Disposable ionic liquid coating for headspace solid-phase microextraction
of benzene, toluene, ethylbenzene, and xylenes in paints followed
by gas chromatography\u2013\ufb02ame 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 \ufb01ber was coated with IL prior to every extraction, then the analytes were extracted and desorbed on the injection port of gas chromatography, and \ufb01nally the IL coating on the \ufb01ber was washed out with solvents. The coating and washing out of IL from the \ufb01ber can be \ufb01nished in a few minutes. This disposable IL-coated \ufb01ber was applied to determine BTEX in water-soluble paints with results in good agreement with that obtained by using commercially available SPME \ufb01bers. 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\u2013271\ue000g g\u22121) were detected with spiked recoveries in the range of 70\u2013114%. Compared to the widely used commercially available SPME \ufb01bers, this proposed disposable IL-coated \ufb01ber 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-speci\ufb01c IL can be designed and synthesized for selective extraction of target analytes, this disposable IL coating SPME might has great potential in sample preparation.
Volatile organic compounds such as benzene, toluene, ethylbenzene, and xylenes (BTEX) have become of particular interest in the \ufb01eld of indoor air quality during the past several years. BTEX pollution in indoor air results from smoking and burning processes, as well as from emission from building or furnishing materials, paints, adhesives, other consumer prod- ucts[1,2]. Since paints are one of the main sources of BTEX in indoor air, it has great signi\ufb01cance to strictly control the
contents of BTEX in paints to decrease its impact on the en- vironment. Therefore, development of analytical method for determination of BTEX in paints has an important relevance. To our knowledge, however, studies on the determination of BTEX in paints are very limited.
Due to the recent trends of using water-soluble paints in- stead of organic solvent-soluble paints, it is necessary to de- velop appropriate sample handling methods that are compat- ible with the determination of BTEX by gas chromatography (GC) in these matrices.
This is because this simple and solvent-free sample prepa- ration technique, which combines extraction, concentration and sample introduction in one step, is portable, sensitive and convenient to couple with various analytical instruments, es- pecially GC. Almost a dozen different \ufb01ber coatings have been commercialized. Among them, the polydimethylsilox- ane (PDMS) shows excellent selectivity for non-polar com- pounds while the polyacrylate (PA) coating facilitates the extraction of relatively polar analytes. To date, most of these \ufb01ber coatings suffered from limited life span (50\u2013100 times of use), relatively low operating temperatures (200\u2013270\u25e6C) in GC applications, and incompatibility with the organic sol- vents in HPLC mobile phases. Several approaches have been proposed to overcome these drawbacks. While the sol\u2013gel technology was adopted to prepare SPME \ufb01bers[5\u20137], also disposable usage of technical grade optical \ufb01bers as SPME \ufb01ber was proposed. Another alternative is to employ liquid-phase microextraction (LPME) performed by using a single drop of solvent[9\u201311] or a small length of porous hollow \ufb01ber protecting the solvent. It was reported that LPME shows comparable extraction ef\ufb01ciency and repro- ducibility to the widely used SPME, in addition to the advan- tage of very low cost and freedom of selection of appropri- ate solvent for extraction of selected analytes. Unfortunately, LPME suffers from relatively low sensitivity and inconve- nient in performance compared with SPME.
Room temperature ionic liquids (IL), resulting from the combination of organic cations and various anions that are liquids at room temperature, are gaining wide recognition as potential environmentally benign solvents. The several unique properties of IL such as negligible vapor pressure, good thermal stability, tunable viscosity and miscibility with water and organic solvents, as well as good extractability for various organic compounds
tion as very potential absorbents for SPME/LPME. Ad- ditionally, IL were successfully used as stationary phases for gas chromatography by Armstrong and co-workers
attractive solvents for drop-based LPME of polycyclic aro- matic hydrocarbons (PAHs). However, this drop-based LPME is incompatible with GC due to the nonvolatility of the IL.
In this present study, a new microextraction technique based on IL and coupled with GC was developed for the analysis of BTEX in paints. The proposed technique, a hy- brid of SPME and LPME, for the \ufb01rst time suggests IL as disposable coating for microextraction. IL was coated on the \ufb01ber of a SPME device before every extraction, the analytes were extracted and desorbed on the injection port of GC, and \ufb01nally the IL-coating on the \ufb01ber was washed out with sol- vents. It was expected that the relatively large viscosity of IL should improve their coating on the SPME \ufb01ber, while the liquid state of the of coating should facilitate easy wash- ing out after sample injection and fast extraction as diffusion rates of analytes in liquid phase are much larger than that in
solid-phase. On the other hand, the nonvolatility and good thermal stability of IL permit them to stay on the \ufb01ber when the analytes were desorbed on the injection port of GC.
Reagents used for synthesis of IL were obtained from Acros Organics. BTEX standards were obtained from In- stitute for Reference Materials of SEPA (Beijing, China). HPLC-grade methanol and dichloromethane were purchased from Scharlau Chemie SA, Barcelona, Spain. All other chemicals were of analytical grade (Beijing Chemicals Cor- poration, Beijing, China) and ultrapure water (EASYpure LF, Barnstead International, Dubuque, IA, USA) was used throughout.
The synthesis and physicochemical properties of 1- octyl-3-methylimidazolium hexa\ufb02uorophosphate ([C8MI- M][PF6]) IL was described in our previous study.
GC analyses were performed using a Hewlett-Packard 6890A gas chromatograph equipped with a split\u2013splitless in- jector and the technique of \ufb02ame ionization detection (FID) (Agilent, Palo Alto, CA, USA). The system was controlled by computer and Chemstation software (Agilent, Ver A.07.01). A HP-5 fused-silica column (25 m\u00d7 0.25 mm I.D.) with 95% dimethylsiloxane and 5% diphenylsiloxane (\ufb01lm thickness 0.25\ue000m) was used. The injector port was operated with split- less mode and temperature was kept at 200\u25e6C, while the de- tector temperature was maintained at 250\u25e6C. The column oven temperature was programmed as follows: initial tem- perature of 40\u25e6C for 3 min, then rising to 200\u25e6C at a rate of 12\u25e6C min\u22121and hold at 200 \u25e6C for 3 min. High purity ni- trogen was used as carrier gas (1.0 ml min\u22121) and make-up gas (30 ml min\u22121). Hydrogen and air were used as detector gases at 30 ml min\u22121and 400 ml min\u22121, respectively. Under this GC condition, the three xylenes isomers were separated into two peaks (one is the mixture ofm-,p-xylene, another iso-xylene). In quanti\ufb01cation, however, we integrated the area of these two peaks together and calculated the whole concentration of xylenes.
The SPME device was adapted from a used 0.5-\ue000l mi- crosyringe as shown inFig. 1. A stainless steel wire was inserted into a movable stainless steel tubing held in the glass body of the microsyringe, and the wire pierces a piece of silicone rubber and gets into the hollow stainless steel
Fig. 1. Schematic diagram of the home-made SPME device: (1) IL-coated \ufb01ber tip; (2) stainless steel needle; (3) silicone rubber O-ring; (4) glass sy- ringe body; (5) moveable stainless steel tubing; (6) stainless steel \ufb01ber or polyimide coated fused-silica \ufb01ber; (7) localizer.
needle. The silicone rubber provides an effective seal dur- ing the movement of the wire. A plastic localizer is \ufb01xed at the up end of the wire to make sure that the lower side of the wire can be moved 1 cm out of the stainless steel nee- dle for coating and extraction. When fused-silica \ufb01ber was used, the stainless steel wire was replaced by a piece of fused- silica optical \ufb01ber. A SPME \ufb01ber holder for manual use and a 100\ue000m polydimethylsiloxane (PDMS) \ufb01ber (Supelco, St. Louis, MO, USA) were used in this study for comparing study.
An aliquot of 900\ue000l of [C8MIM][PF6] and 100\ue000l of dichloromethane was added to a vial with a cap and mixed, and the obtained mixture was ready for the coat- ing of an SPME \ufb01ber. When a stainless steel wire was coated, the 1-cm tip of the wire was washed with methanol and dichloromethane successively, and then conditioned at 200\u25e6C under nitrogen for approximately 3 min in the GC in- jection port. After it was removed from the injector, the wire was cooled to roomtemperature and dipped vertically into the coating solution and held for 1 min, and then removed from the coating solution and kept in air for another 1 min for the dichloromethane to evaporate. This dipping and evaporating process was repeated three times to obtain relatively thick coating and better repeatability of the coating. When a fused- silica \ufb01ber was coated, the 1-cm tip of protective polyimide layer was removed \ufb01rstly by dipped into dichloromethane. Then, the fused-silica \ufb01ber was pretreated and coated ac- cording to the same procedure as coating the stainless steel wire.
A headspace SPME procedure was adopted. For each sam- ple (20 ml water mixed with 3 ml methanol) spiked with 17\ue000g ml\u22121of benzene and toluene, and 8.5\ue000g ml\u22121of ethyl- benzene and xylenes, the SPME \ufb01ber was exposed to the headspace for 30 min. The vial cap was sealed with alu- minium foil and the foil was used only once. The sam- ple was agitated with a magnetic stirring bar at room tem- perature (20\u25e6C) during the extraction process to allow the equilibration of analytes between the aqueous phase and the headspace, then the \ufb01ber was immediately inserted into the GC port for thermal desorption of the extracted analytes. In the experiments for optimization of analytical conditions,
each determination was repeated three times. The mean val- ues were adopted and the standard deviations were shown as error bar in these \ufb01gures. For sample analysis, determination was repeated \ufb01ve times.
To 100 ml of \ufb02ask were added 0.20 g paints, 20 ml water and 3 ml methanol and mixed. Headspace SPME was con- ducted as the above-described procedure for standard solu- tions. Spiked recoveries were determined by spiking stan- dards into 0.20 g sample at concentration levels at 500\ue000g g\u22121 of benzene, 450\ue000g g\u22121toluene, 250\ue000g g\u22121of ethylbenzene, and 350\ue000g g\u22121xylenes, respectively.
Since the relatively high viscosity of [C8MIM][PF6] makes it inconvenient for direct coating, a mixture of di- choloromethane and [C8MIM][PF6] (1 + 9, v + v) was used as coating solution. Experiments showed that both stainless steel wire and fused-silica \ufb01ber could be coated equably by IL, and the stainless steel wire had the advantage of long life span as it is a strong material. Unfortunately, the stain- less steel wire available in our laboratory was relatively thick which made it dif\ufb01cult to move it in the hollow needle after coating and this provided worse repeatability. Therefore, a fused-silica \ufb01ber was adopted in the following studies.
The coating procedure was optimized to obtain better re- peatability and higher sensitivity by using BTEX as model extracts. As can be seen inFig. 2, the peak areas obtained when the \ufb01ber was dipped in the coating solution for 3 min and evaporated in air for 1 min were signi\ufb01cantly smaller
Fig. 2. Peak areas obtained by home-made disposable \ufb01ber coated with IL under different coating conditions: 3 min\u00d7 1, dipped in coating solution for 3 min followed by holding in air for 1 min to evaporated solvent; 1 min\u00d7 3, 2 min\u00d7 3, 3 min\u00d7 3, dipped in coating solution for 1 min, 2 min, 3 min, respectively, and followed by holding in air for 1 min to evaporated solvent, repeating this procedure three times.
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