Determination Of Tributyltin Research Articles

Contribution to the determination of tributyltin in water by stir bar sorptive extraction‒thermal desorption‒gas chromatography‒tandem mass spectrometry

An environmentally friendly method was developed to determine tributyltin (TBT) in water at the levels required by the European Union Water Framework Directive (EU WFD) using stir bar sorptive extraction (SBSE) in combination with thermal desorption‒gas chromatography‒triple quadrupole tandem mass spectrometry. The main focus of the method development was on addressing some aspects of reducing blank values (minimizing the use of chemicals, glassware cleaning, pretreatment of sorptive stir bars) and optimizing the SBSE procedure variables (sample volume, polarity of sample solution, extraction time). The performance of the method was studied in terms of linearity, matrix effect, method limits and accuracy (precision and trueness) using MilliQ, tap and surface water. TBT quantification limit for the studied matrices ranged from 0.049 to 0.055 ng L‒1 and repeatability (RSD%, n = 10) and recovery at the environmental quality standard (EQS) concentration of 0.2 ng L‒1 were in the range of 6‒18% and 88‒107%, respectively, indicating good performance of the method. The matrix effect of river water (‒78%) and artificial seawater (‒83%) compared to MilliQ water showed the necessity to use a matrix-matched calibration when analysing TBT in surface water samples. The developed sample preparation was further evaluated for greenness using the recently introduced AGREEprep assessment, which revealed a much greener performance of the proposed method over the compared CEN/TS 16692 method. The method meets the requirements of the EU WFD and is suitable for monitoring, evaluation and classification of the chemical status of surface waters.

Contribution to the Determination of Tributyltin in Water by Stir Bar Sorptive Extraction‒Thermal Desorption‒Gas Chromatography‒Tandem Mass Spectrometry

Contribution to the Determination of Tributyltin in Water by Stir Bar Sorptive Extraction‒Thermal Desorption‒Gas Chromatography‒Tandem Mass Spectrometry

Modified, optimized method of determination of Tributyltin (TBT) contamination in coastal water, sediment and biota in Sri Lanka

Tributyltin (TBT) is a toxic organotin compound that belongs to the group of Persistent Organic Pollutants (POPs) and it is documented to cause severe sexual disorders development in aquatic fauna. According to the present study, The TBT concentration in coastal water ranged from 303 ± 7.4 ngL−1 to 25 ± 4.2 ngL−1 wherein sediment was from 107 ± 4.1 ngKg−1 to 17 ± 1.4 ngKg−1. TBT in Perna viridis was found to range from 4 ± 1.2 ngKg−1 to 42 ± 2.2 ngKg−1 wet weight and in ascending order of the body weight. The highest TBT level in water and sediment was found in the Colombo port where the highest level of TBT in P. viridis (42 ± 2.2 ngKg−1) was recorded from the Dikkowita fishery harbor. A positive correlation between the number of male P. viridis and TBT level (p < 0.05) suggests possible reproductive impairment in aquatic animals exposed continuously to a high concentration of TBT.

Quantification of tributyltin in seawater using triple isotope dilution gas chromatography–inductively coupled plasma mass spectrometry achieving high accuracy and complying with European Water Framework Directive limits

A triple isotope dilution GC-ICPMS method for the determination of tributyltin (TBT) was developed and validated to meet the European Water Framework Directive (WFD) requirements. The validation procedure involved the evaluation of trueness, precision (repeatability, intermediate precision), limit of detection (LOD) and limit of quantification (LOQ), stability, measurement uncertainty and traceability studies. The method is one of the most sensitive methods published to date with good accuracy, 103% average recovery in the range with %RSDs of 2.8-6.7%. A LOD value of 0.015 ng L−1 for the TBT cation was achieved with a sample volume of 12 mL seawater. TBT was derivatized using 20 µL sodium tetraethylborate solution (0.05% NaBEt4) to make volatile for GC-ICPMS. Measurement uncertainty was in the range of 4.8-13% which was achieved through dissolution of tributyltinchloride (TBTCl) in 1-propanol, a low-volatility solvent combined with the use of a triple isotope dilution (ID) calibration technique. Isotope dilution calibration was performed by adding 117Sn isotopically enriched TBT to the seawater samples. The stability test results showed that TBT concentration was stable for three months in seawater samples after passing through a 0.2 µm filter and stored in amber glass bottles at 4°C. The response surface methodology (RSM) approach was successfully implemented to provide optimal conditions for large volume injection (LVI) to obtain the maximum analytical signal. The key variables selected in the experimental design were evaporation time, evaporation temperature, carrier flow, and injection speed. This method was applied to seawater samples collected from the Bay of Izmit, Kocaeli, Turkey, where TBT pollution has not been measured yet.

Determination of Tributyltin and Triphenyltin in Fish and Shellfish Using Accelerated Solvent Extraction and Liquid Chromatography with Tandem Mass Spectrometry

A determination method for tributyltin (TBT) and triphenyltin (TPT) in fish and shellfish using an accelerated solvent extractor (ASE) and LC-MS/MS was developed. The chromatographic separation was conducted on a Poroshell 120 EC-C18 column using an isocratic mobile phase of 0.1% formic acid in 70% methanol. Sample preparation was performed using ASE at 125℃ with n-hexane and a cleanup using a Florisil cartridge. Internal calibration curves using deuterium-labeled TBT and TPT were employed for quantification. For both TBT and TPT, the calibration curves were linear in the range of 0.2-250 ng/mL, and the method quantification limits were 0.8 ng/g for both TBT and TPT. A National Institute for Environmental Studies certified reference material, No. 15 (adductor muscle of scallop), was analyzed to assess the performance of the developed method. The trueness, relative standard deviations of repeatability, and within laboratory reproducibility of this method, evaluated using a recovery test with four spiked fish species and one shellfish, ranged from 89.3 to 105.3%, 1.0 to 4.5%, and 1.3 to 7.6%, respectively.

Paper Based Photoluminescent Sensing Platform with Recognition Sites for Tributyltin.

In this study, a novel photoluminescence material for the detection of tributyltin (TBT) was developed by using a paper-based nanocomposite system. For this purpose, molecularly imprinted polymeric nanoparticles (MIN) were synthesized with mini-emulsion polymerization technique. Graphene quantum dots obtained by the hydrothermal pyrolysis were immobilized to the nanoparticle surface via EDC-NHS coupling. The fabrication of sensing platform for TBT can be divided into two steps that are the preparation of nanocomposite and the applying the nanocomposite onto nitrocellulose membrane. The selectivity constant and association kinetics were calculated to analyze the interaction of TBT with immobilized MINs. The results proved that the developed nanosensor is promising for the determination of TBT with high selectivity and sensitivity reaching a detection limit of 0.23 ppt in seawater. This novel photoluminescent nanosensor has the potential to pave the way for further studies and applications.

Selective non-chromatographic determination of tributyltin in sediments using EDTA and diphenylcarbazone as masking agent

ABSTRACTTwo analytical procedures based on the generation of volatile tributyltin derivatives, their separation by headspace solid-phase microextraction (HS SPME) and subsequent determination using plasma optical emission spectrometry (OES) have been developed for the selective determination of trace tributyltin (TBT) in the presence of other butyltins and inorganic tin in sediments without the use of chromatography. A microwave-assisted leaching of tin compounds from the sediment using 25%v/v acetic acid is applied for sample pretreatment. The first method takes advantage of TBT chloride releasing from the lecheate after adding 3 M hydrochloric acid, and subsequent separation of the analyte by HS SPME using Carboxen-poly(dimethylsiloxane) (CAR/PDMS). The second method involves the use of masking agents, namely ethylenediaminetetraacetic acid (EDTA) and diphenylcarbazone (DFC), which form stable chelates with monobutyltin (MBT) and dibutyltin (DBT), respectively, followed by the ethylation of tributyltin at pH 5 using sodium tetraethylborate (NaBEt4) solution. The final concentration of NaBEt4 is 0.05%w/v. The parameters affecting the TBT derivatisation and separation by HS SPME have been optimised including the selection of SPME fibre coating (PDMS, CAR/PDMS), the amount of masking agents and NaBEt4 added, sorption time (2–40 min) and sorption temperature (25–60°C). Higher sensitivity and robustness are attained with the method involving ethylation derivatisation, leading to the limit of detection (LOD) of 3 ng L−1. The selective release of TBT is observed from aqueous solutions, where the concentrations of MBT and DBT were in 2–50-fold excess to TBT. The SPME-TD-MIP-OES methods have been validated against several certified reference materials (CRMs), including SOPH-1 marine sediment, PACS-2 marine sediment and BCR 646 freshwater sediment.

Accurate Determination of Tributyltin in Tannery Wastewater by a New Procedure Using ID-HPLC–ICP-MS Combined with Low Temperature Extraction

Isotope dilution mass spectrometry is recognized as a primary method to obtain traceable values in the measurement of substances including trace elements and their organometallic compounds. This paper reports a novel method where isotope dilution high performance liquid chromatography inductively coupled plasma mass spectrometry (ID-HPLC–ICP-MS) was combined with low temperature extraction for the determination of tributyltin (TBT) in tannery wastewater from the leather industry. It has been found that the liquid–liquid extraction at very low temperature is in the favor of extraction of organotin, as the enrichment factor for low temperature (−80 °C) extraction was about 1.3 times higher than for extraction at room temperature (20 °C). The method detection limit of TBT, obtained from the proposed ID-HPLC–ICP-MS procedure after extraction with a sample volume of 7.5 by 2.5 mL of organic phase, was found to be 0.13 ng g−1. When TBT was determined in a range of 10–1000 ng g−1 in tannery wastewater samples, the analyte recoveries were in the range 90.1–107.2% with relative standard deviations of between 2.0 and 7.2%. Finally, the new method of ID-HPLC–ICP-MS combined with low temperature extraction was applied to the determination of TBT in actual tannery wastewater. The TBT contents from three different tanning procedures (chrome tanning, vegetable tanning and aldehyde tanning), expressed as the mean ± the expanded uncertainty (k = 2) were 378.65 ± 20.38, 110.04 ± 5.96 and 690.17 ± 35.31 ng g−1, respectively.

Determination of Tributyltin in Seafood Based on Magnetic Molecularly Imprinted Polymers Coupled with High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

In this study, Fe3O4 was adopted as a carrier for surface molecular imprinting with two-stage polymerization. First, the functional monomer (methacrylic acid, MAA) was modified on the surface of Fe3O4, which was then polymerized with the template molecule (tributyltin, TBT), cross linking agent (ethylene glycol dimethacrylate, EGDMA), and porogen (acetonitrile), hereby successfully preparing Fe3O4@MIPs prone to specifically identify TBT. The physical properties of Fe3O4@MIPs were then characterized, and adsorption and selection capacities were also assessed. Compared with conventional imprinting polymers, this magnetic molecular imprinting polymer (MIP) displayed significantly increased and more specific adsorption. Meanwhile, its pretreatment was simpler and faster due to magnetic separation characteristics. Using magnetic MIPs as adsorbents for enrichment and separation, detection limit, recovery rate, and linear range were 1.0 ng g−1, 79.74–95.72%, and 5 ng g−1~1000 ng g−1, respectively, for a number of seafood samples. High-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was used to analyze Tegillarca granosa, mussels, large yellow croaker, and other specimens, with recovery rates of 79.74–95.72% and RSD of 1.3%–4.7%. Overall, this method has a shorter total analysis time, lower detection limit, and wider linear range and can be more effectively applied to determine MAA in seawater and seafood.

Quantitative Headspace Solid-Phase Microextraction Gas Chromatography Mass Spectrometry (HS-SPME-GC-MS/ MS) Method for the Determination of Tributyltin in Sediment: Validation according to EU Directive Requirement

Quantitative Headspace Solid-Phase Microextraction Gas Chromatography Mass Spectrometry (HS-SPME-GC-MS/ MS) Method for the Determination of Tributyltin in Sediment: Validation according to EU Directive Requirement

Towards tributyltin quantification in natural water at the Environmental Quality Standard level required by the Water Framework Directive

The European Union (EU) has included tributyltin (TBT) and its compounds in the list of priority water pollutants. Quality standards demanded by the EU Water Framework Directive (WFD) require determination of TBT at so low concentration level that chemical analysis is still difficult and further research is needed to improve the sensitivity, the accuracy and the precision of existing methodologies. Within the frame of a joint research project “Traceable measurements for monitoring critical pollutants under the European Water Framework Directive” in the European Metrology Research Programme (EMRP), four metrological and designated institutes have developed a primary method to quantify TBT in natural water using liquid–liquid extraction (LLE) and species-specific isotope dilution mass spectrometry (SSIDMS). The procedure has been validated at the Environmental Quality Standard (EQS) level (0.2ngL−1 as cation) and at the WFD-required limit of quantification (LOQ) (0.06ngL−1 as cation). The LOQ of the methodology was 0.06ngL−1 and the average measurement uncertainty at the LOQ was 36%, which agreed with WFD requirements. The analytical difficulties of the method, namely the presence of TBT in blanks and the sources of measurement uncertainties, as well as the interlaboratory comparison results are discussed in detail.

Determination of tributyltin in whole water matrices under the European Water Framework Directive

Monitoring of water quality is important to control water pollution. Contamination of the aquatic system has a large effect on human health and the environment. Under the European Water Framework Directive (WFD) 2000/60/EC and the related directive on environmental quality standards (EQS) in the field of water policy 2008/105/EC, the need for sensitive reference methods was highlighted. Since tributyltin (TBT) is one of the WFD listed priority substances a method was developed which is capable to qualify and quantify the pollutant at the required low WFD EQS of 0.2ngL−1 in whole water bodies, i.e. in non-filtered water samples with dissolved organic carbon and suspended particulate matter. Therefore special attention was paid on the interaction of TBT with the suspended particulate matter and humic substances to obtain a complete representation of the pollution in surface waters. Different water samples were investigated varying the content of organic dissolved and suspended matter. Quantification was performed using species-specific isotope dilution (SSID) and gas chromatography with inductively coupled plasma mass spectrometry (GC-ICP-MS). Different sample treatment strategies were evaluated and compared. The process of internal standard addition was investigated and optimized, hence the equilibrium between internal standards and matrix is of primary importance to perform accurate SSID. Samples spiked at EQS level were analyzed with a recovery between 95 and 105 %. Additionally real surface water samples were investigated and the TBT concentration for the whole water body was determined and compared with conventional routine analysis method.

A novel application of nylon membranes for tributyltin determination in complex environmental samples by fluorescence spectroscopy and multivariate calibration

The widely distributed pollutant tributyltin (TBT) was analyzed in different environmental samples (waters and sediments) combining preconcentration on a nylon membrane, excitation–emission fluorescence matrices directly measured over the membrane and second-order multivariate calibration. The latter was implemented using unfolded partial least-squares with residual bilinearization (U-PLS/RBL), a flexible algorithm achieving second-order advantage, even under severe spectral overlapping among sample components. Matrix-specific calibrations were required to overcome matrix effects, resulting in good analytical performance. TBT was determined in the concentration ranges 0.043–1.42ng Sn mL−1 in water and 24–400μg Sn kg−1 in sediments, with adequate detection limits in the range 0.03–0.15ng Sn mL−1.

Evaluation of cloud point extraction coupled with fluorescence spectroscopy and multivariate curve resolution–alternating least squares for tributyltin determination in sediment samples

In this work, a new procedure for tributyltin (TBT) detection in marine sediments based on cloud point extraction (CPE) followed by total fluorescence spectroscopy combined with multivariate curve resolution–alternating least squares (MCR–ALS) is proposed. The multivariate model satisfactorily achieved the second order advantage in the presence of uncalibrated interferences, such as butyltin compounds or metallic species that are commonly found in sediment sample extracts. Under optimal conditions, the detection limit reached 3.0μg Sn L−1, and the relative prediction error was lower than 10%. The accuracy of the method was validated with the analysis of a certified sediment sample (marine sediment PACS-2), and there was good agreement between the certified and experimental results. Finally, the proposed methodology was satisfactorily applied to spiked real sediment samples, demonstrating the suitability of the proposed method for TBT detection in contaminated sediment samples.

Levels and assessment of organotin contamination at Futian Mangrove Wetland in Shenzhen, China

The concentrations of organotins (OTs) were measured in the surface sediments, mollusks and mudskippers at Futian Mangrove Wetland in Shenzhen, China, an ecologically important wetland that serves as a wintering ground and a stop-over point for migrating birds. The average concentrations of tributyltin (TBT), dibutyltin (DBT), triphenyltin (TPhT) and diphenyltin (DPhT) were 2.42, 9.11, 1.10 and 13.99 ng Sn⋅g−1 (dry weight, dw) in sediments respectively, 1.19, 5.19, 14.41 and 6.11 ng Sn⋅g−1 dw in organisms respectively. Contamination by OTs in the wetland was considered low and concentrations appeared to be declining; this decline presumably comes on the heels of China adopting in 2011, the International Convention on the Control of Harmful Anti-fouling Systems on Ships (AFS convention). However, the biota-sediment accumulation factor of TPhT was relatively high in mollusks and mudskippers. The potential ecotoxicological risk of OTs contamination to the benthic biota and those organisms at higher trophic levels, especially endangered waterfowl inhabiting wetlands, should be of concern. Further, the present study confirmed the accuracy, high stability and time-saving procedure in determination of TBT, DBT, TPhT and DPhT in sediment and organisms through the use of a high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS), which may potentially be useful to a wider application in environmental monitoring with limitations of the analytical method for analysis of monobutyltin (MBT) and monophenyltin (MPhT).

Determination of tributyltin in environmental water matrices using stir bar sorptive extraction with in-situ derivatisation and large volume injection-gas chromatography–mass spectrometry

Stir bar sorptive extraction with in-situ derivatization using sodium tetrahydridoborate (NaBH4) followed by liquid desorption and large volume injection-gas chromatography–mass spectrometry detection under the selected ion monitoring mode (SBSE(NaBH4)in-situ–LD/LVI-GC–MS(SIM)) was successfully developed for the determination of tributyltin (TBT) in environmental water matrices. NaBH4 proved to be an effective and easy in-situ speciation agent for TBT in aqueous media, allowing the formation of adducts with enough stability and suitable polarity for SBSE analysis. Assays performed on water samples spiked at the 10.0μg/L, yielded convenient recoveries (68.2±3.0%), showed good accuracy, suitable precision (RSD<9.0%), low detection limits (23ng/L) and excellent linear dynamic range (r2=0.9999) from 0.1 to 170.0µg/L, under optimized experimental conditions. By using the standard addition method, the application of the present methodology to real surface water samples allowed very good performance at the trace level. The proposed methodology proved to be a feasible alternative for routine quality control analysis, easy to implement, reliable and sensitive to monitor TBT in environmental water matrices.

Determination of tributyltin in marine sediment and waters by pressurised solvent extraction and liquid chromatography-tandem mass spectrometry

In this study, tributyltin (TBT) was extracted from marine sediment matrix with the use of pressurised solvent extraction (PSE), which uses high-temperature and -pressure conditions to increase extraction efficiency. The analyte was chromatographically resolved using a liquid chromatography-tandem mass spectrometry (LC-MS/MS) system with a pentafluorophenyl (PFP) column and a methanol/aqueous formic acid mobile phase gradient, and was detected by MS/MS as product fragments after collisionally induced dissociation (CID) of the cationic parent molecule. This study represents the first application of PSE extraction combined with LC-MS/MS analysis for the determination of TBT in sediments. The method has been validated according to the International Organisation for Standardisation (ISO) 17025:2001 and affords automated extraction of sediment samples with high-sensitivity analysis. The full method limit of detection was established as 1.25ng Sng(-1) with an instrument detection limit of 0.01ng Sng(-1). The chromatographic procedure may also be applied for the direct analysis of water matrices without the need for sample manipulation, and therefore represents a combined analytical approach for the monitoring of TBT contamination in marine or estuarine ecosystems.

Comparison of Temperature-Controlled Dispersive and Hollow Fiber Microextraction Techniques Using Ionic Liquid for Determination of Tributyltin and Triphenyltin in Water

Comparison of Temperature-Controlled Dispersive and Hollow Fiber Microextraction Techniques Using Ionic Liquid for Determination of Tributyltin and Triphenyltin in Water

Validation of a method for the determination of tributyltin in seawater by stir bar sorptive extraction–liquid chromatography tandem mass spectrometry

The main objective of this work is to develop an accurate, sensitive, simple and cost-effective method for the determination of tributyltin species (as cationic form) in seawater at ultra-trace levels. The method is based on the use of stir bar sorptive extraction (SBSE) followed by solvent desorption and liquid chromatography tandem mass spectrometry (SD–LC–MS/MS (QqQ)) analysis, operating in positive electrospray ionisation (ESI) and in the selected reaction monitoring (SRM) mode. Extraction and LC–MS/MS parameters were accurately optimised to achieve the highest recoveries and to enhance the analytical characteristics of the method. The different parameters that affect the extraction procedure, the chromatographic and spectrometric conditions, and the surrogate selection were evaluated. In contrast with previously proposed methods, the proposed method involves a simplified sample treatment. Quality parameters such as linearity, accuracy in terms of trueness and precision, uncertainty and specificity were examined with good results. The evaluation of two surrogates (tri-n-propyltin chloride and tripentyltin chloride) was also carried out. The limit of detection (LOD) and limit of quantification (LOQ) obtained were 0.8 and 2.5ngL−1, respectively. Precision, expressed as relative standard deviation (%RSD), was lower than 16%, and the determination coefficient (R2) was higher than 0.990 with a residual deviation for each calibration point lower than ±25%. Mean recoveries were between 92% and 102%. The accuracy of the method was also studied by participating in an external proficiency testing scheme. After validation, the method was applied to the analysis of all tributyltin species found in natural seawater samples. The method meets the requirements of the United States Environmental Protection Agency (US-EPA).

A new validated analytical method for the determination of tributyltin in water samples at the quantification level set by the European Union

According to recent directives of the European Union (EU), limits of quantification (LOQ) for the determination of tributyltin (TBT) in surface waters should be ca. 60pg/L (ppq). This put very stringent requirements on analytical methodologies; definitely when they have to be applied in a routine environment. Stir bar sorptive extraction (SBSE), followed by thermal desorption (TD) and capillary gas chromatography–triple quadrupole mass spectrometry (GC–MS/MS) can provide accurate and precise data at the 2ng/L level (ppt). For lower concentrations, matrix and reagent interferences together with contamination may provide too high TBT values. A two-dimensional heart-cut GC method was developed to fractionate TBT from interferences. The GC–GC–MS/MS method shows excellent linearity in the range 50pg/L–4ng/L, good repeatability (RSD<20% at 200pg/L), and a limit of detection of 11pg/L. The method performance is demonstrated with representative samples i.e. harbor water and waste water samples.