Samanta Uclés

Pesticide analysis in teas and chamomile by liquid chromatography and gas chromatography tandem mass spectrometry using a modified QuEChERS method: Validation and pilot survey in real samples

This paper presents the validation of a modified QuEChERS method in four matrices - green tea, red tea, black tea and chamomile. The experiments were carried out using blank samples spiked with a solution of 86 pesticides (insecticides, fungicides and herbicides) at four levels - 10, 25, 50 and 100 μg/kg. The samples were extracted according to the citrate QuEChERS protocol; however, to reduce the amount of coextracted matrix compounds, calcium chloride was employed instead of magnesium sulphate in the clean-up step. The samples were analysed by LC-MS/MS and GC-MS/MS. Included in the scope of validation were: recovery, linearity, matrix effects, limits of detection and quantitation as well as intra-day and inter-day precision. The validated method was used in a real sample survey carried out on 75 samples purchased in ten different countries. In all matrices, recoveries of the majority of compounds were in the 70-120% range and were characterised by precision lower than 20%. In 85% of pesticide/matrix combinations the analytes can be detected quantitatively by the proposed method at the European Union Maximum Residue Level. The analysis of the real samples revealed that large number of teas and chamomiles sold in the European Union contain pesticides whose usage is not approved and also pesticides in concentrations above the EU MRLs.

Development of a solvent-free method for the simultaneous identification/quantification of drugs of abuse and their metabolites in environmental water by LC–MS/MS

This work details a rapid analytical method using direct sample injection for the simultaneous identification/quantification of 22 drugs of abuse, including some of their major metabolites, in environmental samples. This has been developed using a hybrid triple quadrupole-linear ion trap-mass spectrometer (QqLIT). With the increasing sensitivity of todays tandem mass spectrometers, direct injection analysis of water samples has become an attractive alternative to traditional analytical protocols, which often include a preliminary pre-concentration step. Whats more, this kind of analysis is in accordance with many of the main objectives of so-called green analytical chemistry, or environmentally friendly practice. The analytical performance of the LC-MS/MS method was evaluated in three different water matrices (surface water, influent and effluent wastewater). Data acquisition was carried out in selected reaction monitoring (SRM) mode under time-scheduled conditions, monitoring two SRM transitions for simultaneous identification/quantification of all target compounds in the samples. Additionally, an experiment was performed using the information-dependent acquisition (IDA) scan to carry out the identification of those analytes for which the second transition was present at a low intensity. Finally, the two methodologies developed were applied to real samples for evaluation.

Evaluation of zirconium dioxide-based sorbents to decrease the matrix effect in avocado and almond multiresidue pesticide analysis followed by gas chromatography tandem mass spectrometry

Two sorbents containing ZrO₂ (Z-Sep and Z-Sep+) were tested as a d-SPE clean-up in combination with the QuEChERS and ethyl acetate multiresidue method in the pesticide residues extraction in avocado. All extracts were analysed using gas chromatography coupled with a triple quadrupole mass spectrometer working in multi-reaction monitoring mode. GC QToF was used to compare the amount of matrix compounds present in the final extracts, prepared according to different protocols. The highest number of pesticides with acceptable recoveries and the lowest amount of coextracted matrix compounds were provided by QuEChERS with Z-Sep. Subsequently, this method was fully validated in avocado and almonds. Validation studies were carried out according to DG Sanco guidelines including: the evaluation of recoveries at two levels (10 and 50 μg/kg), limit of quantitation, linearity, matrix effects, as well as interday and intraday precision. In avocado, 166 pesticides were fully validated compared to 119 in almonds. The method was operated satisfactorily in routine analysis and was applied to real samples.

Evaluation of selected ubiquitous contaminants in the aquatic environment and their transformation products. A pilot study of their removal from a sewage treatment plant

A simple method using direct sample injection combined with liquid chromatography tandem mass spectrometry has been developed for the simultaneous analysis of six alkaloid compounds in environmental samples. The target list includes two psychostimulants (nicotine and caffeine), three metabolites (cotinine, nicotinic acid and paraxanthine) and a coffee chemical (trigonelline). The analytical method was evaluated in three different matrices (surface water, influent and effluent wastewater). The method developed showed an adequate sensitivity, below 0.6 μg L(-1) for wastewater and 0.1 μg L(-1) for river matrices, without any prior treatment of the samples. Finally, the methodology was applied to real samples for evaluation of their removal from a sewage treatment plant and their persistence/fate in the aquatic environment. All compounds studied in this work were detected at all sampling points collected along the Henares River. However, nicotinic acid was only detected three times in treated sewage samples at levels above its detection limit.

A sensitive and efficient method for routine pesticide multiresidue analysis in bee pollen samples using gas and liquid chromatography coupled to tandem mass spectrometry

Several clean-up methods were evaluated for 253 pesticides in pollen samples concentrating on efficient clean-up and the highest number of pesticides satisfying the recovery and precision criteria. These were: (a) modified QuEChERS using dSPE with PSA+C18; (b) freeze-out prior to QuEChERS using dSPE with PSA+C18; (c) freeze-out prior to QuEChERS using dSPE with PSA+C18+Z-Sep; and (d) freeze-out followed by QuEChERS using dSPE with PSA+C18 and SPE with Z-Sep. Determinations were made using LC-MS/MS and GC-MS/MS. The modified QuEChERS protocol applying a freeze-out followed by dSPE with PSA+C18 and SPE clean-up with Z-Sep was selected because it provided the highest number of pesticides with mean recoveries in the 70-120% range, as well as relative standard deviations (RSDs) typically below 20% (12.2% on average) and ensured much better removal of co-extracted matrix compounds of paramount importance in routine analysis. Limits of quantification at levels as low as 5μgkg(-1) were obtained for the majority of the pesticides. The proposed methodology was applied to the analysis of 41 pollen bee samples from different areas in Spain. Pesticides considered potentially toxic to bees (DL50<2μg/bee) were detected in some samples with concentrations up to 72.7μgkg(-1), which could negatively affect honeybee health.

Large multiresidue analysis of pesticides in edible vegetable oils by using efficient solid-phase extraction sorbents based on quick, easy, cheap, effective, rugged and safe methodology followed by gas chromatography-tandem mass spectrometry.

The aim of this research was to adapt the QuEChERS method for routine pesticide multiresidue analysis in edible vegetable oil samples using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Several clean-up approaches were tested: (a) D-SPE with Enhanced Matrix Removal-Lipid (EMR-Lipid™); (b) D-SPE with PSA; (c) D-SPE with Z-Sep; (d) SPE with Z-Sep. Clean-up methods were evaluated in terms of fat removal from the extracts, recoveries and extraction precision for 213 pesticides in different matrices (soybean, sunflower and extra-virgin olive oil). The QuEChERS protocol with EMR-Lipid d-SPE provided the best reduction of co-extracted matrix compounds with the highest number of pesticides exhibiting mean recoveries in the 70-120% range, and the lowest relative standard deviations values (4% on average). A simple and rapid (only 5min) freeze-out step with dry ice (CO2 at -76°C) prior to d-SPE clean-up ensured much better removal of co-extracted matrix compounds in compliance of the necessity in routine analysis. Procedural Standard Calibration was established in order to compensate for recovery losses of certain pesticides and possible matrix effects. Limits of quantification were 10μgkg(-1) for the majority of the pesticides. The modified methodology was applied for the analysis of different 17 oil samples. Fourteen pesticides were detected with values lower than MRLs and their concentration ranged between 10.2 and 156.0μgkg(-1).

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry.

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.

Analytical improvements of hybrid LC-MS/MS techniques for the efficient evaluation of emerging contaminants in river waters: a case study of the Henares River (Madrid, Spain)

PurposeInstrumental capabilities and software tools of modern hybrid mass spectrometry (MS) instruments such as high-resolution mass spectrometry (HRMS), quadrupole time-of-flight (QTOF), and quadrupole linear ion trap (QLIT) were experimentally investigated for the study of emerging contaminants in Henares River water samples.MethodsAutomated screening and confirmatory capabilities of QTOF working in full-scan MS and tandem MS (MS/MS) were explored when dealing with real samples. Investigations on the effect of sensitivity and resolution power influence on mass accuracy were studied for the correct assignment of the amoxicillin transformation product 5(R) amoxicillin-diketopiperazine-2′,5′ as an example of a nontarget compound. On the other hand, a comparison of quantitative and qualitative strategies based on direct injection analysis and off-line solid-phase extraction sample treatment were assayed using two different QLIT instruments for a selected group of emerging contaminants when operating in selected reaction monitoring (SRM) and information-dependent acquisition (IDA) modes.Results and discussionSoftware-aided screening usually needs a further confirmatory step. Resolving power and MS/MS feature of QTOF showed to confirm/reject most findings in river water, although sensitivity-related limitations are usually found. Superior sensitivity of modern QLIT-MS/MS offered the possibility of direct injection analysis for proper quantitative study of a variety of contaminants, while it simultaneously reduced the matrix effect and increased the reliability of the results. Confirmation of ethylamphetamine, which lacks on a second SRM transition, was accomplished by using the IDA feature.ConclusionHybrid MS instruments equipped with high resolution and high sensitivity contributes to enlarge the scope of targeted analytes in river waters. However, in the tested instruments, there is a margin of improvement principally in required sensitivity and data treatment software tools devoted to reliable confirmation and improved automated data processing.

IDENTIFICATION OF NON-INTENTIONALLY ADDED SUBSTANCES IN FOOD PACKAGING NANO FILMS BY GAS AND LIQUID CHROMATOGRAPHY COUPLED TO ORBITRAP MASS SPECTROMETRY

The control of chemical migration from new functionalized food contact materials (FCMs) is a challenge for meeting food safety requirements. The non-intentionally added substances (NIAS) constitute a group of chemicals that are not applied, but may be introduced or formed during the production process of FCMs. This study describes a multi-analytical approach for the evaluation of unknown substances that migrate from FCMs. A case study is presented using a developed polymer consisting of a monolayer film with polylactic acid (PLA), polylimonene (PL) and zinc oxide nanoparticles (ZnO NPs). This approach incorporates the platforms of ICP-MS (inductively coupled plasma mass spectrometry), to determine whether there is transference of ZnO NPs used as antimicrobial agent and, the systems GC-MS and LC-MS (gas / liquid chromatography coupled to a quadrupole orbitrap mass spectrometer) for the characterization of the chemical structure of NIAS using the molecular mass and specific features of mass fragmentation. The screening of unknown compounds comprised retrospective analysis and data processing using both, a mass spectral library and databases, for GC and LC data, respectively. This approach has provided the tentative identification and quantification of seven NIAS, 3 by GC (Tripropylene glycol diacrylate, 10-Heneicosene and α-Tocopherol acetate) and 4 by LC (N,N-Diethyldodecanamide, N-[(9Z)-9-Octadecen-1-yl]acetamide, 1-Palmitoylglycerol and Glycerol stearate). This migration study was carried out according to the standard protocols established by EU regulation for FCMs.

Shifting the paradigm in gas chromatography mass spectrometry pesticide analysis using high resolution accurate mass spectrometry

In the last 10 years, the majority of the pesticide food control laboratories moved from GC-MS to GC-MS/MS as the preferred analytical technique to address GC amenable compounds. The main reason for this change was the negative impact on the single stage GC-MS analysis caused by the interference from coeluting matrix compounds. The new development of gas chromatography coupled to high resolution accurate mass spectrometry (GC-HRAMS) provides opportunities to overcome such matrix interferences as a result of its much higher selectivity; allowing laboratories to carry out full-scan analysis covering the most exigent analytical performance criteria. The aim of this work is the evaluation of the main analytical performance parameters for the multiresidue screening of pesticide residues by a gas chromatography-Orbitrap™ mass spectrometer in fruits and vegetables. Electron ionization and full-scan high resolution mass spectrometry was selected for this evaluation. Mass resolving power, selectivity, sensitivity, analyte identification and database generation are discussed in light of the analysis of various commodities and a large scope of pesticides. The selected operational conditions provided optimal mass accuracy, within ±1mDa and achieved LOQs of 10μg/kg or lower for practically all the selected pesticides and commodities. Applicability for quantitative residue analysis was verified by the validation of the 210 pesticides in four matrices (tomato, apple, leek and orange). The performance of the GC-EI-full scan Orbitrap HRAMS developed method was confirmed with the analysis of 102 real samples providing good results.