Solid-phase Microextraction GC Research Articles

Analytical methods for detecting butane, propane, and their metabolites in biological samples: Implications for inhalant abuse detection

Worldwide, various inhalants are widely abused for recreational purposes, with butane and propane emerging as among the most commonly misused volatile substances, posing a significant risk of sudden death. The rapid elimination and oxidation of these highly volatile compounds upon inhalation necessitate the identification of butane and propane along with their metabolites in biological samples. Hence, the primary objective of this study is twofold: firstly, to establish a method for analyzing butane, propane, and metabolites, and secondly, to demonstrate the detection window and exposure indicators associated with the inhalation of butane and propane. In pursuit of this objective, we developed analytical methods for the determination of isobutane, n-butane, propane, and their nine metabolites in both blood and urine. Headspace-gas chromatography–mass spectrometry (GC–MS) and solid-phase microextraction-GC–MS were employed for the analyses, demonstrating acceptable precision and accuracy. An animal study revealed that isobutane and n-butane were only detectable below the limit of quantification (LOQ) in rat blood 5 min after exposure. Meanwhile, the three major metabolites—2-methyl-2-propanol, 2-butanol, and 2-butanone—were observed 5 min after exposure but persisted in rat urine even 5 h post-exposure. Additionally, human urine samples identified other metabolites, including acetone, acetoin, and 2,3-butanediol isomers. The presence of specific metabolites corresponding to each inhalant confirmed the abuse of butane and propane. This comprehensive approach provides valuable insights into the detection and assessment of inhalation to these volatile substances.

Screening of Aroma-Producing Performance of Anticlostridial Lacticaseibacillus casei Strains

AbstractThe cheesemaking industry is increasingly interested in using adjunct cultures with potential aromatic and anticlostridial activities. In this study, 34 Lb. paracasei and 2 Lb. rhamnosus strains were isolated from a semi-hard cheese and characterized for their proteolytic, esterase, and anticlostridial activity. Moreover, the strains were inoculated in a curd-based medium and the volatile compounds in the headspace of samples were evaluated by solid-phase microextraction–GC–MS analysis. Proteolytic activity was present in 30 strains, whereas only one Lb. paracasei strain showed esterase activity. All strains inhibited Cl. sporogenes, Cl. beijerinckii, and Cl. butyricum, and 18 isolates inhibited at least one Cl. tyrobutyricum strain. Principal component analysis and clustering analysis based on the volatilome grouped strains into three groups. One of these groups was characterized by high amounts of acids and esters and clustered with control samples inoculated with commercial starter cultures, suggesting similarity in the aroma profile. Strains belonging to this group with inhibitory effects against Cl. tyrobutyricum might be exploited as autochthonous adjunct cultures for the reduction of late-blowing defects in semi-hard cheeses.

Geographical origin classification of Phoebe zhennan and Phoebe bournei by solid phase micro-extraction and gas chromatography-mass spectrometry

Phoebe zhennan and Phoebe bournei are favored for their fine-grain, insect resistance, special fragrance, not easily cracked and deformed, which had been widely used in furniture and construction. Wood authenticity regarding different varieties and geographical origins is increasingly becoming a concern for consumers. Due to the difference in wood quality characteristics and economic value of genus Phoebe species from different geographical origins, it is important to establish a fast, efficient, and reliable method to discriminate the geographical origin of Phoebe zhennan and Phoebe bournei. Solid phase micro-extraction (SPME) was used as sample preparation approach and gas chromatography-mass spectrometry (GC–MS) technique was employed to analyze the volatile compounds. As a result, a total of 40 volatiles were identified by SPME–GC–MS among Phoebe zhennan samples from four origins, while 34 substances identified among Phoebe bournei samples. The wood samples of Phoebe zhennan and Phoebe bournei from different major production areas in China were able be discriminated by GC–MS spectroscopy. This finding indicated that genus Phoebe species from different climate zones had different chemical composition, which verified that the SPME–GC–MS technique can be used to classify different species of wood with characteristic compounds.

Analysis of Volatile Compounds in Jinhua ham Using Three Extraction Methods Combined with Gas Chromatography-Time-of-Flight Mass Spectrometry.

The volatile compounds in Jinhua ham samples after different aging times were characterized using solvent-assisted flavor evaporation (SAFE), solid-phase microextraction (SPME), and needle trap (NT) extraction methods combined with gas chromatography-time-of-flight mass spectrometry (GC-TOF/MS). Hundreds of aroma compounds were identified, including aldehydes, alcohols, ketones, furans, esters, acids, pyrazines, and sulfides. The results showed that NT extracted the greatest number of volatile compounds, whereas the extraction efficiency of SPME headspace adsorption was highest among the three sample preparation methods. Principal component analysis of SPME effectively distinguished the variation in the aroma of the Jinhua hams specific to aging time. Butyrolactone, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, phenylacetaldehyde, and acetic acid were considered as the main volatile compounds in the Jinhua ham samples at three years of aging. The results showed that SPME-GC-TOF/MS effectively discriminated among samples by age. By comparing the three extraction methods, this study provides a theoretical basis for the selection of extraction methods of volatile aroma compounds in Jinhua ham.

Evaluation of New, Sputtered Carbon SPME Fibers with a Multi-Functional Group Test Mixture

We report the first fabrication of sputtered carbon, solid-phase microextraction (SPME) fibers. These fibers have competitive extraction capabilities compared with the commercial carbon wide range (CWR) SPME fiber. This report also includes a demonstration of a newly developed SPME test mix that includes 15 different compounds with a wide range of functional groups and chemical properties. The fiber fabrication process involves sputtering carbon onto fused silica fibers, and the effects of throw distance on the morphology of the carbon coatings were studied. Four different carbon coating thicknesses were evaluated, with PDMS added as a stationary phase. These fibers were characterized with multiple analytical techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA) goniometry, as well as headspace (HS) and direct immersion (DI)–SPME–GC–MS. The best (11.5 µm) sputtered carbon SPME fibers, with and without PDMS, were evaluated using the new evaluation mix and compared with the commercial CWR fiber and a previously sputtered/developed silicon fiber. The new probe mix helped elucidate differences among the fibers, which would have been missed by current commercial test mixes. The sputtered carbon SPME fibers showed similar functional group selectivity as commercial CWR fibers. However, the sputtered carbon fibers showed higher responses per volume compared with the commercial CWR fiber, indicating the porous morphology of the sputtered carbon has the ability to overcome large phase thickness/volume discrepancies and increase the relative recovery for various compounds.

Impact of volatile organic compounds (VOCs) from acrylic double-sided pressure-sensitive adhesives (PSAs) on metals found in cultural heritage environments

An artificial aging protocol known as the Oddy test was combined with headspace solid phase micro-extraction (SPME) gas chromatography-mass spectrometry (GC–MS) data to identify which of 17 double-sided acrylic pressure-sensitive adhesives (PSAs) were safest to use in cultural heritage environments. Traditional Oddy testing showed every PSA corroded lead coupons while 1 also corroded copper and silver coupons. 10 PSAs were suitable for short-term use near cultural heritage artifacts while the remaining 7 were unsuitable. An adapted Oddy test identified whether several known acrylic-based adhesive precursor chemicals, including ethyl acrylate, n‑butyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and abietic acid caused the observed corrosion. Lead coupons were extremely sensitive to acrylic acid, with a 5 × 10−5 mg L-1 Oddy test jar concentration capable of initiating corrosion at 60 °C and 50% RH. SPME GC–MS showed that any evidence of acrylic acid or acetic acid with peak areas larger than 19 million were both markers for unsuitable PSAs. 2-ethylhexyl acrylate was less reactive to metals though a GCMS peak area greater than 200 million was correlated with unsuitable PSAs. 3M™ 465, 3M™ 908, and Tesa® 88,250 tapes were concluded to be the best double-sided PSAs for use in cultural heritage environments.

Detection of Volatiles from Raw Beef Meat from Different Packaging Systems Using Solid-Phase Microextraction GC-Accurate Mass Spectrometry.

The volatile profile of raw beef contains vital information related to meat quality and freshness. This qualitative study examines the effect of packaging system on the formation and release of volatile organic compounds (VOCs) from raw beef over time, relative to the packaging best before date (BBD). The three packaging systems investigated were modified atmospheric packaging, vacuum packaging, and cling-wrapped packaging. Porterhouse steak samples with the same BBD were analysed from 3 days before to 3 days after the BBD. VOCs were detected via preconcentration using solid-phase microextraction combined with gas chromatography–accurate mass quadrupole time-of-flight mass spectrometry. In total, 35 different VOCs were tentatively identified. Interestingly, there was no clear relationship of the VOCs detected between the three packaging systems, with only carbon disulphide and acetoin, both known volatiles of beef, detected in all three. This is the first study to investigate the effects of commercial packaging systems on VOC formation; it provides an understanding of the relationship of VOCs to the BBD that is essential for the development of on-pack freshness and quality sensors.

Diel rhythm of volatile emissions of males and females of the peach fruit fly Bactrocera zonata

Fruit flies in the genus Bactrocera are among the most destructive insect pests of fruits and vegetables throughout the world. A number of studies have identified volatiles from fruit flies, but few reports have demonstrated behavioral effects or sensitivities of fly antennae to these compounds. We applied a recently developed method of automated headspace analysis using SPME (Solid Phase Microextraction) fibers and GC–MS (gas chromatography mass spectrometry), termed SSGA, to reveal volatiles specific to each sex of B. zonata that are emitted in a diel periodicity. The volatiles released primarily at dusk were identified by GC–MS and chemical syntheses as several spiroacetals, pyrazines, and ethyl esters. Solvent extraction of male rectal glands or airborne collections from each sex, followed by GC–MS, showed that certain of the volatiles increase or decrease in quantity sex-specifically with age of the flies. Electroantennographic (EAG) analysis of dose-response indicates differences in sensitivities of male and female antenna to the various volatiles. Our study provides a comprehensive analysis of the volatile chemicals produced and released by B. zonata and their antennal responses. The possible pheromone and semiochemical roles of the various volatiles released by each sex and the difficulties of establishing behavioral functions are discussed.

Effects of Different Steeping Temperatures on the Leaching of Aroma Components in Black Tea by SPME–GC–MS Coupled with Chemometric Method

Abstract Background: Black tea is famous for its unique aroma. The analysis of aroma components has attracted considerable attention worldwide because of its complex chemical composition and low concentration. Objective: Steeping temperature is one of the most important factors affecting the aroma of black tea. This study aims to evaluate the effects of four steeping temperatures [60, 70, 80, and 95°C (boiling water)]. Methods: Two major factors affecting extraction performance, including the type of extraction method [direct headspace injection (HS) and solid-phase microextraction (SPME)] and extraction time (50, 60, and 70 min), were optimized to enrich and analyze the aroma components of Congou black tea by GC–MS. In addition, heuristic evolving latent projection (HELP), an effective chemometric resolution method, was employed to resolve the overlapped peaks. Results: A total of 83 aroma components were tentatively identified by GC–MS, such as alcohol (42.06–50.52%), aldehyde (12.09–15.97%), and hydrocarbon (4.79–15.32%). Linalool and its oxides (25.49–36.24%) were the most abundant aroma components, followed by geraniol (2.55–8.54%), methyl salicylate (1.84–9.50%), and nerol (1.93–4.41%). Conclusions: The black tea steeped at 95°C smelled more pleasant with mild green, roast, and fruity aroma. Moreover, at 80°C, the tea had sweeter fragrance with floral aroma, while steeping at 60 and 70°C resulted in more reinforced woody and fatty aroma. Highlights: A total of 83 aroma components of black tea were tentatively identified by SPME–GC–MS. The overlapped peaks were resolved by the HELP method. Aroma characteristics of different steeping temperatures were revealed.

Methyl jasmonate-induced compositional changes of volatile organic compounds in Polygonum minus leaves

Polygonum minus Huds. is a medicinal aromatic plant rich in terpenes, aldehydes, and phenolic compounds. Methyl jasmonate (MeJA) is a plant signaling molecule commonly applied to elicit stress responses to produce plant secondary metabolites. In this study, the effects of exogenous MeJA treatment on the composition of volatile organic compounds (VOCs) in P. minus leaves were investigated by using a metabolomic approach. Time-course changes in the leaf composition of VOCs on days 1, 3, and 5 after MeJA treatment were analyzed through solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC–MS). The VOCs found in MeJA-elicited leaves were similar to those found in mock-treated leaves but varied in quantity at different time points. We focused our analysis on the content and composition of monoterpenes, sesquiterpenes, and green leaf volatiles (GLVs) within the leaf samples. Our results suggest that MeJA enhances the activity of biosynthetic pathways for aldehydes and terpenes in P. minus. Hence, the production of aromatic compounds in this medicinal herb can be increased by MeJA elicitation. Furthermore, the relationship between MeJA elicitation and terpene biosynthesis in P. minus was shown through SPME–GC–MS analysis of VOCs combined with transcriptomic analysis of MeJA-elicited P. minus leaves from our previous study.

Headspace Solid-Phase Microextraction GC–MS for Rapid Rice Aroma Analysis Using Optimization Tools

A key feature of rice acceptance by consumers is closely related to its aroma. A few decades of research on rice aroma indicated associated difficulties which arise from its complicated volatile composition. Our investigation seeks to resolve this highly complicated aroma profile using an experimental design for headspace solid-phase microextraction GC–MS. The Plackett–Burman methodology was used as a factor screening method for the headspace solid-phase microextraction procedure and GC–MS analysis, and a central composite design was implemented as an optimization methodology for both steps. Optimization of the extraction procedure and GC–MS analysis leads to a highly resolved rice aroma profile resulting in 66 new constituents. A total of 123 constituents were identified by implementing the procedure on Champa rice from the south of Iran.

Profiling the scent of weathered training aids for blood-detection dogs

At outdoor crime scenes, cadaver-detection and blood-detection dogs may be tasked with locating blood that is days, weeks or months old. Although it is known that the odour profile of blood will change during this time, it is currently unknown how the profile changes when exposed to the environment. Such variables must be studied in order to understand when the odour profile is no longer detectable by the scent-detection dogs and other crime scene tools should be implemented. In this study, blood was deposited onto concrete and varnished wood surfaces and weathered in an outdoor environment over a three-month period. Headspace samples were collected using solid phase microextraction (SPME) and analysed using comprehensive two-dimensional gas chromatography – time-of-flight mass spectrometry (GC×GC–TOFMS). The chemical odour profiles were compared with the behavioural responses of cadaver-detection and blood-detection dogs during training. Data interpretation using principal component analysis (PCA) and hierarchical cluster analysis (HCA) established that the blood odour could no longer be detected using SPME–GC×GC–TOFMS after two months of weathering on both surfaces. Conversely, the blood-detection dogs had difficulty locating the blood samples after one month of weathering on concrete and after one week of weathering on varnished wood. The scent-detection dogs evaluated herein had not been previously exposed to environmentally weathered blood samples during training. Given that this study was conducted to test the dogs' baseline abilities, it is expected that with repeated exposure, the dogs' capabilities would likely improve. The knowledge gained from this study can assist in providing law enforcement with more accurate training aids for blood-detection dogs and can improve their efficiency when deployed to outdoor crime scenes.

Odour-active compounds in baby banana Fruit (Musa acuminata AA Simmonds cv. Bocadillo)

ABSTRACTThe contribution of individual compounds to the typical aroma of baby banana cv. Bocadillo fruit would be useful to assess aroma changes caused in the course of fruit processing. Potent odourants in baby banana fruit were determined by combined headspace solid-phase microextraction GC–Olfactometry (HS-SPME-GC–O), solvent-assisted flavour evaporation, gas chromatography−olfactometry (GC–O), gas chromatography-mass spectrometry (GC-MS), aroma extract dilution analysis (AEDA) and calculation of odour activity values. Twenty-three constituents were considered as potentially odour-active compounds contributing to the typical fruit aroma, from which 2-pentyl acetate, 3-methylbutyl acetate, 3-methylbutyl butanoate, 3-methylbutyl 3-methylbutanoate, hexanal, (E)-2-hexenal and 2-pentyl 3-methylbutanoate were the most important contributors to the aroma. HS-SPME-GC-O has a great potential as fast and simple tool to control aroma quality of baby banana fruit.

Quantification of BTEX in Soil by Headspace SPME–GC–MS Using Combined Standard Addition and Internal Standard Calibration

There is a great demand for simple, fast and accurate methods for quantification of volatile organic contaminants in soil samples. Solid-phase microextraction (SPME) has a huge potential for this purpose, but its application is limited by insufficient accuracy caused by a matrix effect. The aim of this research was to develop the method for BTEX quantification in soil using combined standard addition (SA) and internal standard (IS) calibration. Deuterated benzene (benzene-d6) was used as the internal standard for all analytes. The optimized method includes spiking replicate samples with different concentrations of BTEX standards and the same concentration of benzene-d6, equilibration of soil samples at 40 °C during 2 h, and SPME–GC–MS analysis. Precision and accuracy of IS and SA methods were compared on different soil matrices. Combined SA + IS method provided more precise calibration plots compared to the conventional SA calibration. The SA + IS calibration provided more precise and accurate results compared with a reference method based on solvent extraction followed by GC–MS when applied to BTEX quantification in real soil samples (spiked with diesel fuel and aged). Recoveries of BTEX from soil samples spiked with known concentrations of analytes using the developed method were in the range of 73–130% with RSD values less than 15% for all BTEX. The proposed simultaneous standard addition and internal standard approach can be advantageous and adopted for improved quantification of other toxic VOCs in soil.

Influence of fumigants on sunflower seeds: Characteristics of fumigant desorption and changes in volatile profiles

Fumigation of transport containers is common practice to protect stored products from pests. Yet little is known about the desorption times and effects of the highly toxic gases used in this process. To shed light on the behavior of fumigants in real food, we treated sunflower seeds (Helianthus annuus L.) with 100ppm phosphine (PH3), methyl bromide (MeBr) or 1,2-dichloroethane (DCE) for 72h. The compound concentrations in the air were then analyzed by thermal desorption/2D gas chromatography coupled to mass spectrometry and flame photometric detection (TD-2D-GC–MS/FPD). A desorption time of several months was observed for DCE, whereas PH3 and MeBr were outgassed in a matter of days. To investigate possible interactions between gases and constituents of the seeds, non-fumigated, fumigated and outgassed samples were analyzed by headspace solid-phase microextraction GC–MS. We observed significantly different volatile profiles in fumigated and subsequently outgassed seeds compared to non-fumigated seeds. Whereas PH3-treated seeds released far more terpenoids, the volatile pattern of seeds exposed to DCE revealed significantly fewer terpenoids but more aldehydes. These changes are likely to affect food aroma characteristics.

The effect of Maillard reaction products and yeast strain on the synthesis of key higher alcohols and esters in beer fermentations

The effect of Maillard reaction products (MRPs), formed during the production of dark malts, on the synthesis of higher alcohols and esters in beer fermentations was investigated by headspace solid-phase microextraction GC–MS. Higher alcohol levels were significantly (p<0.05) higher in dark malt fermentations, while the synthesis of esters was inhibited, due to possible suppression of enzyme activity and/or gene expression linked to ester synthesis. Yeast strain also affected flavour synthesis with Saccharomyces cerevisiae strain A01 producing considerably lower levels of higher alcohols and esters than S288c and L04. S288c produced approximately double the higher alcohol levels and around twenty times more esters compared to L04. Further investigations into malt type-yeast strain interactions in relation to flavour development are required to gain better understanding of flavour synthesis that could assist in the development of new products and reduce R&D costs for the industry.

Application of polyaniline–multiwalled carbon nanotubes composite fiber for determination of benzaldehyde in injectable pharmaceutical formulations by solid-phase microextraction GC–FID using experimental design

A polyaniline–multiwalled carbon nanotubes composite fiber was electrodeposited onto a platinum wire using cyclic voltammetry. This fiber was used for headspace solid-phase microextraction combined with gas chromatography and flame ionization detector of trace levels of benzaldehyde in some injectable pharmaceutical formulations. Three solid-phase microextraction parameters including temperature, time and stirring rate were investigated simultaneously using a three-level-three-factor Box–Behnken as experimental design on the extraction capability. The as-made fiber has a lifetime of over 300 extractions without any obvious decline in extraction efficiency. At the optimum conditions (extraction temperature 60°C, extraction time 15 min, stirring rate 700 rpm), the method displays excellent linearity over the concentration range of 25–1000 ng/mL of benzaldehyde with RSD values ranging from 1.0 to 6.8%. The limits of quantitation and detection were 25 and 10 ng/mL, respectively.

A salting out system for improving the efficiency of the headspace solid-phase microextraction of short and medium chain free fatty acids

Given the importance of short and medium chain free fatty acids (FFAs) in several fields, this study sought to improve the extraction efficiency of the solid-phase microextraction (SPME) of FFAs by evaluating salting out agents that appear promising for this application. The salts ammonium sulfate ((NH4)2SO4) and sodium dihydrogen phosphate (NaH2PO4) were tried on their own and in combination (3.7/1), in four different total amounts, as salting out agents in the headspace–SPME–gas chromatographic (HS–SPME–GC) analysis of the FFAs from acetic acid (C2) to decanoic acid (C10). Their performance in a model system of an aqueous standard mixture of FFAs at a pH of 3.5 was compared to that of the more commonly used sodium chloride (NaCl) and sodium sulfate (Na2SO4). All of the salts and salt systems evaluated, in proper amount, gave improved results compared to NaCl (saturated), which instead gave interesting results only for the least volatile FFAs C8 and C10. For C2–C6, the salt system that gave the best results compared to NaCl was (NH4)2SO4/NaH2PO4, in the highest of the four amounts evaluated, with factor increases between 1.2 and 4.1-fold, and NaH2PO4, between 1.0 and 4.3-fold. The SPME extraction efficiency given by the mixture (NH4)2SO4/NaH2PO4 was also assessed on biological and food samples, confirming that overall it performed better than NaCl.

Preparation of C18 composite solid-phase microextraction fiber and its application to the determination of organochlorine pesticides in water samples

In this work, a C18 composite solid-phase microextraction (SPME) fiber was prepared with a new method and applied to the analysis of organochlorine pesticides (OCPs) in water sample. A stainless steel wire (o.d. 127μm) was used as the substrate, and a mixture of the C18 particle (3.5μm) and the 184 silicone was used as the coating material. During the process of fiber preparation, a section of capillary column was used to fix the mixture onto the stainless steel wire and to ensure the constant of coating thickness. The prepared fiber showed excellent thermal stability and solvent resistance. By coupling with gas chromatography–mass spectrometry (GC–MS), the fiber exhibited wide linearity (2–500ngL−1) and good sensitivity for the determination of six OCPs in water samples, the OCPs tested included hexachlorobezene, trans-chlordane, cis-chlordane, o,p-DDT, p,p-DDT and mirex. Not only the extraction performance of the newly prepared fiber was more than seven times higher than those of commercial fibers, the limits of detections (LODs) (0.059–0.151ngL−1) for OCPs achieved under optimized conditions were also lower than those of reported SPME methods. The fiber was successfully applied to the determination of OCPs in real water samples by using developed SPME–GC–MS method.

Preparation, characterization, and applications of a novel solid-phase microextraction fiber by sol-gel technology on the surface of stainless steel wire for determination of poly cyclic aromatic hydrocarbons in aquatic environmental samples

A novel solid-phase microextraction(SPME) fiber was prepared using sol–gel technology with ethoxylated nonylphenol as a fiber coating material. The fiber was employed to develop a headspace SPME–GC–MS method suitable for quantification of 13 polycyclic aromatic hydrocarbons (PAHs) in water samples. Surface characteristics of the fibers were inspected by energy dispersive X-ray (EDX) spectroscopy as well as by scanning electron microscopy (SEM). The SEM measurements showed the presence of highly porous nano-sized particles in the coating. Important parameters affecting the extraction efficiency such as extraction temperature and time, desorption conditions as well as ionic strength have been evaluated and optimized. In the next step, the validation of the new method have been performed, finding it to be specific in the trace analysis of PAHs, with the limit of detection (LOD) ranging from 0.01 to 0.5μgL−1 and the linear range from the respective LOD to 200μgL−1with RSD amounting to less than 8%. The thermal stability of the fibers was investigated as well and they were found to be durable at 280°C for 345min. Furthermore, the proposed method was successfully applied for quantification of PAHs in real water samples.