentally from food contamination. The deaths are attributed to [[respiratory]] failure resulting from seizures.<ref name="Public Health Goal" /> Chronic inhalation exposure in humans results in reversible respiratory toxicity.<ref name="EPA Toxaphene" />

A study conducted between 1954 and 1972 of male agricultural workers and [[agronomists]] exposed to toxaphene and other pesticides showed that there are higher proportions of [[bronchial]] [[carcinoma]] in the test group than in the unexposed general population. However, toxaphene may not have been the main pesticide responsible for tumor production.<ref name="Public Health Goal">{{cite web|title=Public Health Goal for TOXAPHENE in Drinking Water|url=http://oehha.ca.gov/water/phg/pdf/Ph4Toxap92603.pdf|publisher=California Environmental Protection Agency}}</ref> Tests on lab animals show that toxaphene causes liver and kidney cancer, so the EPA has classified it as a Group B2 carcinogen, meaning it is a probable human carcinogen. The [[International Agency for Research on Cancer]] has classified it as a Group 2B carcinogen.<ref name="EPA Toxaphene" />

Toxaphene can be detected in blood, urine, breast milk, and body tissues if a person has been exposed to high levels, but it is removed from the body quickly, so detection has to occur within several days of exposure.<ref name="EPA Toxaphene" />

It is not known whether toxaphene can affect reproduction in humans.<ref name=Toxaphene-ToxFAQs />

=== In animals ===

Toxaphene was used to treat [[mange]] in cattle in [[California]] in the 1970s and there were reports of cattle deaths following the toxaphene treatment.<ref>Chancellor, John; Oliver, Don (1979-02-22). "Possible Toxaphene Cattle Poisoning". NBC News. Vanderbilt Television News Archive. http://tvnews.vanderbilt.edu/program.pl?ID=502980. Retrieved on 2008-02-08.</ref>

Chronic oral exposure in animals affects the liver, the kidney, the spleen, the adrenal and thyroid glands, the central nervous system, and the immune system.<ref name="EPA Toxaphene" /> Toxaphene stimulates the central nervous system by antagonizing neurons leading to [[Hyperpolarization (physics)|hyperpolarization]] of neurons and increased neuronal activity.<ref name="Public Health Goal" />

== Regulations ==

Toxaphene has been found on at least 68 of the 1,699 [[National Priorities List]] sites identified by the [[United States Environmental Protection Agency]].<ref name=Toxaphene-ToxFAQs /> Toxaphene has been forbidden in Germany since 1980. Most uses of toxaphene were cancelled in the U.S. in 1982 with the exception of use on [[livestock]] in emergency situations, and for controlling insects on banana and pineapple crops in [[Puerto Rico]] and the [[U.S. Virgin Islands]]. All uses of toxaphene were cancelled in the U.S. in 1990.<ref name="EPA Toxaphene" />

Toxaphene has been banned in 37 countries, including Austria, Belize, Brazil, Costa Rica, Dominican Republic, Egypt, the EU, India, Ireland, Kenya, Korea, Mexico, Panama, Singapore, Thailand and Tonga. Its use has been severely restricted in 11 other countries, including Argentina, Columbia, Dominica, Honduras, Nicaragua, Pakistan, South Africa, Turkey, and Venezuela.<ref>{{cite web|title=Toxaphene|url=http://www.popstoolkit.com/about/chemical/toxaphene.aspx|website=Persistent Organic Pollutants Toolkit|access-date=2015-04-22}}</ref>

In the Stockholm Convention on POPs, which came into effect on 17 May 2004, twelve POPs were listed to be eliminated or their production and use restricted. The OCPs or pesticide-POPs identified on this list have been termed the "dirty dozen" and include [[aldrin]], [[chlordane]], [[DDT]], [[dieldrin]], [[endrin]], [[heptachlor]], [[hexachlorobenzene]], [[mirex]], and toxaphene.<ref name=POPs /><ref>{{cite web |url=http://chm.pops.int/Portals/0/docs/publications/sc_factsheet_004.pdf |title=Stockholm Convention |website=chm.pops.int |access-date=2009-03-05}}</ref>

The EPA has determined that lifetime exposure to 0.01 milligrams per liter of toxaphene in the drinking water is not expected to cause any adverse noncancer effects if the only source of exposure is drinking water,<ref name=Toxaphene-ToxFAQs /> and has established the [[maximum contaminant level]] (MCL) of toxaphene at 0.003&nbsp;mg/L. The [[United States Food and Drug Administration]] (FDA) uses the same level for the maximum level permissible in bottled water.<ref name="Report on Carcinogens" />

The FDA has determined that the concentration of toxaphene in bottled drinking water should not exceed 0.003 milligrams per liter.<ref name=Toxaphene-ToxFAQs />

The [[United States Department of Transportation]] lists toxaphene as a [[hazardous]] material and has special requirements for marking, labeling, and transporting the material.<ref name="Report on Carcinogens" />

It is classified as an [[List of extremely hazardous substances|extremely hazardous substance]] in the United States as defined in Section 302 of the U.S. [[Emergency Planning and Community Right-to-Know Act]] (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.<ref name="gov-right-know">{{Cite journal | publisher = [[United States Government Publishing Office|Government Printing Office]] | title = 40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities | url = http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | edition = July 1, 2008 | access-date = October 29, 2011 }}</ref>

==Trade names==

Trade names and synonyms include Chlorinated camphene, Octachlorocamphene, Camphochlor, Agricide Maggot Killer, Alltex, Allotox, Crestoxo, Compound 3956, Estonox, Fasco-Terpene, Geniphene, Hercules 3956, M5055, Melipax, Motox, Penphene, Phenacide, Phenatox, Strobane-T, Toxadust, Toxakil, Vertac 90%, Toxon 63, Attac, Anatox, Royal Brand Bean Tox 82, Cotton Tox MP82, Security Tox-Sol-6, Security Tox-MP cotton spray, Security Motox 63 cotton spray, Agro-Chem Brand Torbidan 28, and Dr Roger's TOXENE.<ref>{{cite web |url=http://www.epa.gov/safewater/dwh/c-soc/toxaphen.html |title=Consumer Factsheet on: TOXAPHENE |website=www.epa.gov |access-date=2009-03-05 |archive-url=https://web.archive.org/web/20090510042216/http://www.epa.gov/safewater/dwh/c-soc/toxaphen.html |archive-date=2009-05-10 |url-status=dead}}</ref>

==References==

*[http://www.atsdr.cdc.gov/. ASTDR ToxFAQs for Toxaphene]

* [https://www.cdc.gov/niosh/npg/npgd0113.html CDC - NIOSH Pocket Guide for Chemical Hazards - Chlorinated Camphene]

[[Category:Obsolete pesticides]]

[[Category:]]

[[Category:Persistent organic pollutants under the Stockholm Convention]]

[[Category:Persistent organic pollutants under the Convention on Long-Range Transboundary Air Pollution]]

[[Category:Bicyclic compounds]]