Analysis Of Organotin Compounds Research Articles

Rapid and sensitive determination of antifouling organotin compounds in sediments using Gas chromatography with Tandem MS (GC – MSMS / GC – QTOF)

ABSTRACT Organotin compounds are causing deterioration effect on non-targeted aquatic species in the environment, such as shell anomalies in oysters and imposex in gastropods, even at concentrations as low nanograms per litre. Specific analytical methods have been developed for different environmental matrices. Analysis of organotin compounds in sediment because of hydrophobic properties and tend to adsorb onto particulate matter is valuable for assessing the environmental distribution and fate. Therefore, in this study, a rapid, reliable, sensitive and effective method developed for quantification and identification of antifouling organotin butyl- and phenyltin compounds in sediment samples by using Gas chromatography with Tandem MS detector (GC-MSMS and GC-QTOF). The method is based on the single extraction step followed by GC-MSMS and GC-QTOF detection. The sample extraction steps were decreased for low labour laboratory costs and time-consuming. Not only the extraction procedure but instrumental method parameters were carefully optimised in order to increase sensitivity and precision. The QTOF system with the help of mass accuracy and mass resolution showed a good sensitivity and precision to analyse sediment samples. The isotopic disturbance and utilisation isotopic space for confirmation of organotin compounds have been scrutinised in GC-QTOF. GC Triple Quadrupole (GC-MSMS) system also utilised as a secondary confirmation method for organotin compound analysis. Additionally, the sensitivity of both MS detectors under the matrix effect was investigated. The recoveries of extraction were in the range of 82–106%. The acquired results have shown that the concentration range in 10–250 ppb (ng/ml) level was denoted good linearity (r2 = 0.9725–0.9983). Moreover, limits of detection (LOD) for both butyl and phenyl fractions of organotin compounds were ranged between 0.23 and 22.11 pg/ml. Consequently, the developed method successfully was applied to certificated reference material (BCR – 462) and the targeted organotin compounds in a real marine/harbour sediment sample.

Organic compounds migrating from plastic pipes into water

Case studies were carried out to identify potential chemical contaminants migrating to drinking water from polyvinyl chloride (PVC) or polyethylene (PE) pipes, available on the Polish market. Analyses were carried out by gas chromatography (GC) coupled with mass spectrometry (MS). Analysis of organotin compounds in water in contact with PVC pipes from different manufacturers found variability: monobutyltin (169 and 425 ng/L) and dibutyltin (51–72 and 249–263 ng/L) were detected in two of three samples, A1 and A2 respectively. Tributyltin was detected only in the second of these (92 ng/L). No organotin compounds were detected in sample A3, but a considerable quantity of lead (0.13–0.82 mg/L) was observed. Nineteen organic compounds, also volatile organic compounds such as xylene, styrene, phenols, and ethylmethylbenzene, were identified during GC-MS analysis of water samples in contact with high density PE pipe. Phenolic compounds related to antioxidants such as ditertbutyl-hydroxytoluene (0.29–3.6 and 0.84–9.8 ppb) and their degradation products such as t-butyl-methylphenol (0.9–11.8 ppb) were also detected.

Speciation of Organotin Compounds by Capillary Electrophoresis Coupled with Hydride Generation Atomic Fluorescence Spectrometry

Capillary electrophoresis (CE) coupled with hydride generation atomic fluorescence spectrometry (HG‐AFS) was developed for the speciation analysis of organotin compounds. The four organotin cations of trimethyltin (TMT), monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were completely separated by CE in a 50 cm×75 µm i.d. fused‐silica capillary at 15 kV and using a mixture of 50 mmol l−1 H3BO3−50 mmol l−1 Tris‐5% v/v methanol (pH 7.10) as electrolyte. 0.008 mmol l−1 cetyltrimethylammonium bromide (CTAB) added to the electrolyte suppressed the adsorption of the organotin cations on the inner wall of capillary. The generated hydride species were detected on‐line with AFS. The precisions (RSD, n=5) were in the range of 1.7–3.1% for migration time and 3.8–4.7% for peak area response for the four organotin species. The detection limits ranged from 1–10 µmol l−1 (as Sn).

Analysis of organotin compounds by grignard derivatization and gas chromatography–ion trap tandem mass spectrometry

The determination of organotin compounds in water using gas chromatography–tandem mass spectrometry (GC–MS–MS) is described. Several organotin derivatives were synthesized by the reaction of organotin chlorides with Grignard reagents such as methyl-, propyl- and pentylmagnesium halides. After the optimization of the GC–MS–MS conditions, several derivatizations with the Grignard reagents were compared by evaluating the molar responses and volatilities of the derivatives and derivatization yields. As a result, the derivatizing reagent of choice is pentylmagnesium bromide. Calibration curves for the mono-, di- and tributyltins and mono-, di- and triphenyltins with pentylmagnesium bromide were linear in the range of 0.5–100 pg of Sn. The instrumental detection limits of six organotins ranged from 0.20 to 0.35 pg of Sn. The recovery tests from water samples (500 ml) were performed by using sodium diethyldithiocarbamate (DDTC) as a complexing reagent. Except for monophenyltin, the absolute recoveries of organotins from pure water at 200 ng of Sn/l were satisfactory. The recoveries calibrated by surrogate compounds (perdeuterated organotin chlorides) ranged from 71 to 109%. The method detection limits ranged from 0.26 to 0.84 pg of Sn (500-ml sample). This method was applied to the recovery of organotins from river water and seawater. The calibrated recoveries were between 90 and 122%.

Organotin speciation analyses in marine biota using sodium tetraethylborate ethylation and gas chromatography with flame photometric detection

AbstractThe analysis of organotin compounds based on the in situ simultaneous derivatization and extraction with sodium tetraethylborate has been optimized to overcome the most common matrix effect problems with biological samples. To obtain a complete dissolution of the samples, free of colloidal interfaces problems, mechanical agitation has been coupled with stirring in a warmed ultrasonic bath. A strict quality control system using three internal standards was implemented. Tripropyltin chloride was used as internal standard to assess the derivatization reaction and tetraoctyltin was used to check the overall extraction efficiency. Tetrabutyltin was used to verify the gas chromatography (with flame photometric detector) performance of the analyses. The technique was validated using Certified Reference Materials (NIES‐11 and BCR‐477) and has been applied successfully to different biological matrices (fish, mussels, oyster and barnacles). Copyright © 2002 John Wiley & Sons, Ltd.

Extraction procedure for organotin analysis in plant matrices: optimisation and application

Analysis of organotin compounds in vegetal samples is not well documented, and no specific extraction procedure of those species from vegetal matrix can be found in the literature. In order to develop such a procedure, we have compared in a first step the performances of six extracting solutions based on HCl, CH 3COOH, NaOH, TMAH, enzymatic mixture and ethyl ethanoate. HCl-based extraction gives the highest recoveries. The whole extraction process was then optimised by investigating the influence of all the operating parameters. The resulting method, allowed a 100% recovery of tribultyltin and triphenyltin in spiked vegetal powders, without any noticeable degradation. The optimised extraction procedure was applied to the speciation of organotins in French beans and algae. Several μg (Sn) kg −1 of butyltins were found in algae collected in an urban treatment plant and contents up to 800 μg (Sn) kg −1 were detected in French beans cultivated with polluted nutritive solution. These results highlight the existence of a transfer of organotins from polluted waters to plants.

Analysis of organotin compounds in seawater using GC/pulsed flame photometric detection.

A method for a highly sensitive determination of tributyltin (TBT) and triphenyltin (TPT) in seawater has been developed using GC/pulsed flame photometric detector (PFPD). After deuterated TBT and TPT, as surrogates compounds, were added in seawater, TBT and TPT were derivatized by Grignard reagent propylation. Then, derivatized TBT and TPT were extracted with hexane. PFPD showed high selective and sensitivity for the detection of propyl TBTand TPT. The minimum detection limits, defined as the signality equal to three-times the baseline noise, were 0.078 ng/ml and 0.087 ng/ml, respectively. The mean recoveries at 10 ng/l for water were 84 and 98% for TBT and TPT, respectively, and the mean relative standard deviations were 8.2 and 7.4%, respectively. PFPD made it possible to determine TBT and TPT at less than the ng l-1 level in sea water.

Laser-enhanced ionization and laser-induced atomic fluorescence as element-specific detection methods for gas chromatography: Application to organotin analysis

We have demonstrated that flame laser-enhanced ionization (LEI) and flame laser-induced atomic fluorescence (LIAF) techniques can be used as, alternative sensitive detectors for gas chromatographic (GC) analysis of organotin compounds. These two element-specific detection methods are free from interferences from the organic solvent. Two types of LEI schemes for Sn detection are employed. For the two-step LEI scheme (TLEI), the tin atoms in the flame were stepwise excited and then ionized collisionally. In contrast, in detection with the single-step LEI scheme (SLEI), only one dye laser is used. For the analysis of tetramethyltin and tetraethyltin, the GC–TLEI, GC–SLEI, and GC–LIAF systems yield linear dynamic ranges of 0.015–400, 0.39–600 and 0.5–600 ng, respectively. The corresponding detection limits reach 0.15, 3.9 and 5.0 mg/l, with absolute quantities corresponding to 15, 390 and 500 pg, respectively, for an injection volume of 0.1 μl. These detection methods prove to be more sensitive and selective than the conventional flame ionization detection, which achieves absolute detection limits of 800 and 1667 pg for tetraethyltin and tetramethyltin, respectively, under identical GC conditions.

Derivatization methods for the determination of organotin compounds in environmental samples

In the analysis of organotin compounds, derivatization is required in order to achieve more volatile compounds prior to the use of techniques based on GC separation. Derivatization can be considered as one of the main critical steps in organotin analysis, since low yields of derivatization and losses of analytes can easily occur at this stage, and lead to an underestimation of their content in environmental samples. Furthermore, experimental conditions which are not perfectly under control may induce degradations, and alter the original speciation in the sample. Hydride generation, and alkylation by Grignard reagents or by NaBEt 4, are the derivatization methods usually applied for organotins. The advantages and disadvantages of these methods are reported.

Speciation of organotin in sediments by multicapillary gas chromatography with atomic emission detection after microwave-assisted leaching and solvent extraction-derivatization

Microwave-assisted leaching of organotin compounds from sediment samples followed by the simultaneous extraction-derivatization of the extracted species was revisited with the goal to compare the existing procedures, improve their recoveries and extend them to phenyltin compounds. The stability of butyl- and phenyltin compounds under microwave field, real recoveries of the whole analytical procedure, effect of the extraction solvent, and the necessity for an internal standard were evaluated using two candidate reference sediments. The combination of the optimized sample preparation procedure with multicapillary chromatography resulted in a rapid (2 min leaching + 5 min extraction-derivatization + 3 min chromatographic separation) and efficient analytical procedure for speciation analysis of organotin compounds in sediment samples. The detection limit achieved with a microwave-induced plasma atomic emission detector was 2 ng g–1.

Sensitive fluorescence labelling for analysis of organotin compounds with morin

Analytical procedures based on reversed-phase high-performance liquid chromatography combined with post-column derivatization with morin for the determination of organotin compounds in peanut oil, water samples or diet mixtures are described. A mixture of the isooctylesters of monooctyl tin and dioctyl tin thioglycolic acid (ZK 30 434), a mixture of the isooctylesters of monododecyl tin and didodecyl tin thioglycolic acid (ZK 32 283) or dibutyl tin difluoride (ZK 38 068) had to be analysed. The data obtained from validation and during routine analysis show that the post-column derivatization with morin is a powerful tool for the selective and sensitive detection of organotin compounds in complicated matrices. Interferences of peaks related to the organotins and the matrix constituents were not found. The values of the limit of detection were 10 μg ZK 30 434 or ZK 32 283/ml peanut oil, 60 ng ZK 38 068/ml water and 2.5 mg ZK 30 434/kg rodent diet mixture. Regarding to the repeatability, the methods described are characterized by values of the relative standard deviation of mostly less than 5%. In case of the determination of ZK 30 434 dissolved in peanut oil atomic absorption spectrometry was used to investigate the accuracy of the HPLC method. A good correlation between the HPLC and AAS data was found. The limits of quantitation were 0.25 mg ZK 30 434/ml peanut oil, 0.22 mg ZK 32 283/ml peanut oil and 1.0 μg ZK 38 068/ml water. The analytical procedures were applied within the framework of the analytical service for validation of toxicological studies according to the guidelines of good laboratory practices (G.L.P.). Both the correct preparation of the formulations and the homogeneity or stability could be checked.

N J(SnD) Coupling constants: a powerful tool for structural analysis of organotin compounds by 119Sn fourier transform n.m.r. spectroscopy

n J(SnD) coupling constants, very easily deduced from the triplets observed by 119Sn Fourier transform n.m.r. spectroscopy with proton decoupling, may be used for the direct identification of isomeric or diastereoisomeric organotin compounds.