This article was downloaded by: [Northeastern University]On: 11 November 2014, At: 07:03Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Analytical LettersPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/lanl20

Simultaneous Determination ofOrganotin Compounds in White Wine byGas Chromatography-Mass SpectrometryYi-Qun Wan a b , Ya-Qian Ma b & Xue-Jin Mao aa State Key Laboratory of Food Science and Technology, NanchangUniversity , Nanchang , P. R. Chinab Center of Analysis and Testing, Nanchang University , Nanchang , P.R. ChinaAccepted author version posted online: 13 Apr 2012.Publishedonline: 04 Sep 2012.

To cite this article: Yi-Qun Wan , Ya-Qian Ma & Xue-Jin Mao (2012) Simultaneous Determination ofOrganotin Compounds in White Wine by Gas Chromatography-Mass Spectrometry, Analytical Letters,45:13, 1799-1809, DOI: 10.1080/00032719.2012.677973

To link to this article: http://dx.doi.org/10.1080/00032719.2012.677973

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the“Content”) contained in the publications on our platform. However, Taylor & Francis,our agents, and our licensors make no representations or warranties whatsoever as tothe accuracy, completeness, or suitability for any purpose of the Content. Any opinionsand views expressed in this publication are the opinions and views of the authors,and are not the views of or endorsed by Taylor & Francis. The accuracy of the Contentshould not be relied upon and should be independently verified with primary sourcesof information. Taylor and Francis shall not be liable for any losses, actions, claims,proceedings, demands, costs, expenses, damages, and other liabilities whatsoever orhowsoever caused arising directly or indirectly in connection with, in relation to or arisingout of the use of the Content.

This article may be used for research, teaching, and private study purposes. Anysubstantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditions

Mass Spectrometry

SIMULTANEOUS DETERMINATION OF ORGANOTINCOMPOUNDS IN WHITE WINE BY GASCHROMATOGRAPHY-MASS SPECTROMETRY

Yi-Qun Wan,1,2 Ya-Qian Ma,2 and Xue-Jin Mao11State Key Laboratory of Food Science and Technology, NanchangUniversity, Nanchang, P. R. China2Center of Analysis and Testing, Nanchang University, Nanchang,P. R. China

A simple, reliable, and effective analytical method was developed for the simultaneous

determination of five organotin compounds (OTCs) including monobutyltin trichloride

dibutyltin dichloride tributyltin chloride tetrabutyltin and triphenyltin chloride in white

wines. The OTCs were derivatized with sodium tetraethylborate (NaBEt4), and their deri-

vatives were extracted by liquid-liquid extraction (LLE) into n-hexane. The experimental

variables, such as type and volume of extraction solvents, amount of derivatization reagent

NaBEt4 and extraction time were optimized. The determination of ethylated derivatives of

OTCs in the final extracts was carried out by gas chromatography-mass spectrometry

(GC-MS). Under optimized conditions, good linearity was observed when analytical con-

centrations were in the range of 0.01–4.0lg �mL�1, the linearity correlation coefficients

were between 0.9982 and 0.9987, with the LODs in the range of 0.2–3.0lg �L�1, and the

LOQs varied from 0.6 to 10.0lg �L�1. The obtained recoveries were in the range of

78.0–120.0%, with the relative standard deviations equal to or lower than 8.1%. This

method was applied to the determination of OTCs in white wines with satisfactory results.

Keywords: GC-MS; Liquid-liquid extraction; Organotin compounds; White wine

INTRODUCTION

Organotin compounds (OTCs), especially butyl and phenyl species, have beenextensively used in the last 50 years in consumer and industrial products such as

Received 27 December 2011; accepted 25 February 2012.

The financial support of this study from the Natural Science Foundation of China (20965005), the

Research Program of State Key Laboratory of Food Science and Technology in Nanchang University

(SKLF-TS-200918), the Objectives-oriented Project for the State Key Laboratory of Food Science and

Technology in Nanchang University (SKLF-MB-201002), and the Science and Technology Planning

Project of Jiangxi Province (2008BB22400) are gratefully acknowledged.

Address correspondence to Yi-Qun Wan, State Key Laboratory of Food Science and Technology,

Center of Analysis and Testing, Nanchang University, Nanchang 330047, China. E-mail: wanyiqun@

ncu.edu.cn

Analytical Letters, 45: 1799–1809, 2012

Copyright # Taylor & Francis Group, LLC

ISSN: 0003-2719 print=1532-236X online

DOI: 10.1080/00032719.2012.677973

1799

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

wood preservatives, antifouling paints, polyvinyl chloride (PVC) stabilizers,industrial catalysts, and agricultural biocides (Cima, Craig, and Harrington 2003;Hoch 2001). The most toxic forms of OTC are their trisubstituted forms, followedby disubstituted and monosubstituted (Oliveira and Santelli 2010; Segovia-Martinezet al. 2010; Vahcic, Milacic, and Scancar 2011). Most OTCs are considered to be theendocrine disrupting chemicals (EDCs) (Fent 1996), which deliberate risk to humansand living organisms (Azenha et al. 2008). The extensive application of these OTCsin life have posed threats to human health, so it is necessary to monitor the OTCs.

According to the culture of wine and wine-making, OTCs can also be presentin wines (Heroult et al. 2008). The maximum residue limit (MRL) for some OTCsincluding triphenyltin (TPhT), fenbutatin oxide (FBTO), and the sum total ofCyhexatin (TCT) and azocyclotin in wine grapes was established by the EuropeanUnion (EU) legislation, and according to the suggestion of the Organisation Inter-nationale de la Vigne et du Vin, the MRL levels for other OTCs in wines is in therange of 0.005–0.2mg=L (Campillo et al. 2012). Hence, establishing an analyticalmethod for OTCs in white wines is significant.

For the detection of organometallic compounds, various hyphenated chroma-tographic techniques are used (Rastkari et al. 2010). The OTCs have the nature oforganic matter, thus GC technique was considered to be a good candidate for theirdetermination, thanks to its larger resolving power, separation efficiency, fast oper-ation, and many available detectors (Magi, Liscio, and Di Carro 2008; Vahcic,Milacic, and Scancar 2011). Additionally, owing to the OTCs including metal Sn,many detectors, such as atomic absorption spectrometry (AAS) (Vinas et al.2004), atomic emission spectrometry (AES) (Campillo et al. 2004; Campillo et al.2012; Ceulemans et al. 1993; Minganti, Capelli, and Depellegrini 1995), pulsed flamephotometric detection (PFPD) (Heroult et al. 2008; Leermakers, Nuyttens, andBaeyens 2005), and flame photometric detection (FPD) (Aguerre et al. 2000; Cuiet al. 2011; Liu and Jiang 2002) were employed for the detection. However, some dif-ficulties may arise when analyzing some food samples (Zuliani et al. 2010). As theextracts are usually rich in various organic constituents, the probability of insuf-ficient separation between the targeted organotins and matrix compounds is fairlyhigh when an unspecific detector is used. Additionally, the concentration levels ofOTCs in food are very low. For the trace levels of OTCs in these samples, a powerfulmolecule specific detector such as MS is usually employed for this purpose. Thistechnique has been regularly used for the analysis of toxic residues in foods (Azenhaand Vasconcelos 2002; Jiao et al. 2011; Martins et al. 2011).

Due to the low volatility of OTCs in the real samples, derivatization is neededto generate derivatives that are volatile and thermally stable before separation by gaschromatography. The tetra-substituted species like TeBT do not need any derivatiza-tion because they are already nonpolar, this compound has similar behavior with theOTCs after their complete alkylation (Zachariadis and Rosenberg 2009). The deriva-tization methods of alkylation with Grignard reagents, hydride generation withsodium tetrahydroborate (NaBH4), and ethylation with sodium tetraethylborate(NaBEt4) (Morabito, Massanisso, and Quevauviller 2000) were usually used forOTCs analysis. But, NaBEt4 derivatization reaction has been more extensivelyapplied (Beceiro-Gonzalez, Guimaraes, and Alpendurada 2009; Oliveira and Santelli2010; Segovia-Martinez et al. 2010), this method makes the in situ derivatization

1800 Y.-Q. WAN ET AL.

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

possible in aqueous samples and simplifies analytical procedure. In addition, ethyla-tion with sodium tetraethylborate allows derivatization and extraction for OTCs areperformed simultaneously, which further reduces the analytical step. Analytical pro-cedures for OTCs speciation generally attempt to preserve only the organic radicalduring extraction, whereas the counterion and other tin hetero-atomic bonds arecleaved during extraction or derivatization (Abalos et al. 1997; Minganti, Capelli,and Depellegrini 1995). Moreover, with ethylated derivatizations and extraction ofOTCs are carried out simultaneously, further simplifying the analytical procedureand minimizing the loss.

Herein, employing in situ ethylation with subsequent liquid-liquid extractionand GC-MS technique, we developed a simple, reliable, and effective method forthe determination of OTCs in white wines. To the best of our knowledge, it is thefirst time that the five OTCs were derivatized with NaBEt4 and their derivatives wereextracted by liquid-liquid extraction technique and determined by GC-MS in whitewines. Moreover, the method is precise, simple, and easy to implement.

MATERIALS AND METHODS

Reagents and Samples

All organic solvents were of analytical or chromatographic grade. Dichloro-methane, n-hexane and methanol were purchased from Shanghai Reagent Company(Shanghai, P. R. China). The used purification of de-ionized water was obtainedthrough a Milli-Q system (Millipore, USA). All plastic and glassware were washedwith a common detergent, thoroughly rinsed with tap water, and soaked into 10%(v=v) nitric acid solution overnight. Finally, all material was cleaned with Milli-Qquality water. Afterward, all the material was dried in an oven at 80�C. Five kindsof the white wine samples that were respectively produced by different companieswere purchased from a local market in Nanchang, P. R. China.

Sodium tetraethylborate (98%) was obtained from Strem Chemicals (USA).The 2% (w=v) aqueous solution of NaBEt4 was prepared in methanol before analysisevery time. The acetic acid=sodium acetate buffer solution was prepared by dissolv-ing a prescribed amount of sodium acetate in purified water and then adjusted to pHat 4.8 by adding acetic acid, and the buffer solution was used as the pH adjustment inthe derivatization process.

The OTC standards including triphenyltin chloride (96%) and monobutyltintrichloride (97%), dibutyltin dichloride 96%), tributyltin chloride (96.5%), and tetra-butyltin (99%) were purchased fromDr. Ehrenstorfer (Germany). Organotin standardstock solutions (100mgL�1) were prepared in methanol. Working standard solutionsat various concentrations were prepared from stock standard solutions by dilution inmethanol (Chou and Lee 2005). All the standards were stored in the dark at 4�C.

Analytical Procedure

White wine sample (40mL) was introduced into a 250-mL separating funnel andthe pH of solution was adjusted by adding 5mL acetic acid=sodium acetate buffer sol-ution. Then, derivatization and extraction was carried out as follows: adding 1mL

DETERMINATION OF 5 ORGANOTINS IN WINE BY GC-MS 1801

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

of 2% (w=v) NaBEt4 solution and shaking for 5min. The 20mL of n-hexane wasthen introduced to extract the ethylated derivatives. After manual shaking for15min, the supernatant was taken into a 250-mL evaporating flask and the subnatantwas added 20mL of hexane to extract again for 5min in the same way. Then, the twoportions of supernatant were combined in the same evaporating flask and evaporatedto dryness with a RE-52A rotary vacuum evaporator (Shanghai Yarong BiochemistryInstrument Factory, Shanghai, P. R. China) under a 28�C water bath and reconsti-tuted as much as possible with 2mL of n-hexane; the reconstituted solutions wereconcentrated to about 1.0mL using a gentle stream of nitrogen and taken into asampling vial which was then brought to volume of 1mL by n-hexane. The analysiswas performed by injecting this solution into the GC-MS system with an autosampler.

Chromatographic Analysis

Analyses by the gas chromatograph (Agilent 6890N GC series, AgilentTechnologies, Palo Alto, CA, USA) equipped with a HP-5MS capillary column(Agilent Technologies, 30m� 0.25mm i.d., film thickness 0.25 mm) and the quadru-pole mass spectrometer (Agilent 5973I MSD, Agilent Technologies, Palo Alto, CA,USA) were conducted. The injection was performed with an on-column Agilent 7683Auto sampler.

Helium (99.999%) at a constant flow (1.0mL=min) was used as carrier gas. TheGC-MS was operated under the following conditions: the injector port temperaturewas kept at 250�C. Solvent delay was set for 8min. The program temperature ofchromatographic column was applied as follows: 60�C, held for 5min; raised to200�C at 40�C=min and held for 1min; raised to 280�C at 50�C=min and held for20min. An amount of 1 mL of the solution for analysis was injected into the GCcolumn in splitless mode.

The capillary column was connected to the ion source of the mass spectrometerby means of a transfer line maintained at 280�C. Detection was carried out usingelectron impact ionization (70 eV) at the selected ion monitoring (SIM) mode underthe temperature of 230�C. The quadrupole temperature was set at 150�C.

The chromatogram of standard OTC solution is outlined in Figure 1, whichdisplayed a good chromatograph separation in a run. In order to improve sensitivity

Figure 1. Total ion chromatogram of organotins standards (0.5mg �mL�1): 1) MBT; 2) DBT; 3) TBT; 4)

TeBT; 5) TPhT.

1802 Y.-Q. WAN ET AL.

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

and reduce interference, selected ion monitoring (SIM) mode was used for the quali-tative and quantitative analysis of OTCs. For each OTC, three to four ions with highabundances and relatively high mass-to-charge ratios were selected for group SIMdetection. On the basis of the mass spectra of MBT, DBT, TBT, TeBT, and TPhT,the ion with the highest abundance which was different to the ions of fragments ofcolumn bleed was chosen for quantification. According to the total ion chromato-gram of the five organotins studied, the organotins of similar retention time were div-ided into a monitor group as a segment. This work designed two segments (8–11minas Monitor group 1, 11–13min as Monitor group 2), the ions monitored for eachsegment was listed in Table 1.

RESULTS AND DISCUSSION

Optimization of Pretreatment Conditions

The optimization of the experimental parameters for the white wine samplestreatment was quite necessary; the analytical procedure is outlined as previouslymentioned. In this part of the optimization experiments, to all of the analyzed whitewine samples were added 1mL of the 1.0mgL�1 mixed standard solution for thefollowing work.

Effect of the type and volume of extraction solvent. In order to obtaingood selectivity for the studied analytes, the solvent used for extraction needs tobe carefully tested and verified, which also should be beneficial to obtain high extrac-tion efficiency. In this study, the extraction result of n-hexane and dichloromethanewas tested for extracting target analytes from white wine samples in the same con-dition. From the result, n-hexane obtained better extraction efficiency than dichlor-omethane, which is because dichloromethane is a high polar solvent, could emulsifythe sample solution, and would make the organic phase and water phase hard toseparate. As a result, n-hexane was chosen for extraction solvent.

Based on the experiment method previously described, the reagents were pre-pared in the white wine samples as follows: adding 5mL of acetic acid=sodium acet-ate buffer solution with pH at 4.8, 1mL of 2% (w=v) NaBEt4 solution. And, theextraction time was kept at 15min; the extraction efficiency of different volumesof n-hexane was investigated by changing the volume at 10, 15, 20, 25, and 30mL.The different analytical signals of the five ethylated OTCs were obtained. The resultsshowed that the analytical signal of the five ethylated organotins increased gradually

Table 1. Retention time and characteristic fragment ions used for EI=SIM determination of 5 organotins

Organotins Retention time (min) Characteristic ions (m=z) Ions used for quantification (m=z)

MBT 8.35 179, 235, 151, 121 179

DBT 9.05 151, 179, 263,121 151

TBT 9.72 177, 151,121, 263 177

TeBT 10.31 179, 235, 291, 121 179

TPhT 12.90 351, 197, 120 351

DETERMINATION OF 5 ORGANOTINS IN WINE BY GC-MS 1803

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

when the extraction solvent was increased to 20mL, but declined with furtherincreases up to 30mL. Therefore, 20mL n-hexane obtained the best analytical signaland was selected for the following experiments.

Effect of amount of derivatization reagent NaBEt4. The amount ofderivatization reagent NaBEt4 has a great impact on the extraction efficiency(Munoz, Gallego, and Valcarcel 2005). On the one hand, excess reaction reagentstheoretically contributed to the complete reaction; but on the other hand, excessreaction reagents may raise costs and cause the additional side reaction of the studiedanalytes and matrix; therefore, it is not suitable to utilize excess reaction reagents.According to the analysis process of pretreatment, the reagents were prepared: add-ing 5mL of acetic acid=sodium acetate buffer solution with pH at 4.8, 20mL ofn-hexane. And, keeping the extraction time at 15min, the effect of amount of deri-vatization reagent NaBEt4 on the derivatization process was investigated by chan-ging the amount of derivatization reagent NaBEt4 (2%, w=v) solution at 0.1, 0.3,0.5, 1.0, 1.5, and 2.0mL. The results showed that the analytical signal of the fiveethylated organotins was increased when the volume of NaBEt4 increased to1mL, but declined with further increases up to 2mL. Additionally, it can be seenfrom the results that the varied amounts of NaBEt4 produced obvious effects onthe signal intensity of ethylated TPhT. This may be because the ethylation processof TPhT, influenced by the steric effect of the phenyl groups, was slower than theother four organotins. In addition, as the clean-up is not carried out, excessivederivative reagents NaBEt4 did not improve the analytical signal of all the ethylatedOTCs, which was probably because higher NaBEt4 concentrations would enhancethe background level (Magi et al. 2008). Finally, 1mL of 2% (w=v) NaBEt4 as theoptimal value was used for further work.

Effect of the pH. Using NaBEt4 as organotins derivative reagent, the pH ofsample solution is a critical parameter for the in situ ethylation of the organotin spe-cies, which can significantly affect the process of ethylation derivatization. Accordingto various studies, the organotins act as a weak acid (Arnold et al. 1997) that favorsthe reaction with NaBEt4; but, when the pH value is equal to or lower than 2,NaBEt4 is rapidly decomposed to BEt3 and ethane (Magi et al. 2008). As reported,the ethylation reaction with NaBEt4 is favorable at a pH between 4 and 5 (Vercau-teren et al. 2001). Then, the reagents were prepared in the same way: adding 1mL of2.0% (w=v) NaBEt4, 20mL of n-hexane. And, keeping the extraction time at 15min,the effect of pH value was investigated by changing the pH value at 4.0, 4.3, 4.5, 4.8,5.0, and 5.3. The results displayed that analytical signal of the five organotins studiedwas increased when the pH value increased to 4.8, but declined slowly as furtherincreased up to 5.3. Hence, the pH of buffer at 4.8 as optimum value was chosenin this work.

Effect of the extraction time. Considering that the instability of OTCderivatives, the extraction time would produce important influence on the extractionresults of the ethylated organotins. To a certain extent, the derivatives would breakdown when the extraction time was too long. Conversely, not enough time in extrac-tion may lead to incomplete extraction. For routine analyses, it is critical that thetotal analysis time, including the sample preparation, is as short as possible. The

1804 Y.-Q. WAN ET AL.

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

reagents were prepared similarly: adding 5mL of acetic acid=sodium acetate buffersolution with pH at 4.8, 1mL of 2.0% (w=v) NaBEt4, 20mL of n-hexane. Then, theinfluence of extraction time on extraction efficiency was investigated by changing theextraction time at 10, 15, 20, 25, and 30min.

The results showed that analytical signal of the five organotins studied wasincreased when the extraction time increased to 15min, but declined with furtherincreases up to 30min; the equilibrium of extraction and derivatization can bereached at approximately 15min. It has been reported that the derivative reactioncan be finished after 5min (De Smaele et al. 1998). Meanwhile, an approximateextraction time is important for good extraction efficiency. Based on the results,the optimal extraction time at 15min was fixed. But, in order to ensure that theOTC derivatives of different wine samples can be fully extracted, further extractionof 5min in the same way in the subnatant by adding 20mL of n-hexane wascarried out.

Analytical Characteristics

Limits of detection and linearity. The analytical characteristics of thismethod are shown in Table 2 and were evaluated under optimized conditions. Lin-earity, correlation coefficients, and limit of detections for the analytical methodologywere determined by calibration curves created with a series of mixture standard solu-tions at 0.01, 0.05, 0.1, 0.5, 1.0, 2.0, and 4.0 mg �mL�1. The results indicated thatgood linearities were obtained for the five organotins studied with the correlationcoefficients (r2) varying from 0.9968 to 0.9987. The LOD and LOQ values rangefrom 0.2 to 3.0 mg �L�1 and 0.6 to 10.0 mg �L�1, respectively, which were evaluatedbased on a signal-to-noise ratio of 3 and 10, respectively.

Accuracy and precision. In order to verify the accuracy and precision ofselected method, accuracy, and precision were studied in white wine samples, mixedstandard organotins solutions were added at low (0.05 mg �mL�1), medium(0.5 mg �mL�1), and high (2.0 mg �mL�1) concentrations to wine samples. For eachaddition level, six replicate experiments were performed. Before spiked testing, theblank samples were analyzed. If contaminated, the recoveries were calculated by sub-traction of blank samples. The experiment results are illustrated in Table 3. The aver-age recoveries of different levels for all the OTCs analyzed were 78.0–120.0%, andrelative standard deviations (RSDs) of the method were 2.3–8.1%. The obtained datademonstrated that the developed method was available for OTC analyses in routineconditions.

Table 2. Linear equations, correlation coefficients, and LODs for 5 organotins

Organotins Linear equations (mg �mL�1) correlation coefficients LODs (mg �L�1)

MBT A¼ 6.56� 105C� 5.11� 104 0.9980 3.0

DBT A¼ 3.30� 105Cþ 8.55� 102 0.9968 0.2

TBT A¼ 2.69� 105Cþ 1.09� 104 0.9987 0.5

TeBT A¼ 5.36� 105Cþ 2.31� 104 0.9979 0.3

TPhT A¼ 1.37� 106Cþ 2.78� 104 0.9982 0.2

DETERMINATION OF 5 ORGANOTINS IN WINE BY GC-MS 1805

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

Application of the Developed Method to Wine Samples

According to the optimized experiment conditions, a determination of OTCs inChinese white wine was performed. Five samples purchased at a local supermarket

Table 4. Analytical results of 5 organotins in white wine samples (mg �L�1, n¼ 3)

Wine sample MBT DBT TBT TeBT TPhT

1# NDa 6.62� 0.021b 4.62� 0.071 3.87� 0.069 1.62� 0.072

2# ND 2.50� 0.014 4.50� 0.014 3.75� 0.160 1.62� 0.064

3# ND 6.25� 0.042 24.25� 0.057 3.75� 0.007 2.12� 0.007

4# ND 6.15� 0.004 5.12� 0.070 3.88� 0.007 1.75� 0.002

5# ND 9.50� 0.003 4.75� 0.043 6.00� 0.019 ND

aND, not detected (<LOD).bData were shown as mean� SD.

Table 3. Recoveries and relative standard deviations (RSDs) of white wine samples spiked at three

addition levels (n¼ 6)

Organotins

Amount added

(mg �mL�1)

Amount founda

(mg �mL�1) Mean recovery (%) RSD (%)

MBT 0.05 0.046� 0.001 92.0 3.1

0.50 0.60� 0.023 119.7 3.9

2.0 1.92� 0.034 96.0 1.8

DBT 0.05 0.039� 0.002 78.0 5.1

0.50 0.42� 0.023 85.0 5.5

2.0 1.94� 0.070 96.8 3.6

TBT 0.05 0.060� 0.018 120.0 3.0

0.50 0.56� 0.013 112.0 2.3

2.0 2.29� 0.150 114.6 6.4

TeBT 0.05 0.048� 0.002 97.0 3.6

0.50 0.56� 0.046 113.0 8.1

2.0 2.20� 0.110 110.2 5.2

TPhT 0.05 0.054� 0.001 108.3 2.7

0.50 0.57� 0.016 113.3 2.9

2.0 2.32� 0.140 115.9 6.0

aData are shown as mean� SD.

Figure 2. Chromatogram of blank sample extracts exhibiting OTC species (the results from sample 4#): 1)

DBT; 2) TBT; 3) TeBT; 4) TPhT.

1806 Y.-Q. WAN ET AL.

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

were analyzed in routine conditions. The results were listed in Table 4. One of thechromatograms of the samples was presented in Figure 2. As shown in the results,five samples all suffered from different degrees of pollution of OTCs. As organotincompounds (OTCs) are widely used in some human activities in agriculture andindustrial processes, there are several possible sources of pollution such as contami-nation of raw materials, contamination during processing, and storage.

CONCLUSIONS

In this study, a reliable, simple, and effective method for the simultaneousdetermination of five OTCs in white wine was established. Although the detectionof OTCs is common, this method applied for the determination of the analyzedOTCs in white wines has not been reported. With reference to the analytical charac-teristics, this methodology was satisfactory with LODs and LOQs varying from 0.2to 3.0 mg �L�1 and 0.6 to 10.0 mg �L�1 respectively; analytical recoveries were78.0–120.0%, and the RSDs were equal to or lower than 8.1%. The experimentresults obtained considerable linearities, recoveries, and precisions and showed theapplicability and suitability to the white wine analysis for routine screening. Thepresence of some organotins in white wine sample suggests that the wine samples suf-fer from the OTCs pollution and the necessity of organotin determination.

REFERENCES

Abalos, M., J. M. Bayona, R. Compano, M. Granados, C. Leal, and M. D. Prat. 1997.Analytical procedures for the determination of organotin compounds in sediment and biota:a critical review. J. Chromatogr. A 788: 1–49.

Aguerre, S., C. Bancon-Montigny, G. Lespes, and M. Potin-Gautier. 2000. Solid phase micro-extraction (SPME): a new procedure for the control of butyl- and phenyltin pollution in theenvironment by GC-FPD. Analyst 125: 263–268.

Arnold, C. G., A. Weidenhaupt, M. M. David, S. R. Muller, S. B. Haderlein, and R. P.Schwarzenbach. 1997. Aqueous speciation and 1-octanol-water partitioning of tributyl-and triphenyltin: Effect of pH and ion composition. Environ Sci Technol 31: 2596–2602.

Azenha, M. A., R. Evangelista, F. Martel, and M. T. Vasconcelos. 2008. Estimate of thedigestibility, assimilability and intestinal permeability of butyltins occurring in wine. FoodChem. Toxicol. 46: 767–773.

Azenha, M., and M. T. Vasconcelos. 2002. Headspace solid-phase micro-extraction gaschromatography-mass detection method for the determination of butyltin compounds inwines. Anal. Chim. Acta 458: 231–239.

Beceiro-Gonzalez, E., A. Guimaraes, and M. F. Alpendurada. 2009. Optimization of aheadspace-solid-phase micro-extraction method for simultaneous determination of organo-metallic compounds of mercury, lead and tin in water by gas chromatography-tandem massspectrometry. J. Chromatogr. A 1216: 5563–5569.

Campillo, N., N. Aguinaga, P. Vinas, I. Lopez-Garcia, and M. Hernandez-Cordoba. 2004.Speciation of organotin compounds in waters and marine sediments using purge-and-trapcapillary gas chromatographywith atomic emission detection.Anal. Chim. Acta 525: 273–280.

Campillo, N., P. Vinas, R. Penalver, J. I. Cacho, and M. Hernandez-Cordoba. 2012.Solid-phase microextraction followed by gas chromatography for the speciation oforganotin compounds in honey and wine samples: A comparison of atomic emission andmass spectrometry detectors. J. Food. Compos. Anal 25: 66–73.

DETERMINATION OF 5 ORGANOTINS IN WINE BY GC-MS 1807

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

Ceulemans, M., R. Lobinski, W. M. R. Dirkx, and F. C. Adams. 1993. Rapid sensitivespeciation analysis of butyltin and phenyltin compounds in water by capillary gas-chromatography atomic-emission spectrometry (GC-AES) after in-situ ethylation andin-liner preconcentration. Fresenius J. Anal. Chem. 347: 256–262.

Chou, C. C., andM.R. Lee. 2005. Determination of organotin compounds in water by headspacesolid phase microextraction with gas chromatography-mass spectrometry. J. Chromatogr. A1064: 1–8.

Cima, F., P. J. Craig, and C. F. Harrington. 2003. Organometallic Compounds in the Environ-ment second edition, Chapter 3. Chichester, UK: J. Wiley and Sons, Wiley Online Library.

Cui, Z. Y., K. G. Zhang, Q. F. Zhou, J. Y. Liu, and G. B. Jiang. 2011. Determination ofmethyltin compounds in urine of occupationally exposed and general population by in situethylation and headspace SPME coupled with GC-FPD. Talanta 85: 1028–1033.

De Smaele, T., L. Moens, R. Dams, P. Sandra, J. Van der Eycken, and J. Vandyck. 1998.Sodium tetra(n-propyl)borate: A novel aqueous in situ derivatization reagent for the simul-taneous determination of organomercury, -lead and -tin compounds with capillary gas chro-matography inductively coupled plasma mass spectrometry. J. Chromatogr. A 793: 99–106.

Fent, K. 1996. Ecotoxicology of organotin compounds. Crit Rev Toxicol 26: 1–117.Hoch, M. 2001. Organotin compounds in the environment - An overview. Appl. Geochem. 16:

719–743.Heroult, J., M. Bueno, M. Potin-Gautier, and G. Lespes. 2008. Organotin speciation in

French brandies and wines by solid-phase microextraction and gas chromatography -pulsed flame photometric detection. J. Chromatogr. A 1180: 122–130.

Jiao, J., N. Ding, T. Shi, X. Chai, P. Cong, and Z. Zhu. 2011. Study of chromatographicfingerprint of the flavor in beer by HS-SPME-GC. Anal Lett 44: 648–655.

Leermakers, M., J. Nuyttens, and W. Baeyens. 2005. Organotin analysis by gaschromatography-pulsed flame-photometric detection (GC-PFPD). Anal. Bioanal. Chem.381: 1272–1280.

Liu, J. Y., and G. B. Jiang. 2002. Survey on the presence of butyltin compounds in Chinesealcoholic beverages, determined by using headspace solid-phase microextraction coupledwith gas chromatography-flame photometric detection. J. Agric. Food Chem. 50: 6683–6687.

Magi, E., C. Liscio, and M. Di Carro. 2008. Multivariate optimization approach for theanalysis of butyltin compounds in mussel tissues by gas chromatography-mass spec-trometry. J. Chromatogr. A 1210: 99–107.

Martins, J., C. Esteves, A. Limpo-Faria, P. Barros, N. Ribeiro, T. Simoes, M. Correia, and C.Delerue-Matos. 2011. Multiresidue method for the determination of organophosphoruspesticides in still wine and fortified wine using solid-phase microextraction and gas chroma-tography - tandem mass spectrometry. Anal Lett 44: 1021–1035.

Minganti, V., R. Capelli, and R. Depellegrini. 1995. Evaluation of different derivatizationmethods for the multielement detection of hg, pb and sn compounds by gas-chromatography microwave-induced plasma-atomic emission-spectrometry inenvironmental-samples. Fresenius J. Anal. Chem. 351: 471–477.

Morabito, R., P. Massanisso, and P. Quevauviller. 2000. Derivatization methods for the deter-mination of organotin compounds in environmental samples. Trac-Trends Anal. Chem. 19:113–119.

Munoz, J., M. Gallego, and M. Valcarcel. 2005. Speciation analysis of mercury and tincompounds in water and sediments by gas chromatography-mass spectrometry followingpreconcentration on C-60 fullerene. Anal. Chim. Acta 548: 66–72.

Oliveira, R. D., and R. E. Santelli. 2010. Occurrence and chemical speciation analysis oforganotin compounds in the environment: A review. Talanta 82: 9–24.

Rastkari, N., R. Ahmadkhaniha, N. Samadi, A. Shafiee, and M. Yunesian. 2010. Single-walled carbon nanotubes as solid-phase microextraction adsorbent for the determination

1808 Y.-Q. WAN ET AL.

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014

of low-level concentrations of butyltin compounds in seawater. Anal. Chim. Acta 662:90–96.

Segovia-Martinez, L., A. Bouzas-Blanco, P. Campins-Falco, and A. Seco-Torrecillas. 2010.Improving detection limits for organotin compounds in several matrix water samples byderivatization-headspace-solid-phase microextraction and GC-MS. Talanta 80: 1888–1893.

Vahcic, M., R. Milacic, and J. Scancar. 2011. Development of analytical procedure for thedetermination of methyltin, butyltin, phenyltin and octyltin compounds in landfill leachatesby gas chromatography-inductively coupled plasma mass spectrometry. Anal. Chim. Acta694: 21–30.

Vercauteren, J., C. Peres, C. Devos, P. Sandra, F. Vanhaecke, and L. Moens. 2001. Stir barsorptive extraction for the determination of ppq-level traces of organotin compounds inenvironmental samples with thermal desorption-capillary gas chromatography - ICP massspectrometry. Anal. Chem. 73: 1509–1514.

Vinas, P., I. Lopez-Garcia, B. Merino-Merono, N. Campillo, and M. Hernandez-Cordoba.2004. Liquid chromatography-hydride generation-atomic absorption spectrometry for thespeciation of tin in seafoods. J. Environ. Monit. 6: 262–266.

Zachariadis, G. A., and E. Rosenberg. 2009. Speciation of organotin compounds in urine byGC-MIP-AED and GC-MS after ethylation and liquid-liquid extraction. J. Chromatogr. B877: 1140–1144.

Zuliani, T., G. Lespes, R. Milacic, and J. Scancar. 2010. Development of the extractionmethod for the simultaneous determination of butyl-, phenyl- and octyltin compounds insewage sludge. Talanta 80: 1945–1951.

DETERMINATION OF 5 ORGANOTINS IN WINE BY GC-MS 1809

Dow

nloa

ded

by [

Nor

thea

ster

n U

nive

rsity

] at

07:

03 1

1 N

ovem

ber

2014