Headspace Solid-phase Microextraction Method Research Articles

An improved method for the measurement of the isotope ratio of ethanol in various samples, including alcoholic and non‐alcoholic beverages

The isotope ratios of ethanol, an important constituent or ingredient of some foods and various beverages and fuels, provide information about biological and geographical origin and quality. We have developed an improved method for measuring the isotope ratio of ethanol in various samples by gas chromatography-high temperature conversion or combustion-isotope ratio mass spectrometry (GC-TC/C-IRMS) with headspace solid-phase microextraction (HS-SPME). A HS-SPME method was developed by optimizing several different parameters, including salt addition, incubation temperature and time, and extraction time. The HS-SPME method enabled us to determine the isotope ratio at low ethanol concentrations (0.08 mM) in 50 min with good precision (+/-0.3 per thousand for delta(13)C and +/-5 per thousand for deltaD). An advantage of this technique is that it can be adapted for use with samples which have high viscosity and contain many matrix compounds, such as alcoholic and non-alcoholic beverages.

Solid-phase microextraction for the determination of haloanisoles in wines and other alcoholic beverages using gas chromatography and atomic emission detection

A headspace solid-phase microextraction (HS-SPME) method for the determination of 12 haloanisoles in wine and spirit samples using gas chromatography with atomic emission detection (GC–AED) was developed. The different factors affecting the efficiency of the extraction were carefully optimized. The divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most suitable for preconcentrating the analytes from the headspace of the sample solution. Sample:water dilutions of 3:4 and 1:6 for wines and spirits, respectively, and the use of a mixed bromochloroanisole compound as internal standard allowed sample quantification against external standards prepared in the presence of 5% (v/v) ethanol. Detection limits ranged from 1.2 to 18.5 ng L −1, depending on the compound and the sample analyzed, with a fiber time exposure of 60 min at 75 °C. The optimized method was successfully applied to different samples, and several of the studied haloanisoles were detected at concentration levels ranging from 10.3 ng L −1 to 1.14 ng mL −1.

Enhancing extraction rate in solid‐phase microextraction by using nano‐structured polyaniline coating

The decrement of equilibrium extraction time without losing extraction efficiency in solid-phase microextraction (SPME) was achieved using nano-structured coating. Polyaniline (PANI) was used as an extraction phase for the comparison of extraction capacity and equilibrium extraction time of nano- and micro-structured coatings. Polychlorinated biphenyls (PCBs) were used as model compounds to examine the extraction properties of nano- and micro-structured coatings. The results revealed that nano-structured PANI coating showed higher extraction rate and shorter desorption time than micro-structured coating, because of the larger surface area. In order to evaluate the extraction capability of prepared nano-structured PANI coating, headspace-SPME method was used for the determination of PCBs in sediment samples by GC-electron capture detector. The proposed method was validated using the certified reference material.

Variations in the components of Osmanthus fragrans Lour. essential oil at different stages of flowering

A headspace solid-phase microextraction (HS-SPME) method was used to extract the essential oil of Osmanthus fragrans Lour., which was then analysed by gas chromatography–mass spectrometry (GC–MS) at four different stages of flowering. The primary chemical components of the essential oil extracted from O. fragrans were linalool and its oxide, α-ionone, β-ionone, nerol, γ-decalactone, 9,12,15-octadecatrienoic acid, and hexadecanoic acid, most of which were at their highest concentrations in extracts obtained from flowers at the initial flowering stage. HS-SPME using a PDMS/DVB fibre is a simple, rapid, and solvent-free method for the extraction of volatile compounds emitted from living O. fragrans. HS-SPME with GC–MS can be used to determine the aromatic maturity in O. fragrans, to decide the optimal harvest date. The initial flowering stage was the best time to harvest O. fragrans.

Robustness test of a headspace solid-phase microextraction method for the determination of chloroanisoles and chlorophenols related to cork taint in wine using experimental design

A robustness test of a solid-phase microextraction-based method optimised for the simultaneous determination of chloroanisoles and acetyl-chlorophenols implicated in the presence of corky taste in wine has been carried out using a hybrid experimental design. The influence of small changes around the nominal level of four factors ( V s/ V t ratio, extraction temperature, exposure time and sample incubation time) on the measured response were evaluated in order to indicate if the method is robust for the experimental range considered. Moreover, it was also necessary to identify the critical parameters in the validated model in order to keep them under strict control. Experimental design provides an effective approach for robustness testing as a part of the analytical method validation.

Differentiation and quantification of xylene isomers by combining headspace solid‐phase microextraction/gas chromatography and self‐ion molecule reaction in an ion trap tandem mass spectrometry

A headspace solid-phase microextraction (HS-SPME) method using polydimethylsiloxane (PDMS)-coated fiber coupling with GC/self-ion molecule reaction (SIMR)/MS/MS (GC/SIMR/MS/MS) has been developed for the differentiation of o-, m-, and p-xylene isomers. The optimization parameters of this method are: extraction time 20 min, stirring rate 1200 rpm, sampling temperature 28 degrees C, and salt concentration 5%. The LODs were found to be in the range of 3-9 ng/mL under the SIM mode of GC/MS. The RSDs were below 1% (n=5). The linear dynamic range of the calibration curve was from 0.05 to 10.0 microg/mL with correlation coefficient (r2)>0.9089. The advantages of this technique are sensitive, selective, ease of operation, simple device, solvent free, and extremely little sample consumption. This technique is the first example using SIMR combined MS/MS applied in the GC/MS and it can be applied to other volatile compounds for future application.

Comparative Study on the Analysis of Lactic Acid in Feminine Wash Using High Performance Liquid Chromatography (HPLC) and Gas Chromatography -Mass Spectroscopy (GC-MS) with Solid Phase Microextraction (SPME)

Lactic acid is an active ingredient in feminine wash for maintaining the pH level in the female genital area. A high concentration of lactic acid may cause irritation in the said part of the body. With this in mind, the need for an efficient method to monitor the amount of lactic acid in different brands of feminine wash is found to be significant. Lactic acid was extracted using the classical way of precipitation reaction from different brands of commercial feminine wash. The sample obtained was quantified using two instrumentation methods: High Performance Liquid Chromatography (HPLC) and Gas Chromatography-Mass Spectrometry (GC-MS). The sampling technique of Solid Phase Microextraction (SPME) in headspace was also incorporated in the use of GC-MS to maximize the semi-volatile property of the analyte. The conditions for the headspace sampling of lactic acid using SPME were optimized. Two fiber types were tested in this study: polydimethylsiloxane/divinylbenzene (PDMS/DVB) and carboxen/polydimethyl-siloxane(CAR/PDMS). This study showed that PDMS/DVB is most suitable for sampling lactic acid. The optimum sampling temperature was at room temperature. The equilibration time was determined to be 50 minutes. The headspace SPME method was likewise tested for sampling underivatized and methylated lactic acid. This study illustrated that polydimethylsiloxane(PDMS) and polydimethylsiloxane/ divinyl benzene is not suitable for extracting lactic acid when it was derivatized. This study also showed that PDMS/DVB is more sensitive to adsorbing underivatized lactic acid. It was found out that SPME could be more effectively utilized if the standard addition method, rather than a calibration curve, is employed. In HPLC, on the other hand, the calibration curve method is evaluated to be more efficient than standard addition. Furthermore, better results were obtained by using the normal phase column and not subjecting the sample to hydrolysis reaction than by using a reverse phase column and hydrolyzing the samples. Quantitative evaluation of three brands of feminine washes A, B and C revealed that their lactic acid concentrations have an average ranging from 9,000-11,000 ppm which is close to the concentration claimed by the manufacturers. Keywords: lactic acid analysis, solid-phase microextraction (SPME), GC-MS, HPLC DOI: 10.3860/jrsce.v4i2.447 JRSCE Vol.4(2) 2007 pp.13-18

Volatile flavour constituent patterns of Terras Madeirenses red wines extracted by dynamic headspace solid‐phase microextraction

A suitable analytical procedure based on static headspace solid-phase microextraction (SPME) followed by thermal desorption gas chromatography-ion trap mass spectrometry detection (GC-(ITD)MS), was developed and applied for the qualitative and semi-quantitative analysis of volatile components of Portuguese Terras Madeirenses red wines. The headspace SPME method was optimised in terms of fibre coating, extraction time, and extraction temperature. The performance of three commercially available SPME fibres, viz. 100 mum polydimethylsiloxane; 85 mum polyacrylate, PA; and 50/30 mum divinylbenzene/carboxen on polydimethylsiloxane, was evaluated and compared. The highest amounts extracted, in terms of the maximum signal recorded for the total volatile composition, were obtained with a PA coating fibre at 30 degrees C during an extraction time of 60 min with a constant stirring at 750 rpm, after saturation of the sample with NaCl (30%, w/v). More than sixty volatile compounds, belonging to different biosynthetic pathways, have been identified, including fatty acid ethyl esters, higher alcohols, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, and monoterpenols/C(13)-norisoprenoids.

Identification of buckwheat ( Fagopyrum esculentum Moench) aroma compounds with GC–MS

Buckwheat has a strong characteristic aroma, but its phytochemical background has not yet been fully elucidated. The aims of this study were identification and quantification of individual compounds responsible for the buckwheat aroma. Volatiles from a freshly ground buckwheat flour were extracted by different methods: direct extraction with petroleum ether, pentane or methanol, distillation with Clevenger apparatus and a headspace solid-phase microextraction method. The extracts were analysed by GC–MS with electron ionisation. Compounds were identified by MS and by comparison of retention times with reference compounds. Direct extraction with methanol and distillation proved to be very efficient. In these extracts twenty-five and thirty-five compounds were identified, respectively. The first extract contained more hydrophilic compounds and the latter more volatile compounds. Most of the compounds were quantified and their odour activity value (OAV) calculated. Only two compounds (salicylaldehyde and phenylacetaldehyde) were found in both extracts. The compounds with the highest contribution to the buckwheat aroma were: 2,5-dimethyl-4-hydroxy-3(2 H)-furanone, ( E, E)-2,4-decadienal, phenylacetaldehyde, 2-methoxy-4-vinylphenol, ( E)-2-nonenal, decanal, hexanal and salicylaldehyde (2-hydroxybenzaldehyde).

A Solid‐phase Microextraction Method for the Detection of Ignitable Liquids in Fire Debris

A solid-phase microextraction (SPME) procedure involving direct contact between the SPME fibers and the solid matrix and subsequent gas chromatography/mass spectrometric analysis for the detection of accelerants in fire debris is described. The extraction performances of six fibers (100 mum polydimethylsiloxane, 65 mum polydimethylsiloxane-divinylbenzene, 85 mum polyacrylate, 85 mum carboxen-polydimethylsiloxane, 70 mum Carbowax-divinylbenzene, and 50/30 mum divinylbenzene-Carboxen-polydimethylsiloxane) were investigated by directly immersing the fibers into gasoline, kerosene, and diesel fuel. For simulated fire debris, in the direct contact extraction method, the SPME fiber was kept in contact with the fire debris matrix during extraction by penetrating plastic bags wrapping the sample. This method gave comparable results to the headspace SPME method in the extraction of gasoline and kerosene, and gave an improved recovery of low-volatile components in the extraction of diesel fuel from fire debris. The results demonstrate that this procedure is suitable as a simple and rapid screening method for detecting ignitable liquids in fire debris packed in plastic bags.

Determination of Bisphenol Ain Water by Isotope Dilution Headspace Solid-Phase Microextraction and Gas Chromatography/Mass Spectrometry Without Derivatization

The original solid-phase microextraction (SPME) fibers use an epoxy resin adhesive that releases bisphenol A (BPA) during thermal desorption of the fiber. This adversely affects the method detection limit and accuracy when these products are used for the determination of BPA. In this work, 5 new metal alloy SPME fibers that do not use epoxy resins were compared for the extraction of BPA in water. The performance of the optimum SPME fiber with 60 microm carbowax-polyethylene glycol coating for the headspace SPME of BPA in water was investigated systematically under different extraction conditions. Salt was found to increase the partitioning of BPA from water into the headspace until saturation was reached. Partitioning of BPA from water into the headspace also increased at higher extraction temperatures, as did longer extraction times. However, extraction of BPA from water onto the SPME fiber was not improved for solutions adjusted to pH 2 compared to the unadjusted neutral solutions. The new BPA method showed good linearity over the concentration range of 2.5 to 40 microg/L [correlation coefficient (r2) = 0.995] . The method detection limit for BPA was 0.5 microg/L, while the instrument detection limit was as low as 0.05 microg/L. Good repeatability was observed for BPA at levels of 5 and 20 microg/L with relative standard deviation values < 10%. The automated headspace SPME method developed in this work was used to investigate migration of BPA from polycarbonate bottles into water, and levels of BPA in water ranged from 1.7 to 4.1 microg/L.

Development of a rapid and sensitive method for the simultaneous determination of 1,2-dibromoethane, 1,4-dichlorobenzene and naphthalene residues in honey using HS-SPME coupled with GC–MS

A new method for the simultaneous determination of 1,4-dichlorobenzene ( p-DCB), naphthalene and 1,2-dibromoethane (1,2-DBE) residues in honey has been developed. Analysis is carried out using gas chromatography–mass spectrometry (GC/MS) in selected ion monitoring mode (SIM), after extraction and preconcentration of target analytes by headspace solid-phase microextraction (HS-SPME), with a 100 μm film thickness polydimethylsiloxane (PDMS) fiber. Several parameters affecting the extension of the adsorption process (i.e., addition of salt, extraction time, extraction temperature) were studied. The optimal conditions for the determination of these analytes were established. The proposed HS-SPME method showed good sensitivity, without carryover between the samples. Linearity was studied from 5 to 2500 μg kg −1 for p-DCB, 0.5 to 500 μg kg −1 for naphthalene and 5 to 500 μg kg −1 honey for 1,2-DBE with correlation coefficients ( r 2) ranging from 0.9901 to 0.9999. Precision was assessed and both intra and inter-day R.S.D.s (%) were below 6.3%. The detection limits were found to be 1, 0.1 and 2 μg kg −1 honey for p-DCB, naphthalene and 1,2-DBE, respectively. The percentage recoveries that were evaluated with the proposed HS-SPME method and the standard addition calibration technique gave values among 72.8 and 104.3% for measurements in samples spiked with one target analyte or mixtures of the three. This method has been applied for the analysis of unknown honey samples. The results showed an excellent applicability of the proposed method for the determination of the target compounds in honey samples.

Development of a syringe pump assisted dynamic headspace sampling technique for needle trap device

This paper describes a new approach that combines needle trap devices (NTDs) with a dynamic headspace sampling technique (purge and trap) using a bidirectional syringe pump. The needle trap device is a 22-G stainless steel needle 3.5-in. long packed with divinylbenzene sorbent particles. The same sized needle, without packing, was used for purging purposes. We chose an aqueous mixture of benzene, toluene, ethylbenzene, and p-xylene (BTEX) and developed a sequential purge and trap (SPNT) method, in which sampling (trapping) and purging cycles were performed sequentially by the use of syringe pump with different distribution channels. In this technique, a certain volume (1 mL) of headspace was sequentially sampled using the needle trap; afterwards, the same volume of air was purged into the solution at a high flow rate. The proposed technique showed an effective extraction compared to the continuous purge and trap technique, with a minimal dilution effect. Method evaluation was also performed by obtaining the calibration graphs for aqueous BTEX solutions in the concentration range of 1–250 ng/mL. The developed technique was compared to the headspace solid-phase microextraction method for the analysis of aqueous BTEX samples. Detection limits as low as 1 ng/mL were obtained for BTEX by NTD-SPNT.

Optimization of Headspace Solid-Phase Microextraction for the Determination of Pesticide Residues in Vegetables and Fruits

A headspace solid-phase microextraction method has been developed for the determination of 8 pesticides in vegetables and fruits by using gas chromatography with an electron capture detector. Two types of fibers (polyacrylate, 85 microm and polydimethylsiloxane, 100 microm) have been assayed and compared. The main factors: extraction and desorption parameters, ionic strength, and the effects of dilution and organic solvents, were studied and optimized. The optimized procedures resulted in more than 80% recovery for all the investigated vegetable and fruit samples with RSD values below 10%.

Use of headspace SPME-GC-MS for the analysis of the volatiles produced by indoor molds grown on different substrates

An automated headspace solid phase microextraction method followed by GC-MS analysis was used to evaluate and compare the in vitro production of microbial volatile organic compounds (MVOCs) on malt extract agar, plasterboard and wallpaper. Five fungal strains were isolated from the walls of water-damaged houses and identified. In addition, four other common molds were studied. In general, MVOC production was the highest on malt extract agar. On this synthetic medium, molds typically produced 2-methylpropanol, 2-methylbutanol and 3-methylbutanol. On wallpaper, mainly 2-ethylhexanol, methyl 2-ethylhexanoate and compounds of the C8-complex such as 1-octene-3-ol, 3-octanone, 3-octanol and 1,3-octadiene were detected. The detection of 2-ethylhexanol and methyl 2-ethylhexanoate indicates an enhanced degradation of the substrate by most fungi. For growth on plasterboard, no typical metabolites were detected. Despite these metabolite differences on malt extract agar, wallpaper and plasterboard, some molds also produced specific compounds independently of the used substrate, such as trichodiene from Fusarium sporotrichioides and aristolochene from Penicillium roqueforti. Therefore, these metabolites can be used as markers for the identification and maybe also mycotoxin production of these molds. All five investigated Penicillium spp. in this study were able to produce two specific diterpenes, which were not produced by the other species studied. These two compounds, which remain unidentified until now, therefore seem specific for Penicillium spp. and are potentially interesting for the monitoring of this fungal genus. Further experiments will be performed with other Penicillium spp. to study the possibility that these two compounds are specific for this group of molds.

Characterization of monovarietal virgin olive oils from six crossing varieties

Volatile composition of virgin olive oil (VOO) from six Tunisian new cultivars was evaluated using headspace solid-phase microextraction method coupled to GC–MS and GC–FID. Various chemical classes were identified such as aldehydes, alcohols, esters, ketones, terpenes and carboxylic acids. The results showed that the most important contributors to olive oil aroma are C 6 aldehydes. These compounds are biogenerated from polyunsaturated fatty acids through the lipoxygenase pathway. Furthermore, they pointed out the predominance of the linolenic acid oxidation over linoleic acid one. The main volatile compounds present in the oil samples were C 6 derivatives such as ( E)-hex-2-enal, ( E)-hex-2-enol and hexanol. In addition to C 6 compounds, the aroma of the studied VOOs contains reasonable amounts of various classes of C 5 components. The tested oil samples showed different volatile profiles. Some components seem to occur exclusively in a specific oil samples and, consequently, their presence might be initially used to establish compositional differences. All results put in evidence that olive oil aroma compounds accumulate differently according to the cultivar.

Determination of phthalates and adipate in bottled water by headspace solid-phase microextraction and gas chromatography/mass spectrometry

The performance of three fibres for the headspace solid-phase microextraction (SPME) of di-2-ethylhexyl adipate (DEHA) and eight phthalates in water was investigated systematically under different extraction conditions. Good responses on the 65 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB) SPME fibre were observed for DEHA and all phthalates. The polydimethylsiloxane (PDMS) SPME fibre had very poor responses for the lighter and slightly polar phthalates, dimethyl phthalate (DMP) and diethyl phthalate (DEP), while the divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) SPME fibre had very poor responses for the heavier and non-polar adipate and phthalates. The salt (NaCl) was found to increase the partitioning of DMP, DEP, diisobutyl phthalate (DiBP), di- n-butyl phthalate, and benzyl butyl phthalate (BBP) from water into the headspace, while partitioning of heavier adipate and phthalates from water into headspace was suppressed when the concentration of NaCl was above 10%. The automated headspace SPME methods were developed and validated under two different salting conditions (30% NaCl for DMP, DEP and BBP, and 10% for DEHA, DiBP, DBP, di- n-hexyl phthalate (DHP), di-2-ethylhexyl phthalate (DEHP), and di- n-octyl phthalate (DOP)). Linearity with R 2 values better than 0.9949 was observed for DEHA and eight phthalates over the range from 0.1 to 20 μg L −1. Method detection limits ranged from 0.003 μg L −1 for DOP to 0.085 μg L −1 for BBP. Good repeatability was observed for DEHA and most phthalates with relative standard deviation (RSD) values less than 10%. The methods were used to analyse bottled water samples for DEHA and eight phthalates. DMP, DHP, BBP, DEHA and DOP were not detected in any samples. Concentrations of the other phthalates were low (around sub-ppb) except for DBP in the water from a polycarbonate bottle at 1.72 μg L −1.

Sol-Gel-based SPME and GC–MS for Trace Determination of Geosmin in Water and Apple Juice Samples

A headspace solid-phase microextraction (HS-SPME) method was developed for the trace determination of geosmin in water and apple juice samples. A poly(dimethylsiloxane) (PDMS) fiber was synthesized as coated fiber using sol-gel methodology. After performing the extraction in the headspace, the fiber was introduced directly into the injection port of a gas chromatography-mass spectrometry (GC–MS) using electron impact (EI) ionization mode. One-at-the-time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature and time, ionic strength, headspace volume, and desorption temperature and time. The analytical data exhibited an RSD of 2–15%, a linear calibration range of 1–1,000 ng L−1, and a detection limit of 0.30 ng L−1 using selected ion monitoring (SIM) mode. The proposed method was successfully applied to the extraction and determination of geosmin in the spiked real water and apple juice samples and a relative recovery of 95–102% were achieved. The developed method offers the advantage of being simple to use, with shorter analysis times, lower cost of equipment, very little matrix effect, and high relative recovery in comparison to conventional methods of analysis.

Study of the volatile composition of tomato during storage by a combination sampling method coupled with gas chromatography/mass spectrometry

AbstractBACKGROUND: The volatile compositions of common tomato (Lycopersicon esculentum var. commune) and cherry tomato (Lycopersicon esculentum var. cerasiforme) during storage were studied by a combination sampling method, including headspace solid phase microextraction (HSSPME), simultaneous distillation extraction (SDE) and steam distillation (SD), coupled with gas chromatography/mass spectrometry (GC/MS) detection.RESULTS: Twenty‐one and 14 volatile compounds of fresh and stale common tomatoes and 27 and 17 volatile compounds of fresh and stale cherry tomatoes were identified with various degrees of certainty. The main identified volatile compounds of common and cherry tomatoes were C6 alcohols and aldehydes. During storage, saturated hexanal increased gradually whereas unsaturated (E)‐2‐hexenal decreased. Different volatile compositional characteristics at the fresh and stale storage phases obtained by HSSPME were specified by principal component analysis (PCA). Different metabolic pathways and enzyme catalyses resulted in the various volatile compositional characteristics during tomato storage. Five typical volatile compounds contributing greatly to the difference in volatile compositional characteristics of common and cherry tomatoes at the fresh and stale storage phases were distilled by a common model strategy. These compounds are potential biomarkers for tomato degradation, but further study is needed.CONCLUSION: The preliminary results suggest that the combination of HSSPME and conventional sampling methods would yield more representative information on changes in tomato volatile composition during storage. Copyright © 2007 Society of Chemical Industry

Multiple headspace solid-phase microextraction for eliminating matrix effect in the simultaneous determination of haloanisoles and volatile phenols in wines

This paper proposes a multiple headspace solid-phase microextraction (MHS-SPME) method coupled to gas chromatography–tandem mass spectrometry detection (GC/MS/MS) for the simultaneous determination of 2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, pentachloroanisole, 2,4,6-tribromoanisole, 4-ethylphenol, 4-ethylguaiacol, 4-vinylphenol and 4-vinylguaiacol in wines. These compounds are involved in the presence of “cork taint” and Brett character in wines. The MHS-SPME method is a modification of SPME developed for quantitative analysis that avoids possible matrix effects based on an exhaustive analyte extraction from the sample. After demonstrating the existence of matrix effect in the analysis of the target compounds by HS-SPME with a divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibre, the MHS-SPME method was developed and validated. The proposed method showed satisfactory linearity, precision and detection limits, all below the odour detection thresholds of the compounds in wine matrices. Good recoveries were observed for all compounds, always above 90%, and the repeatability obtained was considered acceptable, ranging between 2 and 11%. After checking the applicability of the method by comparing the results recorded with those obtained with the standard addition method, the method was applied successfully to the analysis of wine samples. To our knowledge, this is the first time that MHS-SPME combined with GC/MS/MS has been applied to simultaneously determine haloanisoles and volatile phenols in wine.