Organotin Compounds In Water Research Articles

Possibilities and Limitations of ICP-Spectrometric Determination of the Total Content of Tin and Its Inorganic and Organic Speciations in Waters with Different Salinity Levels-Part 2: Separate Determination of Inorganic and Organic Speciations of Tin.

In this study, determination of the inorganic and organic forms of tin in waters of different salinities is considered. The possibility of the separation of speciations of tin using liquid-liquid extraction (LLE); precipitation with fluorides, iodides, ammonia, and iron (III) chloride; and sorption of organotin compounds (OTCs) was studied. The LLE and analyte precipitation methods proved to be ineffective. Inorganic and organic forms of tin were separated by the sorption of OTCs using silica gel sorbent Diapak C18. Under optimized conditions, a technique for the separate determination of the forms of tin in natural waters was developed. The technique combines hydride generation and microwave mineralization of solutions followed by ICP spectrometry. The inorganic forms of tin were determined after their solid-phase separation from organotin compounds. The lower limits of analyte quantification were 0.03 μg/L (ICP-MS) and 0.05 μg/L (ICP-OES), which provide separate determinations of inorganic and organic forms of tin in waters with different salinities. The content of OTCs in water was determined by subtracting the inorganic concentration from the total concentration of tin. The technique will allow a comprehensive assessment of the toxicological impact of tin speciations on the aquatic ecosystem.

Speciation of organotin compounds in water and seafood samples by online hyphenation of porous polymer-based magnetism-enhanced in-tube solid phase microextraction and HPLC

A new strategy based on online hyphenation of magnetism-enhanced in-tube solid phase microextraction (ME-SPME) and HPLC was developed for speciation of organotin compounds (OTCs) in water and seafood samples. Task specific porous polymer embedded magnetic nanoparticles (TPM) was fabricated in capillary and utilized as the microextraction column (MEC) of ME-SPME. The implement of magnetic field during extraction duration obviously improved extraction efficiencies of prepared TPM/MEC towards studied TOCs from 48.0-77.0% to 84.2–99.7%. Under the optimized extraction parameters, sensitive and automatic approach for the quantification of TOCs was developed by online hyphenation of ME-SPME and HPLC with fluorescence detection. The limits of detection for water and seafood samples were in the ranges of 0.0030–1.5 μg/L and 0.71–14 μg/kg, respectively. The established method was employed to measure low contents of studied OTCs in actual samples, and the recoveries at different fortified contents varied from 80.2% to 116% with satisfactory reproducibility (RSDs below 10%). In addition, confirmation experiments were adopted to inspect the accuracy of introduced method.

Determination of organotin compounds in waters by headspace solid phase microextraction gas chromatography triple quadrupole tandem mass spectrometry under the European Water Framework Directive

The European Union Water Framework Directive (2013/39/EU) sets very restrictive environmental quality standards for 45 priority substances and other pollutants, including organotin compounds (OTCs). Therefore, it is necessary to develop analytical methods in compliance with the environmental quality standard (EQSs) proposed to protect the aquatic environment and humans. The proposed method (HS-SPME-GC–QqQ-MS/MS) allows the determination of OTCs, i.e. monobutyltin (MBT), dibutyltin (DBT) and TBT in water in the range of few ngL−1. The method is nearly full automated, sensitive and simple; it involves less reagents, reduces waste, and is less-time consuming than traditional methods for OTCs. As such, the procedure connects with the principles of green analytical chemistry. Additionally, good precision (RSD<20%), a very low method quantification limit (MQL) (0.76ngL−1 for TBT by using only 10mL of sample) and excellent linearity (range MQL–20ngL−1) are achieved. Under these conditions, the very restrictive limits for the environmental quality standards (EQS) fixed by the 2013/39/EU Directive are achieved.

Seasonal changes in organotin compounds in water and sediment samples from the semi-closed Port of Gdynia

The effect of seasonal changes on the distribution of organotin compounds (OTC) in the sediments and seawater from the docks of the Port of Gdynia was investigated. Sediment and seawater samples were collected from four industrial docks in February (winter) and June (summer) in 2009. The samples were analyzed for butyltin, phenyltin, octyltin, and tricyclohexyltin (total of 9 OTC derivatives). The fine fraction (<0.063mm) accumulated the highest concentration of OTC, although it was not the dominant fraction in the sediment samples from the Port of Gdynia. The average concentration of TBT, DBT and MBT in collected samples were as follows: 4400; 2188; 730ngcationg−1d.w. (February) 3638; 1590; 474ngcationg−1d.w. (June) in the fine sediment samples, 2805; 1266; 485ngcationg−1d.w. (February) in <2.00mm sediment fractions and 118.6; 39.2; 25.3ngcationL−1 (February) and 46.5; 12.6; 8.2ngcationL−1 (June) in the water samples. Higher concentrations of butyltin derivatives (BT) were observed in samples collected in February than in those collected in June. Seasonal changes in BT correlate well with changes in the water pH and concentrations of organic matter and can be attributed to sorption/desorption to sediments, photodegradation and biodegradation. Although the Port of Gdynia does not represent the natural features of a marine environment, seasonal variations recorded in the pH values as well as BT, organic carbon and biogenic element concentrations seem to be influenced by temperature and microbial activity.

Identification of organotin compounds in Tunisian surface water by liquid chromatography-electrospray-tandem mass spectrometry

Liquid chromatography coupled to electrospray ionization mass spectrometry (LC-ESI-MS) with positive ion detection was applied for the identification of organotin compounds in water samples. The separation was performed in the gradient mode on reversed phase column with a mobile phase containing 0.05% TFA in acetonitrile–water. Sensitive detection of the selected organotin compounds by ESI-MS was performed on the basis of selected ion monitoring (SIM) mode. Limits of detection (LODs) were ranged between 0.02 and 0.08 μg L-1. Solid phase extraction (SPE) was carried out on C18 cartridges to preconcentrate the analytes from water samples. Under the experimental conditions used, recoveries of organotin compounds obtained for spiked water samples are in the range of 62–98% and the R.S.D.s are 2–11%. Conditions for tandem mass spectrometry (MS–MS) detection of characteristic product ions formed by collision-induced dissociation (CID) of the parent ion are described. A principle of analysis is proposed based on triple quadrupole MS as a method for quantitative determination followed by verification of positive findings by CID-MS–MS. Application of the method for detecting organotin compounds in tap and surface water (river, dam and lagoon) samples is demonstrated.

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.

Calibration and use of the Chemcatcher ® passive sampler for monitoring organotin compounds in water

An integrative passive sampler (Chemcatcher ®) consisting of a 47 mm C 18 Empore™ disk as the receiving phase overlaid with a thin cellulose acetate diffusion membrane was developed and calibrated for the measurement of time-weighted average water concentrations of organotin compounds [monobutyltin (MBT), dibutyltin (DBT), tributlytin (TBT) and triphenyltin (TPhT)] in water. The effect of water temperature and turbulence on the uptake rate of these analytes was evaluated in the laboratory using a flow-through tank. Uptake was linear over a 14-day period being in the range: MBT (3–23 mL day −1), DBT (40–200 mL day −1), TBT (30–200 mL day −1) and TPhT (30–190 mL day −1) for all the different conditions tested. These sampling rates were high enough to permit the use of the Chemcatcher ® to monitor levels of organotin compounds typically found in polluted aquatic environments. Using gas chromatography (GC) with either ICP-MS or flame photometric detection, limits of detection for the device (14-day deployment) for the different organotin compounds in water were in the range of 0.2–7.5 ng L −1, and once accumulated in the receiving phase the compounds were stable over prolonged periods. Due to anisotropic exchange kinetics, performance reference compounds could not be used with this passive sampling system to compensate for changes in sampling rate due to variations in water temperature, turbulence and biofouling of the surface of the diffusion membrane during field deployments. The performance of the Chemcatcher ® was evaluated alongside spot water sampling in Alicante Habour, Spain which is known to contain elevated levels of organotin compounds. The samplers provided time-weighted average concentrations of the bioavailable fractions of the tin compounds where environmental concentrations fluctuated markedly in time.

Assessment of Chemcatcher passive sampler for the monitoring of inorganic mercury and organotin compounds in water

Several configurations of receiving disks and diffusion membranes were tested for monitoring mercury and organotin compounds (monobutyltin, dibutyltin, tributyltin, and triphenyltin) in water with a passive sampler. This passive sampler is based on the diffusion of these compounds through a specific diffusion-limiting membrane and their subsequent accumulation on a specific receiving phase, all materials being commercially available. The proposed sampler for inorganic mercury comprises a 47-mm Empore™ chelating disk as receiving phase and polyethersulfone as diffusion membrane. For monitoring organotins, the receiving phase is a 47-mm Empore™ C18 disk, and the diffusion membrane is cellulose acetate. ICP-MS and GC-ICPMS/GC-FPD were used for inorganic mercury and the organotins analysis, respectively. The effects of environmental variables such as pH and salinity that could influence accumulation of test substances in receiving phase were studied. Linear uptake for all compounds was observed for at least 14 days of exposure at a constant aqueous analyte concentration in a flow-through system under controlled conditions of temperature, turbulence, and analyte concentration. Compound-specific sampling rates at 11°C and simulated water turbulence of 40cms−1 varied between 0.018 and 0.137Ld−1. Compounds collected by the sampler exhibited detection limits ranging between 0.7 and 5.9ngL−1. The feasibility of using these samplers in the field was tested in a polluted commercial harbour. The behaviour of the samplers to monitor target compounds was compared with those obtained from spot samples of water taken throughout the field deployment period. Data from laboratory studies and field trial support the feasibility of these samplers to measure the freely dissolved fraction of these important target analytes in water.

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 Sn 118 and Sn 120 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 μg 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 μg kg −1 in the port of Antwerp up to 43 mg kg −1 near a ship repair unit.

Distribution of antifouling substances in aquatic environment

The temporal trend of antifouling substances in aquatic environment has been clarified by measurement of the organotin compounds in water, sediment, and biological samples. The concentrations of tributyltin (TBT) compounds in water and mussels decreased dramatically after regulation, and no changes of TBT concentrations were then observed. TBTs in fish also decreased moderately, Whereas no changes of TBTs were observed in sediment. Although triphenyltin (TPT) compounds in water, sediment, and biological samples decreased after regulation, TPTs were still detected in fish. The partition coefficients of organotin compounds for water and sediment or biological samples ranged from 103 to 105. The concentrations of Sea-Nine 211, Diuron, Irgarol 1051, pyrithions, and M1 were measured in an aquatic environment for 2 years. Higher concentrations of Diuron and Irgarol 1051 occurred in the summer season. The concentrations of Sea-Nine 211, Diuron, and Irgarol 1051 in sediment increased during the observation period. The partition coefficients of Sea-Nine 211, Diuron and Irgarol 1051 for water and sediment ranged of 102-103.

Determination of organotin compounds in water by headspace solid phase microextraction with gas chromatography–mass spectrometry

This investigation evaluates headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) to determine trace levels of organotins in water. The organotins were derivatized in situ with sodium tetraethylborate and adsorbed on a poly(dimethysiloxane) (PDMS)-coated fused silica fiber. The SPME experimental procedures to extract organotins in water were at pH 5, with extraction and derivatization simultaneously at 45 degrees C for 30 min in a 2% sodium tetraethylborate solution and a sample solution volume in the ratio of 1:1, and desorption in the splitless injection port of the GC at 260 degrees C for 2 min. Detection limits are determined to be in the low ng/L range. According to the analysis, the linearity range is from 10 to 10,000 ng/L with R.S.D. values below 12% except triphenyltin (24%). The proposed method was tested by analyzing surface seawater from the harbors on the Taiwanese coast for organotins residues. Some organotins studied were detected in the analyzed samples. Results of this study demonstrate the adequacy of the headspace SPME-GC-MS method for analyzing organotins in sea water samples.

Speciation of organotin compounds in waters and marine sediments using purge-and-trap capillary gas chromatography with atomic emission detection

A procedure for the simultaneous determination of six organotin compounds, including methyl-, butyl- and phenyltins, in waters and marine sediments is developed. The analytes were leached from the solid samples into an acetic acid:methanol mixture by using an ultrasonic probe. The organotins were derivatized with sodium tetraethylborate (NaBEt 4) in the aqueous phase, stripped by a flow of helium, pre-concentrated in a trap and thermally desorbed. This was followed by capillary gas chromatography with microwave-induced plasma atomic emission spectrometry as the detection system (GC–AED). Each chromatographic run took 22 min, including the purge time. Calibration curves were obtained by plotting peak area versus concentration and the correlation coefficients for linear calibration were at least 0.9991. Detection limits ranged from 11 to 50 ng Sn l −1 for tributyltin and tetramethyltin, respectively. The seawater samples analyzed contained variable concentrations of mono-, di- and tributyl- and monophenyltin, ranging from 0.05 to 0.48 μg Sn l −1, depending on the compound. Some of the sediments analyzed contained concentrations of dibutyl- and tributyltin of between 6.0 and 13.0 ng Sn g −1. Analysis of the certified reference material PACS-2, as well as of spiked water and sediment samples showed the accuracy of the method. The proposed method is selective and reproducible, and is considered suitable for monitoring organotin compounds in water and sediment samples.

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).

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).

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 compounds in the marine environment of the Bay of Piran, northern Adriatic Sea.

In the year 2000, organotin pollution was investigated in the Bay of Piran, Slovenia, at the northern extremity of the Adriatic Sea. Gas chromatography-mass spectrometry with single ion monitoring GC/MS-SIM was applied for speciation analysis of pentylated organotin compounds in water and mussels. Sampling of marine waters was performed in summer and autumn at 8 locations. Mussels Mytilus galloprovincialis were collected only in summer at 3 locations. The highest concentrations of tributyltin (TBT) in marine water ranged from 500 to 630 ng L(-1) (as Sn) in summer and from 180 to 230 ng L(-1) (as Sn) in autumn. TBT concentration in mussels varied from 500 to 3500 ng g(-1) dry weight (d.w.) (as Sn). The study indicated remarkable butyltin pollution of the Slovenian coastline. Accuracy of the analytical procedure was verified by BCR CRM 477.

Occurrence of Organotin Compounds in Water, Sediments and Mollusca in Estuarine Systems in the Southwest of Spain

Six organotin species – tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT) andmonophenyltin (MPT) – have been determined in seawater (255 samples), sediments (85 samples) and bivalves (558 samples) collected at seventeen locations in the southwest of Spain in five occasions between May 1992 and August 1994. No phenyltinspecies were found but butyltin species were present in all the stations. The TBT concentrations ranged between 23 and 1500 ng g-1 Sn in biota, from less than 0.6 to 160 ng g-1 Sn in sediments and from less than 0.5 to 31 ng L-1 Sn in water, with the highest values closely related with boating activity and decreasing according to the distance from the potential sources. For biota and water, a consistent seasonal pattern of fluctuation of TBT concentrations was evident, with the highest values found in spring and summer except for a fishing harbour. A slow decreaseof TBT concentration was observed between 1992 and 1994. Percentages of DBT and MBT in biota (22±7 and 13±6,respectively) were lower than those in water (33±10 and 31±15, respectively) and sediments (48±16 and 25±16, respectively). Sediment-water partition coefficients for TBT were 240–65 000 and bioconcentration factors 17 000–350 000. This article discusses the significance of the pollution in our study area in comparison with other world coastal areas.

Organotin compounds and their adsorption behavior on sediments

This paper present a brief overview of the occurrence and degradation of organotin compounds in water and sediments, and their sorption behavior on natural sediment particles and pure clay minerals. Oraganotins change in their form from cation to hydroxides in accordance with an increase of pH values, and they would exist as simple neutral hydroxides in aqueous solution under natural environment pH. The concentrations of organotins in water and sediments vary in a wide range according to the degree of contamination of aquatic environment. The concentration of triorganotins in aquatic sediments are generally orders of magnitude higher than the aqueous concentrations. Hence, sorption is a key process determining the transport and fate of triorganotins in aquatic environment. Published sorption coefficients (K) for aqueous tributyltin (TBT) in sediment or particulate matter range from 3.4 × 10 2 to 1.9 × 10 6 (L kg -1 ), but the majority of reported K values have been in the order of 10 3 . It was suggested that the K value increases with increasing the amount of fine particles and expandable minerals in sediment. The effects of salinity on the K value were different depending on the sorbent-to-solution mass ratios used in an experiment. The K values for homo-ionic clay minerals were affected by the type of exchangeable cations and pH. An example of the biological degradation of Bu 3 Sn + in water and sediment was also presented.

Organotin compounds in water, sediment, and biological samples from the port of osaka, japan

Butyltin (Bts) and phenyltin compounds (Pts) were measured in water, sediment, plankton, and mussels collected from eight stations in the harbor area of the Port of Osaka in 1996, and were compared with those of Otsuchi Bay. The levels of tributyltin (TBT) compounds in all samples from the Port of Osaka were slightly high in marinas and mooring areas of small and medium-hull vessels. Of total Bts, the ratio of TBT was under 50% in water and was dominant in sediment, plankton, and mussels. Triphenyltin (TPT) compounds in water were not detected. TPT was present at lower levels than TBT in sediment, plankton, and mussels. Of total Pts, monophenyltin (MPT) compounds and diphenyltin (DPT) compounds represented a high proportion in sediment, while TPT was dominant in plankton and mussels. The concentrations of TBT in water from the Port of Osaka were lower than those from Otsuchi Bay, however TBT concentrations in sediment, plankton, and mussels from the Port of Osaka were higher than those from Otsuchi Bay. The difference of TBT concentration among stations in the Port of Osaka was slight. In contrast, the levels of TBT in Otsuchi Bay were markedly higher at a station near the shipyard. Though TPT in water from the Port of Osaka was not detected, trace amounts of TPT was found in seawater from Otsuchi Bay. The levels and detected frequencies of TPT in sediment, plankton, and mussels from the Port of Osaka were lower than in those from Otsuchi Bay. The partition coefficients of Bts to sediment, plankton, and mussels from the Port of Osaka were higher than those of dibutyltin (DBT) compounds and MBT and those of TBT to plankton and mussels were higher than those in sediment. The partition coefficients of TBT to sediment and biological samples from the Port of Osaka were higher level than those in Otsuchi Bay.

Determination of Organotin Compounds in Water, Sediments, and Sewage Sludge Using Perdeuterated Internal Standards, Accelerated Solvent Extraction, and Large-Volume-Injection GC/MS

Two new methods for the simultaneous identification and quantification of organotin compounds (OTs) including monobutyltin, dibutyltin, tributyltin, monophenyltin, diphenyltin, triphenyltin, and tricyclohexyltin (TCyT) in natural waters and sediments, respectively, are presented. For water samples, aqueous ethylation followed by liquid−liquid extraction (LLE) or solid-phase extraction and large-volume-injection GC/MS (50−200 μL) were used. For sediment samples, accelerated solvent extraction at 100 °C with a methanolic mixture of sodium acetate and acetic acid was developed. By using for the first time perdeuterated OTs as internal standards, excellent precision (relative standard deviations <5%) and low method detection limits ranging from 0.3 to 1.5 ng/L for 50 mL of aqueous samples and from 0.4 to 2 ng/g for 2.5 g of dried sediments were achieved. Using LLE, recoveries determined in spiked harbor water (+5 ng/L) and sediment pore water (+25 ng/L) were in the range of 93−103 (RSD 0.5−4.6%) and 97−108% (RSD 0.8−4.2%), respectively. For spiked sediment samples (+10 ng/g) recoveries of 98−105% (RSD 1−7%) were achieved for all OTs, except for TCyT (51%, RSD 4%). The developed analytical procedures were validated with reference material and applied to various environmental samples, such as fresh- and seawater, field runoff, wastewater, sediments, and sewage sludge.