Comparison of two analytical methods for the determination of organotin compounds in marine organisms

Two analytical procedures were used for the determination of butyltin compounds in mussels.Both methods include extraction with methanol containing tropolone, derivatization, purification on Florisil and GC–MS analysis. The main difference between the procedures is in the derivatization step: one employs a Grignard reagent (n-pentylmagnesium bromide) while the other uses sodium tetraethylborate (STEB).Quantitative determinations were carried out in single ion monitoring using tripropyltin as internal standard. The accuracy of the procedures was verified on a certified reference material (ERM 477), providing good results for both methods.All the considered compounds showed lower detection limits with STEB derivatization; in particular for tributyltin (TBT), the difference between the two methods overcame one order of magnitude.An in vivo experiment was then performed, exposing mussels (Mytilus galloprovincialis) to known amount of TBT for 7 days; control and contaminated tissues were analyzed using the STEB derivatization method. Results showed the accumulation of TBT, especially in the gills.     

Comparison of sulphur-mode and tin-mode flame photometric detectors for the gas chromatographic determination of organotin compounds

A comparison of sulphur-mode (393 nm) and tin-mode (610 nm) flame photometric detectors for the gas chromatographic determination of butyl- and phenyltin compounds is described. The chromatographic peaks of the butyl- and phenyltin compounds were well separated, and high sensitivity was achieved in both modes; however, the tin-mode was more specific for tin compounds than the sulphur-mode. The absolute detection limits with the sulphur-mode and the tin-mode were 3.9-7.6 pg and 2.6-5.1 pg as tin, respectively. The application of the tin-mode gas chromatographic method to the determination of organotin compounds in fish is presented. For this application, organotins are extracted (as chloride) with hydrochloric acid and n-hexane-benzene (3:2, containing 0.05% tropolone) and the extracts are pentylated by a Grignard reagent prior to gas chromatography. The absolute recoveries of butyl- and phenyltin compounds added to fish samples ranged from 68.5 to 84.4% (the coefficients of variation were less than 6.6% for all substances, n = 8). Significant amounts of three organotin compounds (di- and tributyltin and triphenyltin) in fish samples were detected by this method. This technique may have application for other organotin compounds and the monitoring of butyl- and phenyltin compounds in the environment.     

Microanalytical determination of tin in organotin compounds

Existing procedures for the determination of tin in organotin compounds are reviewed, and a new procedure is described which can be used for the rapid microanalysis of most organotin compounds. Wet oxidation with sulphuric acid and 30% hydrogen peroxide is followed by spectrophotometric determination of the extracted ternary tin(IV)-chloride-oxine complex in chloroform. Time for a single determination is 20 min, and the relative standard deviation is 0.7% for 1-5 mg of tin. On account of their volatility, methyltin compounds must be subjected to a sealed-tube wet oxidation in sulphuric-nitric acid mixture. Addition of sulphamic acid after boiling to remove most of the nitric acid makes this compatible with the solvent extraction step. Tin present as organotin stabilizer in PVC samples can also be determined by this method, after destruction of the organic matter with sulphuric acid and 50% hydrogen peroxide.     

Speciation and GC retention indices of some organotin compounds in water

Analytical methods have been developed for the quantitative determination of Bu₄Sn, Bu₃Sn⁺, Bu₂Sn²⁺, BuSn³⁺, Me₃BuSn, Me₂Bu₂Sn, MeBu₃Sn, MeBuSn²⁺, Me₂BuSn⁺ and MeBu₂Sn⁺ in water. Organotin compounds are extracted from water with tropolone at 0.1 % in n-pentane, derivatized with n-pentylmagnesium bromide and determined by gas chromatography with flame photometric detection or flame ionization detection. Absolute detection limits are 0.05-0.12 ng and 1.2-13 ng as tin, respectively. The method was applied to the analysis of spiked tap-water containing 0.3-1000 ng cm^?3 of each of the organotin compounds.     

Substoichiometric determination of inorganic tin in organotin compounds

Inorganic tin(IV) present in organotin compounds is determined substoichiometrically by complexation with salicylideneamino-2-thiophenol in a non-aqueous medium, after isolation of the tin(IV) by iodide extraction. The method is applied to the degradation products in commercial chemicals and those formed by u.v.-irradiation.     

Speciation for analysis of organotin compounds by GC AA and GC MS after ethylation by sodium tetraethylborate

A range of organotin compounds has been ethylated using the reagent sodium tetraethylborate in a simple one-step procedure. Analysis of the volatile, fully alkylated derivatives has been achieved by GC AA with confirmation of the identity of the resulting ethylated derivatives by GC MS. Conditions for the GC AA and GC MS analysis of the organometallic ethyl derivatives are given.     

GC/MSD detection of the metabolic residues of metolachlor in tomato fruit

Summary A gas chromatograph/mass selective detector method is presented for the analysis of the major metabolic residues of metolachlor by acid hydrolysis of tomato fruit. The two major hydrolysis products, CGA-37913 (2-[2-ethyl-6-methylphenyl]amino-1-propanol) and derivatised CGA-49751 (4-[2-ethyl-6-methylphenyl]-2-hydroxy-5-methyl-3-morpholinone) were monitored in the selective ion mode atm/z 162 andm/z 160, respectively. Recoveries from 87 to 96% were obtained for tomato fortified at 50 to 200g kg^–1. The proposed method of analysis will allow for a detection limit of 11 g kg^–1 for CGA-37913 and 12 g kg^–1 for the derivatised CGA-49751.     

尿中4种麻黄素类药物的GC／MSD测定

麻黄素、伪麻黄素、去甲麻黄素、去甲伪麻黄素作为兴奋剂药物及相关化合物被国际奥委会规定为禁用药物~[1],并对其作了限量规定~[2].前文曾用气相色谱法对该类药物进行了分离与测定~[3].本文采用色质联用技术,对含有这4种药物的尿样进行了分离,并采用选择离子检测(SIM)方式,以二苯胺为内标准物建立了对这4种药物同时定量的测定方法.本方法最低检测限为1μg/mL尿.其它兴奋剂药物及尿中化合物对检测无干扰.     

GC/MS法分析奶油中的脂肪酸

利用气相色谱/质谱/计算机联用技术分析人造奶油、天然奶油和新西兰奶油中的脂肪酸,从中鉴定出7种酸:棕榈酸、棕榈油酸、硬脂酸、油酸、亚油酸、亚麻油酸及花生酸。人造奶油含亚油酸比天然奶油含的高。     

Rapid determination of organotin compounds by headspace solid-phase microextraction

Headspace solid-phase microextraction (SPME) followed by gas chromatography (GC) coupled to pulsed flame photometric detection have been investigated for the simultaneous speciation analysis of 14 organotin compounds, including methyl-, butyl-, phenyl-, and octyltins compounds. The analytical process (sorption on SPME fibre and thermal desorption in GC injection port) has been optimised using experimental designs. Six operating factors were considered in order to evaluate their influence on the performances of a SPME-based procedure. The evaluation of accuracy, precision and limits of detection (LODs) according to ISO standards and IUPAC recommendations has allowed the method to be validated. The LODs obtained for the 14 studied organotins compounds are widely sub-ng(Sn) l(-1). The precision evaluated using relative standard deviation ranges between 9 and 25% from five determinations of the analytes at 0.25-125 ng(Sn) l(-1) concentrations. The accuracy was studied throughout the analysis of spiked environmental samples. These first results show that headspace SPME appears really as attractive for organotins determination in the environment and the monitoring of their biogeochemical cycle.     

Occurrence and chemical speciation analysis of organotin compounds in the environment: A review

Environmental concerns regarding organotin compounds have increased remarkably in the past 20 years, due in large part to the use of these compounds as active components in antifouling paints [mainly tributyltin (TBT)] and pesticide formulations [mainly triphenyltin (TPhT)]. Their direct introduction into the environment, their bio-accumulation and the high toxicity of these compounds towards “non-target” organisms (for example: oysters and mussels) causes environmental and economic damage around the world. As a consequence, the presence and absence of organotin compounds is currently monitored in a range of environmental matrices (e.g., water, sediment and shellfish) to examine the utility of controls meant to regulate the level of contamination as required in some EC Directives and the Water Framework Directive 2000/60/EC. To evaluate the environmental distribution and fate of these compounds and to determine the effectives of legal provisions adopted by a number of countries, a variety of analytical methods have been developed for organotin determination in the environment. Most of these methods include different steps such as extraction, derivatisation and clean up. The aim of the present review is to evaluate the environmental distribution, fate and chemical speciation of organotin compounds in the environment.     

Software tool for coupling chromatographic total ion current dependencies of GC/MSD and MCC/IMS

More than 90,000 ion mobility spectrometer (IMS) are in use worldwide, mostly without coupling to chromatographic columns for pre-separation of the neutrals entering the ionization region of the IMS. Related to new application fields e.g. breath analysis or determination of volatile metabolites of cell cultures and bacteria/fungi an effective way for pre-separation is needed strongly. The acceptance of IMS within the analytical world will be enhanced by supplying automatic procedures for peak finding, referencing and database-related identification of the signals within IMS-Chromatograms. Some papers are available concerning the internal loop of relation of IMS signals between different instruments, alignment for automatic interpretation with respect of reference analytes used and interpolation within the different members of classes of analytes in case that some missed e.g. within a homologous row of chemicals. With respect to inter comparison of recent findings using MCC/IMS and GC/MS experiments effective alignment procedures are developed. In the present paper we describe a software tool making the visualization of the total ion current (TIC) from chromatograms of GC/MSD possible in direct relation to the corresponding IMS-Chromatogram of MCC/IMS. Thus, parallel measurements of e.g. samples of human breath using MCC/IMS and thermodesorption (TD)-GC/MSD become comparable directly. On the other hand, the direct identification and relation of so far unknown peaks found in IMS-Chromatograms will be supported using the TIC results of GC/MSD.     

Analytical methods and problems related to the determination of organotin compounds in marine sediments

The determination of organotin compounds in bottom sediments is a complex process that requires a number of analytical steps, i.e. sample collection, transport and storage; extraction of analytes from sediment; derivatization; extract purification; enrichment; and the final chromatographic measurement. The whole process is time and labour consuming, and subject to securing sample representativeness. In this review the most frequently encountered problems and the examples of possible analytical solutions are presented, which encompass the specific steps of speciation analysis of these toxic compounds.     

Differential pulse-polarographic determination of organotin compounds coated on fishing nets

Summary The pulse-polarographic behaviour of tributyltin chloride (TBTC) and dibutyltin dichloride (DBTC) in ethanol-water mixtures has been studied. The effects of temperature, pH, modulation amplitude, solvent and supporting electrolyte compositions were investigated. The reduction processes are complicated and pH-dependent. DBTC gave one reversible reduction wave and TBTC showed a quasi-reversible one and also several irreversible waves. Both the organotin compounds in the concentration of 10^–7 mol/l were determined by differential pulse polarography. The method was successfully applied to the analysis of commercially available fishing nets. Detection limits were 2.2×10^–7 and 6.2×10^–8 mol/l for TBTC and DBTC, respectively.

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Differential-puls-polarographische Bestimmung von Organozinnverbindungen auf Fischernetzen

Zusammenfassung Das puls-polarographische Verhalten von Tributylzinnchlorid (TBTC) und Dibutylzinndichlorid (DBTC) in Ethanol-Wasser-Gemischen wurde untersucht und die Wirkung von Temperatur, pH, Modulationsamplitude sowie Zusammensetzung des Lösungsmittels und Leitelektrolyts geprüft. Die Reduktionsprozesse waren kompliziert und abhÄngig vom pH. DBTC ergab eine reversible Reduktionswelle, TBTC eine quasireversible Welle, sowie daneben einige irreversible Wellen. Beide Organozinnverbindungen konnten in einer Konzentration von 10^–7 mol/l durch Differential-Puls-Polarographie bestimmt werden. Die Methode wurde erfolgreich auf die Analyse von handelsüblichen Fischernetzen angewandt. Die Nachweisgrenzen lagen bei 2,2·10^–7 (TBTC) bzw. 6,2 · 10^–8 mol/l (DBTC).

This work was supported in part by a Grant-in-Aid for Scientific Research No. 554164 from the Ministry of Education. The authors wish to thank Mr. Y. Komatsu, Clean Kagaku Co., Tokyo, who offered the fishing net samples.     

Examination of the different procedural steps in the determination of organotin compounds in water samples

Previous animal experiments suggested that the Magos cold vapor atomic absorption spectroscopic (CVAAS) method might overestimate the concentrations of inorganic mercury (I-Hg) in the presence of methylmercury (MeHg). In the present study it is shown that this error is due to a fast degradation of MeHg during the formation of the analytical signal. For brain samples, about 5% of the total amount of MeHg in the reaction vessel is degraded to I-Hg. Speciation of Hg in aqueous solution of MeHg chloride, after purification with ionexchange chromatography using the Magos method, showed that about 9% was I-Hg. Analysis by NMR of MeHg chloride and MeHg hydroxide showed that less than 1% was in the form of I-Hg. The absolute magnitude of the error in the CVAAS method is dependent on the amounts of SnCl₂ and MeHg in the reaction vessel; however, the ratio of I-Hg to total (T-Hg) is shown to be independent of the amount of MeHg (25.5–255 ng as Hg) in the reaction vessel. A procedure for corrections is proposed, based on the results from these studies and empirical data from speciation analyses of brain tissue from MeHg-exposed rats and rabbits.     

气相色谱-质谱联用法同时测定动物尿液中克伦特罗和沙丁胺醇

建立了尿液中克伦特罗和沙丁胺醇同时测定的GC-MS方法. 尿液在碱性条件下以异丁醇提取后, 用Waters Oasis MCX小柱净化, 吹干后用BSTFA进行硅烷化衍生, 采用GC-EI-MS法, 选择离子方式采集数据. 结果表明, 克伦特罗和沙丁胺醇的线性范围为0.002～1.00 mg/L, 相关系数分别为0.9993和0.9985, 方法检出限可达0.5 μg/L (S/N=10). 尿液中克伦特罗和沙丁胺醇的回收率分别为75.9%～89.2%和73.6%～89.5%, 相对标准偏差(RSD)均不大于10%.     

毛细管气相色谱/质谱法测定柑籽中的脂肪酸

用乙醚/正已烷混合溶剂萃取柑籽中的脂肪酸甘油酯,用KOH-CH_3OH法甲酯化,以毛细管色谱/质谱/计算机法测定其脂肪酸组成,共检出7种脂肪酯,其中以棕榈酸(35.48%)、油酸(26.6%)及亚油酸(27.27%)为主。     

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).     

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.