Determination of butyltin species in natural waters using aqueous phase ethylation and off-line room temperature trapping

Monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) were determined in natural water samples by aqueous phase ethylation with sodium tetraethylborate (STEB), room temperature trapping of the resulting volatile derivatives on Tenax TA^®, followed by gas chromatography-quartz furnace atomic absorption spectrometry (GC-QFAAS). Recoveries of butyltin spikes from natural water samples were 90-109% at concentrations of ∼100 ng Sn/l. The method precision at ∼100 ng Sn/l was ≤6% RSD for butyltins spiked into natural waters. The detection limits for 1 l water samples were <1 ng Sn/l for all butyltin species. Sample throughput of the method is high (greater than three samples per hour) due to the two-stage nature of the procedure, which allows derivatisation/trapping and GC-QFAAS quantitation to be performed separately. Off-line trapping is also advantageous as it extends the life of the GC column and quartz furnace to at least 12 months due to minimisation of carry-over of co-purged material.     

Determination of butyl- and phenyltin compounds in sediments by GC-FPD after NaBEt(4) ethylation

A reliable and rapid speciation method for the simultaneous determination of butyl- and phenyltin species in sediment samples has been developed. Two extraction procedures are compared: methanolic hydrochloric acid (at four different concentrations) and ethanoic acid leaching. Derivatization is carried out by the one-step ethylation/extraction procedure using the sodium tetraethylborate reagent directly in aqueous phase in the presence of an isooctane layer. Analysis is performed by capillary gas chromatography hyphenated to flame photometric detection (GC-FPD). Detection limits range from 0.5 to 1.5 ng(Sn) g(-1)(dry weight). Analysis of environmental samples and certified reference materials demonstrate the accuracy of the analytical method.     

An improved speciation method for mercury by GC/CVAFS after aqueous phase ethylation and room temperature precollection

An improvement has been made in previous mercury speciation methods, which omits the use of liquid nitrogen by modifying the GC conditions. In addition, the sometimes observed thermal decomposition of ethylation derivatives in the process of desorbing the compounds to the GC column has been investigated and overcome. The resulting improvements have allowed simultaneous determination of methylmercury (MMHg) and inorganic mercury (Hg(II)). They have also increased the precision of the ethylation reaction and refined the MMHg determination. Optimal conditions for MMHg were confirmed and supplemented, while the parameters for dimethyl mercury (DMHg) and Hg(II) were thoroughly investigated for the first time. The absolute detection limits (DL) for 2sigma of the reagent blanks as Hg and about 0.6, 0.6 and 1.3 pg for DMHg, MMHg and Hg(II), respectively. The improved method is five-fold faster than the original method, allowing up to 80 samples to be analyzed within 8 hr.     

Biotransformation of butyltin compounds using pure strains of microorganisms

The debutylation of tributyltin chloride by several strains of fungi, yeasts and bacteria is described. Under standard conditions and with low initial concentration of substrate, significant biotic degradation of tributyltin (6–32%) was detected after five days at 28°C. Dibutyltin and monobutyltin were formed in all cases, with higher yields of the latter. Two microorganisms catalysed the transformation of monobutyltin to dimethyltin and trimethytin whereas all microorganisms were able to methylate inorganic tin(IV) to trimethyltin. Our results suggest that tributyltin biodegradation by microorganisms is generally possible, provided sufficiently low concentrations of substrate are used.     

Simultaneous determination of butyltin and phenyltin species in sediments using ultrasound-assisted leaching

A fast and simple procedure is presented for the simultaneous leaching of butyl (mono, di and tributyl) and phenyl organotin species from sediment samples. Leached compounds are further ethylated with sodium tetraethylborate in aqueous medium, and analyzed by gas chromatography. After testing the stability of triphenyltin under different extraction conditions, ultrasound-assisted leaching at room temperature in the presence of acetic acid was been proposed as an extraction procedure compatible with the simultaneous determination of phenyl- and butyltin compounds in sediments. Recoveries between 70 and 90% were obtained for phenyl species in spiked samples prepared in the laboratory. Results for butyltin species were validated by use of the reference material PACS-2. Quantification limits, using GC-MIP-AES as measurement technique, were approximately 5-10 ng g(-1). Precision in the consecutive analysis of three sediment samples varied between 3 and 10%.     

Simultaneous determination of butyltin and phenyltin species in sediments using ultrasound-assisted leaching

A fast and simple procedure is presented for the simultaneous leaching of butyl (mono, di and tributyl) and phenyl organotin species from sediment samples. Leached compounds are further ethylated with sodium tetraethylborate in aqueous medium, and analyzed by gas chromatography. After testing the stability of triphenyltin under different extraction conditions, ultrasound-assisted leaching at room temperature in the presence of acetic acid was been proposed as an extraction procedure compatible with the simultaneous determination of phenyl- and butyltin compounds in sediments. Recoveries between 70 and 90% were obtained for phenyl species in spiked samples prepared in the laboratory. Results for butyltin species were validated by use of the reference material PACS-2. Quantification limits, using GC–MIP–AES as measurement technique, were approximately 5–10 ng g^–1. Precision in the consecutive analysis of three sediment samples varied between 3 and 10%. Received: 16 January 2001 / Revised: 12 March 2001 / Accepted: 13 April 2001     

Voltammetric speciation of butyltin compounds

A sensitive and selective procedure for the determination of tributyltin chloride (TBT), dibutyltin dichloride (DBT) and monobutyltin trichloride (MBT) based on solid phase extraction (SPE) with ENVI-Carb non-porous carbon as column material followed by adsorptive cathodic stripping voltammetry (AdSV) in the presence of tropolone is reported. The determination limits achieved using a 500 mL water sample were 210 ng L^–1 (as Sn) for TBT, 30 ng L^–1 (as Sn) for DBT and 40 ng L^–1 (as Sn) for MBT. The method was used to determine the levels of butyltin species in surface water from the yacht harbour at Zewen on the Mosel River and in the tap water supply in Trier.Dedicated to Professor Dr. K. Doerffel and Professor Dr. H. Kriegsmann on the occasion of their 70th birthdays     

Determination of methylmercury in environmental samples using static headspace gas chromatography and atomic fluorescence detection after aqueous phase ethylation

A rapid and automated method for the determination of monomethylmercury (MMHg) in environmental samples was developed using headspace gas chromatography with atomic fluorescence detection in combination with aqueous phase ethylation. Sample preparation steps were optimized for sediments, biological samples, and water samples using certified reference materials and real samples with a broad range of MMHg concentrations. Different extraction procedures were compared for both sediments and biological samples. The methods were applied in the intercomparison exercises for the certification of MMHg in sediments (IAEA 405) and in Oyster tissue (BCR 710) and the results were accepted for certification. The detection limits for MMHg are 0.002 ng Hg/g for sediments and biological samples and 0.01 ng Hg/L for water samples. The method was tested for methylation artifacts; no artifact was observed in the sediment samples and CRMs tested.     

Speciation of butyltin compounds in oyster samples

Experimental instrumentation for the speciation of butyltin compounds by hydride generation and gas chromatography-quartz furnace atomic absorption spectrometry is described. Evaluation of a number of extraction methods revealed that simple acid leaching of oyster samples gave adequate recoveries. The levels of each butyltin species in oyster flesh and gill are reported together with the tentative identification of a mixed methylbutyltin compound.     

Isotope dilution GC-MS routine method for the determination of butyltin compounds in water

A standard GC-MS instrument with electron impact ionisation has been used to develop a fast, simple and reliable method for the simultaneous determination of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) in water samples. Isotope dilution analysis (IDA) is used for the determination of species, taking advantage of a commercially available spike solution containing a mixture of MBT, DBT and TBT enriched in ¹¹⁹Sn. Method detection limits for 100-mL samples were between 0.18 and 0.25 ng L⁻¹ for the three butyltin compounds with typical RSD between 2 and 4% at levels between 100 and 10 ng L⁻¹, respectively. Recovery of tin species in spiked samples (natural water, wastewater and seawater) was quantitative. The stability of butyltin compounds in collected seawater samples was also studied. The addition of a 1% (v/v) glacial acetic acid preserved tin species in the samples for at least 5 days at room temperature. The IDA method was finally implemented in a routine testing laboratory and it was subsequently accredited by the Spanish National Accreditation Body according to the requirements of UNE-EN ISO/IEC 17025.     

Speciation of butyltin compounds in marine sediments by preconcentration on C60 and gas chromatography-mass spectrometry

A new method for the speciation of butyltin compounds by solid phase extraction and direct injection using gas chromatography-mass spectrometry (GC/MS) is described. The compounds were complexed with sodium diethyldithiocarbamate and retained on a C60 sorbent column. The neutral chelates of butyltin compounds were eluted with ethyl acetate containing NaBPr4 as derivatising reagent. The main analytical figures of merit of the proposed method for 10 ml of sample are: linear range 0.2-35 ng/g expressed as Sn; limits of detection, 0.07, 0.09 and 0.10 ng/g as Sn for monobutyltin, dibutyltin and tributyltin, respectively. No interferences from metal ions such as Zn2+, Fe3+, Sb3t, Pb2+, Ni2+ and Mn2+ were observed in the determination of organotin compounds. The validation of method was performed out by the analysis of a standard reference sediment (CRM 462). The method was also applied to the determination of butyltin compounds in marine sediment samples.     

Speciation of butyltin compounds in marine sediments with headspace solid phase microextraction and gas chromatography mass spectrometry

A method for the determination of organotin compounds (monobutyl = MBT, dibutyl = DBT, and tributyltin = TBT) in marine sediments by headspace Solid Phase Microextraction (SPME) has been developed. The analytical procedure involved 1) extraction of TBT, DBT and MBT from sediments with HCl and methanol mixture, 2) in situ derivatization with sodium tetraethylborate and 3) headspace SPME extraction using a fiber coated with poly(dimethylsiloxane). The derivatized organotin compounds were desorbed into the splitless injector and simultaneously analyzed by gas chromatography - mass spectrometry. The analytical method was optimized with respect to derivatization reaction and extraction conditions. The detection limits obtained for MBT, DBT and TBT ranged from 730 to 969 pg/g as Sn dry weight. Linear calibration curves were obtained for all analytes in the range of 30-1000 ng/L as Sn. Analysis of a standard reference sediment (CRM 462) demonstrates the suitability of this method for the determination of butyltin compounds in marine sediments. The application to the determination of TBT, DBT and MBT in a coastal marine sediment is shown.     

Determination of organotin compounds in marine sediments using graphite furnace atomic absorption spectrometry

Organotin compounds, especially tributyltin, began to cause concern 10 years ago due to a high toxicity towards marine organisms. Several methods of analysing organotin compounds in various matrices have already been developed to determine organotin species simultaneously, but these are quite expensive as special equipment and specialized staff are needed. A simple screening method, which determines the organic tin compounds in the sediment, has therefore been developed and validated. The method can easily be implemented in laboratories accustomed to tracelement analyses; the sediment is extracted by a two-phase extraction and the organic extract is analysed using graphite furnace atomic absorption spectrometry (GF AA.) The screening method has been validated using high-pressure liquid chromatography-inductively coupled plasma mass spectrometry (HPLC–ICP MS).     

Determination of thiabendazole in aqueous solutions using a cucurbituril-enhanced fluorescence method

The complexation of thiabendazole (TBZ) with the cucurbit[6]uril (Q[6]), cucurbit[7]uril (Q[7]) and symmetric tetramethyl-cucurbit[6]uril (TMeQ[6]) in aqueous solution has been investigated using UV–vis and fluorespectrometry. The experimental results show 1:1 host–guest inclusion complexes at pH 6.5 for all three macrocyclic hosts, and the corresponding formation constants by UV and fluorescence methods are (5.37?±?1.05)?×?10⁴?L?mol^?1 and (1.47?±?0.41)?×?10⁴?L?mol^?1 for the Q[6]-TBZ system (7.76?±?0.51)?×?10⁴?L?mol^?1 and (9.36?±?0.22)?×?10⁴?L?mol^?1 for the Q[7]-TBZ system (1.28?±?0.78)?×?10⁴?L?mol^?1 and (2.69?±?0.55)?×?10⁴?L?mol^?1 for the TMeQ[6]-TBZ system, respectively. Based on the enhancement of the fluorescence intensity of TBZ with the addition of Q[n]s in neutral media, a fluorespectrometry method for the determination of TBZ in aqueous solution in the presence of Q[n] was established. In the range of 6.0?×?10^?8?mol?L^?1–8.0?×?10^?6?mol?L^?1 a linear relationship was obtained between fluorescence intensity and TBZ concentration. The detection limit was found to be between 5.51 and 8.85?×?10^?9?mol?L^?1. The interference of coexisting ions was found to be slight. The proposed method has been successfully applied to the determination of TBZ in different aqueous solutions with satisfactory recoveries of 92–103%. The method seems to be suitable for environmental water analysis.     

Allylation reactions of carbonyl compounds using an organosilicon reagent in aqueous media

Allylation reactions of carbonyl compounds such as aldehydes and reactive ketones using allyltrimethoxysilane in aqueous media proceeded smoothly in the presence of 5 mol% of a CdF2-terpyridine complex; the presence of the ligand plays an important role for the catalytic activity; the catalyst was easily recovered and reused without loss of activity.     

GC FPD method for the simultaneous speciation of butyltin and phenyltin compounds in waters

A method is described for the simultaneous determination of nanogram amounts of mono-, di- and tri-butyltin compounds in water. The procedure is based on the conversion of tin compounds to volatile species by Grignard pentylation and analysis using GC with flame photometric detection (GC FPD). The ionic compounds are extracted from diluted acidified (HBr) aqueous solutions by using a pentane-tropolone solution. The extracted organotin compounds are pentylated by a Grignard reagent and purified on a Fluorisil column before analysis by GC FPD. The detection limits are 20 ng dm^?3 for butyltin compounds and 50 ng dm^?3 for phenyltin compounds. Recoveries from spiking experiments in tap-water and natural seawater matrices, in which no organotin compounds were detected, were greater than 90% for most of the alkyltin compounds.     

A simple method for concentrating volatile flavor compounds in aqueous systems using RP-HPLC

Summary Volatile flavor compounds in aqueous model systems, distillates of coffee extract and juices such as apple, tomato, pineapple and grape were adsorbed on an ODS column during HPLC and monitoring absorption at 280nm. The adsorbed volatile compounds were eluted with a small volume of ethanol. Volatile compounds in the eluates were concentrated 22 to 100 times those in the distillates. Recovery of compounds was 50–90%. Breakthrough of specific compounds such as -valerolactone, furfuryl acetate and t-2-hexenal in the model systems and several compounds in the juice distillates was detected by capillary GC. Pattern similarity calculated between the GC profiles of a juice distillate and the corresponding eluate gave a qualitative comparison. This novel and versatile method utilizing conventional RP-HPLC may be widely applicable for concentrating volatiles in aqueous systems, at levels from ppm to ppb.     

Headspace solid-phase micro-extraction gas chromatography-mass detection method for the determination of butyltin compounds in wines

Butyltin compounds are widespread contaminants which have also been found in some wines, determined by liquid-liquid extraction followed by alkylation with a Grignard reagent and gas chromatography-mass spectrometric (GC-MS) analysis. A promising alternative to this extraction/derivatization method is the one-step tetraethylborate in situ ethylation/solid-phase micro-extraction (SPME) method. In this work, a SPME-GC-MS method for the determination of butyltin compounds in wine was optimised. The optimised parameters concerned the pre-treatment with tetramethylammonium hydroxide, matrix modification with sodium chloride, tetraethylborate concentration, extraction time and temperature, and the GC separation program. The analytical figures of merit of the optimised method (range, limit of detection (LOD) and reproducibility) were evaluated. The sensitivity (range 20-1421 kcounts μg⁻¹ l⁻¹ as Sn) and LOD (range, 0.01-0.2 μg l⁻¹ as Sn) depended greatly on the butyltin species to be measured and on the type of wine. For the tested species (monobutyltin, dibutyltin and tributyltin) the highest sensitivities were achieved for Port wine samples, followed by red wine>white wine>white Verde wine. The method allowed acceptable repeatability (relative standard deviation (R.S.D.), 6-8%; n=4) and reproducibility (R.S.D., 8-9%; n=3).