Commercial Solid-phase Microextraction Research Articles

Development of In-Needle SPME Devices for Microextraction Applied to the Quantification of Pesticides in Agricultural Water.

The chemical industry explosion in the 20th century has led to increased environmental pollution, affecting fauna, flora, and waterways. These substances alter water's taste, color, and smell, making it unfit for consumption or toxic. Agricultural water networks face threats from pollution before and after treatment. Some chemical contaminants, like pesticides, are embedded in natural biogeochemical cycles. In this study, we developed a simple and low-cost procedure for the fabrication of needles coated with polydimethylsiloxane (PDMS) as an efficient sorbent for the microextraction of organic pollutant traces from water. The prepared needles were used as an alternative for commercial solid-phase micro-extraction (SPME) devices in analytical chemistry. The PDMS polymeric phase was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The PDMS-coated needles were used for extraction of thirteen pesticides by direct-immersion solid-phase microextraction (DI-SPME) from contaminated waters, followed by determination with gas chromatography-mass spectrometry (GC-MS). The developed analytical method showed limits of detection (LODs) between 0.3 and 2.5 ng mL-1 and RSDs in the range of 0.8-12.2%. The homemade needles were applied for the extraction of pesticides in surface and ground aqueous samples collected from an agricultural area. Several target pesticides were identified and quantified in the investigated water samples.

Post-synthetic modification of covalent organic framework for efficient adsorption of organochlorine pesticides from cattle's milk

Analysis of organochlorine pesticides (OCPs) residues in milk faces a significant challenge. Herein, a sea urchin structured covalent organic framework bearing boric acid groups named COF-B(OH)2 was synthesized and applied as a coating material for solid-phase microextraction (SPME) of the OCPs in cattle's milk. Its performance was superior to that of three commonly used commercial SPME fibers, which could be due to the coexistence of hydrogen bonding, halogen bonding, π-stacking and electrostatic interactions. Besides, the fiber coating displayed good stability and reusability. After optimization, a COF-B(OH)2 based SPME coupled with gas chromatography-electron capture detection was established for the sensitive detection of the OCPs from milk samples. The limits of detection (S/N=3) were between 0.04 and 1.00μgkg-1. Satisfactory accuracy was achieved with the method recoveries in the range of 87.5% to 112.5%. These results manifest the feasibility of the COF-B(OH)2 coated fiber for the enrichment of the trace OCPs from milk samples.

A durable hydrophobicity hydrazone covalent organic framework coating for solid phase microextraction of polycyclic aromatic hydrocarbons in food and environmental sample

A durable hydrophobicity hydrazone covalent organic framework coating for solid phase microextraction of polycyclic aromatic hydrocarbons in food and environmental sample

Hierarchical porous MOFs@COFs-based molecular trap solid-phase microextraction for efficient capture of PAHs and adsorption mechanisms

Hierarchical porous MOFs@COFs-based molecular trap solid-phase microextraction for efficient capture of PAHs and adsorption mechanisms

A Hybrid Stainless-Steel SPME Microneedle Electrode Sensor for Dual Electrochemical and GC-MS Analysis.

A mechanically robust in-tube stainless steel microneedle solid phase microextraction (SPME) platform for dual electrochemical and chromatographic detection has been demonstrated. The SPME microneedle was fabricated by layer-by-layer (LbL) in-tube coating, consisting of carbon nanotube (CNT)/cellulose nanocrystal (CNC) film layered with an electrically conductive polyaniline (PANI) hydrogel layer (PANI@CNT/CNC SPME microneedle (MN)). The PANI@CNT/CNC SPME MN showed effective analysis of caffeine by GC-MS with an LOD of 26 mg/L and excellent precision across the dynamic range. Additionally, the PANI@CNT/CNC SPME MN demonstrated a 67% increase in sensitivity compared to a commercial SPME fiber, while being highly robust for repeated use without loss in performance. For electrochemical detection, the PANI@CNT/CNC SPME MN showed excellent performance for the detection of 3-caffeoylquinic acid (3-CQA). The dynamic range and limits of detection (LOD) for 3-CQA analysis were 75-448 mg/L and 11 mg/L, respectively. The PANI@CNT/CNC SPME MN was demonstrated to accurately determine the caffeine content and 3-CQA in tea samples and dark roast coffee, respectively. The PANI@CNT/CNC SPME MN was used for semiquantitative antioxidant determination and composition analysis in kiwi fruit using electrochemistry and SPME-coupled GC-MS, respectively.

A multi-site recognition molecularly imprinted solid-phase microextraction fiber for selective enrichment of three cross-class environmental endocrine disruptors.

Molecularly imprinted solid-phase microextraction fibers with multi-site recognition were prepared for the simultaneous enrichment of three cross-class environmental endocrine disruptors (EEDs) in environmental water. The surface morphology of the multi-site recognition molecularly imprinted fibers was characterized using scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and surface area and pore size analyzer. Under optimal extraction conditions, the molecularly imprinted fibers showed higher extraction capacity to bisphenol F, diethyl phthalate, and methyl paraben than non-imprinted polymer fibers and commercial fibers. Compared with commercial solid-phase microextraction fibers, the multi-site recognition molecularly imprinted fibers showed superior extraction performance at different concentrations of analytes. The selectivity study confirmed that the multi-site recognition molecularly imprinted solid-phase microextraction fibers were highly selective not only for specific template molecules but also for bisphenols, parabens, and phthalates. Furthermore, the method achieved a limit of detection of 0.003-0.02 μg L-1 for the three cross-class EEDs in environmental water samples with recoveries ranging from 75.76% to 112.69% and relative standard deviations below 11.46%. Thus, the novel MIP fibers with multi-site recognition prepared in this work have provided a promising approach in the field of specific adsorption and a strategy for the simultaneous and sensitive monitoring of multiple cross-class trace EEDs.

Cellulose nanocrystal regulated ultra-loose, lightweight, and hierarchical porous reduced graphene oxide hybrid aerogel for capturing and determining organic pollutants from water

Cellulose nanocrystal regulated ultra-loose, lightweight, and hierarchical porous reduced graphene oxide hybrid aerogel for capturing and determining organic pollutants from water

Polyacrylic Acid Functionalized Biomass-Derived Carbon Skeleton with Highly Porous Hierarchical Structures for Efficient Solid-Phase Microextraction of Volatile Halogenated Hydrocarbons.

In this study, polyacrylic acid functionalized N-doped porous carbon derived from shaddock peels (PAA/N-SPCs) was fabricated and used as a solid-phase microextraction (SPME) coating for capturing and determining volatile halogenated hydrocarbons (VHCs) from water. Characterizations results demonstrated that the PAA/N-SPCs presented a highly meso/macro-porous hierarchical structure consisting of a carbon skeleton. The introduction of PAA promoted the formation of polar chemical groups on the carbon skeleton. Consequently, large specific surface area, highly hierarchical structures, and abundant chemical groups endowed the PAA/N-SPCs, which exhibited superior SPME capacities for VHCs in comparison to pristine N-SPCs and commercial SPME coatings. Under the optimum extraction conditions, the proposed analytical method presented wide linearity in the concentration range of 0.5-50 ng mL-1, excellent reproducibility with relative standard deviations of 5.8%-7.2%, and low limits of detection varying from 0.0005 to 0.0086 ng mL-1. Finally, the proposed method was applied to analyze VHCs from real water samples and observed satisfactory recoveries ranging from 75% to 116%. This study proposed a novel functionalized porous carbon skeleton as SPME coating for analyzing pollutants from environmental samples.

In-situ synthesis of carbon dots embedded wrinkled-mesoporous silica microspheres for efficiently capturing and monitoring organochlorine pesticides from water and fruit juice

• CDs/WMS microspheres were successfully fabricated by in-situ strategy. • CDs/WMS exhibited superior extraction efficiencies for OCPs than pure WMS and commercial coatings. • The mechanisms of CDs/WMS preparation and enhanced SPME performance were investigated. • The proposed method was finally applied for analysis of OCPs in real water and fruit juice samples. An in-situ synthesis strategy was proposed for fabrication of carbon dots embedded wrinkled mesoporous silica (CDs/WMS) microspheres. Characterizations results demonstrated that the doping of CDs with a moderate content still allowed the microspheres to maintain wrinkled and highly mesoporous structures. The CDs/WMS composite was subsequently employed as solid phase microextraction (SPME) coating for sensitive determination of ultra-trace organochlorine pesticides (OCPs) from aqueous solutions. High surface area, abundant chemical groups, and plentiful porosity made CDs/WMS microspheres present superior extraction capacities for OCPs compared with commercial SPME coatings and pure WMS. Under the optimum extraction conditions, the proposed analytical method exhibited wide linearity range (0.2−1000 ng L -1 ), low detection of limits (0.0023−0.073 ng L -1 for water, 0.0062 to 0.41 ng L -1 for fruit juice), and satisfactory reproducibility with relative standard deviations of 6.2%−13.3% and 7.3%−13.2% for water and fruit juice, respectively. Finally, the proposed method was successfully used for determination of OCPs in real water and fruit juice samples. The recoveries varied from 80.1% to 105.2% for water and 71% to 106.8% for fruit juice. This study developed a novel strategy for synthesis of CDs/WMS microspheres, and proposed a new type of SPME coating, which expanded the potential of CDs in capturing organic pollutants from aqueous solutions.

Facile fabrication of a novel SPME fiber based on silicone sealant/hollow ZnO@CeO2 composite with super-hydrophobicity for the enhanced capture of pesticides from water

A novel SPME fiber based on silicone sealant/hollow ZnO@CeO 2 composite was developed for the enhanced capture of pesticides in water. • A novel SPME fiber based on silicone sealant/hollow ZnO@CeO 2 composite with super-hydrophobicity was developed. • Hollow core–shell channels in ZnO@CeO 2 was conducive to the mass transfer to realize the enhanced capture. • The excellent adsorption property was attributed to π-π interaction, and hydrophobic interaction. • The prepared fiber was successfully applied in the analysis of pesticides in surface water. Herein, a novel solid phase microextraction (SPME) fiber coating based on silicone sealant/hollow ZnO@CeO 2 composite with super-hydrophobicity was designed, which could capture rapidly and determine efficiently-six pesticides combined with high-performance liquid chromatography (HPLC). The synthesis mechanism of ZnO@CeO 2 with core–shell structure was discussed. Under the optimized conditions, the developed method showed a wide linear range (0.026–200 µg/L) with good linearity (R 2 greater than 0.9988), low detection limits (0.008–0.353 µg/L, S/N = 3), and quantification limits (0.026–1.175 µg/L, S/N = 10) for six pesticides. The relative standard deviations (RSD) of single fiber and different batches of fibers were 0.4–4.8 % and 0.6–5.3 %, respectively. In addition, compared with the commercial SPME fiber, the fiber showed better enrichment ability and extraction efficiency for pesticides, which might be due to the solid π-π accumulation, hydrophobic interaction, abundant adsorption sites, and hydrogen bonding between the coating and the target analyte. Besides, the hollow structure of the composite material, the rare earth metal oxide CeO 2 on the surface of the coating, and the silicone sealant all played a crucial role in the extraction process. Finally, the method had been successfully applied to determine the pesticides in real water samples, with the recovery rate ranging from 80.1 % to 108.2 % and RSD < 5.67 %. The experimental results showed that the Ss/ZnO@CeO 2 with a hollow core–shell structure had great application potential as a composite coating for solid-phase microextraction.

Facile one-step synthesis of graphene oxide/polyhedral oligomeric silsesquioxane composite-coated fiber for high-efficiency solid-phase microextraction of polycyclic musks

Efficient fabrication of excellent fiber coatings for high-performance solid-phase microextraction (SPME) is interesting. Here, a high-efficiency synthesis strategy on graphene oxide/polyhedral oligomeric silsesquioxane (GO/POSS) composite-coated fiber was exploited via an ultra-fast UV polymerization in one step, and applied to excellent SPME of polycyclic musks (PCMs). Using methacryloxy siloxane-grafted GO and POSS-methacryl substituted (POSS-MA) as functional monomers, a facile and direct UV polymerization of multiple reactions including alkenyl radical reaction and thiol-ene click chemistry was fulfilled on thiol-pretreated fiber in only 5min without tedious process. Characteristics such as morphology, FT-IR, XPS, BET and TG of fiber coating were studied in detail, as well as the SPME performance. Attributing to the rigid stereo conformation of POSS and large conjugate plane of GO-based nanosheet, the significant surface area, high hydrophobicity and intrinsic π-π interactions were adopted in fiber coating. In comparison of commercial SPME fibers, POSS-based or GO-based SPME fibers, a superior extraction performance towards PCMs was achieved with GO/POSS-coated fiber. High-efficiency extraction of PCMs was gained with prominent enrichment factors and the sensitive detection limits of PCMs were of 0.04-0.12ng/L. In particular, the extraction efficiency was robust and still maintained a high level above 93% for PCMs even after 150 cycle's applications. Good recoveries of PCMs reached 86.6%-102.1% and 86.7%-101.3% in river water and cosmetic samples, respectively. It lights an attractive approach to efficiently fabricating robust GO/POSS-coated fiber for high-performance SPME of PCMs.

Ultrasound-assisted one-step reduction and self-assembly of carbon dots-reduced graphene oxide: Mechanism investigation and solid phase microextraction of ultra-trace organochlorine pesticides

• CDs/RGO composites were fabricated by ultrasound-assisted one-step reduction and self-assembly of CDs and GO. • The potential reduction mechanisms were confirmed by DFT caculations. • CDs/RGO presented excellent solid phase microextraction performance for OCPs. In this work, carbon dots-reduction graphene oxide (CDs/RGO) composite was synthesized by a facile and green strategy with one-step reduction and self-assembly of GO and CDs under ultrasonic treatment. CDs was successfully applied to reduce GO to RGO, and anchored on the surface of RGO simultaneously under ultrasonic treatment within 20 min. The reduction mechanism was demonstrated by density functional theory calculations, which confirmed the electron transfer from CDs to GO and supplemented the reduction mechanism of GO by CDs. Characterizations results showed that the as-prepared CDs/RGO composite exhibited lamellar spacing and wrinkled structures, and abundant chemical groups in comparison to RGO reduced by sodium borohydride. In view of excellent morphology and chemical structures, the CDs/RGO composite was used for the first time in extraction and determination of ultra-trace organochlorine pesticides (OCPs) from water by means of solid phase microextraction (SPME) coupled with gas chromatography-mass spectrometry. The CDs/RGO coating presented superior extraction capacities for OCPs compared with commercial SPME coatings and sodium borohydride reduced RGO. The proposed analytical method exhibited high sensitivity with detection limit of 0.003–0.051 ng L -1 , excellent linearity in concentration range of 0.050–2500 ng L -1 , and satisfactory precision for seven OCPs. The excellent performances made the proposed method to be applied in determination of ultra-trace OCPs in real water successfully. This work proposed a green approach to synthesize CDs/RGO composite and a potential coating sorbent for SPME.

Mussel Inspired Polydopamine as Silica Fibers Coating for Solid-Phase Microextraction

Commercial solid-phase microextraction fibers are available in a limited number of expensive coatings, which often contain environmentally harmful substances. Consequently, several different approaches have been used in the attempt to develop new sorbents that should possess intrinsic characteristics such as duration, selectivity, stability, and eco-friendliness. Herein we reported a straightforward, green, and easy coating method of silica fibers for solid-phase microextraction with polydopamine (PDA), an adhesive, biocompatible organic polymer that is easily produced by oxidative polymerization of dopamine in mild basic aqueous conditions. After FT-ATR and SEM characterization, the PDA fibers were tested via chromatographic analyses performed on UHPLC system using biphenyl and benzo(a)pyrene as model compounds, and their performances were compared with those of some commercial fibers. The new PDA fiber was finally used for the determination of selected PAHs in soot samples and the results compared with those obtained using the commercial PA fiber. Good reproducibility, extraction stability, and linearity were obtained using the PDA coating, which proved to be a very promising new material for SPME.

Comparison of four commercial solid-phase micro-extraction (SPME) fibres for the headspace characterisation and profiling of gunshot exhausts in spent cartridge casings

Headspace solid-phase micro-extraction (SPME) is a promising technique for the characterisation and profiling of gunshot exhausts in spent cartridge casings, especially for health and environmental risk assessments, as well as forensic purposes. To date, however, no comprehensive investigation has been carried out to objectively assess the kinds of compound released during a discharge that can be recovered by this approach, the selectivity of the main commercially available fibres, and their relative performances for the analysis of gunshot exhausts and the discrimination of different ammunition types. This study aimed to fill this gap. Gunshot exhausts in spent cartridge casings from four different ammunition types were analysed by GC–MS, after extraction with four different commercial fibres: 100 μm polydimethylsiloxane (PDMS), 85 μm polyacrylate (PA), 65 μm polydimethylsiloxane/divinylbenzene (DVB), and 85 μm carboxen/polydimethylsiloxane (CAR). Results showed that, overall, a total of 120 analytes could be observed across the cartridges, but the different tested fibres also displayed distinct performances, which were, to some extent, complementary for the characterisation of gunshot exhausts. DVB, in particular, recovered the most compounds simultaneously. On the other hand, the observed variability between measurements was also high, making it a poor candidate for (semi-)quantitative applications (e.g. estimation of time since discharge and/or source profiling). In this regard, PA demonstrated the highest potential for broad use and implementation in multi-purpose methods.

Preparation of a Novel Solid Phase Microextraction Fiber for Headspace GC-MS Analysis of Hazardous Odorants in Landfill Leachate

The practice of odorant analysis can often be very challenging because odorants are usually composed of a host of volatile organic compounds (VOCs) at low concentrations. Preconcentration with solid phase microextraction (SPME) is a conventional technique for the enrichment of these volatile compounds before analysis by headspace gas chromatography-mass spectrometry (GC-MS). However, commercially available SPME products usually bear the defects of weak mechanical strength and high cost. In this work, novel SPME fibers were prepared by a one-pot synthesis procedure from divinylbenzene (DVB), porous carbon powder (Carbon) and polydimethylsiloxane (PDMS). Factors that influence the extraction efficiency, such as extraction temperature, extraction time, salting effects, pH, stirring rate, desorption temperature and time, were optimized. VOCs in landfills pose a great threat to human health and the environment. The new SPME fibers were successfully applied in the analysis of VOCs from the leachate of a cyanobacteria landfill. Quantification methods of major odor contributors were established, and a good linearity (r &gt; 0.998) was obtained, with detection limits in the range of 0.30–0.50 ng/L. Compared to commercial SPME fibers, the new material has higher extraction efficacy and higher precision. Hence, it is suitable for the determination of hazardous odorants of various sources.

Integration of a micropreconcentrator with solid-phase microextraction for analysis of trace volatile organic compounds by gas chromatography-mass spectrometry

The analysis of toxic volatile organic compounds (VOCs) in environmental air is important because toxic VOCs induce adverse effects on human health. Although gas chromatography- mass spectrometry (GC-MS) is the standard instrument for analysis of trace VOCs in air, this mode of analysis requires preconcentration and cryogenic processes. The preconcentration and subsequent thermal desorption of VOCs require special instruments and a long time of processing sample that significantly limit applications of GC-MS for monitoring indoor and outdoor VOC levels. Using a microfabricated preconcentrator for VOC analysis also has the challenge of a large sample volume for concentration. Using solid-phase microextraction (SPME) for VOC analysis by GC-MS often approaches the limit of detection of the GC-MS instrument for trace VOCs in air. This work reports a simple method to integrate microfabricated preconcentrators with commercial SPME fibers in a two-stage concentration processes to achieve rapid and reliable measurement of trace VOCs in air by GC-MS. We designed and fabricated a preconcentrator with micropillars in a microfluidic chamber to support sorbents and to increase the heat transfer rate to the sorbents for rapid thermal desorption. The effects of air flow rates through the preconcentrator on VOCs adsorption and thermal desorption were optimized for increasing analytical accuracy of VOCs measurements. The integration of a micropreconcentrator with SPME enabled measurements of sub-ppb levels of benzene, toluene, ethylbenzene, and xylene (BTEX), and trichloroethylene (TCE) in environmental air by GC-MS.

Lotus-like Ni@NiO nanoparticles embedded porous carbon derived from MOF-74/cellulose nanocrystal hybrids as solid phase microextraction coating for ultrasensitive determination of chlorobenzenes from water

Lotus-like Ni@NiO embedded porous carbons (Ni@NiO/PCs) were fabricated by pyrolysis of MOF-74/cellulose nanocrystal hybrids, and used as a solid phase microextraction (SPME) coating for ultrasensitive determination of chlorobenzenes (CBs) from water combined with gas chromatography-mass spectrometry. Owing to its abundant chemical groups, high porosity, and excellent thermal stability, the as-prepared Ni@NiO/PCs presented superior extraction performance compared to commercial SPME coatings. Notably, Ni@NiO/PCs derived from MOF-74/CNC hybrids presented higher extraction efficiencies towards CBs than that derived from pristine CNC and MOF-74 due to the formation of micro/mesopores and more abundant oxygen-containing groups. Under the optimum extraction conditions, the proposed analytical method presented wide linearity range (0.5-1500ngL-1), ultra-low detection of limit (0.005-0.049ngL-1), and excellent precision with relative standard deviations of 4.7-9.2% for a single fiber and 8.8-10.9% for 5 fibers, and long lifetime (≥160 times). The proposed analytical method was finally applied for determination of CBs from real water samples, and the recoveries were in the range of 93.2-116.8% towards eight CBs. This study delivered a novel and efficient sorbent as SPME coating to extraction and determination of CBs from water.

Ketoenamine Covalent Organic Framework Coating for Efficient Solid-Phase Microextraction of Trace Organochlorine Pesticides.

Fiber coating is a key part of solid-phase microextraction (SPME) technology, and it determines the selectivity, sensitivity, and reproducibility of the analytical method. A ketoenamine covalent organic framework called Tp-Azo-COF with rich electronegative N atoms was prepared as an SPME coating in this work. The Tp-Azo-COF coating had a large surface area of 1218 m2 g-1 and good thermal and chemical stability, and it was applied for the extraction of organochlorine pesticides (OCPs). According to quantum chemistry calculations, the adsorption affinity of the Tp-Azo-COF coating for five OCPs was primarily affected by the halogen bond and hydrophobicity interaction. The extraction efficiencies of the Tp-Azo-COF coating for five OCPs were higher than those of three commercial SPME fiber coatings, and the enrichment factors ranged from 1061 to 3693. When combined with gas chromatography-tandem mass spectrometry, a wide linear range (0.1-1000 ng L-1), low limits of detection (0.002-0.08 ng L-1), and good fiber-to-fiber accuracy (4.3-10.9%) were achieved under optimal conditions. Moreover, the applicability of the developed method was evaluated by analyzing four samples (milk, green tea, tap water, and well water), and the recoveries were in the range of 83.4-101.6%, with relative standard deviations <8.6%. This research extends the application of the stabilized ketoenamine COF as a sample enrichment probe for OCP analysis.

Nitrogen-doped porous biochar derived from marine algae for efficient solid-phase microextraction of chlorobenzenes from aqueous solution

Nitrogen-doped porous biochar (NPB) with a large specific surface area, wide pore size distribution, graphitized structure, nitrogen doping, and hydrophobicity was fabricated by high-temperature modification of algal biochar with potassium carbonate. This NPB was then uniformly coated on stainless steel wire as a novel solid-phase microextraction (SPME) fiber. The extraction efficiency of NPB-coated fiber for seven chlorobenzenes (CBs) was excellent; it was 1.0-112.2 times higher than that of commercial SPME fibers. A trace determination method was developed for seven CBs in water with the optimized extraction conditions by NPB-coated fiber and gas chromatography-electron capture detector, which showed wide linear ranges (1-1000ngL-1), low detection limits (0.007-0.079ngL-1), great repeatability (2.5-6.5% for intra-day, and 3.1-6.8% for inter-day), and excellent reproducibility (3.5-6.3%, n=5). The practicality of the developed method was evaluated using real water samples and showed great recoveries (89.55-105.19%). This study showed that low-cost biomass wastes could be converted to advanced biochar materials by a facile method, and displayed excellent performance in SPME applications.

Sputtered silicon solid phase microextraction fibers with a polydimethylsiloxane stationary phase with negligible carry-over and phase bleed

We report the preparation of high performance, sputtered, polydimethylsiloxane (PDMS)-coated solid phase microextraction (SPME) fibers that show negligible carry-over and phase bleed. This process involves sputtering silicon onto silica fibers and functionalizing the resulting porous nanostructures with ultrathin films of vapor-deposited PDMS. Different thicknesses of silicon (0.25, 0.8, and 1.8µm) and PDMS (8, 16, and 36nm) were produced and their extraction efficiencies evaluated. The deposition of PDMS was confirmed by time-of-fight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), and contact angle goniometry on model, planar silicon substrates. These fibers were investigated using direct immersion SPME coupled with gas chromatography-mass spectrometry (GC-MS) analysis of a series of polycyclic aromatic hydrocarbons (PAHs), which are carcinogenic pollutants. The 1.8µm thick silicon coating with 16nm of PDMS (Si (1.8µm)/PDMS (16nm)) produced the best response among the combinations tested. Conditions for the extraction of PAHs with this fiber were optimized and its extraction performance was compared to that of a commercial 7μm PDMS fiber. The linearity (1-110µgL-1), repeatability (RSD%, n=3) (17% ave.), and minimum detection limits (0.6-1.5µgL-1) of the sputtered fibers were determined and found to be superior to the commercial 7µm PDMS fiber in many respects. Carry-over and phase bleed from commercial PDMS-based SPME fibers are two of their major drawbacks, which decrease their lifetimes and usefulness. Minimal carry-over and phase bleed were observed for our sputtered PDMS-coated fibers. In particular, our fiber only shows 12% of the phase bleed of the comparable commercial fiber. In addition, it shows no carry-over for analytes with retention times greater than pyrene, and only 5% of the carry-over of the other analytes. Our fibers could be used for at least 300 injections without any significant loss of performance.