Speciation of organotin compounds in water and sediments by gas chromatography/atomic absorption spectrometry (GC-AAS)

A commercially available atomic absorption detector coupled to a wide-bore column-containing gas Chromatograph (GC-AAS) was utilized to detect organotin compounds. Speciation was performed by pentane extraction of the organotin species as the corresponding sodium diethyldithiocarbamate complexes, enrichment by rotary evaporation, derivatization with Grignard reagent and finally the extracted water and sediment samples were separated and detected on the GC-AAS system.     

Speciation of butyltin compounds by ion chromatography coupled to electrothermal atomic absorption spectrometry

A new method for the determination of butyltin species by ion-exchange chromatography linked with graphite-furnace electrothermal atomic absorption spectrometry (ETAAS) is presented. The separation is achieved on a strong cation-exchange column with a 0.18 mol dm^?3 solution of diammonium citrate at pH 6.5 with a step change to pH 4.0 in 60:40 methanol/water solvent. ETAAS detection is performed on-line using an oxidizing matrix modifier. Mono-, di- and tri-butyltin may be determined in a single experiment with detection limits of (respectively) 0.5, 1.1 and 0.8 ng (Sn). Applications to actual samples are reported.     

Determination of alkylselenide compounds in air by gas chromatography—atomic absorption spectrometry

Dimethylselenide, dimethyldiselenide and diethylselenide are sampled from air by cryogenic trapping and determined by gas chromatography with electrothermal atomicabsorption spectrometric detection. Important considerations in the optimization of sensitivity and selectivity of this approach are discussed. Molecular absorption at the selenium atomic absorption wavelength is reduced by the addition of 10% hydrogen to the argon flow in the graphite oven. Detection limits down to 0.2 ng m^-3 allow the ready detection of the methyl compounds in rural air with a precision of about 10% at the nanogram level.     

Speciation of organotin compounds in marine sediments by capillary column gas chromatography-atomic absorption spectrometry coupled with hydride generation

A method for speciation of organotin compounds in marine sediments by solvent extraction combined with hydride generation gas chromatography-atomic absorption spectrometry has been developed. Sediment samples spiked with tributyltin and triphenyltin chlorides were homogenized in hydrochloric acid. The chlorides were extracted twice into toluene. Recoveries of the organotin compounds from the spiked sediment samples were improved by the addition of 8-quinolinol. Tributyltin and triphenyltin chlorides form ion-associates with 8-quinolinol in aqueous hydrochloric acid. The method was optimized with respect to derivatization reactions and extraction conditions. Interferences from Sn(II/IV) and additional 13 ions were investigated. Recoveries of 84-100% for tributyltin and 86-100% for triphenyltin were achieved using this method. The detection limits obtained for tributyltin and triphenyltin chlorides were 95 and 145 pg, respectively, corresponding to a relative detection limit of 95 and 145 ng kg(-1) in the sediment.     

Speciation of organotin compounds by tandem mass spectrometry

The collison-induced dissociation of a range of organotin compounds has been examined by tandem (MS–MS) mass spectrometry in order to investigate the potential of the technique for speciation without prior chromatographic separation. Tables of parent–daughte ion relationships are prepared for a group of six closely related compounds. The results obtained are sufficiently characteristic to distinguish between the isolated compounds and to identify the individual components of a simple mixture. This procedure has potential applications for less volatile compounds and for quantitative analysis.     

Determination of alkyl lead compounds in air by gas chromatography and atomic absorption spectrometry

Alkyl lead compounds are condensed from a 70-l street air sample in a series of four traps at-72°C, separated by gas chromatography and determined by atomic absorption spectrometry with electrothermal atomization. Total atmospheric alkyl lead averaged 14 ng Pb m^-3. Vehicular exhaust fumes are an insignificant contributor to this total. Tetraethyllead, the only alkyl lead compound used in southern Ontario gasoline, is unstable in air. Besides decomposing, it reacts to give other alkyl lead compounds, which can be determined by the technique described. Evaporation of gasoline is almost exclusively the source of alkyl lead compounds in street air.     

Determination of methylarsenic compounds in airborne particulate matter by gas chromatography with atomic absorption spectrometry

A sensitive method is described for the determination of mono-, di- and tri-methylarsenic compounds in airborne particulate matter by hydride-generation and gas-liquid chromatography with atomic absorption spectrometric detection. Interferences of various species are discussed. Absolute detection limits are 70, 80 and 100 pg As, respectively for the mono-, di- and tri-methylarsenic species. Recoveries of methylarsenic compounds added to airborne particulate matter are almost 100%. An iron/nitrate mixture interfered strongly but this was overcome by adding EDTA.     

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 (NaBEt₄) 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.     

The determination of organotin compounds in edible oils by gas chromatography-atomic absorption spectrometry

An extraction method for butyl-, cyclohexyl-, octyl- and phenyltin compounds from edible oils was developed using 0.05% tropolone in 0.04M HCl/methanol. Cooling the methanol extracts in a dry ice/methanol bath removed approximately 64% of nonvolatile coextractives without affecting recoveries. Methyl derivatives formed by Grignard reaction were quantitated by gas chromatography-atomic absorption spectrometry. Edible oils sold in poly(vinyl chloride) containers had ng/g levels of dioctyl- and monooctyltin. GCMS confirmed the presence of octyltin and did not detect any other organotin compounds in the extracts.     

Speciation of organotin compounds by complex chromatography and reaction detection

Summary The conditions for complex chromatography of organotin compounds have been studied. On-column complex formation with mobile phases containing oxine as reagent is a suitable method for the determination of mono- and di-organotin compounds. Owing to the weak interactions between tri-organotin compounds and oxine and the non-ionic nature of tetra-organotin compounds these species need to be decomposed to lower substituted fragments after their liquid chromatographic separation. This can be achieved by means of photodegradation in a simple nonsegmented post-column-photo-reactor. With the systems investigated sub-g sensitivities and linearitiy of the calibration curves over several orders of magnitude were found.

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Bestimmung von Organozinnverbindungen durch Komplex-Chromatographie und Reaktions-Detektion

Zusammenfassung Zur Bestimmung von Organozinnverbindungen wurde eine komplexchromatographische Methode entwickelt. On-column Komplexbildung mit Oxin als Reagens in der mobilen Phase erweist sich als einfaches und zuverlässiges Verfahren zur Analyse von mono- und di-Organozinnverbindungen. Tri- und tetra-Organozinnverbindungen, die nur mehr bedingt oder gar nicht Komplexe mit Oxin bilden, werden nach ihrer flüssigkeits-chromato-graphischen Auftrennung in einem einfachen, nichtsegmentierten Photoreaktor in niedriger substitutierte, mit Oxin gut reagierende Fragmente zerlegt. Die Empfindlichkeit dieser Systeme reicht in den Submikrogrammbereich und die Eichkurven weisen Linearität über mehrere Zehnerpotenzen auf.

     

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).     

A sensitive,specific method for the determination of tetraalkyllead compounds in air by gas chromatography/atomic absorption spectrometry

The development of a sensitive and specific method of determining individually the five tetraalkyllead compounds normally present in ambient air is described. The method is based on collection of the analytes on a porous polymer using a prefilter to destroy ozone and prevent decomposition of the sample during collection and storage. Two-stage thermal desorption, separation by gas chromatography and detection by modified flame atomic absorption spectrometry gives detection limits (3σ) of ca. 0.25 ng Pb m^?3 for tetramethyllead and 0.37 ng Pb m^?3 for tetraethyllead in an air sample of 80 dm³ collected over a 3–24 h period. Environmental sampling by this method in paralle with a wet chemical (iodine monochloride) method was used to validate the method. During the comparative study, higher organic lead levels were consistently found by the iodine monochloride method; it is postulated that this indicates the presence of vapour-phase tri-(or di)-alkyllead in excess of 1 ng Pb m^?3 in rural air. The versatility of the method is demonstrated by the results of atmospheric sampling at two locations, one rural and one at the kerbside in a city centre.     

Determination of methylmercury in organic matrices with gas chromatography/ atomic absorption spectrometry

Determinations of methylmercury in biological tissues by gas chromatography with electron-capture detection are often disturbed by electron-capturing compounds simultaneously eluting with the organo-mercury compound.Identification and quantification of methylmercury is improved by interfacing the gas chromatograph to the gas cell of a flameless atomic absorption spectrometer. The construction of the transfer line used is described.     

Environmental analysis using gas chromatography — atomic absorption spectrometry

The combination of gas chromatography and atomic absorption spectrophotometry offers high sensitivity and specificity in the analysis of volatile organometallic species, and has been applied to alkyl derivatives of As, Pb, Se and Sn in environmental samples of air, water, sediment and biological tissues. Techniques of sample introduction and detector design are discussed with regard to the sensitivity attainable.     

The determination of organotin compounds in fruit juices using gas chromatography-atomic absorption spectrometry

A method for extracting butyl-, cyclohexyl-, octyland phenyl-tin compounds in fruit juices was developed using 0.05% tropolone in 25% pentane/diethyl ether. Methyl derivatives formed by Grignard reaction were quantified by gas chromatography-atomic absorption spectrometry. Several fruit juices contained low ng cm^?3 levels of butyl- and octyl-tins. Gas chromatography-mass spectrometry, used for the confirmation of the butyl- and octyl-tins, also detected phenyl- and cyclohexyl-tin compounds at levels below the GC AA detection limits (0.03–0.05 ng Sn cm^?3).     

Speciation of organotin in sediments by multicapillary gas chromatography with atomic emission detection after microwave-assisted leaching and solvent extraction-derivatization

Microwave-assisted leaching of organotin compounds from sediment samples followed by the simultaneous extraction-derivatization of the extracted species was revisited with the goal to compare the existing procedures, improve their recoveries and extend them to phenyltin compounds. The stability of butyl- and phenyltin compounds under microwave field, real recoveries of the whole analytical procedure, effect of the extraction solvent, and the necessity for an internal standard were evaluated using two candidate reference sediments. The combination of the optimized sample preparation procedure with multicapillary chromatography resulted in a rapid (2 min leaching + 5 min extraction-derivatization + 3 min chromatographic separation) and efficient analytical procedure for speciation analysis of organotin compounds in sediment samples. The detection limit achieved with a microwave-induced plasma atomic emission detector was 2 ng g^–1. Received: 27 July 1998 / Revised: 31 August 1998 / Accepted: 4 September 1998     

Factors influencing sensitivity and accuracy for the determination of alkylselenides and tetra alkyllead compounds by gas chromatography/atomic absorption spectrometry

Factors affecting the quantitative collection of dimethylselenide, diethylselenide and dimethyldiselenide, as well as of tetraalkyllead compounds fromt he air by the cryogenic trap technique and their determination, by gas chromatography/atomic absorption spectrometry are described. Flash injection (and the addition of ca 10% of hydrogen to the carrier gas0 provide a highly sensitive detection.     

Speciation of four selenium compounds using high performance liquid chromatography with on-line detection by inductively coupled plasma mass spectrometry or flame atomic absorption spectrometry

An analytical method for the speciation of selenomethionine, selenocystine, selenite and selenate by high performance liquid chromatography (HPLC) with atomic spectrometric detection is presented. An organic polymeric strong anion exchange column was used as the stationary phase in combination with an aqueous solution of 6 mmol L^–1 of salicylate ion at pH 8.5 as the mobile phase which allowed the isocratic separation of the four selenium analytes within 8 minutes. The separated selenium species were detected on-line by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma mass spectrometry (ICP-MS). The signal-to-noise ratio of the FAAS detector was optimized using a hydrogen-argon entrained-air flame and a slotted-tube atom trap (STAT) in the flame. The limit of detection (3 σ) achieved by the HPLC-FAAS system was 1 mg L^–1 of selenium (100 μL injections) for each of the four selenium species. More powerful selenium detection was achieved using an ELAN 5000 ICP-MS instrument. Selenium was measured at m/z = 82. The ICP-MS signal intensity was enhanced by a factor of 3–4 after addition of 3% methanol to the chromatographic mobile phase and by using an increased plasma power input of 1300 W. The limit of detection achieved under these conditions was 1 μg L^–1 (100 μL injections). The HPLC-ICP-MS system was used for selenium speciation of selenite and selenate in aqueous solutions during a BCR certification exercise and for selenium speciation in the certified reference material, BCR No. 402 White Clover. Extraction experiments revealed that the selenium species in the biological material were extractable only in the presence of water in the extraction medium. The results indicated that selenate and a compound of unknown identity U were present in the plant sample. Received: 4 September 1996 / Accepted: 12 December 1996     

Graphite-furnace atomic absorption spectrometry as a metal-specific detection system for tetraalkyllead compounds separated by gas—liquid chromatography

The use of a gas—liquid chromatograph in combination with a graphite-furnace atomic absorption spectrometer is described for the determination of tetraalkyllead compounds. Various important analytical parameters affecting the sensitivity and precision are discussed. Absolute detection limits range between 40 pg for tetramethyllead and 90 pg for tetraethyllead. For all species the reproducibility is better than 2% at the nanogram level. The absolute selectivity is demonstrated by the analysis of gasoline samples, including the National Bureau of Standards gasoline standards reference material.     

Speciation of four selenium compounds using high performance liquid chromatography with on-line detection by inductively coupled plasma mass spectrometry or flame atomic absorption spectrometry

An analytical method for the speciation of selenomethionine, selenocystine, selenite and selenate by high performance liquid chromatography (HPLC) with atomic spectrometric detection is presented. An organic polymeric strong anion exchange column was used as the stationary phase in combination with an aqueous solution of 6 mmol L^–1 of salicylate ion at pH 8.5 as the mobile phase which allowed the isocratic separation of the four selenium analytes within 8 minutes. The separated selenium species were detected on-line by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma mass spectrometry (ICP-MS). The signal-to-noise ratio of the FAAS detector was optimized using a hydrogen-argon entrained-air flame and a slotted-tube atom trap (STAT) in the flame. The limit of detection (3 σ) achieved by the HPLC-FAAS system was 1 mg L^–1 of selenium (100 μL injections) for each of the four selenium species. More powerful selenium detection was achieved using an ELAN 5000 ICP-MS instrument. Selenium was measured at m/z = 82. The ICP-MS signal intensity was enhanced by a factor of 3–4 after addition of 3% methanol to the chromatographic mobile phase and by using an increased plasma power input of 1300 W. The limit of detection achieved under these conditions was 1 μg L^–1 (100 μL injections). The HPLC-ICP-MS system was used for selenium speciation of selenite and selenate in aqueous solutions during a BCR certification exercise and for selenium speciation in the certified reference material, BCR No. 402 White Clover. Extraction experiments revealed that the selenium species in the biological material were extractable only in the presence of water in the extraction medium. The results indicated that selenate and a compound of unknown identity U were present in the plant sample.