In this work, the interconversion of GHB and GBL in a variety of aqueous media was studied. The effects of solution pH and time were determined by spiking GHB or GBL into pure water and buffered aqueous solutions, and determining the GHB and GBL contents at various time intervals. The degree of GBL hydrolysis to GHB was determined for several commercial aqueousbased GBL products, and further studied as a function of time. The effects of temperature and time were also determined for five commercial beverages spiked with GHB or GBL. GHB and GBL contents were determined using high performance liquid chromatography (HPLC). GHB and/or GBL confirmations were made using gas chromatography-mass spectrometry (GC-MS) and/or infrared spectroscopy (IR). Solution pH, time, and storage temperature were determined to be important factors affecting the rate and extent of GBL hydrolysis to GHB. Under strongly alkaline conditions (pH 12.0), GBL was completely converted to GHB within minutes. In pure water, GBL reacted to form an equilibrium mixture comprising ca. 2:1 GBL:GHB over a period of months. This same equilibrium mixture was established from either GHB or GBL in strongly acidic solution (pH 2.0) within days. A substantial portion of GBL (ca. 1 ⁄ 3) was hydrolyzed to GHB in aqueous-based GBL products, and in spiked commercial beverages, after ambient storage for a period ranging from several weeks to several months. Heat increased and refrigeration decreased the rate of GBL hydrolysis relative to ambient conditions. These studies show that hydrolysis of GBL to GHB does occur in aqueous-based solutions, with samples and time frames that are relevant to forensic testing. Implications for forensic testing and recommendations are discussed.

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The recent surge in the sale of cannabis-based consumer products in the US includes foods, candies, beverages, topicals, vapes/eliquids, oral supplements in various forms, recreational marijuana plants, and plant extracts or preparations. The wide variety of product and sample types has resulted in a host of new matrix interferences when conducting qualitative testing for the cannabis cannabinoids such as cannabidiol and d9-tetrahydrocannabinol. A qualitative GC-MS method is presented in this work, which uses a commercial 35% silphenylene phase to provide chromatographic resolution for 11 target cannabinoids as their trimethylsilyl derivatives (CBD, CBDA, d9THC, THCA, CBN, d8THC, CBG, CBGA, CBDV, THCV, and CBC). The method uses variants of ethanol- and acetonitrile-based extractants to successfully minimize or eliminate several types of interferents, and also provides protocols to address specific interferents such as glycerin and lactose. Method validation included spike/recovery for five cannabinoids of primary interest (spiking level 50μg/g) from a series of edible oils, foods, beverages, candies, topicals, oral OTC pharmaceuticals, glycerin, and propylene glycol. The minimum detectable concentration was established as 1.0μg/g. The method was applied to about sixty diverse commercial products, as well as to recreational marijuana plants, plant preparations, hempseed oils, and dronabinol capsules.

A rapid, sensitive, and accurate method for the screening and determination of polycyclic aromatic hydrocarbons (PAHs) in edible seafood is described. The method uses quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based extraction and HPLC with fluorescence detection (FLD). The method was developed and validated in response to the massive Deepwater Horizon oil spill in the Gulf of Mexico. Rapid and highly sensitive PAH screening methods are critical tools needed for oil spill response; they help to assess when seafood is safe for harvesting and consumption. Sample preparation involves SPE of edible seafood portions with acetonitrile, followed by the addition of salts to induce water partitioning. After centrifugation, a portion of the acetonitrile layer is filtered prior to analysis via HPLC-FLD. The chromatographic method uses a polymeric C18 stationary phase designed for PAH analysis with gradient elution, and it resolves 15 U.S. Environmental Protection Agency priority parent PAHs in fewer than 20 min. The procedure was validated in three laboratories for the parent PAHs using spike recovery experiments at PAH fortification levels ranging from 25 to 10 000 microg/kg in oysters, shrimp, crab, and finfish, with recoveries ranging from 78 to 99%. Additional validation was conducted for a series of alkylated homologs of naphthalene, dibenzothiophene, and phenanthrene, with recoveries ranging from 87 to 128%. Method accuracy was further assessed based on analysis of National Institute of Standards and Technology Standard Reference Material 1974b. The method provides method detection limits in the sub to low ppb (microg/kg) range, and practical LOQs in the low ppb (microg/kg) range for most of the PAH compounds studied.

No abstract

Commercial moist snuff products are used by placing a portion of tobacco inside the mouth between the inner cheek or lip and gum. Nicotine is absorbed into the blood stream via transfer across various oral membranes including the buccal mucosa (cheek lining). The resulting salivary pH when a given moist snuff product is placed in the mouth is an important factor for nicotine absorption because it will affect the proportion of free base nicotine that is readily available for absorption. The resulting salivary pH for a given moist snuff product will be determined in part by the relative acid-base buffering capacities of the saliva and moist snuff, as well as the pHs of the saliva and moist snuff prior to coming in contact with one another. In the current study, the acid-base buffering capacities (mu eq/g) of a series of commercial moist snuff products were determined and compared to the acid-base buffering capacity for unstimulated, whole human saliva. The buffering capacities of the moist snuff products were determined to be 10-20 times higher than the buffering capacity of human saliva. The resulting salivary pH ranges after contact between an artifical saliva and the various moist snuff products were also determined; the results were used to predict the proportion of free base nicotine that can be expected to occur in the mouth during the first few minutes of product use. These studies provide a basis for examining and understanding the effects that moist snuff product pHs and buffering capacities may be expected to have on nicotine absorption.

In forensic evidence, gamma-hydroxybutyric acid (GHB) has frequently been encountered in one of its salt forms (gamma-hydroxybutyrate), but has also been encountered in its free acid form (GHB). Owing to the physical properties, encounters of the free acid have been largely restricted to forensic exhibits comprising aqueous solutions, such as acidic beverages that have been "spiked" or formulated with GHB salts or gamma-butyrolactone (GBL). The analysis of GHB free acid presents particular difficulties including the potential for altering the original proportions of GHB free acid, GHB carboxylate, and GBL in the course of analysis, and discrimination between GHB free acid and carboxylate forms. In this work, the formation of GHB free acid in aqueous solutions (water and/or D2O) was studied as a function of solution pH. Proton nuclear magnetic resonance (1HNMR) and Fourier-transform infrared spectrometry (FT-IR) measurements were obtained on freshly prepared mixtures of NaGHB and HCl stock solutions representing a series of points along the GHB titration curve. Both 1HNMR and FT-IR were shown to track the changing proportions of GHB free acid and carboxylate forms as a function of pH, while simultaneously monitoring for the formation of the lactone (GBL). The results were consistent with acid-base conversion behavior for a carboxylic acid. 1HNMR was shown to provide an ideal means for analysis of aqueous-based GHB/GBL forensic exhibits based on simple dilution of the neat liquid exhibit, without altering the original proportions of GHB free acid, carboxylate, and GBL in the samples.

Tetrahydrocannabinol (THC)-containing products played a major role in the 2019 US nationwide outbreak of pulmonary lung illness associated with e-cigarettes or vaping liquids (EVALI). Due to the severity of the illness which resulted in 68 deaths, a comprehensive identification of the components in the vaping liquids was required. Our laboratory received over 1000 vaping liquid products for analysis including hundreds of vaping products from EVALI patients. In this work, we present the results for the GC-MS identification of the cannabinoids from a large subset of ca. 300 Cannabis-based vaping liquids, with emphasis on the identification of a series of unnatural THC isomers. GC-MS analysis was conducted using a validated, published method in which the cannabinoids were identified as the trimethylsilyl derivatives after separation on a commercial 35% silphenylene phase. Δ9- Tetrahydrocannabinol is the naturally occurring THC isomer found in the Cannabis plant, and was found in the majority of the vaping liquids. However, we also identified the presence of one or more additional THC isomers in many of the vaping liquids including Δ8-tetrahydrocannabinol, Δ6a,10a–tetrahydrocannabinol, Δ10-tetrahydrocannabinol, and exo-tetrahydrocannabinol. Significant or major amounts of unnatural THC isomers were found in over 10% of the THC vaping liquids, with lesser amounts found in another 60% of the vaping liquids. Exposure of the Cannabis source materials (such as marijuana concentrates or converted hemp materials) to chemical and thermal treatments during manufacturing, is proposed as the primary cause for the THC isomerizations.