Endosulfan: Difference between revisions

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| PPhrases = {{P-phrases|264|270|273|301+310|301+312|321|330|391|405|501}}
| PPhrases = {{P-phrases|264|270|273|301+310|301+312|321|330|391|405|501}}
| FlashPt = noncombustible
| FlashPt = noncombustible
| FlashPt_notes = <ref name=PGCH/>
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Revision as of 17:42, 3 April 2022

Endosulfan
Skeletal formula with undefined stereochemistry at the sulfur atom
Ball-and-stick model
Names
IUPAC name
6,7,8,9,10,10-Hexachloro-1,5,5a,6,9,9a-hexahydro- 6,9-methano-2,4,3-benzodioxathiepine-3-oxide
Other names
Benzoepin, Endocel, Parrysulfan, Phaser, Thiodan, Thionex
Identifiers
3D model (
JSmol
)
1262315
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
100.003.709 Edit this at Wikidata
EC Number
  • 204-079-4
KEGG
RTECS number
  • RB9275000
UNII
UN number 2761
  • InChI=1S/C9H6Cl6O3S/c10-5-6(11)8(13)4-2-18-19(16)17-1-3(4)7(5,12)9(8,14)15/h3-4H,1-2H2/t3-,4-,7-,8+,19+/m0/s1 checkY
    Key: RDYMFSUJUZBWLH-QDLMHMFQSA-N checkY
  • InChI=1/C9H6Cl6O3S/c10-5-6(11)8(13)4-2-18-19(16)17-1-3(4)7(5,12)9(8,14)15/h3-4H,1-2H2
    Key: RDYMFSUJUZBWLH-UHFFFAOYAH
  • InChI=1/C9H6Cl6O3S/c10-5-6(11)8(13)4-2-18-19(16)17-1-3(4)7(5,12)9(8,14)15/h3-4H,1-2H2/t3-,4-,7-,8+,19+/m0/s1
    Key: RDYMFSUJUZBWLH-QDLMHMFQBI
  • Cl[C@@]3(Cl)[C@]1(Cl)C(/Cl)=C(/Cl)[C@@]3(Cl)[C@H]2[C@@H2]OS(=O)O[C@@H2][C@H]12
Properties
C9H6Cl6O3S
Molar mass 406.90 g·mol−1
Appearance Brown crystals[1]
Odor slight sulfur dioxide odor[1]
Density 1.745 g/cm3
Melting point 70 to 100 °C (158 to 212 °F; 343 to 373 K)
Boiling point decomposes[1]
0.33 mg/L
Vapor pressure 0.00001 mmHg (25 °C)[1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
T, Xi, N
GHS labelling:
GHS06: ToxicGHS07: Exclamation markGHS09: Environmental hazard
Danger
H301, H302, H410
P264, P270, P273, P301+P310, P301+P312, P321, P330, P391, P405, P501
NFPA 704 (fire diamond)
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
Flash point noncombustible[1]
NIOSH (US health exposure limits):
PEL (Permissible)
none[1]
REL (Recommended)
TWA 0.1 mg/m3 [skin][1]
IDLH
(Immediate danger)
N.D.[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Endosulfan is an off-

Makhteshim Agan and several manufacturers in India and China. Although, the Supreme Court had, by an order dated 13.05.2011, put a ban on the production and sale of endosulfan in India till further orders.[10]

Uses

Endosulfan has been used in agriculture around the world to control insect pests including

aphids, leafhoppers, Colorado potato beetles and cabbage worms.[11] Due to its unique mode of action, it is useful in resistance management; however, as it is not specific, it can negatively impact populations of beneficial insects.[12] It is, however, considered to be moderately toxic to honey bees,[13] and it is less toxic to bees than organophosphate insecticides.[14]

Production

The World Health Organization estimated worldwide annual production to be about 9,000 tonnes (t) in the early 1980s.[15] From 1980 to 1989, worldwide consumption averaged 10,500 tonnes per year, and for the 1990s use increased to 12,800 tonnes per year.

Endosulfan is a derivative of

isomers arising from the pyramidal stereochemistry of the tetravalent sulfur. α-Endosulfan is the more thermodynamically stable of the two, thus β-endosulfan irreversibly converts to the α form, although the conversion is slow.[16][17]

History of commercialization and regulation

Health effects

Endosulfan is alleged to be responsible for many fatal pesticide poisoning incidents around the world by NGOs opposing pesticide usage.[39] Endosulfan is also a xenoestrogen—a synthetic substance that imitates or enhances the effect of estrogens—and it can act as an endocrine disruptor, causing reproductive and developmental damage in both animals and humans.[40] It has also been found to act as an aromatase inhibitor.[40] Whether endosulfan can cause cancer is debated. With regard to consumers' intake of endosulfan from residues on food, the Food and Agriculture Organization of United Nations has concluded that long-term exposure from food is unlikely to present a public health concern, but short-term exposure can exceed acute reference doses.[41]

Toxicity

Endosulfan is acutely

chronic endosulfan exposure are at risk of rashes and skin irritation.[14]

EPA's acute reference dose for dietary exposure to endosulfan is 0.015 mg/kg for adults and 0.0015 mg/kg for children. For chronic dietary expsoure, the EPA references doses are 0.006 mg/(kg·day) and 0.0006 mg/(kg·day) for adults and children, respectively.[14]

Endocrine disruption

teratogen (an agent that causes birth defects), though it has significant teratogenic effects in laboratory rats.[48] A 2009 assessment concluded the endocrine disruption in rats occurs only at endosulfan doses that cause neurotoxicity.[49]

Reproductive and developmental effects

Some studies have documented that endosulfan can also affect human development. Researchers studying children from many villages in

Birth defects of the male reproductive system, including cryptorchidism, were also more prevalent in the study group. The researchers concluded, "our study results suggest that endosulfan exposure in male children may delay sexual maturity and interfere with sex hormone synthesis."[50] Increased incidences of cryptorchidism have been observed in other studies of endosulfan exposed populations.[51][52]

A 2007 study by the California Department of Public Health found that women who lived near farm fields sprayed with endosulfan and the related organochloride pesticide dicofol during the first eight weeks of pregnancy are several times more likely to give birth to children with autism.[53] However a 2009 assessment concluded that epidemiology and rodent studies that suggest male reproductive and autism effects are open to other interpretations, and that developmental or reproductive toxicity in rats occurs only at endosulfan doses that cause neurotoxicity.[49]

Cancer

Endosulfan is not listed as known, probable, or possible carcinogen by the EPA, IARC, or other agencies. No epidemiological studies link exposure to endosulfan specifically to cancer in humans, but in vitro assays have shown that endosulfan can promote proliferation of human breast cancer cells.[54] Evidence of carcinogenicity in animals is mixed.[18]

In a 2016 study[55] by the Department of Biochemistry, Indian Institute of Science, Bangalore published in Carcinogenesis, endosulfan was found to induce reactive oxygen species (ROS) in a concentration and time-dependent manner leading to double-stranded breaks in the DNA and also found to favour subsequent erroneous DNA repair.

Environmental fate

Endosulfan is a ubiquitous environmental contaminant. The chemical is

Sahara Desert collected in the Caribbean after being blown across the Atlantic Ocean.[58] The compound has been shown to be one of the most abundant organochlorine pesticides in the global atmosphere.[57]

The compound breaks down into endosulfan sulfate, endosulfan diol, and endosulfan furan, all of which have structures similar to the parent compound and, according to the EPA, "are also of toxicological concern…The estimated half-lives for the combined toxic residues (endosulfan plus endosulfan sulfate) [range] from roughly 9 months to 6 years." The EPA concluded, "[b]ased on environmental fate laboratory studies, terrestrial field dissipation studies, available models, monitoring studies, and published literature, it can be concluded that endosulfan is a very persistent chemical which may stay in the environment for lengthy periods of time, particularly in acid media." The EPA also concluded, "[e]ndosulfan has relatively high potential to

amphibians; low levels have been found to kill tadpoles.[59]

In 2009, the committee of scientific experts of the Stockholm Convention concluded, "endosulfan is likely, as a result of long range environmental transport, to lead to significant adverse human health and environmental effects such that global action is warranted."[60] In May 2011, the Stockholm Convention committee approved the recommendation for elimination of production and use of endosulfan and its isomers worldwide. This is, however, subject to certain exemptions. Overall, this will lead to its elimination from the global markets.[61]

Status by region

India

The yellow toxicity label for endosulfan in India

Although classified as a

Kasargod District (of Kerala) were publicised.[63][64] This inspired protests, and the pesticide was banned in Kerala as early as 2001, following a report by the National Institute of Occupational Health. In the Stockholm Convention on Persistent Organic Pollutants of 2011, when an international consensus arose for the global ban of the pesticide, India opposed this move due to pressure from the endosulfan manufacturing companies.[21][65] This flared up the protest,[66][67][68] and while India still maintained its stance, the global conference decided on a global ban, for which India asked a remission for 10 years. Later, on a petition filed in the Supreme Court of India, the production, storage, sale and use of the pesticide was temporarily banned on 13 May 2011, and later permanently by the end of 2011.[69][70]

The

B.S. Yeddyurappa and members of the Cabinet for approving the ban.[71]

Rajendra Singh Rana has written a letter to

Mrs. Vibhavari Dave, local leader and

Member of Legislative Assembly (MLA), from Bhavnagar, Gujarat, voiced her concerns on the impact of ban of endosulfan on families and workers of Bhavnagar. She was a part of the delegation with Bhavnagar MP, Rajendra Singh Rana, which submitted a memorandum to the district collector's office to withdraw the NIOH report calling for ban of endosulfan.[74][75]
The Pollution Control Board of the Government of Kerala, prohibited the use of endosulfan in the state of Kerala on 10 November 2010.[76] On February 18, 2011, the Karnataka government followed suit and suspended the use of endosulfan for a period of 60 days in the state.[77] Indian Union Minister of Agriculture Sharad Pawar has ruled out implementing a similar ban at the national level despite the fact that endosulfan has banned in 63 countries, including the European Union, Australia, and New Zealand.[78]

The

genotoxic. The highlight of this report is the farmer exposure study based on analysis of their blood reports for residues of endosulfan and the absence of any residues. This corroborates the lack of residues in worker-exposure studies.[79][80]

The Supreme Court passed interim order on May 13, 2011, in a Writ Petition filed by Democratic Youth Federation of India, (DYFI), a youth wing of Communist Party of India (Marxist) in the backdrop of the incidents reported in Kasargode, Kerala, and banned the production, distribution and use of endosulfan in India because the pesticide has debilitating effects on humans and the environment.[69][70] The Centre for Science and Environment (CSE) welcomed this order, and called it a 'resounding defeat' for the pesticide industry which has been promoting this deadly toxin. A 2001 study by CSE had linked the aerial spraying of the pesticide with the growing health disorders in Kasaragode. However some scientists have called this study flawed.[81] KM Sreekumar of the Padannakkad College of Agriculture in Kasargod and Prathapan KD of the Kerala Agricultural University in a paper claim that the extensive spread of diseases in the area cannot be solely attributed to the use of Endosulfan and criticised the CSE for inflating the level of endosulfan reported in the blood.[82] In July 2012, the Government asked the Supreme Court to allow use of the pesticide in all states except Kerala and Karnataka, as these states are ready to use it for pest control.[83] But the court did not consider this request. India will phase out all endosulfan use by 2017.[84] On January 10, 2017, The Supreme Court ordered the State Governments to release the remaining undisbursed payment of compensation quantified (Rupees Five lakhs each) to all the affected persons within three months.[85]

New Zealand

Endosulfan was banned in New Zealand by the Environmental Risk Management Authority effective January 2009[33] after a concerted campaign by environmental groups and the Green Party.

Philippines

A shipment of about 10

tonnes of endosulfan was illegally stowed on the ill-fated MV Princess of the Stars, a ferry that sank off the waters of Romblon (Sibuyan Island), Philippines, during a storm in June 2008. Search, rescue, and salvage efforts were suspended when the endosulfan shipment was discovered, and blood samples from divers at the scene were sent to Malaysia for analysis.[86] The Department of Health of the Philippines has temporarily banned the consumption of fish caught in the area.[87] Endosulfan is classified as a "Severe Marine Pollutant" by the International Maritime Dangerous Goods Code.[20]

United States

Endosulfan use in the US in pounds per square mile by county in 2013
Endosulfan use in the US in pounds per square mile by county in 2002

In the United States, endosulfan is only registered for agricultural use, and these uses are being phased out.

apples according to the EPA.[88] The EPA estimates that 626 thousand kg of endosulfan were used annually from 1987 to 1997.[14] The US exported more than 140,000 lb of endosulfan from 2001 to 2003, mostly to Latin America,[89]
but production and export has since stopped.

In California, endosulfan contamination from the

Sierra Nevada.[90] In Florida, levels of contamination the Everglades and Biscayne Bay are high enough to pose a threat to some aquatic organisms.[91][92][93]

In 2007, the EPA announced it was rereviewing the safety of endosulfan.

Makhteshim Agan, and a complete ban on the compound.[7]

An official statement by

Makhteshim Agan of North America (MANA) states, "From a scientific standpoint, MANA continues to disagree fundamentally with EPA's conclusions regarding endosulfan and believes that key uses are still eligible for re-registration." The statement adds, "However, given the fact that the endosulfan market is quite small and the cost of developing and submitting additional data high, we have decided to voluntarily negotiate an agreement with EPA that provides growers with an adequate time frame to find alternatives for the damaging insect pests currently controlled by endosulfan."[96][97]

Australia

Australia banned endosulfan on October 12, 2010,[98][99][100] with a two-year phase-out for stock of endosulfan-containing products.[98] Australia had, in 2008, announced endosulfan would not be banned.[101] Citing New Zealand's ban, the Australian Greens called for "zero tolerance" of endosulfan residue on food.[5]

Taiwan

US apples with endosulfan are now allowed to be exported to Taiwan, although the ROC government denied any US pressure on it.[102]

Brazil

Brazil decreed total ban of the substance from July 31, 2013, being forbidden imports of the product from July 31, 2011, date in which national production and utilization begins to be phased out gradually.[103]

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