Chlorpyrifos


Chlorpyrifos
Chlorpyrifos
Identifiers
CAS number 2921-88-2 YesY
PubChem 2730
ChemSpider 2629 YesY
UNII JCS58I644W YesY
KEGG D07688 YesY
ChEBI CHEBI:34631 YesY
ChEMBL CHEMBL463210 YesY
Jmol-3D images Image 1
Properties
Molecular formula C9H11Cl3NO3PS
Molar mass 350.59 g/mol
Appearance colourless crystals[1]
Density 1.398 g/cm3 (43.5 °C)
Melting point

42 °C[2]

Solubility in water 2 mg/L (25 °C)
log P 4.96 (octanol/water)[3]
 YesY (verify) (what is: YesY/N?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Chlorpyrifos (IUPAC name: O,O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) is a crystalline organophosphate insecticide that inhibits acetylcholinesterase and is used to control insect pests. It is known by many trade names (see table). Chlorpyrifos is moderately toxic and chronic exposure has been linked to neurological effects, developmental disorders, and autoimmune disorders.

Contents

Manufacture and use

Chlorpyrifos is manufactured by reacting 3,5,6-trichloro-2-pyridinol with diethylthiophosphoryl chloride.[1]

In the US, chlorpyrifos is registered only for agricultural use, where it is "one of the most widely used organophosphate insecticides", according to the United States Environmental Protection Agency (EPA).[4] The crops with the most intense chlorpyrifos use are cotton, corn, almonds, and fruit trees including oranges and apples.[5] It is produced via a multistep synthesis from 3-methylpyridine.

Chlorpyrifos is normally supplied as a 23.5% or 50% liquid concentrate. The recommended concentration for direct-spray pin point application is 0.5% and for wide area application a 0.03 – 0.12% mix is recommended (US).[6][7]

History

First registered in 1965 and marketed by Dow Chemical Company under the tradenames Dursban and Lorsban, chlorpyrifos was a well known home and garden insecticide, and at one time it was one of the most widely used household pesticides in the US. Facing impending regulatory action by the EPA, Dow agreed to withdraw registration of chlorpyrifos for use in homes and other places where children could be exposed, and severely restricted its use on crops. These changes took effect on Dec. 31, 2001.[8] It is still widely used in agriculture, and Dow continues to market Dursban for home use in developing countries. In Iran, Dow claims Dursban is safe for people,[9] and its sales literature claimed Dursban has "an established record of safety regarding humans and pets."[10]

In 1995, Dow was fined US$732,000 for not sending the EPA reports it had received on 249 Dursban poisoning incidents, and in 2003, Dow agreed to pay US$2 million – the largest penalty ever in a pesticide case – to the state of New York, in response to a lawsuit filed by the Attorney General to end Dow's illegal advertising of Dursban as "safe".[11]

On July 31, 2007, a coalition of farmworker and advocacy groups filed a lawsuit against the EPA seeking to end agricultural use of the chlorpyrifos. The suit claims that the continued use of chlorpyrifos poses an unnecessary risk to farmworkers and their families.[12]

In August 2007, Dow's Indian offices were raided by Indian authorities for allegedly bribing officials to allow chlorpyrifos to be sold in the country.[13]

In 2008, the National Marine Fisheries Service (NMFS) imposed 1000 ft buffer zones around salmon habitat to protect endangered salmon and steelhead species. Aerial applications of chlorpyrifos will be prohibited within these zones.[14]

Health effects

Chlorpyrifos is an organophosphate, with potential for both acute toxicity at larger amounts and neurological effects in fetuses and children even at very small amounts. For acute effects, the EPA classifies chlorpyrifos as Class II: moderately toxic. The oral LD50 for chlorpyrifos in experimental animals is 32 to 1000 mg/kg. The dermal LD50 in rats is greater than 2000 mg/kg and 1000 to 2000 mg/kg in rabbits. The 4-hour inhalation LC50 for chlorpyrifos in rats is greater than 200 mg/m3.[15]

Chlorpyrifos poisoning has been described by New Zealand scientists as the likely cause of death of several tourists in Thailand who developed myocarditis in 2011.[16][17][18] Thai investigators have come to no conclusion as to what caused the deaths,[19] but maintain that chlorpyrifos was not responsible, and that the deaths were not linked.[20]

Recent research indicates that children exposed to chlorpyrifos while in the womb have an increased risk of delays in mental and motor development at age 3 and an increased occurrence of pervasive developmental disorders such as ADHD.[21] An earlier study demonstrated a correlation between prenatal chlorpyrifos exposure and lower weight and smaller head circumference at birth.[22]

Among 50 farm pesticides studied, chlorpyrifos was one of two found to be associated with higher risks of lung cancer among frequent pesticide applicators than among infrequent or non-users. Pesticide applicators as a whole were found to have a 50% lower cancer risk than the general public, which is attributable to the nearly 50% lower smoking rate found among farm workers. However, applicators of chlorpyrifos had a 15% lower cancer risk than the general public, which the study suggests indicates a likely link between chlorpyrifos application and lung cancer.[23]

A 2010 study found that each 10-fold increase in urinary concentration of organophosphate metabolites was associated with a 55% to 72% increase in the odds of ADHD in children.[24]

Studies have shown evidence of "deficits in Working Memory Index and Full-Scale IQ as a function of prenatal CPF exposure [as measured when the children reach] 7 years of age."[25]

A 2011 study on the neurotoxic effects of chlorpyrifos showed that chlorpyrifos and its more toxic metabolite, chlorpyrifos oxon, altered firing rates in the locus coeruleus. These results indicate that the pesticide may be involved in Gulf War Syndrome and other neurodegenerative disorders.[26]

Effects on aquatic life and bees

Chlorpyrifos is highly toxic to amphibians, and a recent study by the United States Geological Survey found that its main breakdown product in the environment, chlorpyrifos oxon, is even more toxic to these animals.[27]

The substance is very toxic for aquaculture (fish) and bees[citation needed].

Exposure

A body burden study conducted by the Centers for Disease Control and Prevention found TCPy, a metabolite specific to chlorpyrifos, in the urine of 91% of people tested.[28] An independent analysis of the CDC data claims that Dow has contributed 80% of the chlorpyrifos body burden of people living in the US.[29] A 2008 study found dramatic drops in the urinary levels of chlorpyrifos metabolites when children switched from conventional to organic diets.[30]

Air monitoring studies conducted by the California Air Resources Board (CARB) have documented chlorpyrifos in the air of California communities.[31] Analyses of the CARB data indicate that children living in areas of high chlorpyrifos use are often exposed to levels of the insecticide that exceed levels considered acceptable by the EPA.[32][33] Recent air monitoring studies in Washington and Lindsay, CA have yielded comparable results.[34][35] Grower and pesticide industry groups have argued that the air levels documented in these studies are not high enough to cause significant exposure or adverse effects,[36] but a follow-up biomonitoring study in Lindsay, CA has shown that people there have higher than normal chlorpyrifos levels in their bodies.[37][38]

A study of the effects of chlorpyrifos on humans exposed over time showed that people exposed to high levels have autoimmune antibodies that are common in people with autoimmune disorders. There is a strong correlation to chronic illness associated with autoimmune disorders after exposure to chlorpyrifos.[39]

Before it was banned from residential use in the US, chlorpyrifos was detected in 100% of personal indoor air samples and 70% of umbilical-cord blood collected from pregnant women 18–35 years old who self-identified as African American or Dominican and living in New York City public housing.[40]

See also

References

  1. ^ a b Muller, Franz, ed (2000). Agrochemicals: Composition, Production, Toxicology, Applications. Toronto: Wiley-VCH. p. 541. ISBN 3-527-29852-5. 
  2. ^ Lide, David R. (1998). Handbook of Chemistry and Physics (87 ed.). Boca Raton, FL: CRC Press. pp. 3–126. ISBN 0849305942. 
  3. ^ Sangster J; LOGKOW Databank. Sangster Res. Lab., Montreal Quebec, Canada (1994)
  4. ^ "Reregistration Eligibility Decision for Chlorpyrifos" (PDF). http://www.epa.gov/oppsrrd1/REDs/chlorpyrifos_ired.pdf. Retrieved November 20, 2011. 
  5. ^ "NASS Agricultural Chemical Database". Pestmanagement.info. http://www.pestmanagement.info/nass/app_usage.cfm. Retrieved November 20, 2011. 
  6. ^ http://www.cdms.net/ldat/ld0AT004.pdf
  7. ^ http://www.farmoz.com.au/label/farmoz/STRIKE_OUT_500WP_16103844.pdf
  8. ^ EPA's Chlorpyrifos Page[dead link]
  9. ^ "Islamic Republic News Agency, Feb 17th, 2007". .irna.ir. http://www2.irna.ir/en/news/view/menu-234/0702177222193606.htm. Retrieved November 20, 2011. 
  10. ^ "Bhopal.net". Bhopal.net. June 8, 2000. http://www.bhopal.net/oldsite/oldwebsite/mergerinfo2.html. Retrieved November 20, 2011. 
  11. ^ mindfully.org. "Mindfully.org". Mindfully.org. http://www.mindfully.org/Pesticide/2003/Dow-Pesticide-Safety16dec03.htm. Retrieved November 20, 2011. 
  12. ^ Press Release: Lawsuit Challenges EPA on Deadly Pesticide, EarthJustice, July 31, 2007.
  13. ^ CBI raids Dow Chemical's Indian subsidiary for graft. Monsters and Critics, August 21, 2007.
  14. ^ "Federal Government Announces Plan to Protect Salmon from Pesticides". Earthjustice. http://www.earthjustice.org/news/press/2008/federal-government-announces-plan-to-protect-salmon-from-pesticides.html. Retrieved 2009-09-02. 
  15. ^ "Chlorpyrifos". Pmep.cce.cornell.edu. http://pmep.cce.cornell.edu/profiles/extoxnet/carbaryl-dicrotophos/chlorpyrifos-ext.html. Retrieved November 20, 2011. 
  16. ^ "Toxin 'likely' cause of Sarah Carter's death". stuff.co.nz. http://www.stuff.co.nz/world/asia/4976814/Toxin-likely-cause-of-Sarah-Carters-death. Retrieved May 8, 2011. 
  17. ^ "Sarah Carter's likely cause of death – insecticide". 3 News. http://www.3news.co.nz/Sarah-Carters-likely-cause-of-death---insecticide/tabid/423/articleID/210265/Default.aspx. 
  18. ^ "Thailand death cover-up suspected". NZ Herald Online. http://www.nzherald.co.nz/nz/news/article.cfm?c_id=1&objectid=10724455. 
  19. ^ Hayden Donnell (May 11, 2011). "Thai experts: Bed bug spray didn't kill Kiwi tourist". http://www.nzherald.co.nz/nz/news/article.cfm?c_id=1&objectid=10724871. Retrieved May 11, 2011. 
  20. ^ "Thais deny tourists' deaths linked". Dominion Post. May 26, 2011. http://www.stuff.co.nz/dominion-post/news/5055760/Thais-deny-tourists-deaths-linked. Retrieved May 26, 2011. 
  21. ^ "Rauh VA, et al., Pediatrics, 2006, 118, e1845-e1859". Pediatrics.aappublications.org. http://pediatrics.aappublications.org/cgi/content/abstract/peds.2006-0338. Retrieved November 20, 2011. 
  22. ^ "Whyatt RM, et al., Environmental Health Perspectives, 2004, 112, 1125–32". Ehponline.org. http://www.ehponline.org/docs/2004/6641/abstract.html. Retrieved November 20, 2011. 
  23. ^ "Lung Cancer in the Agricultural Health Study (IA)" http://aghealth.nci.nih.gov/pdfs/IALungCancer2006.pdf
  24. ^ "Access". Medscape. http://www.medscape.com/viewarticle/721892. Retrieved November 20, 2011. 
  25. ^ Rauh, V.; Arunajadai, S.; Horton, M.; Perera, F.; Hoepner, L.; Barr, D. B.; Whyatt, R. (2011). "7-Year Neurodevelopmental Scores and Prenatal Exposure to Chlorpyrifos, a Common Agricultural Pesticide". Environmental Health Perspectives. doi:10.1289/ehp.1003160.  edit
  26. ^ Cao, Jun-li , Varnell, Andrew, and Cooper, Donald.(2011) Gulf War Syndrome: A role for organophosphate induced plasticity of locus coeruleus neurons. Available from Nature Precedings <http://hdl.handle.net/10101/npre.2011.6057.1> (2011)
  27. ^ Breakdown Products Of Widely Used Pesticides Are Acutely Lethal To Amphibians, Study Finds, Science Daily, June 25, 2007, accessed July 2, 2006.
  28. ^ CDC Third National Exposure Report[dead link]
  29. ^ ""Chemical Trepass," Pesticide Action Network North America, 2004". Panna.org. November 3, 2011. http://www.panna.org/campaigns/docsTrespass/chemicalTrespass2004.dv.html. Retrieved November 20, 2011. 
  30. ^ Lu, Chensheng; Dana B. Barr, Melanie A. Pearson, and Lance A. Waller (2008). "Dietary Intake and Its Contribution to Longitudinal Organophosphorus Pesticide Exposure in Urban/Suburban Children". Environ. Health Perspect. published ahead of print (4): 537–42. doi:10.1289/ehp.10912. PMC 2290988. PMID 18414640. http://www.ehponline.org/members/2008/10912/10912.pdf. 
  31. ^ "CARB Chlorpyrifos Monitoring Studies". Cdpr.ca.gov. http://www.cdpr.ca.gov/docs/empm/pubs/tac/chlrpfs.htm. Retrieved November 20, 2011. 
  32. ^ "S Lee et al., Environmental Health Perspectives, 2002, 110, 1175–1184". Ehponline.org. doi:10.1289/ehp.021101175. http://www.ehponline.org/docs/2002/110p1175-1184lee/abstract.html. Retrieved November 20, 2011. 
  33. ^ S Kegley et al., "Secondhand Pesticides", Pesticide Action Network North America, 2003[dead link]
  34. ^ C Dansereau et al., "Poisons on the Wind", Farm Worker Pesticide Project, 2006[dead link]
  35. ^ S Kegley et al., "Drift Catching In Lindsay, California", Pesticide Action Network North America, 2006[dead link]
  36. ^ Hansen, Heather (January 18, 2007). "Heather Hansen, "Proper Pest Management Keeps Washington Fruit Crop Healthy", Seattle Post Intellegencer, Jan 19, 2007". Seattlepi.com. http://www.seattlepi.com/opinion/300312_foodrebut19.html. Retrieved November 20, 2011. 
  37. ^ "Douglas Fischer, "Toxins permeate Central Valley town", ''Tri-Valley Herald'', May 15th, 2007". Origin.insidebayarea.com. http://origin.insidebayarea.com/trivalleyherald/localnews/ci_5907782. Retrieved November 20, 2011. 
  38. ^ "Californians For Pesticide Reform, ''Airborne Poisons: Pesticides in Our Air, and in Our Bodies'', May 16th, 2007." (PDF). http://pesticidereform.org/downloads/Biodrift-Summary-Eng.pdf. Retrieved November 20, 2011. 
  39. ^ Thrasher, PhD, Jack D.; Gunnar Heuser, M.D., PhD, Alan Broughton, M.D., PhD (2002). "Immunological Abnormalities in Humans Chronically Exposed to Chlorpyrifos". Archives of Environmental Health, 2002, 57:181–187 2002 (57): 181–187. http://www.drthrasher.org/Chlorpyrifos_2002.html. 
  40. ^ Whyatt, R. M.; Barr, D. B.; Camann, D. E.; Kinney, P. L.; Barr, J. R.; Andrews, H. F.; Hoepner, L. A.; Garfinkel, R. et al. (2002). "Contemporary-Use Pesticides in Personal Air Samples during Pregnancy and Blood Samples at Delivery among Urban Minority Mothers and Newborns". Environmental Health Perspectives 111 (5): 749–756. doi:10.1289/ehp.5768. PMC 1241486. PMID 12727605. http://www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=1241486.  edit

External links