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[Migration behavior and toxicology of methyltin stabilizers].

With a view to studying the possible use of methyltin compounds as PVC stabilizers in food industry, the authors elaborated a method for the thin-layer chromatographic and subsequent spectrophotometric or polarographic determination of mono-, di- and trimethyltin compounds in the stabilizer and after migration. Monmethyltin compounds are determined spectrophotometrically after reaction with quercetin. Dimethyltin compounds are incinerated by the wet method using sulphuric and nitric acids, and inorganic tin is then estimated polarographically. Prior to identification trimethyltin compounds must be converted into dimethyltin compounds by ultraviolet irradiation or by treatment with triethylamine and bromine. Corresponding to the different conditions of use, the authors investigated the migration of the methyltin stabilizer from PVC into distilled water, 3% acetic acid, 20% alcohol, 50% alcohol und Fettsimulans HB 307. They stated that its tendency to migration into foods is not greater than that of the octyltin stabilizer. The experimentally obtained migration values are discussed in connexion with toxicological data.

Acetates↗

Triphenyltin chloride inhibits superoxide production by human neutrophils stimulated with a surface active agent.

Treatment of human neutrophils with triphenyltin chloride (TPTCl)-inhibited superoxide (O-2) production stimulated with phorbol myristate acetate (PMA). TPTCl was more potent as inhibitor of O-2 production than other phenyltin compounds. The O-2 production by the xanthine oxidase-acetaldehyde system was not inhibited by TPTCl. This finding indicates that TPTCl does not itself react with O-2. Furthermore, TPTCl did not influence the isolated NADPH oxidase at all, though O-2 production of neutrophils stimulated with PMA in the presence of TPTCl was inhibited. These results indicate that TPTCl inhibits the activation process of the O-2 generating system.

Adult↗

Synthesis, structure, spectroscopic properties and biological activity of mixed diorganotin(IV) complexes containing pyridine-2-carbaldehyde thiosemicarbazonato and diphenyldithiophosphinato ligands.

Reaction of the title ligands (HPyTSC and HS(S)PPh2, respectively) with R2SnO (R = Me, Et, Bu) in ethanol (EtOH) afforded the complexes [SnMe2(PyTSC) (S2PPh2)].EtOH (1) and [SnR2(PyTSC) (S2PPh2)] (R = Et (2), Bu (3)). The structures of 1 and 2 were determined by single-crystal X-ray diffractometry. In both these complexes the tin atom is coordinated to an N,N,S-dentate thiosemicarbazonate ligand, an anisobidentate dithiophosphinato ligand and the two R groups. The coordination polyhedrons can be described as distorted pentagonal bipyramids. A comparative study of the IR spectra of 1, 2 and 3 indicates that the butyl complex has a similar structure. Multinuclear (1H, 13C, 31P and 119Sn) NMR data suggest that the structures of 1 and 2 probably remain in CDCl3 (or DMSO-d6) solution but compound 3 partially decomposes in these media. Preliminary results on the effects of the complexes on the proliferation and differentiation of FLC, CEM, U937, K562 and TOM-1 leukaemia cells, and on the clonogenic activity of K562 cells are also described.

Cell Differentiation↗

Effect of alkyltins on rabbit articular and growth-plate chondrocytes in monolayer culture.

The effect of four different alkyltins (trimethyltin, triethyltin, dibutyltin, and dioctyltin) on the metabolism of rabbit articular and growth-plate chondrocytes was investigated using a monolayer cell-culture system. In most instances the compounds tested exhibited a general cytotoxic effect on these cells, inhibiting the synthesis of both DNA and sulfated proteoglycans. The effect of these compounds on proteoglycan synthesis was both quantitative and qualitative, as demonstrated by CsCl isopycnic density gradient centrifugation and gel exclusion chromatographic techniques. However, certain tin compounds tested, at specific concentrations, exerted a stimulatory effect on chondrocyte proliferation. Regarding DNA synthesis, growth-plate chondrocytes were more sensitive to the effect of the triethyltin, dibutyltin, and dioctyltin than were articular chondrocytes. The data are discussed in relation to the possible effects of the alkyltins on skeletal growth and development as well as the mechanism of action of the alkyltins at the molecular level.

Animals↗

Behavioural retardation in the neuropathology of mental retardation.

A series of experiments, involving diverse perinatal treatments of either rats or mice, have been performed in order to investigate the effects of these treatments upon certain selected spontaneous and learned behaviours in the laboratory in order to derive animal models of behavioural retardation. Rat dams were administered either methylazoxymethanol, metallic mercury, organic tin or neuroleptic compounds, and the offspring of these dams were studied on the behavioural tests at adult ages, prenatal studies. Newborn rat pups were administered either 6-OHDA (at various doses), or metallic mercury and then tested at adult ages. Newborn mice were administered either metaclopramide, an antiemetic compound or haloperidol, a neuroleptic compound, and tested for spontaneous and d-amphetamine induced activity as adult. The behavioural battery that the rats were tested with consisted of measures of spontaneous motor activity, including locomotion/ambulation, rearing, and head dipping behaviours, and a parameter under which diverse behaviours were collected, total activity. Alterations to instrumental maze learning performance were studied through application of the spacial learning tasks: the radial arm maze and the circular swim maze. Possible changes in dopaminergic pathways were assessed by measuring the effects of perinatal treatments upon d-amphetamine induced activity. It was shown that prenatal methylazoxymethanol, metallic mercury, organic tin and the neuroleptic compounds, haloperidol and remoxipride, altered various parameters of spontaneous motor activity, retarded maze learning in the radial arm maze and potentiated d-amphetamine induced activity. Metallic mercury rats were not subjected to the amphetamine test and remoxipride rats were not retarded on the learning task. Postnatal metallic mercury, 6-OHDA, haloperidol and the antiemetic compound, metaclopramide, also altered spontaneous and d-amphetamine induced activity as well as radial arm maze performance, excluding in this case haloperidol and metaclopramide. None of these treatments altered performance in the circular swim maze, except for 6-OHDA where doses inflicting severe depletions (greater than 85% depletion compared to control values) caused notable impairments. These diverse findings seem to implicate dopaminergic processes in brain development.

Animals↗

Collection and analysis of butyltin compounds in air at nanogram-per-cubic-meter levels.

An analytical method for determining butyltin chlorides in air at low nanogram-per-cubic-meter levels was developed. Butyltin chlorides investigated were mono-n-butyltin trichloride (MBTC), di-n-butyltin dichloride (DBTC), and tri-n-butyltin chloride (TBTC). These tin chlorides were trapped on cartridges packed with Porapak-N, eluted with methylene chloride containing 0.3% HCl, hydridized with sodium borohydride, and analyzed by capillary gas chromatography with flame photometric detection. On the basis of a 20 m3 sample, a detection limit of 0.05 ng/m3 can be achieved.

Air Pollutants↗

Studies on transfer ribonucleic acids and related compounds. IX. Ribooligonucleotide synthesis using a photosensitive o-nitrobenzyl protection at the 2'-hydroxyl group.

o-Nitrobenzyl group was introduced to the 2'-hydroxyl function of uridine via 2',3'-O-(dibutylstannylene) uridine. The benzylated uridine was protected at the 5'-hydroxyl group with monomethoxytrityl chloride and condensed with 2',3'-O-dibenzoyluridine 5'-phosphate or N,N',2',3'-O-tetrabenzoyladenosine 5'-phosphate using dicyclohexylcarbodiimide (DCC). o-Nitrobenzyl ether linkage of the dinucleotides was removed by UV irradiation with wavelength longer than 320 nm. Deprotected UpU and UpA thus obtained were characterized by RNase A digestion.

Chromatography, Paper↗

Certification of mono-, di-, and tributyltin compounds in marine sediment certified reference material by species-specific isotope dilution mass spectrometric analysis using synthesized 118Sn-labeled butyltins.

A new marine sediment reference material (NMIJ CRM 7301-a) for butyltins analysis was prepared and certified by the National Metrological Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original material of the sediment was collected at a bay near industrial activities in Japan. The sediment material was air-dried, sieved, homogenized, and packaged into 1,000 glass bottles (60 g each). Certification of NMIJ CRM 7301-a was carried out at NMIJ using two different types of species-specific isotope dilution mass spectrometry: isotope dilution-ethylation-gas chromatography/inductively coupled plasma mass spectrometry (GC/ICPMS) and isotope dilution-ethylation-gas chromatography/mass spectrometry (GC/MS). A mixture of (118)Sn-enriched monobutyltin, dibutyltin, and tributyltin was synthesized in our laboratory and was used as a spike for both techniques. Certified values are given for tributyltin (0.044+/-0.004 mg kg(-1) as Sn), dibutyltin (0.056+/-0.006 mg kg(-1) as Sn, and monobutyltin (0.058+/-0.013 mg kg(-1) as Sn), being at lower levels than currently available sediment CRMs for the analysis of organotins.

Certification↗

Proton double quantum coherence and cross-relaxation in (NH4)2SnBr6.

A proton double quantum coherence signal can be observed exclusively from the T species NH4 groups (with the total spin I = 1) in ammonium compounds at low temperatures by the three-pulse sequence 90x degrees - tpr - 90x degrees - tev - 90x degrees - ta, where tpr and ta are of the magnitude of the inverse line width and tev very short. The usefulness of this pulse sequence, preceded by the additional pulse sequence 90x degrees - t1 -90(-x) degrees - t2 for creating an unbalance between the A and T species magnetizations, was demonstrated by applying it to cross-relaxation studies in (NH4)2SnBr6.

Magnetic Resonance Spectroscopy↗

Seasonal variation in the composition and concentration of butyltin compounds in marine fish of Taiwan.

For the first time, strong evidence is presented to demonstrate that the accumulations of butyltin compounds (BTs) exhibit seasonal variations with respect to their compositions and concentrations in marine fishes. Measurements were made on the benthic ponyfish Leiogenathus splendens and lizardfish Trachinocephalus myops inhabiting the west coast of Taiwan. In the whole body samples of the ponyfish, BT concentrations ranged from 236 to 2501 ng/g wet wt, with those in winter considerably higher than in the other seasons (p < 0.05 ). In a similar vein, proportions of mono- (MBT), di- (DBT) and tributyltin (TBT) differed significantly (p < 0.001) depending upon the season, with TBT (75 and 50%) dominant in winter and spring and DBT (37 and 57%) and MBT (42 and 24%) dominant in summer and autumn, respectively. In the lizardfish, the concentrations of BTs were one to two orders of magnitude higher in the liver than in the muscle, i.e. 3058-11,473 vs. 36-159 ng/g wet wt, respectively. Concentrations of MBT, DBT and TBT in the muscle ranged, respectively, from 5 to 14, 8 to 35 and 23 to 110 ng/g wet wt, with the major compound being TBT (57-69%) in all seasons. However, in the liver, DBT concentrations, ranging from 992 to 7797 ng/g wet wt, differed seasonally with a descending order of autumn>summer>spring (p < 0.05). Meanwhile, TBT (41%) was predominant in spring, whereas DBT (50 and 68%) was most heavily concentrated in summer and autumn (p < 0.001). Seasonally mediated physiological changes, such as dilution due to growth and metabolic compensation, may play important roles in forming different BT accumulation patterns among seasons and organisms.

Animals↗

Preparation, preservation and application of pure isotope-enriched phenyltin species.

A method combining liquid/liquid extraction and chromatographic fractionation has been developed for the preparation of pure monophenyltin (MPhT), diphenyltin (DPhT), and triphenyltin (TPhT), synthesized from isotope-enriched Sn metal using phenylation of SnI(4) in diethylether (DEE) followed by quenching with HBr and water. After two successive extractions of the aqueous HBr phase with DEE, >99% of both DPhT and TPhT was recovered in the combined DEE phase and 94% of the MPhT remained in the aqueous phase. The MPhT in the aqueous phase was extracted into dichloromethane. The organic phases were vaporized and the PhTs were redissolved in MeOH/water/acetic acid/sodium acetate (59/30/6/8, v/v/v/w), which was also used as storing solution. Aliquots of the two solutions containing either DPhT and TPhT or MPhT were injected into a silica-based C(18) column for isolating and purifying single species. The yields of pure MPhT, DPhT, and TPhT, each synthesized from isotope-enriched (118)Sn metal, (122)Sn metal, and (124)Sn metal, were better than 99%. After chromatographic separation, the single phenyltin compounds were mixed to prepare a spike for multiple-isotope species-specific isotope dilution (MI-SSID). MI-SSID was successfully used to determine phenyltin compounds in the certified reference material, mussel tissue BCR CRM-477. At -20 degrees C, all of the fractionated phenyltin species were stable in the storage solution for at least 197 days. When these standards were stored at 4 degrees C or 22 degrees C, 4-6% of the DPhT and TPhT degraded within 27 days. The degradation of DPhT and TPhT increased with the ionic strength and acidity of the storage solution.

Chemical Fractionation↗

Growth of plants on TBT-contaminated harbour sludge and effect on TBT removal.

BACKGROUND: Worldwide, large amounts of sediments have to be dredged annually from waterways and harbours. These sediments are sometimes polluted with a variety of toxic compounds. In some countries, including Belgium, the load with the biocide tributyltin (TBT) from ship coatings prohibits the dumping of harbour sludge into the sea. Land-based dumping is a commonly used alternative. OBJECTIVE: This research investigated the feasibility to use land-deposited harbour sludge for plant production. In a field trial, the growth of 38 more or less salt-tolerant plant species on low and high TBT-contaminated sediments was studied. The elimination of TBT from sludge with and without vegetation was compared. The uptake of TBT and its degradation products di- and monobutyltin (DBT and MBT) into harvest products under field conditions was determined. EXPERIMENTAL SET-UP: Sediments dredged in May 2003 from the brackish waters of the port of Antwerp were analysed in the laboratory for soil texture, pH, electroconductivity, sodium, magnesium, potassium, calcium, ammonium, nitrate, total nitrogen, chloride, sulphur and the organotins TBT, DBT and MBT. The sediments were lagooned for one year to dewater, desalinate and improve their structure. Salt-tolerant domestic and wild plants were selected and sown in May 2004. In August 2004, plants were harvested and the produced biomass was determined. Samples were taken from vegetated and non-vegetated top and bottom sediments and from plants growing above soil and analysed for TBT, DBT and MBT. RESULTS: The fresh sediments showed a good supply with nutrients and a neutral pH, but were rather saline (EC 14 mS cm(-1) of the saturated paste extract). The salinity decreased to 3.7 mS cm(-1) during lagoonation. The high and the low contaminated sediment had initially 43 and 1.6 mg TBT kg(-1) dry weight, respectively. Besides TBT, several other contaminants were present in the sediments at critical levels. The biomass production of the plant species from the field trial ranged from 0.2 to 13 tons dry mass per hectare. Plants performing excellently were barley, sorghum, rape seed, a clover/grass mix and reed. If at all, a positive influence of TBT on plant growth was seen. TBT was degraded significantly faster (>40%) below barley. The uptake of TBT, DBT and MBT into stem and leaves of reed, grass and clover was very low, but measurable and not related to concentrations in soil. No uptake of TBT or its metabolites into corn of barley was found. DISCUSSION: This study confirmed former results: the toxicity of TBT to higher plants is low, and even high levels in soils would not be a hindrance for crop production. The removal of TBT seemed to be increased by both lagooning and plant growth, although the target values for sea dumping in use in certain European countries were not reached. A plausible explanation for the faster degradation of TBT under vegetation is that oxygen is a limiting factor, and plants dewater the soil, thus aerating it. The uptake of the organotins TBT, DBT and MBT into harvest products is probably due to attached soil particles. CONCLUSIONS: To summarize, barley was the optimal species: it grew very well despite the salinity of the dredged sediments, it had a significantly positive effect on TBT removal; it showed no measurable uptake of TBT or the other butyltins into the harvested product; and it is a cash crop well established in European agriculture. OUTLOOK: The amounts of dredged sediments are high, and good soils are becoming increasingly rare. The feasibility of using dredged sediments for non-food production, such as energy crops, should be investigated by a critical risk assessment.

Belgium↗

In-situ partitioning of butyltin compounds in estuarine sediments.

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.

Carbon↗

New approach of solid-phase microextraction improving the extraction yield of butyl and phenyltin compounds by combining the effects of pressure and type of agitation.

A new methodology for the simultaneous and fast solid-phase microextraction (SPME) of butyl- and phenyltin compounds, as ethylated derivates, is proposed in this paper. The effects of pressure and type of agitation during headspace SPME sampling are evaluated and discussed on the basis of thermodynamic considerations. Quantitative structure-activity relationships were used to estimate analytes partition coefficients allowing to explain the different behaviours experimentally observed. SPME sampling conditions including mechanical stirring and reduced pressure result in simultaneous higher efficiency (detection limits especially lowered for phenyltins up to a eight-fold reduction) and shorter sampling time (two-fold reduction).

Atmospheric Pressure↗

Determination of tri-, di-, and monobutyltin and inorganic tin in biological materials and some aspects of their metabolism in rats.

A chromatographic method to separate and determine simultaneously trace amounts of tri-, di-, and monobutyltin and inorganic tin (IV) in biological materials has been established. These compounds were eluted stepwise on a silica gel column with an organic solvent system and were sensitively determined by flameless atomic absorption spectrophotometry. The calibration curves show linearity up to 6 mumol/L. The detection limit was 1.5 ng of tin for each of the tin compounds. The reproducibility and recovery were satisfactory. Tetra- and tributyltin were also sensitively determined by the gas chromatographic application of this method. This new method was applied to the study on the metabolism of tributyltin in rats. The contents of tributyltin in the liver of rats, to which a single oral dose of tributyltin fluoride had been administered, showed a rapid decrease following an initial transient increase. The tributyltin, once transported to the liver, seemed to be rapidly dealkylated. The most significant finding was the remarkable retention of monobutyltin and inorganic tin (IV) in the brain.

Animals↗

Toxicity of triphenyltin and tributyltin to the freshwater mudsnail Potamopyrgus antipodarum in a new sediment biotest.

The effects of two suspected endocrine-disrupting chemicals, the xeno-androgens triphenyltin (TPT) and tributyltin (TBT), were investigated in a new whole-sediment biotest with the freshwater mudsnail Potamopyrgus antipodarum (Gastropoda, Prosobranchia). Artificial sediments were spiked with seven concentrations, ranging from 10 to 500 microg nominal TPT-Sn/kg dry weight and TBT-Sn/kg dry weight, respectively. We analyzed the responses of the test species after two, four, and eight weeks exposure. For both compounds, P. antipodarum exhibited a sharp decline in the number of embryos sheltered in its brood pouch in a time- and concentration-dependent manner in comparison to the control sediment. The number of new, still unshelled embryos turned out to be the most sensitive parameter. The lowest-observed-effect concentration (LOEC) was equivalent to the lowest administered concentration (10 microg/kg of each test compound) for most parameters and thus no no-observed-effect concentration (NOEC) could be established. The calculation of effect concentrations (EC10) resulted in even lower values for both substances (EC10 after eight weeks for unshelled embryos: 0.03 microg TPT-Sn/kg, EC10 after four weeks for unshelled embryos: 0.98 microg TBT-Sn/kg). Our results indicate that P. antipodarum is highly sensitive to both endocrine disruptors TPT and TBT at environmentally relevant concentrations.

Animals↗

Butyltin compounds in retail mollusc products.

Butyltin was found in 62 of 74 mollusc products purchased from major supermarket outlets in seven cities across Canada. Tribuyltin was detected in 41 samples, with levels up to 233 ng g(-1). Dibutyltin and monobutyltin levels ranged up to 88 and 53 ng g(-1), respectively. Products originating from East and South East Asia generally contained the highest levels. Gastropods contained lower levels than other molluscs. Enzymatically hydrolysed samples were extracted with 0.05% tropolone in hexane-diethyl ether (1 : 1). Ethyl derivatives were made by Grignard reaction and analysed by gas chromatography coupled to an atomic emission detector. Gas chromatograph-mass spectrometry confirmed the presence of butyltins in the mollusc samples.

Animals↗

[Tin compounds in pharmacy and nutrition].

The occurrence of tin in plants, animals and humans is discussed, in relation to its abundance in the lithosphere and hydrosphere and the range of the different tin(II) and tin(IV) complexes formed. A reasoned consideration of its essentiality for living species is provided. It is concluded that tin is beneficial, even if not yet proved to be an essential element. After reference to the chemistry of tin compounds, there is a detailed discussion of their toxicity in animals and humans. Feasible routes for tin intake and uptake into humans are described. The past and current use of tin pharmaceuticals is reviewed and the areas for which they are currently permitted for use in humans as dentifrices and mouth washes, as radio-pharmaceuticals and for the treatment of jaundiced newborns are described. A detailed review of tin-containing antitumour agents as representative tin pharmaceuticals is also given. Finally, a list of tin-containing drugs and drug candidates is also shown.

Animal Nutritional Physiological Phenomena↗