Kinetics and the on-site application of standards in a solid-phase microextraction fiber

The kinetics of the desorption of analytes from a SPME fiber into an agitated sample matrix was studied, and a theoretical model was proposed to describe the dynamic desorption process, based on the steady-state diffusion of analytes in the extraction phase and in the boundary layer. It was found that the desorption of analytes from a SPME fiber into an agitated sampling matrix is isotropic to the absorption of the analytes onto the SPME fiber from the sample matrix under the same agitation conditions, and this allows for the calibration of absorption using desorption. The calibration was accomplished by exposing a SPME fiber, preloaded with a standard, to an agitated sample matrix, during which desorption of the standard and absorption of analytes occurred simultaneously. When the standard was the isotopically labeled analogue of the target analyte, the information from the desorption process, i.e., time constant a, could be directly used for estimating the concentration of the target analyte. When the standard varied from the target analyte, the mass-transfer coefficient of the analyte could be extrapolated from that of the standard. These predictions agree well with experimental results. This approach facilitates the full integration of sampling, sample preparation, and sample introduction, especially for on-site or in vivo investigations, where the addition of standards to the sample matrix, or control of the velocity of the sample matrix, is very difficult.     

Electrochemically controlled solid-phase microextraction based on conductive polypyrrole films

Solid-phase microextraction (SPME) fiber coatings based on conductive polypyrrole films were prepared for the electrochemical extraction and desorption of ionic analytes. Simple preparation of each of the PPY extraction coatings on a platinum wire was possible with a constant potential method, but more importantly, cycling of the film between oxidation and reduction potentials facilitated the extraction and desorption of ionic analytes. The analytes were desorbed into a sample aliquot of water and were determined by flow injection analysis using a mass spectrometer. The fiber coatings and the developed electrochemical SPME method were found to be stable and reproducible (RSD < 5%; N = 5) and could be extended to several cations and anions, confirming the versatility of the approach. Preconcentration of the analyte on the fiber was also possible by repeating the processes to increase the amount of analyte extracted.     

Sampling and analysis of airborne particulate matter and aerosols using in-needle trap and SPME fiber devices

A needle trap device (NTD) and commercial poly(dimethylsiloxane) (PDMS) 7-microm film thickness solid-phase microextraction (SPME) fibers were used for the sampling and analysis of aerosols and airborne particulate matter (PM) from an inhaler-administered drug, spray insect repellant, and tailpipe diesel exhaust. The NTD consisted of a 0.53-mm o.d. stainless steel needle having 5 mm of quartz wool packing section near the needle tip. Samples were collected by drawing air across the NTD with a Luertip syringe or via direct exposure of the SPME fiber. The mass loading of PM was varied by adjusting the volume of air pulled through the NTD or by varying the sampling time for the SPME fiber. The air volumes ranged from 0.1 to 50 mL, and sampling times varied from 10 s to 16 min. Particulates were either trapped on the needle packing or sorbed onto the SPME fiber. The devices were introduced to a chromatograph/mass spectrometer (GC/MS) injector for 5 min desorption. In the case of the NTD, 10 microL of clean air was delivered by a gas-tight syringe to aid the introduction of desorbed analytes. The compounds sorbed onto particles extracted by the SPME fiber or trapped in the needle device were desorbed in the injector and no carry-over was observed. Both devices performed well in extracting airborne polycyclic aromatic hydrocarbons (PAHs) in diesel exhaust, triamcinolone acetonide in a dose of asthma drug and DEET in a dose of insect repellant spray. Results suggest that the NTDs and PDMS 7-microm fibers can be used for airborne particulate sampling and analysis, providing a simple, fast, reusable, and cost-effective screening tool. The advantage of the SPME fiber is the open-bed geometry allowing spectroscopic investigations of particulates; for example, with Raman microspectroscopy.     

Pre-equilibrium solid-phase microextraction of free analyte in complex samples: correction for mass transfer variation from protein binding and matrix tortuosity

The accurate measurement of free analyte concentrations within complex sample matrixes by pre-equilibrium solid-phase microextraction (SPME) has proven challenging due to variations in mass uptake kinetics. For the first time, the effects of the sample binding matrix and tortuosity on the kinetics of analyte extraction (from the sample to the SPME fiber) are demonstrated to be quantitatively symmetrical with those of the desorption of preloaded deuterated standards (from the fiber to the sample matrix). Consequently, kinetic calibration methods can be employed to correct for variation in SPME sampling kinetics, facilitating the application of pre-equilibrium SPME within complex sample systems. This approach was applied ex vivo to measure pharmaceuticals in fish muscle tissues, with results consistent with those obtained from equilibrium SPME and microdialysis. The developed method has the inherent advantages of being more accurate, precise, and reproducible, thus providing the framework for applications where rapid measurement of free analyte concentrations (within complicated sample matrixes such as biological tissues, sediment, and surface water) are required.     

Determining chemical activity of (semi)volatile compounds by headspace solid-phase microextraction

This research introduces a new analytical methodology for measuring chemical activity of nonpolar (semi)volatile organic compounds in different sample matrices using automated solid-phase microextraction (SPME). The chemical activity of an analyte is known to determine its equilibrium concentration in the SPME fiber coating. On this basis, SPME was utilized for the analytical determination of chemical activity, fugacity, and freely dissolved concentration using these steps: (1) a sample is brought into a vial, (2) the SPME fiber is introduced into the headspace and equilibrated with the sample, (3) the SPME fiber is injected into the GC for thermal desorption and analysis, and (4) the method is calibrated by SPME above partitioning standards in methanol. Model substances were BTEX, naphthalene, and alkanes, which were measured in a variety of sample types: liquid polydimethylsiloxane (PDMS), wood, soil, and nonaqueous phase liquid (NAPL). Variable sample types (i.e., matrices) had no influence on sampling kinetics because diffusion through the headspace was rate limiting for the overall sampling process. Sampling time was 30 min, and relative standard deviations were generally below 5% for homogeneous solutions and somewhat higher for soil and NAPL. This type of activity measurement is fast, reliable, almost solvent free, and applicable for mixed-media sampling.     

Application of solid-phase microextraction in the determination of diazepam binding to human serum albumin

In this paper, protein-drug interactions were studied by solid-phase microextraction (SPME) using diazepam binding to human serum albumin as a model system. Since drug compounds are normally polar and nonvolatile by nature, direct SPME is used in this work. The SPME extraction is an equilibrium process among the concentrations of the analyte partitioned onto the SPME fiber, free and bound drug in the solution. A calibration curve was first constructed by employing the amount of the analytes partitioned on the fiber versus the free analyte concentration in the solution in the absence of protein. In method I, the extraction was performed in the protein solution with known diazepam concentration. In method II, diazepam was first loaded onto the fiber by extracting in solution with known diazepam concentration. This fiber was subsequently transferred into the protein solution for desorption. The amount of the analyte left on the fiber was analyzed after the system reached equilibrium. The free drug concentration was then obtained from the calibration curve for both methods. The Scatchard plot was finally employed to obtain the number of binding sites and the equilibrium binding constants. Since only a very small amount of the protein solution is required (150 microL for each extraction), method II is very useful for circumstances where the protein amount is very limited. The direct measurement method proposed in this paper does not need a GC response factor, which significantly decreases the experimental error. The only measurement needed is the area count change (ratio) of the fiber injections before and after the protein was introduced into the solution. The difference between the direct measurement method for method I and method II is discussed. The result illustrated that the SPME direct measurement method provided both theoretical accuracy and simplicity in such applications.     

Diffusion-based calibration for SPME analysis of aqueous samples

When an SPME fiber is exposed for a short period of time to a flowing fluid sample, the amount of extracted analyte depends on its diffusion coefficient in the matrix medium, and it can be correlated to its concentration using a simple mathematical model. This work discusses the extension of this approach, already validated for gaseous samples and SPME fibers coated with strong adsorbent coatings, to the diffusion-based quantification of analytes present in aqueous samples. Dilute aqueous solutions of aromatic hydrocarbons were used as model samples and vials were modified to use conventional magnetic agitation with controlled tangential flow of the test solution around the fiber. It was demonstrated that, with proper selection of the stirring speed and sampling time, the same diffusion-based quantitative model used for gas samples could be employed. Under optimal conditions, the concentrations of the evaluated aromatic hydrocarbons were estimated with relative standard deviations between 0.8 and 3.6% and without deviation from the expected values within this precision range. Considering the extraction times involved, between 30 and 60 s, the approach here presented is the fastest possible technique for direct extraction of analytes from liquid samples.     

Preparation and characterization of porous silica-coated multifibers for solid-phase microextraction

C18-bonded silica-coated multifibers were prepared and studied as a stationary phase for solid-phase microextraction (SPME). The porous multifiber SPME provided larger absorption capacity and higher absorption rate compared to a polymer-coated single fiber. Its absorption rate was 10 times higher than that of a commercial 100-microm poly(dimethylsiloxane) (PDMS)-coated fiber. Its high extraction efficiency enabled the positive identification of unknown compounds at sub-part-per-billion level in full-scan mode with a benchtop quadruple GC/MS. The desorption temperature indicated that the analyte interactions with the C18-bonded silica were stronger than those with the PDMS polymer. The dependence of the equilibration time on the molecular weight was not observed for the porous multifiber SPME. The boundary layer between the fiber coating and the sample matrix could be the absorption control step in SPME under mild agitation. The special experimental conditions in the porous multifiber SPME, such as air interference and polar organic solvent wetting, were investigated.     

Influence of albumin on sorption kinetics in solid-phase microextraction: consequences for chemical analyses and uptake processes

Because of its simplicity, solid-phase microextraction (SPME) is an increasingly popular technique to use in experiments measuring freely dissolved concentrations of compounds in biological and environmental samples. However, a number of studies have shown that sorption kinetics of compounds in such SPME systems is dependent on the presence of a binding matrix. This affects the interpretability of nonequilibrium SPME data. In this study, this phenomenon was investigated by measuring the rate of depletion of pyrene from a "loaded" poly(dimethylsiloxane) fiber into surrounding cell culture medium containing different concentrations of bovine serum albumin (BSA). The rate of depletion was found to steadily increase with increasing concentrations of BSA. It was postulated that BSA facilitated the transport of pyrene through the medium. This phenomenon was modeled by considering diffusion of BSA-bound pyrene in addition to diffusion of unbound pyrene in the aqueous boundary layer (BL) around the fiber. The model closely fit the experimental data and illustrated that diffusion in the BL was rate limiting because the analyte's affinity for the fiber was high and the BL thickness significant. The concentration of binding matrix and the analyte's affinity for the matrix further determined the extent to which BSA-facilitated transport contributed to the kinetics of the system.     

Quantitative in vivo microsampling for pharmacokinetic studies based on an integrated solid-phase microextraction system

An integrated microsampling approach based on solid-phase microextraction (SPME) was developed to provide a complete solution to highly efficient and accurate pharmacokinetic studies. The microsampling system included SPME probes that are made of poly(ethylene glycol) (PEG) and C18-bonded silica, a fast and efficient sampling strategy with accurate kinetic calibration, and a high-throughput desorption device based on a modified 96-well plate. The sampling system greatly improved the quantitative capability of SPME in two ways. First, the use of the C18-bonded silica/PEG fibers minimized the competition effect from analogues of the target analytes in a complicated sample matrix such as blood or plasma samples, which is a common problem associated with solid coating SPME fibers for quantitative analysis. Moreover, the C18-bonded silica/PEG fibers provide high sensitivity and a large dynamic range that covers the possible sample concentration range during diazepam administration and elimination. Second, the kinetic calibration method offers more accurate quantitation than the calibration curve method for in vivo SPME, because it compensates for convection and matrix effects during sampling. Therefore, it is especially suitable as a fast sampling technique for pre-equilibrium SPME. Furthermore, with the high-throughput desorption device, the integrated system offers compactness and high efficiency. Its feasibility for in vivo sampling was demonstrated by monitoring diazepam pharmacokinetics and validated by conventional chemical assays and equilibrium SPME. In addition, we propose a simple method to determine the apparent distribution constant between an SPME fiber and a blood matix (Kfs) and the distribution constant between an SPME fiber and a pure PBS buffer sample matrix (Kfb). As a result, both total and free concentrations of the drug and its metabolites can be detected simultaneously. Accordingly, the binding constants to the blood matrix can be obtained, which are of special significance for clinical diagnosis and drug discovery.     

Sample depletion of the matrix-assisted laser desorption process monitored using radionuclide detection

To investigate analyte consumption during the laser desorption process, matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) is combined with radionuclide detection. Radionuclide detection provides highly sensitive and quantitative information on the amount of radiolabeled analytes in a MALDI MS sample spot. 14C-Labeled cytochrome c is deposited with 2,5-dihydroxybenzoic acid in 10-nL volume spots. By comparing radioactivity levels of the labeled cytochrome c both before and after spectral acquisition, the reduction in labeled analyte molecules on the target allows monitoring of the moles of desorbed sample. Through a depletion study on this sample, the amount of analyte consumed for MALDI time-of-flight spectral acquisition and the average number of molecules desorbed per laser ablation are determined. When [14C]-cytochrome c is no longer detected by MALDI MS, approximately 70% of the original analyte remains in the sample spots. Redissolving the spots produced further desorption, indicating that the analyte before dissolution was in a physical environment that did not facilitate the desorption process. As a technique with a response that does not depend on the environment of the analyte, radionuclide detection allows characterization of mass-limited sampling methods to better understand the MALDI process.     

Analysis of freely dissolved alcohol ethoxylate homologues in various seawater matrixes using solid-phase microextraction

Solid-phase microextraction fibers (SPME) were tested as tools to determine freely dissolved alcohol ethoxylate (AE) surfactants in seawater matrixes. Partitioning of a wide range of AE homologues into a 35-mum polyacrylate fiber coating was linearly related to aqueous concentrations as low as submicrograms per liter, with high reproducibility. The exposure time needed to reach equilibrium between aqueous phase and the SPME fiber depended on the fiber-water partitioning coefficient (Kfw) of the AE homologue. Specific attention was given to the influence of various matrixes on the analysis via SPME. The presence of sediment increases the uptake kinetics of AE homologues for which diffusion in the aqueous phase is rate limiting. The Kfw in equilibrated systems was not affected by the presence of other homologues, micelles, or varying amounts of sediment phase. SPME is therefore a suitable tool for analysis of AE in sorption studies and sediment toxicity tests. A strong linear relation was observed between Kfw and the hydrophobicity of the AE homologue, using estimated octanol-water partition coefficients. This relation can be used to predict the partitioning coefficient of any AE homologue to the SPME fiber, which facilitates the analysis of complex mixtures.     

CE in a nonuniform capillary modulated by a cylindrical insert, and zone-narrowing effects during sample injection

The electrophoretic behavior of an analyte in a capillary consisting of two parts of different cross section has been investigated. Modulation of the cross-sectional area of the separation channel has been achieved by inserting a cylindrical fiber different distances into the capillary. It was shown that the zone injected into the capillary part with smaller cross section could be moved using electromigration into the wider part of the capillary with zone compression. As we observed, the zone narrowed longitudinally in the wide part of the capillary in accordance with the ratio of the electric field strength in the two parts of the capillary. The concentration of plug introduced into the capillary by electroinjection can be increased by use of low-conductivity sample buffer. Efficient introduction of extracted analytes desorbed from an SPME fiber to the separation channel was achieved using this approach. Thermoinduced effects caused by temperature increase in the narrow part of the capillary and their influence on sample stacking are analyzed. Possible applications of the effect observed to the sample introduction optimization are also discussed in this study.     

Laser desorption/ionization time-of-flight mass spectrometry on sol-gel-derived 2,5-dihydroxybenzoic acid film

This work presents a novel method for direct desorption/ ionization of analytes from sol-gel-derived film. 2,5-Dihydroxy benzoic acid (DHB), a common MALDI matrix, was incorporated into a sol-gel polymeric structure. The sol-gel-derived DHB thin film can assist the mass analysis of analytes by laser desorption/ionization, with a matrix interference-free background in the mass spectra. The sol-gel-derived film can function as an energy absorber during laser irradiation because it contains DHB molecules. Furthermore, laser irradiation with normal laser power (70-110 microJ) is not likely to generate any background ions from this sol-gel-DHB derived film. The samples were prepared straightforwardly. After a thin film was formed on a Parafilm membrane from the sol-gel-derived DHB solution coating, the sample solution was directly added to the top of the film, for laser desorption/ ionization mass analysis. The analyte signals were homogeneously obtained on the sol-gel-derived DHB film. Experimental results show that the optimum concentrations of DHB incorporated in the sol-gel solution were between 7,500 ppm and 10,000 ppm, providing a matrix interference-free background. Analytes, including small proteins, peptides, amino acids, and small organics, were used to demonstrate the effectiveness of the proposed method. However, a higher laser power (> 110 microJ) than normal was required to desorb small proteins from the sol-gel-derived DHB film. Therefore, a few matrix ions desorbed from the thin film were generated during laser irradiation. The detection limit for both small molecules and proteins, using this sol-gel-assisted laser desorption/ ionization (SGALDI) mass spectrometry (MS), was as low as 81 fmol. However, a mass spectrometer with cutoff-mass selection could detect 8.1 fmol of cytochrome c. The largest analyte observed by the SGALDI-MS in this study was myoglobin.     

Equilibrium sampling of freely dissolved alkylphenols into a thin film of 1-octanol supported on a hollow fiber membrane

A new negligible depletion extraction procedure was proposed for equilibrium sampling of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) into a thin film of 1-octanol supported on a hollow fiber membrane. This thin liquid film extraction technique was directed at the determination of (1) freely dissolved concentrations, (2) distribution coefficients to 1-octanol (D(ow)), and (3) binding to dissolved organic matter (DDOC). The sampling device was prepared by dipping pieces of polypropylene microporous hollow fiber membrane (10-mm length, 30-microm wall thickness, 240-microm inner diameter) into 1-octanol for a few seconds to impregnate the pores of the hollow fiber wall. After stirring in 100 mL of sample solution for 24 h, the sampling device was harvested and desorbed with 30 microL of methanol, of which 20 microL was injected for HPLC analysis. With the measured D(ow) of a chemical and its equilibrium concentration in the 1-octanol sampling phase (C(octanol)), the freely dissolved concentration (Cfree) was calibrated based on Cfree = C(octanol)/D(ow). Measured log Dow values of OP (4.32 +/- 0.06) and NP (4.79 +/- 0.02) were independent of the chemical concentration, only minimally affected by the environmentally relevant pH, buffering capacity, and salinity of samples, and agreed well with reported values. Log DDOC values of OP (4.89 +/- 0.43) and NP (5.14 +/- 0.37), determined in Aldrich humic acid solution, agreed with reported partition coefficients to organic carbon (log Koc) for particles in river water and effluent wastewater. Short equilibration times and high enrichment factors were obtained for both analytes due to the high surface to volume ratio of the new sampler. The technique was successfully applied to determine Cfree of OP and NP in real water samples and to study their association with humic acids and bovine albumin.     

Thin-film microextraction

The properties of a thin sheet of poly(dimethylsiloxane) (PDMS) membrane as an extraction phase were examined and compared to solid-phase microextraction (SPME) PDMS-coated fiber for application to semivolatile analytes in direct and headspace modes. This new PDMS extraction approach showed much higher extraction rates because of the larger surface area to extraction-phase volume ratio of the thin film. Unlike the coated rod formats of SPME using thick coatings, the high extraction rate of the membrane SPME technique allows larger amounts of analytes to be extracted within a short period of time. Therefore, higher extraction efficiency and sensitivity can be achieved without sacrificing analysis time. In direct membrane SPME extraction, a linear relationship was found between the initial rate of extraction and the surface area of the extraction phase. However, for headspace extraction, the rates were somewhat lower because of the resistance to analyte transport at the sample matrix/headspace barrier. It was found that the effect of this barrier could be reduced by increasing either agitation, temperature, or surface area of the sample matrix/headspace interface. A method for the determination of PAHs in spiked lake water samples was developed based on the membrane PDMS extraction coupled with GC/MS. A linearity of 0.9960 and detection limits in the low-ppt level were found. The reproducibility was found to vary from 2.8% to 10.7%.     

Sol-gel coating technology for the preparation of solid-phase microextraction fibers of enhanced thermal stability

A novel sol-gel method is described for the preparation of solid-phase microextraction (SPME) fibers. The protective polyimide coating was removed from a 1-cm end segment of a 200 μm o.d. fused-silica fiber, and the exposed outer surface was coated with a bonded sol-gel layer of poly(dimethylsiloxane) (PDMS). The chemistry behind this coating technique is presented. Efficient SPME-GC analyses of polycyclic aromatic hydrocarbons, alkanes, aniline derivatives, alcohols, and phenolic compounds in dilute aqueous solutions were achieved using sol-gel-coated PDMS fibers. The extracted analytes were transferred to a GC injector using an in-house-designed SPME syringe that also allowed for easy change of SPME fibers. Electron microscopy experiments suggested a porous structure for the sol-gel coating with a thickness of ～10 μm. The coating porosity provided higher surface area and allowed for the use of thinner coatings (compared with 100-μm-thick coatings for conventional SPME fibers) to achieve acceptable stationary-phase loadings and sample capacities. Enhanced surface area of sol-gel coatings, in turn, provided efficient analyte extraction rates from solution. Experimental results on thermal stability of sol-gel PDMS fibers were compared with those for commercial 100-μm PDMS fibers. Our findings suggest that sol-gel PDMS fibers possess significantly higher thermal stability (>320 °C) than conventionally coated PDMS fibers that often start bleeding at 200 °C. This is due, in part, to the strong chemical bonding between the sol-gel-generated organic-inorganic composite coating and the silica surface. Enhanced thermal stability allowed the use of higher injection port temperatures for efficient desorption of less-volatile analytes and should translate into extended range of analytes that can be handled by SPME-GC techniques. Experimental evidence is provided that supports the operational advantages of sol-gel coatings in SPME-GC analysis.     

Evaluation of solid-phase microextraction for time-weighted average sampling of volatile sulfur compounds at ppb concentrations

The potential of solid-phase microextraction (SPME) for time-weighted average (TWA) sampling of volatile sulfur compounds in air at ppb concentrations was investigated. The target compounds (hydrogen sulfide, methanethiol (MeSH), ethanethiol (EtSH), dimethyl sulfide (Me2S), and dimethyl disulfide (Me2S2)) were extracted using SPME with a Carboxen-poly(dimethylsiloxane) fiber coating, and diffusion was controlled by keeping the fiber retracted within the needle of the sampling device. The effects of several important experimental variables (air velocity, direction of air flow, analyte concentration, humidity, temperature, extraction time) were studied. The uptake by the fiber was not affected by the direction of the air flow or the air velocity. The effects of concentration, humidity, temperature, and extraction time were examined in experiments with a central composite face design. The results showed that all or most of the investigated parameters had a significant impact on the uptake rates of H2S, MeSH, EtSH, and Me2S, which invalidated time-weighted average sampling of these compounds by SPME under the tested conditions. Moreover, reverse diffusion of H2S, MeSH, and EtSH occurred at 40% relative humidity. For Me2S2, the uptake rate had a variation of only 8% within the whole experimental domain, and the experimental value derived for the uptake rate was consistent with the theoretical value. This result was confirmed by comparative analyses of industrial samples by the standard addition method. Therefore, SPME appears to be a suitable technique for TWA sampling of Me2S2 using the Carboxen-poly(dimethylsiloxane) fiber coating. Finally, in an investigation of potential losses during storage of the fiber, no significant losses of the target compounds were detected after 3 days at -80 degrees C.     

Adsorption effect of aqueous bichlorobiphenyls onto UV-illuminated titanium dioxide

Bichlorobiphenyls were adsorbed onto TiO(2) (Degussa P25) in batch equilibrium experiments. The results demonstrated that a triple-layer model (TLM) surface complex formation model described the adsorption of chlorobiphenyls onto the surface of the TiO(2) solid. The surface complex configuration and the adsorption reaction may have followed the equation derived from the TLM, involving the loss of a proton during the adsorption process. This dependence indicates that the oxidation reaction between surface-adsorbed substrates and photogenerated oxidants dominates. Both sorbed and dissolved components contribute to the observed degradation rate, that is, the 4,4'-CBP degradation rates might be stated as linear functions of the sorbed and dissolved concentrations. The contribution of the concentration of solution phase in degradation pathways is not negligible.     

Time-weighted average passive sampling with a solid-phase microextraction device

A modified Solid-Phase Microextraction (SPME) device has been used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. Unlike conventional sampling with SPME, in which the fiber is extended outside its needle housing, during TWA passive sampling, the fiber is retracted a known distance into its needle housing. The SPME passive sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process has been shown to be described by Fick's first law of diffusion, whereby determination of the amounts of analytes accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. A series of fibers, 100-microm poly(dimethylsiloxane), 65-microm poly(dimethylsiloxane)/divinylbenzene, and 75-microm Carboxen/poly(dimethylsiloxane), were tested for their "zero sink", face velocity, and response time behavior. Of the fibers tested, that coated with 75-microm Carboxen/poly(dimethylsiloxane) was found to be an excellent passive sampler for VOCs. TWA passive sampling with a SPME device was shown to be almost independent of face velocity and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusion path length could be changed. It was found that environmental conditions, e.g., temperature, pressure, relative humidity, and ozone, have little or no effect on sampling. The 75-microm Carboxen/poly(dimethylsiloxane) fiber can retain VOCs for up to two weeks without significant loss. When the SPME device was tested in the field and the results were compared with those from National Institute of Occupational Health and Safety method 1501, good agreement was obtained.