Headspace Solid-phase Microextraction Technique Research Articles

Rearing and 60Co radiation do not affect attractiveness but alter the volatile profiles released by Anastrepha obliqua calling males.

Calling males of Anastrepha obliqua release volatile compounds to attract conspecific males to form leks and females to mate. Male volatiles from Mexican and Brazilian populations of A. obliqua have been previously identified. However, there are differences in the number and identity of volatile compounds between the populations. These differences in volatile profiles may be due to male origin (e.g. wild or mass-reared flies) or methodological issues (e.g. sampling techniques). In this study, we evaluated the attractiveness of wild, laboratory non-irradiated, and laboratory-irradiated flies under semi-field conditions. Male volatiles were collected using dynamic headspace sampling (DHS) and solid-phase microextraction (SPME) techniques, and identified using gas chromatography-coupled mass spectrometry. The results showed no difference in the attractiveness of wild, laboratory non-irradiated, and irradiated males to females. However, the number of captured females differed according to the origin; wild and non-irradiated females were captured more frequently than the irradiated flies. A total of 21 compounds were found using SPME, whereas only 12 were collected using DHS, although the relative amounts of these compounds were higher than those obtained using the former sampling technique. In addition, only laboratory non-irradiated males released α-pinene and menthol, which have not been previously reported in this fruit fly species. Additionally, we identified novel compounds in A. obliqua; however, certain compounds previously reported were not detected. This study suggests that despite the qualitative and quantitative variations in the volatile profiles of A. obliqua males, their attractiveness was unaffected.

Optimization and validation for identification of volatile organic com-pounds released from Trogoderma variabile Ballion using headspace solid-phase microextraction and GC-FID/MS

Volatile organic compounds (VOC) emitted by Trogoderma variabile at different life stages (larvae, female and male) can help us to understand the chemical signals that are released by the beetle which can serve as biomarkers for diagnostic purpose. There are several factors that effect on the optimization of VOC extraction including, temperature, jar size, number of insects, duration of extraction, and gas chromatography (GC) conditions. This study used headspace solid phase microextraction (HS-SPME) fibre coupled with flame ionization detection (FID) and gas chromatography with mass spectrometry (GC-MS) to determine the optimal method for accurate, rapid and cost-effective extraction and identification of VOC from different life stages of T. variabile. The HS-SPME technique and the analytical conditions with GC and GCMS were optimized and validated for the determination of VOCs released from T. variabile. Selection of the number of insects was based on the height and the number of peaks. Results showed that 15 and 20 larvae and adults respectively gave the best number of peaks. Sixteen hours were optimized as the best extraction time for larvae and adults to get maximum number of emitted VOCs. The number of compound released from T.variabile different stages was 7, 9 and 11 for male, female and larvae respectively. Furthermore, some compounds were identified in all stages such as oxime-, methoxy-phenyl, 2(3H)-furanone, 5-ethyldihydro- and nonanal. Also, most of the compounds were significantly different in peak area between different life stages.

A Study of Headspace Solid-Phase Microextraction in the Analysis of 54 Hydrophobic Pollutants in Remote Alpine Lake Waters with an Emphasis on Analyte Recovery and Storage Time.

Commercially available headspace solid-phase microextraction (HS-SPME) fibers have been used for years to extract pesticides and polychlorinated biphenyls from aqueous samples at the expected ultratrace levels (picograms per liter or parts per quadrillion) in alpine lakes. Several variables of the HS-SPME technique have been adequately evaluated, including water temperature, pH, salt content, fiber type and coating thickness, length of fiber-sample exposure, and liquid immersion versus headspace exposure; but surprisingly, analyte recovery as a function of analyte concentration and storage time has not been included in previous studies, which can be important for remote sampling sites. Seven hydrophobic chlorinated pollutants were identified in alpine lake water (out of 54 analyzed); but recovery using the common SPME technique was found to be inconsistent as the analyte concentration decreases, and the recovery trend as a function of concentration varies on a compound-to-compound basis that could result in a large underestimation of analyte concentrations in field samples. Of the 54 compounds surveyed, o,p'-dichlorodiphenyltrichloroethane (DDT), p,p'-DDT, p,p'-dichlorodiphenyldichloroethylene (DDE), o,p'-DDE, chlorthal-dimethyl, endosulfan I, γ-hexachlorocyclohexane, heptachlor, and trans-nonachlor were generally measured at concentrations between 1 and 150 pg/L (parts per quadrillion). No study to date has evaluated this commonly used but unstandardized technique for analyte recovery as a function of analyte concentration or storage time of aqueous samples. Environ Toxicol Chem 2023;42:1199-1211. © 2023 SETAC.

Headspace Solid Phase Micro-Extraction of Volatile Constituents Produced from Saudi Ruta chalepensis and Molecular Docking Study of Potential Antioxidant Activity.

Ruta chalepensis L., commonly known as Shazab in Saudi Arabia, is one of the famous culinary plants belonging to the Rutaceae family. It is commonly used in ethnomedicine in treating numerous diseases. This study was performed to characterize the essential oil isolated from Saudi species using a relatively new advanced headspace solid-phase microextraction technique. Following that, the antioxidant activity of the extracted oil was assessed using in vitro techniques such as the DPPH and nitric oxide scavenging tests, as well as the reducing power FRAP study and the molecular docking tool. The essential oil yield of the dried plant was 0.83% (v/w). Gas chromatography joined with a mass spectrometer was used to determine the chemical composition of the pale-yellow essential oil. Sixty-eight constituents were detected, representing 97.70% of the total oil content. The major constituents were aliphatic ketones dominated by 2-undecanone (37.30%) and 2-nonanone (20.00%), with minor constituents of mono and sesquiterpenoids chemical classes. Nicotinamide adenine dinucleotide phosphate (NADPH) oxidase is one of the major causes of many contemporary diseases due to its ability to create a reactive oxygen species (ROS). Thus, molecular docking was used to confirm that some oil phytoconstituents have good docking scores compared to the standard antioxidant drug (Vitamin C), indicating great binding compatibility between the (NADPH) oxidase receptor site and the ligand. In conclusion, our findings suggest that the oil could be used safely and as a cost-effective remedy in treating various modern diseases caused by free radical formation.

INVESTIGATIONS ON MORPHO-ANATOMICAL AND VOLATILE COMPOUNDS OF CULTIVATED Fritillaria persica L. (LILIACEAE)

In this study, cultivated Fritillaria persica L. (Liliaceae) investigated morpho-anatomical and volatile compounds of bulbs. Purple tepals, 12-28 flowers in inflorescence, yellow-green filaments and dark yellow or purple anthers were notable morphological properties. For the anatomical study, sections were prepared from root, stem and leaf. The cortex of the stem was comprised of parenchyma and sclerenchyma. The collateral vascular bundles were scattered. The leaves were unifacial and amphistomatic. The stomata type was anomocytic. The crushed bulb volatiles of F. persica were trapped by the headspace-solid phase microextraction technique and determined by analysis by gas chromatography/mass spectrometry. Eight compounds (83.9%) were identified and the major compounds were found as 1,3-dichlorobenzene (60%), limonene (8.1%) and p-cymene (5.1%).

Analize ugljovodonika (PAH, alkana i bteks) u morskoj vodi luke Valona

In this study, levels of polycyclic aromatic hydrocarbons (PAH), aliphatic hydrocarbons (n-alkanes) and volatile hydrocarbons were determined in water samples of the port of Vlora which is the second largest port in Albania. It is located in Vlora Bay, near Vlora city. Presence of these pollutants in port area is mainly because of ships transport, commercial/passengers processing and the water currents in-side/out-side the port area. Hydrocarbons (PAHs, n-alkanes and BTEX) are generated mainly by the transport (automobiles, ships, trains, etc), extracting/processing of oil industry, coal mine and other industries. Forest burning and their natural background make them very often in environment. Water samples were taken in May 2022 in different stations of the Vlora's port (inside and outside its area). Aromatic and aliphatic hydrocarbons were extracted simultaneously using two steps liquid-liquid extraction (LLE) technique. Firstly, dichloromethane (MeCl2) and after that n-hexane were used as extraction solvents. After extraction, the organic phase was dried with sodium sulfate anhydrous, for water removing. "Clean-up" procedure was realized in an alumina column. After the concentration to 2 ml, the samples were injected in Varian 450 GC equipped with FID detectors. BTEX were analyzed using head space solid phase micro-extraction technique (HS/SPME) by using polydimethylsiloxane fiber (PDMS) followed by GC/FID technique. PAH, n-alkanes and BTEX were found almost in all water samples of Vlora's port. Their presence could be because of anthropogenic factors (elevated activity and ship transport) in the port area. The levels of hydrocarbons in water samples of Vlora's port were higher / comparable than reported levels for them in other stations of the Adriatic Sea, Albania part.

Headspace Solid-Phase Micro-Extraction Versus Hydrodistillation of Volatile Compounds from Leaves of Cultivated Mentha Taxa: Markers of Safe Chemotypes.

Various mint taxa are widely cultivated and are used not only for medicinal purposes but also in cosmetic and industrial applications. The development of new varieties or cultivars of mint generates difficulties in their correct identification and safe use. Volatile organic compounds (VOCs) from the leaves of seven different taxa of the genus Mentha obtained by hydrodistillation (HD) and headspace solid-phase microextraction (HS-SPME) were analyzed using gas chromatography–mass spectrometry (GC-MS). Principal component analysis (PCA) was also performed. Comparative GC-MS analysis of the obtained extracts showed similarity in the major compounds. PCA data allowed the separation of two groups of chemotypes among the analyzed mints, characterized by the abundance of piperitenone oxide and carvone. Two out of seven analyzed taxa were not previously examined for VOC profile, one was examined only for patent application purposes, and six out of seven were investigated for the first time using the HS-SPME technique. The presented analysis provides new data on the abundance and qualitative characterization of VOCs in the studied mint plants and on the safety of their use, related to the possibility of the presence of potentially toxic components. HS-SPME is a valuable method to extend the characterization of the VOC profile obtained by hydrodistillation.

Volatile compounds released by acid hydrolysis in jackfruit (Artocarpus heterophyllus Lam.). A comparative study by using SDE and HS-SPME techniques

The volatile compounds of jackfruit (Artocarpus heterophyllus Lam.) released using acid hydrolysis were comprehensively investigated by using simultaneous distillation-extraction (SDE) and headspace-solid phase microextraction (HS-SPME); both coupled to gas chromatography-mass spectrometry (GC-MS). Hydrolyses were carried out at pH 3 to promote the release of aglycones and pH 7 to inhibit enzymatic reactions. Volatile profiles were analyzed by extraction technique. Besides, the aroma potential (AP) of jackfruit was determined. Sixty-nine volatile compounds were identified. Limonene, pentyl 3-methylbutanoate, 1-butanol, butyl 3-methylbutanoate, butanal, and β-cyclocitral were the prominent compounds. The AP of jackfruit was 3.1 and 3.8 mg/kg by utilizing SDE and HS-SPME respectively. The AP of jackfruit released by acid hydrolysis suggests its use as raw material for foodstuffs prepared under thermal and acid conditions at low pH values, promoting the release of aroma precursors and enhancing the flavor of the final product.

Quality and Metabolomics Analysis of Houttuynia cordata Based on HS-SPME/GC-MS.

Houttuynia cordata is a medicinal and edible plant with a wide biological interest. Many parts were discarded due to various modes of consumption, resulting in resource waste. In this study, a comprehensive study was conducted on various edible indicators and medicinal components of Houttuynia cordata to understand its edible and medicinal value. The edible indexes of each root, stem, and leaf were determined, and the metabolites of different parts were investigated using the headspace solid-phase micro-extraction technique (HS-SPME-GC-MS). The differential metabolites were screened by orthogonal partial least squares discriminant analysis (OPLS-DA) and clustering analysis. The results of the study showed that the parts of Houttuynia cordata with high edibility values as a vegetable were mainly the roots and leaves, with the highest vitamin C content in the roots and the highest total flavonoids, soluble sugars, and total protein in the leaves. The nutrient content of all the stems of Houttuynia cordata was lower and significantly different from the roots and leaves (p < 0.05). In addition, 209 metabolites were isolated from Houttuynia cordata, 135 in the roots, 146 in the stems, 158 in the leaves, and 91 shared metabolites. The clustering analysis and OPLS-DA found that the parts of Houttuynia cordata can be mainly divided into above-ground parts (leaves and stems) and underground parts (roots). When comparing the differential metabolites between the above-ground parts and underground parts, it was found that the most important medicinal component of Houttuynia cordata, 2-undecanone, was mainly concentrated in the underground parts. The cluster analysis resulted in 28 metabolites with up-regulation and 17 metabolites with down-regulation in the underground parts. Most of the main components of the underground part have pharmacological effects such as anti-inflammatory, anti-bacterial and antiviral, which are more suitable for drug development. Furthermore, the above-ground part has more spice components and good antioxidant capacity, which is suitable for the extraction of edible flavors. Therefore, by comparing and analyzing the differences between the edible and medicinal uses of different parts of Houttuynia cordata as a medicinal and food plant, good insights can be obtained into food development, pharmaceutical applications, agricultural development, and the hygiene and cosmetic industries. This paper provides a scientific basis for quality control and clinical use.

Urinary Volatomic Expression Pattern: Paving the Way for Identification of Potential Candidate Biosignatures for Lung Cancer.

The urinary volatomic profiling of Indian cohorts composed of 28 lung cancer (LC) patients and 27 healthy subjects (control group, CTRL) was established using headspace solid phase microextraction technique combined with gas chromatography mass spectrometry methodology as a powerful approach to identify urinary volatile organic metabolites (uVOMs) to discriminate among LC patients from CTRL. Overall, 147 VOMs of several chemistries were identified in the intervention groups—including naphthalene derivatives, phenols, and organosulphurs—augmented in the LC group. In contrast, benzene and terpenic derivatives were found to be more prevalent in the CTRL group. The volatomic data obtained were processed using advanced statistical analysis, namely partial least square discriminative analysis (PLS-DA), support vector machine (SVM), random forest (RF), and multilayer perceptron (MLP) methods. This resulted in the identification of nine uVOMs with a higher potential to discriminate LC patients from CTRL subjects. These were furan, o-cymene, furfural, linalool oxide, viridiflorene, 2-bromo-phenol, tricyclazole, 4-methyl-phenol, and 1-(4-hydroxy-3,5-di-tert-butylphenyl)-2-methyl-3-morpholinopropan-1-one. The metabolic pathway analysis of the data obtained identified several altered biochemical pathways in LC mainly affecting glycolysis/gluconeogenesis, pyruvate metabolism, and fatty acid biosynthesis. Moreover, acetate and octanoic, decanoic, and dodecanoic fatty acids were identified as the key metabolites responsible for such deregulation. Furthermore, studies involving larger cohorts of LC patients would allow us to consolidate the data obtained and challenge the potential of the uVOMs as candidate biomarkers for LC.

GNP/Al-MOF nanocomposite as an efficient fiber coating of headspace solid-phase micro-extraction for the determination of organophosphorus pesticides in food samples.

Thesynthesis and utilization of a high porous nanocomposite comprising MIL-53(Al) metal-organic framework (Al-MOF) and graphene nanopowder (GNP) is reportedas a fiber coating for headspace solid-phase micro-extraction (HS-SPME) of selected organophosphorus pesticides (OPPs) from apple, potato, grape juice, tomato, and river water. The adsorbed OPPs on the coated fiber were subsequently determined using GC-MS. Several parameters affecting the efficiency of extraction including time and temperature of extraction, desorption condition of extracted analytes, pH and agitation of sample solution, and salt concentration were investigated. The optimum extraction condition was achieved at 70°C with an extraction time of 40min, pH = 4-8, and NaCl concentration of 6.0% (w/v). The best condition of desorption wereobserved at280°C for 2.0min under a flow of helium gas in the GC inlet. Under optimal conditions, the detection limits ranged from 0.2 to 1.5ngg-1 and the linear ranges between 0.8 and 600ngg-1. The proposed method showed very good repeatability with RSD values ranging from 4.5 to 7.3% (n = 5). The relative recoveries were between 88% and 109% at the spiked level of 25.0ngg-1 for the tomato sample. The fabricated fiber exhibited good enrichment factor (62-195) at optimum condition of HS-SPME. The applied HS-SPME technique is facile, fast, and inexpensive. The thermally stable GNP/Al-MOF exhibited a high sensitivity toward OPPs. So, this nanocomposite can be considered as a sorbent for the micro-extraction of other pesticides in food.

Potential of Industrial Pineapple (Ananas comosus (L.) Merrill) By-Products as Aromatic and Antioxidant Sources.

Pineapple is meanly commercially processed. However, it is a fruit that generates a high proportion of nonedible wastes, which are rich in antioxidant compounds and have a varied aromatic profile. These characteristics turn these by-products into potential agri-food waste that can be revalued and applied in different fields such as medical, pharmaceutical, or food applications. The aim of the present work was the characterization and extraction of the volatile compounds present in two pineapple by-products (peel and core) and the subsequent evaluation of their antioxidant capacity. For this purpose, the analysis of the aromatic profile of both by-products has been carried out using the headspace solid-phase microextraction technique coupled to gas chromatography with a mass spectrometry detector (HS-SPME-GC-MS). The optimization of the extraction conditions of the volatile compounds has been validated using a Box–Behnken experimental design. In addition, a quantitative analysis was carried out to determine the contents of two important volatiles in pineapple wastes, isopentyl, and ethyl acetate. Moreover, the estimation of the antioxidant capacity of the subproducts extracts was carried out using different methods All the antioxidant assays demonstrated that pineapple subproducts are rich in easily extractable antioxidants with possible applications in the food industry.

Optimization of headspace solid-phase microextraction technique for the volatile compounds of Prunus mahaleb L. (mahaleb) kernel

Optimization of headspace solid-phase microextraction technique for the volatile compounds of Prunus mahaleb L. (mahaleb) kernel

Kinetic response of conformational variation of duck liver globular protein to ultrasonic stimulation and its impact on the binding behavior of n-alkenals

This work investigated the effects of low-frequency ultrasound (US) induced conformational variation of duck liver globular proteins (DLGPs) on the binding behavior of n-alkenals based on multi-spectroscopic analysis combined with headspace solid phase microextraction technique. Results suggested that US-treatments, with the frequency of 40 kHz and the power density of 26.7 W/L, induced obvious tertiary and quaternary structure changes of DLGPs, as revealed by fluorescence and ultraviolet–visible absorption spectroscopy, whereas the secondary and primary structures of DLGPs remained almost unaffected, suggesting the presence of molten-globule (MG) intermediates due to US-treatment. Meanwhile, the particles size and absolute values of ζ-potential exhibited significant increases as the functions of ultrasonic durations. According to multivariate results, the conformational variations, involving natural, MG and post-MG states, could be differentiated successfully. The US-induced conformational changes of DGLPs allowed it easier to interact with volatile n-alkenals, attributed to the enhanced hydrophobic interaction and covalent binding. Correspondingly, the headspace fractions of n-alkenals were greatly reduced after ultrasound pretreatments, with different degrees ranging from 5.61 to 59.39%, depending on chemical structures and processing conditions. This work suggests the great potential of specific conformational variations of DLGPs induced by ultrasonic pretreatments to modulate flavor features of protein-based products.

Extraction of volatile organic compounds from leaves of Ambrosia artemisiifolia L. and Artemisia annua L. by headspace-solid phase micro extraction and simultaneous distillation extraction and analysis by gas chromatography/mass spectrometry

This study was designed to analyze the volatile organic compounds in the leaves of Ambrosia artemisiifolia L. and Artemisia annua L. from Korea. For extraction of volatile compounds, headspace-solid phase micro extraction (HS-SPME) and simultaneous distillation extraction (SDE) were applied and analyzed by gas chromatography/mass spectrometry (GC/MS). From the results, SDE extraction was found to give the highest concentration of volatile compounds with an average concentration of 1,237.79 mg/kg for A. annua L. leaves compared to 1,122.73 mg/kg by HS-SPME technique. A total of 116 volatile organic compounds were identified, including 76 similar volatile organic compounds detected by both the methods of extraction in leaves of subject species at varying concentrations. Among these 33 volatile organic compounds were reported for the first time from the subject plant species. Thus the present research findings extend the characterization of volatile organic compounds from leaves of A. annua L. and A. artemisiifolia L. species and reported some distinguishing compounds which may be used for their discrimination.

In vivo and in vitro Volatile Constituents of the Flowers of Xylopia aromatica by HS‑SPME/GC-MS

Xylopia aromatica (Lam.) Mart. (Annonaceae) is a typical species from the Brazilian cerrado that presents medicinal properties. The plant is distinguished by its large white flowers which produce a pleasant fragrance. X. aromatica is characterized by a wide range of medicinal application. These characteristics have motivated us to investigate the flowers volatile organic compounds (VOCs) via in vivo and in vitro protocols by a headspace solid-phase microextraction (HS‑SPME) technique combined with gas chromatography-mass spectrometry (HS-SPME/GC‑MS). Four different fibers, extraction times and temperatures were the parameters changed to lead to the maximum profiling of the volatile constituents. Data were analyzed using principal component analysis (PCA). A total of 77 VOCs were extracted from the floral scent, with 52 and 68 extracted from in vivo and in vitro sampling, respectively, of which 48 were reported for the first time in the literature as volatile constituents from X. aromatica flowers. The extraction and identification of VOCs were successfully performed through HS-SPME/GC-MS. The PCA data allowed the identification of parameters that led to the maximum number of VOCs, which were polyacrylate (PA) and carboxen/polydimethylsiloxane (CAR/PDMS) fibers, 60 min extraction time and temperature of 29.0 °C. Among the volatile constituents identified, sesquiterpenes predominated, comprising about 61.04%.

Chemometric tools applied to optimize a fast solid-phase microextraction method for analysis of polycyclic aromatic hydrocarbons in produced water.

Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase microextraction procedure, which was used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in oil-based produced water using a Headspace-Solid Phase Microextraction technique (HS-SPME/GC-MS). This optimization was achieved with a 24 factorial design approach, where the final conditions for this extraction procedure were 10 μg L-1, 1 h, 92 °C (at headspace), and 0.62 mol L-1 for PAHs concentration, fiber exposition to headspace, temperature, and NaCl concentration, respectively. The limit of detection (LOD) in this protocol ranged from 0.2 to 41.4 ng L-1, while recovery values from 67.65 to 113.10%. Besides that, relative standard deviation (RSD) were lower than 8.39% considering high molecular weight compounds. Moreover, the proposed methodology in this work does not require any previous treatment of the sample and allows to quantify a higher number of PAHs. Notably, naphthalene was the major PAHs compound quantified in all samples of the produced water at 99.99 μg L-1. Altogether, these results supported this methodology as a suitable analytical strategy for fast determination of PAHs in produced water from oil-based industry.

Determination of volatile compounds responsible for sensory characteristics from Brazilian extra virgin olive oil using HS-SPME/GC-MS direct method.

Producing of extra virgin olive oils (EVOOs) containing pleasant sensory notes depends on fruits quality and production process and is strongly associated with their classification that is based on aroma and sensory taste. Consolidated as an efficient method, the direct headspace solid phase microextraction technique (HS-SPME) was utilized to characterize the volatile organic compounds (VOCs) profile, which contributes to the aroma of olive oils from southwestern (Serra da Mantiqueira region) and southern (Campanha Gaúcha region) Brazil. In this work, the relationship between the VOCs and sensory characteristics has been established; 19 EVOO samples (12 from Campanha Gaúcha and 7 from Serra da Mantiqueira) were studied. Indeed, the main volatile compounds were analyzed and grouped by their classification as well stood up with the trained sensorial panel perceptions. Relevant correlation between artichoke notes and ripe EVOO and between herbaceous notes and green EVOO was found. Additional correlations were observed for C5 and C6 VOCs with green and fruit/floral notes. The results denote the high quality among the samples and imply that besides the genetic factor, ripe or green classification influenced the volatile composition. PRACTICAL APPLICATION: As the Brazilian olive oil production is increasing, knowing about different sensory characteristics and its correlation with the volatile compounds of extra virgin olive oil represents a good tool to improve the quality. Moreover, the application of direct SPME method was possible evidence in the differentiation of ripe and green olive oils, beyond the production region and in consonance with its sensory notes and characteristics.

Enhancement of volatile profiling using multiple-cumulative trapping solid-phase microextraction. Consideration on sample volume

In the present work, the performance of the multiple-cumulative trapping headspace solid-phase microextraction technique used in the headspace linearity range and saturated headspace was investigated and compared, with the ultimate goal of maximizing the fingerprinting information extractable using a cross-sample comparison algorithm for olive oil quality assessment. It was highlighted as the use of 0.1 g of olive oil provides comparable or even better profiling than 1.5 g at a little expense of sensitivity. However, the use of multiple-cumulative-solid-phase microextraction, along with the correct sample volume, improved not only the overall sensitivity but significantly burst the level of information for cross-sample studies.

Development of the Method for Determination of Volatile Sulfur Compounds (VSCs) in Fruit Brandy with the Use of HS-SPME/GC-MS.

Volatile sulfur compounds (VSCs) play an important role in the aroma profile of fermented beverages. However, because of their low concentration in samples, their analysis is difficult. The headspace solid-phase microextraction (HS–SPME) technique coupled with gas chromatography and mass spectrometry (GC–MS) is one of the methods successfully used to identify VSCs in wine and beer samples. However, this method encounters more obstacles when spirit beverages are analyzed, as the ethanol content of the matrix decreases the method sensitivity. In this work, different conditions applied during HS–SPME/GC–MS analysis, namely: ethanol concentration, salt addition, time and temperature of extraction, as well as fiber coating, were evaluated in regard to 19 sulfur compounds. The best results were obtained when 50/30 μm Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS) was used to preconcentrate the analytes from the sample at 35 °C for 30 min. The dilution of samples to 2.5% v/v ethanol and the addition of 20% w/v NaCl along with 1% EDTA significantly improves the sensitivity of extraction. The optimized method was applied to three fruit brandy samples (plum, pear, and apple) and quantification of VSCs was performed. A total of 10 compounds were identified in brandy samples and their concentration varied greatly depending on the raw material used from production. The highest concentration of identified VSCs was found in apple brandy (82 µg/L).