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Improved routine speciation of organotin compounds in environmental samples by pulsed flame photometric detection.

The high toxicity of the organotin species requires sensitive analytical methods in order to understand the origins of pollution and perform monitoring programs in the water cycle. The optimisation of a new detection method, pulsed flame photometric detection (PFPD), is reported for the simultaneous determination of butyl-, phenyl- and octyltins. The methodology of the experimental designs at two levels was used. It allows the evaluation of the influence of the three gas flow-rates on the peak heights and resolution between the closest peaks obtained using two different wavelengths of detection (390 and 611 nm). The modelling of these two responses, according to second-order polynomials, leads to the precise adjustment of the operating conditions. PFPD has shown two significant improvements over conventional flame photometric detection: increased sensitivity (absolute detection limits: 0.07 to 2 pg as Sn) and greater selectivity, whatever the wavelength used. This new analytical process was validated by the analysis of certified reference material and spiked river water. It was used in routine analysis of environmental samples (wastewater, sludge, sand and oyster).

Gas Chromatography-Mass Spectrometry↗

The effect of organotin compounds on chloride secretion by the in vitro perfused rectal gland of Squalus acanthias.

The effects of various organotins on membrane function and electrolyte transport were studied in the marine elasmobranch, Squalus acanthias. The isolated perfused rectal gland was used as a model of electrolyte transport. This gland can be stimulated to secrete chloride by atrial natriuretic peptide, veratrine, and vasoactive intestinal polypeptide although the mechanism of action of each secretagogue is different. By analysis of the inhibitory effect of an organotin in the presence of each secretagogue, the mechanism of inhibition can be inferred. Tributyltin (TBT) produced a reversible inhibition of epithelial transport at 10(-8) to 10(-7) M which resulted from inhibition of stimulus-secretion coupling in VIP-containing neurons within the gland. The transporting epithelial cells were unaffected at these concentrations. Trimethytin (TMT) produced inhibition at 10(-7) M which was not reversible and which affected primarily the transporting epithelial cells. Triethyltin and triphenyltin were without effect. The inhibitory effect of TBT and TMT was not affected by simultaneous administration of dithiothreitol. TBT also produced inhibition of oxygen consumption, Na+,K-ATPase, and proton ATPase in dispersed rectal gland cells. These results indicate that organotins are toxic to cell membrane functions which are intimately involved in the movement of electrolytes. This is the first evidence of toxicity to membrane transport functions in a marine species which is at risk from environmental exposure.

Animals↗

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000.

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.

Agriculture↗

Histopathologic investigations of acute and subchronic toxicities of some organotin compounds in chickens.

The acute and subchronic oral toxicities of 4 organotin derivatives were investigated in chickens. The LD50 values oscillated between 200 and 400 mg/kg bw and revealed a moderate or weak toxicity. Subchronic dosing with 2 doses from each compound at 2 and 10 mg/kg bw induced dose-dependent lesions seen at necropsy and histologic examinations. Involution of the thymus and bursa Fabricius, fatty degeneration of the liver, and nephrotic syndromes were the most evident effects. The butyltin derivatives induced more drastic lesions than did the phenyltins.

Animals↗

Accumulation of organotin compounds in the deep-sea environment of Nankai Trough, Japan.

The concentration of butyltin (BT) and phenyltin (PT) compounds was measured in sediment, gastropods (Colliloconcha nankaiensis), sea cucumbers (Psychropotes verrucosa), galatheid crabs (Munidopsis albatrossae and Munidopsis subsquamosa), and bivalves (Clyptogena tsubasa and Clyptogena nautilei) collected from the Nankai Trough (water depth about 3000 m). Sediment at depths of up to 1 cm was taken by a core sampler and at depths of up to 15 cm was taken by rake. The concentration of BTs in sediment core from a depth of 0-1 cm (0.041 mg kg(-1) dry) was higher than in sediment core from 0-15 cm (0.021 mg kg(-1) dry). The relative proportion of different BTs in the 0-1-cm sediment core was similar to that in the 0-15-cm sediment core, but the concentration of PTs in the former (0.028 mg kg(-1) dry) was lower than in the latter 0-15 cm (0.052 mg kg(-1) dry). Organotin (OT) compounds were also detected in deep-sea organisms. The means of BT concentrations in C. nankaiensis, P. verrucosa, M. albatrossae, M. subsquamosa, Cl. tsubasa, and Cl. nautilei were, respectively, 0.089, 0.057, 0.018, 0.016, 0.019, and 0.026 mg kg(-1). The corresponding concentrations of PTs were 0.212, 0.363, 0.166, 0.186, 0.030, and 0.025 mg kg(-1). High concentrations of BTs and PTs were observed in gastropods and sea cucumbers. The species of deep-sea organism can be classified by delta(13)C value into two groups (A and B). The organisms in group A use organic matter chemosynthesized by symbiotic bacteria while those in group B depend on photosynthesis carried out near the surface by phytoplankton. No difference in BT or TBT concentration is observed between the two groups, but PT and TPT concentrations are higher in group B. Trophic levels in the food chain are often estimated using delta(15)N values. Group B showed a higher trophic level than group A. Although no change in BT and TBT concentration was observed to accompany increases of delta(15)N values, PT and TPT concentrations generally increased with increasing delta(15)N values. The compositions of BTs in deep-sea organisms were calculated. An increasing proportion of MBT and a declining proportion of DBT were observed at higher trophic levels. No correlation between the shell length of Cl. nautilei and BT or PT concentration was observed. The average partition coefficients of TBT for C. nankaiensis, P. verrucosa, M. albatrossae, M. subsquamosa, Cl. Tsubasa, and Cl. nautilei were 2.6, 0.72, 0.63, 0.19, 0.43, 0.30, and 0.46.

Animals↗

Speciation of organotin compounds in marine biomaterials after basic leaching in a non-focused microwave extractor equipped with pressurized vessels.

A rapid method for the speciation of butyl- and triphenyltin compounds in marine biotissues is described. A non-focused microwave extractor, operating at a power of 950 W and equipped with 12 pressurized vessels, was used to achieve fast sample leaching with tetramethylammonium hydroxide. The pH of the liquid extract was adjusted to 5. Organotins were ethylated with sodium tetraethylborate, extracted in isooctane and determined by means of a microwave-induced plasma atomic emission detector coupled to a gas chromatograph. The stability of butyl and phenyl compounds, exposed to the microwave energy, was studied as a function of the vessel temperature. The possibility of simultaneous carried-out extractions and the use of microwave to perform the ethylation and extraction of organotin compounds was also studied. The full procedure was validated with certified material NIES-11 and with real samples, by comparison with a classic leaching method using tetramethylammonium hydroxide without microwave.

Animals↗

Inductively coupled plasma mass spectrometry and atomic emission spectrometry coupled to high-performance liquid chromatography for speciation and detection of organotin compounds.

Inductively coupled plasma mass spectrometry (ICP/MS) is utilized as a detector for several organotin species separated by high-performance liquid chromatography. Detection limits obtained by ICP/MS are 3 orders of magnitude lower than those obtained with inductively coupled plasma atomic emission spectrometry (ICP/AES) detection under the same chromatographic conditions. Chromatographic detection limits are higher than conventional solution nebulization for the same compound by a factor of 20. Ion-exchange chromatography yields linear response over 3 orders of magnitude, while ion pair chromatography gives a linear response of only 2 orders of magnitude as a result of poor resolution. The relative standard deviation for the injection of 20 ng of tin compounds is less than 10%.

Chromatography, High Pressure Liquid↗