Chlorpyrifos

from Wikipedia, the free encyclopedia
Structural formula
Structure of chlorpyrifos
General
Surname Chlorpyrifos
other names
  • O , O -Diethyl- O- (3,5,6-trichloropyridin-2-yl) thiophosphate
  • Chlorpyrifos-ethyl
Molecular formula C 9 H 11 Cl 3 NO 3 PS
Brief description

colorless crystals

External identifiers / databases
CAS number 2921-88-2
EC number 220-864-4
ECHA InfoCard 100,018,969
PubChem 2730
Wikidata Q414915
properties
Molar mass 350.58 g mol −1
Physical state

firmly

Melting point

42 ° C

solubility

practically insoluble in water (1.4 mg l −1 at 25 ° C)

safety instructions
GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
06 - Toxic or very toxic 09 - Dangerous for the environment

danger

H and P phrases H: 301-410
P: 273-301 + 310 + 330-391-501
MAK

Switzerland: 0.2 mg m −3 (measured as inhalable dust )

Toxicological data

60 mg kg −1 ( LD 50 ,  mouse ,  oral )

As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Chlorpyrifos is an insecticide introduced by Dow Chemical in the mid-1960s. To date, it is one of the most widely used agricultural pesticides in the United States. Trade names include Dursban, Empire, Eradex, Lorsban (Dow), Pyrinex and Stipend. In Germany, Chlorpyrifos was sold under names like Schwabex, Hyganex, Insektenil, Microsol, Killgerm and Ketolac. Chemically, chlorpyrifos is a thiophosphoric acid ester .

In the EU , approval as an active ingredient in plant protection products was not extended in January 2020. The German authorities are currently preparing, on behalf of the EU, a nomination of chlorpyrifos for inclusion in the list of prohibited substances under the Stockholm Convention .

effect

Chlorpyrifos has contact, food and breath poison effects. It acts on the insect nervous system by inhibiting the enzyme acetylcholinesterase .

use

Chlorpyriphos is used in a variety of ways to combat sucking and biting insects as well as against soil pests in numerous agricultural crops, against ants in the house and garden, against house flies, household and storage pests, against clothes moths, for combating mosquitoes, as stall spray and against ectoparasites on animals. In forestry , the piles are often treated with chlorpyrifos to protect them from bark beetles and other forest pests .

Until the ban in accordance with the EC Biocide Directive 98/8 / EC from August 2008, chlorpyrifos was used as an insecticide with long-term effects against parasites that are difficult to control, such as bed bugs .

Admission

EU

In the European Union , this active ingredient has been approved for plant protection products since 2005. The approval originally expired on June 30, 2016. Since the examination of the application for a license extension could not be completed in the allotted time, the license was initially extended to January 31, 2018, then to January 31, 2019 and finally to January 31, 2020 on November 20, 2018. At national level, pesticides containing this active ingredient are approved in 20 EU countries. The permitted daily dose is 0.01, the acute reference dose 0.1 and the acceptable user exposure 0.01 milligrams per kilogram of body weight and day.

In Austria, products containing chlorpyrifos were approved for a large number of uses in arable, fruit and wine growing as well as in forestry.

After the use of chlorpyrifos had been banned years earlier in Germany and seven other EU countries and could still be detected on imported citrus fruits, the responsible committee of the EU Commission voted on December 6, 2019 for the approval, which expires in 2020 not to extend. At the same time, the chlorpyrifos-methyl variant was banned. The Commission followed an assessment by the European Food Safety Authority (EFSA), which warned of dangers especially for children. Member States had to withdraw their authorizations for plant protection products containing chlorpyrifos as an active ingredient by February 16, 2020 at the latest. Any use-by dates ended on April 16, 2020 at the latest.

Switzerland

In Switzerland, products containing chloropyrifos are approved for use in arable, fruit and wine growing. The Federal Office for Agriculture (FOAG) decided in May 2019 to withdraw the license for all plant protection products with the active ingredients chlorpyrifos and chlorpyrifos-methyl and to take them off the market step by step; However, the decision is not yet final. The Federal Administrative Court confirmed that eight complaints had been received in this context. According to Greenpeace and WWF Switzerland , Dow AgroSciences , Syngenta and Sintrago , among others , have filed a complaint against the decision. The plant protection products concerned are expected to be banned from July 2020.

United States

Chlorpyrifos USA 2011.png
 In the United States, chlorpyrifos was used against cockroaches and other insects in houses and apartments. Because of health hazards for children, this use has been severely restricted since 2001.

Agricultural use is still legal in the United States. In agriculture, the amount used in maize cultivation has fallen sharply from originally more than 3500 tons per year since the introduction of genetically modified Bt maize .

Use by year and harvest

other
pastures and hay
orchards and grapes
rice
vegetables and fruits
cotton
wheat
soybeans
corn

Analytics

For reliable qualitative and quantitative determination, after appropriate sample preparation, the coupling of HPLC or gas chromatography with mass spectrometry is used. These methods are also used in studies of bee mortality due to pesticides .

toxicology

Symptoms of poisoning correspond to those of other inhibitors of cholinesterases: colic , nausea , diarrhea and vomiting , dizziness , headache , blurred vision ( accommodation disorders ), contracted and unresponsive pupils ( miosis ), bradycardia , drop in blood pressure up to cramps and respiratory failure occur. Chlorpyrifos is contaminated with O , O , O , O -tetraethyl-dithiopyrophosphate ( Sulfotep ), which is considered toxicologically questionable. The EU has set the maximum content of Sulfotep at 3 g / kg chlorpyrifos. In Switzerland a. for wine grapes and raspberries a relatively high maximum residue level of 0.5 milligrams of chlorpyrifos per kilogram.

In children who were exposed to sub-toxic doses of chlorpyrifos in the womb, morphological changes in the cerebrum , including gender-specific features, as well as impairments in mental performance were found.

Studies in the United States showed that prior to the ban, chlorpyrifos was found in the indoor air of almost all of the homes tested, as well as in the blood of the majority of African-American mothers in certain residential areas in New York. It was also shown that the chlorpyrifos values ​​found in the body of children decreased drastically after the children's diet was switched from conventional to organic products and thus chlorpyrifos-free foods.

In 2018, scientists discovered inconsistencies in a 1998 manufacturer study submitted for approval. In the raw data, they found clear indications of impairments in the brain even at low doses. However, these effects were not mentioned in the conclusion of the study.

Chlorpyrifos is also toxic to animals, especially amphibians , but also bees and fish .

Metabolite chlorpyrifos-oxone

The metabolite, chlorpyrifos-oxone, is particularly toxic.

literature

Web links

Commons : Chlorpyrifos  - collection of images, videos and audio files

Individual evidence

  1. ↑ a b c d Entry on Chlorpyrifos. In: Römpp Online . Georg Thieme Verlag, accessed on May 4, 2014.
  2. ↑ a b Entry on Chlorpyriphos in the GESTIS substance database of the IFA , accessed on January 8, 2018(JavaScript required) .
  3. ↑ Entry on Chlorpyrifos in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on February 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .
  4. ↑ Swiss Accident Insurance Fund (Suva): Limit values ​​- current MAK and BAT values , accessed on November 2, 2015.
  5. ^ Entry on Chlorpyrifos in the ChemIDplus database of the United States National Library of Medicine (NLM), accessed on November 20, 2018.
  6. ↑ Handelsblatt : US Court of Appeals Bans Pesticide and Accuses Environmental Protection Agency , August 9, 2018, accessed November 26, 2018.
  7. ↑ Announcement of the tested and recognized means and procedures for combating animal pests according to § 18 Infection Protection Act, Part A: Arthropods [Disinfestation] 18th edition, Part B: Vertebrates (Rodentia, Muridae), 15th edition, Federal Office for Consumer Protection and food safety, as of June 20, 2008, published in the Federal Health Gazette; accessed in December 2016.
  8. ↑ a b Implementing Regulation (EU) 2020/18 of the Commission of 10 January 2020 on the non-renewal of the approval of the active substance chlorpyrifos in accordance with Regulation (EC) No. 1107/2009 of the European Parliament and of the Council on the placing of plant protection products on the market and amending the Annex of the Commission Implementing Regulation (EU) No. 540/2011
  9. ↑ Summary Report of the 24th PBT Expert Group Meeting. ECHA, 2020, accessed on June 9, 2020 .
  10. ↑ Dana Liechti: Forbidden insecticides in the Swiss forest. In: blick.ch . May 11, 2019, accessed October 1, 2019 .
  11. ↑ Directive 98/8 / EC of the European Parliament and of the Council of February 16, 1998 on the placing of biocidal products on the market , published on April 24, 1998.
  12. ↑ Declaration by Frowein GmbH & Co. KG on the discontinuation of the production of products containing chlorpyrifos, accessed in September 2016.
  13. ↑ a b Commission Directive 2005/72 / EC of October 21, 2005 amending Council Directive 91/414 / EEC on the inclusion of the active substances Chlorpyrifos, Chlorpyrifos-methyl, Mancozeb, Maneb and Metiram .
  14. ↑ Implementing Regulation (EU) No. 762/2013 of the Commission of August 7, 2013 , accessed on November 28, 2018
  15. ↑ Implementing Regulation (EU) 2018/84 of the Commission of January 19, 2018 , accessed on November 28, 2018
  16. ↑ Implementing Regulation (EU) 2018/1796 of the Commission of November 20, 2018 , accessed on November 28, 2018
  17. ↑ a b c Directorate-General for Health and Food Safety of the European Commission: Entry on chlorpyrifos in the EU pesticide database; Entry in the national registers of plant protection products in Switzerland , Austria and Germany ; accessed on March 14, 2016.
  18. ↑ EU Commission bans controversial insecticide. In: time online. December 6, 2019, accessed December 6, 2019 .
  19. ↑ a b c EU prohibits chlorpyrifos. In: Spiegel online. December 6, 2019, accessed December 6, 2019 .
  20. ↑ Controversial insecticide is banned across the EU. In: deutschlandfunk.de. December 6, 2019, accessed December 6, 2019 .
  21. ↑ Federal government wants to ban harmful pesticides. In: naturschutz.ch. June 12, 2019, accessed June 13, 2019 .
  22. ↑ Ban on pesticides: Agrochemicals resist. In: schweizerbauer.ch . July 19, 2019, accessed August 12, 2019 .
  23. ↑ Insecticide banned from July. In: schweizerbauer.ch. January 28, 2020, accessed January 28, 2020 .
  24. ↑ Common Insecticide May Harm Boys 'Brains More Than Girls' , Scientific American , August 21, 2012.
  25. ↑ a b USEPA : Chlorpyrifos. Retrieved June 8, 2020 .
  26. ↑ chlorpyrifos.com: Protecting Important Crops
  27. ↑ Li AJ, Kannan K: Urinary concentrations and profiles of organophosphate and pyrethroid pesticide metabolites and phenoxyacid herbicides in populations in eight countries. , Environ Int. 2018 Dec; 121 (Pt 2): 1148-1154, PMID 30808487
  28. ↑ Varela-Martínez DA, González-Curbelo MÁ, González-Sálamo J, Hernández-Borges J: Analysis of multiclass pesticides in dried fruits using QuEChERS-gas chromatography tandem mass spectrometry. , Food Chem. 2019 Nov 1; 297: 124961, PMID 31253315
  29. ↑ Calatayud-Vernich P, Calatayud F, Simó E, Pascual Aguilar JA, Picó Y: A two-year monitoring of pesticide hazard in-hive: High honey bee mortality rates during insecticide poisoning episodes in apiaries located near agricultural settings. , Chemosphere. 2019 Oct; 232: 471-480, PMID 31163323
  30. ↑ Ordinance of the EDI on the maximum levels for pesticide residues in or on products of plant and animal origin. In: admin.ch . Retrieved February 6, 2020 .
  31. ^ VA Rauh, FP Perera, MK Horton, RM Whyatt, R. Bansal, X. Hao, J. Liu, DB Barr, TA Slotkin, BS Peterson: Brain anomalies in children exposed prenatally to a common organophosphate pesticide. In: Proceedings of the National Academy of Sciences. 109 no.20, 2012, pp. 7871-7876. doi: 10.1073 / pnas.1203396109 .
  32. ↑ Agricultural poison: pesticide damages the brains of unborn babies . In: Spiegel Online . May 1, 2012.
  33. ↑ RM Whyatt, DB Barr, DE Camann, PL Kinney, JR Barr, HF Andrews, LA Hoepner, R. Garfinkel et al .: Contemporary-Use Pesticides in Personal Air Samples during Pregnancy and Blood Samples at Delivery among Urban Minority Mothers and Newborns. In: Environmental Health Perspectives. 111 (5), 2002, pp. 749-756. doi: 10.1289 / ehp.5768 , PMID 12727605 , PMC 1241486 (free full text).
  34. ↑ C. Lu, DB Barr, MA Pearson, LA Waller: Dietary intake and its contribution to longitudinal organophosphorus pesticide exposure in urban / suburban children. In: Environmental Health Perspectives. Volume 116, number 4, April 2008, pp. 537-542, doi: 10.1289 / ehp.10912 , PMID 18414640 , PMC 2290988 (free full text).
  35. ↑ Axel Mie, Christina Rudén, Philippe Grandjean: Safety of Safety Evaluation of Pesticides: developmental neurotoxicity of chlorpyrifos and chlorpyrifos-methyl . In: Environmental Health . tape 17 , no. 1 , December 2018, doi : 10.1186 / s12940-018-0421-y .
  36. ↑ Chlorpyrifos. In: bafu.admin.ch . March 6, 2018, accessed June 24, 2019 .
  37. ↑ John Flaskos: The developmental neurotoxicity of organophosphorus insecticides: A direct role for the oxon metabolites . In: Toxicology Letters . tape 209 , no. 1 , 2012, p. 86-93 , doi : 10.1016 / j.toxlet.2011.11.026 .
  38. ↑ Jie Gao, Sean X. Naughton, Wayne D. Beck, Caterina M. Hernandez, Guangyu Wu, Zhe Wei, Xiangkun Yang, Michael G. Bartlett, Alvin V. Terry: Chlorpyrifos and chlorpyrifos oxon impair the transport of membrane bound organelles in rat cortical axons . In: NeuroToxicology . tape 62 , 2017, p. 111–123 , doi : 10.1016 / j.neuro.2017.06.003 .