Gas chromatography-high-resolution mass spectrometry based method for the simultaneous determination of nine organotin compounds in water,sediment and tissue

A GC-HRMS based method for the accurate and sensitive determination of nine organotin compounds, tetrabutyltin (TeBT), tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT), monophenyltin (MPhT), tricyclohexyltin (TCyT), and dicyclohexyltin (DCyT) in sediment, tissue and water samples is presented and discussed. Mass spectral features of these analytes via both low resolution quadrupole and high resolution magnetic sector, GC-HRMS conditions under selective ion monitoring mode and QA/QC criteria for the positive identification of analyte are all provided. Linearity of response and minimal detectable limits are illustrated for each of the nine compounds monitored and the estimates of method limits-of-detection were 7-29 ppt for water and 0.35-1.45 ppb for tissue or sediments. Sample preparation considerations and precision are discussed for spiked water and sediment samples, whereas method accuracy was established by analysing a certified reference material (CRM) mussel sample and comparing our results to the assigned values. Good agreement was found between our results and assigned or indicative values for MBT, DBT, TBT, DPhT and TPhT (cyclohexyl-tins were not present in the CRM).     

Spindle-inhibiting effects of organotin compounds. II. Induction of chromosomal supercontraction by di- and tri-alkyl and -aryl compounds

Spindle-inhibiting effects of chemical compounds may be studied indirectly by quantitation of chromosomal contraction. The effects of the trimethyltin (TMT), dimethyltin (DMT), tributyltin (TBT), dibutyltin (DBT), triphenyltin (TPhT) and diphenyltin (DPht) moieties as the chloride on chromosomal contraction was studied by measurement of the average length of chromosome No. 1 from asynchronous cultures of human peripheral lymphocytes. TMT, TBT, TPhT and DPhT appear to be very strong inducers of chromosomal supercontraction, indicating that these compounds conceivably are spindle inhibitors, whilst DMT and DBT seem to be ineffective. The different effects of aryl versus alkyl and trivalent versus divalent organic substituents of tin on chromosome length may relate to different modes of action.     

Solid-phase extraction-liquid chromatography-fluorimetry for organotin speciation in natural waters

Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT) species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C₁₈ enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole process have been determined. The method has been applied to the determination of organotin species in spiked natural water samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low ng L⁻¹ level (1–3 ng Sn L⁻¹ for DPhT, DBT, and PhT and 40 ng Sn L⁻¹ for TBT when 250 mL spiked sea water is processed.)     

Automated headspace-solid-phase micro extraction-retention time locked-isotope dilution gas chromatography-mass spectrometry for the analysis of organotin compounds in water and sediment samples

An automated method for the simultaneous determination of six important organotin compounds namely monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), diphenyltin (DPhT) and triphenyltin (TPhT) in water and sediment samples is described. The method is based on derivatization with sodium tetraethylborate followed by automated headspace-solid-phase micro extraction (SPME) combined with GC-MS under retention time locked (RTL) conditions. Home-synthesized deuterated organotin analogues were used as internal standards. Two high abundant fragment ions corresponding to the main tin isotopes Sn118 and Sn120 were chosen; one for quantification and one as qualifier ion. The method was validated and excellent figures of merit were obtained. Limits of quantification (LOQs) are from 1.3 to 15 ng l(-1) (ppt) for water samples and from 1.0 to 6.3 microg kg(-1) (ppb) for sediment samples. Accuracy for sediment samples was tested on spiked real-life sediment samples and on a reference PACS-2 marine harbor sediment. The developed method was used in a case-study at the harbor of Antwerp where sediment samples in different areas were taken and subsequently screened for TBT contamination. Concentrations ranged from 15 microg kg(-1) in the port of Antwerp up to 43 mg kg(-1) near a ship repair unit.     

气相色谱-质谱法测定纺织助剂中的有机锡

建立了纺织助剂中二丁基锡(dibutyltin, DBT)、三丁基锡(tributyltin, TBT)及三苯基锡(triphenyltin, TPhT)化合物的气相色谱-质谱联用(gas chromatography-mass spectrometry, GC-MS)检测方法。在乙酸-乙酸钠缓冲溶液(pH 4.0)中,用正己烷超声萃取(对疏水性样品)或振荡萃取(对亲水性样品)试样中的有机锡,然后以四乙基硼化钠的四氢呋喃溶液为衍生化试剂进行衍生化,用GC-MS测定,依据保留时间和选择离子定性,外标法定量。实验结果表明,在0.1～8.0 mg/L(对于DBT和TBT)或0.1～4.0 mg/L(对于TPhT)的范围内,有机锡化合物的浓度（以有机锡阳离子计）与其衍生物峰面积呈良好的线性关系,线性相关系数(r2)为0.9994～0.9998,检出限为0.003～0.005 mg/L; 4种聚氨酯类助剂基质中3种有机锡化合物的平均加标回收率为92.6%～108.0%,相对标准偏差为2.5%～10.2%。该方法的技术指标满足纺织助剂中有机锡化合物的测定要求。     

A quantitative extraction method for the determination of trace amounts of both butyl- and phenyltin compounds in sediments by gas chromatography-inductively coupled plasma mass spectrometry

A simple and reliable extraction method was developed for quantitative determination of both butyl- and phenyltin compounds in sediments by capillary gas chromatography combined with inductively coupled plasma mass spectrometry (GC-ICP-MS). Both types of organotin compounds were extracted quantitatively from sediment by mechanical shaking into tropolone-toluene and HCl-methanol. After phase separation and pH adjustment, these organotins were ethylated with sodium tetraethylborate. The method was evaluated by analyzing PACS-2 and NIES No. 12 sediment certified reference materials. The dibutyltin (DBT; 1.14 +/- 0.02 micrograms g-1) and tributyltin (TBT; 1.01 +/- 0.04 micrograms g-1) values observed in PACS-2 sediment closely matched the certified values (DBT, 1.09 +/- 0.15; TBT, 0.98 +/- 0.13 microgram g-1 as tin). The monobutyltin (MBT) value was higher (0.62 +/- 0.02 microgram g-1) by more than two fold over the reference value (0.3 microgram g-1 as tin). The concentrations of TBT (0.18 +/- 0.04 microgram g-1) and triphenyltin (TPhT; 0.0099 +/- 0.002 microgram g-1) in the NIES No. 12 sediment were also in good agreement with the certified and reference values of TBT (0.19 +/- 0.03 microgram g-1 as compound) and TPhT (0.008 microgram g-1 as compound), respectively. Recoveries of TBT, tripentyltin (TPeT) and TPhT from spiked sediments were satisfactory (TBT, 102 +/- 3.4%; TPrT, 96 +/- 3.4%; TPhT, 99 +/- 8.5%). The detection limits as tin were in the range 0.23-0.48 ng g-1 for a 0.5 g sample size. It is also noteworthy that clean-up of the extract is not necessary because of the superior selectivity of ICP-MS detection. The present method was successfully applied to marine sediment samples.     

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 SnI₄ 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 C₁₈ column for isolating and purifying single species. The yields of pure MPhT, DPhT, and TPhT, each synthesized from isotope-enriched ¹¹⁸Sn metal, ¹²²Sn metal, and ¹²⁴Sn 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 °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 °C or 22 °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.      

Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized <Superscript>118</Superscript>Sn-enriched organotin compounds

A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with γ-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at −30 °C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID–MS)—SSID–GC–ICP–MS, SSID–GC–MS, and SSID–LC–ICP–MS, with ¹¹⁸Sn-enriched organotin compounds synthesized from ¹¹⁸Sn-enriched metal used as a spike. The ¹¹⁸Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the ¹¹⁸Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44±3 μg kg⁻¹ as Sn, DBT 51 ± 2 μg kg⁻¹ as Sn, MBT 67 ± 3 μg kg⁻¹ as Sn, TPhT 6.9 ± 1.2 μg kg⁻¹ as Sn, and DPhT 3.4 ± 1.2 μg kg⁻¹ as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds.     

气相色谱-质谱法同时测定聚氯乙烯塑料制品中的10种有机锡化合物

采用气相色谱-质谱法(GC-MS)同时快速有效地测定了聚氯乙烯（PVC）塑料制品中的二丁基氯化锡、单丁基氯化锡、三乙基氯化锡、三苯基氯化锡、三丁基氯化锡、三丙基氯化锡、二苯基氯化锡、四丁基锡、二辛基氯化锡和单苯基氯化锡等10种有机锡化合物。使用四氢呋喃溶解PVC样品,甲醇沉淀样品中的聚合物,超声萃取其中的有机锡化合物,将提取液衍生化后用正己烷萃取,采用GC-MS总离子流和选择离子进行定性定量测定。对衍生化时间、衍生化pH值、衍生化试剂用量、沉淀试剂用量等样品前处理条件进行了优化,并进行了线性关系、回收率、精密度等考察。结果表明,方法的线性范围为0.5～50 mg/L,线性相关系数为0.9978～0.9997。10种有机锡化合物的回收率及相对标准偏差(n=9)分别为84.23%～109.1%和4.24%～10.75%。所建立的方法能很好地应用于PVC塑料制品中有机锡化合物的检测。     

Trace determination of organotin compounds in water,sediment and mussel samples by low-pressure gas chromatography coupled to tandem mass spectrometry

A fast method for the determination of eight organotin compounds (OTs), monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TeBT), monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT) and tetraphenyltin (TePhT), in water, sediments and mussels, was developed using low-pressure gas chromatography/tandem mass spectrometry (LPGC/MS/MS). The method is based on sodium diethyldithiocarbamate (DDTC) complexation of the ionic organotins, followed by extraction of the target matrices and derivatization by a Grignard reagent, as described in a previously published method for water samples. Solid-phase extraction was selected as extraction method from water samples after comparison with liquid-liquid extraction, but extraction of the OTs from sediment and mussel samples was performed using toluene. Matrix-matched calibration standards were used to minimize matrix effects. The analytical process was validated by the analysis of spiked blank samples. Performance characteristics such as linearity, detection limit (LOD), quantitation limit (LOQ), precision, and recovery were determined. Recoveries of OTs in spiked matrices ranged from 86-108% in water and from 78-110% in sediments and mussels, with precision values lower than 18%. Detection limits ranged from 0.1-9.6 ng L(-1) in water, and 0.03-6.10 microg kg(-1) in the other matrices. The present implementation of LPGC rather than conventional capillary GC permitted use of large-volume injection and reduced analysis time by a factor of two. The proposed methodology was applied to the determination of OTs in real samples of water, marine sediments and mussels from the west coast of the Mediterranean Sea (Spain).     

The effect of some phenyltin compounds on the thermotropic phase behaviour and the structure of model membranes

The effects of diphenyltin dichloride (DPhT), triphenyltin chloride (TPhT) and tetraphenyltin (TTPhT) on the thermotropic phase behaviour of phosphatidylcholine bilayers were studied. All the phenyltin compounds investigated affected phase transitions differently. TTPhT broadened the main phase transition but it left the transition temperatures and enthalpy unchanged. TPhT reduced the transition temperatures and the enthalpies while DPhT showed a dual effect on the pretransition and the main transition. At low concentrations DPhT reduced the temperatures of the transitions slightly and at higher concentrations it increased them. Based on differential scanning calorimetry (DSC) and also ¹H NMR and ³¹P NMR measurements, it is suggested that DPhT induces interdigitated gel phase formation and TPhT induces hexagonal phase formation. TTPhT seems to affect the structure only a little. The toxic activity of DPhT and TPhT seems to be connected with their ability to induce changes in the membrane structure. Copyright © 2000 John Wiley & Sons, Ltd.     

Determination of organotin compounds by headspace solid-phase microextraction–gas chromatography–pulsed flame-photometric detection (HS-SPME–GC–PFPD)

A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 μm PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L⁻¹ in water and close to ng (Sn) kg⁻¹ in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME–GC–PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices.     

The effect of phenyltin chlorides on the phase polymorphism of dipalmitoylphosphatidylcholine

The effects of diphenyltin dichloride (DPhT) and triphenyltin chloride (TPhT) on polymorphic phase behaviour of aqueous dispersions of a dipalmitoylphosphatidylcholine (DPPC) bilayer were investigated by means of ³¹P NMR. It is suggested that DPhT induces interdigitated gel phase formation and TPhT induces hexagonal phase formation. The toxic activities of DPhT and TPhT seem to be connected with their ability to induce changes in the membrane structure. Copyright © 2001 John Wiley & Sons, Ltd.     

Optimisation of the headspace-solid phase microextraction for organomercury and organotin compound determination in sediment and biota

Headspace solid-phase microextraction was optimised for the simultaneous preconcentration of methylmercury (MeHg+), monobutyltin, dibutyltin, tributyltin, monophenyltin (MPhT), diphenyltin (DPhT), and triphenyltin (TPhT) from sediments and biota. Extraction time (3-24 min), extraction temperature (20-90 degrees C), desorption time (1-10.4 min), desorption temperature (152-260 degrees C), and sample volume (5-22 mL) were simultaneously optimised, while variables such as fibre type (30 microm polydimethylsiloxane, PDMS), pH (acetic acid/sodium acetate, HOAc/NaOAc, 2 mol/L, pH approximately 4.8), the concentration of the derivatisation agent (sodium tetraethylborate, NaBEt4, 0.1% m/v), and the ionic strength (fixed by the buffer solution) were kept constant. The variables were optimised according to the experiments proposed by the MultiSimplex program and the responses were considered in order to establish the optimum conditions. The repeatability (relative standard deviation, RSD, 5-20.6%) and limits of detection (LODs, 0.05-0.97 ng/g) of the overall method were also estimated. The lowest precisions were obtained for DPhT and TPhT. The optimised preconcentration method was applied to the determination of MeHg+), butyl- and phenyltins in certified reference materials (IAEA-405 MeHg+) in estuarine sediment, BCR-646 butyl- and phenyltins in marine sediment, BCR-463 MeHg+ in tuna fish, DOLT-2 MeHg+ in dogfish liver, and BCR-477 butyltins in mussel tissue) by GC with microwave-induced plasma/atomic-emission detection.     

Trace analysis of tributyltin and triphenyltin compounds in sea water by gas chromatography–negative ion chemical ionization mass spectrometry

An analytical gas chromatography–mass spectrometry (GC–MS) method using negative ion chemical ionization (NICI) has been investigated for the determination of trace tributyltin (TBT) and triphenyltin (TPhT) compounds in sea water. TBT and TPhT were extracted from samples as chloride under the acidic condition of HCl. Doping of the GC system with a dilute HBr–methanolic solution resulted in direct detection of the chlorides of TBT, TPhT and tripentyltin (TPenT, internal standard). As the result of HBr doping, a sharp peak of the respective organotin bromides appeared: during GC analysis, halogen exchange from the chloride to the bromide occurred. NICI-MS was highly selective and sensitive for the detection of TBT, TPhT and TPenT bromides. In the selected ion monitoring mode of NICI-MS, the minimum detectable amounts defined as the signal equal to three times the standard deviation (3σ) of the baseline noise were 20 and 25 pg ml⁻¹ for TBT and TPhT, respectively. These amounts are approximately 250–400 times better than those in electron impact mode. The combination of GC using an apolar capillary column doped with a dilute HBr–methanolic solution and NICI-MS made it possible to determine TBT and TPhT at less than the ng l⁻¹ level in sea water.     

On‐line solid‐phase extraction coupled with liquid chromatography/electrospray ionization mass spectrometry for the determination of trace tributyltin and triphenyltin in water samples

On‐line solid‐phase extraction (SPE) for pre‐concentration and sample cleanup is one strategy to reduce matrix effects and to simultaneously improve detection sensitivity in liquid chromatography/mass spectrometry (LC/MS). This paper describes an on‐line SPE‐LC/MS method for the determination of tributyltin (TBT) and triphenyltin (TPhT) at trace levels in water samples. The direct coupling of an on‐line C₁₈ pre‐column to LC/MS was used to pre‐concentrate TBT and TPhT at trace levels from waters and to remove interfering matrix effects. Pre‐concentration was followed by separation of TBT and TPhT on a C₁₈ column using a mobile phase containing 0.1% (v/v) HCOOH/5 mM HCOONH₄ and methanol. While both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) can be interfaced with MS for the detection of TBT and TPhT, ESI‐MS was preferred for this application. The calibration curve for the targets was linear in the concentration range 0.1–30 µg L^?1. The detection limit (signal‐to‐noise (S/N) ratio = 3) was 0.02 µg L^?1 when 3.0 mL of sample was enriched on the C₁₈ pre‐column. The recoveries of TBT and TPhT in spiked waters were from 81.0 to 101.9%. The reproducibilities for the analysis of the standard mixture (10 µg L^?1) for TBT and TPhT were 13.1 and 5.0%, respectively. The developed method was an easy and fast way to analyze TBT and TPhT in water samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Di‐ and tri‐phenyltin chlorides transfer across a model lipid bilayer

A compound's ability to penetrate the plasma membrane of a cell is the critical parameter that determines its potential to become a biologically potent factor. A well‐known group of organotin compounds that exhibit toxic properties in relation to biological systems are phenyltins. There are as yet no studies that in a direct manner have established whether organotin compounds such as diphenyltin dichloride (DPhT) and triphenyltin chloride (TPhT) diffuse, or not, through the lipid bilayer, although we know that at least some organotins absorb in both liposome and biological membranes. In this paper we present a series of experiments that show transfer of these compounds across the lipid membrane using the stopped‐flow technique. The results obtained demonstrate that DPhT and TPhT first adsorb onto the lipid bilayer surface, in a diffusion‐controlled manner and within a very short time (0.05 s), whereas the membrane crossing was observed to be on the order of a minute. The adsorption process was easily fitted with a single exponential for both the compounds studied, indicating a single process phenomenon. The longer time kinetics (characteristic of membrane crossing) showed a complex dependence on compound concentration and the presence of cholesterol in the membrane. On passing from the outer to the inner surface of the bilayer, organotins undergo desorption and enter the liposome interior, which has been shown in lipid monolayer desorption studies. In conclusion, it can be stated that amphiphilic DPhT and TPhT permeate the liposome membrane. Copyright © 2005 John Wiley & Sons, Ltd.     

阳离子固相萃取-超高效液相色谱-串联质谱法测定皮革制品中的4种三取代有机锡化合物

建立了超高效液相色谱-串联质谱测定皮革制品中三丁基锡、三苯基锡、双-三苯基锡氧化物、三环锡等4种三取代有机锡化合物(TOT)的方法。采用盐酸溶液提取皮革制品中的有机锡化合物,使其呈阳离子态,经阳离子固相萃取净化,有机锡化合物在超高效C18色谱柱中完成分离,在正离子模式下采用多反应监测模式进行串联质谱测定。三丁基锡、三苯基锡、双-三苯基锡氧化物(以三苯基锡计)的定量限为10 μg/kg,三环锡的定量限为20 μg/kg;分别添加4种待测物于空白皮革样品中,加标回收率为54.1%～101.4%,相对标准偏差为4.3%～9.8%。实验结果表明,该方法简单、灵敏、准确,各项技术指标均满足国内外法规的要求,可用于皮革制品中4种三取代有机锡化合物残留的确证检测。     

液相色谱-质谱法对电子电气产品塑料部件中有机锡的测定

建立了液相色谱-质谱法同时测定电子电气产品塑料部件中3种有机锡的方法.样品经四氢呋喃溶解,并经甲醇沉淀杂质后,用液相色谱-质谱仪进行测定和确证.色谱柱为ZORBAX 300-SCX柱(250 mm×4.6 mm×5 μm i.d.),流动相为体积比80 : 20的甲醇-20 mmol/L醋酸铵(含0.01%冰乙酸),等度洗脱,流速为1.0 mL/min,选择离子监测模式.三丁基锡、三苯基锡、三辛基锡的线性范围分别为0.1 ～10.0、0.1 ～10.0、0.05 ～5.0 mg/L(相关系数r~2≥0.999 2),方法定量下限(LOQ)依次为0.005%、0.005%、0.0025%;平均加标回收率为80% ～100%,相对标准偏差为1.6% ～11.5%(n=6).     

Organotin speciation in textile and plastics by microwave-assisted extraction HPLC-ESI-MS

The HPLC coupled with electrospray ionization mass spectrometry (ESI-MS) was applied for the determination of tributyltin chloride (TBT), triphenyltin chloride (TPhT), triethyltin chloride (TET) in textile and plastic samples. The separation was performed in the isocratic mode on ion exchange SCX column with a mobile phase containing methanol-ammonium acetate (50 mmol l(-1))-acetic acid (90/9.98/0.02, v/v/v). Sensitive detection of three organotin compounds by ESI-MS was performed on the basis of multiple reaction monitoring (MRM) mode. Limits of detection were 0.4, 20, 4 ng ml(-1) for TBT, TPhT, and TET, respectively. Microwave-assisted extraction (MAE) of organotin compounds was finished in 60% (v/v) methanol aqueous solution. Under the experimental conditions used, recoveries of three organotin compounds obtained for spiked textile and plastic samples are in the range of 55-95% and the R.S.D.s are 3-9%.