固相微萃取气质联用分析茉莉花的香气成分

利用顶空固相微萃取技术,采用气质联用仪分析茉莉花的香气成分,在弱极性和极性毛细管色谱柱条件下,分别用PDMS、PDMS/DVB、PA三种萃取头富集香气,分离出100多种香气成分,鉴定出含量大于0.1%的55种组分,占香气成分的97%,三种萃取头所得主成分完全一致,均为芳樟醇、乙酸苄酯、反式-金合欢烯、顺式-苯甲酸-3-己烯酯和吲哚。     

四川乌龙茶香气化学成分的剖析

四川乌龙茶在低温减压蒸馏所得香气浓缩物经气相色谱-质谱联用测定,以气相色谱保留值验证,鉴定出19个化合物,它们是:丙酮,乙酸乙酯,顺-3-己烯醇-[1],乙酸顺-3-己烯酯,苯甲醇,反-芳樟醇氧化物(呋喃型),顺-芳樟醇氧化物(呋喃型),芳樟醇,苯乙醇,反-芳樟醇氧化物(吡喃型),丁酸顺-3-己烯酯,香叶烯,己酸顺-3-己烯酯,茉莉酮,橙花叔醇,金台欢醇,茉莉酮酸甲酯,正十六烷和2,6,10,14-四甲基十五烷。     

Analysis of organic volatile flavor compounds in fermented stinky tofu using SPME with different fiber coatings

The organic volatile flavor compounds in fermented stinky tofu (FST) were studied using SPME-GC/MS. A total of 39 volatile compounds were identified, including nine esters, seven alcohols, five alkenes, four sulfides, three heterocycles, three carboxylic acids, three ketones, two aldehydes, one phenol, one amine and one ether. These compounds were determined by MS, and conformed by comparison of the retention times of the separated constituents with those of authentic samples and by comparison of retention indexes (RIs) of separated constituents with the RIs reported in the literature. The predominant volatile compound in FST was indole, followed by dimethyl trisulfide, phenol, dimethyl disulfide and dimethyl tetrasulfide. In order to find a better extraction time, the extraction times was optimized for each type of SPME fiber; the results show that the best extraction time for Carboxen/PDMS is 60 min, for PDMS/DVB 30 min, for DVB/CAR/PDMS 60 min and for PDMS 75 min. Of the four fibers used in this work, Carboxen/PDMS is found to be the most suitable to extract the organic volatile flavor compounds in fermented stinky tofu.     

Development of fluorinated low temperature glassy carbon films for solid-phase microextraction

Solid-phase microextraction (SPME) fibers with supported fluorinated glassy carbon are demonstrated for the first time. Oligo[1,3-dibutadiynylene-1,3-(tetrafluoro)phenylene] was synthesized and heated to temperatures that varied from 200 to 1000 degrees C to produce the fluorinated glassy carbon. The extent of graphitization of the glassy carbon increased as the processing temperature increased. The fluorinated glassy carbon selectively extracted monohalogenated benzenes from an aqueous solution when compared to the extraction of toluene. The selectivity increased in the order of phi-F < phi-Cl < phi-Br < phi-I. The selectivity for the halogenated compounds was greatest for the fluorinated glassy carbon phase processed at temperature below approximately 400 degrees C. Preliminary studies on the retention mechanism of the LTGC phase show that dispersive interactions are very important to the retention of halocarbons on the fluorinated LTGC. Finally, the selectivity of the fluorinated LTGC for halogenated compounds was compared to that of commercially available SPME fibers, such as poly(dimethylsiloxane), poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB), and poly(dimethylsiloxane)/Carboxen (PDMS/Carboxen) fibers. As expected the fluorinated LTGC was more selectivity for the halogenated compounds. Interestingly the order of the increase in selectivity is opposite when comparing the fluorinated-LTGC and the three commercial fibers. A decrease in selectivity was observed going from fluorobenzene to iodobenzene using PDMS/DVB and PDMS/Carboxen fibers. While for the pure PDMS phase, there is a slight increase in selectivity from fluorobenzene to chlorobenzene but the remaining trend shows little change for bromobenzene and iodobenzene.     

固相微萃取-气相色谱/质谱分析栀子花的头香成分

 分别用固相微萃取和动态顶空法分离栀子鲜花的头香成分,用GC/MS技术分析鉴定,并用GC/MS总离子流色谱峰的峰面积进行归一化定量。在固相微萃取方法中,共鉴定了54种化学成分,占总峰面积的99.98%。主要成分(质量分数)依次为金合欢烯（64.86%）、罗勒烯（29.33%）、芳樟醇（2.74%）、惕各酸顺式叶醇酯（1.34%）和苯甲酸甲酯（0.25%）等。经与动态顶空法的分析结果比较发现,固相微萃取法不仅操作简便,而且具有较高的采样灵敏度,获得的化学成分的信息量多于动态顶空法。     

固相微萃取-气相色谱/质谱测定植物叶片中的挥发性物质

采用固相微萃取（SPME)方法吸附植物叶片中的挥发性物质,然后采用气相色谱/质谱法（GC/MS）分析了挥发性物 质的成分。在45 ℃水浴温度下,采用Polyacrylate(85 μm)固相微萃取头,在广口瓶中植物叶片的上方顶空吸附60 min,然后进行GC/MS分析。结果表明,植物叶片中的挥发性物质得到了很好的分离,受山楂叶螨(Tetraychus vienneis) 危害严重的植物的完好叶片中的挥发性物质均含有顺-3-己烯-1-醇乙酸酯、顺-3-己烯-1-醇丁酸酯和α-法呢烯,且含量 较大。初步确定这些物质是对山楂叶螨具有引诱作用的主要物质,从而为利用天然生物活性物质防治山楂叶螨提供了理论 依据。     

Development of a sensitive methodology for the analysis of chlorobenzenes in air by combination of solid-phase extraction and headspace solid-phase microextraction

In this study, a combination of solid-phase extraction (SPE) and solid-phase microextraction (SPME) has been used to determine chlorobenzenes in air. Analytes were sampled by pumping a known volume of air through a porous polymer (Tenax TA). Then, the adsorbent was transferred into a glass vial and SPME was performed. The quantification was carried out using gas chromatography (GC)-electron-capture detection or GC-MS. Several SPME coatings (100 microm poly(dimethylsiloxane) (PDMS), 75 microm Carboxen (CAR)-PDMS, 65 microm PDMS-divinylbenzene (DVB), 65 microm PDMS-DVB and 85 microm polyacrylate (PA) were evaluated, obtaining the highest responses with Carbowax (CW)- PDMS for the most volatile chlorobenzenes, and with PDMS-DVB or CW-DVB fibers for the semivolatile compounds. To optimize some other factors that could affect the SPME step, a factorial design was used. Kinetic studies of the SPME process were also performed. Concerning the SPE step, breakthrough was studied, showing that 2.5 m3 of air could be processed without losses of the most volatile compounds. The performance of the method was evaluated. External calibration, which does not require the complete sampling process, demonstrated to be suitable, obtaining good linearity (R2 > 0.99) for all chlorobenzenes. Recovery studies were performed at two concentration levels (4 and 40 ng/m3), obtaining quantitative recoveries (>80%). Limits of detection at the sub ng/m3 were achieved for all the target compounds.     

Comparative study of the whisky aroma profile based on headspace solid phase microextraction using different fibre coatings

A dynamic headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to ion trap mass spectrometry (GC-(IT)MS) method was developed and applied for the qualitative determination of the volatile compounds present in commercial whisky samples which alcoholic content was previously adjusted to 13% (v/v). Headspace SPME experimental conditions, such as fibre coating, extraction temperature and extraction time, were optimized in order to improve the extraction process. Five different SPME fibres were used in this study, namely, poly(dimethylsiloxane) (PDMS), poly(acrylate) (PA), Carboxen-poly(dimethylsiloxane) (CAR/PDMS), Carbowax-divinylbenzene (CW/DVB) and Carboxen-poly(dimethylsiloxane)-divinylbenzene (CAR/PDMS/DVB). The best results were obtained using a 75 microm CAR/PDMS fibre during headspace extraction at 40 degrees C with stirring at 750 rpm for 60 min, after saturating the samples with salt. The optimised methodology was then applied to investigate the volatile composition profile of three Scotch whisky samples--Black Label, Ballantines and Highland Clan. Approximately seventy volatile compounds were identified in the these samples, pertaining at several chemical groups, mainly fatty acids ethyl esters, higher alcohols, fatty acids, carbonyl compounds, monoterpenols, C13 norisoprenoids and some volatile phenols. The ethyl esters form an essential group of aroma components in whisky, to which they confer a pleasant aroma, with "fruity" odours. Qualitatively, the isoamyl acetate, with "banana" aroma, was the most interesting. Quantitatively, significant components are ethyl esters of caprilic, capric and lauric acids. The highest concentration of fatty acids, were observed for caprilic and capric acids. From the higher alcohols the fusel oils (3-methylbutan-1-ol and 2.phenyletanol) are the most important ones.     

Determination of phthalates in water using fiber introduction mass spectrometry

Fiber introduction mass spectrometry (FIMS)-a direct coupling of SPME and MS-using selective ion monitoring (SIM) was used to detect and quantify dimethylphthalate (DMP), diethylphthalate (DEP) and dipropylphthalate (DPP) in mineral water. In FIMS, a chromatographic silicone septum is the only barrier between ambient and the high-vacuum mass spectrometer, permitting direct introduction of the SPME fiber into the ionization region of the equipment. After their thermal desorption and ionization and dissociation, the extracted phthalates are detected and quantitated by MS. Three types of SPME fibers were screened for best analyte sorption/desorption behaviors: 100 microm polydimethylsiloxane (PDMS), 65 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) and 65 microm Carbowax/divinylbenzene (CW/DVB). The PDMS/DVB and CW/DVB fibers were then evaluated for precision, and quantitative figures of merit were assessed for extractions using the PDMS/DVB fiber, which displayed the best overall performance. FIMS with the PDMS/DVB fiber allows simple extraction and MS detection and quantitation of DMP in water with good linearity and precision, and at concentrations as low as 3.6 microg L(-1). The LD and LQ of FIMS are below the maximum phthalate concentration allowed by the USEPA for drinking water (6 microg L(-1)).     

Determination of haloanisoles in paper samples for food packaging by solid-phase microextraction and gas chromatography

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.     

Liquid CO2 extraction of Jasminum grandiflorum and comparison with conventional processes

The concrete (0.35%) of Jasminum grandiflorum L. flowers was prepared by extraction in n-pentane, and the absolute (0.27%) by fractionation of the n-pentane extract (concrete) with cold methanol. Direct extraction of flowers with liquid CO2 gave a relatively fat-free product in 0.26% yield. The liquid CO2 extract was enriched with terpenoids and benzenoids, thus providing the organoleptically accepted product. The major compounds, such as benzyl acetate, (E,E)-alpha-farnesene and (Z)-3-hexenyl benzoate, along with compounds like indole, methyl anthranilate, (Z)-jasmone, (Z)-methyl jasmonoate and (Z)-methyl epi-jasmonoate, are responsible for the high diffusivity of the jasmine fragrance. These compounds have been obtained with improved recoveries in the liquid CO2 extract. On the other hand, the yield of the essential oil was poor (0.05%), and some polar compounds (oxygenated terpenoids) were recovered in less amounts in comparison with either the n-pentane or liquid CO2 extract.     

Needle trap micro-extraction for VOC analysis: Effects of packing materials and desorption parameters

Combining advantages of SPE and SPME needle trap devices (NTD) represent promising new tools for a robust and reproducible sample preparation. This study was intended to investigate the effect of different packing materials on efficacy and reproducibility of VOC analysis by means of needle trap micro extraction (NTME). NTDs with a side hole design and containing different combinations of PDMS, DVB and Carbopack X and Carboxen 1000 and NTDs containing a single layer organic polymer of methacrylic acid and ethylene glycol dimethacrylate were investigated with respect to reproducibility, LODs and LOQs, carry over and storage. NTDs were loaded with VOC standard gas mixtures containing saturated and unsaturated hydrocarbons, oxygenated and aromatic compounds. Volatile substances were thermally desorbed from the NTDs using fast expansive flow technique and separated, identified and quantified by means of GC–MS. Optimal desorption temperatures between 200 and 290 °C could be identified for the different types of NTDs with respect to desorption efficiency and variation. Carry over was below 6% for polymer packed needles and up to 67% in PDMS/Carboxen 1000 NTDs. Intra and inter needle variation was best for polymer NTDs and consistently below 9% for this type of NTD. LODs and LOQs were in the range of some ng/L. Sensitivity of the method could be improved by increasing sample volume. NTDs packed with a copolymer of methacrylic acid and ethylene glycol dimethacrylate were universally applicable for sample preparation in VOC analysis. If aromatic compounds were to be determined DVB/Carboxen 1000 and DVB/Carbopack X/Carboxen 1000 devices could be considered as an alternative. PDMS/Carbopack X/Carboxen 1000 NTDs may represent a good alternative for the analysis of hydrocarbons and aldehydes. NTME represents a powerful tool for different application areas, from environmental monitoring to breath analysis.     

Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile--identification of novel compounds

A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate - PA, 100 μm polydimethylsiloxane - PDMS, 65 μm polydimethylsiloxane/divinylbenzene - PDMS/DVB, 70 μm carbowax/divinylbenzene - CW/DVB and 85 μm carboxen/polydimethylsiloxane - CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography-quadrupole mass spectrometry (GC-qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and ethanedioic acid), 4 in plum (4-hydroxydihydro-2(3H)-furanone, 5-methyl-2-pyrazinylmethanol, cyclohexylene oxide and 1-methylcyclohexene), 4 in papaya (octaethyleneglycol, 1,2-cyclopentanedione, 3-methyl-1,2-cyclopentanedione and 2-furyl methyl ketone) and 2 in lemon (geranyl farnesate and safranal). It is noteworthy that among the 15 volatile metabolites identified in papaya, 3-methyl-1,2-cyclopentanedione was previously described as a novel PPARγ (peroxisome proliferator-activated receptor γ) agonist, having a potential to minimize inflammation.     

Optimization of Modern Analytical SPME and SPDE Methods for Determination of <Emphasis Type="Italic">Trans</Emphasis>-2-nonenal in Barley,Malt and Beer

Trans-2-nonenal is an aldehyde contributing to an unpleasant off-flavor and odor of rancid butter in stored beer. The automated solid-phase microextraction technique (SPME) coupled with gas chromatography (GC) and solid-phase dynamic extraction (SPDE) coupled with gas chromatography were optimized and introduced to determine trans-2-nonenal in barley, malt and beer. Five types of SPME fibers coated with different stationary phases (100 μm PDMS, 65 μm PDMS/DVB, 85 μm CAR/PDMS, 50/30 μm DVB/CAR/PDMS, 85 μm PA) and two needles (PDMS, PDMS/AC) were compared and tested for their efficiencies in the headspace (HS) SPME and SPDE determination of trans-2-nonenal in barley, malt and beer. The highest extraction efficiency of HS-SPME was achieved with the PDMS/DVB fiber, and addition of 1.5 g of NaCl, extraction time was 20 min at 60 °C. The highest extraction efficiency of HS-SPDE was obtained with the PDMS needle, 15 extraction strokes at 60 °C and addition of 1.5 g of NaCl. Trans-2-nonenal was identified with the method of HS-SPME coupled gas chromatography-mass spectrometry (GC–MS); the samples were analyzed using the HS-SPME-GC-coupled gas chromatography-flame ionization detector (GC-FID) technique.     

Use of solid-phase microextraction to detect and quantify gas-phase dicarbonyls in indoor environments

Solid-phase microextraction (SPME) was evaluated for the detection and quantification of the gas-phase dicarbonyls, glyoxal (GLY) and methylglyoxal (MGLY). Additionally, polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), and carbowax/divinylbenzene (CW/DVB) fibers were tested to determine the optimum fiber for detection of these species. GLY and MGLY were derivatized with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride (PFBHA), extracted with SPME from headspace or bag chamber and then analyzed by GC/MS. The PDMS/DVB SPME fiber for on-fiber derivatization and subsequent sampling for gas-phase methylglyoxal provided the optimum combination of analytical reproducibility and sensitivity. Linearity of the calibration curve was achieved across a range of 11-222 microg/m(3) (4-75 ppb).     

Study of the effect of different fiber coatings and extraction conditions on dry cured ham volatile compounds extracted by solid-phase microextraction (SPME)

Extraction of dry cured ham volatile compounds by solid-phase microextraction (SPME) was optimized. Different fiber coatings (carboxen/polydimethylsiloxane (CAR/PDMS), divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB)), times of extraction (15, 30, 60 min) and sample preparation (ground samples and homogenates with NaCl saturated solution) were assayed. CAR/PDMS and DVB/CAR/PDMS fiber coatings extracted more than 100 volatile compounds and showed the highest area counts for most volatile compounds. CAR/PDMS coating extracted better those compounds whose Kovats index (KI) was lower than 980 (on average) and DVB/CAR/PDMS those with higher KI. Fifteen minutes of extraction provided a volatile compound profile with lower area counts for most compounds and qualitatively different to that obtained with 30 and 60 min of extraction. Homogenates gave a different profile compared to ground samples, with lower total counts for most compounds but higher proportion of aldehydes, and presence of several compounds not found in ground samples.     

Optimization of the SPME device design for field applications

Solid Phase Microextraction (SPME) is a powerful tool for field investigations. With the help of a portable gas chromatograph it can be used for fast analysis directly on-site, or it can be utilized for field sampling and then transported to the laboratory for instrumental analysis. In the latter case, it is important for the reliability of the results that losses of volatiles and contamination of the fiber during storage and transport are minimized. A number of dedicated devices, designed and built for SPME field sampling and storage, have been developed and tested. Sealing capacity of the prototypes was investigated by storing compounds ranging in volatility from methylene chloride to 1,3-dichlorobenzene on selected SPME fibers (100 μm PDMS, 65 μm PDMS/DVB and 75 μm Carboxen/PDMS) at different temperatures. Significant differences were noticed in storage capacity from coating to coating. A comparison between the field samplers optimized in this study and the field sampler commercially available from Supelco revealed advantages and limitations of each of the designs. A gas-tight valve syringe (50 μL SampleLock by Hamilton), modified in order to accommodate the SPME fiber, had the best storage capacity for very volatile compounds. With this device, over 80% of the initial amount of methylene chloride was retained by the 100 μm PDMS fiber after 24 h of refrigerated storage, which is a very good result considering that the PDMS coating is characterized by very low storage capacity for volatiles. Field sampling investigations with the SPME prototypes confirmed the usefulness of these devices for field analysis. Received: 9 November 1998 / Accepted: 15 January 1999     

Optimization of the SPME device design for field applications

Solid Phase Microextraction (SPME) is a powerful tool for field investigations. With the help of a portable gas chromatograph it can be used for fast analysis directly on-site, or it can be utilized for field sampling and then transported to the laboratory for instrumental analysis. In the latter case, it is important for the reliability of the results that losses of volatiles and contamination of the fiber during storage and transport are minimized. A number of dedicated devices, designed and built for SPME field sampling and storage, have been developed and tested. Sealing capacity of the prototypes was investigated by storing compounds ranging in volatility from methylene chloride to 1,3-dichlorobenzene on selected SPME fibers (100 μm PDMS, 65 μm PDMS/DVB and 75 μm Carboxen/PDMS) at different temperatures. Significant differences were noticed in storage capacity from coating to coating. A comparison between the field samplers optimized in this study and the field sampler commercially available from Supelco revealed advantages and limitations of each of the designs. A gas-tight valve syringe (50 μL SampleLock by Hamilton), modified in order to accommodate the SPME fiber, had the best storage capacity for very volatile compounds. With this device, over 80% of the initial amount of methylene chloride was retained by the 100 μm PDMS fiber after 24 h of refrigerated storage, which is a very good result considering that the PDMS coating is characterized by very low storage capacity for volatiles. Field sampling investigations with the SPME prototypes confirmed the usefulness of these devices for field analysis. Received: 9 November 1998 / Accepted: 15 January 1999     

Evaluation of solid-phase micro-extraction coupled to gas chromatography-mass spectrometry for the headspace analysis of volatile compounds in cocoa products

The aroma profile of cocoa products was investigated by headspace solid-phase micro-extraction (HS-SPME) combined with gas chromatography–mass spectrometry (GC–MS). SPME fibers coated with 100 μm polydimethylsiloxane coating (PDMS), 65 μm polydimethylsiloxane/divinylbenzene coating (PDMS-DVB), 75 μm carboxen/polydimethylsiloxane coating (CAR-PDMS) and 50/30 μm divinylbenzene/carboxen on polydimethylsiloxane on a StableFlex fiber (DVB/CAR-PDMS) were evaluated. Several extraction times and temperature conditions were also tested to achieve optimum recovery. Suspensions of the samples in distilled water or in brine (25% NaCl in distilled water) were investigated to examine their effect on the composition of the headspace. The SPME fiber coated with 50/30 μm DVB/CAR-PDMS afforded the highest extraction efficiency, particularly when the samples were extracted at 60 °C for 15 min under dry conditions with toluene as an internal standard. Forty-five compounds were extracted and tentatively identified, most of which have previously been reported as odor-active compounds. The method developed allows sensitive and representative analysis of cocoa products with high reproducibility. Further research is ongoing to study chocolate making processes using this method for the quantitative analysis of volatile compounds contributing to the flavor/odor profile.     

Determination of diphenylether herbicides in water samples by solid-phase microextraction coupled to liquid chromatography

Solid-phase microextraction (SPME) coupled to LC for the analysis of five diphenylether herbicides (aclonifen, bifenox, fluoroglycofen-ethyl, oxyfluorfen, and lactofen) is described. Various parameters of extraction of analytes onto the fiber (such as type of fiber, extraction time and temperature, pH, impact of salt and organic solute) and desorption from the fiber in the desorption chamber prior to separation (such as type and composition of desorption solvent, desorption mode, soaking time, and flush-out time) were studied and optimized. Four commercially available SPME fibers were studied. PDMS/divinylbenzene (PDMS/DVB, 60 microm) and carbowax/ templated resin (CW/TPR, 50 microm) fibers were selected due to better extraction efficiencies. Repeatability (RSD, < 7%), correlation coefficient (> 0.994), and detection limit (0.33-1.74 and 0.22-1.94 ng/mL, respectively, for PDMS/DVB and CW/TPR) were investigated. Relative recovery (81-104% for PDMS/DVB and 83-100% for CW/TPR fiber) values have also been calculated. The developed method was successfully applied to the analysis of river water and water collected from a vegetable garden.