Adverse Effects
Tributyltin fluoride (TBTF)
CAS No.
1983-10-4

 
 

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Activity: Antifoulant, Fungicide, Microbiocide (Organotin)
Structure:

Adverse Effects:
Brain
Developmental / Reproductive
Diabetes
Eye

Endocrine: Suspected Disruptor
Environmental

A little history...
In the early 1960s, both tributyltin oxide (TBTO) and TBT fluoride were tested, mainly in Africa, as molluscicides against several freshwater snail species that are vectors of the disease schistosomiasis, the snails being the intermediate hosts of the trematode parasite. This use led to the introduction of TBT, during the mid 1960s, as an antifouling paint on boats. At the same time TBT compounds were being registered as wood preservatives (the first registration was in 1958).
Ref: Tributyltin Compounds. Environmental Health Criteria 116. International Programme on Chemical Safety. http://www.inchem.org/documents/ehc/ehc/ehc116.htm


Table 5-1. Current U.S. Manufacturers of Selected Tin Compounds
ATOFINA Chemicals, Inc. Specialty Chemicals Division Carrollton, Kentucky
Derived from SRI 2003. SRI reports production of chemicals produced in commercial quantities (defined as exceeding 5,000 pounds or $10,000 in value annually) by the companies listed.
Ref: DRAFT TOXICOLOGICAL PROFILE FOR TIN AND COMPOUNDS. U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES. Public Health Service Agency for Toxic Substances and Disease Registry. September 2003.

http://www.atsdr.cdc.gov/toxprofiles/tp55.pdf

Table 14. Acute toxicity of tributyltin [TBT] to RAT
Ref: Tributyltin Compounds. Environmental Health Criteria 116. International Programme on Chemical Safety. http://www.inchem.org/documents/ehc/ehc/ehc116.htm
TBT Route Observation period (days) LD50 (mg/kg body weight) Reference
oxide oral 7 194 (165-227)b Elsea & Paynter (1958)
oxide oral 7 148 (113-195)c Elsea & Paynter (1958)
oxide oral 7 180 (132-228) Truhaut et al. (1976)
oxide oral 21 197 (137-273) Funahashi et al. (1980)
oxide oral   127 Schweinfurth (1985)
oxide ip 14 20 (18-21) Poitou et al. (1978)
oxide oral   234 Sheldon (1975)
fluoride oral   200 Sheldon (1975)
fluoride oral 14 94 Schweinfurth (1985)
chloride oral 14 122 Schweinfurth (1985)
acetate oral   113.5 Klimmer (1969)
benzoate oral   141 Klimmer (1969)
benzoate oral 14 99/203 Schweinfurth (1985)
oleate oral   225 Klimmer (1969)
linoleate oral 14 190 Schweinfurth (1985)
abietate oral 14 158 Schweinfurth (1985)
naphthenate oral 14 224 Schweinfurth (1985)

b Application as aqueous suspension.
c Application in corn oil.


From Science Direct

Marine Chemistry; Volume 85, Issues 3-4 , March 2004, Pages 157-167

Speciation of trialkyltin(IV) cations in natural fluids

Claudia Foti (a), Antonio Gianguzza (b), Demetrio Milea (a), Frank J. Millero (c) and Silvio Sammartano (a)

a Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone 31, Vill. S. Agata di Messina, 98166, Messina, Italy
b Dipartimento di Chimica Inorganica e Chimica Analitica "Stanislao Cannizzaro", Università di Palermo, Viale delle Scienze, Parco d'Orleans, 90128, Palermo, Italy
c Rosenstiel School of Marine and Atmospheric Science, University of Miami, 4600 Rickenbacker Causeway, Miami, FL 33149, USA

The hydrolysis of (CH3)3Sn+, (C2H5)3Sn+ and (C3H7)3Sn+ has been studied in a Synthetic Seawater (SSW) ionic medium simulating the major composition of natural seawater, at different salinities (5≤S≤45), and at t=25 °C. Interactions with anionic components of SSW, considered as single sea salt, are determined by means of a complex formation model. By potentiometric measurements (ISE-H+ and ISE-F- electrodes), the model has been extended to also consider interactions of organotins with carbonate and fluoride ions, which are other important components of seawater. Literature and new values of hydrolysis constants in different ionic media (NaNO3, NaCl, Na2SO4 and SSW) are used to determine Pitzer interaction parameters. Predictive equations for the calculation of unknown hydrolysis constants and Pitzer interaction parameters of other trialkyltin(IV) cations, such as tributyltin(IV), are proposed.

Excerpts:

... Concentrations of fluoride and bicarbonate+carbonate anions are much lower than those of other macro-components of seawater (0.7 and 2.7 mmol l-1 for fluoride and bicarbonate+carbonate, respectively, in seawater, S=35), such as chloride and sulfate, but their complexes are often stronger. Moreover, since carbonates and fluorides play a very important role in many geo-chemical and bio-chemical processes in seawater, their contribution to the speciation studies of organotin compounds in that medium cannot be neglected. ...

3.4. Interactions with carbonate and fluoride
In spite of the amount of literature data concerning the interactions of fluoride and carbonate ligands with most of the metal ions, no data are reported on their interactions with organotin(IV) cations. In order to give a complete picture of trialkyltin(IV) cations speciation in natural fluids, we studied interactions of (CH3)3Sn+ with fluoride and carbonate. First, it was necessary to determine the protonation constants of fluoride and carbonate anions. Results are reported in Table 4, in the ionic strength range 0<I≤1.0 mol l-1 (for NaCl) and at t=25 °C. As can be seen, in the fluoride system, the formation constant of the binuclear species HF2- is also reported.

Potentiometric data (ISE-H+ and ISE-F- electrodes) of (CH3)3Sn+ cation in the presence of NaF and Na2CO3 salts, indicate the formation of (CH3)3SnF0, (CH3)3Sn(OH)F-, and (CH3)3Sn(OH)CO32- species. These formation constants are reported in Table 5 and Table 6, at different ionic strengths in NaCl or NaNO3 at t=25 °C. As expected, the stability of fluoride species is greater than the chloride species [(CH3)3SnCl0: log K=-0.6, at I=0 mol l-1] (Fig. 3a). The formation of the (CH3)3SnF0 species is dominant, whilst, the mixed (CH3)3Sn(OH)F- species is negligible. The mixed (CH3)3Sn(OH)CO32- species is formed in significant percentages over pH=9, as can be seen in Fig. 4a for the speciation diagram of (CH3)3Sn+ vs. pH.

Brain (click on for all fluorinated pesticides)

... In rats given a single oral dose of 40 mg/kg tributyltin fluoride (15 mg Sn/kg), transient elevations in tributyltin, dibutyltin, monobutyltin, and inorganic tin were observed in brain and liver over the 8-day period following the dose, indicating that dealkylation had occurred (Iwai et al. 1981, see Section 3.4.3). ..
Ref: DRAFT TOXICOLOGICAL PROFILE FOR TIN AND COMPOUNDS. U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES. Public Health Service Agency for Toxic Substances and Disease Registry. September 2003.

http://www.atsdr.cdc.gov/toxprofiles/tp55.pdf

• Defintion:
Dealkylation: The removing of alkyl groups from a compound.

Developmental / Reproductive (click on for all fluorinated pesticides)

-- Lee and Xu (1984) reported that exposure to 25 mgl TPT acetate or TPTF caused 46-47% reduction in 1-methyladenine induced germnal vesicle breakdown for oocytes of the starfish Patiro pectinefera. Having recorded such an effect on mitosis, it is postulated that fertilization and developmental effects would be induced in this species (page 46)
-- Cotta-Ramusino and Doci (1987) conducted tests using TPT acetate to assess the sensitivity of some aquatic organisms. The least senstive of those tested was Asellus aquaticus, which gave a 48 h TLm of 1100 ugl. In contrast to this, Linden et al (1979) found that the harpacticoid Nitrocra spinipes was very sensitive to TPT. The authors established a 96 hr LC50 of 8 ugl TPTF (page 55).
Ref: Evaluation on: A Review of the Environmental Effects of Triorganotin Compounds. October 1994. Issue No. 111. Prepared by: The Health and Safety Executive, Biocides & Pesticides Assessment Unit. Available from: Department for Environment, Food and Rural Affairs, Pesticides Safety Directorate, Mallard House, Kings Pool, 3 Peasholme Greene, York YO1 7PX. Available online at http://www.pesticides.gov.uk/citizen/evaluations/evallist_alphabet.htm

• Excellent "Mitosis animation" available at (scroll down): http://www.biology.arizona.edu/cell_bio/tutorials/cell_cycle/cells3.html

Diabetes (click on for all fluorinated pesticides)

Pub Med abstract: ... These results suggest that hyperlipidemia induced in rabbits by tributyltin fluoride is due to decreased LPL [Lipoprotein lipase] activity. The decrease in LPL activity seems to be related to the inhibition of insulin release from islets by TBTF.
Ref:
[Properties and mechanism of hyperlipidemia induced in rabbits by tributyltin fluoride] by Matsui H, Wada O, Manabe S, Ono T, Iwai H, Fujikura T. Sangyo Igaku 1982 Mar;24(2):163-71.

Hyperlipidemia = High Cholesterol

Endocrine: Suspected Disruptor (click on for all fluorinated pesticides)

Table 9 Organotin compounds suspected of being endocrine disruptors.
Common name CAS-no. Y /g l 1 log P ow
Bis(tributyltin)oxide 56-35-9 8000 10 000 3.62
Triphenyltinhydroxide 76-87-9 400 -
Tributyltin fluoride 1983-10-4 - -
Ysat :Water solubility in seawater at 22 C.
P ow :Partition coefficient octanol/water.
Ref: Endocrine Disruptors in the Environment (IUPAC Technical Report). Prepared for publication by J.LINTELMANN et al. INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY. Pure Appl.Chem.,Vol.75,No.5,pp.631 681,2003. 2003 IUPAC. Full report available at
http://www.iupac.org/publications/pac/2003/pdf/7505x0631.pdf

Suspected Endocrine Disruptor
Ref: June 14, 2001 - Implementation of the Community Strategy for Endocrine Disruptors - a range of substances suspected of interfering with the hormone systems of humans and wildlife. Communication from the Commission to the Council and the European Parliament. Commission of the European Communities, Brussels COM (2001) 262 final.

http://www.fluoridealert.org/pesticides/Endocrine.Disruptors.EC2001.pdf
- More information available at:
http://europa.eu.int/eur-lex/en/com/cnc/2001/com2001_0262en01.pdf

Eye (click on for all fluorinated pesticides)

Abstract: The acute and chronic toxicities of anti fouling coatings were studied in animals. The acute oral median lethal dose (LD50) was determined for bis(tri-n-butyltin)oxide (56359), tributyltin-fluoride (1983104) and triphenyltin-fluoride (379522) for rats and rabbits... All were severe or extreme eye irritants and most were moderate to severe skin irritants.
Ref:
1975 Journal of Paint Technology, Vol. 47, No. 600, pages 54-58. Effects Of Organotin Anti-Fouling Coatings On Man And His Environment by Sheldon AW.
http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~AAAjCaaO4:1

Environmental (click on for all fluorinated pesticides)

Tributyltin fluoride: Acute Aquatic Ecotoxicity Summaries for Tributyltin fluoride on All Taxa Groups.
Ref: PAN Pesticides Database - Chemical Toxicity Studies on Aquatic Organisms.
http://www.pesticideinfo.org/List_AquireAcuteSum.jsp?CAS_No=1983-10-4&Rec_Id=PC34614
Common Name Scientific Name Avg Species LC50 (ug/L) LC50 Std Dev Number of Studies Avg Species Rating
Amphibians
Frog Rana temporaria
30.0
-
1
Very Highly Toxic
Crustaceans
Fiddler crab Uca pugilator
800.0
-
1
Highly Toxic
Fish
Channel catfish Ictalurus punctatus
8.15
3.85
2
Very Highly Toxic
Bluegill Lepomis macrochirus
7.35
3.65
2
Very Highly Toxic
Rainbow trout,donaldson trout Oncorhynchus mykiss
11.2
7.80
1
Very Highly Toxic

Shell thickening. Alzieu et al. (1982) reported that adult oysters (Crassostrea gigas) developed gel centres in the shell when they were exposed to TBT fluoride at a concentration of 0.2 g/litre.
Ref: C Alziieu et al. (1982). Influence des peintures antisalissures base d'organostanniques sur la calcification de la coquille de l'huitre Crassostrea gigas. Rev. Trav. Inst. Pches Marit., 45: 101-116.
Ref: Tributyltin Compounds. Environmental Health Criteria 116. International Programme on Chemical Safety.
http://www.inchem.org/documents/ehc/ehc/ehc116.htm

Aquatic acute toxicity values for tributyltin fluoride include a bleak fish 96-hour LC 50 of 2.3 ppb, an algae 72-hour EC50 of 9.3 ppb, and a Harpacticoid copepod 96-hour LC 50 of 0.8 ppb. EPA believes that there is sufficient evidence for listing tributyltin fluoride on EPCRA section 313 pursuant to EPCRA section 313(d)(2)(C) based on the available environmental toxicity data.
Ref: USEPA/OPP. Support Document for the Addition of Chemicals from Federal Insecticide, Fungicide, Rodenticide Act (FIFRA) Active Ingredients to EPCRA Section 313. U. S. Environmental Protection Agency, Washington, DC (1993). As cited by US EPA in: Federal Register: January 12, 1994. Part IV. 40 CFR Part 372. Addition of Certain Chemicals; Toxic Chemical Release Reporting; Community Right-to-Know; Proposed Rule


Tributyltin Compounds. The acute toxicity of tributyltin compounds has been studied on several species of freshwater fish. LC50s range from 6 to 240 ugl TBT. The most sensitive species was the cyprinid Alburnus alburnus with a 96 hr LC50 of 6-8 ugl TBTF. When the same species was tested against TBTO, a 96 hr LC50 of 15 ugl was reported (Linden et al. 1979). - page 57.

In soils, risk of TBT contamination comes essentially from TBTO and TBTF and their use as wood preservatives. - page 4.

Acute toxicity. Tributyltin Compounds ... Adult bivalves are more resistant to short term exposure to TBT than long term exposure, since they can isolate themselves from their environment by closing their valves. For example, the pacific oyster showed tolerance of short term exposure to high concentrations of TBT (96hr LC50 290 ugl) yet this same species showed 30% mortality after 113 days exposure to 0.2 ugl TBT and 100% mortality after both 30 days exposure to 2.0 ugl TBT and 35 days exposure to 0.5 ugl TBTF (Thain, 1983; Heral et al. 1983; Alzieu et al. 1981) - ... Histopathological studies on adult pacific oysters (Crassostrea gigas) have revealed that the digestive gland is the primary target organ for TBT toxicity (Chagot et al. 1990). These studies revealed that histological modification of cells occurred in pacific oysters for 2 weeks to concentrations as low as 0.002 ugl TBTF. Such modifications were reversible within 6 days during depuration. However, pacific oysters exposed for 2 weeks to 0.131 ugl TBTF showed more severe cell damage (limited necrosis) and no recovery was observed in gill epithelium 21 days after exposure (Chagot et al. 1990)... - pages 26-27.

6.2.2.4 Shell thickening. Tributyltin Compounds. ... Chagot et al (1990) reported anomalies in shell calcification for 13% of adult pacific oysters exposed to 0.002 ugl TBTF or less, and it was concluded that 0.002 ugl TBT was the threshold limit for induction of chambers in the shells of such oysters. 47% of pacific oysters exposed to 0.065 ugl TBTF showed shell chamber formation. It was observed that such shell chamber formation did not occur during the 18 day accumulation (exposure period) phase but during the 21 day depuration phase (Chagot et al. 1990)... - page 35.

Ref: Evaluation on: A Review of the Environmental Effects of Triorganotin Compounds. October 1994. Issue No. 111. Prepared by: The Health and Safety Executive, Biocides & Pesticides Assessment Unit. Available from: Department for Environment, Food and Rural Affairs, Pesticides Safety Directorate, Mallard House, Kings Pool, 3 Peasholme Greene, York YO1 7PX. Available online at http://www.pesticides.gov.uk/citizen/evaluations/evallist_alphabet.htm

 
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