Fipronil

Source: Wikipedia, the free encyclopedia.

Fipronil
2D chemical structure of fipronil
3D chemical structure of fipronil
Names
Preferred IUPAC name
5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(trifluoromethylsulfinyl)pyrazole-3-carbonitrile[1]
Other names
Fipronil
Fluocyanobenpyrazole
Taurus
Termidor
Identifiers
3D model (
JSmol
)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
 100.102.312 Edit this at Wikidata
KEGG
UNII
  • InChI=1S/C12H4Cl2F6N4OS/c13-5-1-4(11(15,16)17)2-6(14)8(5)24-10(22)9(7(3-21)23-24)26(25)12(18,19)20/h1-2H,22H2 checkY
    Key: ZOCSXAVNDGMNBV-UHFFFAOYSA-N checkY
  • InChI=1/C12H4Cl2F6N4OS/c13-5-1-4(11(15,16)17)2-6(14)8(5)24-10(22)9(7(3-21)23-24)26(25)12(18,19)20/h1-2H,22H2
    Key: ZOCSXAVNDGMNBV-UHFFFAOYAP
  • FC(F)(F)S(=O)c2c(C#N)nn(c1c(Cl)cc(cc1Cl)C(F)(F)F)c2N
Properties
C12H4Cl2F6N4OS
Molar mass 437.14 g·mol−1
Density 1.477-1.626 g/cm3
Melting point 200.5 °C (392.9 °F; 473.6 K)
Pharmacology
QP53AX15 (WHO
)
Hazards
GHS labelling:
GHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
Danger
NFPA 704 (fire diamond)
[2]
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
1
0
Lethal dose or concentration (LD, LC):
97 mg/kg (rat, oral)
0.25 mg/L (rainbow trout, aquatic)
Safety data sheet (SDS) Fipronil
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Fipronil is a broad-spectrum

binding affinity for the GABAA receptors of insects than to those of mammals, and for its action on GluCl channels, which do not exist in mammals.[3] As of 2017, there does not appear to be significant resistance among fleas to fipronil.[4]

Because of its effectiveness on various pests, fipronil is used as the active ingredient in

flea control products for pets and home roach baits as well as field pest control for corn, golf courses, and commercial turf. Its widespread use makes its specific effects the subject of considerable attention. Observations on possible harm to humans or ecosystems are ongoing as well as the monitoring of pesticide resistance development.[5]

Physical properties

Fipronil (

metal ions.[6]

Use

Fipronil is/was used against many different pests on different crops, it is used against major

coleopteran (beetle) larvae in soils. it is employed for cockroach and ant control as well as locust control and termite pest control. In the United States of America, fipronil was approved for use against the Rasberry crazy ant until 2022[7][needs update] in counties of Texas where positive identification had been made by entomologists from the Texas Department of Agriculture and the Environmental Protection Agency. In New Zealand, fipronil was used in trials to control wasps (Vespula spp.), which are a threat to indigenous biodiversity.[8] It is now being used by the Department of Conservation to attempt local eradication of wasps,[9][10][11] and is being recommended for control of the invasive Argentine ant.[12] Fipronil is also the active ingredient in many commercial tick and flea treatments for pets.[13]

Effects

Toxicity

Fipronil is classed as a

acute oral LD50
of 97 mg/kg.

It has moderate acute toxicity by the oral and inhalation routes in rats. Dermal absorption in rats is less than 1% after 24 hours exposure and toxicity is considered to be low. It has been found to be very toxic to rabbits.[14]

The photodegradate MB46513 or desulfinylfipronil, appears to have a higher acute toxicity to mammals than fipronil itself by a factor of about 10.[15]

Symptoms of acute toxicity via ingestion includes sweating, nausea, vomiting, headache, abdominal pain, dizziness, agitation, weakness, and tonic-clonic seizures. Clinical signs of exposure to fipronil are generally reversible and resolve spontaneously. As of 2011, no data were available regarding the chronic effects of fipronil on humans. The United States Environmental Protection Agency has classified fipronil as a group C (possible human) carcinogen based on an increase in thyroid follicular cell tumors in both sexes of the rat. However, as of 2011, no human data are available regarding the carcinogenic effects of fipronil.[16]

Two Frontline TopSpot products were determined by the

veterinary physicians were considered to be at risk from chronic exposure via inhalation and dermal absorption during the application of the spray, assuming they may have to treat up to 20 large dogs per day.[17] Fipronil is not volatile, so the likelihood of humans being exposed to this compound in the air is low.[16]

In contrast to neonicotinoids such as acetamiprid, clothianidin, imidacloprid, and thiamethoxam, which are absorbed through the skin to some extent, fipronil is not absorbed substantially through the skin.[18]

Drinking water contamination

In 2021, the US EPA put fipronil on the Draft Fifth Contaminant Candidate List (CCL 5) which can lead to future regulation under the Safe Drinking Water Act.[19]

Detection in body fluids

Fipronil may be quantitated in plasma by gas chromatography-mass spectrometry or liquid chromatography-mass spectrometry to confirm a diagnosis of poisoning in hospitalized patients or to provide evidence in a medicolegal death investigation.[20]

Ecological toxicity

Further information: Pesticide toxicity to bees

Fipronil is highly toxic to

wildfowl, and earthworms
.

Its

photolysis) than water (hydrolysis).[21]

Few studies of effects on

Madagascar bee-eater
).

Nontarget effects on some insects (predatory and

German wasps. All colonies within foraging range were eliminated within one week.[24][25]

In May 2003, the French Directorate-General of Food at the Ministry of Agriculture determined that a case of mass bee mortality observed in southern France was related to acute fipronil toxicity. Toxicity was linked to defective seed treatment, which generated dust. In February 2003, the ministry decided to temporarily suspend the sale of BASF crop protection products containing fipronil in France.[26] The seed treatment involved has since been banned.[citation needed]

Notable results from wildlife studies include:

  • Fipronil is highly
    toxic to fish and aquatic invertebrates. Its tendency to bind to sediments and its low water solubility may reduce the potential hazard to aquatic wildlife.[27]
  • Fipronil is toxic to bees and should not be applied to vegetation when bees are foraging.[27]
  • Based on ecological effects, fipronil is highly toxic to upland game birds on an acute oral basis and very highly toxic on a subacute dietary basis, but is practically nontoxic to waterfowl on both acute and subacute bases.[6]
  • Chronic (
    NOEC = 1000 ppm) or quail (NOEC = 10 ppm). The metabolite MB 46136 is more toxic than the parent to avian species tested (very highly toxic to upland game birds and moderately toxic to waterfowl on an acute oral basis).[6]
  • Fipronil is highly toxic to bluegill sunfish and highly toxic to rainbow trout on an acute basis.[6]
  • An early-lifestage toxicity study in rainbow trout found that fipronil affects larval growth with a NOEC of 0.0066 ppm and an LOEC of 0.015 ppm. The metabolite MB 46136 is more toxic than the parent to freshwater fish (6.3 times more toxic to rainbow trout and 3.3 times more toxic to bluegill sunfish). Based on an acute daphnia study using fipronil and three supplemental studies using its metabolites, fipronil is characterized as highly toxic to aquatic invertebrates.[6]
  • An invertebrate lifecycle daphnia study showed that fipronil affects length in daphnids at concentrations greater than 9.8 ppb.[6]
  • A lifecycle study in mysids shows fipronil affects reproduction, survival, and growth of mysids at concentrations less than 5 ppt.[6]
  • Acute studies of estuarine animals using oysters, mysids, and sheepshead minnows show that fipronil is highly acutely toxic to oysters and sheepshead minnows, and very highly toxic to mysids. Metabolites MB 46136 and MB 45950 are more toxic than the parent to freshwater invertebrates (MB 46136 is 6.6 times more toxic and MB 45950 is 1.9 times more toxic to freshwater invertebrates).[6]

Colony collapse disorder

Main article: Colony collapse disorder

Fipronil is one of the main chemical causes blamed for the spread of colony collapse disorder among bees[citation needed]. It has been found by the Minutes-Association for Technical Coordination Fund in France that even at very low nonlethal doses for bees, the pesticide still impairs their ability to locate their hive, resulting in large numbers of forager bees lost with every pollen-finding expedition.[28] A synergistic toxic effect of fipronil with the fungal pathogen Nosema ceranae was recently reported.[29] The functional basis for this toxic effect is now understood: the synergy between fipronil and the pathogenic fungus induces changes in male bee physiology leading to infertility.[30] A 2013 report by the European Food Safety Authority identified fipronil as "a high acute risk to honeybees when used as a seed treatment for maize" and on July 16, 2013, the EU voted to ban the use of fipronil on maize and sunflowers within the EU. The ban took effect at the end of 2013.[31][32]

Pharmacodynamics

Fipronil acts by binding to allosteric sites of GABAA receptors and GluCl receptors (of insects) as an antagonist (a form of noncompetitive inhibition). This prevents the opening of chloride ion channels normally encouraged by GABA, reducing the chloride ions' ability to lower a neuron's membrane potential. This results in an overabundance of neurons reaching action potential and likewise CNS toxicity via overstimulation.[33][34][35][36]

Acute oral LD50 (rat) 97 mg/kg
Acute dermal LD50 (rat) >2000 mg/kg

In mammals (including humans) fipronil overdose is characterized by vomiting, agitation, and seizures. Intravenous or intramuscular benzodiazepines are a useful antidote.[37][38]

History

Development

Fipronil was discovered and developed by Rhône-Poulenc between 1985 and 1987, and placed on the market in 1993 under the B2 U.S. patent 5,232,940 B2. Between 1987 and 1996, fipronil was evaluated on more than 250 insect pests on 60 crops worldwide, and crop protection accounted for about 39% of total fipronil production in 1997. Since 2003, BASF holds the patent rights for producing and selling fipronil-based products in many countries.

2017 fipronil eggs contamination

Main article: 2017 fipronil eggs contamination

The 2017 fipronil eggs contamination is an incident in Europe and South Korea involving the spread of

Chicken eggs were found to contain fipronil and distributed to 15 European Union countries, Switzerland, and Hong Kong.[39][40] Approximately 700,000 eggs are thought to have reached shelves in the UK alone.[41]
Eggs at 44 farms in Taiwan were also found with excessive fipronil levels.[42]

See also

References

  1. ^ a b "Compound Summary | 5-Amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-1H-pyrazole-3-carbonitrile". PubChem. Bethesda, Md.: National Library of Medicine. n.d.
  2. ^ "Safety Date Sheet" (PDF). Santa Cruz Biotechnology, Inc. 23 April 2019. SC-201546 - Fipronil. Retrieved 30 October 2023.
  3. S2CID 12654353
    .
  4. ^ Todd-Jenkins, Karen (18 June 2017). "Perception Versus Reality: Insecticide Resistance in Fleas". American Veterinarian. 2 (3). Archived from the original on 11 April 2020.{{cite journal}}: CS1 maint: unfit URL (link)
  5. ISBN 978-0-7020-2858-8
    .
  6. ^ a b c d e f g h "New Pesticide Fact Sheet". Office of Pesticide Programs; Office of Prevention, Pesticides, and Toxic Substances; United States Environmental Protection Agency. May 1996. EPA-737-F-96-005. Retrieved 30 October 2023 – via nepis.epa.gov.
  7. ^ Keigwin, Richard C. Jr. (6 May 2019). "Quarantine exemption under the provisions of Section 18 of the Federal Insecticide, Fungicide and Rodenticide Act" (PDF). Letter to Texas Department of Agriculture. United States Environmental Protection Agency. Retrieved 30 October 2023 – via Texasagriculture.gov.
  8. ^ "Wasp Warfare" (PDF). Revive Rotoiti. No. 24. St Arnaud: Department of Conservation; New Zealand Government. Autumn 2011. p. 2. Retrieved 30 October 2011.
  9. ^ Neal, Tracy (10 February 2016). "War on wasps in Abel Tasman". RNZ. Radio New Zealand. Retrieved 30 October 2023.
  10. ^ "Vespex: Making wide-area wasp control a reality - WWF's Conservation Innovation Awards". wwf-nz.crowdicity.com. Archived from the original on 2 August 2017. Retrieved 5 March 2016.
  11. ^ "Wasp control Using Vespex". Department of Conservation; New Zealand Government. n.d. Retrieved 30 October 2023.
  12. ^ "Argentine Ants". Department of Conservation; New Zealand Government. n.d. Retrieved 30 October 2023.
  13. ^ "Vet Strength Flea & Tick Treatments for Cats & Dogs | FRONTLINE". uk.frontline.com. Retrieved 26 June 2023.
  14. ^ "Fipronil Toxicity: Keep Flea Products Away from Rabbits". Veterinary Medicine at Illinois. Retrieved 20 November 2023.
  15. PMID 8917493
    .
  16. ^ a b Jackson, D.; Cornell, C. B.; Luukinen, B.; Buhl, K.; Stone, D. (2009). "Fipronil Technical Fact Sheet". National Pesticide Information Center, Oregon State University Extension Services. Retrieved 30 October 2023.
  17. ^
    better source needed
    ]
  18. better source needed
    ]
  19. ^ "Contaminant Candidate List 5 – CCL 5". United States Environmental Protection Agency. n.d. Retrieved 30 October 2023.
  20. ISBN 978-0-692-77499-1
    .
  21. ISSN 1349-0923
    . Retrieved 30 October 2023.
  22. ^ Kirby, Alex (27 June 2000). "Anti-locust drive 'created havoc'". Sci/Tech. BBC News. Retrieved 30 October 2023.
  23. S2CID 35297535
    .
  24. PMID 11561837
    .
  25. PMID 22392920
    .
  26. ^ Kissling, Elise; BASF SE (2003). "BASF statement regarding temporary suspension of sales of crop protection products containing fipronil in France" (Press release).[dead link]
  27. ^ a b "Fipronil" (PDF). National Pesticide Telecommunications Network; Oregon State University. n.d. p. 3. Retrieved 30 October 2023 – via Livingwithbugs.com.
  28. ^ Lima, Pedro (n.d.). "Abelhas com microchip". Globo Rural (in Portuguese). Archived from the original on 12 January 2010.
  29. PMID 22442753
    . Article number: 326.
  30. PMID 28819220
    . Article number: 8556.
  31. ^ "EFSA assesses risks to bees from fipronil" (Press release). European Food Safety Authority. 27 May 2013. Retrieved 30 October 2023.
  32. ^ Carrington, Damian (16 July 2013). "EU to ban fipronil to protect honeybees". The Guardian. London.
  33. doi:10.1006/pest.1993.1035
    .
  34. PMID 11489356
    .
  35. ISBN 978-0-397-51820-3
    .
  36. ISSN 0259-2517
    . M-84.
  37. ISBN 978-0-12-370467-2
    .
  38. PMID 15641641
    .
  39. ^ "Eggs containing fipronil found in 15 EU countries and Hong Kong". BBC News. 11 August 2017. Retrieved 30 October 2023.
  40. ^ "EU: 17 nations get tainted eggs, products in growing scandal". ABC News. Associated Press. Archived from the original on 11 August 2017.
  41. ^ Boffey, Daniel (11 August 2017). "Egg contamination scandal widens as 15 EU states, Switzerland and Hong Kong affected". The Guardian. Retrieved 11 August 2017.
  42. ^ "Eggs at 44 farms in Taiwan found with excessive insecticide levels". Taiwan News. 26 August 2017. Archived from the original on 26 August 2017. Retrieved 26 August 2017.

External links

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