# Optimisation of a pressurised liquid extraction method for haloanisoles in cork stoppers

ArticleinAnalytica Chimica Acta 540(1):17-24 · May 2005with 86 Reads
Abstract
Cork taint is a musty off-flavour in wines mainly caused by 2,4,6-trichloroanisole, but other haloanisoles can contribute. In this work, a method for the extraction of 2,4,6-trichloroanisole, 2,4,6-tribromoanisole and 2,6-dichloroanisole has been developed. The procedure involves the extraction of the haloanisoles from cork by pressurised liquid extraction and the analysis of the extracts by both GC–μECD and GC–MS–MS. A central composite design was used to investigate the dependence of the recoveries of the analytes on the temperature, percentage pentane–diethyl ether ratio and the extraction time. Experimental data were then processed by using the multiple regression analysis in order to calculate a mathematical model representing the relationship between factors and responses and to determine the best experimental conditions for PLE method. These conditions corresponded to a temperature of 176°C, an extraction time between 2.8 and 4min and an 80:20 pentane:diethyl ether ratio.
• ... SPE methods have been reported for chloroanisoles (Insa et al., 2005;Soleas et al., 2002) and for both chloroanisoles, and chlorophenols with derivatisation (). Other solvent extraction methods include supercritical fluid extraction for 2,4,6trichloroanisole (TCA) in cork (Taylor et al., 2000) and androsterone and skatole in pigs (Zabolotsky et al., 1995), Soxhlet extraction for analysis of trichloroanisole from corks (Juanola et al., 2002) as well as microwave extraction and pressurized fluid extraction (Ezquerro et al., 2006;Gomez-Ariza et al., 2005). ...
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Taints and off-flavours in foods are a major concern to the food industry. Identification of the compound(s) causing a taint or off-flavour in food and accurate quantification are critical in assessing the potential safety risks of a product or ingredient. Even when the tainting compound(s) are not at a level that would cause a safety concern, taints and off-flavours can have a significant impact on the quality and consumers' acceptability of products. The analysis of taints and off-flavour compounds presents an analytical challenge especially in an industrial laboratory environment because of the low levels, often complex matrices and potential for contamination from external laboratory sources. This review gives an outline of the origins of chemical taints and off-flavours and looks at the methods used for analysis and the merits and drawbacks of each technique. Extraction methods and instrumentation are covered along with possible future developments. Generic screening methods currently lack the sensitivity required to detect the low levels required for some tainting compounds and a more targeted approach is often required. This review highlights the need for a rapid but sensitive universal method of extraction for the unequivocal determination of tainting compounds in food.
• ... The maximum of the COMB surface is the simultaneous optimum. This optimization method has been applied in several studies, with good results [62,63]. The COMBINED 3D and contour plot showing surface shape against the axis temperature, time and length is plotted optimum point is displayed in Fig. S2. ...
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Trihalomethanes (THMs) are regulated disinfection by-products (DBPs) most commonly analyzed in quality control water supply due to their harmful effects on health. However, few data exist about the content of emerging iodo-trihalomethanes (I-THMs) which are present in drinking water at very low concentrations (in the order of ngL(-1)). For this reason a two-phase hollow fiber liquid phase microextraction method for the simultaneous determination of four regulated trihalomethanes and six emerging iodo-trihalomethanes using GC-μECD and GC-MS with detection limits in the range of few ngL(-1) has been developed. A central composite design was used to optimize conditions for simultaneous extraction. The best extraction recovery was obtained with 19.2min at 27.1°C and 900rpm, without salt addition, using a supported hollow fiber membrane of 10.5cm (0.6mm id) and 1-octanol as acceptor phase. The limits of detection for the regulated THMs and I-THMs were 3-44ngL(-1) and 1-3ngL(-1), respectively. The calibration curves showed good linearity (R(2)>0.995) and good repeatibility (3-22%). The relative recoveries in water were between 96.5% and 105.2%. The method was applied for the simultaneous determination of trihalomethanes in supply water samples from seven water distribution systems (WDS) in the Huelva area, located at the southwest Spain, which use different water-treatment processes. The highest concentrations of I-THMs, particularly CHBrClI and CHCl2I, were detected in water treated with advanced treatment process using pre-ozonation, however these compounds were not detected or decreased along distribution system. In the samples of treated water with conventional treatment, using pre-oxidation by permanganate and distribution network, CHCl2I, CHBrClI, CHClI2, CHBrI2 and CHI3 were detected at very low concentrations (1-18ngL(-1)). Finally, in water samples from underground origin without oxidation treatment, in which only disinfection with sodium hypochlorite was applied, I-THMs were not detected. Copyright © 2015 Elsevier B.V. All rights reserved.
• Article
Analytical methods of haloanisoles and halophenols quantification in cork matrix are summarized in the current review. Sample-preparation and sample-treatment techniques have been compared and discussed from the perspective of their efficiency, time- and extractant-optimization, easiness of performance. Primary interest of these analyses usually addresses to 2,4,6-trichloroanisole (TCA), which is a major wine contaminant among haloanisoles. Two concepts of TCA determination are described in the review: releasable TCA and total TCA analyses. Chromatographic, bioanalytical and sensorial methods were compared according to their application in the cork industry and in scientific investigations. Finally, it was shown that modern analytical techniques are able to provide required sensitivity, selectivity and repeatability for haloanisoles and halophenols determination.
• Article
This work describes the development of a trace level (<1 ngL(-1)) analysis of haloanisoles in complex wine matrix. The suggested method involves sample preparation based on solid phase extraction, a clean-up to remove acidic compounds, concentration of the haloanisole fraction and large volume on-column injection into a multidimensional GC-MS system. Mass spectrometric detection in the selected ion mode allowed reliable quantification of 2,4,6-trichloroanisole (TCA) or 2,4,6-tribromoanisole (TBA), via their highly deuterated ([(2)H5]) isotopologues as internal standards (stable isotope dilution analysis; SIDA), which had prior been synthesized in house. The development of this new method had become necessary, as a one-dimensional HS-SPME-GC-ECD method, routinely applied for analysis of TCA in cork soaks, had to be extended for TeCA and TBA determination, but failed due to co-elutions within wine matrices. The newly developed SPE//MDGC-MS method provided detection limits well below olfactory thresholds of the analytes with 0.05 ngL(-1) (LOD), 0.19 ngL(-1) (LOQ) for TCA, 0.06 ngL(-1) (LOD), 0.21 ngL(-1) (LOQ) for TeCA, and 0.09 ngL(-1) (LOD), 0.34 ngL(-1) (LOQ) for TBA.
• Article
This study presents a method based on the use of microwave-assisted extraction (MAE) for the quantitative analysis of 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), pentachloroanisole (PCA), 2,4,6-tribromoanisole (TBA), 2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol (TeCP), pentachlorophenol (PCP) and 2,4,6-tribromophenol (TBP) in cork stoppers. The influential parameters of the MAE procedure (extraction time, temperature and solvent volume) were optimised using a central composite experimental design combined with desirability functions. The optimal conditions identified were temperature 170 degrees C, solvent volume 35 mL and extraction time 90 min. MAE extracts were concentrated and derivatised prior to separation and quantification by gas chromatography with electron capture detection. To evaluate the applicability of the proposed MAE method, recovery results were compared with those obtained with the Soxhlet extraction method; the results were similar with both extraction methods. The new method was also satisfactorily applied to real cork stopper samples.
• Article
A solid-phase microextraction (SPME) procedure for the determination of four haloanisoles (2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, pentachloroanisole and 2,4,6-tribromoanisole), as well as their precursor halophenols (2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol and 2,4,6-tribromophenol), involved in the presence of cork taint in wine, was developed. Firstly, analytes were concentrated on a SPME fiber, and then halophenols were derivatised using N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA). The compounds were desorbed for 5 min in the gas chromatography injector port and then determined with an electron capture detector. The influence of different parameters on the efficiency of extraction (volume of sample, type of fibre coating and time) and derivatisation (time, temperature and volume of MSTFA) steps was evaluated. Polyacrylate (PA) was selected as the extraction fiber, optimised parameters for SPME were 10 ml of wine, temperature 70 degrees C and extraction time 60 min. The optimal conditions identified for the derivatisation step were temperature 25 degrees C, reagent volume 50 microl and extraction time 25 min. Under optimal conditions, the proposed method showed satisfactory linearity, precision and detection limits. The method was applied successfully to the analysis of red wine samples. To our knowledge, this is the first time that headspace (HS) SPME combined with on-fiber derivatisation has been applied to determine cork taint responsible compounds in wine.
• Article
A method for the simultaneous determination of the chloroanisoles and chlorophenols in cork samples with gas chromatography has been evaluated in view to its application. All the stages of the suggested procedure have been submitted to an in-depth examination using spiked ground corks. The recoveries of the method, which involves a simultaneous extraction with n-pentane followed by a second extraction using an aqueous basic solution where the phenolic derivates are transferred and, subsequently, derivatised, have been satisfactory for the all analytes at the studied spiking concentration levels. Good precision data and limits of detection between 1 ng/g and 2 ng/g were obtained for almost all compounds. As real samples, naturally contaminated cork slabs taken from different sources have been analysed, showing the presence of 2,4,6-trichloroanisole (TCA) and, in lesser extent, its direct precursor, 2,4,6-trichlorophenol (TCP). Removal studies have been performed by washing these tainted cork slabs with different solutions: Milli-Q water, sodium hydroxide and commercial products. Sodium hydroxide solutions have led to better analyte elimination, and the complete removal of TCP from the cork has been accomplished together with 72% of TCA reduction has been achieved.
• Article
The occurrence of off-flavours in wines and especially the so-called "cork taint defect" represents one of the most serious problem in wine industry in which 2,4,6-trichloroanisole has been blamed as the main responsible. The development of analytical methods for haloanisoles determination in wine/cork represent a challenge, mainly due to food matrix complexity and low taste and odour (T&O) threshold levels which are generally beyond the sensitivity of the analytical systems. In this work, a method based on the combined use of the recently developed multiple headspace solid-phase microextraction (MHS-SPME) and gas chromatography-ion-trap mass spectrometry has been optimised for the determination of haloanisoles in wines. This powerful analytical methodology is compared with several analytical approaches based on pervaporation, an innovative membrane-based technique similar to dynamic headspace. Analytical features of the methods assayed reveal their suitability for the appraisal of haloanisoles in this matrix in which threshold odor concentrations are in the range 4-40 ng l(-1). The analytical approaches have been applied to the analysis of haloanisoles in different Spanish white and red wines, in which spiking experiments showed good recoveries for the methodologies assayed.
• Article
This paper describes the development of an analytical method consisting of pressurised fluid extraction (PFE) and gas chromatography-mass spectrometry (GC-MS) using experimental designs to determine two volatile compounds in naturally-tainted cork stoppers. The target analytes, 2,4,6-trichloroanisole (2,4,6-TCA) and guaiacol, are involved in the cork taint of wine. First, a Plackett-Burman experimental design was carried out in order to determine the significant experimental parameters affecting the PFE process, and then a central composite design was used to optimise these significant parameters. Once the method had been optimised, the influence of the number of extraction cycles was studied. The method was applied to determine the concentration of 2,4,6-TCA and guaiacol in three cork samples, and the results were compared with the ones obtained by multiple headspace-solid-phase microextraction (MHS-SPME) and by Soxhlet extraction.
• Article
Multiple HS-solid-phase microextraction (MHS-SPME) is a modification of SPME developed for quantitative analysis that avoids possible matrix effects based on an exhaustive analyte extraction from the sample. In this paper, the theory of this process associated with a non-equilibrium situation has been presented. The application of an optimised HS-SPME-based method in the analysis of chloroanisoles and chlorophenols, previously acetylated, associated with the occurrence of cork taint in different red, white and rosé wine samples, has revealed the existence of matrix effects. This fact determines the choice of standard addition as the adequate technique for the quantification of these compounds in real samples. MHS-SPME is proposed as a good alternative technique with respect to HS-SPME because it avoids matrix effects, simplifies the quantification of these compounds in real samples and reduces analysis time, providing sensitivity below chloroanisole sensory threshold with acceptable precision.
• Article
A complete methodology for the determination of chloroanisoles and chlorophenols in cork material is proposed. The determination is accomplished by means of a previous liquid-solid extraction followed by stir bar sorptive extraction (SBSE) coupled to gas chromatography-mass spectrometry (GC-MS). Two different liquid-solid extraction experiments were conducted and eight compounds considered (2,6-dichloroanisole, 2,4-dichloroanisole, 2,4,6-trichloroanisole, 2,4,6-trichlorophenol, 2,3,4,6-tetrachloroanisole, 2,3,4,6-tetrachlorophenol, pentachloroanisole and pentachlorophenol). From the results obtained we can conclude that high volume extraction extending extraction time up to 24h is the best choice if we have to release compounds from the inner surfaces of cork stoppers. Recovery percentages ranged from 51% for pentachloroanisole to 81% for 2,4-dichloroanisole. This method allows the determination of an array of compounds involved in cork taint at very low levels from 1.2ng g(-1) for 2,4,6-tricholoroanisole to 23.03ng g(-1) for 2,3,4,6-tetrachlorophenol.
• Article
Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was evaluated for the simultaneous determination of five chlorophenols and seven haloanisoles in wines and cork stoppers. Parameters, such as the nature and volume of the extracting and disperser solvents, extraction time, salt addition, centrifugation time and sample volume or mass, affecting the DLLME were carefully optimized to extract and preconcentrate chlorophenols, in the form of their acetylated derivatives, and haloanisoles. In this extraction method, 1mL of acetone (disperser solvent) containing 30μL of carbon tetrachloride (extraction solvent) was rapidly injected by a syringe into 5mL of sample solution containing 200μL of acetic anhydride (derivatizing reagent) and 0.5mL of phosphate buffer solution, thereby forming a cloudy solution. After extraction, phase separation was performed by centrifugation, and a volume of 4μL of the sedimented phase was analyzed by GC-MS. The wine samples were directly used for the DLLME extraction (red wines required a 1:1 dilution with water). For cork samples, the target analytes were first extracted with pentane, the solvent was evaporated and the residue reconstituted with acetone before DLLME. The use of an internal standard (2,4-dibromoanisole) notably improved the repeatability of the procedure. Under the optimized conditions, detection limits ranged from 0.004 to 0.108ngmL(-1) in wine samples (24-220pgg(-1) in corks), depending on the compound and the sample analyzed. The enrichment factors for haloanisoles were in the 380-700-fold range.
• Article
This article evaluates the capability of single drop ionic liquid microextraction coupled with multicapillary column (MCC) and ion mobility spectrometry (IMS) for the determination of 2,4,6-trichloroanisole (2,4,6-TCA) in wines. The proposed methodology permits the direct analysis of the samples without any additional treatment other than dilution. This is achieved thanks to the selectivity provided by the ionic liquid selected as extractant, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide, as well as the response of the analyte in the IMS working in negative ionization mode. Moreover, the multicapillary column avoids the interference of ethanol in the ion mobility spectra. The analysis of the sample takes ca. 35 min to be completed. The limit of detection was low as 0.01 ng L(-1) using 2 mL of wine sample. Different calibration curves were constructed using aqueous standards, red and white wines, being the signals comparable, with an RSD similar to the method variability. Finally, a set of samples of different nature and packed in different containers were analysed. It was found than those with cork stoppers presented the highest concentration of 2,4,6-TCA.
• Article
Nowadays, hollow fibre membrane extraction techniques are widely used but they are usually applied to water or very simple matrices such as water. In this paper, we propose a new assembly that allows the extraction of forty persistent organic pollutants in real world samples, namely orange juice, porcine plasma and tomatoes. The limits of detection obtained are very low even in the analysis of real samples (9-182 ng L(-1)). The relative standard deviations vary from 1 to 18% and the averaged recoveries in the spike experiments are very high (65-120%) in the different types of samples studied. The new assembly allows a very good precision overcoming in one of the most important shortcomings of membrane extraction techniques. A central composite design has been performed to get optimal extraction conditions for the analytes and also the combined response of all the analytes has been obtained to attain the simultaneous optimum.
• Article
A method was developed for the determination of trichloroanisole, tribromoanisole and pentachloroanisol by solid-phase microextraction and gas chromatography in paper samples (Kraft liner, Test liner and Miolo). Four commercial SPME fibers were evaluated: Polydimethylsiloxane (PDMS), Polyacrylate (PA), Carbowax/Divinylbenzene (CW/DVB) and Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS). DVB/CAR/PDMS gave the best results and was therefore selected. Other variables involved in the extraction procedure were studied and optimized, such as: sample volume, salting-out effect, temperature and extraction time, effect of organic solvent and previous sample preparation. Optimum conditions were obtained using 20 mL of sample with 5 mol L−1 NaCl in a 40 mL vial, extraction temperature of 70 °C and sonication and extraction time of 30 and 40 min, respectively. Detection limits ranged from 0.43 to 1.32 ng g−1 for all analytes. Recoveries between 70 and 100% were obtained and relative standard deviation was below 10% for all compounds.
• Article
In this work, an ultrasound-assisted emulsification-microextraction method has been optimised for the determination in wine of haloanisoles (2,4,6-trichloranisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,4,6-tribromoanisole (TBA) and pentachloranisole (PCA)) responsible for the so-called cork taint. Their halophenolic precursors (2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol (TeCP), 2,4,6-tribromophenol (TBP) and pentachlorophenol (PCP)) have also been simultaneously determined. For this purpose, parameters affecting the USAEME-derivatisation procedure were exhaustively investigated. Firstly, extraction solvent, basic conditions and extraction time were selected to, subsequently, employ experimental design methodology for the simultaneous optimisation of the volumes of acetic anhydride and extraction solvent, temperature and ionic strength conditions. Once optimised, the evaluation of the analytical performance of the method confirmed its suitability for the determination of the studied compounds in wines. The proposed method showed satisfactory linearity (correlation coefficients over 0.981), repeatability (below 10.9%) and inter-day precision (below 11.0%). Detection limits obtained were similar or even lower than previously reported. In addition, the proposed method was successfully applied to the analysis of real samples. To our knowledge, this is the first time that USAME method has been optimised for the simultaneous determination of haloanisoles and halophenols in wine.
• Article
Mass spectrometry (MS) has emerged as a tool that can analyze nearly all classes of molecules, with its scope rapidly expanding in the areas of post-translational modifications, MS instrumentation, and many others. Yet integration of novel analyte preparatory and purification methods with existing or novel mass spectrometers can introduce new challenges for MS sensitivity. The mechanisms that govern detection by MS are particularly complex and interdependent, including ionization efficiency, ion suppression, and transmission. Performance of both off-line and MS methods can be optimized separately or, when appropriate, simultaneously through statistical designs, broadly referred to as "design of experiments" (DOE). The following review provides a tutorial-like guide into the selection of DOE for MS experiments, the practices for modeling and optimization of response variables, and the available software tools that support DOE implementation in any laboratory. This review comes 3 years after the latest DOE review (Hibbert DB, 2012), which provided a comprehensive overview on the types of designs available and their statistical construction. Since that time, new classes of DOE, such as the definitive screening design, have emerged and new calls have been made for mass spectrometrists to adopt the practice. Rather than exhaustively cover all possible designs, we have highlighted the three most practical DOE classes available to mass spectrometrists. This review further differentiates itself by providing expert recommendations for experimental setup and defining DOE entirely in the context of three case-studies that highlight the utility of different designs to achieve different goals. A step-by-step tutorial is also provided. Graphical Abstract ᅟ.
• Article
This study describes an application of ZrO2 electrolytically deposited onto an NiTi alloy (NiTi-ZrO2) as a solid-phase microextraction (SPME) fiber to the determination of 2,4,6-trichloroanisole, 2,4,6-tribromoanisole and pentachloroanisole in red wine samples at the ng L−1 level. Separation and detection was carried out by gas chromatography and electron capture, respectively. The parameters affecting extraction efficiency, such as extraction time and temperature, salting-out effect and sample pH, were simultaneously optimized firstly by means of a two-level full factorial experimental design including a center point, and subsequently through a Doehlert design for three-variables. Excellent robustness, evaluated through a factorial design study, was obtained for all variables considered in the extraction procedure. Detection limits in the range of 6.8 to 8.0ng L−1 were obtained. Precision was excellent, relative standard deviations being lower than 7.0%. Good accuracy was obtained with calibration against a synthetic solution and 25% dilution of wine samples. The extraction capability of the fiber was stable for more than 700 extractions. Thus, it is an excellent alternative for use in SPME.
• Article
A procedure for the determination of three chloroanisoles (2,4,6-trichloro, 2,3,4,6-tetrachloro and pentachloroanisol), as well as their precursor chlorophenols (2,4,6-trichloro, 2,3,4,6-tetrachloro and pentachlorophenol), involved in the presence of cork taint in red wine has been developed. Samples, up to 1l, were concentrated using a 200mg Oasis HLB solid-phase extraction (SPE) cartridge. Chlorophenols were quantitatively eluted from this sorbent with 3ml of methanol. Chloroanisoles were mainly recovered in a second fraction of n-hexane (2ml). Both fractions were combined and mixed with an aqueous solution of sodium bicarbonate and 50μl of acetic anhydride. Chlorophenols were acetylated in the aqueous-methanolic phase and extracted to n-hexane. Chloroanisoles remained unaffected in the n-hexane layer. Both groups of compounds were determined by gas chromatography–tandem mass spectrometry in the same chromatographic analysis. Using a temperature programmable vaporization injector detection limits from 0.2 to 2.4ngl−1, below their sensorial threshold level in red wine, were obtained for all compounds. Average recoveries higher than 80% and acceptable precision were achieved using red wine samples spiked with the analytes at different concentration levels.
• Article
This paper deals with the application of a new headspace solid-phase microextraction (HS-SPME) method developed in order to analyse the total amount of chloroanisoles in different kinds of cork stoppers (natural, agglomerated and sparkling wine stoppers). This parameter must be determined because these compounds can migrate from cork to wine giving it unpleasant musty taint and, therefore, undermine its organoleptic quality. Unlike the releasable amount of chloroanisoles, the total amount of chloroanisoles has no dependence of the method used for its determination so it can be used as a quality control parameter. The application of this method allowed the simultaneous determination of 2,4-dichloroanisole, 2,6-dichloroanisole, 2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole and 2,3,4,5,6-pentachloroanisole.
• Article
"Cork taint'', a musty-mouldy off-odour, represents one of the most serious problems in the wine industry. 2,4,6-Trichloroanisole (TCA), along with other compounds, is known to be responsible for this effect. For this purpose, the present work reports a new method based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatographic (GC) separation and a two-dimensional detection by coupling an electron capture detector (ECD) to an inductively coupled plasma mass spectrometer (ICP-MS) for TCA, 2,6-dichloroanisole (DCA) and 2,4,6-tribromoanisole (TBA) determination. The in-series use of ECD and ICP-MS detectors combine halogen sensitivity from ECD with the selectivity of ICP-MS to confirm these compounds in complex matrices. Different ICP-MS conditions, such as forward power, carrier gas flow and the addition of small percentages of alternate gases have been optimised in the coupling HS-SPME-GC-ECD-ICP-MS. A chemometric approach has been performed for this purpose to obtain the highest sensitivity for all the analytes simultaneously inside the experimental domain. The optimised method shows good detection limits for all the analytes, as well as high precision and sample throughput. Finally, the method has been applied to the analysis of haloanisoles in different red and white Spanish wines. Recovery experiments performed on these matrices proved the method reliability.
• Article
An analytical method for the detection and quantification of haloanisoles and their corresponding halophenols in wineries' ambient air was developed. The target analytes were haloanisoles and halophenols, reported by previous scientific literature as responsible for wine taint. A calibrated pump and active tubes filled with Tenax GR™ were used for sampling. These tubes were thermally desorbed and analyzed using gas chromatography-triple quadrupole mass spectrometry in the selected reaction monitoring mode. The adsorption efficiencies of five commercial sampling tubes filled with different materials were evaluated. The efficiencies of the selected adsorbent were close to 100% for all sampled compounds. Desorption, chromatographic and mass spectrometric conditions were accurately optimized allowing very low limits of quantification and wide linear ranges. The limits of quantification in ambient air ranged from 0.8pgtube(-1) for 2,4,6-trichlorophenol, to 28pgtube(-1) for pentachlorophenol. These results are of great importance because human sensory threshold for haloanisoles is very low. The chromatographic method was also validated and the instrumental precision and trueness were established, a maximum RSD of 9% and a mean recovery of 91-106% were obtained. The proposed method involves an easy and sensitive technique for the early detection of haloanisoles and their precursor halophenols in ambient air avoiding contamination of wine or winery facilities.
• Article
In this paper, a method based on microwave assisted extraction (MAE) in combination with dispersive liquid–liquid microextraction (DLLME) has been proposed as a new approach for the sensitive determination of cork taint responsible compounds in cork stoppers and oak barrel sawdust. For this purpose, haloanisoles and halophenols were extracted from the solid samples using a MAE method. Subsequently, a DLLME-derivatisation procedure was applied on the MAE extracts and the analytes were determined by gas chromatography–electron capture detection (GC–ECD). Parameters affecting the DLLME-derivatisation method were exhaustively investigated by means of experimental design methodology. Once optimised, the proposed method showed satisfactory linearity (correlation coefficients over 0.991), repeatability (below 10.4%) and inter-day precision (below 11.2%). Detection limits obtained were similar or even lower than previously reported. The results obtained proved the suitability of the combination of MAE with DLLME as a sensitive sample preparation methodology for the analysis of haloanisoles and halophenols in solid enological matrices.
• Article
Chloroanisoles, namely 2,4,6-trichloroanisole, are pointed out as the primary responsible of the development of musty off-flavours in bottled wine, due to their migration from cork stoppers, which results in huge economical losses for wine industry. A prevention step is the detection of these compounds in cork planks before stoppers are produced. Mass spectrometry gas chromatography is the reference method used although it is far beyond economical possibilities of the majority of cork stoppers producers. In this work, a portable cyclic voltammetry approach was used to detect 2,4,6-trichloroanisole extracted from natural cork planks to the aqueous phase during the cork boiling industrial treatment process. Analyses were carried out under ambient conditions, in less than 15min with a low use of solvent and without any sample pre-treatment. The proposed technique had detection (0.31±0.01ng/L) and quantification (0.95±0.05ng/L) limits lower than the human threshold detection level. For blank solutions, without 2,4,6-trichloroanisole addition, a concentration in the order of the quantification limit was estimated (1.0±0.2ng/L), which confirms the satisfactory performance of the proposed methodology. For aqueous samples from the industrial cork planks boiling procedure, intra-day repeatabilities were lower than 3%, respectively. Also, 2,4,6-trichloroanisole contents in the aqueous samples determined by this novel approach were in good agreement with those obtained by GC-MS (correlation coefficient equal to 0.98), confirming the satisfactory accuracy of the proposed methodology. So, since this novel approach is a fast, low-cost, portable and user-friendly method, it can be an alternative and helpful tool for in-situ industrial applications, allowing accurate detection of releasable 2,4,6-trichloroanisole in an earlier phase of cork stoppers production, which may allow implementing more effective cork treatments to reduce or avoid future 2,4,6-trichloroanisole contaminations of wine.
• Article
The present paper describes the calibration of selected passive samplers used in the quantitation of trichlorophenol and trichloroanisole in wineries' ambient air, by calculating the corresponding sampling rates. The method is based on passive sampling with sorbent tubes and involves thermal desorption-gas chromatography-triple quadrupole mass spectrometry analysis. Three commercially available sorbents were tested using sampling cartridges with a radial design instead of axial ones. The best results were found for Tenax TA™. Sampling rates (R-values) for the selected sorbents were determined. Passive sampling was also used for accurately determining the amount of compounds present in the air. Adequate correlation coefficients between the mass of the target analytes and exposure time were obtained. The proposed validated method is a useful tool for the early detection of trichloroanisole and its precursor trichlorophenol in wineries' ambient air while avoiding contamination of wine or winery facilities. Copyright © 2015. Published by Elsevier B.V.
• Article
The design and operation of a wine bottle screening device that noninvasively and nondestructively determines the presence of 2,4,6-trichloroanisole (TCA), or cork taint, in bottle-mounted corks is described. The approach uses commercially available solid-phase microextraction fibers for reduced pressure preconcentration and gas chromatography mass spectrometry to detect TCA in wine bottle-mounted corks, instrument calibration experiments and data corresponding to intentionally contaminated free and wine bottle mounted corks are described. This study suggests that reduced-pressure full-bottle screening is a viable qualitative method for identifying bottle-mounted TCA tainted corks without violating the bottle or harming the bottle seal and label.
• Article
The development of accelerated solvent extraction (ASE) is discussed. The effects of the various operating parameters (temperature, pressure, time, solvent composition, etc.) on extraction efficiency are discussed as well. The impact of the treatment of samples prior to extraction is presented. The means for method optimization as well as procedures for changing the selectivity during extraction are given. The properties of liquid water at temperatures exceeding the atmospheric boiling point are presented and the exploitation of these properties for the use of analytical extractions is demonstrated. A case is made for potential analytical decomposition. Advantages of high-temperature water as a solvent are discussed and applications of the technique presented.
• Article
Haloanisoles (e.g., 2,4,6-trichloroanisole, TCA; 2,4- dichloroanisole, 2,4-DCA; 2,6-dichloroanisole, 2,6-DCA; 2,3,4,6-tetrachloroanisole, TeCA; pentachloroanisole, PCA; and 2,4,6-tribromoanisole, TBA) cause musty off-aromas in many consumer products, including wine. In wines, the most common source of haloanisole contamination is cork closures, although barrels and other winery sources may also be sources of contamination. Human sensory thresholds for many haloanisoles are in the low ng L-1 level, therefore analytical methods for identification and quantification of these compounds requires limits of detection and quantitation at similar levels or lower. Gas chromatography-mass spectrometry is commonly used for analysis of haloanisoles and numerous sample preparation techniques have been reported. This chapter will briefly review information about sources of haloanisole contamination in consumer products and then review analytical approaches for measuring these important compounds in wines.
• Article
The use of different response functions to be optimized in the frame of the use of near infrared spectrometry for quality control of active principles in agrochemical formulations has been evaluated. Both, simple functions, based on parameters like sensitivity, repeatability, accuracy, signal to noise ratio, limit of detection or sample throughput, and a complex function, considering all the aforementioned aspects, were employed in the development of a new method for Iprodione determination in agrochemicals. Optimization strategies were based on the previous screening of the most important instrumental factors like number of cumulated scans, nominal resolution, mirror velocity and zero filling factor, based on a two-level full factorial design and on the search for the optimum conditions using central composite designs. Data found evidenced the influence of the response function on the optimum values of experimental conditions and could be employed as a general guide to evaluate the experimental factors in routine use of near infrared spectrometry. Finally the optimized method for Iprodione has been applied to the determination of Diuron and results found compared with those obtained by a conventional approach.
• Article
A procedure for fast, reliable and precise analysis of 2,4,6-trichloroanisole (TCA) and other anisoles [2,6-dichloroanisole (DCA) and 2,4,6-tribomoanisole (TBA)] in cork-tainted wines has been performed. The method is based on compounds separation by pervaporation (PV) and later on-line clean-up, using a Carbofrit packed liner (CPL) fitted to the gas chromatograph–mass spectrometer injector (PV–CPL–GC–MS). Detection limit was about 54 pg for TCA (5 ng l−1 when aliquots of 10 ml were used in the analysis). These results were comparable with those obtained from the coupling pervaporation solid-phase cryogenic trap–thermal desorption GC–MS (PV–CT–TD–GC–MS) and solid-phase microextraction gas chromatography. Precision of PV–CPL–GC–MS, expressed as relative standard deviation, was 5.2, 2.0 and 6.2% for DCA, TCA and TBA, respectively. Linear range of calibration curves ranged from quantification limit to 2 ng for all the anisoles. In addition, the method based on the PV–CPL–GC–MS coupling was more rapid and reliable than that using PV–CT–TD–GC–MS, due to the one-step direct on-line introduction of analytes from the PV unit to the GC–MS system facilitated by CPL, which increases the analysis precision and sample throughput.
• Article
About 20% of Brazil coffee production presents the so-called Rio defect characterized by a strong off-flavor, often described as medicinal, phenolic, or iodine-like. Occasionally, this defect also occurs in coffees from other origins. An extensive investigation was carried out to identify the compound(s) responsible for the coffee samples. Volatiles were isolated from green beans by simultaneous distillation-extraction and analyzed by capillary GC, GC-sniffing, and GC-MS. 2,4,6-Trichloroanisole (TCA) was identified as the most likely key compound for the Rio off-flavor. TCA was found in all Rio samples in concentrations ranging from 1 to 100 ppb. Less than 50% of TCA present in green beans was lost during roasting. 2,4,6-Trichlorophenol (TCP), the probable precursor of TCA, was also found in most of these samples. Adding TCA to freshly brewed coffee imparted to it the same off-flavor notes as described in actual Rio coffee. The perception threshold of TCA in coffee brew was found to be 8 ppt for direct odor perception and 1-2 ppt for flavor by mouth.
• Article
Suppose that a relationship $\eta = \varphi(\xi_1, \xi_2, \cdots, \xi_k)$ exists between a response $\eta$ and the levels $\xi_1, \xi_2, \cdots, \xi_k$ of $k$ quantitative variables or factors, and that nothing is assumed about the function $\varphi$ except that, within a limited region of immediate interest in the space of the variables, it can be adequately represented by a polynomial of degree $d$. A $k$-dimensional experimental design of order $d$ is a set of $N$ points in the $k$-dimensional space of the variables so chosen that, using the data generated by making one observation at each of the points, all the coefficients in the $d$th degree polynomial can be estimated. The problem of selecting practically useful designs is discussed, and in this connection the concept of the variance function for an experimental design is introduced. Reasons are advanced for preferring designs having a "spherical" or nearly "spherical" variance function. Such designs insure that the estimated response has a constant variance at all points which are the same distance from the center of the design. Designs having this property are called rotatable designs. When such arrangements are submitted to rotation about the fixed center, the variances and covariances of the estimated coefficients in the fitted series remain constant. Rotatable designs having satisfactory variance functions are given for $d = 1, 2$; and $k = 2, 3, \cdots, \infty$. Blocking arrangements are derived. The simplification in the form of the confidence region for a stationary point resulting from the use of a second order rotatable design is discussed.
• Article
A “MUSTY” taint in chicken eggs has been attributed to the presence of 2,3,4,6-tetrachloroanisole (I) in litter shavings by Engel, de Groot and Weurman1, who showed that the feeding of small amounts of this compound to chickens caused a musty taint in both eggs and broiler meat. The samples of shavings that contained 2,3,4,6-tetrachloroanisole (I) also contained pentachloroanisole (II). Following recent occurrences of musty taint in the UK broiler industry, we have examined chicken carcasses and broiler house litter for the presence of chloroanisoles and investigated their origin.
• Article
Strains of the ubiquitous xerophilic fungus Paecilomyces variotii can quantitatively convert the fungicide 2,4,6-tribromophenol to its musty-smelling metabolite, 2,4,6-tribromoanisole. Conversion was complete at the end of 6 weeks. A trained sensory panel found the odor threshold concentrations of 2,4,6-tribromoanisole to be 2 × 10-5 μg/L in water and 2 × 10-3 μg/kg in sultanas. Studies also showed that 2,4,6-tribromoanisole could produce a musty taint in sultanas packaged in polyethylene pouches after only 1 week of storage in the presence of fiberboard that contained 300 ng of this compound; the taint was produced at both 22 and 30 °C. An analytical method based on multiple-ion detection GC−MS was used for the measurement of 2,4,6-tribromoanisole in packaging materials and food. Keywords: 2,4,6-Tribromoanisole; 2,4,6-tribromophenol; fungal metabolite; musty odor; odor threshold; GC−MS analysis
• Article
Fungi isolated from fibreboard cartons, paper sacks and jute sacks were assessed for their ability to methylate 2, 4, 6-trichlorophenol in a defined, reduced-water-activity growth medium. When extracts of individual cultures were analysed by gas chromatography-multiple ion monitoring mass spectrometry, 17 of the 31 species, initially selected by sensory techniques, were found to produce 2, 4, 6-trichloroanisole. Quantitative analyses showed that the most efficient methylators in the defined liquid medium were Paecilomyces variotii, Fusarium oxysporum, Penicillium crustosum, Pen citrinum, Pen brevicompactum and one strain of Aspergillus flavus. The role of these fungi in the production of 2, 4, 6-trichloroanisole in packaging materials contaminated with 2, 4, 6-trichlorophenol is discussed.
• Article
In a study aiming to characterize cork off-flavour for quality control purposes, chloroanisoles were extracted and identified from cork stoppers by means of solid-phase microextraction (SPME)–gas chromatography–ion-trap mass spectrometry (GC–ITMS). An experimental design procedure was used to investigate the effects of some experimental parameters on the SPME of 2,4-dichloroanisole, 2,6-dichloroanisole, and 2,4,6-trichloroanisole from cork stoppers by using a Carboxen-PDMS 75 μm fibre. Variables such as extraction temperature, extraction time, and percentage of ethanol added to the matrix were optimized to improve extraction efficiency of chloroanisoles onto SPME fibre. Instrumental analysis was performed by GC–ITMS in the MS/MS mode. Preliminary analyses on standard solutions allowed selection of the appropriate ionization mode (i. e. electron impact or chemical ionization), providing for each analyte the highest instrumental response. In order to find polynomial functions describing the relationships between variables and responses, the analytical responses, i.e. the chromatographic peak areas, were processed by using the backward multiple regression analysis. For all the analytes the operating conditions providing the highest extraction yield inside the experimental domain considered were found.
• Article
A new method has been developed for the analysis, by gas chromatography/mass spectrometry, of 2,4,6-trichloroanisole (TCA) and other chloroanisoles in cork-tainted wines, using a polydeuterated form of TCA as an internal standard. In a survey of wines presented at a wine assessment course, 4.8% (i.e. 18 bottles out of 374) were assessed by at least 20% of the participants as being affected by cork taint. TCA was present in each of these 18 wines at a concentration close to, or above the sensory detection threshold. All cases of taint seen by the participants could therefore be attributed, at least in part, to the presence of TCA, and this in turn could be attributed to the cork, since variation in apparent taint between bottles of the same wine was observed in every case. TCA was also found in the corks from the wines. Randomly selected bottles of wines considered to be affected by a high proportion of cork taint, and the corks from those bottles, were also analysed. There was considerable variation in the distribution of TCA and other chloroanisoles between wine and cork. In many cases, chloroanisoles were found only in the cork. TCA in corks was accompanied by varying amounts of 2,4– or 2,6-dichloroanisoles, 2,3,4,6-tetrachloroanisole and pentachloroanisole, indicating more than one origin for chloroanisoles in corks. No chloroanisoles, other than those derived by methylation of products formed by non-enzymatic chlorination of phenol, were detected in any of the samples.
• Article
The effect of different corks stoppers on the sensory and instrumental determination of 2,4,6-trichloroanisole (TCA) was studied in wine and cork. A relationship between both measurements was also established.Four types of cork were used to seal white wine bottles for 8 months. The stoppers were from different raw material: a high quality commercial batch (C), slabs with yellow stain (YS) and slabs with a high musty and mouldy taint (T). Spiked samples (S) were prepared from C batch by injecting 1002 ng of TCA into the cork stoppers.TCA was determined by gas chromatography with electron capture detection after headspace solid phase microextraction in bottled wine (12 per group) and after extraction with pentane in the case of corks (six per group). Seven semi-trained assessors evaluated the different samples using a ranking test in 12 and six sessions for wine and cork stoppers, respectively.Wines and corks from S samples showed the highest TCA values in both sensory and instrumental measurements, the lowest values being for C samples. YS and T corks had intermediate values, although in general TCA concentration was higher in T. A slight tendency to increase the TCA content in stoppers with yellow stain compared to C samples was observed in wine. A high correlation coefficient (r=0.82) was found between sensory and instrumental analysis for wine, whereas this coefficient was much lower (r=0.56) for cork stoppers. Some hypotheses are given in order to explain these differences.
• Article
A program for optimizing central composite experimental designs, called ccdopt, has been devised and implemented in QuickBasic. The principal procedures involved are discussed. In order to illustrate how the program works several worked examples have been selected.
• Article
Determination of pesticides in food is often complicated by the presence of fats and requires multiple clean-up steps before analysis. Cost-effective methods are needed for analyzing the large number of samples generated in large-scale exposure studies. We examined two extraction methods, supercritical fluid extraction (SFE) and accelerated solvent extraction (ASE), coupled with various clean-up techniques for the analysis of pesticides in baby foods and exposure samples. The SFE-gas chromatogram/mass spectrometry (GC/MS) method did not provide quantitative recoveries (<50%) of the pesticides spiked into fatty baby foods. This led to the evaluation of ASE-enzyme-linked immunosorbent assay (ELISA) and ASE-GC/MS. Two solvents (acetonitrile (ACN) and ethyl acetate), three extraction temperatures (80, 100, and 120°C), and several different sample clean-up procedures were evaluated. A set of ASE conditions was developed that consisted of extracting baby food with ACN at 80°C under 2000 psi pressure. An ENVI-Carb solid phase extraction (SPE) condition was also developed to clean the ACN extract. The clean-up fraction was analyzed by ELISA for chlorpyrifos and by GC/MS for malathion, chlorpyrifos, and 4,4′-DDT. Duplicate-diet samples were analyzed for target pesticides by ASE-ELISA and by ASE-GC/MS. Concentrations of these compounds ranged from <0.3 to 110 ppb.
• Article
The formation of pentachloroanisole by methylation from pentachlorophenol by Trichoderma virgatum in liquid cultures was detected using gas chromatography and confirmed by melting point determination and infrared (i.r.) spectroscopy. The formation of pentachloroanisole, however, did not account for the total loss of pentachlorophenol in the medium, suggesting that this reaction is only the first step in the metabolism of this compound or a parallel reaction to degradation. Pentachloroanisole was much less toxic than pentachlorophenol to Trichoderma virgatum, Cephaloascus fragrans, and Penicillium sp., as well as to fish in laboratory toxicity tests.
• Article
Ingestion by hens and broilers of specific chloroanisols present in some wood shavings used in poultry cages can result in a musty taste in poultry products.
• Article
Cork taint in wine is a serious problem which is exacerbated by the difficulty of its assessment. Current analytical procedures are costly, time consuming and require the use of large amounts of solvents. We developed and evaluated a rapid method for the detection of the cork taint compound, 2,4,6-trichloroanisole (TCA), in wine samples. The method employs solid-phase microextraction, a solventless, automated sampling procedure, coupled to GC-MS-selected ion monitoring analysis. Quantification is enabled by a fully deuterated [2H5]TCA analog used as an internal standard. Accuracy (+/- 8%), precision (R.S.D. 5-13%), and limit of quantification (5 ng/l) are comparable to existing methods.
• Article
Pressurised liquid extraction (PLE) was used to extract pentachlorophenol from cotton and dyestuffs. Five dyes and one dyed cotton were investigated for pentachlorophenol. The dyed cotton was found to have between 5.3 and 5.9 microg g(-1) pentachlorophenol, while the dyes were found to have between 42 and 2569 microg g(-1) pentachlorophenol present. The latter were found to be dye and manufacturing site dependant. Recovery experiments, in all cases, were found to be quantitative indicating appropriate sample work-up and manipulations.
• Article
2,4,6-Trichloroanisole (TCA) is the compound most often associated with cork taint in wines and has been shown to have a very low sensory threshold ( approximately 5 ng/L in wine). A supercritical fluid extraction (SFE) method for TCA in bark cork stoppers was developed with quantification via gas chromatography-mass spectrometry with selected ion monitoring. Supercritical carbon dioxide functioned as the extracting solvent, and temperature and pressure were optimized for the extraction. The method was validated using the stable isotope (2)H(5)-TCA as the internal standard. Recovery of TCA from spiked corks was found to be within 1-4% of the theoretical concentration with a coefficient of variation ranging from 2.6 to 9.7%. TCA levels in corks pulled from wines described as tainted by experienced judges ranged from 0.13 to 2.11 microg/g of cork. The SFE procedure offers a rapid, quantitative, nearly solvent-free, and automated method for the extraction of TCA from complex solid matrices such as cork.
• Article
The reliability and efficiency of the pressurised liquid extraction technique (PLE) for extracting polycyclic aromatic hydrocarbons (PAHs) from contaminated soil has been investigated. Experimental design was used to study the influence of seven extraction variables (sample load, solvents used, solvent ratios, pressure, temperature, extraction time, and rinse volume). The results show that large sample loads in combination with small solvent volumes may result in low extraction efficiency. They also indicate that the recovery of low-molecular-mass PAHs is reduced by low extraction temperatures. The exact settings of the other variables are, however, less significant for the extraction efficiency. Repeated extractions at optimised settings of the tested variables show that PLE is an exhaustive extraction technique that generally results in high yields. In addition, extraction of a certified reference material (CRM 103-100) revealed that the method is both accurate and precise. Another finding was that adding the internal standard on top of the soil in the extraction cell causes considerable over-estimation of the concentrations when large samples are extracted with small solvent volumes. This is because the PLE-cell resembles a chromatographic column, so compounds added to the top of the soil layer have a longer distance to travel through the soil compared to the average distance of the native compounds, which are distributed evenly throughout the column. We therefore recommend that the internal standard should be added to the extract immediately after the extraction or, alternatively, carefully mixed with the sample prior to extraction.
• Article
A method based on solvent extraction and GC-electron-capture detection analysis for the determination of 2,4,6-trichloroanisole (TCA) from cork has been evaluated and optimised. Our sample treatment consists of an extraction stage with pentane while the sample and solvent are kept in contact in a mechanical shaker (shake-flask extraction). Different extraction conditions have been tested in order to find the best compromise between efficiency and time of analysis. Different columns were evaluated for use in the concentration and purification step. A silica column was found to give the best performance in terms of recovery of TCA and repeatability. Pentane and mixtures of pentane-diethyl ether at different ratios were tested as eluting agents. It was found that 10 ml pentane allowed the recovery of retained TCA. Finally, the eluate was concentrated and injected into the chromatograph for TCA determination. The optimised chromatographic conditions enabled the quantification of TCA and 2,6-dichloroanisole, which was assayed as the internal standard. The shake-flask extraction method was compared with Soxhlet and ultrasound assisted extraction procedures using pentane as a solvent. Similar results were obtained for the shake-flask and Soxhlet extraction methods, while sonication gave significantly lower recoveries. The optimised shake-flask method was applied to determine the distribution of TCA in naturally contaminated cork bark.
• Article
One of the most important problems in the wine world, today, is cork taint, which often has been chemically identified as 2,4,6-trichloroanisole (TCA). The perception limit of this compound is very low (close to 10 and 40 ng/l for white and red wines, respectively), so, even at such low concentrations, its presence becomes a problem in wine quality. A method for the analysis of TCA in white and red wines has been developed in our laboratory, using headspace solid-phase microextraction and gas chromatography with electron-capture detection. The method, which has been optimized using an experimental design, involves the use of fibres coated with polydimethylsiloxane (PDMS) and allows the analysis of TCA at very low concentrations (under 500 ng/l) with good accuracy (RSD < or = 10%). The limits of quantification of the method are 5 and 8 ng/l for white and red wines, respectively, while the limit of detection is 1 ng/l for both types of wine.
• Article
Full-text available
Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used.
• Article
The off-flavor compounds 2-methylisoborneol (MIB), geosmin, 2,4,6-trichloroanisole, 2,3,6-trichloroanisole, 2,3,4-trichloroanisole, and 2,4,6-tribromoanisole were analyzed in water samples by stir bar sorptive extraction (SBSE) followed by on-line thermal desorption (TD) capillary GC/MS. Quantification was performed using the MS in the single-ion-monitoring mode (SIM) with 2,4,6-trichloroanisole-D(5 )as internal standard. Quantification limits are 0.1-0.2 ng L(-1) for the haloanisoles, 0.5 ng L(-1) for geosmin, and 1 ng L(-1) for MIB. The relative standard deviations at the quantification limit ranged from 7 to 14.6%. SBSE recovery was evaluated by spiking real water samples and varied from 87 to 117%. More than twenty samples per day can be analyzed by SBSE-TD-capillary GC-MS. The same technique in combination with olfactometry was used to elucidate unknown odorous compounds in water samples.
• Article
The system based on coupling a headspace sampler to a mass spectrometer (HS-MS), which is considered one kind of electronic nose, is an emergent technique for ensuring and controlling quality in industry. It involves injecting the headspace of the sample into the ionization chamber of the mass spectrometer where the analytes are fragmented. The result is a complex mass spectrum for each sample analyzed. When several samples are analyzed the data matrix generated is processed with chemometric techniques to compare and classify the substances from their volatile composition, in other words, to compare and classify their flavor. So far, information from electronic nose applications has mainly been qualitative. In this paper we present a quantitative study that uses a multivariate calibration. We analyzed several white wines using HS-MS to determine 2,4,6-tricholoranisole (TCA). This is an off-flavor that is a serious problem for the wine industry. The method is simple because it does not require sample preparation, only addition of sodium chloride being necessary for sample conditioning. Also, it provides a fast screening (10 min/sample) of the quantity of TCA in wines at ultratrace (sub microg L(-1)) levels.
• Article
A headspace solid-phase microextraction (HS-SPME) procedure at 30 degrees C with a 100 microm PDMS fiber of a saturated NaCl solution stirred at 1100 rpm combined to GC-ECD for the 2,4,6-trichloroanisol (TCA) determination in wines has been developed. Due to the matrix complexity and ethanol absorption into the fiber, the internal standard selection was crucial to obtain unbiased results. Thus, matrix effects were observed when analyzing different types of Spanish wines (white, early, and vintage red wines) spiked with TCA at low concentration levels (i.e., <40 ng L(-)(1)). In contrast, the use of 2,4,6-tribromoanisole (TBA) as internal standard overcame these matrix effects, whereas the use of 2,4,6-trichlorophenyl ethyl ether led to inconsistent results. The developed HS-SPME-GC-ECD methodology reaches a limit of quantitation for TCA in wine within 2.9-18 ng L(-)(1), with a relative standard deviation of 2.5-13.4%, depending on the TCA concentration level and wine characteristics. This analytical method is comparable to the existing methodologies based on HS-SPME followed by GC-MS in terms of accuracy, precision, length of determination, and length of quantification; however, analysis cost is reduced.
• Article
In this work, gas phase chromatography analysis coupled with selective selected ion monitoring (SIM) identified 2,4,6-tribromoanisole (TBA) in wines found on tasting to have significant "musty or corked" character, although they did not contain noteworthy quantities of chloroanisoles or chlorophenols, the contaminants generally reported to cause this type of defect. The perception thresholds were studied, together with contamination conditions during winemaking, storage, and bottle-aging. A "musty" off-odor was perceptible on smelling wine containing as little as 4 ng L(-)(1) TBA, and spoilage may be detected by retro-olfaction at even lower concentrations. TBA, produced by O-methylation of its direct precursor, 2,4,6-tribromophenol, generally comes from sources in the winery environment. This paper is the first to identify the sources of a large number of cases of wines polluted during storage in premises where the atmosphere was contaminated with TBA used recently to treat wood, or originating from much older structural elements of the winery, or from used wooden containers. In certain cases, although the initial source had been eliminated, residual pollution adsorbed on walls could be sufficient to make a building unsuitable for storing wooden barrels and plastics, as well as corks, which have been found to be particularly susceptible to contamination by the TBA in the winery atmosphere.
• Article
A magnetic stir bar with a polydimethylsiloxane coating was used to absorb 2,4,6-trichloroanisole, 2,3,4,5-tetrachloroanisole, pentachloroanisole and their respective phenols from synthetic and real wine samples. The stir bar sorptive extraction method was optimised to obtain the best extraction conditions in terms of temperature, time, pH and NaCl addition. The stir bar was desorbed in a thermal desorption system coupled to a gas chromatograph-mass spectrometer. The method proposed showed good linearity over the concentration range tested and correlation coefficients ranged from 0.96 to 0.99 for all the analytes. The reproducibility and repeatability of the method was estimated between 1.29 and 4.02%. With no a pre-concentration step and with a much reduced analysis time, all the analyzed compounds showed detection and quantification limits that were lower than those observed with other methods found in the bibliography. Except for pentachlorophenol due to its poor absorptivity in polydimethysiloxane, in red wines, LOD ranged between 7.56 and 61.56 pg/l, and LOQ ranged between 17.21 and 205.11 pg/l; while in white wines, the LOD ranged between 5.82 and 30.50 pg/l and LOQ ranged between 19.41 and 101.61 pg/l. These concentrations were always lower than their respective olfactory thresholds values.
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