Investigation of operational fundamentals for vacuum-assisted headspace high-capacity solid-phase microextraction and gas chromatographic analysis of semivolatile compounds from a model solid sample.

Vacuum-assisted headspace solid-phase microextraction (Vac-HS-SPME) is a technique used to enhance SPME sampling of semi-volatile organic compounds. Here, it was combined with a high-capacity SPME Arrow, which features a larger volume of extraction phase and a more rugged configuration than traditional extraction fibers. An in-depth assessment of the critical parameters was conducted to achieve optimal extraction of representative compounds from a model solid sample matrix (Ottawa sand). Operational fundamentals investigated included the types of seals needed to create a leak-free environment under vacuum conditions; the magnitude of the vacuum applied and time needed to activate the Vac kinetics; order of sample vial preparation methods (VPMs); and other standard variables associated with extract analysis by gas chromatography-mass spectrometry. When exploring the limits of sample VPMs, results indicated an ideal workflow requires the solid sample to be spiked before sealing the vial, allow the sample to rest overnight, then apply vacuum at a pressure of -677 mbar (out of -789 mbar maximum possible vacuum with pump and compressor used), exerted on the vial for 90 s. This work provides the necessary workflow for the optimization of Vac-HS-SPME sampling of analytes from solid matrices.

6-Phenylhexyl silane derivatized, sputtered silicon solid phase microextraction fiber for the parts-per-trillion detection of polyaromatic hydrocarbons in water and baby formula.

We report the fabrication of 6-phenylhexylsilane derivatized, sputtered silicon, solid phase microextraction fibers that show parts per trillion detection limits for polyaromatic hydrocarbons, and negligible carry over and phase bleed. Their fabrication involves sputtering silicon on silica fibers under various conditions. Six different fibers were evaluated by generating three different thicknesses of sputtered silicon at two different throw distances, which altered the morphologies of the silicon surfaces. All of the fibers were coated with similar thicknesses of 6-phenylhexylsilane (ca. 2 nm). These fibers were characterized with multiple analytical techniques. The optimum fiber configuration was then used to analyze polyaromatic hydrocarbons via direct immersion, gas chromatography mass spectrometry. Our best fiber for the extraction of low molecular weight polyaromatic hydrocarbons in water had similar performance to that of a commercial fiber. However, our fiber demonstrated ca. 3 times the extraction efficiency for higher molecular weight polyaromatic hydrocarbons. In addition, it outperformed the commercial fiber by showing better linearity, repeatability, and detection limits. A method for analyzing polyaromatic hydrocarbons in baby formula was developed, which showed very good linearity (0.5-125 ppb), repeatability (2-26%), detection limits (0.12-0.81 ppb), and recoveries (103-135%). In addition, our fiber showed much less (negligible) carry over and phase bleed than the commercially available fibers.

Accelerated Solvent Extraction of Terpenes in Cannabis Coupled With Various Injection Techniques for GC-MS Analysis.

The cannabis market is expanding exponentially in the United States. As state-wide legalization increases, so do demands for analytical testing methodologies. One of the main tests conducted on cannabis products is the analysis for terpenes. This research focused on implementation of accelerated solvent extraction (ASE), utilizing surrogate matrix matching, and evaluation of traditional vs. more modern sample introduction techniques for analyzing terpenes via gas chromatography-mass spectrometry (GC-MS). Introduction techniques included Headspace-Syringe (HS-Syringe), HS-Solid Phase Microextraction Arrow (HS-SPME Arrow), Direct Immersion-SPME Arrow (DI-SPME Arrow), and Liquid Injection-Syringe (LI-Syringe). The LI-Syringe approach was deemed the most straightforward and robust method with terpene working ranges of 0.04-5.12 µg/mL; r 2 values of 0.988-0.996 (0.993 average); limit of quantitation values of 0.017-0.129 µg/mL (0.047 average); analytical precisions of 2.58-9.64% RSD (1.56 average); overall ASE-LI-Syringe-GC-MS method precisions of 1.73-14.6% RSD (4.97 average); and % recoveries of 84.6-98.9% (90.2 average) for the 23 terpenes of interest. Sample workflows and results are discussed, with an evaluation of the advantages/limitations of each approach and opportunities for future work.

Analysis of the California list of pesticides, mycotoxins, and cannabinoids in chocolate using liquid chromatography and low-pressure gas chromatography-based platforms.

Cannabis legalization has led to the development of a variety of cannabis-infused products with edibles being one of the most popular. The state of California has implemented comprehensive cannabis testing regulations requiring the analysis of cannabinoids (potency) and contaminants, such as pesticides and mycotoxins, in any type of cannabis good. In this work, we propose an analytical workflow for the quantification of the California list of pesticides and mycotoxins, as well as six cannabinoids, in chocolate, using 3 mL of solvent for the extraction. For the analysis of pesticides and mycotoxins, clean-up steps employing a C18 solid-phase extraction cartridge and dispersive solid-phase extraction sorbents were implemented. Gas chromatography amenable pesticides were analyzed using low-pressure gas chromatography coupled to tandem mass spectrometry which allowed for a total method run of 12 min. Both liquid chromatography and gas chromatography instrumental methods had the same analysis time, ensuring satisfactory sample throughput. For the determination of cannabinoids, a dilution of the original organic extract collected for pesticides and mycotoxins analysis (and prior to any clean-up step) was used. Excellent results in terms of analytical figures of merit were obtained for all target analytes.

Electronic cigarette solutions and resultant aerosol profiles.

Electronic cigarettes (e-cigarettes) are growing in popularity exponentially. Despite their ever-growing acceptance, their aerosol has not been fully characterized. The current study focused on evaluating e-cigarette solutions and their resultant aerosol for potential differences. A simple sampling device was developed to draw e-cigarette aerosol into a multi-sorbent thermal desorption (TD) tube, which was then thermally extracted and analyzed via a gas chromatography (GC) mass spectrometry (GC-MS) method. This novel application provided detectable levels of over one hundred fifteen volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) from a single 40mL puff. The aerosol profiles from four commercially available e-cigarettes were compared to their respective solution profiles with the same GC-MS method. Solution profiles produced upwards of sixty four unidentified and identified (some only tentatively) constituents and aerosol profiles produced upwards of eighty two compounds. Results demonstrated distinct analyte profiles between liquid and aerosol samples. Most notably, formaldehyde, acetaldehyde, acrolein, and siloxanes were found in the aerosol profiles; however, these compounds were never present in the solutions. These results implicate the aerosolization process in the formation of compounds not found in solutions; have potential implications for human health; and stress the need for an emphasis on electronic cigarette aerosol testing.