Determination of ethoprop, diazinon, disulfoton and fenthion using dynamic hollow fiber-protected liquid-phase microextraction coupled with gas chromatography-mass spectrometry

A technique for the analysis of organophosphorus pesticides (ethoprop, diazinon, disulfoton, fenthion) in aqueous sample using liquid-phase microextraction (LPME), coupled with gas chromatography-mass spectrometry (GC-MS) was developed. A small section of a hollow fiber inserted into the needle of GC syringe and filled with the 3.5 μl of organic solvent was used to extract pesticides from a 20 ml aqueous sample. The limits of detection (LOD) with the selected ion monitoring (SIM) mode varied from 0.2 to 0.006 μg/l. The calibration curves were linear over three orders of magnitude with R² ≥ 0.996. The relative standard deviations of the analysis (inter- and intra-day) were 5-8%, and the relative recoveries from the lake water sample were greater than 83%. The results were compared with results obtained using solid-phase microextraction (SPME/GC/MS).     

Determination of haloethers in water with dynamic hollow fiber liquid-phase microextraction using GC-FID and GC-ECD

Dynamic hollow fiber liquid-phase microextraction (HF-LPME) coupled with gas chromatography with flame ionization detection (GC-FID) and GC-electron capture detecion (GC-ECD) was used for quantification of toxic haloethers in lake water. The analytes were extracted from 5 ml of aqueous sample using 4 μl of organic solvent through a porous polypropylene hollow fiber. The effects on extraction performance of solvent selection, agitation rate, extraction time, extraction temperature, concentration of salt added and volumes of solvent for extraction and injection were optimized. The proposed method provided a good average enrichment factor of up to 231-fold, reasonable reproducibility ranging from 9 to 12% (n = 3), and good linearity (R² ≧ 0.9973) for spiked water samples. Method detection limits (MDLs) ranged from 0.55 to 4.30 μg/l for FID and 0.11-0.34 μg/l for ECD (n = 7).     

Environmental and bioanalytical applications of hollow fiber membrane liquid-phase microextraction: a review

In hollow fiber membrane liquid-phase microextraction (LPME), target analytes are extracted from aqueous samples and into a supported liquid membrane (SLM) sustained in the pores in the wall of a small porous hollow fiber, and further into an acceptor phase present inside the lumen of the hollow fiber. The acceptor phase can be organic, providing a two-phase extraction system compatible with capillary gas chromatography, or the acceptor phase can be aqueous resulting in a three-phase system compatible with high-performance liquid chromatography or capillary electrophoresis. Due to high enrichment, efficient sample clean-up, and the low consumption of organic solvent, substantial interest has been devoted to LPME in recent years. This paper reviews important applications of LPME with special focus on bioanalytical and environmental chemistry, and also covers a new possible direction for LPME namely electromembrane extraction, where analytes are extracted through the SLM and into the acceptor phase by the application of electrical potentials.     

A new liquid-phase microextraction method based on solidification of floating organic drop

In the present study, a new and versatile liquid-phase microextraction method is described. This method requires very simple and cheap apparatus and also a small amount of organic solvent. Eight microliters of 1-undecanol was delivered to the surface of solution containing analytes and solution was stirred for a desired time. Then sample vial was cooled by inserting it into an ice bath for 5 min. The solidified 1-undecanol was transferred into a suitable vial and immediately melted; then, 2 μL of it was injected into a gas chromatograph for analysis.Some polycyclic aromatic hydrocarbons (PAHs) were used as model compounds for developing and evaluating of the method performance. Analysis was carried out by gas chromatography/flame ionization detection (GC/FID).Several factors influencing the microextraction efficiency, such as the nature and volume of organic solvent, the temperature and volume of sample solution, stirring rate and extraction time were investigated and optimized. The applicability of the technique was evaluated by determination of trace amounts of PAHs in environmental samples. Under the optimized conditions, the detection limits (LOD) of the method were in the range of 0.07-1.67 μg L⁻¹ and relative standard deviations (R.S.D.) for 10 μg L⁻¹ PAHs were <7%. A good linearity (r² > 0.995) in a calibration range of 0.25-300.00 μg L⁻¹ was obtained. After 30 min extraction duration, enrichment factors were in the range of 594-1940. Finally, the proposed method was applied to the determination of trace amounts of PAHs in several real water samples, and satisfactory results were resulted. Since very simple devices were used, this new technique is affordable, efficient, and convenient for extraction and determination of low concentrations of PAHs in water samples.     

Determination of organophosphorous pesticides in wastewater samples using binary-solvent liquid-phase microextraction and solid-phase microextraction: a comparative study

A simple and efficient binary solvent-based two-phase hollow fiber membrane (HFM)-protected liquid-phase microextraction (BN-LPME) technique for moderately polar compounds was developed. Six organophosphorous pesticides (OPPs) (triethylphosphorothioate, thionazin, sulfotep, phorate, disulfoton, methyl parathion and ethyl parathion) were used as model compounds and extracted from 10-mL wastewater with a binary-solvent (toluene:hexane, 1:1) mixture. Some important extraction parameters, such as extraction time, effect of salt, sample pH and solvent ratio composition were optimized. BN-LPME combined with gas chromatography/mass spectrometric (GC/MS) analysis provided repeatability (R.S.D.s ≤ 12%, n = 4), and linearity (r ≤ 0.994) and solid-phase microextraction provides comparable of R.S.D.s ≤ 13%, n = 4 and linearity (r = ≤0.966) for spiked water samples. The limits of detection (LODs) were in the range of 0.3-11.4 ng L⁻¹ for BN-LPME and 3.1-120.5 ng L⁻¹ for SPME at (S/N = 3) under GC/MS selective ion monitoring mode. In addition to high enrichment, BN-LPME also served as a sample cleanup procedure, with the HFM act as a filtering medium to prevent large particles and extraneous materials from being extracted. To investigate and compare their applicability, the BN-LPME and SPME procedures were applied to the detection of OPPs in domestic wastewater samples.     

中空纤维膜液相微萃取-高效液相色谱联用技术测定尿液中痕量己烯雌酚

采用中空纤维液相微萃取与高效液相色谱联用技术测定了尿液样品中的痕量己烯雌酚;考察了样品相酸度、中间相种类、接收相浓度、搅拌速度、萃取时间等对液-液-液三相微萃取效率的影响,进而确定了最佳萃取条件.结果表明,当样品相pH为2.5,中间相为甲苯,接收相为3μL 0.25mol/L氢氧化钠溶液,搅拌速度为800r/min,萃取时间为50min时,萃取效率最佳.在最佳萃取条件下,样品的回收率为76.4%,相对标准偏差为3.8%.     

Determination of polychlorinated biphenyls in water using dynamic hollow fiber liquid-phase microextraction and gas chromatography-mass spectrometry

The application of dynamic hollow fiber liquid-phase microextraction (dynamic HF-LPME) and gas chromatography-mass spectrometry (GC-MS) for the determination of trace amounts of polychlorinated biphenyls (PCBs) in water was investigated. The experimental parameters were optimized. Under the optimum conditions, the concentration enrichment factors for PCBs were from 718-fold to 840-fold. The calibration curves were linear over a range of 0.05-90mug/L, with a correlation coefficient (r(2)) of 0.9957-0.9979. The relative standard deviation (RSD) ranged from 3.4% to 5.8% for intra-day variation and from 4.1% to 7.3% for inter-day variation. The limits of detection (LODs, S/N=3:1) were in the range of 13-41ng/L. The recoveries for spiked water samples ranged from 85.9% to 92.0%.     

Screening method for phthalate esters in water using liquid-phase microextraction based on the solidification of a floating organic microdrop combined with gas chromatography-mass spectrometry

A simple and efficient liquid-phase microextraction (LPME) technique was developed using directly suspended organic microdrop coupled with gas chromatography–mass spectrometry (GC–MS), for the extraction and the determination of phthalate esters (dimethyl phthalate, diethyl phthalate, diallyl phthalate, di-n-butyl phthalate (DnBP), benzyl butyl phthalate (BBP), dicyclohexyl phthalate and di-2-ethylhexyl phthalate (DEHP)) in water samples. Microextraction efficiency factors, such as nature and volume of the organic solvent, temperature, salt effect, stirring rate and the extraction time were investigated and optimized. Under the optimized extraction conditions (extraction solvent: 1-dodecanol; extraction temperature: 60 °C; microdrop volume: 7 μL; stirring rate: 750 rpm, without salt addition and extraction time: 25 min), figures of merit of the proposed method were evaluated. The values of the detection limit were in the range of 0.02–0.05 μg L⁻¹, while the R.S.D.% value for the analysis of 5.0 μg L⁻¹ of the analytes was below 7.7% (n = 4). A good linearity (r² ≥ 0.9940) and a broad linear range (0.05–100 μg L⁻¹) were obtained. The method exhibited enrichment factor values ranging from 307 to 412. Finally, the designed method was successfully applied for the preconcentration and determination of the studied phthalate esters in different real water samples and satisfactory results were attained.     

Determination of ochratoxin A in wine using liquid-phase microextraction combined with liquid chromatography with fluorescence detection

A liquid-liquid microextraction technique (LPME) has been applied to the extraction of ochratoxin A (OTA) from wine prior to its quantification by HPLC-fluorescence detection. OTA was extracted from wine, through 1-octanol immobilized in the pores of a porous hollow fiber, and introduced into 1-octanol inside the fiber. Recovery was 77%. The method was adequate for quantification of OTA in wine at levels within the range 0.25-10 ng/ml with a LOD of 0.2 ng/ml, and can be a simple and inexpensive alternative to the use of inmunoaffinity columns in order to quantify OTA levels in wine.     

Determination of 16 polycyclic aromatic hydrocarbons in milk and related products using solid-phase microextraction coupled to gas chromatography-mass spectrometry

A method for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in milk and related products based on direct immersion-solid phase microextraction (DI-SPME) followed by gas chromatography-mass spectrometry detection (GC-MS) has been developed. The influence of various parameters on PAH extraction efficiency was carefully monitored. Good performance (recovery, precision and quantitation limits) was attained when a PDMS/DVB fiber was immersed in the sample for 60 min at 55 °C. Detection limits ranged from 0.003 to 1.5 μg L⁻¹ at a signal-to-noise ratio of 3, depending on the compound and the sample. The proposed method was successfully applied to infant formulas, milk and related products and the presence of both fluoranthene and pyrene in two samples was confirmed.     

Development and application of polymer-coated hollow fiber membrane microextraction to the determination of organochlorine pesticides in water

A novel extraction procedure coupled with gas chromatography-mass spectrometric detection for quantification of organochlorine pesticides (OCPs) in water is described. Amphiphilic polyhydroxylated polyparaphenylene (PH-PPP) was synthesized and coated on the surfaces of a porous polypropylene hollow fiber membrane (HFM). Due to the high porosity of the HFM, maximum active surface area to achieve high extraction efficiency is expected. The polymer-coated HFM was used for the extraction of 15 OCPs from water. The extraction efficiency was compared with emerging and established methods such as liquid-phase microextraction (LPME), solid-phase microextraction (SPME) and stir bar sorptive extraction (SBSE) techniques. We term the current procedure as polymer-coated hollow fiber microextraction (PC-HFME). PC-HFME showed good selectivity and sensitivity. Detection limits for OCPs were in the range of 0.001-0.008 microg l(-1). The sensitivity and selectivity of the coated HFM could be adjusted by changing the characteristics of the coated PH-PPP film.     

Determination of organochlorine pesticides in water using microwave assisted headspace solid-phase microextraction and gas chromatography

A coupled technique, microwave-assisted headspace solid-phase microextraction (MA-HS-SPME), was investigated for one-step in situ sample pretreatment for organochlorine pesticides (OCPs) prior to gas chromatographic determination. The OCPs, aldrin, o,p'-DDE, p,p'-DDE, o,p'-DDT, p,p'-DDT, dieldrin, alpha-endosulfan, beta-endosulfan, endosulfan sulfate, endrin, delta-HCH, gamma-HCH, heptachlor, heptachlor epoxide, methoxychlor and trifluralin were collected by the proposed method and analyzed by gas chromatography with electron-capture detection (GC-ECD). To perform the MA-HS-SPME, six types of SPME fibers were examined and compared. The parameters affecting the efficiency in MA-HS-SPME process such as sampling time and temperature, microwave irradiation power, desorption temperature and time were studied to obtain the optimal conditions. The method was developed using spiked water samples such as field water and with 0.05% humic acid in a concentration range of 0.05-2.5 microg/l except endosulfan sulfate in 0.25-2.5 microg/l. The detection was linear over the studied concentration range with r2>0.9978. The detection limits varied from 0.002 to 0.070 microg/l based on S/N=3 and the relative standard deviations for repeatability were <15%. A certified reference sample of OCPs in aqueous solution was analyzed by the proposed method and compared with the conventional liquid-liquid extraction procedure. These results are in good agreement. The results indicate that the proposed method provides a very simple, fast, and solvent-free procedure to achieve sample pretreatment prior to the trace-level screening determination of organochloride pesticides by gas chromatography.     

Determination of aristolochic acid in urine using hollow fiber liquid-phase microextraction combined with high-performance liquid chromatography

A simple and efficient hollow fiber liquid‐phase microextraction (HF‐LPME) technique in conjunction with high‐performance liquid chromatography is presented for extraction and quantitative determination of aristolochic acid I in human urine samples. Several parameters influencing the efficiency of HF‐LPME were investigated and optimized, including extraction solvent, stirring rate, extraction time, pH of donor phase and acceptor phase. Excellent sample clean‐up was observed and good linearity with coefficient of 0.9999 was obtained in the range of 15.4–960 µg/L. This method provided a 230‐fold enrichment factor and good repeatability with relative standard deviations (RSD) lower than 6.0%. The limit of detection value for the analyte in urine sample was 0.01 µg/L at a signal‐to‐noise ratio of 3. The extraction recovery from urine samples was 61.8% with an RSD of 9.71%. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of organochlorine pesticides in water samples by dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry

A rapid and simple dispersive liquid-liquid microextraction (DLLME) has been developed to preconcentrate eighteen organochlorine pesticides (OCPs) from water samples prior to analysis by gas chromatography-mass spectrometry (GC-MS). The studied variables were extraction solvent type and volume, disperser solvent type and volume, aqueous sample volume and temperature. The optimum experimental conditions of the proposed DLLME method were: a mixture of 10 μL tetrachloroethylene (extraction solvent) and 1 mL acetone (disperser solvent) exposed for 30 s to 10 mL of the aqueous sample at room temperature (20 °C). Centrifugation of cloudy solution was carried out at 2300 rpm for 3 min to allow phases separation. Finally, 2 μL of extractant was recovered and injected into the GC-MS instrument. Under the optimum conditions, the enrichment factors ranged between 46 and 316. The calculated calibration curves gave a high-level linearity for all target analytes with correlation coefficients ranging between 0.9967 and 0.9999. The repeatability of the proposed method, expressed as relative standard deviation, varied between 5% and 15% (n = 8), and the detection limits were in the range of 1-25 ng L⁻¹. The LOD values obtained are able to detect these OCPs in aqueous matrices as required by EPA methods 525.2 and 625. Analysis of spiked real water samples revealed that the matrix had no effect on extraction for river, surface and tap waters; however, urban wastewater sample shown a little effect for five out of eighteen analytes.     

Sampling and analysis of volatile organic compounds in bovine breath by solid-phase microextraction and gas chromatography-mass spectrometry

A relatively noninvasive method consisting of a face mask sampling device, solid-phase microextraction (SPME) fibers, and a gas chromatography-mass spectrometry (GC-MS) for the identification of volatile organic compounds (VOCs) in bovine breath was developed. Breath of three morbid steers with respiratory tract infections and three healthy steers were sampled seven times in 19 days for 15 min at each sampling. The breath VOCs adsorbed on the divinylbenzene (DVB)-Carboxen-polydimethyl siloxane (PDMS) 50/30 microm SPME fibers were transported to a laboratory GC-MS system for separation and identification with an in-house spectral library of standard chemicals. A total of 21 VOCs were detected, many of them for the first time in cattle breath. Statistical analyses using Chi-square test on the frequency of detection of each VOC in each group was performed. The presence of acetaldehyde (P < or = 0.05) and decanal (P < or = 0.10) were associated more with clinically morbid steers while methyl acetate, heptane, octanal, 2,3-butadione, hexanoic acid, and phenol were associated with healthy steers at P < or = 0.10. The results suggest that noninvasive heath screening using breath analyses could become a useful diagnostic tool for animals and humans.     

Determination of polycyclic aromatic hydrocarbons (PAHs) from organic aerosols using hollow fiber micro-porous membrane liquid-liquid extraction (HF-MMLLE) followed by gas chromatography-mass spectrometry analysis

A method for determination of polycyclic aromatic hydrocarbons (PAHs) from aerosols was developed. Instead of conventionally used non-polar or slightly polar phenylmethylpolysiloxane column a highly polar, highly substituted, cyanopropyl column (VF-23 MS) was used for separation of PAHs. Based on hollow fiber micro-porous membrane liquid-liquid extraction (HF-MMLLE) a method was developed for sample clean up and pretreatment. An enrichment factor of 617-1022 was obtained with extraction efficiency 10.2-18.9% for different PAHs analyzed in this study. The optimized method was successfully applied to aerosol samples and limits of detection between 1.2 pg m⁻³ and 180 pg m⁻³ was obtained. Almost all PAHs were found in most of the aerosol samples.     

Cryotrapping gas chromatography-Fourier transform infrared spectrometry in environmental analysis: A pilot study

The potential applicability of cryotrapping gas chromatography-Fourier transform infrared spectrometry in environmental analysis was studied. First results of on-the-flight measurements on pesticides and polynuclear aromatic hydrocarbons show detection limits in the 100–500 pg range. The low-temperature spectra obtained appear to be closely comparable to conventionally recorded spectra. Library search procedures based on existing solid-phase spectra appear to be useful.     

Comparison of gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry for the determination of fatty and resin acids in paper mill process waters

A comparative study of the performance of liquid chromatography (LC)-atmospheric pressure chemical ionisation (APCI)-mass spectrometry (MS) and gas chromatography (GC)-mass spectrometry techniques for the determination of resin and fatty acids from paper mill process waters was carried out. These compounds are responsible for the high toxicity of paper mill effluents and little research has been carried out regarding their analysis using mass spectrometric techniques. To prove the usability of GC and LC-MS, 16 treated and untreated water samples of recycle, kraft and pulp paper mills were analysed and good agreement was observed as regards to compounds detected and corresponding concentrations. This paper also reports the limits of detection, recoveries, reproducibility, linearity and precision using the two methods. GC-MS presented better selectivity and lower detection limits (below 0.2 microg/l), but derivatization of the extracts and the short life of derivatives (12-24 h) made the technique tedious and prone to high variations. Although LC-APCI-MS presented coelution of the non-aromatic resin acids, it also showed good sensitivity (limits of detection <3 microg/l) and permitted the detection of resin and fatty acids at microg/l level. In addition, since samples could be directly injected to the chromatographic system, LC-APCI-MS was proven as a powerful technique for quick and unequivocal quality control during papermaking.     

Determination of aromatic hydrocarbons in asphalt release agents using headspace solid-phase microextraction and gas chromatography-mass spectrometry

The possibility of quantitative analysis of aromatic hydrocarbons in oil-based asphalt release agents was investigated using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS). The target analytes studied were benzene, toluene, ethylbenzene, p-, m-, and o-xylene (BTEX) and 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene. Experimental parameters influencing HS-SPME efficiency were studied (equilibration time between sample and headspace and between headspace and SPME fiber, sample amount and sample matrice effects). A HS-SPME method using hexadecane as a surrogate matrice was developed. The detection limit was estimated as 0.03-0.08 ppm (w/w) for the target analytes investigated. Good linearity was observed (R2 > 0.999) for all calibration curves at high, medium and low concentration level. The repeatability of the method (RSD, relative standard deviation) was found to be less than 10% (generally less than 5%) in triplicate samples and approximately 2% at eight consecutive tests on one and the same sample. The accuracy of the method given by recovery of spiked samples was between 85 and 106% (generally between 95 and 105%). The HS-SPME method developed was applied to four commercially available asphalt release agents. External calibration and standard addition approaches were investigated regarding accuracy. The results showed that standard addition generates higher accuracy than external calibration. The contents of target aromatic hydrocarbons in the asphalt release agents studied varied greatly from approximately 0.1-700 ppm. The method described looks promising, and could be a valuable tool for determination of aromatic hydrocarbons in different types of organic matrices.     

Polymer-coated hollow-fiber microextraction of estrogens in water samples with analysis by gas chromatography-mass spectrometry

A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples.