Use Of Solid-phase Microextraction Research Articles

Effect of a Composite Alginate/Grape Pomace Extract Packaging Material for Improving Meat Storage.

The development of food packaging materials that reduce the production of plastic, preserving at the same time the quality of food, is a topic of great interest today for the scientific community. Therefore, this article aims to report the effectiveness of an eco-friendly packaging material based on alginic acid and grape pomace extract from Vitis vinifera L. (winemaking by-products) for storing red meat in a domestic refrigerator. Specifically, biogenic amines are considered "sentinels" of the putrefactive processes, and their presence was thus monitored. For this purpose, an experimental analytical protocol based on the use of solid-phase microextraction coupled with gas chromatography-mass spectrometry was developed during this work for the determination of six biogenic amines (butylamine, cadaverine, isobutylamine, isopentylamine, putrescine, and tyramine). Moreover, by combining the analytical results with those of pH and weight loss measurements, differential scanning calorimetry, and microbiological analysis, it was proved that the studied materials could be proposed as an alternative packaging material for storing foods of animal origin, thus lowering the environmental impact according to sustainability principles.

Solid-Phase Microextraction-Gas Chromatography Analytical Strategies for Pesticide Analysis.

Due to their extensive use and the globalized commerce of agricultural goods, pesticides have become a global concern. Despite the undoubtful advantages of their use in agricultural practices, their misuse is a threat to the environment and human health. Their analysis in environmental samples and in food products continues to gain interest in the analytical chemistry community as they are challenging matrices, and legal concentration limits are particularly low (in the order of ppb). In particular, the use of solid-phase microextraction (SPME) has gained special attention in this field thanks to its potential to minimize the matrix effect, while enriching its concentration, allowing very low limits of detection, and without the need of a large amount of solvents or lengthy procedures. Moreover, its combination with gas chromatography (GC) can be easily automated, making it a very interesting approach for routine analysis. In this review, advances and analytical strategies for the use of SPME coupled with GC are discussed and compared for the analysis of pesticides in food and environmental samples, hopefully encouraging its further development and routine application in this field.

Use of solid phase microextraction in tips (SPME-Tips) for analysis of cocaine and biotransformation products in oral fluid by liquid chromatography tandem mass spectrometry (LC-MS/MS)

To develop and validate a method for analyzing cocaine and its metabolites using SPME-Tips and LC-MS/MS. Among the biological matrices used for analytical toxicology, oral fluid has advantages such as simplicity and non-invasive collection, the difficulty of adulteration, the low level of contamination risk and the possibility of recent abuse evaluation. Recently, nearly two million users have used cocaine in the US/Europe. When abused, cocaine is rapidly metabolized, mainly into methylecgonine and benzoylecgonine. Cocaethylene is formed in the concomitant use of cocaine with ethanol, and anhydroecgonine methyl ester (AEME) (in the crack abuse). Currently, in (green) analytical toxicology there is a growing interest in the use of new sample preparation techniques that are fast, efficient, automatable, and ecologically correct. Thus, methods based on microextraction processes have been developed, such as solid phase microextraction (SPME), a miniaturization of solid phase extraction. A variation of SPME technique was recently developed, consisting of a microfiber coated with extractor phase installed in a micropipette tip. In SPME-Tips, the extraction of analytes occurs in a extractor phase, allowing the direct immersion of the tip in biological fluids, causing the analytes to be adsorbed on the fiber and allowing the desorption to be carried out using small volume of more polar and less toxic solvents. The procedure was optimized, studying parameters such as salting-out effect, extraction time, sample agitation speed, elution solvent volume, and constitution. For extraction, SPME-Tips were immersed in 150 μL of oral fluid (collected with Quantisal) and kept under agitation at 500 rpm for 80 min. For the elution, 125 μL of methanolic solution with 0.1% formic acid was used, kept under agitation at 500 rpm for 30 min. The elution content was taken to LC-MS/MS, in which 5 μL were analyzed. The analyses were performed in a Nexera-UHPLC chromatographic system, coupled with a LCMS8060 mass spectrometer. The chromatographic separation was performed with Atlantis-T3 column (150 × 3.0 mm, 3.0 μm), maintained at 40 °C. The mobile phase consisted of ultra-pure water (A) and methanol (B), both containing formic acid (0.1%) and 2 mmol/L ammonium formate. The flow rate was set to 0.4 mL/min, and the elution gradient used started with 10%B for 1 min, followed by a linear increase to 100%B for 2 min and then maintained at 100%B for 2 min and returning to the proportion start in 0.1 min. This condition was maintained for another 3 min, completing a total of 8 min of chromatographic run. With this optimization, the method validation began, as recommended by the AAFS Standard Practices for Method Validation in Forensic Toxicology. For cocaine, benzoylecgonine, and cocaethylene, the correlation coefficient r 2 was greater than 0.98 (50 to 500 ng/mL). Good accuracy and precision results were obtained for low, medium and high QC. In this way, low extraction efficiency was observed to AEME and methylecgonine in C18 SPME-Tips. For the other analytes, the precision and accuracy values were in accordance to the criteria of the method validation guideline. Also, to prove the applicability of the method in real situations, 10 samples of oral fluid collected from individuals who participated in university parties will be analyzed. The samples were already collected and are stored in the Laboratory. A green analytical toxicology method was developed using SPME-Tips for the analysis of cocaine and its metabolites in oral fluid.

Understanding the early-stage release of volatile organic compounds from rapeseed oil during deep-frying of tubers by targeted and omics-inspired approaches using PTR-MS and gas chromatography

During deep-frying, a plethora of volatile products is emitted with the fumes. These compounds could act as oil quality indicators and change the indoor air composition leading to health risks for occupants. The presented experiments focus on deep-frying of different tubers in rapeseed oil at different frying temperatures. Here, two scenarios for real-time monitoring of volatile organic compounds (VOCs) using proton transfer reaction mass spectrometry (PTR-MS) were proposed. The first, targeted, involved the application of gas chromatography with a flame ionization detector (GC-FID). The second, omics-inspired, involved the use of solid-phase microextraction (SPME) along with gas chromatography-mass spectrometry (GC-MS) and molecular networking algorithm as a complementary tool to the PTR-MS analysis. In a targeted approach, it was shown that the emission profile of pentanal and hexanal depends on the frying temperature and as the temperature increases, a sudden release of these compounds can be observed in the first minutes of frying. Meanwhile, using an omics-inspired protocol enables finding the relation between 1,4-heptadienal and 2-heptanone, octanal and limonene emissions. Using both approaches it was possible to record real-time changes in emission profiles of various oils’ degradation products. It was also observed that the emission profiles of VOCs are strictly related to the frying temperature and the type of fried tuber.

Machine Learning Approaches to Identify Discriminative Signatures of Volatile Organic Compounds (VOCs) from Bacteria and Fungi Using SPME-DART-MS.

Point-of-care screening tools are essential to expedite patient care and decrease reliance on slow diagnostic tools (e.g., microbial cultures) to identify pathogens and their associated antibiotic resistance. Analysis of volatile organic compounds (VOC) emitted from biological media has seen increased attention in recent years as a potential non-invasive diagnostic procedure. This work explores the use of solid phase micro-extraction (SPME) and ambient plasma ionization mass spectrometry (MS) to rapidly acquire VOC signatures of bacteria and fungi. The MS spectrum of each pathogen goes through a preprocessing and feature extraction pipeline. Various supervised and unsupervised machine learning (ML) classification algorithms are trained and evaluated on the extracted feature set. These are able to classify the type of pathogen as bacteria or fungi with high accuracy, while marked progress is also made in identifying specific strains of bacteria. This study presents a new approach for the identification of pathogens from VOC signatures collected using SPME and ambient ionization MS by training classifiers on just a few samples of data. This ambient plasma ionization and ML approach is robust, rapid, precise, and can potentially be used as a non-invasive clinical diagnostic tool for point-of-care applications.

Secretory Products in Petals of Centaurea cyanus L. Flowers: A Histochemistry, Ultrastructure, and Phytochemical Study of Volatile Compounds.

(1) Background: Centaurea cyanus L. is a medicinal plant whose flowers are widely used in herbal medicine. The aim of the study was to localise flower tissues that are responsible for the production of secretory products in petals and to analyse the volatile compounds. The volatile compounds of the flowers of this species have not been investigated to date. (2) Methods: Light, fluorescence, scanning and transmission electron microscopy techniques were used in the study. Lipophilic compounds were localised in the tissues using histochemical assays. Volatile compounds were determined with the use of solid phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS). (3) Results: The study showed production of secretion in the petal parenchyma, whose ultrastructure has features of a secretory tissue. The lipophilic secretion was localised in the cells and intercellular spaces of the parenchyma and in the walls and surface of epidermal cells, where it accumulated after release through cuticle microchannels. Sesquiterpenes were found to constitute the main group of volatile compounds, with the highest content of β-caryophyllene (26.17%) and α-humulene (9.77%). (4) Conclusions: Given the presence of some volatile components that are often found in resins (caryophyllene, delta-cadinene) and the abundant secretion residues on the epidermal surface, we suppose that the C. cyanus secretion released by the flowers is a resinaceous mixture (oleoresin), which is frequently found in plants, as shown by literature data. This secretion may play an important role in the therapeutic effects of C. cyanus flowers.

New chemical biopsy tool for spatially resolved profiling of human brain tissue in vivo

It is extremely challenging to perform chemical analyses of the brain, particularly in humans, due to the restricted access to this organ. Imaging techniques are the primary approach used in clinical practice, but they only provide limited information about brain chemistry. Solid-phase microextraction (SPME) has been presented recently as a chemical biopsy tool for the study of animal brains. The current work demonstrates for the first time the use of SPME for the spatially resolved sampling of the human brain in vivo. Specially designed multi-probe sampling device was used to simultaneously extract metabolites from the white and grey matter of patients undergoing brain tumor biopsies. Samples were collected by inserting the probes along the planned trajectory of the biopsy needle prior to the procedure, which was followed by metabolomic and lipidomic analyses. The results revealed that studied brain structures were predominantly composed of lipids, while the concentration and diversity of detected metabolites was higher in white than in grey matter. Although the small number of participants in this research precluded conclusions of a biological nature, the results highlight the advantages of the proposed SPME approach, as well as disadvantages that should be addressed in future studies.

Solid-phase microextraction (SPME) for determination of geosmin and 2-methylisoborneol in volatile emissions from soil disturbance

A method is described here for the concentration and determination of geosmin and 2-methylisoborneol (2-MIB) from the gaseous phase, with translation to field collection and quantification from soil disturbances in situ. The method is based on the use of solid-phase microextraction (SPME) fibers for adsorption of volatile chemicals from the vapor phase, followed by desorption into a gas chromatograph-mass spectrometer (GC-MS) for analysis. The use of a SPME fiber allows simple introduction to the GC-MS without further sample preparation. Several fiber sorbent types were studied and the 50/30 μm DVB/CAR/PDMS was the best performer to maximize the detected peak areas of both analytes combined. Factors such as extraction temperature and time along with desorption temperature and time were explored with respect to analyte recovery. An extraction temperature of 30 °C for 10 min, with a desorption temperature of 230 °C for 4 min was best for the simultaneous analysis of both geosmin and 2-MIB without complete loss of either one. The developed method was used successfully to measure geosmin and 2-MIB emission from just above disturbed and undisturbed soils, indicating that this method detects both compounds readily from atmospheric samples. Both geosmin and 2-MIB were present as background concentrations in the open air, while disturbed soils emitted much higher concentrations of both compounds. Surprisingly, 2-MIB was always detected at higher concentrations than geosmin, indicating that a focus on its detection may be more useful for soil emission monitoring and more sensitive to low levels of soil disturbance.

Detection of trace drugs of abuse in baby formula using solid-phase microextraction direct analysis in real-time mass spectrometry (SPME-DART-MS).

The intentional or unintentional adulteration of baby formula with drugs of abuse is one of the many increasingly complex samples forensic chemists may have to analyze. This sample type presents a challenge because of a complex matrix that can mask the detection of trace drug residues. To enable screening of baby formula for trace levels of drugs, the use of solid-phase microextraction (SPME) coupled with direct analysis in real-time mass spectrometry (DART-MS) was investigated. A suite of five drugs was used as adulterants and spiked into baby formula. Samples were then extracted using SPME fibers which were analyzed by DART-MS. Development of a proof-of-concept method was completed by investigating the effects of the DART gas stream temperature and the linear speed of the sample holder. Optimal values of 350°C and 0.2mm/s were found. Once the method was established, representative responses and sensitivities for the five drugs were measured and found to be in the range of single ng/mL to hundreds ng/mL. Additional studies found that the presence of the baby formula matrix increased analyte signal (relative to methanolic solutions) by greater than 200%. Comparison of the SPME-DART-MS method to a traditional DART-MS method for trace drug detection found at least a factor of 13 improvement in signal for the drugs investigated. This work demonstrates that SPME-DART-MS is a viable technique for the screening of complex matrices, such as baby formula, for trace drug residues and that development of a comprehensive method is warranted.

In Vivo Brain Sampling Using a Microextraction Probe Reveals Metabolic Changes in Rodents after Deep Brain Stimulation.

Brain metabolomics is an emerging field that complements the more traditional approaches of neuroscience. However, typical brain metabolomics workflows require that animals be sacrificed and tend to involve tedious sample preparation steps. Microdialysis, the standard technique to study brain metabolites in vivo, is encumbered by significant limitations in the analysis of hydrophobic metabolites, which are prone to adsorption losses on microdialysis equipment. An alternative sampling method suitable for in vivo brain studies is solid-phase microextraction (SPME). In SPME, a small probe coated with a biocompatible polymer is employed to extract/enrich analytes from biological matrices. In this work, we report the use of SPME and liquid chromatography-mass spectrometry for untargeted in vivo analysis of rodent's brains after deep brain stimulation (DBS). First, metabolite changes occurring in brain hippocampi after application of 3 h of DBS to the animals' prefrontal cortex were monitored with the proposed approach. As SPME allows for nonlethal sampling, the same group of animals was sampled again after 8 days of daily DBS therapy. After acute DBS, we detected changes in a broad range of metabolites, including the amino acid citrulline, which may reflect changes in nitric oxide production, as well as various phospho- and glycosphingolipids. Measurements conducted after chronic DBS showed a decrease in hippocampal corticosterone, indicating that DBS may have a regulatory effect in the hypothalamic-pituitary-adrenal axis. Our findings demonstrate the potential of in vivo SPME as a tool of scientific and clinical interest capable of revealing changes in a wide range of metabolites in brain tissue.

The use of solid phase microextraction for metabolomic analysis of non-small cell lung carcinoma cell line (A549) after administration of combretastatin A4

Use of solid phase microextraction (SPME) for cell culture metabolomic analysis allows for the attainment of more sophisticated data from in vitro cell cultures. Moreover, considering that SPME allows the implementation of multiple extractions from the same sample due to its non/low-depletive nature, time course studies using the same set of samples are thus facilitated via this method. Such an approach results in a reduction in the number of samples needed for analysis thus eliminates inter-batch variability related to biological variation occurring during cell culturing. The current work aims to demonstrate the capability of SPME for measurements of combretastatin A4 (CA4) effectiveness on non-small cell cancer cell line. A cultivation protocol was established in the 96-well plate, and a fiber format of SPME was selected for metabolite extraction. The extracellular metabolic pattern of cells was changed after administration of the tested drug. This suggests pharmacological activity of the administered compound towards the studied cell line model. Results support that the use of direct immersion SPME for analysis of cell cultures does not affect cells growth or contaminate sample. Consequently, SPME allows the attainment of accurate information regarding drug uptake, metabolism, and metabolomic changes in the studied cells induced by exposure to the drug simultaneously in a single experiment.

New method based on Solid Phase Microextraction and Multidimensional gas chromatography-mass spectrometry to determine pesticides in strawberry jam

Although, the use of pesticides is necessary in agriculture to prevent crops destruction and to avoid the attack to leaves and stems of the plants, which cause quality defects of fruits and yield reduction, the control of pesticide is important in order to guarantee human safety. In the present study, a new method based on the use of solid-phase microextraction (SPME) followed by multidimensional gas chromatography-mass spectrometry (MDGC-MS) analysis was developed to detect pesticides in strawberry jam. Commercial and home-made jams as well as spiked non-spiked samples were included in the study. The method was validated by analysing commercial jam samples spiked with a pesticide mixture (ie, standard Mix 101). As a result, Relative Standard Deviation estimated from five replicates, was always below 16%. Limit detection values varied from 0.11 to 0.42 ng/kg on the first dimension and from 0.013 to 0.093 ng/kg on the second dimension. These levels are considerably lower than the Maximum Residue Levels established for strawberry pesticides by EU Regulations. Also, the matrix effect of the strawberry jam on the effectiveness of the SPME extraction was evaluated. The data presented demonstrate that the method proposed is capable of detecting reliably very low concentrations of pesticides in strawberry jams between 0.013 and 0.093 ng/kg. Additional advantages of the method are its repeatability, rapidity, simplicity, selectivity and environmental friendly nature.

Development of a fast and simple gas chromatographic protocol based on the combined use of alkyl chloroformate and solid phase microextraction for the assay of polyamines in human urine

Polyamines are aliphatic amines with low molecular weight that are widely recognized as one of the most important cancer biomarkers for early diagnosis and treatment. The goal of the work herein presented is the development of a rapid and simple method for the quantification of free polyamines (i.e., putrescine, cadaverine, spermidine, spermine) and N-monoacetylated polyamines (i.e., N1-Acetylspermidine, N8-Acetylspermidine, and N1-Acetylspermine) in human urine. A preliminary derivatization with propyl chloroformate combined with the use of solid phase microextraction (SPME) allowed for an easy and automatable protocol involving minimal sample handling and no consumption of organic solvents. The affinity of the analytes toward five commercial SPME coatings was evaluated in univariate mode, and the best result in terms of analyte extraction was achieved using the divinylbenzene/carboxen/polydimethylsiloxane fiber. The variables affecting the performance of SPME analysis were optimized by the multivariate approach of experimental design and, in particular, using a central composite design (CCD). The optimal working conditions in terms of response values are the following: extraction temperature 40 °C, extraction time of 15 min and no addition of NaCl. Analyses were carried out by gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) in selected reaction monitoring (SRM) acquisition mode. The developed method was validated according to the guidelines issued by the Food and Drug Administration (FDA). The satisfactory performances reached in terms of linearity, sensitivity (LOQs between 0.01 and 0.1 μg/mL), matrix effect (68–121%), accuracy, and precision (inter-day values between −24% and +16% and in the range 3.3–28.4%, respectively) make the proposed protocol suitable to be adopted for quantification of these important biomarkers in urine samples.

Use of solid phase microextraction to identify volatile organic compounds in brazilian wines from different grape varieties

Abstract The Brazilian wine industry has shown significant growth in recent years and the insertion of new concepts, such as geographical indications as signs of quality, has placed Brazil in tune with the tendencies of world wine production. The aim of this work was to apply the Solid Phase Microextraction technique in combination with Gas Chromatography-Mass Spectrometry to study Brazilian wines made from different grape varieties, in order to separate and identify their volatile organic compounds. These substances were identified by comparisons between the spectra obtained with those presented in the NIST library database, and by comparisons with linear retention indices and literature data. The amounts of the compounds were calculated based on the total peak areas of the chromatograms. Forty-seven volatile compounds were identified and grouped into alcohols, aldehydes, fatty acids, esters, hydrocarbons, ketones and terpenes. Most of them belonged to the ester function, conferring a fruity aroma on the wines. The alcohols may have originated from the yeast metabolism, contributing to the alcoholic and floral aromas. Ethyl lactate, 1-hexanol and diethyl maleate were identified in all the varieties, except Merlot. Decanal, methyl citronellate, (E)-2-hexenyl-3-methylbutyrate were only found in Merlot, while 2,3-butanediol was only present in the Tannat wines. 2-Phenylethanol was present in all varieties and is recognized as giving pleasant rose and honey attributes to wines. This study showed that the volatile profile of red wines is mainly characterized by esters and higher alcohols. The statistical analysis of the comparison of averages showed a greater amount of averages significantly different in the relative areas of Merlot wine. The Principal Component Analysis showed one grouping composed only of the Merlot wine samples, and this was probably related to the existence of the volatile organic compounds that were specifically identified in these wines.

Polymerization Inhibitors and Promoters for Unsaturated Polyester Resins; Use of Solid Phase MicroExtraction and Gas Chromatography Coupled to Mass Spectrometry for the Determination of 4-tert-Butyl Catechol and Acetylacetone

Polymerization Inhibitors and Promoters for Unsaturated Polyester Resins; Use of Solid Phase MicroExtraction and Gas Chromatography Coupled to Mass Spectrometry for the Determination of 4-tert-Butyl Catechol and Acetylacetone

Nuclear Magnetic Resonance and Headspace Solid-Phase Microextraction Gas Chromatography as Complementary Methods for the Analysis of Beer Samples

Chemical analysis of the organic components in beer has applications to quality control, authenticity and improvements to the flavor characteristics and brewing process. This study aims to show the complementary nature of two instrumental techniques which, in combination, can identify and quantify a number of organic components in a beer sample. Nuclear Magnetic Resonance (NMR) was used to provide concentrations of 26 different organic compounds including alcohols, organic acids, carbohydrates, and amino acids. Calorie content was also estimated for the samples. NMR data for ethanol concentrations were validated by comparison to a Fourier Transform Infrared Spectrometry (FTIR) method. Headspace Solid-Phase Microextraction (SPME) Gas Chromatography Mass Spectrometry (GCMS) was used to identify a range of volatile compounds such as alcohols, esters and hop-derived aroma compounds. A simple and inexpensive conversion of a Gas Chromatography Flame Ionization Detector (GC FID) instrument to allow the use of Solid-Phase Microextraction was found to be useful for the quantification of volatile esters.

Identification of Volatile Compounds from a Brewery with SPME Technique

Abstract The paper presents results of the analysis of the volatile compounds arising from the production processes in a brewery. The investigated material comprised the unhoped brewer’s wort which was taken from the fermentation tanks during the industrial process. The identification of volatile compounds was conducted with the use of Solid-Phase MicroExtraction (SPME) technique by extracting the compounds from the headspace of the brewer’s wort (HS-SPME). The procedure was optimized by modifying the parameters potentially influencing the process efficiency. The analytes adsorbed on the fibers were subsequently placed in the injector of a gas chromatograph, where they were released in the course of thermal desorption. Three types of fibers were chosen for the experiments: 65 μm PDMS/DVB, 50/30 μm DVB/CAR/PDMS and 100 μm PDMS. The greatest number of peaks corresponding to compounds found in the examined material was observed on the 50/30 μm DVB/CAR/PDMS fiber while the lowest was identified on the 100 μm PDMS fiber. The detected compounds are mainly the derivatives of aliphatic, alicyclic and aromatic hydrocarbons with different functional groups e.g. carbonyl, aldehyde or ester and possessing O-heteroatom in their structure.

Development and Validation of a SPME-GC-MS Method for In situ Passive Sampling of Root Volatiles from Glasshouse-Grown Broccoli Plants Undergoing Below-Ground Herbivory by Larvae of Cabbage Root Fly, Delia radicum L.

Research on plant root chemical ecology has benefited greatly from recent developments in analytical chemistry. Numerous reports document techniques for sampling root volatiles, although only a limited number describe in situ collection. To demonstrate a new method for non-invasive in situ passive sampling using solid phase micro extraction (SPME), from the immediate vicinity of growing roots. SPME fibres inserted into polyfluorotetrafluoroethylene (PTFE) sampling tubes located in situ which were either perforated, covered with stainless steel mesh or with microporous PTFE tubing, were used for non-invasive sub-surface sampling of root volatiles from glasshouse-grown broccoli. Sampling methods were compared with above surface headspace collection using Tenax TA. The roots were either mechanically damaged or infested with Delia radicum larvae. Principal component analysis (PCA) was used to investigate the effect of damage on the composition of volatiles released by broccoli roots. Analyses by gas chromatography-mass spectrometry (GC-MS) with SPME and automated thermal desorption (ATD) confirmed that sulphur compounds, showing characteristic temporal emission patterns, were the principal volatiles released by roots following insect larval damage. Use of SPME with in situ perforated PTFE sampling tubes was the most robust method for out-of-lab sampling. This study describes a new method for non-invasive passive sampling of volatiles in situ from intact and insect damaged roots using SPME. The method is highly suitable for remote sampling and has potential for wide application in chemical ecology/root/soil research. Copyright © 2016 John Wiley & Sons, Ltd.

Characterizing the Smell of Marijuana by Odor Impact of Volatile Compounds: An Application of Simultaneous Chemical and Sensory Analysis.

Recent US legislation permitting recreational use of marijuana in certain states brings the use of marijuana odor as probable cause for search and seizure to the forefront of forensic science, once again. This study showed the use of solid-phase microextraction with multidimensional gas chromatography—mass spectrometry and simultaneous human olfaction to characterize the total aroma of marijuana. The application of odor activity analysis offers an explanation as to why high volatile chemical concentration does not equate to most potent odor impact of a certain compound. This suggests that more attention should be focused on highly odorous compounds typically present in low concentrations, such as nonanal, decanol, o-cymene, benzaldehyde, which have more potent odor impact than previously reported marijuana headspace volatiles.

The relationship between chemical concentration and odor activity value explains the inconsistency in making a comprehensive surrogate scent training tool representative of illicit drugs

This report highlights the importance of an individual chemical's odor impact in the olfactory identification of marijuana, cocaine, and heroin. There are small amounts of highly odorous compounds present in headspace of these drugs, with very low odor detection thresholds, that are more likely responsible for contributing to the overall odor of these drugs. Previous reports of the most abundant compounds in headspace can mislead researchers when dealing with whole odor of these drugs. Surrogate scent formulations, therefore, must match the odor impact of key compounds and not just the chemical abundance of compounds. The objective of this study was to compare odorous volatile organic compounds (VOCs) emitted from illicit drug samples of marijuana, cocaine, and heroin to surrogate smell formulations using simultaneous sensory (via human olfaction) and chemical analyses. Use of solid phase microextraction (SPME) allowed VOCs in drug headspace to be extracted and pre-concentrated on site, and analyzed by multidimensional gas chromatography–mass spectrometry–olfactometry (MDGC–MS-O). Use of MDGC–MS-O allowed for further separation of odorous compounds and simultaneous detection by the human nose of the separate odor parts that make up the total aroma of these drugs. The compounds most abundant in headspace were not the most odor impactful when ranked by odor activity values (OAVs) (defined as ratio of concentration to odor detection threshold, ODT). There were no apparent correlations between concentrations and OAVs. A 1g marijuana surrogate lacked in odor active acids, aldehydes, ethers, hydrocarbons, N-containing, and S-containing VOCs and was overabundant in odor active alcohols and aromatics compared with real marijuana. A 1g cocaine surrogate was overabundant in odor active alcohols, aldehydes, aromatics, esters, ethers, halogenates, hydrocarbons, ketones and N-containing compounds compared with real. A 1g heroin surrogate should contain less odor active acids, alcohols, aromatics, esters, ketones, and N-containing compounds. Drug quantity, age and adulterants can affect VOC emissions and their odor impact. The concept of odor activity value, then, is useful to researchers without access to more sophisticated instrumentation. Odor activity values can be calculated from published odor detection thresholds. More research is warranted to expand the database, and determine odor detection thresholds for compounds of interest. Additional information could be obtained from establishing ODTs of key odorants for canines.