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.     

Development of headspace solid-phase microextraction-gas chromatography method for the determination of solvent residues in edible oils and pharmaceuticals

The application of headspace solid-phase microextraction for isolation and enrichment of solvent residues from oils and pharmaceuticals is discussed. The optimal parameters for isolation and preconcentration of common process solvents (hexane, benzene, toluene and selected chloroderivatives of hydrocarbons) were established. Four fiber types (100 microm polydimethylsiloxane (PDMS), 75 microm Carboxen-PDMS, 65 microm PDMS-divinylbenzene and 85 microm polyacrylate) were evaluated to choose the most efficient coating, able to absorb the greatest amount of analytes. GC-flame ionization detection (FID) and GC-electron-capture detection systems were used for quantitative and qualitative analysis, adequately to the appropriate group of the analytes. For all compounds the limit of detection (LOD), linearity, dynamic range, repeatability and intermediate precision were estimated.     

Detection of substituted benzenes in water at the pg/ml level using solid-phase microextraction and gas chromatography-ion trap mass spectrometry.

Solid-phase microextraction (SPME) is combined with gas chromatography-ion trap mass spectrometry (GC-IT-MS) for the analysis of benzene, toluene, ethyl benzene and xylene isomers (BTEX) in water. SPME is a recent technique for extracting organics from an aqueous matrix into a stationary phase immobilized on a fused-silica fiber. The analytes are thermally desorbed directly in the injector of a gas chromatograph. The wide linear dynamic range (five orders of magnitude) and pg sensitivity of the ion trap mass spectrometer in its full scan mode is an ideal detector for identifying and quantifying the analytes extracted with an SPME device. The combined method SPME-GC-IT-MS, using fibers coated with a 100-microns polydimethylsiloxane coating, showed a limit of quantitation (LOQ) of 50 pg/ml benzene in water. This corresponds to 5 pg of benzene absorbed onto the fiber. The limit of detection (LOD) was 15 pg/ml benzene. For o-xylene spiked at 50 pg/ml in water 50 pg were absorbed by the fiber indicating an LOQ and LOD 10 times better than for benzene. The detection limits obtained exceed the requirements of both the United States Environmental Protection Agency method 524.2 and the Ontario Municipal/Industrial Strategy for Abatement program, which range from 30 to 80 pg/ml and 500 to 1100 pg/ml, respectively. The linearity of the method extended over five orders of magnitude. Relative standard deviation ranged from 2.7 to 5.2% for 15 ng/ml BTEX in water and from 5.5 to 7.5% for 50 pg/ml BTEX in water. SPME-GC-IT-MS was used to evaluate the contamination level in laboratory, potable and wastewater sources.     

Preparation of a Carbon-Coated SPME Fiber and Application to the Analysis of BTEX and Halocarbons in Water

A carbon-coated fiber for solid-phase microextraction (SPME) has been prepared from powdered activated carbon (PAC) and a fused-silica fiber. Scanning electron microscopy of the coating revealed the carbon particles were uniformly distributed on the surface of the fiber substrate. Efficient extraction of BTEX (benzene, toluene, ethylbenzene, p-xylene, and o-xylene) and halocarbons (chloroform, trichloroethylene, and carbon tetrachloride), with short extraction and desorption times, was achieved by use of the coated fiber. The maximum working temperature of the coated fiber was 300 °C and the lifetime was over 140 desorption operations at 260 °C. Limits of quantification (LOQ) of the SPME method for the eight analytes ranged from 0.01 to 0.94 μg L⁻¹, and relative standard deviations (RSD) were below 7.2% (n=6). Recoveries were 87.9–113.4% when the method was applied to the analysis of BTEX and the halocarbons in real aqueous samples. An erratum to this article is available at .     

Standard-free kinetic calibration for rapid on-site analysis by solid-phase microextraction

In this study, a new calibration method, standard-free kinetic calibration, is proposed for rapid on-site analysis by solid-phase microextraction (SPME), based on the diffusion-controlled mass transfer model and equilibrium extraction. With this calibration method, all analytes can be directly calibrated with only two samplings. The feasibility of this calibration method was validated in a standard aqueous solution flow-through system and a standard gas flow-through system. The distribution coefficients of five polycyclic aromatic hydrocarbons (PAHs), including naphthalene, acenaphthene, fluorene, anthracene, and pyrene, between water and the PDMS fiber coating were determined and the concentrations of the PAHs in the flow-through system were successfully calibrated with the proposed standard-free calibration method. The extracted amounts of BTEX (benzene, toluene, ethylbezene, o-xylene) at equilibrium were also successfully calibrated with this method with two rapid sampling periods at 5 and 10 s. Compared with the previous calibration methods for rapid on-site analysis by SPME, this method does not require a standard to calibrate the extraction, nor does it require additional equipment to control or measure the flow velocity of the sample matrix. In addition, all of the extracted analytes can be quantified without considering whether the system reached equilibrium. The newly proposed standard-free kinetic calibration approach enriched the calibration methods available for on-site analysis by SPME.     

Headspace Solid‐Phase Microextraction (HS‐SPME) for the Determination of Benzene,Toluene, Ethylbenzene,and Xylenes (BTEX) in Foundry Molding Sand

Abstract

The use of headspace solid‐phase microextraction (HS‐SPME) to determine benzene, toluene, ethylbenzene, and xylenes (BTEX) in foundry molding sand, specifically a “green sand” (clay‐bonded sand) was investigated. The BTEX extraction was conducted using a 75 µM Carboxen‐polydimethylsiloxane (CAR‐PDMS) fiber, which was suspended above 10 g of sample. The SPME fiber was desorbed in a gas chromatograph injector port (280°C for 1 min) and the analytes were characterized by mass spectrometry. The effects of extraction time and temperature, water content, and clay and bituminous coal percentage on HS‐SPME of BTEX were investigated. Because green sands contain bentonite clay and carbonaceous material such as crushed bituminous coal, a matrix effect was observed. The detection limits for BTEX were determined to be ≤0.18 ng g^?1 of green sand.     

Preparation of a polymeric ionic liquid-coated solid-phase microextraction fiber by surface radical chain-transfer polymerization with stainless steel wire as support

Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%.     

Determination of benzene, toluene, ethylbenzene and xylenes in soils by multiple headspace solid-phase microextraction

Multiple headspace-solid phase microextraction (MHS-SPME) is a recently developed technique for the quantification of analytes in solid samples that avoids the matrix effect. This method implies several consecutive extractions from the same sample. In this way, the total area corresponding to complete extraction can be directly calculated as the sum of the areas of each individual extraction when the extraction is exhaustive, or through a mathematical equation when it is not exhaustive. In this paper, the quantitative determination of benzene, toluene, ethylbenzene and xylene isomers (BTEX) in a certified soil (RTC-CRM304, LGC Promochem) and in a contaminated soil by multiple HS-SPME coupled to a gas chromatography-flame ionisation detector (GC-FID) is presented. BTEX extraction was carried out using soil suspensions in water at 30 degrees C with a 75 microm carboxen-polydimethylsiloxane (CAR-PDMS) fibre and calibration was carried out using aqueous BTEX solutions at 30 degrees C for 30 min with the same fibre. BTEX concentration was calculated by interpolating the total peak area found for the soils in the calibration graphs obtained from aqueous solutions. The toluene, ethylbenzene, o-xylene and m,p-xylene concentrations obtained were statistically equal to the certified values.     

Solid phase microextraction of volatile organic compounds using carboxen-polydimethylsiloxane fibers

Summary A new 80 μm Carboxen-polydimethylsiloxane (PDMS) fiber for solid phase microextraction (SPME) was tested for the enrichment of volatile organic compounds from water and air. Detection limits between 13 ng L⁻¹ (CH₂Cl₂) and 0.1 ng L⁻¹ (CHCl₂Br and CHClBr₂) for the combination: Carboxen-PDMS fiber and GC-ECD and between 35 ng L⁻¹ and 45 ng L⁻¹ (BTEX compounds) for the combination: Carboxen-PDMS and GC-FID using the headspace procedure were determined. Comparisons with the 100 μm PDMS fiber and further coatings show the advantages of the Carboxen-PDMS fiber with respect to extraction efficiency. Disadvantages of the new fiber compared with the 100 μm PDMS fiber are poorer repeatability and prolongation of equilibrium time. Distribution coefficients of the BTEX compounds between aqueous solution and SPME fiber coating were calculated and compared with the results of other researchers and with octanol-water partition coefficients.     

Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase microextraction fiber

Metal-organic frameworks (MOFs) have received great attention as novel sorbents due to their fascinating structures and intriguing potential applications in various fields. In this work, a MIL-101(Cr)-coated solid-phase microextraction (SPME) fiber was fabricated by a simple direct coating method and applied to the determination of volatile compounds (BTEX, benzene, toluene, ethylbenzene, m-xylene and o-xylene) and semi-volatile compounds (PAHs, polycyclic aromatic hydrocarbons) from water samples. The extraction and desorption conditions of headspace SPME (HS-SPME) were optimized. Under the optimized conditions, the established methods exhibited excellent extraction performance. Good precision (<7.7%) and low detection limits (0.32–1.7 ng L⁻¹ and 0.12–2.1 ng L⁻¹ for BTEX and PAHs, respectively) were achieved. In addition, the MIL-101(Cr)-coated fiber possessed good thermal stability, and the fiber can be reused over 150 times. The fiber was successfully applied to the analysis of BTEX and PAHs in river water by coupling with gas chromatography–mass spectrometry (GC–MS). The analytes at low concentrations (1.7 and 10 ng L⁻¹) were detected, and the recoveries obtained with the spiked river water samples were in the range of 80.0–113% and 84.8–106% for BTEX and PAHs, respectively, which demonstrated the applicability of the self-made fiber.     

Determination of BTEX in urine samples using cooling/heating-assisted headspace solid-phase microextraction

Excessive and uncontrolled exposures of the workers to benzene, toluene, ethylbenzene and xylene (BTEX) have currently raised great concerns among industrial hygienist all over the world. Therefore, the effective monitoring of such exposures is assumed to be of prime importance. A cold fiber solid-phase microextraction device based on a cooling capsule as a cooling unit and CO₂ as a coolant was applied to quantitatively analyze BTEX in aqueous samples. A gas chromatography with flame ionization detection was recruited to analyze the target analytes, which had been identified according to their retention times. Several factors such as coating temperature, extraction time and temperature, sample volume and sodium content were optimized. Two modes of extraction, i.e., headspace (HS) and headspace cold fiber (HS-CF) in SPME, were investigated and compared under optimized conditions. The results revealed that HS-CF-SPME has the most appropriate outcome for the extraction of BTEX from aqueous samples. Under the optimized conditions, the calibration curves were linear within the range of 0.2–500 ng ml^?1 and the detection limits were between 0.02 and 0.07 ng ml^?1.The intraday relative standard deviations was lower than about 10%. The method was successfully applied to the determination of BTEX in urine samples with good recovery.     

Dispersive solid phase extraction combined with dispersive liquid–liquid extraction for the determination of BTEX in soil samples: ant colony optimization–artificial neural network

In this study, dispersive solid phase extraction combined with dispersive liquid–liquid extraction has been developed for the extraction of benzene, toluene, ethylbenzene, and xylenes isomers (BTEX) in soil samples prior to gas chromatography–mass spectrometry. The BTEX were extracted from soil sample into acetonitrile by dispersive solid phase extraction method, and the extract was then used as dispersive solvent in dispersive liquid–liquid extraction procedure. Ant colony optimization–artificial neural network (ACO–ANN) has been employed to develop the model for simulation and optimization of this method. The volume of dispersive solvent, volume of extraction solvent, extraction time, and ultrasonic time were the input variables, while the multiple response function (R_m) of analytes was the output. The optimum operating condition was then determined by ant colony optimization method. At the optimum conditions, the limit of detections of 0.12–0.75 ng g⁻¹ was obtained for the BTEX. The developed procedure was then applied to the extraction and determination of BTEX in the soil samples and one certified soil. Copyright © 2015 John Wiley & Sons, Ltd.     

Gaseous and Particle‐bound VOC Products of Combustion Extracted by Needle Trap Samplers

Gaseous benzene, toluene, ethylbenzene and o‐xylene (BTEX) were extracted by using the divinylbenzene (DVB) particles (mesh sizes 60–80, 80–100 and 100–120) as sorbents packed in passive needle trap samplers (NTS). This study performed feasibility tests of these self‐designed DVB‐NTS as diffusive time‐weighted average (TWA) samplers and compared extraction efficiency with that of 100 mm polydimethylsiloxane‐solid phase microextration (PDMS‐SPME) fiber for sampling gaseous and particle‐bound volatile organic compounds (VOCs) from burning mosquito coils. Experimental results indicated that extraction rate of NTS is a reliable index in extracting VOCs. Additionally, comparisons of the NTS in extracting BTEX mass showed the NTS packed with the smallest diameters of adsorbent particles (100–120 mesh DVB) were the most effective. The mass of gaseous BTEX extracted by 100 μm PDMS‐SPME fiber were substantially lower than that extracted by DVB‐NTS of all meshes for the 30‐min TWA sampling of burning mosquito coils, and NTS packed with 100–120 mesh DVB adsorbed BTEX 50–120 ng BTEX. Particles clogging inside the packed phase of NTS inhibited VOC extraction performance after 3–5 samplings of burning particles, especially NTS packed with small‐diameter adsorbents.     

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.     

Liquid core waveguide-based optical spectrometry for field estimation of dissolved BTEX compounds in groundwater: A feasibility study

The utility of a liquid core waveguide (LCW) system for acting as a sentry monitor for compounds such as benzene, toluene, ethylbenzene, xylene (BTEX) in water was examined. A vapor-permeable LCW suitable for long path length absorbance spectroscopy based on a Teflon AF 2400 tube was fabricated. Multiwavelength spectroscopy in the near-UV was carried out using a fiber optic-based flashlamp-photodiode array (PDA) combination with hexane as the solvent in the waveguide core. Using multicomponent calibration, quantitation of benzene and toluene accurate to 6±5% could be conducted at sub-mg l⁻¹ levels in mixtures after a sampling period of 10 min.     

A new porous-layer activated-charcoal-coated fused silica fiber: Application for determination of BTEX compounds in water samples using headspace solid-phase microextraction and capillary gas chromatography

Summary Extra-fine powdered activated charcoal has been used as stationary phase (coating layer) in solid-phase microextraction (SPME). The efficiency and reliability of the prepared device have been investigated for the extraction of some volatile organic compounds such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) from the headspace of water samples. Monitoring of the extracted compounds and further quantitative analysis of the real samples have been performed by capillary GC-FID. Effects of several factors such as temperature, addition of salt, and stirring speed on extraction efficiency and exposure time have been studied. Under optimum conditions, extraction recoveries for these compounds from 50 mL water were >95%. The calibration graphs were linear in the range 5 to 10⁴ pg mL⁻¹ and the detection limit for each BTEX compound was 1.5–2 pg mL⁻¹. The results obtained by use of this porous layer activated charcoal (PLAC)-coated fiber have also been compared with results reported in the literature by use of a polydimethylsiloxane (PDMS)-coated fiber. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Cobalt oxide nanoparticles as a novel high-efficiency fiber coating for solid phase microextraction of benzene,toluene, ethylbenzene and xylene from aqueous solutions

In this work cobalt oxide nanoparticles were introduced for preparation of a novel solid phase microextraction (SPME) fiber coating. Chemical bath deposition (CBD) technique was used in order for synthesis and immobilization of the Co₃O₄ nanomaterials on a Pt wire for fabrication of SPME fiber. The prepared cobalt oxide coating was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The fiber was evaluated for the extraction of benzene, toluene, ethylbenzene and xylene (BTEX) in combination with GC–MS. A simplex optimization method was used to optimize the factors affecting the extraction efficiency. Under optimized conditions, the proposed fiber showed extraction efficiencies comparable to those of a commercial polydimethylsiloxane (PDMS) fiber toward the BTEX compounds. The repeatability of the fiber and its reproducibility, expressed as relative standard deviation (RSD), were lower than about 11%. No significant change was observed in the extraction efficiency of the new SPME fiber after over 50 extractions. The fiber was successfully applied to the determination of BTEX compounds in real samples. The proposed nanostructure cobalt oxide fiber is a promising alternative to the commercial fibers as it is robust, inexpensive and easily prepared.     

Development of plasticised PVC sensing films for the determination of BTEX compounds in aqueous samples

A novel plasticised PVC polymer membrane as a sensing film for the determination of BTEX compounds using ATR-FTIR spectroscopy is demonstrated. A range of 10 plasticised PVC phases have been investigated using toluene and tetrachloroethylene as test analytes. Both analyte enrichment rates and infrared absorbance values were considered when choosing a suitable polymer for sensing. An enhancement in analyte absorbance at the characteristic IR absorption bands was noted as the plasticiser concentration in the film was increased. 2% PVC with 75% diisooctyl azelate was found to show promising results for simultaneous determination of the BTEX compounds. All BTEX analytes can be measured in less than 8 min. A study of a multicomponent sample demonstrated that analyte enrichment times were influenced by the presence of even one additional analyte component in the sample.     

Titanium dioxide nanotube fiber using in headspace solid-phase microextraction with GC–MS for BTEX detection

Anodized TiO₂ nanotube fibers using in-headspace solid-phase microextraction (SPME) with gas chromatography–mass spectrometry (GC–MS) have been exploited as an analytical method for volatile organic compounds such as benzene, toluene, ethylbenzene, and xylenes (BTEX) detection. The factors of anodizing time and annealing temperature for TiO₂ nanotube production are studied and the adsorption factors (time, ionic strength, and temperature) and desorption factors (time and temperature) for BTEX analysis are optimized. The limit of detections (LODs) for benzene, toluene, ethylbenzene o-xylene, and m, p-xylene are 0.5, 0.1, 1.0, 1.0, and 2.0 μg L⁻¹, respectively. The linear ranges for BTEX (0.5–15,000 μg L⁻¹) and satisfactory linearity (R² ≥ 0.9954) are obtained. This method is successfully applied in real samples with the recoveries ranging from 92% to 97%. TiO₂ nanotube fiber is a promising technique for BTEX analysis.     

Triptycene‐Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air

Two novel triptycene quinoxaline cavitands ( DiTriptyQxCav and MonoTriptyQxCav ) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the triptycene moieties at the upper rim of the tetraquinoxaline walls, promoting the confinement of the aromatic hydrocarbons within the cavity. The two cavitands were used as fiber coatings for solid‐phase microextraction (SPME) BTEX monitoring in air. The best performances in terms of enrichment factors, selectivity, and LOD (limit of detection) values were obtained by using the DiTriptyQxCav coating. The corresponding SPME fiber was successfully tested under real urban monitoring conditions, outperforming the commercial divinylbenzene–Carboxen–polydimethylsiloxane (DVB–CAR–PDMS) fiber in BTEX adsorption.