Atomic absorption spectrometric/hydride generation determination of tributyltin and dibutyltin in sea water at the nanogram per litre level

A relatively simple system is described for the determination of tributyltin and dibutyltin in sea water at the ng l^?1 level. It is based on hydride generation followed by cryogenic trapping on a silanized glass wool column, transport to a quartz cuvette atomizer, and detection by atomic absorption spectrometry. Detection limits (3σ) of 2 ng Sn l^?1 are obtained for both species.     

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 1.25 ng Sn g^?1 with an instrument detection limit of 0.01 ng Sn g^?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.     

Determination of tri-n-butyltin in oysters by reaction-gas chromatography of hydride derivatives

A reaction-gas chromatography method for determining tri-n-butyltin (TBT) as the hydride derivative has been adapted to allow determination of TBT in oysters. The extraction method has been modified to prevent fouling of the hydride formation reactor and the gas chromatography has been made faster by employing a different column and temperature program. The detection limit is 3-6 ng/g in oyster tissue. Apparent recoveries of TBT from oyster tissue at 25 and 125 ng/g levels are 107 and 97%, respectively.     

Determination of lead in sea water by electrothermal atomic absorption spectrometry after electrolytic accumulation on a glassy carbon furnace

Lead in sea water is determined by combining in situ preconcentration of the analyte on a proper glassy carbon furnace from flowing solutions, with electrothermal atomic absorption spectrometry. The apparatus is a modified version of a prototype previously tested for lead determination in different salt solutions and for mercury determination in sea water. The effects of experimental parameters such as pH, flow rate, electrolysis current, electrolysis time, etc., are described and the optimum conditions for determination of lead are given. The relative standard deviation at 1.5 ng Pb ml^-1 is ±1%, and the detection limit (twice the standard deviation of the blank) is 0.03 ng ml^-1.     

Speciation analysis of thallium in water samples after separation/preconcentration with the Empore™ chelating disk

A simple, reliable and novel solid phase extraction procedure using the Empore? chelating disk has been developed for determination of Tl(I) and Tl(III) in environmental water samples by electrothermal atomic absorption spectrometry (ETAAS). The influence of humic acids on separation/preconcentration of thallium species with the Empore? chelating disk is investigated. The preconcentration factor and detection limit are 500 and 5?ng?L^?1, respectively. The recoveries are in the range 93–103% for mineral, pond, sea, snowmelt, waste waters at 28–500?ng?L^?1 Tl and in the range 82–112% for river waters at 18–28?ng?L^?1 Tl.     

Atomic absorption spectrometric determination of trace tellurium after hydride trapping on platinum-coated tungsten coil

In this work, a sensitive and simple method for the determination of tellurium was developed by hyphenation of electrically heated quartz tube atomic absorption spectrometry and tellurium hydride trapping on platinum-coated tungsten coil. With a mixture of Ar and H₂, tellurium hydride was transported to tungsten coil for trapping at 390 °C and releasing at 1200 °C. A limit of detection (LOD, 3σ) of 0.08 ng mL^{− 1} was obtained with 1 min trapping (1.5 mL sampling volume), and enhancement factor was 28 compared to conventional hydride generation atomic absorption spectrometry. The LOD was better or at least comparable to literature levels involving on-line trapping and some other sophisticated instrumental method such as graphite furnace atomic absorption spectrometry (GF-AAS) and inductively coupled plasma mass spectrometry (ICP-MS), and it can be further lowered down to 0.03 ng mL^{− 1} by increasing the trapping time to 4 min. The platinum coating was stable for 300 firings without sensitivity loss. Interference and its alleviation were studied in detail. The proposed method was applied to the determination of tellurium in several geological standard reference materials, and the results were found in good agreement with the certified values.     

Determination of tributyltin in toluene extract from sea water by graphite furnace atomic absorption spectrometry with a new matrix modifier

A new matrix modifier composed of calcium and chromium[VI] was proposed for the determination of tributyltin (TBT) in toluene extract from sea water containing sediment by graphite furnace atomic absorption spectrometry (GFAAS). Fourteen inorganic and organic compounds (barium, calcium, chromium[VI], lanthanum, magnesium, nickel, palladium, strontium, calcium-chromium[VI], calcium-strontium, nickel isocaprylate, 5%-, 10%-aqueous solution of ascorbic acid and toluene-saturated solution of ascorbic acid) as a matrix modifier were comparatively studied and a matrix modifier composed from 5 microg of calcium and 1 microg of chromium[VI] was found to give the best performance. The interference effects of co-existing elements in sea water containing sediment (aluminium, iron, magnesium, sodium and strontium) were studied. TBT in eight toluene extracts was determined by GFAAS with the proposed matrix modifier. The relative standard deviation was 3.0% for 63 ng ml(-1) of TBT (n = 11). The recoveries were 88-104%. The characteristic mass was 7 pg. The linearity range was 0-250 ng mg(-1).     

Determination of silver in sea water by coprecipitation with cobalt pyrrolidinedithiocarbamate and Zeeman graphite-furnace atomic absorption spectrometry

A preconcentration technique is described for silver, which allows the precise and accurate determination of silver in sea water at nanogram per liter levels. Silver is co-precipitated with cobalt(II) pyrrolidinedithiocarbamate from 200-ml samples. The precipitate is dissolved in concentrated nitric acid and silver is quantified by Zeeman graphite-furnace atomic absorption spectrometry, with acid phosphate matrix modification. The detection limit is 0.1 ng l^?. The method is simple and rapid, and also allows the simultaneous extraction of lead, copper, cadmium, and nickel.     

Determination of arsenic at the picogram level by atomic absorption spectrometry with miniaturized suction-flow hydride generation

A continuous-flow hydride generator is modified and miniaturized for the determination of picogram amounts of arsenic by atomic absorption spectrometry. A 300-μl sample is dropped into a teflon cup and pumped into an alkaline sodium tetrahydroborate stream, which is acidified in a reaction coil. The evolved hydride is swept with argon through a phase separator into an electrically-heated quartz absorption cell and the absorbance is recorded. To eliminate differences in sensitivity between arsenic(III) and arsenic(V) without prereduction by potassium iodide, it is important that arsenic(V) be mixed with tetrahydroborate prior to mixing with hydrochloric acid. The method has a detection limit of 0.08 ng As ml^?1 (24 pg) and the calibrations is linear up to 50 ng As ml^?1. The relative standard deviation for 10 replicate measurements is 5.4% for 0.5 ng As ml^?1. The addition of potassium iodide and hydroxylamine is confirmed to be effective in minimizing some interferences. The sampling rate is 90 h^?1. Results for NBS biological and steel reference materials demonstrate applicability of the technique.     

Determination of selenium by atomic absorption spectrometry with miniaturized suction-flow hydride generation and on-line removal of interferences

On-line removal of transition metal interferences in microscale suction-flow hydride generation atomic absorption spectrometry is described for the determination of selenium at μg l^?1 levels. A mini-column of a chelating resin with iminodiacetate groups is used. Selenium in solutions containing ? 2.5 mg of copper or nickel was determined at a rate of 30 samples per hour; the detection limit was 0.1 ng of selenium. The relative standard deviation for ten replicate measurements of 5 ng of selenium was 3.8%. The method was applied successfully to the determination of selenium in standard copper alloys and nickel sponge.     

Electrochemical speciation of organotin compounds in water and sediments. Application to sea water after ion-exchange separation

For the quantitative speciation of tributyltin, Bu₃Sn⁺ (TBT), in the presence of dibutyltin, Bu₂Sn²⁺ (DBT), monobutyltin, BuSn³⁺ (MBT), triphenyltin, Ph₃Sn⁺ (TPT), and inorganic tin in water samples and sediments, an accurate, reproducible, simple and rapid electrochemical method was developed. After extraction of the organotin compounds with dichloromethane, TBT could be selectively determined as species by alternating current polarography directly in the organic phase without any derivatisation. The successful application of this technique could be proved by the results obtained by intercomparison exercises on TBT in water samples and sediments, organized by the Community Bureau of Reference (BCR). For the application of this technique to sea water samples a preliminary ion exchange separation of TBT from the major components of sea water was performed, achieving a detection limit for TBT in the ppt range.     

Determination of Trace Butyltin Compounds in Sea Water by Gas Chromatography-Atomic Absorption Spectrometry

A gas chromatography-atomic absorption spectrometric (GC-AAS) method has been developed for the determination of trace butyltin compounds in sea water. Aqueous butyltin compounds were reduced to the volatile hydride forms by NaBH₄ and were extracted with dichloromethane simultaneously. The dichloromethane extract was concentrated under reduced pressure, followed by direct injection into the GC-AAS system for analysis. The butyltin species were separated with a 2-m glass column packed with 2% OV-101 on Chromosorb G HP (100-120 mesh). Following GC separation, each species was transferred into an electrothermally heated (800 °C) quartz furnace for atomization. The tin atoms produced from individual butyltin compound were detected at 224.6 nm by an atomic absorption spectrometer. With a sea water sample (1 L), the detection limits (3σ) for monobutyltin, dibutyltin and tributyltin were approximately 20, 20 and 70 ng Sn L^?1, respectively. The method has been applied to the analysis of trace butyltin compounds in the sea water of Keelung Harbor.     

Chromium determination in sea water by electrothermal atomic absorption spectrometry using Zeeman effect background correction and a multi-injection technique

Electrothermal atomic absorption spectrometry (ETAAS) applying a Zeeman effect background correction system (ZEBC) and a tranverse heated atomizer was used to directly determine chromium in sea water. Calcium chloride (at a concentration of 20 mg L^–1) was applied as chemical modifier with optimum charring and atomization temperatures of 1600°C and 2000°C, respectively. The detection limit was 0.2 μg L^–1, by injecting 20 μL aliquot of sea water sample. This detection limit could be reduced further to 0.05 μg L^–1, using multiple injections (injection of five 20 μL aliquot of sea water). The accuracy of the methods developed were confirmed by analyses of different certified reference materials. Finally, interferences from major and minor components of sea water are studied.     

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.     

Decomposition of organoarsenic compounds by using a microwave oven and subsequent determination by flow injection-hydride generation-atomic absorption spectrometry

Environmentally important organoarsenicals such as arsenobetaine, arsenocholine and tetramethylarsonium ion do not form volatile hydrides under the commonly used analytical conditions on treatment with borohydride and it has been difficult to determine their concentrations without further derivatization. This paper describes a rapid method which completely decomposes and oxidizes these arsenicals to arsenate by using potassium persulphate and sodium hydroxide with the aid of microwave energy. The quantitative decomposition of these species permits their determination at low nanogram levels, by hydride generation atomic absorption spectromety (HG AA). A new hydride generator which has high efficiency and minimum dead volume and therefore is suitable for flow injection analysis (FIA) is also described. A system combining flow injection analysis, online microwave oven digestion, and hydride generation followed by atomic absorption measurement, is developed. This system is capable of performing analysis at a sample throughput of 100-120 per hour. Calibration curves were linear from 10 to 200 ng cm^?3 of arsenic and the detection limit was 5 ng cm^?3 for a 100-μ injection or 0.5 ng of arsenic. All ten organoarsenic compounds studied gave arsenate as the decomposition product, which was confirmed by using molybdenum blue photometric measurement.     

Optimization of dimethyltin chloride determination by hydride generation gas phase molecular absorption spectrometry using a central composite design

A factorial design is applied to the optimization of the determination of dimethyltin chloride by hydride generation gas phase molecular absorption spectrometry (HG-GPMAS). A method is described for the determination of dimethyltin chloride after conversion into gaseous dimethyltin hydride by adding a sodium tetrahydroborate (III) solution. The hydride generated is collected in a liquid nitrogen cryogenic trap. This is revolatilized, driven to the quartz flow cell and measured with gas phase molecular absorption spectrometry (GPMAS) with diode array detection. A Plackett-Burmann design is used for the study of the factors that influence the absorption signal. The optimization of these factors is performed using a central composite design. The spectra obtained over a wide range of wavelengths, 190-220 nm, allow the multivariate calibration to be studied. The parameters affecting the production and collection of the dimethyltin hydride are studied. The detection limit obtained is 3.2 ng ml(-1). The precision (RSD=4.1%) is calculated from a solution containing ten times the corresponding detection limit. The recoveries (99-108%) are satisfactory. A study is made of the influence of several interferent ions (hydride generators, transition metals and anions) in the presence of dimethyltin chloride.     

Determination of butyltin stabilizers in PVC using Liquid-Phase microextraction with electrothermal atomic absorption spectrometry

A rapid and highly sensitive method is described for the extraction and determination of di- and tributyltin in PVC samples using headspace liquid phase microextraction followed by an analysis with graphite furnace atomic absorption spectrometry (HSLPME/ GFAAS). The analytes were derivatized in situ with sodium tetraethylborate and concentrated in a 2 ??l microdrop of benzyl alcohol suspended from the tip of a conventional GC microsyringe. The ethylated species then were directly transferred into a graphite furnace and quantified. The extractions were carried out for 5 ml sample solution (8 ml vial) adjusted at pH 5, with derivatization at 22 °C for 15 min in a 2% sodium tetraethylborate. The experimental parameters impacting the performance of HS-LPME were also investigated. According to the analysis, the linearity range was from 5.0 to 250.0 ng l^-1 with a detection limit of 0.5 ng l^-1 for dibutyltin and from 1.7 to 170.0 ng l^-1 with a detection limit of 0.17 ng l^-1 for tributyltin. Method RSD values were below 1.5%. Finally, the analysis of spiked PVC and water samples revealed that matrix had little effect upon extraction.     

Determination of inorganic arsenic species As(III) and As(V) by high performance liquid chromatography with hydride generation atomic absorption spectrometry detection

The paper presents the principles and advantages of a technique combining high performance liquid chromatography and hydride generation atomic absorption spectrometry (HPLC-HGAAS) applied to speciation analysis of inorganic species of arsenic As(III) and As(V) in ground water samples. With separation of the arsenic species on an ion-exchange column in the chromatographic system and their detection by the hydride generation atomic absorption spectrometry, the separation of the analytical signals of the arsenic species was excellent at the limits of determination of 1.5 ng/ml As(III) and 2.2 ng/ml As(V) and RSD of 4.3% and 7.8% for the concentration of 25 ng/ml. The hyphenated technique has been applied for determination of arsenic in polluted ground water in the course of the study on migration of micropollutants. For total arsenic concentration two independent methods: HGICP-OES and HGAAS were used for comparison of results of real samples analysis.     

Tributyltin speciation in aquatic matrices by CGC-FPD and CGC-MS confirmation

An analytical procedure for the determination of tributyltin (TBT) in seawater, sediments and biota is described. Extraction of TBT as chloride is achieved by hydrochloric acid treatment followed by a liquid extraction using a modified solvent with a metal coordinating ligand, and a Grignard derivatization (CH₃MgCl). The organotin fraction was isolated from the derivatized extract by column chromatography. The final determination was accomplished by on-column capillary gas chromatography (CGC) coupled to a flame photometric detector (FPD) and mass spectrometry (MS) confirmation. The relative detection limits of the analytical procedure were dependent of the environmental compartment, 0.5 ng 1^–1 (as TBT) for seawater, and 0.1 ng g^–1 and 0.4 ng g^–1 for sediments and biota, respectively. The TBT recovery of fortified samples was in the range of 90% for water and biota, and of 60% in case of sediments. The reproducibility (RSD) of the whole procedure for three independent replicates was around 15%.     

Degradation of dibutyltin in sea water by pyoverdins isolated from Pseudomonas chlororaphis

The yellow compounds pyoverdins were isolated from Pseudomonas chlororaphis, which was isolated from mud in Japan. Degradation of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) by pyoverdin (20 mg) was carried in sea water (30 ml) containing a 6 µg l^?1 concentration of TBT, DBT, and MBT at 24 °C for 24 h in aerobic conditions. TBT, DBT, and MBT in sea water were analyzed by gas chromatography–mass spectrometry in selected ion monitoring mode. DBT in sea water was degraded to MBT by pyoverdins isolated from P. chlororaphis. However, TBT and MBT in sea water was not degraded by pyoverdins. The optimum degradation of DBT in sea water was at pH 4.8–8.2, at a temperature 25–30 °C. Copyright © 2002 John Wiley & Sons, Ltd.