The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution ...mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r 2 > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.
The solid-waste treatment plant of RECIPLASA is located in the municipality of Onda (Castellón province), which is an important agricultural area of Spain, with predominance of citrus crops. In this ...plant, all urban solid wastes from the town of Castellón (around 200,000 inhabitants) and other smaller towns as Almassora, Benicàssim, Betxí, Borriana, L'Alcora, Onda and Vila-Real are treated. In order to evaluate the potential impact of this plant on the surrounding water, both surface and groundwater, a comprehensive monitoring of organic pollutants has been carried out along 2011, 2012 and 2013. To this aim, an advanced analytical strategy was applied for wide-scope screening, consisting on the complementary use of liquid chromatography (LC) and gas chromatography (GC) coupled to mass spectrometry (MS) with quadrupole (Q)-time of flight analyser (TOF). A generic solid-phase extraction with Oasis HLB cartridges was applied prior to the chromatographic analysis. The screening included more than 1500 organic pollutants as target compounds, such as pesticides, pharmaceuticals, veterinary drugs, drugs of abuse, UV-filters, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), among others. Pesticides, mainly herbicides, were the compounds more frequently detected. Other compounds as antioxidants, cosmetics, drugs of abuse, PAHs, pharmaceuticals and UV filters, were also identified in the screening though at much lower frequency.
Once the screening was made, quantitative analysis focused on the compounds more frequently detected was subsequently applied using LC coupled to tandem MS with triple quadrupole analyser. In this way, up to 24 pesticides and transformation products (TPs), 7 pharmaceuticals, one drug of abuse and its metabolite could be quantified at sub-ppb concentrations. Along the three years of study, ten compounds were found at concentrations higher than 0.1μg/L. Most of them were pesticides and TPs, a fact that illustrates that the main source of pollution seems to be the agricultural activities in this area.
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•Evaluation of the impact of a solid waste treatment plant on the surrounding water•Screening of around 1500 organic contaminants in surface and groundwater•Complementary use of LC–QTOF MS and GC–(Q)TOF MS•Quantitation of target contaminants by LC–MS/MS QqQ
Currently, there is a growing demand by our society, authorities and science to increase the knowledge about the quality of food and its relationship with health and disease. Untargeted metabolomics ...approaches are emerging as powerful tools for exploring metabolic changes in biological systems under different conditions with great potential in the food field. To this aim, it is necessary to apply advanced analytical techniques, such as chromatography hyphenated to high resolution mass spectrometry, which provides enough sensitivity and selectivity to cover a wide range of metabolites in complex samples, as food and biological samples. The objective of this work is to provide an overview of the most widely adopted strategies based on the use of high resolution mass spectrometry-based techniques for the identification of food (bio)markers through the untargeted metabolomics workflow. Detailed information is provided about the trends in each stage of the metabolomics process from updated literature with the objective to help researchers to select the most appropriate metabolic approaches.
•Updated review (2017–2020) of untargeted metabolomics strategies applied on food field.•Advances in LC, GC and HRMS greatly contributed to food (bio)markers research.•Trends and future of HRMS-based untargeted metabolomics strategies are discussed.•Applications on food processing, food intake and food health effects are reviewed.
The characterization of very long-chain (>C24) polyunsaturated fatty acids (VLC-PUFAs), which are essential in the vision, neural function, and reproduction of vertebrates, is challenging because of ...the lack of reference standards and their very low concentrations in certain lipid classes. In this research, we have developed a new methodology for VLC-PUFA identification based on gas chromatography coupled to quadrupole/time-of-flight mass spectrometry with an atmospheric pressure chemical ionization source (GC-APCI-QTOF MS). The mass accuracy attainable with the innovative QTOF instrument, together with the soft ionization of the APCI source, provides valuable information on the intact molecule, traditionally lost with electron ionization sources due to the extensive fragmentation suffered. We have identified, for the first time, VLC-PUFAs with chains up to 44 carbons in eyes, brain, and gonads of gilthead sea bream, a commercially important fish in the Mediterranean. The added value of ion mobility-mass spectrometry (IMS), recently developed in combination with GC-QTOF MS, and the contribution of the collisional cross section (CCS) parameter in the characterization of novel VLC-PUFAs (for which reference standards are not available) have been also evaluated. The methodology developed has allowed assessing qualitative differences between farmed and wild fish, and opens new perspectives in a still scarcely known field of research.
Abstract
Very long-chain (> C24) polyunsaturated fatty acids (VLC-PUFA) play an important role in the development of nervous system, retinal function and reproductive processes in vertebrates. Their ...presence in very small amounts in specific lipid classes, the lack of reference standards and their late elution in chromatographic analyses render their identification and, most important, their quantification, still a challenge. Consequently, a sensitive and feasible analytical methodology is needed. In this work, we have studied the effect of chain length, as well as the number and position of unsaturations (or double bonds) on the response of GC-APCI-(Q)TOF MS, to establish an analytical method for VLC-PUFA quantification. The developed methodology allows the quantification of these compounds down to 2.5 × 10
–3
pmol/mg lipid. The reduction of VLC-PUFA levels in lipid fractions of the organs from the herein sampled farmed fish suggesting a yet undetected effect on these compounds of high vegetable oil aquafeed formulations, that currently dominate the market.
This paper reports a wide-scope screening for detection and identification of pesticides and polycyclic aromatic hydrocarbons (PAHs) in feeds and fish tissues. QuEChERS sample treatment was applied, ...using freezing as an additional cleanup. Analysis was carried out by gas chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC-(APCI) QTOF MS). The qualitative validation was performed for over 133 representative pesticides and 24 PAHs at 0.01 and 0.05 mg/kg. Subsequent application of the screening method to aquaculture samples made it possible to detect several compounds from the target list, such as chlorpyrifos-methyl, pirimiphos-methyl, and ethoxyquin, among others. Light PAHs (≤4 rings) were found in both animal and vegetable samples. The reliable identification of the compounds was supported by accurate mass measurements and the presence of at least two representative m/z ions in the spectrum together with the retention time of the peak, in agreement with the reference standard. Additionally, the search was widened to include other pesticides for which standards were not available, thanks to the expected presence of the protonated molecule and/or molecular ion in the APCI spectra. This could allow the detection and tentative identification of other pesticides different from those included in the validated target list.
Cold smoking enhances the appeal of fish products, offering consumers a smooth texture and a delicate smoky flavor. This study aims to explore variations in the volatile profile from different ...exposure times during cold smoking processing (light, moderate, and full-cure) in tune samples. An innovative untargeted analytical approach, headspace solid-phase microextraction combined with gas chromatography and a hybrid quadrupole-orbitrap mass analyzer, was employed to identify 86 volatiles associated with the cold smoking process. Most of these compounds, including phenols, furan derivates, aldehydes, cyclic ketones, and different aromatic species, were found to contribute to the smoke odor. The development of a QuEChERS-based extraction and clean-up method facilitated the quantification of 25 relevant smoky markers across all smoking degrees, revealing significant concentration differences after 15 h of smoking. This research sheds light on the dynamics of cold smoking impact and its on the flavor profile and safety quality of processed fish products.
•HS-SPME-GC-(Q)-Orbitrap as a powerful methodology to assess volatile profiles.•Cold smoking produces a wide range of smoked-related compounds.•QuEChERS is an efficient methodology for the quantification of smoked-related compounds.•Moderate cold smoking yields significant changes in the phenol content.
•The new APCI designed for GC promotes soft ionization.•Wide scope screening is favoured by the expected presence of the M+·/MH+.•Fragmentation occurred under MSE acquisition mode allows identity ...confirmation.
A new approach has been developed for multiclass screening of organic contaminants in water based on the use of gas chromatography coupled to hybrid quadrupole high-resolution time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC–(APCI)QTOF MS). The soft ionization promoted by the APCI source allows effective and wide-scope screening based on the investigation of the molecular ion and/or protonated molecule. This is in contrast to electron ionization (EI) where ionization typically results in extensive fragmentation, and diagnostic ions and/or spectra need to be known a priori to facilitate detection of the analytes in the raw data. Around 170 organic contaminants from different chemical families were initially investigated by both approaches, i.e. GC-(EI)TOF and GC-(APCI)QTOF, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and a notable number of pesticides and relevant metabolites. The new GC–(APCI)QTOF MS approach easily allowed widening the number of compounds investigated (85 additional compounds), with more pesticides, personal care products (UV filters, musks), polychloronaphthalenes (PCNs), antimicrobials, insect repellents, etc., most of them considered as emerging contaminants. Both GC-(EI)TOF and GC-(APCI)QTOF methodologies have been applied, evaluating their potential for a wide-scope screening in the environmental field.
In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target ...screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that non-target analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a “fully-automated identification workflow” remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases.
Graphical Abstract
Matrix of identification approach versus identification confidence
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