Novel cationic surfactant ion pair based solid phase microextraction fiber for nano-level analysis of BTEX

Ion pair of cationic surfactant (cetytrimethylammonium bromide) and tungestosilicic acid incorporated in PVC matrix, was used for coating a piece of copper wire as a new high sensitive SPME fiber in extraction and determination of BTEX compounds from the headspace of water samples prior to GC/FID analysis. Under optimum extraction conditions, limits of detection for benzene, toluene, ethylbenzene, p-xylene, m-xylene and o-xylene were found to be 1.18, 5.61, 0.87, 0.29, 0.22 and 0.33 ng L(-1) respectively. Low detection limits, wide linear dynamic ranges, good reproducibility (RSD% 1.48-4.27), high fiber capacity and high mechanical durability are some of the most important advantages of the new fiber.     

Gas chromatographic determination of benzene, toluene, ethylbenzene and xylenes using flame ionization detector in water samples with direct aqueous injection up to 250 microl

A simple method of solventless extraction of volatile organic compounds (benzene, toluene, ethylbenzene and xylenes) from aqueous samples was developed. This method allows direct injection of large volume of water sample into a gas chromatograph using the sorption capacity of the sorbent Chromosorb P NAW applied directly in the injection port of gas chromatograph. The system prevent water penetration into a column, keep it adsorbed on its surface until the analytes are stripped into a column, and the residual water is purging using split flow. The limit of detection ranging from 0.6 for benzene to 1.1 microg l(-1) for o-xylene and limit of quantification ranging 2.0-3.6 microg l(-1) are lower that those reached by gas chromatography with flame ionization detection and direct aqueous injection before.     

Multivariate optimization of a solid phase microextraction-headspace procedure for the determination of benzene, toluene, ethylbenzene and xylenes in effluent samples from a waste treatment plant

A method based on solid-phase microextraction (SPME) and gas chromatography with flame ionization detection (GC-FID) has been optimized for the determination of benzene, toluene, ethylbenzene and xylenes (BTEX) in water released from a waste treatment plant. The extraction step was optimized using fractional factorial and central composite designs including the following experimental factors: saline concentration; extraction time; desorption time; agitation velocity; headspace volume. A multiple function was used to describe the experimental conditions for simultaneous extraction of the compounds. The procedure, based on direct SPME at 50 degrees C, using a polydimethylsiloxane fiber, showed good linearity (r>0.997 over a concentration range 2-200 microg L(-1)) and repeatability (relative standard deviation (RSD)<4.23%) for all compounds, with limits of detection ranging from 0.05 to 0.28 microg L(-1), and limits of quantification ranging from 0.14 to 0.84 microg L(-1). Concentrations of the target compounds in these samples were between 145.8 and 1891 microg L(-1).     

顶空-气相色谱法同时测定饮用水中八种挥发性苯系物

利用顶空-毛细管柱气相色谱技术对饮用水中的苯、甲苯、乙苯、邻二甲笨、对二甲笨、间二甲笨、异丙苯、苯乙烯的测定方法进行了研究,并对平衡时间、气／液体积比、水中含盐量等影响测定因素进行了探讨,对色谱条件和顶空进样条件进行了优化。该方法选用HP-INNOWAX色谱柱,使一直较难分离的间、对二甲苯得到了很好的分离。对八种苯系物进行了最低检出限、线性、回收率、精密度试验,其平均回收率为97．4％～1063％（n=7）,相对标准偏差为2．55％～3．83％（n=7）,最低检出限为0．06～0．10μg／L。测定结果表明,该法操作简单,重现性好,灵敏度高,完全可以满足饮用水中挥发性苯系物的测定。     

Coupling of stir bar sorptive extraction with single photon ionization mass spectrometry for determination of volatile organic compounds in water

A home-made stir bar sorptive extraction (SBSE) apparatus was combined to a single photon ionization time-of-flight mass spectrometer (SPI-TOFMS) for rapid and sensitive determination of trace volatile organic compounds (VOCs) in water. The home-made SBSE bar, low-cost and disposable, was used for VOCs extraction. A thermal desorption (TD) device was designed to desorb the analytes from the SBSE bar, and a high throughput interface was developed to transfer the analytes into the ionization chamber of the SPI-TOFMS. The combination of large extraction volume of SBSE bar, and the direct measurement power of SPI-TOFMS enable a short analysis time for VOCs in water with high sensitivity, for example the limits of detection (LODs) were in the range of 7.4-11.1 ng L(-1) for benzene, toluene, and p-xylene (BTX) within 15 min. BTX aqueous solutions were chosen to demonstrate the quantitative capability, the linear range was from 0.05 to 100 μg L(-1) and the correlation coefficients were better than 0.996. The proposed method was successfully applied for the analysis of VOCs in urban river water.     

Analysis of benzene, toluene, ethylbenzene, xylenes and n-aldehydes in melted snow water via solid-phase dynamic extraction combined with gas chromatography/mass spectrometry

The present study describes a method based on headspace-solid-phase dynamic extraction (HS-SPDE) followed by GC/MS for the qualitative and quantitative analysis of benzene, toluene, ethylbenzene, o-, m- and p-xylene (BTEX), and n-aldehydes (C(6)-C(10)) in water. To enhance the extraction capability of the HS-SPDE a new cooling device was tested that controls the temperature of the SPDE needle during extraction. Extraction and desorption parameters such as the number of extraction cycles, extraction temperature, desorption volume and desorption flow rate have been optimized. Detection limits for BTEX ranged from 19 ng/L (benzene) to 30 ng/L (m/p-xylene), while those for n-aldehydes ranged from 21 ng/L (n-heptanal) to 63 ng/L (n-hexanal). At a concentration level of 2 microg/L, the relative standard deviations (RSDs) for BTEX ranged from 3.9% (benzene) to 15.3% (ethylbenzene), while RSDs for n-aldehydes were between 6.1% (n-octanal) and 16.5% (n-hexanal) (n=7). Best results were obtained when the analyzed water samples were heated to 50 degrees C. At a water temperature of 70 degrees C GC responses decreased for all analyzed compounds. At a defined water temperature, a significant improvement of the GC response was achieved by cooling of the SPDE fiber during water extraction in comparison to an extraction keeping the fiber at room temperature. Evaluating the extraction cycles, for BTEX, the sensitivity was almost similar using 20, 40 and 60 extraction cycles. In contrast, the highest GC responses for n-aldehydes were achieved by the use of 60 extraction cycles. Optimizing the desorption parameters, best results were achieved using the smallest technical available desorption volume of 500 microL and the highest technical desorption flow rate of 50 microL/s. The method was applied to the analysis of melted snow samples taken from the Jungfraujoch, Switzerland (3580 m asl), revealing the presence of BTEX and aldehydes in snow.     

Trace determination of organotin compounds in water,sediment and mussel samples by low-pressure gas chromatography coupled to tandem mass spectrometry

A fast method for the determination of eight organotin compounds (OTs), monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TeBT), monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT) and tetraphenyltin (TePhT), in water, sediments and mussels, was developed using low-pressure gas chromatography/tandem mass spectrometry (LPGC/MS/MS). The method is based on sodium diethyldithiocarbamate (DDTC) complexation of the ionic organotins, followed by extraction of the target matrices and derivatization by a Grignard reagent, as described in a previously published method for water samples. Solid-phase extraction was selected as extraction method from water samples after comparison with liquid-liquid extraction, but extraction of the OTs from sediment and mussel samples was performed using toluene. Matrix-matched calibration standards were used to minimize matrix effects. The analytical process was validated by the analysis of spiked blank samples. Performance characteristics such as linearity, detection limit (LOD), quantitation limit (LOQ), precision, and recovery were determined. Recoveries of OTs in spiked matrices ranged from 86-108% in water and from 78-110% in sediments and mussels, with precision values lower than 18%. Detection limits ranged from 0.1-9.6 ng L(-1) in water, and 0.03-6.10 microg kg(-1) in the other matrices. The present implementation of LPGC rather than conventional capillary GC permitted use of large-volume injection and reduced analysis time by a factor of two. The proposed methodology was applied to the determination of OTs in real samples of water, marine sediments and mussels from the west coast of the Mediterranean Sea (Spain).     

Fingerprint identification of volatile organic compounds in gasoline contaminated groundwater using gas chromatography differential ion mobility spectrometry

Groundwater can be contaminated when e.g. gasoline tanks leak. Due to sampling and lab analysis, groundwater monitoring is time consuming and expensive. The technologies developed for rapid on-site analysis of gasoline contaminated groundwater face the technical limitation to distinguish the gasoline from complex matrices. In the present study the fingerprint identification of volatile organic components (VOCs) in gasoline contaminated groundwater using gas chromatography (GC) differential ion mobility spectrometry (DMS) is investigated. Groundwater was spiked with five sorts of gasoline (one reformulated gasoline, gasoline without additives and three different brand gasoline collected on petrol stations) and analyzed by GC-DMS. Seven VOCs (benzene, toluene, ethyl benzene, m-xylene, p-xylene, o-xylene, 1,2,4-trimethylbenzene) were identified by GC mass spectrometry (GC-MS) as well as by GC-DMS and selected as markers. The semi-quantitative determination of the selected compounds was achieved. The limits of detection of the GC-DMS are 46.42?ng for benzene, 1.13?ng for toluene, 1.80?ng for ethylbenzene, 0.22?ng for m-xylene, 1.13?ng for p-xylene, 0.61?ng for o-xylene and 0.37?ng for 1,2,4-trimethylbenzene, respectively. These results reveal the feasibility of GC-DMS for on-site monitoring of contaminated groundwater.     

Disposable ionic liquid coating for headspace solid-phase microextraction of benzene, toluene, ethylbenzene, and xylenes in paints followed by gas chromatography-flame ionization detection

Solid-phase microextraction (SPME) with a disposable ionic liquid (IL) coating was developed for headspace extraction of benzene, toluene, ethylbenzene, and xylenes (BTEX) in paints. The SPME fiber was coated with IL prior to every extraction, then the analytes were extracted and desorbed on the injection port of gas chromatography, and finally the IL coating on the fiber was washed out with solvents. The coating and washing out of IL from the fiber can be finished in a few minutes. This disposable IL-coated fiber was applied to determine BTEX in water-soluble paints with results in good agreement with that obtained by using commercially available SPME fibers. For all the four studied paints samples, the benzene contents were under the detection limits, but relatively high contents of toluene, ethylbenzene and xylenes (56-271 microg g(-1)) were detected with spiked recoveries in the range of 70-114%. Compared to the widely used commercially available SPME fibers, this proposed disposable IL-coated fiber has much lower cost per determination, comparable reproducibility (RSD < 11%), and no carryover between each determination. Considering that IL possess good extractability for various organic compounds and metals ions, and that task-specific IL can be designed and synthesized for selective extraction of target analytes, this disposable IL coating SPME might has great potential in sample preparation.     

Biomonitoring of benzene and toluene in human blood by headspace-solid-phase microextraction

A simple and rapid method for the determination of benzene and toluene in whole blood by headspace-solid-phase microextraction (HS-SPME) is described. Using SPME fibres coated with 65 μm carboxene/polydimethylsiloxane, limits of quantification (LOQ) of 5 ng/L for benzene and 25 ng/L for toluene are achieved. As a result of its large linear range (i.e. 5–5000 ng/L for benzene) the method is suitable for biomonitoring of both occupationally and environmentally exposed people. The reproducibility of the determination of benzene is ≤ 8%. An interlaboratory comparison demonstrated that the method proposed here compares favorably with existing methods (dynamic headspace, purge and trap).     

PDMS extraction bars for the determination of volatile aromatic hydrocarbons in water and wastewater

In this study, the preparation and application of extraction bars of PDMS were investigated to preconcentrate and determine benzene, toluene, ethylbenzene, and xylene in water and wastewater by means of HPLC with fluorescence detection. Aliquot samples from hospital wastewater were used as the model effluent. The independent variables for the sorptive extraction were as follows: ionic strength (added amounts of NaCl); pH; temperature and time of absorption; temperature and time of desorption. Under optimized conditions, by using a factorial design, the suspended extraction bars could allow the determination of benzene, toluene, ethylbenzene, and xylene (1.20 ± 0.05 μg/L; 10.40 ± 0.02 μg/L; 1.80 ± 0.04 μg/L; 15.9 ± 0.04 μg/L, respectively) in hospital effluent (fortified samples), by recoveries of 71.9 ± 4.9 to 74.8 ± 5.6%. This procedure represents an innovation that eliminates the time‐consuming stage of vacuum microfiltration, and allows the determination of volatile organic compounds by HPLC. As far as we know, this procedure is original and represents an important contribution to the field.     

Samplers for VOCs in air based on cyclodextrin-silica hybrid microporous solid phases

Samplers for VOCs in air based on cyclodextrin-silica hybrid microporous solid phases are proposed. The solid phase preparation is very easy and inexpensive. Proposed samplers compared with other solid phases present the advantages of a wider range of operative conditions for VOCs desorption. Samplers are tested based on results for the determination of benzene, toluene, ethylbenzene and o-xylene, m-xylene and p-xylene (BTEX) in air. Operational parameters are optimized and quantitative recovery is obtained using a solid phase from 2-hydroxypropyl-β-cyclodextrin and acetonitrile as the extraction solvent. The recoveries obtained are 89 ± 4%, 90 ± 6%, 91 ± 2%, 87.0 ± 0.9%, 88 ± 4%, and 88 ± 4% for benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene, respectively. Moreover results indicate a good reproducibility with a coefficient of variation below 6% and no significant difference between the reproducibility intra-synthesis and inter-synthesis. The proposed procedure has been applied to the determination of BTEX in several contaminated air samples and compared with results provided by a reference method.     

Biomonitoring of benzene and toluene in human blood by headspace-solid-phase microextraction

A simple and rapid method for the determination of benzene and toluene in whole blood by headspace-solid-phase microextraction (HS-SPME) is described. Using SPME fibres coated with 65 μm carboxene/polydimethylsiloxane, limits of quantification (LOQ) of 5 ng/L for benzene and 25 ng/L for toluene are achieved. As a result of its large linear range (i.e. 5–5000 ng/L for benzene) the method is suitable for biomonitoring of both occupationally and environmentally exposed people. The reproducibility of the determination of benzene is ≤ 8%. An interlaboratory comparison demonstrated that the method proposed here compares favorably with existing methods (dynamic headspace, purge and trap). Received: 9 February 1998 / Revised: 6 July 1998 / Accepted: 18 July 1998     

Quantitative evaluation of benzene, toluene, and xylene in the larvae of Drosophila melanogaster by solid-phase microextraction/gas chromatography/mass spectrometry for potential use in toxicological studies

A simple, rapid, and solvent-free method for quantitative determination of benzene, toluene, and Xylene in exposed Drosophila larvae was developed using headspace solid-phase microextraction (HS-SPME) coupled to GC/MS. Larvae fed on standard Drosophila food mixed with benzene, toluene, and Xylene for 48 h were homogenized in Milli-Q water. Extraction of benzene, toluene, and Xylene was performed at 65 degrees C for 30 min on the SPME fiber (silica-fused). Subsequently, the fiber was desorbed in the GC injection port, followed by GC/MS analysis in the selected-ion monitoring mode. An external calibration curve was used for the quantification of benzene, toluene, and Xylene in the exposed organism. Recoveries were in the range of 78-82% (intraday) and 76-81% (interday) in larvae, and 91-96% (intraday) and 87-92% (interday) in the diet. LOD with an S/N of 3:1 and LOQ with an S/N of 10:1 were in the range of 0.01-0.023 and 0.034-0.077 microg/L, respectively. Percent RSD values for benzene, toluene, and Xylene were in the range of 0.50-0.81 (intraday) and 0.89-1.23 (interday) for retention time, and 2.16--3.85 (intraday) and 2.99-4.95 (interday) for peak concentration, showing good repeatability. This method was sensitive enough to quantitate benzene, toluene, and Xylene in small exposed organisms like Drosophila larvae. The SPME/GC/MS method developed may have wider applications in various in vivo toxicological studies.     

Determination of organic compounds in water using dispersive liquid-liquid microextraction

A new microextraction technique termed dispersive liquid-liquid microextraction (DLLME) was developed. DLLME is a very simple and rapid method for extraction and preconcentration of organic compounds from water samples. In this method, the appropriate mixture of extraction solvent (8.0 microL C2Cl4) and disperser solvent (1.00 mL acetone) are injected into the aqueous sample (5.00 mL) by syringe, rapidly. Therefore, cloudy solution is formed. In fact, it is consisted of fine particles of extraction solvent which is dispersed entirely into aqueous phase. After centrifuging, the fine particles of extraction solvent are sedimented in the bottom of the conical test tube (5.0 +/- 0.2 microL). The performance of DLLME is illustrated with the determination of polycyclic aromatic hydrocarbons (PAHs) in water samples by using gas chromatography-flame ionization detection (GC-FID). Some important parameters, such as kind of extraction and disperser solvent and volume of them, and extraction time were investigated. Under the optimum conditions the enrichment factor ranged from 603 to 1113 and the recovery ranged from 60.3 to 111.3%. The linear range was 0.02-200 microg/L (four orders of magnitude) and limit of detection was 0.007-0.030 microg/L for most of analytes. The relative standard deviations (RSDs) for 2 microg/L of PAHs in water by using internal standard were in the range 1.4-10.2% (n = 5). The recoveries of PAHs from surface water at spiking level of 5.0 microg/L were 82.0-111.0%. The ability of DLLME technique in the extraction of other organic compounds such as organochlorine pesticides, organophosphorus pesticides and substituted benzene compounds (benzene, toluene, ethyl benzene, and xylenes) from water samples were studied. The advantages of DLLME method are simplicity of operation, rapidity, low cost, high recovery, and enrichment factor.     

Use of a novel medium, the ionic liquid 1-butyl-3-trimethylsilylimidazolium hexafluorophosphate, for liquid-liquid extraction of lead in water and its determination by graphite furnace atomic absorption spectrometry

The ionic liquid 1-butyl-3-trimethylsilylimidazolium hexafluorophosphate, abbreviated as [C4tmsim][PF6], was developed as a novel medium for liquid-liquid extraction of lead(II) in water, in which dithizone was used as a metal chelator to form a neutral lead-dithizone complex. Under optimal conditions, the complex was extracted into the [C4tmsim][PF6] phase from aqueous solution and back-extracted with nitric acid solution into the aqueous phase that was used directly for the subsequent determination of Pb. The system using the ionic liquid demonstrated good extraction performance; the extraction and back-extraction efficiencies were 99.8 and 99.7%, respectively, for Pb(II) at 20 microg/L. The above procedure, including the extraction and back-extraction, was used to enrich trace levels of Pb(ll) in a relatively large volume of water samples (1000 mL water), and an enrichment factor of 400 was obtained. The enrichment coupled with graphite furnace atomic absorption spectrometry was successfully applied to the determination of Pb in water. The calibration graph was linear at levels near the detection limits up to > or = 100 ng/L Pb(II). The limits of quantitation and detection for lead in real water samples were 2.5 and 1.0 ng/L, respectively. Lead recoveries of 96.2-103.8% from spiked samples demonstrate the accuracy of the proposed method.     

Direct screening of water samples for benzene hydrocarbon compounds by headspace liquid-phase microextraction-gas chromatography

The applicability of headspace liquid-phase microextraction and gas chromatography is evaluated for the expeditious and reliable screening of tap and drinking water samples for selected volatile organic compounds (viz., benzene, toluene, ethylbenzene, and xylene isomers, BTEX). The method uses 3.5 microL of n-hexadecane as extraction solvent, 10 min extraction time with stirring at 1250 rpm, at 20 degrees C and 0.38 g/mL salt addition. The enrichment factors of this method are from 135 to 213. Limits of detection are in the range of 4.1-23.5 ng/L. The relative standard deviations at 0.05, 50, 200, and 400 microg/L of spiking levels are in the range of 0.61%-4.01%. Recoveries of six BTEX from drinking water at these spiking levels are between 95.4% and 104.4%.     

Fabrication of a novel hydrophobic/ion‐exchange mixed‐mode adsorbent for the dispersive solid‐phase extraction of chlorophenols from environmental water samples

A novel mixed‐mode adsorbent was prepared by functionalizing silica with tris(2‐aminoethyl)amine and 3‐phenoxybenzaldehyde as the main mixed‐mode scaffold due to the presence of the plentiful amino groups and benzene rings in their molecules. The adsorption mechanism was probed with acidic, natural and basic compounds, and the mixed hydrophobic and ion‐exchange interactions were found to be responsible for the adsorption of analytes. The suitability of dispersive solid‐phase extraction was demonstrated in the determination of chlorophenols in environmental water. Several parameters, including sample pH, desorption solvent, ionic strength, adsorbent dose, and extraction time were optimized. Under the optimal extraction conditions, the proposed dispersive solid‐phase extraction coupled with high‐performance liquid chromatography showed good linearity range and acceptable limits of detection (0.22∽0.54 ng/mL) for five chlorophenols. Notably, the higher extraction recoveries (88.7∽109.7%) for five chlorophenols were obtained with smaller adsorbent dose (10 mg) and shorter extraction time (15 min) compared with the reported methods. The proposed method might be potentially applied in the determination of trace chlorophenols in real water samples.     

Simultaneous determination of inorganic mercury and methylmercury compounds in natural waters

The purpose of the present work was to develop a simple, rapid, sensitive and accurate method for the simultaneous determination of inorganic mercury (Hg(2+)) and monomethylmercury compounds (MeHg) in natural water samples at the pg L(-1) level. The method is based on the simultaneous extraction of MeHg and Hg(2+)dithizonates into an organic solvent (toluene) after acidification of about 300 mL of a water sample, followed by back extraction into an aqueous solution of Na(2)S, removal of H(2)S by purging with N(2), subsequent ethylation with sodium tetraethylborate, room temperature precollection on Tenax, isothermal gas chromatographic separation (GC), pyrolysis and cold vapour atomic fluorescence spectrometric detection (CV AFS) of mercury. The limit of detection calculated on the basis of three times the standard deviation of the blank was about 0.006 ng L(-1) for MeHg and 0.06 ng L(-1) for Hg(2+)when 300 mL of water was analysed. The repeatability of the results was about 5% for MeHg and 10% for Hg(2+). Recoveries were 90-110% for both species.     

生活饮用水中苯系物的顶空气相色谱测定法

建立顶空气相色谱法测定生活饮用水中微量苯系物的方法,各组分的分离度较好.苯、甲苯、乙苯、对二甲苯、间二甲苯、邻二甲苯、异丙苯的检出限分别为0.002、0.004、0.005、0.007、0.007、0.008、0.005 mg/L,样品的平均加标回收率为97.0%～100.8%,测量结果的相对标准偏差不大于5.1%(n=5),该方法可满足水中苯系物的检测要求.