Exploring the contamination profile of multi-class emerging contaminants (ECs) in wastewater is highly desirable. To this end, the occurrence, removal, mass loading and risks associated with a large ...panel of pharmaceuticals and personal care products, illicit drugs, perfluorinated compounds and organophosphate flame retardants in two wastewater treatment plants (WWTPs) in the region of Thessaloniki (Greece) after a survey is illustrated. Influent and effluent wastewaters were submitted to solid phase extraction on Oasis HLB cartridges, followed by ultra-high-performance liquid chromatography Orbitrap high-resolution mass spectrometry (UHPLC–Orbitrap MS). Influent concentrations in both WWTPs were notably higher than effluent, with caffeine, acetaminophen, irbesartan and valsartan being the most ubiquitous compounds, exhibiting elevated concentrations. Average effluent concentrations ranged from below the method quantification limits (<MQL) to remarkably high values (μg L−1 scale), such as for caffeine, acetaminophen, diclofenac, irbesartan and valsartan, among others. Removal efficiencies ranged between −273% for lamotrigine and 100%, i.e., for the UV filter BP1. Notably, the polar compounds such as cytarabine, methotrexate and capecitabine were removed at a rate >80% in both WWTPs, allowing the correlation between logKow and removals. Interesting trends for the illicit drugs were revealed by means of mass loading estimation, as in the case of benzoylecgonine (71.6 mg/day/1000 inhabitants). Ecotoxicological risk assessment was evaluated for both single components and mixture, using three approaches: risk quotient (RQ), risk quotient considering frequency (RQf) and toxic units (TU). Irbesartan and telmisartan posed a high risk in all trophic levels, while fish was the most sensitive taxa for diclofenac. This work aspires to intensify the surveillance programs for the receiving water bodies, as well as to motivate the investigation of toxicity to non-target organisms.
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•172 multi-class emerging contaminants were monitored in two Greek municipal WWTPs.•80 compounds (46% of the method's total scope) were detected at least in one sample.•12% and 33% of the identified target ECs were eliminated in each WWTP, respectively.•Risk assessment was performed for both individual ECs and observed mixtures.•Optimized RQf, considering mean concentration and detection frequency was employed.
Lipids are vital biological molecules and play multiple roles in cellular function of mammalian organisms such as cellular membrane anchoring, signal transduction, material trafficking and energy ...storage. Driven by the biological significance of lipids, lipidomics has become an emerging science in the field of omics. Lipidome in biological systems consists of hundreds of thousands of individual lipid molecules that possess complex structures, multiple categories, and diverse physicochemical properties assembled by different combinations of polar headgroups and hydrophobic fatty acyl chains. Such structural complexity poses a huge challenge for comprehensive lipidome analysis. Thanks to the great innovations in chromatographic separation techniques and the continuous advances in mass spectrometric detection tools, analytical strategies for lipidomics have been highly diversified so that the depth and breadth of lipidomics have been greatly enhanced. This review will present the current state of mass spectrometry-based analytical strategies including untargeted, targeted and pseudotargeted lipidomics. Recent typical applications of lipidomics in biomarker discovery, pathogenic mechanism and therapeutic strategy are summarized, and the challenges facing to the field of lipidomics are also discussed.
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•Recent advances in analytical techniques allow rapid, reliable and sensitive detection of hundreds to thousands of lipids•The diversified MS-based analytical strategies have greatly enhanced the development and application of lipidomics.•The integration of multi-omics has a bright prospect in studying the pathogenesis and potentially targetable therapy.•Comprehensive analysis of the lipidome still faces considerable challenges in analytical techniques.
This study presents the validation of a sensitive method for the determination of 6‐nitrodopa, 6‐nitrodopamine, 6‐nitroadrenaline and 6‐cyanodopamine in Krebs–Henseleit solution by LC–MS/MS with ...ESI+. HRMS was used to precisely characterize the structures of the fragment ions. The method was applied to investigate the catecholamine basal release from rabbit isolated atria and ventricles. The atria and ventricles were suspended separately in a 5 ml organ bath containing Krebs–Henseleit solution with ascorbic acid (3 mM), gassed (95%O2/5%CO2) at 37°C for 30 min. Strata‐X 33 μm SPE cartridges were employed for the extraction of the catecholamines and the internal standard 6‐nitrodopamine‐d4. The catecholamines were separated employing a 150 × 3 mm Shim‐pack GIST C18‐AQ (3 mm particle size), placed in an oven at 40°C and perfused by 65% of mobile phase A (MeCN/H2O; 90/10, v/v) + 0.4% CH3COOH and 35% mobile phase B (deionized H2O) + 0.2% CH2O2 at 320 μl/min in isocratic mode. The method was linear at 0.1–20 ng/ml. The method was used to identify for the first‐time basal release of the three nitrocatecholamines mentioned above and a member of a novel class of catecholamines, the cyanocatecholamines.
•Deethylene-ENR was screened and detected in real fish samples for the first time.•A new method for residue analysis of ENR and its metabolites in fish was developed.•The detection rate of ENR ...metabolites in the analyzed crucian carp samples was high.•Deethylene-ENR may be of concern as a possible risk candidate in aquatic products.
The abuse of enrofloxacin (ENR) in aquaculture and the lack of monitoring of other metabolites except ciprofloxacin (CIP) may lead to unknown harmful effects on human health. In this study, ENR metabolites were screened in real fish samples based on ultrahigh-performance liquid chromatography coupled with Q-Orbitrap mass spectrometry combined with Compound Discoverer software, and another metabolite deethylene-ENR besides CIP was detected and identified for the first time. Correspondingly, a method for the determination of ENR and CIP and the semi-quantitative analysis of deethylene-ENR in aquatic products was established. Method validation illustrated that excellent linearity and satisfactory recoveries of analytes were obtained. Limits of detection of ENR and CIP were both 0.1 μg kg−1, and their limits of quantification both 1 μg kg−1. CIP and deethylene-ENR were detected in 12 of 14 ENR-positive fish samples, so deethylene-ENR should be of concern as a possible risk candidate in aquatic products.
A single workflow based on three approaches (target, suspected and non-target screening) using liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS) in data ...independent acquisition mode (DIA) was developed to assess the presence of emerging pollutants (EPs) in water and sediments from a Mediterranean River Basin. Identification of potential contaminants was based on mass accuracy, isotopic ratio pattern, theoretical fragmentation, and retention time using Waters UNIFI software. In the suspect screening against a library containing 2200 components, 68 contaminants were tentatively identified, 6 of which were confirmed and quantified with analytical standards. Non-target screening (NTS) required additional manual processing and the aid of an on-line database (ChemSpider) to tentatively identify compounds. Eprosartan, an antihypertensive drug not included in the library used for suspected screening, was confirmed and semi-quantified. The identification of Eprosartan proved the workflow to be functional for NTS. Target screening of 171 pesticides and 33 pharmaceuticals and personal care products (PPCPs) including the compounds confirmed using suspect (6) and non target (1) screening achieved monitoring of the most abundant contaminants from the head to the mouth of the Turia basin to establish their spatial distribution. QTOF-MS screening versatility with its high-resolution capability allows for a comprehensive assessment of EPs in the aquatic environment.
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•Suspected, non-target and target screening to establish River contamination profile•Identification 68 contaminants against a database of 2000 compounds•Non-target screening identifies additional compounds as Eprosartan•New findings enrich target screening up to 171 pesticides and 33 pharmaceuticals
Direct surface analysis in ambient conditions provides information on the position and chemical composition of an object at the time of investigation. An angled sampling probe is developed in this ...work for direct analysis in real time (DART) ionization high-resolution mass spectrometry. The DART ion source and the interface were modified for improved surface resolution, increased ion transfer efficiency, as well as enabling two-dimensional surface scanning. The angled probe DART-MS system was used for investigating a variety of food samples including fruit peels, ginseng root, plant leaves and sections of radish. Abundant signals and distinct chemical profiles are obtained in seconds, and spatial distribution of different molecules across the sample surfaces can be observed. In addition, the developed system can quickly identify the chemical changes when the surfaces were treated. The method is capable of directly evaluating food sample surfaces with different shapes, hardness, and conditions, without any sample pretreatments.
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•Direct analysis in real time ion source with angled sampling was modified.•Direct surface analysis was achieved in ambient conditions without sample preparation.•Abundant chemical profiles and spatial distribution of molecules were obtained.•Applicable for food surfaces with different shapes, textures, hardness and conditions.
Investigation on transformation products (TPs) of environmental contaminants is important for chemical exposure risk assessments. However, the task of identifying potential TPs in complex ...environmental matrices is very challenging. Advanced data-mining techniques have greatly accelerated the process of TP recognition and identification, which should be included as part of an integrated analytical workflow along with robust sample preparation and data acquisition protocols. In this review, the methods for enrichment of TPs from various sample matrix and the data acquisition modes by high-resolution mass spectrometry (HRMS) are summarized. Further, advanced data-mining techniques including suspect screening by in-silico prediction, case-control strategy, stable isotope labeling, mass defect filtering, and product ion filtering are critically reviewed. The gaps in the current knowledge and future trends for the identification of TPs are also discussed.
•Measurement of TPs are summarized as an integrated analytical workflow.•Recent data-mining techniques for the identification of TPs are reviewed.•Challenges and trends on TP prediction, separation, and recognition are discussed.
•488 sphingolipid, glycerophospholipids, and glycolipids species were quantified.•TG was the highest levels in both standard and magnetic fermented goat milk.•Standard fermentation promoted the ...degradation of SM and SPH to Cer and HexCer.•Magnetic fermentation improved the TG, DG and HexCer and reduced Cer yield.•Magnetic stimulation may be a promising method for goat milk fermentation.
Standard fermentation (SF) mainly affected the metabolism of glycerophospholipid and sphingolipid, and increased the total lipid content of goat milk. Content of total lipid was decreased by magnetic fermentation compared with SF, mainly due to triacylglycerol and diacylglycerol. Comprehensive characteristic of lipids dynamic changes during standard and magnetic fermentation was performed using high-throughput quantitative lipidomics. Totally, 488 lipid molecular species covering 12 subclasses were detected, and triacylglycerol was the highest levels, followed by diacylglycerol and phosphoethanolamine in the whole fermentation stage. Specifically, except for ceramide and simple Glc series, the content of all polar lipids in SF was dropped and neutral lipids subjoined. Compared with SF, the decrease of triacylglycerol (1752.47 to 784.78 μg/mL), diacylglycerol (60.36 to 24.89 μg/mL) and simple Glc series (4.36 to 2.40 μg/mL) were observed, while ceramide (6.54 to 25.87 μg/mL) increased, suggesting magnetic fermentation as effective approach to potentially improve the nutritional of goat milk.
•A study on thermal decomposition of PFAS and GenX that has been poorly understood.•The decomposition involves initiation, chain propagation, and termination reactions.•Dual thermal decomposition ...pathways of PFAS seem to exist.•GAC dramatically altered the thermal decomposition rate and pathway of PFCAs.•Raw, non-activated charcoals/biochars had little effect on this process.
Thermal treatment is routinely used to reactivate the spent granular activated carbon (GAC) from water purification facilities. It is also an integral part of sewage sludge treatment and municipal solid waste management. This study presents a detailed investigation of the fate of per- and polyfluoroalkyl substances (PFAS) and one PFAS alternative (GenX) in thermal processes, focusing on the effect of GAC. We demonstrate that the thermolysis of perfluoroalkyl carboxylic acids (PFCAs), including perfluorooctanoic acid (PFOA), and GenX can occur at temperatures of 150‒200 °C. Three temperature zones were discovered for PFOA, including a stable and nonvolatile zone (≤90 °C), a phase-transfer and thermal decomposition zone (90‒400 °C), and a fast decomposition zone (≥400 °C). The thermal decomposition began with the homolysis of a C‒C bond next to the carboxyl group of PFCAs, which formed unstable perfluoroalkyl radicals. Dual decomposition pathways seem to exist. The addition of a highly porous adsorbent, such as GAC or a copolymer resin, compressed the intermediate sublimation zone of PFCAs, changed their thermal decomposition pathways, and increased the decomposition rate constant by up to 150-fold at 250 °C. The results indicate that the observed thermal decomposition acceleration was linked to the adsorption of gas-phase PFCA molecules on GAC. The presence of non-activated charcoals/biochars with a low affinity for PFOA did not accelerate its thermal decomposition, suggesting that the π electron-rich, polyaromatic surface of charcoal/GAC played an insignificant role compared to the adsorbent's porosity. Overall, the results indicate that (1) substantial decomposition of PFCAs and GenX during conventional thermal GAC/sludge/waste treatment is very likely, and (2) the presence or addition of GAC or other highly porous materials can accelerate thermal PFAS decomposition and alter decomposition pathways.
Scutellaria barbata D. Don (S. barbata) is one of the most frequently used anticancer herb medicine in China. Mechanistic understanding of the biological activities of S. barbata is hindered by ...limited knowledge regarding its components and metabolic profile. In this study, ultra‐high‐performance liquid chromatography coupled with high resolution mass spectrometry (quadrupole time‐of‐flight mass spectrometry) was used to identify the chemical constituents in S. barbata and their metabolic profiles in rats. By applying cleavage rules and comparison with reference substances, 89 components were identified in S. barbata, which included 45 flavonoids, 28 diterpenoids, 10 phenolics, and 6 others. A total of 110 compounds, including 32 prototype compounds and 78 metabolites, were identified or tentatively characterized in vivo. Methylation, sulfonation, and glucuronidation were the main metabolic pathways, which could be attributed to the fact that several of the compounds in S. barbata have phenolic hydroxyl groups. This is the first systematic study on the chemical constituents and in vivo metabolic profile of S. barbata. The analytical method features a quick and comprehensive dissection of the chemical composition and metabolic profile of S. barbata and provides a basis for exploring its various biological activities.
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