Search Results (25)

In Romania, groundwater is an important source of drinking water, especially in rural areas. This study investigated the concentrations of organophosphorus, carbamate, and triazine pesticides (OPs) along with organochlorine pesticides (OCPs) in groundwater samples collected from the Titu-Sarata Plain. Sensitive analytical techniques were employed, including Ultrahigh-Performance Liquid Chromatography coupled with Q Exactive™ HF Hybrid Quadrupole-Orbitrap™ Mass Spectrometry (UHPLC-Orbitrap-MS/MS) and Gas Chromatography coupled with an electron capture detector (GC-ECD). Environmental and human health risks were assessed in the case of pesticides that exceeded the maximum allowed concentration. The environmental risk assessment (ERA) revealed significant risks associated with Phosdrin, Phorate, and pp’DDE. Additionally, particular concerns arose from the presence of Aldrin and Dieldrin, which pose a high carcinogenic risk, especially through groundwater consumption in agricultural areas. The results of this research highlight the need for the implementation of a continuous quality monitoring program for groundwater in the agricultural regions that were studied. Full article

Forsythia suspensa is a crucial plant resource due to its considerable edible and medicinal value. Its fruit, named Forsythiae Fructus (FF), has been widely used in Traditional Chinese Medicine (TCM). According to the fruit maturity stage, FF is categorized into GFF (green Forsythiae Fructus) and RFF (ripe Forsythiae Fructus). In this study, metabolomics based on UPLC-Q/Orbitrap MS and HS-GC-MS, combined with chemometric methods, was employed to differentiate GFF from RFF and identify potential differential metabolites. Additionally, the mid-level data fusion method was employed to integrate data from both techniques, and the performance of the OPLS-DA model (R²Y = 0.986, Q² = 0.974) surpassed that of the single HS-GC-MS technique (R²Y = 0.968, Q² = 0.930). Moreover, using the criteria of VIP > 1 and p-value < 0.05, 30 differential compounds were selected via mid-level data fusion, compared to the initial 61 differential compounds identified by single techniques, effectively reducing data noise and eliminating irrelevant variables. This study provides a comprehensive analysis of volatile and non-volatile compounds in FF, offering valuable insights into quality control and clinical differentiation between GFF and RFF. The findings highlight the potential use of multi-technology metabolomics in the quality control of TCM and offer new perspectives for future research on medicinal plants. Full article

Background: The rapid development of refrigerated transportation technology for fresh vegetables has extended their shelf life. Some vegetables may appear undamaged on the surface, but their freshness may have decreased, often resulting in the phenomenon of passing off inferior vegetables as good. It is very important to establish a detection method for identifying and assessing the freshness of vegetables. Methods: Therefore, based on metabolomics methods, this study innovatively employed UHPLC-Q-Exactive Orbitrap MS and GC–MS techniques to investigate the metabolites in the refrigerated storage of four vegetables, namely chard (Beta vulgaris var. cicla L), lettuce (Lactuca sativa var. ramose Hort.), crown daisy (Glebionis coronaria (L.) Cass. ex Spach), and tomato (Solanum lycopersicum L.), exploring key biomarkers for assessing their freshness. UPLC-TQ MS was used for the quantitative analysis of key metabolites. Results: The results showed that arginine biosynthesis and the metabolism of alanine, aspartate, and glutamate are key pathways in vegetable metabolism. Four key metabolites were selected from chard, five from lettuce, three from crown daisy, and five from tomato. Conclusions: Comparing the content of substances such as alanine and arginine can help infer the freshness and nutritional value of the vegetables, providing important references for detecting spoilage, determining storage time, and improving transportation conditions. This research holds significant relevance for the vegetable transportation industry. Full article

Coffee consumption is expected to steadily rise in the next few years, with an increasing incidence of Coffea canephora on the market. To date, consumers are demanding high-quality and healthy beverages produced in an environmentally respectful manner. The study aimed to determine the optimal combination of acrylamide formation, sensory quality, and energy efficiency for blockchain-driven environmental accounting during the roasting process of C. canephora of different cups and market quality. Coffee was roasted in a professional 5 kg drum roaster at three speeds (fast, intermediate, and slow) and profiles, resulting in a medium roast degree. The quantification of acrylamide complied with the European legal benchmark across all roasting speeds, enabling a qualified panel to perform a sensory analysis of coffees in an espresso brew, including aroma and taste attributes. The chemical fingerprint of coffee was initially investigated through an untargeted metabolomics approach based on high-resolution mass spectrometry (UHPLC-Q-Orbitrap-HRMS). An ANOVA Multiblock Orthogonal Partial Least Squares analysis (AMOPLS) applied to metabolomics data enabled an accurate discrimination of coffee samples based on coffee market quality and roasting speed. Notably, their interaction was identified as a statistically significant discriminant factor (Residual Structure Ratio p-value = 0.01), with the highest contribution to the model (Relative Sum of Squares = 32.6%). The majority of metabolites detected through the VIP² approach belong to the lipid and lipid-like molecules chemical class, highlighting their pivotal role in defining the signature of C. canephora coffee. Regarding energy efficiency, the consumption recorded by the natural gas meter at the fast, intermediate, and slow speeds did not show significant differences. The roaster and gas valve employed may influence the efficacy of the “Energy Calculator” of the roasting program “Artisan” (v. 2.10.4), requiring an appropriate configuration. The optimized program resulted in a mean underestimation of real methane consumption by 0.207 kWh (SD 0.124), making it a promising tool for carbon emission calculation in coffee roasting. Moreover, further investigations will be performed to build a multi-omics approach by integrating the UHPLC-Q-Orbitrap-HRMS database with the volatilomic analysis performed by the GCxGC-MS technique to reveal the potential network between the chemical profile and the sensory characteristics of the samples. Full article

Egg products after thermal treatment possess a unique flavor and are favored by consumers. In this study, the key aroma-active compounds of egg yolk products and their formation mechanism during thermal treatment were investigated. The volatile aroma compounds in egg yolks were monitored using an electronic nose, gas chromatography-mass spectrometry (GC–MS) and gas chromatography–olfactometry–mass spectrometry (GC–O–MS), and the lipid molecular species were explored using ultra-high-performance liquid chromatography– mass spectrometry with a Q-Exactive HF-X Orbitrap (UPLC-Q-Exactive HF-X). A total of 68 volatile compounds were identified. Boiled eggs mainly derived their flavor from hexanal, 2-pentyl-furan, 2-butanone, 3-methyl-butanal and heptane. Meanwhile, fried eggs relied mainly on 14 compounds, the most important of which were 2-ethyl-3-methyl-pyrazine, 3-ethyl-2,5-dimethyl-pyrazine, 2-ethyl-3,5-dimethyl-pyrazine, nonanal and 2,3-diethyl-5-methyl-pyrazine, providing a baked and burnt sugar flavor. A total of 201 lipid molecules, belonging to 21 lipid subclasses, were identified in egg yolks, and 13 oxidized lipids were characterized using a molecular network. Phosphoethanolamines (PEs) containing polyunsaturated fatty acids were the primary flavor precursors contributing to the development of egg yolks’ flavor, participating in lipid oxidation reactions and the Maillard reaction and regulating the production of aldehydes and pyrazine compounds. This study provides reference and guidance for the development of egg yolk flavor products. Full article

Honeybee drone larvae are male bees that develop from unfertilized eggs and play a role in colony reproduction. The nutritional value of honeybee drone larvae is due to their high protein, lipid, and other nutrient contents, making them a profitable food source for humans in some cultures. Drone larvae lipids (DLLs) contribute to drone development; however, few studies have explored their substantial compositions and bioactive functions. In this study, we carried out DLL lipidomics analysis using UPLC-Q-Exactive-Orbitrap–MS prior to in vitro anti-inflammatory activity analysis. The results highlighted the importance of the extraction temperature on the DLL composition. A total of 21 lipids were found in the DLL extract, mostly categorized into five groups: nine phospholipids, three sphingolipids, two neutral lipids, one plant glycoglycerolipid, four lipid acyl, and others. Drying extraction at −20 °C produced more sphingolipids, phospholipids, and unsaturated fatty acids. Of 37 fatty acids, 18 were displayed at −20 °C degrees, as shown by GC–MS quantitative analysis. Myristic (246.99 ± 13.19 μg/g), palmitic (1707.87 ± 60.53 μg/g), stearic (852.32 ± 24.17 μg/g), and oleic (2463.03 ± 149.61 μg/g) acids were the predominant fatty acids. Furthermore, we examined the significant in vitro anti-inflammatory effects of DLL (−20 °C) using lipopolysaccharide (LPS)-challenged RAW264.7 cells. Nitric oxide (NO) and reactive oxygen (ROS) production and mRNA expression of IL-6, IL-10, COX-2, and iNOS were significantly decreased, demonstrating the anti-inflammatory function of DLL. Overall, this study provided insight into the lipid composition of DLL, revealed the influence of temperature, and explored the functionality of DLL (−20 °C), allowing for further application of DLLs as functional foods. Full article

Lipids are crucial components for the maintenance oof normal structure and function in the nervous system. Elucidating the diversity of lipids in spinal cords may contribute to our understanding of neurodevelopment. This study comprehensively analyzed the fatty acid (FA) compositions and lipidomes of the spinal cords of eight domesticated animal species: pig, cattle, yak, goat, horse, donkey, camel, and sika deer. Gas chromatography–mass spectrometry (GC-MS) analysis revealed that saturated fatty acids (SFAs) and monounsaturated fatty acids (MUFAs) were the primary FAs in the spinal cords of these domesticated animals, accounting for 72.54–94.23% of total FAs. Notably, oleic acid, stearic acid and palmitic acid emerged as the most abundant FA species. Moreover, untargeted lipidomics by UPLC-Q-Exactive Orbitrap-MS demonstrated that five lipid classes, including glycerophospholipids (GPs), sphingolipids (SPs), glycerolipids (GLs), FAs and saccharolipids (SLs), were identified in the investigated spinal cords, with phosphatidylcholine (PC) being the most abundant among all identified lipid classes. Furthermore, canonical correlation analysis showed that PC, PE, TAG, HexCer-NS and SM were significantly associated with genome sequence data. These informative data provide insight into the structure and function of mammalian nervous tissues and represent a novel contribution to lipidomics. Full article

Ketamine analogues have been emerging in recent years and are causing severe health and social problems worldwide. Ketamine analogues use 2-phenyl-2-aminocyclohexanone as the basic structure and achieve physiological reactions similar to or even more robust than the prototype of ketamine by changing the substituents on the benzene ring (R₁ and R₂) and amine group (R_N1). Therefore, the mass spectrometry (MS) fragmentation pathways and fragments of ketamine analogues have certain regularity. Eight ketamine analogues are systematically investigated by GC-QTOF/MS and LC-Q-Orbitrap MS/MS with the positive mode of electrospray ionization. The MS fragmentation patterns of ketamine analogues are summarized according to high-resolution MS data. The α-cleavage of carbon bond C₁-C₂ in the cyclohexanone moiety and further losses of CO, methyl radical, ethyl radical and propyl radical are the characteristic fragmentation pathways of ketamine analogues in EI-MS mode. The loss of H₂O or the sequential loss of R_N1NH₂, CO and C₄H₆ are the distinctive fragmentation pathways of ketamine analogues in ESI-MS/MS mode. Moreover, these MS fragmentation patterns are first introduced for the rapid screening of ketamine analogues in suspicious powder. Furthermore, the structure of the ketamine analogue in suspicious powder is 2-(Methylamino)-2-(o-tolyl)cyclohexan-1-one, which is further confirmed by NMR. This study contributes to the identification of the chemical structure of ketamine analogues, which can be used for the rapid screening of ketamine analogues in seized chemicals. Full article

This work was designed to investigate the dynamic changes process of non-volatile organic compounds (n-VOCs) and volatile organic compounds (VOCs) in mulberries during different growth periods using UPLC-Q-Orbitrap-MS, HS-SPME-GC-MS, and HS-GC-IMS. A total of 166 compounds were identified, including 68 n-VOCs and 98 VOCs. Furthermore, principal component analysis (PCA), random forest analysis (RFA) and orthogonal partial least squares discriminant analysis (OPLS-DA) were used to analyze differences in mulberries at different ripening stages. A total of 74 compounds appeared or disappeared at different ripening periods and 24 compounds were presented throughout the growth process. Quantitative analysis and antioxidant experiments revealed that as the mulberries continued to mature, flavonoids and phenolic acids continued to increase, and the best antioxidant activity occurred from stage IV. Conclusively, an effective strategy was established for analyzing the composition change process during different growth periods, which could assist in achieving dynamic change process analysis and quality control. Full article

Zanthoxylum myriacanthum Wall. ex Hook. f., a plant belonging to the Rutaceae family and the Zanthoxylum genus, is extensively utilized for its medicinal properties and as a culinary seasoning in China and Southeast Asian countries. However, the chemical composition and biological activities of Z. myriacanthum branches and leaves remain insufficiently explored. In this study, the volatile and non-volatile components of Z. myriacanthum branches and leaves were analyzed using GC-MS and UPLC-Q-Orbitrap HRMS techniques. A total of 78 volatile compounds and 66 non-volatile compounds were identified. The volatile compounds were predominantly terpenoids and aliphatic compounds, while the non-volatile compounds were primarily flavonoids and alkaloids. The branches contained 52 volatile compounds and 33 non-volatile compounds, whereas the leaves contained 48 volatile compounds and 40 non-volatile compounds. The antioxidant activities of the methanol extracts from Z. myriacanthum branches and leaves were evaluated using ABTS and DPPH free-radical-scavenging assays, both of which demonstrated certain antioxidant activity. The methanol extract of leaves demonstrated significantly higher antioxidant activity compared to that of the branches, possibly due to the higher presence of flavonoids and phenols in the leaves, with IC₅₀ values of 7.12 ± 0.257 μg/mL and 1.22 × 10² ± 5.01 μg/mL for ABTS and DPPH, respectively. These findings enhance our understanding of the chemical composition and antioxidant potential of Z. myriacanthum. The plant holds promise as a natural source of antioxidants for applications in pharmaceuticals, cosmetics, and functional foods. Further research can explore its broader biological activities and potential applications. Full article

A new polyvalent wide-scope analytical method, valid for both raw and processed (juices) fruits, combining target and non-target strategies, has been developed and validated to determine low concentrations of 260 pesticides, as well as many potential non-target substances and metabolites. The target approach has been validated according to SANTE Guide requirements. Trueness, precision, linearity, and robustness values were validated in raw fruit (apple) and juice (apple juice) as representative solid and liquid food commodities. Recoveries were between 70–120% and two ranges of linearity were observed: 0.5–20 μg kg⁻¹ (0.5–20 μg L⁻¹ apple juice) and 20–100 μg kg⁻¹ (20–100 μg L⁻¹ apple juice). The limits of quantification (LOQs) reached were lower than 0.2 μg kg⁻¹ in apple (0.2 μg L⁻¹ apple juice) in most cases. The developed method, based on QuEChERS extraction followed by gas chromatography-high resolution mass spectrometry (GC-HRMS), achieves part-per-trillions lower limits, which allowed the detection of 18 pesticides in commercial samples. The non-target approach is based on a retrospective analysis of suspect compounds, which has been optimized to detect up to 25 additional compounds, increasing the scope of the method. This made it possible to confirm the presence of two pesticide metabolites which were not considered in the target screening, phtamlimide and tetrahydrophthalimide. Full article

The Posidonia oceanica decline due to climate change and other anthropogenic pressures, such as chemical pollution, is well known in the scientific community. However, a comprehensive study of the full content of the organic micropollutants found in this significant seagrass has not yet been carried out. Second, an eco-friendly extraction procedure that does not require a large sample, preserves the seagrass’s ecological integrity and functions, and follows green-chemistry principles, is lacking. These information gaps represent the aims of this study. For this purpose, trials with diverse simple and affordable extraction methods to detect one of the most ubiquitous contaminants (polycyclic aromatic hydrocarbons or PAHs) were conducted. As a result, the use and validation of a polytron homogenizer and an ultrasonic bath were proposed for the extraction of priority PAHs from tissues of P. oceanica and marine sediments, respectively. Tissues (leaves and rhizomes) of P. oceanica and sediment samples were collected, extracted, and subjected to a thorough analysis, i.e., target, suspect, and unknown screenings, using gas chromatography coupled to high resolution mass spectrometry (GC-Q-Orbitrap MS). Target analysis revealed seven priority parent-PAHs, whilst during the suspect screening, four PAH-derivatives and three other parent-PAHs were tentatively identified. In the additional third unknown analysis, 11 structures, several with concerning toxicity, were also tentatively identified. Numerous of the identified compounds showed elevated detection frequency in the environmental samples, even reaching 100%, such as the cases of the parent-PAHs (naphthalene, phenanthrene and retene), some PAH-derivatives, one UV stabilizer, and plastic additives along with pesticides. The methods proposed here should be considered for future monitoring of P. oceanica, as well as the three-way analytic approach (target, suspect and unknown), to obtain a more real and accurate idea of the organic micropollutants content in the environment. Full article

The increasing number of contaminants in the environment has pushed water monitoring programs to find out the most hazardous known and unknown chemicals in the environment. Sample treatment-simplification methods and non-target screening approaches can help researchers to not overlook potential chemicals present in complex aqueous samples. In this work, an effect-directed analysis (EDA) protocol using the sea urchin embryo test (SET) as a toxicological in vivo bioassay was used as simplified strategy to identify potential unknown chemicals present in a very complex aqueous matrix such as hospital effluent. The SET bioassay was used for the first time here to evaluate potential toxic fractions in hospital effluent, which were obtained after a two-step fractionation using C₁₈ and aminopropyl chromatographic semi-preparative columns. The unknown compounds present in the toxic fractions were identified by means of liquid chromatography coupled to a Q Exactive Orbitrap high-resolution mass spectrometer (LC-HRMS) and using a suspect analysis approach. The results were complemented by gas chromatography-mass spectrometry analysis (GC-MS) in order to identify the widest range of chemical compounds present in the sample and the toxic fractions. Using EDA as sample treatment simplification method, the number of unknown chemicals (>446 features) detected in the raw sample was narrowed down to 94 potential toxic candidates identified in the significantly toxic fractions. Among them, the presence of 25 compounds was confirmed with available chemical standards including 14 pharmaceuticals, a personal care product, six pesticides and four industrial products. The observations found in this work emphasize the difficulties in identifying potential toxicity drivers in complex water samples, as in the case of hospital wastewater. Full article

This study enables the simultaneous monitoring of persistent organics pollutants (POPs) in the relevant marine seagrass Posidonia oceanica (L.) Delile (P. oceanica), without causing damage and preserving their ecological integrity and their key ecosystem services, and in marine sediments. Two classes of POPs that suppose a current threat to the environmental health status are investigated: polychlorinated biphenyls (PCBs) and pesticides. Comparisons between tissues and sediment compartmentation are studied for the first time. For these purposes, the sediments, P. oceanica leaves and, as a novelty, rhizomes, were studied. Samples were analyzed by gas chromatography coupled with high-resolution mass spectrometry (GC-Q-Orbitrap MS) for a comprehensive study. Eco-friendly methods were developed and validated for the determination of 38 POPs, 25 PCBs and 13 priority pesticides. The results showed that, when detected, regulated contaminants were localized mainly in the long-lived rhizomes, and 7 PCBs (the most abundant being PCB 44) and 4 priority pesticides (trifluralin, chlorpyrifos, isodrin and o,p’-DDT) were seen. Additionally, a retrospective analysis (suspect screening) was conducted, exhibiting up to 13 current-use pesticide residues in leaves and rhizomes alike. The results suggest that P. oceanica might be acting as a sink to contaminants in coastal areas and that rhizomes, due to their longer lifespan, reflect past and legacy contamination. Full article

This study investigated the volatile composition and aromatic features of passion fruit wines using a combination of gas chromatography–quadrupole mass spectrometry (GC-qMS), gas chromatography–Orbitrap–mass spectrometry (GC-Orbitrap-MS), electronic nose (E-nose) and sensory evaluation. The results showed that these passion fruit wines possessed different aromatic features confirmed by E-nose. Seventeen sulfur compounds and seventy-eight volatiles were detected in these passion fruit wines using GC-Orbitrap-MS and GC-qMS, respectively. Forty-four volatiles significantly contributed to the overall wine aroma. These wines possessed passion fruit, mango, green apple, lemon and floral aromas confirmed by sensory evaluation. The partial least squares regression analysis indicated that sulfides, esters and terpenes, and terpenes mainly correlated to the passion fruit, mango and green apple aroma, respectively. Sulfur compounds significantly affected the aroma of passion fruit wine. The findings in this study could provide useful insight toward the quality control of passion fruit wine. Full article