Tributyltin Oxide Research Articles

Reproductive and histopathological effects of long‐term experimental exposure to bis(tributyltin)oxide (TBTO) on the three‐spined stickleback, Gasterosteus aculeatus Linnaeus

Three‐spined sticklebacks, Gasterosteus aculeatus Linnaeus, were exposed to 0, 0.1, 1.0, 2.5 and 10 μg bis(tributyltin)oxide (TBTO) 1−1 for up to 7.5 months in a flow‐through system of sea water. As early as 4 weeks after the start of the experiment, fish from the 10 μg TBTO 1−1 group showed diminishing appetite, increasing lethargy and opaque eyes. The mortality in this group after 2 months of exposure was 80%. No significant differences between the control and the exposed groups were noted concerning fecundity, hatched fry and frequencies of malformed fry. The gonad somatic index (GSI) was determined before and during the spawning period. GSI in control fish increased significantly, while that in the exposed groups remained unchanged between the two sampling occasions. Structural examination of the gills from fish exposed for 2 months to 10 μg TBTO I−1 revealed fusion between secondary lamellae and gradual cell degeneration. The chloride cells were characterized by degenerating mitochondria. Hepatocytes in fish exposed to 2.5 and 10 μg TBTO I−1 contained an increased number of lipid‐containing vacuoles and the nucleoli were disorganized and fragmented.

Marine pollution bioassay by using sea urchin eggs in the Tanabe Bay, Wakayama Prefecture, Japan, 1970–1987

The results of 18 years bioassays of the water at the Seto Marine Biological Lavoratory and around the Hatakejima island, Shirahama, Wakayama Pref., was shown according to the methods of Kobayashi's. During 1982 and 1987, very polluted water (Grade 3–5)was observed around Hatakejima island and Tsunashirazu cove in early autumn to winter. As these phenomena differed from the tendency of polluted water observed mainly in summer of each year, the presence of very polluted water mass was suggested at that time, such as containing tributyltin oxide(TBTO).

119Sn-NMR Study on Bis(Tri-Butyltin)oxide Derivatives of Phenolic Compounds

Abstract 119Sn-NMR spectroscopy has been utilized in the characterization of various phenolics as their bis(tri-butyltin)oxide, TBTO, derivatives. The present method has been applied both for determination of simple model compounds and for characterization of complex biopolymeric material originating from spent bleach liquor fractionated by an ultrafiltration technique. Based on the large range of 119Sn-NMR chemical shifts of TBTO derivatives of the phenolic compounds and the similar relaxation properties of 119Sn nuclei located in those derivatives, both qualitative and quantitative analytical conclusions can be drawn.

The toxicity of the biocides zineb, nabam and their derivatives to the ship‐fouling diatomAmphora coffeaeformis

The toxicity of the fungicides zineb and nabam has been studied, using the persistent ship‐fouling diatom Amphora coffeaeformis. Growth and oxygen evolution/consumption studies showed that time was required for zineb to exert a toxic effect, suggesting that toxicity may be due to the degradation products 5,6‐dihydro‐3H‐imidazo (2,1‐c)‐1,2,4‐dithiazole‐3‐thione (DIDT) and ethylene diisothiocyanate (EDI). These were found to be more toxic than zineb and nabam, EDI being the most potent of the compounds tested. A marked synergism was observed between zineb and copper (from cuprous oxide and copper thio‐cyanate) and nabam and copper. Zineb and tributyltin oxide (TBTO) showed an antagonistic response. The zineb derivative DIDT and copper showed the most pronounced synergistic effect. EDI and cuprous oxide showed an additive or mildly antagonistic effect.

Immune alterations in rats following subacute exposure to tributyltin oxide

Adult male Fischer 344 rats were dosed by oral gavage with bis(tri- n-butyltin)oxide (TBTO) in peanut oil for 10 consecutive days, at dosages ranging from 1.25 to 15 mg/kg/day. Other groups of rats were dosed daily for 10 days by oral gavage with cyclophosphamide (CY) at dosages ranging from 0.75 to 6 mg/kg/day. These rats served as positive controls for the immune assays employed. The immune function parameters examined included the following: delayed-type hypersensitivity (DTH) and antibody responses to bovine serum albumin (BSA), primary antibody responses to sheep red blood cells (SRBC) and trinitrophenyl lipopolysaccaride (TNP-LPS) and enumeration of splenic lymphocyte populations. The DTH and antibody responses to BSA were not affected by TBTO exposure; however these responses were suppressed in rats dosed with CY at 6 g/kg/day. The plaque forming cell (PFC) response to the T cell-dependent antigen SRBC was enhanced in rats dosed with TBTO at from 5 to 15 mg/kg/day. On the other hand, the PFC response to the T cell-independent antigen TNP-LPS was unaffected by TBTO exposure. Rats dosed with CY had suppressed PFC responses to SRBC and TNP-LPS at dosages of 3 and 6 mg/kg/day, respectively. Enumeration of splenic lymphocyte populations from TBTO-exposed rats revealed a reduction in OX8- but not W3/25- or IgG-positive cells. These results, as well as results from an earlier study from this lab, suggest that T lymphocytes are a primary target for TBTO-induced immune alterations and that the enhancement of the PFC response to SRBC in TBTO-exposed rats may be mediated by alterations in the suppressor (OX8-positive) T lymphocyte population.

Effects of tributyltin oxide on the skeletal structures of developing and regenerating limbs of the axolotl larvae,Ambystoma mexicanum

Effects of tributyltin oxide on the skeletal structures of developing and regenerating limbs of the axolotl larvae,Ambystoma mexicanum

Tributyltin oxide induced alterations in exuvial weight and calcium content of the prawn,Caridina rajadhari

Moulting is the predominent feature of crustaceans. Cyclic cuticle deposition and resorption of calcium from old cuticle occur in relation to the crustacean moult cycle. Prolonged exposure of the prawn,Caridina rajadhari to media containing sublethal doses (0·015, 0·020, 0·025 and 0·040 ppm) of tributyltin oxide led to an apparent increase in dry weight of exuvia as well as an increase in the total quantity of calcium. The increase in weight and calcium content of exuvia was not significant in the initial two moults whereas it was significant (P<0·05) in the third moult when exposed to minimum (0·015 ppm) dose. However significant (P<0·01) rise in both exuvial weight and calcium quantity in the first two moults and highly significant (P<0·001) in the third moult exuvia were observed when exposed to maximum (0·040 ppm) dose. The observed changes in exuvia from prawns exposed to tributyltin oxide might be due to a decrease in the resorption of the old cuticle and/or due to the inhibition of chitinolytic enzymes.

Effects of pentachlorophenol and other chemical preservatives on the health of wood-treating workers in Hawaii

The morbidity and mortality of workers occupationally exposed to wood treating chemicals used in Hawaii for the years 1960 to 1981 were evaluated. The specific chemical exposures investigated were CCA (chromated copper-arsenate), TBTO (tributyl tin oxide) and PCP (pentachlorophenol). Results of detailed medical histories, laboratory and physiological tests, and physical examinations of 88 wood treaters were compared with those of 58 matched controls. The occupationally exposed cases had a significantly higher mean level of urinary PCP as compared to the controls (mean of 174 ppb vs. 35 ppb, micrograms/kg). There were no significant differences between the groups for the other urinary pesticide residues. The medical histories and physical examinations revealed no significant variations between the wood treaters and the comparison group. Review of all organ systems and laboratory data showed no clinically significant differences between exposed and nonexposed cohorts, although elevated hepatic enzymes in both groups merit further study. The results indicated no adverse health effects or increased incidence of mortality resulting from exposure to wood preservative chemicals in wood treaters who had worked in the industry for 0.33 to 26.3 years with a median of 6.5 years. Only 6 deaths were reported, 5 of cardiovascular disease, one of cause undetermined and none of cancer. Total number of deaths were less than the 8 anticipated for this age group.

ChemInform Abstract: Bimetallic Oxidation Catalysts: Oxidations with tert‐Butyl Hydroperoxide Mediated by Bis(tributyltin oxide) Dioxochromium(VI).

AbstractThe reagent system mentioned in the title is employed in the oxidation of activated methylene groups or benzylic alcohols to form the corresponding ketones.

Study of the polycyclotrimerization of 1,6-hexamethylenediisocyanate and gel permeation chromatographic analysis of the products

The cyclotrimerization of 1,6-hexamethylenediisocyanate has been investigated in the presence of bis(tributyl tin)oxide without a solvent in the 353–393 K range by microcalorimetry, IR spectroscopy and gel permeation chromatography. The polycyclotrimerization of hexamethylenediisocyanate was found to be a first-order reaction. The activation parameters have been determined for this reaction. The polycyclotrimerization proceeds with the formation of isocyanurate rings; the monomer and trimer are present in the system up to the end of the reaction.

Immunotoxicity of tributyltin oxide in rats exposed as adults or pre-weanlings

A comparison was made between adult and pre-weanling rats of the immunotoxic effects of subacute dosing with bis(tri- n-butyltin) oxide (TBTO). Adult (9 weeks old) male Fischer rats were dosed by oral gavage with TBTO for 10 consecutive days at 1.25–10 mg/kg per dose or 3 times/week for a total of 10 doses at 5–20 mg/kg per dose. Adults rats similarly dosed by oral gavage with 6 mg/kg per dose cyclophosphamide (CY) served as positive controls. Pre-weanling rats (3–24 days old) were dosed 3 times/week for a total of 10 doses at 2.5, 5 or 10 mg/kg per dose. At various times after dosing rats were evaluated for alterations in body and lymphoid organ weights, mitogen and mixed lymphocyte reaction (MLR) lymphoproliferative (LP) responses, natural killer (NK) cell activity, cytotoxic T lymphocyte (CTL) responses and primary antibody plaque-forming cell (PFC) responses. In adult rats given 10 daily doses of TBTO, thymic involution was observed at a dosage of 2.5 mg/ kg and mitogen responses to Con A and PHA were suppressed at 5 mg/kg. The PFC response was enhanced in adult rats dosed daily at 2.5 mg/kg. A dosage of 5 mg/kg given intermittently (3 times/week) to adults or pre-weanlings resulted in thymic involution. Reductions in mitogen responses were observed in adults dosed intermittently at 10 and 20 mg/kg and in pre-weanlings at 5 and 10 mg/kg. The MLR response was suppressed in adult rats dosed intermittently at 20 mg/kg and in pre-weanling rats at 10 mg/kg. NK cell activity was suppressed only in pups dosed intermittently at 10 mg/ kg. CTL responses were not affected in either age group. Within 3 weeks following the last exposure of adult rats to TBTO all parameters returned to normal. On the other hand, LP responses to mitogens were suppressed in 10-week-old rats that were dosed with 10 mg/kg TBTO as pre-weanlings. However, this exposure regimen resulted in reductions in body weight that persisted for up to 13 weeks of age, which suggests that TBTO may be a developmental toxicant. These data indicate that while exposure of young rats to TBTO resulted in immune alterations at doses lower than those required to suppress responses in adults, the observed effects may also be influenced by the developmental toxicity of this compound.

Bimetallic Oxidation Catalysts: Oxidations with Tert Butylhydroperoxide Mediated by Bis-(Tributyltin Oxide) Dioxochromium (VI)

Abstract At 40–80°C, t.BuOOH in conjunction with catalytic amounts of (n.Bu3 SnO)2 CrO2 1 oxidizes benzylic alcohols, methylenes in α-position of aryl, ethylenic or acetylenic groups into ketones, anthracene into anthraquinone, adamantane into adamantan-1-ol and 2-one. Except for propargylic oxidations, yields are generally superior to those obtained when CrO3 is used as catalyst instead of 1.

ChemInform Abstract: Mild and Effective Cleavage of Esters with Bis(tributyltin) Oxide: A Useful Application in the Deprotection of Pom Penicillanate Esters.

AbstractThe pivaloyloxymethyl(Pom) penicillanates (I) are cleaved with bis(tributyltin) oxide to form the acids (II).

Toxicity of dibutyltin, tributyltin and other organotin compounds to humans and to experimental animals

Alkyltin compounds are used as stabilizers and antifouling agents. Food chain accumulation and bioconcentration have been demonstrated in crabs, oysters and salmon exposed to tributyltin oxide. In mammalian species, tributylin compounds may be metabolized to dibutyltin derivatives and related metabolites. Di- and tributyltins appear to be less potent neurotoxicants than trimethyltins and triethyltins. Dibutyltins and tributyltins produced bile duct damage in rats, mice and hamsters. Tributyltin oxide and dibutyltin and dioctyltin compounds are potent thymolytic and immunotoxic agents in rats. Tributyltin oxide at 5 ppm in the rat diet produced immunotoxicity in a 2-year feeding study, and at 50 ppm increased the incidence of tumors of endocrine origin. In preliminary reports, 5 ppm tributyltin produced no detectable increase in tumor incidence, and 0.5 ppm produced no detectable immunotoxicity in long-term studies. Tributyltin oxide and dibutyltin acetate did not appear to be mutagenic in a large battery of mutagenicity assays but produced base-pair substitutions in one of the bacterial strains tested. Tributyltin oxide produced mutations in Chinese hamster ovary cells, increased the incidence of micronuclei in the erythrocytes of exposed male BALB/c mice, and was highly embryotoxic in vitro. Embryotoxic and teratogenic effects in mice exposed to tributyltin oxide in vivo may have been due either to direct tributyltin oxide action or responses secondary to maternal toxicity. More information is needed to determine the applicability to human risk assessments of the immunotoxicity data derived from rat studies and to establish a definitive tolerable daily intake for tributyltin oxide.

Inter-laboratory determination of bis(tributyltin) oxide in timber and timber-treatment solutions

Accurate analysis of timber preservatives in timber-treatment solutions and in treated timber is an essential aspect of quality control in the New Zealand wood preservation industry. The increasing use of light organic solvent preservatives in recent years has drawn attention to the need for dependable methods for the determination of bis(tributyltin) oxide (TBTO). As part of an on-going programme of timber preservative analyses at the Forest Research Institute the determination of TBTO was studied in detail by an inter-laboratory comparison between six laboratories. Significant differences between laboratories were found in the determination of TBTO (or tin) in timber preservative treatment solutions and preservative-treated timber. To rectify this situation, recommendations on the necessity to intensify quality assurance programmes are suggested.

Simple Method for Gas Chromatographic Determination of Tributyltin Compounds in Fish and Shellfish

A simple and practical method was developed for quantitative analysis of tributyltin (TBT) in fish and shellfish by gas chromatography. Samples were homogenized in centrifugal tubes with a mixture of hydrochloric acid and methanol, to which hexane was added to extract TBT by shaking, followed by centrifugal separation in the form of tributyltin chloride (TBTC). The extract was charged onto a silica gel column which had been pretreated with hydrochloric acid. TBTC was eluted with hexane, concentrated in a rotary evaporator, and determined by gas chromatography on a Thermon Hg column.The mean recovery from yellowtail fish of bis(tributyltin)oxide (TBTO)added at the level of 0.2μg/g was 84.8% (n=4), and those from scorpionfish after addition of 0.08 and 0.4μg/g were 79.0 and 89.4% (n=4), respectively. The detection limit of TBTO was 0.02μg/g in samples. The concentration of TBTO in cultured yellowtails ranged between 0.02 and 0.9μg/g, and that in natural fishes ranged between 0 and 0.64μg/g, as determined by this method.

Polarographic studies on tributyltin oxide in dichloromethane and tetrahydrofuran with application to antifouling paint

In the presence of tributyltin oxide, (Bu 3Sn) 2O, an oxidation process is observed at mercury electrodes in non-aqueous solvents. On the polarographic time-scale, the oxidation involves the mercury electrode and is believed to occur according to the following reaction scheme: 2Bu 3SnOSnBu 3 + 2Hg⇌[Bu 3SnHgSnBu 3] 2+ + Hg (OSnBu 3) 2 + 2e − Hg(OSnBu 3) 2+2Hg⇌[BuSnHgSnBu 3] 2+ + 2HgO+2e − to give the overall process Bu 3SnOSnBu 3+2Hg⇌[Bu 3SnHgSnBu 3] 2+ + HgO+2e −. On the time scale of controlled-potential electrolysis, [Bu 3SnHgSnBu 3] 2+ is unstable and additional electron transfer occurs. The oxidation process forms the basis of a specific high-performance liquid chromatographic method for the determination of tributylin oxide in antifouling paint. A static mercury drop electrode in the hanging drop mode is used as an amperometric detector in a flow-cell configuration.

Aliphatic polyisocyanurate-urethanes for paper coatings

Hexamethylene diisocyanate and the sterically hindered trimethyl hexamethylene diisocyanate in the presence of tributyltin oxide catalyst were used to coat paper either in monomeric form or as cyclic isocyanurate trimers. Flame-resistant coatings were obtained on applying the isocyanates together with bromine-containing diols. The coatings were moisture-cured at room temperature. The mechanical properties of the coated paper were studied at room temperature, 90 and 120°. The tensile strength decreased with increasing temperature.

Electrochemical study of triphenyltin piperidyl dithiocarbamate

The reduction of triphenyltin piperidyl dithiocarbamate in acetone has been investigated using d.c. polarography and cyclic voltammetry. Polarographic reduction yielded four well-defined waves, two of which were diffusion-controlled and two of which appear to represent adsorption processes. The cyclic voltammetric study yielded results in close agreement with the polarographic data. Results appear to indicate the release of the dithiocarbamate moiety, followed by reduction to form the triphenyltin radical, which undergoes dimerization, as well as reduction to the triphenyltin anion. For comparison, the polarographic reduction of triphenyltinchloride was investigated. A mechanism similar to that proposed by earlier authors for the polarographic behaviour of tributyltin oxide was found.

Synnema induction in Penicillium funiculosum by tributyltin compounds

Synnema development was induced in Penicillium funiculosum when grown in the presence of sub-lethal concentrations of tributyltin oxide (TBTO) or tributyltin chloride (TBTC). The possible role of such structures in evasion of toxicity is discussed.