Search Results (155)

Due to the ultra-trace concentrations of perfluoroalkyl compounds (PFCs) existing in environmental aqueous matrices, it is imperative to develop sensitive and high-enrichment-efficiency approaches for the determination of these emerging pollutants. In this study, a nitrogen-doped carbon dot-functionalized hollow fiber membrane (NCDs@HFM) was fabricated and employed in solid-phase microextraction (SPME) mode for the simultaneous identification of eight perfluoroalkyl carboxylates (PFCAs). The NCDs@HFM offers several advantages, including multiple active binding sites, chemical durability, a large specific surface area and environmental compatibility. Owing to these properties, the NCDs@HFM-based SPME demonstrated high extraction efficiency for PFCAs, where enrichment factors for target molecules could reach 35–61 fold under the optimum conditions. This established method was then integrated with liquid chromatography–tandem mass spectrometry (LC-MS/MS) for the qualitative and quantitative analysis of eight representative PFCAs in drinking and environmental water samples. The limits of detection (LODs, S/N = 3) and quantitation (LOQs, S/N = 10) of the method were at the scale of 0.0018–0.015 μg/L and 0.006–0.050 μg/L, respectively. This proposed method exhibited good precision, with RSDs below 13.2% and satisfactory accuracy, with recoveries ranging from 70.6% to 122.5%. The developed method was successfully applied in the identification of eight typical PFCAs in drinking and environmental water samples. This method exhibits several merits, including low cost, high sensitivity, good reliability and reusability, representing a promising alternative for measuring trace levels of PFCAs in aqueous matrices. Full article

C₁₃-Norisoprenoids are important contributors to the aroma of Riesling wine. Their quantification is analytically challenging due to their low concentrations, the lack of commercial standards and their pronounced sensitivity to analytical conditions, reflecting their chemical lability, as well as the dynamic nature of the wine matrix, leading to high reactivity and, consequently, remarkable structural diversity. Here, we developed an assay for the analysis of C₁₃-norisoprenoids in wine using headspace solid-phase microextraction coupled to gas chromatography–mass spectrometry (HS-SPME–GC-MS/MS). After evaluating different fiber materials, a statistical design of experiments (DoE) approach was employed to systematically optimize key HS-SPME parameters, including incubation, extraction and desorption conditions. Selected reaction monitoring (SRM) transitions were established for all targeted C₁₃-norisoprenoids, allowing the assay to provide relative quantification of more than 40 compounds using representative labeled and unlabeled standards to generate linear calibration curves. Following method validation, this approach was applied to a young German Riesling wine to investigate the effect of various acidic hydrolysis conditions on the norisoprenoid profile as well as on specific compounds. A central composite design (CCD) was used to systematically study the impact of pH, temperature, and hydrolysis time. Quantitative data were obtained for 22 C₁₃-norisoprenoids demonstrating that hydrolysis conditions strongly affected the norisoprenoid composition. pH and temperature showed a greater influence than reaction time. Response surface models (RSM) indicated that TDN, Vitispirane and TPB in particular are predominantly formed under strongly acidic and high-temperature conditions, whereas others such as Riesling acetal and actinidols are formed under milder conditions. The results indicate that hydrolysis conditions should be tailored to the specific norisoprenoid under investigation and the research question, particularly when simulating conditions of accelerated wine ageing for analytical purposes. Full article

Background: Alecrim-do-campo (Baccharis dracunculifolia) is a species of agroindustrial and medicinal relevance that has attracted increasing interest in recent years due to its distinctive chemical profile rich in bioactive compounds. In this context, the present study evaluated the efficiency of different extraction conditions for volatile compounds in alecrim-do-campo, aiming to contribute to the traceability of products that use this species as a source of metabolites. Methods: A 2³ factorial design was employed to assess the best conditions for extracting volatiles by headspace solid-phase microextraction (HS-SPME), using three different semipolar fibers (PDMS/DVB, DVB/CAR/PDMS and CAR/PDMS). Regarding the effect of the variation factors to which the samples were subjected, only the extraction time (min) had a significant effect on compound extraction using the CAR/PDMS fiber. Results: In total, 79 volatile compounds were detected using the three fibers, with CAR/PDMS (43 compounds) and DVB/CAR/PDMS (44 compounds) showing the highest diversity. The nature of this study is important for the industry because it optimizes the search for quality parameters in plant-derived products. Full article

Background/Objectives: Volatile organic compounds (VOCs) are emerging as non-invasive biomarkers of metabolic and disease-related processes, yet their reliable detection from complex biological matrices such as urine remains analytically challenging. This study aimed to establish a robust, non-targeted headspace solid-phase microextraction gas chromatography–mass spectrometry (HS–SPME GC–MS) workflow optimized for very small-volume urinary samples. Methods: We systematically evaluated the effects of pH adjustment and NaCl addition on VOC extraction efficiency using a 75 µm CAR/PDMS fiber and a sample volume of only 0.75 mL. Method performance was further assessed using concentration-dependent experiments with representative VOC standards and by application to real human urine samples analyzed in technical triplicates. Results: Acidification to pH 3 markedly improved extraction performance, increasing both total signal intensity and the number of detectable VOCs, whereas alkaline conditions and additional NaCl produced only minor effects. Representative VOC standards showed compound-specific linear dynamic ranges with minimal carry-over within the relevant analytical range. Application to real urine samples confirmed high analytical reproducibility, with triplicates clustering tightly in principal component analysis and most metabolites exhibiting relative standard deviations below 25%. Conclusions: The optimized HS–SPME GC–MS method enables comprehensive, non-targeted urinary VOC profiling from limited sample volumes. This workflow provides a robust analytical foundation for exploratory volatilomics studies under sample-limited conditions and supports subsequent targeted method refinement once specific compounds or chemical classes have been prioritized. Full article

Volatile organic compounds (VOCs) emitted from human skin are promising biomarkers for non-invasive health assessment and disease diagnosis. However, efficient collection and sensitive analytical methods for skin VOCs remain challenging. We developed a method for measuring ethanol, acetaldehyde, and acetone from palmar skin using glass cup aqueous sampling followed by headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Compounds were extracted using a carboxen/polydimethylsiloxane fiber by HS-SPME and separated using a DB-1 capillary column within 5 min. The HS-SPME/GC-MS method showed linearity (5–1000 ng/mL, r ≥ 0.990) with detection limits of 0.56, 1.01, and 0.15 ng/mL for ethanol, acetaldehyde, and acetone, respectively. Intra-day and inter-day precision were ≤9.3% and ≤9.7%, with accuracy ranged of 94–110%. Five-minute palm contact with water caused VOC release to increase linearly, and samples remained stable for 24 h at −20 °C. Following ingestion of a 500 mL alcoholic beverage (5% ethanol), ethanol and acetaldehyde emissions peaked at 95 and 24 ng/cm²/min after 1 h, while acetone gradually increased to 1.3 ng/cm²/min after 6 h. This simple, rapid method enables practical assessment of skin VOCs for health monitoring and environmental exposure evaluation. Full article

Propolis is a substance produced by bees from the collection of plant resins, with a chemical composition that varies according to the available flora and region, and it has several biological activities. Stingless bee propolis is often produced in reduced amounts, posing a challenge to the study of their volatile compounds, as traditional hydrodistillation extraction would demand more raw propolis than available. These bees collect resins from various sources, resulting in a variable composition, so a standardized reproducible method is fundamental for their analysis. Headspace solid-phase microextraction (HS-SPME), associated with gas chromatography, appears to be an efficient alternative for the analysis of these volatiles. In this study, the GC-MS results of three types of SPME fibers were compared to those of extracts obtained by hydrodistillation to evaluate their efficiency in representing the composition of essential oils from (geo)propolis of different species. The extraction time and temperature were also standardized. Among the fibers tested, PDMS/DVB extracted the volatiles in a similar manner to the essential oil obtained by hydrodistillation for all the samples tested, indicating this to be the best choice of fiber coating for propolis volatile extraction and analysis. Full article

Odorous emissions from hot-mix asphalt (HMA) plants are a growing environmental concern, particularly due to airborne aldehydes and ketones, which have low odor thresholds and a strong sensory impact. This study presents a field-ready analytical method for monitoring odor-active volatile compounds. The system uses dynamic solid-phase microextraction (SPME and SPME Arrow) with on-fiber derivatization via O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and is coupled to gas chromatography–mass spectrometry (GC–MS) for direct detection. A flow-cell sampling unit enables the real-time capture of aliphatic aldehydes and ketones under transient emission conditions. Calibration using permeation tubes demonstrated sensitivity (limits of detection (LODs) below 0.13 μg/m³), recovery above 85% and consistent reproducibility. Compound identity was confirmed using retention indices and fragmentation patterns. Uncertainty assessment followed ISO GUM (Guide to the Expression of Uncertainty in Measurement) standards, thereby validating the method’s environmental applicability. Field deployment 200 m from an HMA facility identified measurable concentrations that aligned with CALPUFF model predictions. The method’s dual-isomer resolution and 10 min runtime make it ideal for responding to time-sensitive odor complaints. Overall, this approach supports regulatory efforts by enabling high-throughput on-site chemical monitoring and improving source attribution in cases of odor nuisance. Full article

Smokeless powders are a commonly used low explosive within the ammunition industry. Their ease of purchase has allowed criminals to use these products to build improvised explosive devices. Canines have become a vital tool in locating such improvised devices. With differing fabrication processes, one of the most difficult challenges for canine handlers is the optimal selection of training aids to choose as odor targets to allow for broad generalization. Several studies have been underway to understand the chemical odor characterization of smokeless powders, which can help provide canine teams with essential information to understand odor signatures from powder varieties. In this study, a SPME method optimization was conducted using unburned smokeless powders to provide a chemical odor profile assessment. Concurrently, statistical analysis using PCA and Spearman’s rank correlations was performed to explore whether odor volatile composition depicted associations between and within powder brands. The results showed that a longer extraction time (24 h) was optimal across all powders, as this yielded higher compound abundance and number of extracted odor volatiles. The optimal SPME fiber varied per powder, depicting the complexity of powder composition. There were 66 highly frequent compounds among the 18 powders, including 2-ethyl-1-hexanol, diphenylamine (DPA), and dibutyl phthalate. Principal component analysis (PCA) showed that while powders may be of the same type (single/double base), they can still portray clustering differences across and within brands. The Spearman’s rank correlation within powder type suggested that the double-base powders had a slightly higher similarity index when compared with the single-base powder types. Understanding the volatile odor profiles of various smokeless powders can enhance canine training by informing the selection of effective training aids and supporting odor generalization. Full article

This study presents the first comprehensive characterization of Brazilian propolis residue, revealing its rich content of bioactive compounds, essential nutrients, and volatile substances, showcasing its potential for sustainable utilization. The term “residue” refers to the solid by-product remaining after ethanolic extraction of raw propolis, which is typically discarded, despite retaining significant nutritional value. HPLC-ESI-MS/MS analysis identified significant concentrations of p-coumaric acid (637.80 mg/kg), chlorogenic acid (497.93 mg/kg), kaempferol (295.82 mg/kg), and caffeic acid (115.11 mg/kg); while HPLC-DAD revealed also artepillin-C (56.56 mg/kg), illustrating strong antioxidant properties. Nutritional analyses showed high moisture content (37.08%), protein (12.56%) and dietary fiber (24.2%). Additionally, the mineral profile highlighted potassium (9800 mg/kg), phosphorus (2520 mg/kg), and calcium (2100 mg/kg). Volatile compounds analysis via HS-SPME-GC-MS identified a diverse class of components, predominantly terpenoids such as α-pinene (20.09%) and caryophyllene (9.76%), suggesting potential applications in fragrance and flavor industries. The multifunctional nature of propolis residue aligns with circular economy principles and highlights its value as a resource for diverse applications. Full article

A solid phase microextraction (SPME) method coupled with liquid chromatography (LC) and fluorescence/ultraviolet-diode array detection was developed for the simultaneous determination of quercetin and trans-resveratrol. The chromatographic, detection, and SPME extraction/desorption conditions were systematically optimized. The performance of four commercial SPME fibers—polyacrylate (PA), polyethylene glycol (PEG), polydimethylsiloxane (PDMS), and polydimethylsiloxane-divinylbenzene (PDMS-DVB)—was evaluated and compared with a homemade polydopamine (PDA)-coated fiber. While all of the fibers successfully extracted the target analytes, their efficiencies varied significantly. The PA, PEG, and PDA fibers demonstrated superior performance, exhibiting wide linearity ranges (0.03–1 µg/mL (PA and PEG) and 0.06–1 µg/mL (PDA) for quercetin, 0.01–1 µg/mL for trans-resveratrol); high sensitivity (LODs of 0.01 µg/mL (PA and PEG) and 0.02 µg/mL (PDA) for quercetin, 0.003 µg/mL for trans-resveratrol); and excellent precision. Among these, the polyacrylate coating delivered the best analytical performance and was selected for further application. The optimized method was applied to analyze winemaking by-products (seeds, skins, and stalks) using SPME on ethanol-macerated extracts subjected to brief ultrasonication. Quercetin and trans-resveratrol were quantified in pomace extracts at concentrations of 104.3 ± 8.2 µg/g and 38.5 ± 4.1 µg/g, respectively. Recovery experiments confirmed the method’s accuracy, with recoveries of 99.1 ± 7.4% for quercetin and 98.5 ± 9.8% for trans-resveratrol. This study establishes a reliable, sensitive, and efficient approach for the determination of these bioactive compounds in complex matrices, with potential applications in the food and pharmaceutical industries. Full article

In this review, a 5-year overview on environmentally friendly approaches for the extraction of the most relevant organic pollutants in soil, sediment, particulate matter, and sewage sludge coupled with chromatographic analysis is reported. Organic contaminants encompass various compounds derived from personal care products, industrial chemicals, microplastics, organic matter combustion, agricultural practices, and plasticizer material. The principles of green analytical chemistry (GAC) and green sample preparation (GSP) serve as a guideline for the development of more environmentally sustainable analytical protocols. This study focuses attention on microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE), matrix solid-phase dispersion (MSPD), and microextraction techniques, such as solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE), hollow-fiber liquid-phase microextraction (HF-LPME), spray-assisted droplet formation-based liquid-phase microextraction (SADF-LPME), and dispersive liquid–liquid extraction (DLLME). These approaches represent the most relevant eco-friendly sample preparation for the advanced extraction of target analytes from environmental solid samples. Full article

A covalent organic framework TPB-DMTP was physically coated onto the gully-like surface of stainless-steel fiber. The fabricated TPB-DMTP-coated stainless-steel fiber was used to extract five phthalic acid esters (PAEs) prior to the GC-FID separation and determination in bottled tea beverages. The developed SPME-GC-FID method gave limits of detection (S/N = 3) from 0.04 µg·L⁻¹ (DBP) to 0.44 µg·L⁻¹ (BBP), with the enrichment factors from 268 (DEHP) to 2657 (DPP). The relative standard deviations (RSDs) of the built method for inter-day and fiber-to-fiber were 4.1–11.8% and 2.3–9.9%, respectively. The prepared TPB-DMTP-coated stainless-steel fibers could stand at least 180 cycles without a significant loss of extraction efficiency. The developed method was successfully applied for the determination of trace PAEs in different bottled tea beverages, with recoveries from 85.5% to 115%. Full article

In this paper, a novel robust TFPA–TTA–COF coating with nano pores was grafted to the gully-like surface of stainless steel fibers (GS-SSF). The GS-SSF were prepared using a two-step electrochemical etching method, and the covalent organic framework (COF) TFPA–TTA–COF coating was chemically bonded to the gully-like surface via in situ growth. The prepared metal fibers were applied as the headspace solid-phase microextraction (HS-SPME) fibers and combined with gas chromatography (GC) to develop a detection method for phenolic compounds (PCs) in water. The developed method gave the limits of detection (S/N = 3) from 0.07 µg·L⁻¹ to 0.52 µg·L⁻¹ with enrichment factors from 243 to 2405. The relative standard deviations for inter-day study (n = 5) and fiber-to-fiber were from 3.94% to 8.89% and 2.17% to 8.05%, respectively. The prepared fiber could stand at least 180 cycles without remarkable loss of extraction efficiency. The developed method was successfully employed for the determination of trace PCs in environmental water with recoveries from 84.76% to 124.84%. Full article

In addition to the immature edible flower heads, the cultivation of globe artichoke (Cynara cardunculus L. var. scolymus (L.) Fiori) generates substantial quantities of by-products, including leaves, stems, and roots, which constitute potential sources of bioactive compounds and prebiotic dietary fiber. Preserving agricultural biodiversity and promoting socioeconomic development are essential for enhancing domestic production and fostering innovation. In the search for new biomolecules with antioxidant properties, this research focused on a globe artichoke landrace at risk of genetic erosion, still cultivated in the northern part of the Lazio region, known as the “Carciofo Ortano”. To investigate the antioxidant properties of various globe artichoke tissues from the “Carciofo Ortano” landrace, methanolic extracts were prepared from the immature main and secondary flower heads, stems, and leaves of representative genotypes of this landrace. Additionally, extracts were obtained from the same tissues of four landraces/clones included in the varietal platform of the PGI “Carciofo Romanesco del Lazio”, which served as reference genotypes: Campagnano, Castellammare, C3, and Grato 1. The antioxidant properties of these extracts were assessed using FRAP, ABTS, DPPH assays, and total phenolic content (TPC). The stem and secondary flower head extracts of two representative “Carciofo Ortano” genotypes and the Grato 1 clone, which have higher phenolic content, demonstrated the highest antioxidant activity. These extracts were therefore studied for their chemical profile using HPLC-DAD and SPME-GC/MS analysis. Additionally, the same extracts were investigated in vitro for their antioxidant capacity in differentiated SH-SY5Y cells, assessing their effects on ROS levels and the restoration of GSH levels. Furthermore, the in vivo beneficial effects of counteracting oxidative stress were evaluated in high sucrose-fed Drosophila melanogaster, as oxidative stress is a typical hallmark of hyperglycemic status. Overall, the results indicated that the edible immature inflorescences of the “Carciofo Ortano” landrace, along with the byproducts of its cultivation, are sources of raw materials containing biomolecules whose properties can be exploited for further applications in the pharmaceutical and medical sectors. Full article

This review explores the advances in developing adsorbent materials for solid-phase microextraction (SPME), focusing on nanoparticles, nanocomposites, and nanoporous structures. Nanoparticles, including those of metals (e.g., gold, silver), metal oxides (e.g., TiO₂, ZnO), and carbon-based materials (e.g., carbon nanotubes, graphene), offer enhanced surface area, improved extraction efficiency, and increased selectivity compared to traditional coatings. Nanocomposites, such as those combining metal oxides with polymers or carbon-based materials, exhibit synergistic properties, further improving extraction performance. Nanoporous materials, including metal–organic frameworks (MOFs) and ordered mesoporous carbons, provide high surface area and tunable pore structures, enabling selective adsorption of analytes. These advanced materials have been successfully applied to various analytes, including volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), pesticides, and heavy metals, demonstrating improved sensitivity, selectivity, and reproducibility compared to conventional SPME fibers. The incorporation of nanomaterials has significantly expanded the scope and applicability of SPME, enabling the analysis of trace-level analytes in complex matrices. This review highlights the significant potential of nanomaterials in revolutionizing SPME technology, offering new possibilities for sensitive and selective analysis in environmental monitoring, food safety, and other critical applications. Full article