Nonterpenoid Chemical Diversity of Cannabis Phenotypes Predicts Differentiated Aroma Characteristics.

The recent increase in legality of Cannabis Sativa L. has led to interest in developing new varieties with unique aromatic or effect-driven traits. Selectively breeding plants for the genetic stability and consistency of their secondary metabolite profiles is one application of phenotyping. While this horticultural process is used extensively in the cannabis industry, few studies exist examining the chemical data that may differentiate phenotypes aromatically. To gain insight into the diversity of secondary metabolite profiles between progeny, we analyzed five ice water hash rosin extracts created from five different phenotypes of the same crossing using comprehensive 2-dimensional gas chromatography coupled to time-of-flight mass spectrometry, flame ionization detection, and sulfur chemiluminescence detection. These results were then correlated to results from a human sensory panel, which revealed specific low-concentration compounds that strongly influence sensory perception. We found aroma differences between certain phenotypes that are driven by key minor, nonterpenoid compounds, including the newly reported 3-mercaptohexyl hexanoate. We further report the identification of octanoic and decanoic acids, which are implicated in the production of cheese-like aromas in cannabis. These results establish that even genetically similar phenotypes can possess diverse and distinct aromas arising not from the dominant terpenes, but rather from key minor volatile compounds. Moreover, our study underscores the value of detailed chemical analyses in enhancing cannabis selective breeding practices, offering insights into the chemical basis of aroma and sensory differences.

Minor, Nonterpenoid Volatile Compounds Drive the Aroma Differences of Exotic Cannabis.

Cannabis sativa L. produces a wide variety of volatile secondary metabolites that contribute to its unique aroma. The major volatile constituents include monoterpenes, sesquiterpenes, and their oxygenated derivates. In particular, the compounds ß-myrcene, D-(+)-limonene, ß-caryophyllene, and terpinolene are often found in greatest amounts, which has led to their use in chemotaxonomic classification schemes and legal Cannabis sativa L. product labeling. While these compounds contribute to the characteristic aroma of Cannabis sativa L. and may help differentiate varieties on a broad level, their importance in producing specific aromas is not well understood. Here, we show that across Cannabis sativa L. varieties with divergent aromas, terpene expression remains remarkably similar, indicating their benign contribution to these unique, specific scents. Instead, we found that many minor, nonterpenoid compounds correlate strongly with nonprototypical sweet or savory aromas produced by Cannabis sativa L. Coupling sensory studies to our chemical analysis, we derive correlations between groups of compounds, or in some cases, individual compounds, that produce many of these diverse scents. In particular, we identified a new class of volatile sulfur compounds (VSCs) containing the 3-mercaptohexyl functional group responsible for the distinct citrus aromas in certain varieties and skatole (3-methylindole) as the key source of the chemical aroma in others. Our results provide not only a rich understanding of the chemistry of Cannabis sativa L. but also highlight how the importance of terpenes in the context of the aroma of Cannabis sativa L. has been overemphasized.

Direct immersion thin film solid phase microextraction of polychlorinated n-alkanes in cod liver oil.

A thin film-solid phase microextraction (TF-SPME) method was developed to test for 5 individual polychlorinated n-alkanes (PCAs) from commercial cod liver oil samples. This was accomplished by preparing a novel aluminum supported, hydrophilic-lipophilic balance/polydimethylsiloxane (HLB/PDMS) TF-SPME device that enabled direct immersion extraction from fish oil. Matrix-matched calibration gave a linear range from 0.075 µg/g to 0.75 µg/g with method limits of quantitation (MLOQ) ranging from 0.07 µg/g to 0.217 µg/g in oil. Standard addition calibration was performed using other fish oils demonstrating comparable slope to the external calibration. As a proof of concept, four fish oil brands were tested for contaminants; 1,1,1,3-tetrachlorodecane, 1,2,9,10-tetrachlorodecane, 1,2,13,14-tetrachlorotetradecane, and 1,1,1,3,14,15-hexachloropentadecane were detected above the MLOQ but below the range provided by the Stockholm Convention. This method provides an effective approach for cleanup and preconcentration of PCAs from oily matrices using inexpensive, and reusable microextraction devices that limit environmental impact of the sample preparation protocol.

Overcoming matrix effects in the analysis of pyrethroids in honey by a fully automated direct immersion solid-phase microextraction method using a matrix-compatible fiber.

Pyrethroids insecticides may constitute a major hazard to honeybees, leading to colony collapse disorder. However, the determination of pyrethroids in honey has remained a challenging undertaking for analysts to date due to the high complexity of this matrix as well as the MRLs. This paper presents a fully automated method to overcome matrix influences using matrix-compatible overcoated SPME fiber for quantitative analysis of pyrethroids in diluted honey by GC-MS. The developed method was optimized using a multivariate approach providing LOQ values much lower than the stablished MRL (0.10-10 ng/g), while granting satisfactory linearity (R2 > 0.998) in a wide linear range of 0.1-2000 ng/g, repeatability with RSDs < 10%, reproducibility RSDs < 20%, and accuracy ranging from 75 to 118% and from 82 to 120 % for inter-day and intra-day assays, respectively by using five replicates. The method herein proposed overcomes challenges presented by complex matrices while minimizing sample handling and the overall complexity of the procedure.

Comprehensive Analysis of Multiresidue Pesticides from Process Water Obtained from Wastewater Treatment Facilities Using Solid-Phase Microextraction.

A novel magnetic blade spray-tandem mass spectrometry (MBS-MS/MS) assay was developed and optimized, and its performance was characterized for the analysis of 204 pesticides from wastewater treatment facility (WWTF) process water. These results were compared and experimentally validated with an untargeted, high-resolution MS (HRMS) approach that employed liquid chromatography (LC)-amenable thin-film microextraction (TFME) devices to further elucidate the fate of pesticides through the WWTF process. As a result of our optimizations, we report an optimized workflow with an extraction time of 10 min, 150 µg of magnetic HLB particles, and 5 s of desorption. Excellent linearity was obtained for 168 of the 204 pesticides in deionized water, where 90% of the quantifiable pesticides had a determination coefficient (R2) of 0.99 across 3 orders of magnitude and 80% had limits of quantification below 0.5 ng/mL. We subsequently applied our optimized MBS-MS/MS method for the analysis of samples collected during the various stages of wastewater treatment from two WWTFs in Southern Ontario. This article presents a new streamlined methodology with a fast turnaround time for analyzing a large panel of pesticides, ultimately providing us the opportunity to evaluate the performance of two WWTFs for their efficacy in removing these toxic chemicals.

Development and validation of an improved, thin film solid phase microextraction based, standard gas generating vial for the repeatable generation of gaseous standards.

This work presents the development and validation of novel thin film solid phase micro extraction (TF-SPME) based standard gas generating vials suitable for repeatable generation of gaseous standards for GC-MS analysis and quality control. The vials were developed using carbon mesh membranes loaded with pure polydimethylsiloxane (PDMS), divinylbenzene (DVB/PDMS), hydrophilic-lipophilic balance (HLB/PDMS), and carboxen (Car/PDMS) sorbents that were then spiked with modified McReynolds standards including benzene, 2-pentanone, 1-nitropropane, pyridine, 1-pentanol, octane, dodecane, and hexadecane. Sorbent strength was determined to follow the aforementioned order, with pure PDMS presenting the weakest sorption capabilities and Car/PDMS the strongest. While the weaker, pure PDMS based gas generating vials transferred an instrument-overloading amount of McReynolds probes to the 1.1 mm DVB/PDMS SPME arrows used for extraction, vials prepared using Car/PDMS TF-SPME as a sorbent failed to provide consistently detectable amounts of analytes less volatile than 1-nitropropane. The DVB/PDMS and HLB/PDMS based vials were found to maintain optimal sorption capabilities for the tested analytes, providing a sorption strength strong enough to not exhibit any depletion in 10 replicate runs, while still delivering a consistent amount of all the regular McReynolds components. Moreover, with intra-vial%RSDs of 5% or less for all analytes tested, these HLB and DVB vials were found to deliver very good repeatability. After purposely submitting vials to 200 accelerated depletion extractions (1.1 mm DVB/PDMS arrow at 55 °C for 3 min), vials prepared with DVB/PDMS were found to deplete by 33%, 38%, 34%, 33%, 40%, and 33% while vials prepared with HLB/PDMS were found to deplete by 21%, 16%, 12%, 31%, 16% and 0% for benzene, 2-pentanone, 1-nitropropane, pyridine, 1-pentanol, and octane, respectively. When user typical extractions conditions were used instead (50/30 µm DVB/Car/PDMS SPME fiber at 35 °C for 1 min), no depletion could be observed from the HLB/PDMS based vial while%RSDs ranged from 1.1-3.0% after the 300 extraction/desorption cycles. Finally, in efforts to demonstrate its real world applicability, the DVB/PDMS vial was used to evaluate the inter-fiber repeatability of commercial DVB/PDMS SPME arrows, with results demonstrating that arrows from a single package were statistically similar (ANOVA at 95% confidence).

Development of a Drone-Based Thin-Film Solid-Phase Microextraction Water Sampler to Facilitate On-Site Screening of Environmental Pollutants.

To simplify on-site water sampling and screening, particularly in hard-to-reach or dangerous sites, a drone equipped with a hydrophilic-lipophilic balance (HLB), thin-film solid-phase microextraction (TF-SPME) sampler was developed. The drone-based sampler was shown to protect the sorbent phase from external contamination while preventing any detectable loss of components of a spiked modified McReynolds mixture on the membrane in the sampler for at least 10 min. HLB/poly(dimethylsiloxane) (PDMS) membranes deployed in flight on the drone sampler were demonstrated to extract disinfection by-products, including trichloromethane, dichloroacetonitrile, 1,1,1-trichloro-2-propanone, 2,2,2-trichloroethanol, benzonitrile, and benzyl nitrile, from hot tub water. When analyzed on-site, in duplicate, using hand-portable instrumentation, reasonably repeatable results were achieved (%relative standard deviations (RSD's) 5-16%). Finally, drone TF-SPME sampling of an anthropogenically impacted watercourse indicated that impact from the suspected nearby landfill site was minimal, instead suggesting that internal combustion by-products from vehicles on the nearby Highway 401 played a much larger role in contaminating the watercourse. This conclusion was supported by the confirmed presence of BTEX, styrene, isopropylbenzene, propylbenzene, and 1,3,5-trimethylbenzene. In addition to immediately identifying these compounds on-site using portable gas chromatography-mass spectrometry (GC-MS), samples were taken back to the laboratory for benchtop analysis, further supporting this conclusion.

Development of thin-film solid-phase microextraction coating and method for determination of artificial sweeteners in surface waters.

A semi-automated and sensitive method was developed for simultaneous determination of the six most consumed artificial sweeteners (AS) in surface waters using thin-film solid-phase microextraction (TF-SPME) and high-performance liquid chromatography (HPLC). A triple quadrupole mass spectrometer and an electrospray ionization source (ESI-MS) run in negative ionization and multiple reaction monitoring modes were employed for instrumental analysis. The TF-SPME method was optimized for the extraction phase, sample pH, desorption solvent, extraction time, and desorption time. In-house-synthetized-hydrophilic-lipophilic balance weak anion exchange (HLB-WAX) particles imbedded within a polyacrylonitrile (PAN) binder were selected as the extraction phase for the thin-film coating due to their cost-effectiveness and enhanced sensitivity for artificial sweeteners. Suitable analytical parameters that include linearity (R2 > 0.9914), recovery > 80%, inter, and intra-reproducibility less than 18% were obtained for the AS compounds studied. The developed method estimated limits of detection (LODs) ranging from 0.004 to 0.038 ng mL-1 The SPME method was successfully applied for the determination of ultra-trace levels of AS in water samples collected from Grand River (Ontario, Canada), downstream of three municipal wastewater treatment plants (WWTPs). Concentrations ranging from 0.03 to 20.3 ng mL-1 were found for the AS compounds studied.

Unique Solid Phase Microextraction Sampler Reveals Distinctive Biogeochemical Profiles among Various Deep-Sea Hydrothermal Vents.

Current methods for biochemical and biogeochemical analysis of the deep-sea hydrothermal vent ecosystems rely on water sample recovery, or in situ analysis using underwater instruments with limited range of analyte detection and limited sensitivity. Even in cases where large quantities of sample are recovered, labile dissolved organic compounds may not be detected due to time delays between sampling and preservation. Here, we present a novel approach for in situ extraction of organic compounds from hydrothermal vent fluids through a unique solid phase microextraction (SPME) sampler. These samplers were deployed to sample effluent of vents on sulphide chimneys, located on Axial Seamount in the North-East Pacific, in the Urashima field on the southern Mariana back-arc, and at the Hafa Adai site in the central Mariana back-arc. Among the compounds that were extracted, a wide range of unique organic compounds, including labile dissolved organic sulfur compounds, were detected through high-resolution LC-MS/MS, among which were biomarkers of anammox bacteria, fungi, and lower animals. This report is the first to show that SPME can contribute to a broader understanding of deep sea ecology and biogeochemical cycles in hydrothermal vent ecosystems.

Recent advances in breath analysis to track human health by new enrichment technologies.

Detection of biomarkers in exhaled breath has been gaining increasing attention as a tool for diagnosis of specific diseases. However, rapid and accurate quantification of biomarkers associated with specific diseases requires the use of analytical methods capable of fast sampling and preconcentration from breath matrix. In this regard, solid phase microextraction and needle trap technology are becoming increasingly popular in the field of breath analysis due to the unique benefits imparted by such methods, such as the integration of sampling, extraction, and preconcentration in a single step. This review discusses recent advances in breath analysis using these sample preparation techniques, providing a summary of recent developments of analytical methods based on breath volatile organic compounds analysis, including the successful identification of various biomarkers related to human diseases.

Introducing a mechanically robust SPME sampler for the on-site sampling and extraction of a wide range of untargeted pollutants in environmental waters.

The present study introduces a mechanically robust, sealable SPME sampler for the on-site sampling and extraction of a wide range of untargeted pollutants in environmental waters. Spray-coating and dip coating methodologies were used to coat the surfaces of six stainless steel bolts with a layer of HLB/PAN particles, which served as the extractive substrate in the proposed device. In addition, this sampler was designed to withstand rough handling, long storage times, and various environmental conditions. In order to identify whether the sampler was able to stabilize extracted compounds for long periods of time, the effects of storage time and temperature were evaluated. The results of these tests showed no significant differences in the quantity and quality of the extracted chemicals following 12 days storage at room temperature, thus confirming the device's suitability for use at sampling sites that are far away from the laboratory facilities. The proposed device was also used to perform extraction and untargeted analyses of river waters in five different geographical locations. The constituent chemicals in the samplers were analyzed and determined using high-resolution HPLC-Orbitrap MS. Toxin and Toxin-Target Database was used as a reference database for toxins and environmental contaminants. Ultimately, over 80 tentative chemicals with widely varying hydrophobicities ranging within -2.43 < logP <11.9-including drugs, metabolites, wide ranges of toxins, pesticide, and insecticides-were identified in the samplers used in the different rivers. The log P values for the tentative analytes confirmed that the introduced device is suitable for the extraction and trace analysis of wide ranges of targeted and untargeted pollutants.

Development of a Hydrophilic Lipophilic Balanced Thin Film Solid Phase Microextraction Device for Balanced Determination of Volatile Organic Compounds.

A novel hydrophilic-lipophilic balanced (HLB) thin film solid-phase microextraction (TF-SPME) device is proposed for polarity-balanced determinations of volatile organic compounds. The proposed HLB particles used in the preparation of these membranes were prepared using a precipitation polymerization technique and determined to have a specific surface area of 335 m2/g with an average pore diameter of 13 Å. Membranes prepared from these particles were found to extract 1.8, 2.2, 1.9, 1.7, 2.0, and 1.3 times more benzene, 2-pentanone, 1-nitropropane, pyridine, 1-pentanol, and octane, respectively, than the established divinylbenzene/polydimethylsiloxane (DVB/PDMS)-based membranes. Furthermore, membranes prepared from these lab-made particles were shown to extract significantly ( p = 0.00047) larger amounts of these analytes than membranes prepared from comparative commercial HLB particles. The intermembrane extraction efficiency between 3 membranes was determined to be reproducible at 95% confidence for 4 different coating chemistries tested, including the DVB/PDMS membranes, and those prepared with 3 different HLB compositions. Furthermore, method reliability was established by confirming that, once extracted, modified McReynolds standards were stable on the HLB/PDMS membranes stored in thermal desorption tubes on an autosampler rack for at least 120 h, for 5 of the 6 standards, but only for 24 h for pyridine at a 95% level of confidence. Finally, using a TF-SPME enabled, portable GC/MS instrument, an entirely on-site proof of concept application was performed for the determination and quantitation of chlorination byproducts in a private hot tub, successfully identifying chloroform, bromodichloromethane, dichloroacetonitrile, chlorobenzene, benzonitrile, and benzyl chloride, while further quantifying chloroform and dichloroacetonitrile at levels of 270 and 79 ppb with %RSD values of 13% and 5%, respectively.

Development and validation of eco-friendly strategies based on thin film microextraction for water analysis.

The aim of the current study is the establishment of Green Analytical Chemistry strategies for water analysis by elimination/reduction of hazardous chemicals, energy consumption, and waste generation throughout the entire analytical workflow. The first approach introduced in this manuscript consists of addition of water to a sampling vessel that contains a thin film microextraction (TFME) device, followed by removal of the device after equilibration, and subsequent quantification of the extracted components by thermal desorption GC/MS. In this approach, namely the in-bottle TFME approach, analyte-loss associated errors that stem from analyte adherence to glass surfaces and/or degradation are avoided as extraction occurs in situ, while analytes are isolated from a complex matrix that contains degradation agents (bacteria, oxidizing or reducing species, etc.). This procedure also circumvents the splitting of original samples into sub-samples. The second approach involves the use of portable TFME devices that facilitate on-site extraction of compounds, therefore eliminating the use of collection vessels, a factor known to potentially introduce errors into analysis. The herein described procedure involves attachment of the TFME device to drill accessories, analyte extraction via direct immersion into sampled site, and subsequent on-site instrumental analysis, which is carried out with the use of a portable GC/MS containing an appropriate thermal desorption interface, or alternatively, by transferring the membrane to the laboratory for bench-top GC/MS analysis. To facilitate a better understanding of the processes governing the developed approaches, modeling by COMSOL Multiphysics® software was performed. The findings of this study were applied for further method optimization, and the optimized developed methods were then applied for on-site surface water analyses. Finally, the greenness of the developed methods was evaluated with use of the eco-scale assessment, with obtained scores compared to that of the US EPA 8270 method.

Deposition of a Sorbent into a Recession on a Solid Support To Provide a New, Mechanically Robust Solid-Phase Microextraction Device.

To date, solid-phase microextraction (SPME) fibers used for in vivo bioanalysis can be too fragile and flexible, which limits suitability for direct tissue sampling. As a result, these devices often require a sheathing needle to prepuncture robust sample matrixes and protect the extraction phase from mechanical damage. To address this limitation, a new SPME device is herein presented which incorporates an extraction phase recessed into the body of a solid needle. This device requires no additional support or shielding during puncture events through protective tissue. The presented device was thoroughly tested, being fired at 90 m·s-1 through fish scales, forced through vial septa, and employed in a targeted study of polyunsaturated fatty acids in salmon where the protective outer skin was repetitively punctured during sampling. Finally, the recessed SPME device was applied to an on-site application for the tissue analysis of wild muskellunge. With this advancement, rapid, minimally invasive, and easily executed in vivo SPME is now possible opening the door to near endless sampling opportunities.

Inter-laboratory validation of a thin film microextraction technique for determination of pesticides in surface water samples.

The primary goal of the present study is the inter-laboratory evaluation of a thin film microextraction (TFME) technique to be used as an alternative approach to liquid-liquid extraction (LLE). Polydimethylsiloxane/divinylbenzene (PDMS/DVB) and PDMS/DVB-carbon mesh supported membranes were used for the extraction of 23 targeted pesticides, while a thermal desorption unit (TDU) was employed to transfer these analytes to a GC/MS instrument for separation and detection. After optimization of the most critical parameters, both membranes were capable of achieving limits of detection (LOD) in the low ng L-1 range while demonstrating excellent robustness, withstanding up to 100 extractions/desorption cycles. Furthermore, limits of quantification (LOQ) between 0.025 and 0.50 µg L-1 were achieved for the 23 compounds selected from several classes of pesticides with a wide range of polarities. A wide linear range of 0.025-10.0 µg L-1 with strong correlation to response (R2 > 0.99) was attained for most of the studied analytes. Both membranes showed good accuracy and repeatability at three levels of concentration. Moreover, the method was also validated through blind split analyses of 18 surface water samples, collected within 3 months, using TFME at the University of Waterloo and LLE at Maxxam Analytics (Mississauga, ON) which is an accredited commercial analytical laboratory. Good agreement between the two methods was achieved with accuracy values ranging from 70 to 130%, for the majority of analytes in the samples collected. At the concentration levels investigated, 90% of the analytes were quantifiable by TFME, whereas only 53% of the compounds were reportable using the LLE method particularly at concentrations lower than 1 µg L-1. The comparison of TFME and LLE from several analytical aspects demonstrated that the novel TFME method gave similar accuracy to LLE, while providing additional advantages including higher sensitivity, lower sample volume, thus reduced waste production, and faster analytical throughput. Given the sensitivity, simplicity, low cost, accuracy, greenness and relatively fast procedure of TFME, it shows great potential for adoption in analytical laboratories as an alternative to LLE.

Solid Phase Microextraction On-Fiber Derivatization Using a Stable, Portable, and Reusable Pentafluorophenyl Hydrazine Standard Gas Generating Vial.

Solid phase microextraction (SPME) on-fiber derivatization methods have facilitated the achievement of lower detection limits and targeted analysis of various substances that exhibit poor chromatographic behavior, thermal instability, or high reactivity while limiting the use of organic solvents. However, previously developed on-fiber derivatization methods have been hindered by poor loading reproducibility and standard lifetime due to derivatization reagent reactivity. In addition, this reactivity often results in these reagents demonstrating toxic effects, complicating handling and standard formulation. To address this, a reusable standard gas generating vial containing pentafluorophenyl hydrazine (PFPH) has been developed. With this development, SPME fibers can now be reproducibly loaded with derivatization reagent, from an easy to use and safe platform. Validation of the vial using C4-C9 linear aldehyde standards as target analytes demonstrated intrabatch vial reproducibility (2% relative standard deviation (RSD), n = 4), along with PFPH headspace stability over a period of 11 weeks, facilitating reduced reagent consumption due to standard longevity. In addition, reproducibility of the derivatization reaction was observed over 1 week (RSD < 9%), and the linear concentration range was evaluated using headspace extractions from aqueous aldehyde solutions (R(2) > 0.996, 10-200 ppb v/v). Finally, the PFPH-generating vial was applied to the monitoring of volatile aldehydes generated during meat spoilage, as well as an on-site application where the free and total concentration of formaldehyde was determined in car exhaust using a portable GC/MS. To the best of our knowledge, the standard gas generating vial proposed in this work is the first documented device for the long-term storage of reusable headspace standards for a reactive, toxic, and otherwise unstable derivatization reagent standard.

Development of a Carbon Mesh Supported Thin Film Microextraction Membrane As a Means to Lower the Detection Limits of Benchtop and Portable GC/MS Instrumentation.

In this work, a durable and easy to handle thin film microextraction (TFME) device is reported. The membrane is comprised of poly(divinylbenzene) (DVB) resin particles suspended in a high-density polydimethylsiloxane (PDMS) glue, which is spread onto a carbon fiber mesh. The currently presented membrane was shown to exhibit a substantially lesser amount of siloxane bleed during thermal desorption, while providing a statistically similar extraction efficiency toward a broad spectrum of analytes varying in polarity when compared to an unsupported DVB/PDMS membrane of similar shape and size which was prepared with previously published methods. With the use of hand-portable GC-TMS instrumentation, membranes cut with dimensions 40 mm long by 4.85 mm wide and 40 ± 5 µm thick (per side) were shown to extract 21.2, 19.8, 18.5, 18,4, 26.8, and 23.7 times the amount of 2,4 dichlorophenol, 2,4,6 trichlorophenol, phorate D10, fonofos, chloropyrifos, and parathion, respectively, within 15 min from a 10 ppb aqueous solution as compared to a 65 µm DVB/PDMS solid phase microextraction (SPME) fiber. A portable high volume desorption module prototype was also evaluated and shown to be appropriate for the desorption of analytes with a volatility equal to or lesser than benzene when employed in conjunction with TFME membranes. Indeed, the coupling of these TFME devices to hand-portable gas chromatography toroidial ion trap mass spectrometry (GC-TMS) instrumentation was shown to push detection limits for these pesticides down to the hundreds of ppt levels, nearing that which can be achieved with benchtop instrumentation. Where these membranes can also be coupled to benchtop instrumentation it is reasonable to assume that detection limits could be pushed down even further. As a final proof of the concept, the first ever, entirely on-site TFME-GC-TMS analysis was performed at a construction impacted lake. Results had indicated the presence of contaminants such as toluene, ethylbenzene, xylene, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and tris(1-chloro-2-propyl)phosphate, which stood out from other naturally occurring compounds detected.

Development of a standard gas generating vial comprised of a silicon oil-polystyrene/divinylbenzene composite sorbent.

In this work, a highly reproducible standard gas generating vial is proposed. The vial is comprised of a silicon diffusion pump oil spiked with an appropriate calibration compound, such as modified McReynolds probes (benzene, 2-pentanone, pyridine, 1-nitropropane, 1-pentanol, and n-octane), and then mixed with polystyrene/divinylbenzene (PS/DVB) particles. The concentrations of these compounds in gaseous headspace were found to substantially decrease in comparison to previously developed hydrocarbon pump oil based vials; hence, the amount of standard loaded onto SPME fibers was at most, half that of the previous vial design. Depletion for all compounds after 208 successive extractions was shown to be less than 3.5%. Smaller quantities of standards being used resulted in a vial that depleted slower while remaining statistically repeatable over a wider number of runs. Indeed, it was found that depletion could be largely predicted by using a mass balance theoretical model. This behavior allowed a further increase in the number of loadings that could be performed repeatedly. At a 95% level of confidence, the ANOVA test demonstrated that the prepared vials were statistically identical, with no significant intra- or inter-batch differences. In addition, it was found that vials stored under different conditions (e.g. under light exposure, room temperature, and within a refrigerator) were stable over 10 weeks. Silicon based vials proved to be ideal for performing instrument quality control and loading of internal standards onto fibers, both of which are of great importance when performing on-site analysis using portable GC-MS instrumentation and high throughput determinations in laboratory.