Screening and quantification of pesticide residues in fruits and vegetables making use of gas chromatography-quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization.

An atmospheric pressure chemical ionization source has been used to enhance the potential of gas chromatography coupled with quadrupole time-of-flight (QTOF) mass spectrometry (MS) for screening and quantification purposes in pesticide residue analysis. A screening method developed in our laboratory for around 130 pesticides has been applied to fruit and vegetable samples, including strawberries, oranges, apples, carrots, lettuces, courgettes, red peppers, and tomatoes. Samples were analyzed together with quality control samples (at 0.05 mg/kg) for each matrix and for matrix-matched calibration standards. The screening strategy consisted in first rapid searching and detection, and then a refined identification step using the QTOF capabilities (MS(E) and accurate mass). Identification was based on the presence of one characteristic m/z ion (Q) obtained with the low collision energy function and at least one fragment ion (q) obtained with the high collision energy function, both with mass errors of less than 5 ppm, and an ion intensity ratio (q/Q) within the tolerances permitted. Following this strategy, 15 of 130 pesticides were identified in the samples. Afterwards, the quantitation capabilities were tested by performing a quantitative validation for those pesticides detected in the samples. To this aim, five matrices were selected (orange, apple, tomato, lettuce, and carrot) and spiked at two concentrations (0.01 and 0.1 mg/kg), and quantification was done using matrix-matched calibration standards (relative responses versus triphenyl phosphate used as an internal standard). Acceptable average recoveries and relative standard deviations were obtained for many but not all pesticide-matrix combinations. These figures allowed us to perform a retrospective quantification of positives found in the screening without the need for additional analysis. Taking advantage of the accurate-mass full-spectrum data provided by QTOF MS, we searched for a higher number of compounds (up to 416 pesticides) in a second stage by performing extra data processing without any new sample injection. Several more pesticides were detected, confirmed, and/or tentatively identified when the reference standard was unavailable, illustrating in this way the potential of gas chromatography-QTOF MS to detect pesticides in addition to the ones targeted in quantitative analysis of pesticides in food matrices.

Advantages of atmospheric pressure chemical ionization in gas chromatography tandem mass spectrometry: pyrethroid insecticides as a case study.

Gas chromatography coupled to mass spectrometry (GC/MS) has been extensively applied for determination of volatile, nonpolar, compounds in many applied fields like food safety, environment, or toxicology. The wide majority of methods reported use electron ionization (EI), which may result in extensive fragmentation of analytes compromising selectivity and sensitivity. This might also complicate the application of tandem MS due to lack of specific/abundant precursor ions. Pyrethroids are examples of compounds with this behavior. In this work, the potential of atmospheric pressure chemical ionization (APCI), a softer form of ionization, combined with GC and a triple quadrupole mass analyzer was investigated, taking pyrethroids as a case study and their determination in fruit and vegetables as example application. Ionization and fragmentation behavior of eight pyrethroids (bifenthrin, cyfluthrin, cypermethrin, permethrin, λ-cyhalothrin, fluvalinate, fenvalerate, and deltamethrin) by APCI were studied. The formation of a highly abundant (quasi) molecular ion was the main goal because of the enhanced selectivity when used as precursor ion in tandem MS. The addition of water as a modifier was tested to promote the generation of protonated molecules, resulting in notable improvement of sensitivity and selectivity for most compounds. The excellent detectability (low detection limits (LODs) <20 fg achieved) when using APCI combined with state-of-the-art tandem MS was demonstrated for real samples. Additionally, matrix effects were evaluated in terms of signal enhancement/suppression. Depending on the matrix, different degrees of suppression were observed, on average reducing the signal in matrix to 55% of that in solvent. The results presented in this paper demonstrate the potential of APCI as new source for GC/MS that could be applied to other analytical problems apart from those illustrated in this work.

In vitro biocompatibility and antimicrobial activity of poly(ε-caprolactone)/montmorillonite nanocomposites.

A triblock copolymer based on poly(ε-caprolactone) (PCL) and 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA)/2-(methyl-7-nitrobenzofurazan)amino ethyl acrylate (NBD-NAcri), was synthesized via atom transfer radical polymerization (ATRP). The corresponding chlorohydrated copolymer, named as PCL-b-DEAEMA, was prepared and anchored via cationic exchange on montmorillonite (MMT) surface. (PCL)/layered silicate nanocomposites were prepared through melt intercalation, and XRD and TEM analysis showed an exfoliated/intercalated morphology for organomodified clay. The surface characterization of the nanocomposites was undertaken by using contact angle and AFM. An increase in the contact angle was observed in the PCL/MMT(PCL-b-DEAEMA) nanocomposites with respect to PCL. The AFM analysis showed that the surface of the nanocomposites became rougher with respect to the PCL when MMTk10 or MMT(PCL-b-DEAEMA) was incorporated, and the value increased with the clay content. The antimicrobial activity of the nanocomposites against B. subtilis and P. putida was tested. It is remarkable that the biodegradation of PCL/MMT(PCL-b-DEAEMA) nanocomposites, monitored by the production of carbon dioxide and by chemiluminescence emission, was inhibited or retarded with respect to the PCL and PCL/1-MMTk10. It would indicate that nature of organomodifier in the clay play an important role in B. subtilis and P. putida adhesion processes. Biocompatibility studies demonstrate that both PCL and PCL/MMT materials allow the culture of murine L929 fibroblasts on its surface with high viability, very low apoptosis, and without plasma membrane damage, making these materials very adequate for tissue engineering.

Current use of high-resolution mass spectrometry in the environmental sciences.

During the last two decades, mass spectrometry (MS) has been increasingly used in the environmental sciences with the objective of investigating the presence of organic pollutants. MS has been widely coupled with chromatographic techniques, both gas chromatography (GC) and liquid chromatography (LC), because of their complementary nature when facing a broad range of organic pollutants of different polarity and volatility. A clear trend has been observed, from the very popular GC-MS with a single quadrupole mass analyser, to tandem mass spectrometry (MS-MS) and, more recently, high-resolution mass spectrometry (HRMS). For years GC has been coupled to HR magnetic sector instruments, mostly for dioxin analysis, although in the last ten years there has been growing interest in HRMS with time-of-flight (TOF) and Orbitrap mass analyzers, especially in LC-MS analysis. The increasing interest in the use of HRMS in the environmental sciences is because of its suitability for both targeted and untargeted analysis, owing to its sensitivity in full-scan acquisition mode and high mass accuracy. With the same instrument one can perform a variety of tasks: pre- and post-target analysis, retrospective analysis, discovery of metabolite and transformation products, and non-target analysis. All these functions are relevant to the environmental sciences, in which the analyst encounters thousands of different organic contaminants. Thus, wide-scope screening of environmental samples is one of the main applications of HRMS. This paper is a critical review of current use of HRMS in the environmental sciences. Needless to say, it is not the intention of the authors to summarise all contributions of HRMS in this field, as in classic descriptive reviews, but to give an overview of the main characteristics of HRMS, its strong potential in environmental mass spectrometry and the trends observed over the last few years. Most of the literature has been acquired since 2005, coinciding with the growth and popularity of HRMS in this field, with a few exceptions that deserve to be mentioned because of their relevance.

Analytical strategy based on the use of liquid chromatography and gas chromatography with triple-quadrupole and time-of-flight MS analyzers for investigating organic contaminants in wastewater.

The presence of a wide variety of organic pollutants with different physicochemical characteristics has been investigated in wastewater samples from a municipal solid-waste-treatment plant in Castellón, Spain. An advanced analytical strategy was applied--combined used of two powerful and complementary techniques, GC and LC, both hyphenated with tandem mass spectrometry with triple-quadrupole analyzers. The GC-MS-MS method was based on sample extraction using C(18) SPE cartridges and enabled the determination of approximately 60 compounds from different chemical families, for example PAHs, octyl/nonylphenols, PCBs, organochlorine compounds, insecticides, herbicides, and PBDEs. Most of the compounds selected are included as priority contaminants in the European Union (EU) Water Directive. The UHPLC-MS-MS method, which provided high chromatographic resolution and sensitivity and short analysis time, used sample extraction with Oasis HLB SPE cartridges and enabled the determination of 37 (more polar) pesticides. The methodology developed was applied to the analysis of 41 water samples (20 untreated raw leachates and 21 treated samples) collected between March 2007 and February 2009. Amounts of the contaminants investigated rarely exceeded 0.5 microg L(-1) in the treated (reverse osmosis) water samples analyzed. As expected, in untreated leachates the number of compounds detected and the concentrations found were notably higher than in treated waters. The most commonly detected pollutants were herbicides (simazine, terbuthylazine, terbutryn, terbumeton, terbacil, and diuron), fungicides (thiabendazole and carbendazim), and 4-t-octylphenol. The results obtained proved that use of reverse osmosis for water treatment was efficient and notably reduced the amounts of organic contaminants found in raw leachate samples. In order to investigate the presence of other non-target contaminants, water samples were also analyzed by using GC-TOF MS and LC-QTOF MS. Several organic pollutants that did not form a part of the previous list of target contaminants were identified in the samples, because of the high sensitivity of TOF MS in full-spectrum acquisition mode and the valuable accurate-mass information provided by these instruments. The insecticide diazinon, the fungicide diphenylamide, the UV filter benzophenone, N-butylbenzenesulfonamide (N-BBSA), the insect repellent diethyltoluamide, caffeine, and the pharmaceuticals erythromycin, benzenesulfonanilide, ibuprofen, atenolol, and paracetamol were some of the compounds identified in the water samples analyzed.

Multi-residue determination of 130 multiclass pesticides in fruits and vegetables by gas chromatography coupled to triple quadrupole tandem mass spectrometry.

A multi-residue method has been developed and validated for the simultaneous quantification and confirmation of around 130 multiclass pesticides in orange, nectarine and spinach samples by GC-MS/MS with a triple quadrupole analyzer. Compounds have been selected from different chemical families including insecticides, herbicides, fungicides and acaricides. Three isotopically labeled standards have been used as surrogates in order to improve accurate quantitation. Samples were extracted by using accelerated solvent extraction (ASE) with ethyl acetate. In the case of spinach, an additional clean-up step by gel permeation chromatography was applied. Determination was performed by GC-MS/MS in electron ionization mode acquiring two MS/MS transitions for each analyte. The intensity ratio between quantitation transition (Q) and identification transition (q) was used as confirmatory parameter (Q/q ratio). Accuracy and precision were evaluated by means of recovery experiments in orange, nectarine, and spinach samples spiked at two concentration levels (0.01 and 0.05 mg/kg). Recoveries were, in most cases, between 70% and 120% and RSD were below 20%. The limits of quantification objective for which the method was satisfactorily validated in the three samples matrices were for most pesticides 0.01 mg/kg. Matrix effects over the GC-MS/MS determination were tested by comparison of reference standards in pure solvent with matrix-matched standards of each matrix. Data obtained showed enhancement of signal for the majority of analytes in the three matrices investigated. Consequently, in order to reduce the systematic error due to this effect, quantification was performed using matrix-matched standard calibration curves. The matrix effect study was extended to other food matrices such as raisin, paprika, cabbage, pear, rice, legume, and gherkin, showing in all cases a similar signal enhancement effect.

Olive oil quality classification and measurement of its organoleptic attributes by untargeted GC-MS and multivariate statistical-based approach.

The capabilities of dynamic headspace entrainment followed by thermal desorption in combination with gas chromatography (GC) coupled to single quadrupole mass spectrometry (MS) have been tested for the determination of volatile components of olive oil. This technique has shown a great potential for olive oil quality classification by using an untargeted approach. The data processing strategy consisted of three different steps: component detection from GC-MS data using novel data treatment software PARADISe, a multivariate analysis using EZ-Info, and the creation of the statistical models. The great number of compounds determined enabled not only the development of a quality classification method as a complementary tool to the official established method "PANEL TEST" but also a correlation between these compounds and different types of defect. Classification method was finally validated using blind samples. An accuracy of 85% in oil classification was obtained, with 100% of extra virgin samples correctly classified.

Identification of very long-chain (>C24) fatty acid methyl esters using gas chromatography coupled to quadrupole/time-of-flight mass spectrometry with atmospheric pressure chemical ionization source.

Gas chromatography coupled to a quadrupole time-of-flight mass analyzer (QTOF) with an atmospheric pressure chemical ionization (APCI) source has been tested to study the ionization and mass spectrometric behavior of long-chain and very long-chain polyunsaturated fatty acids (LC-PUFAs, C18-24; VLC-PUFAs, >C24). The protonated molecule ([M+H]+), measured at accurate mass, became the base peak of the spectrum for all the studied compounds and was promoted by the addition of water into the source. This fact overcame the existing difficulties for the identification of VLC-PUFAs when using an electron ionization source (EI). The extensive fragmentation of PUFAs in this source is the main drawback due to the fact that since reference standards are not commercially available, final identification relies on retention time estimation. The application of GC-APCI-QTOF to the screening of lipid extracts from the eyes of different fish species added confidence to the identification of several VLC-PUFAs. Further investigation of ion ratios allowed to predict the position of key double bonds enabling the classification of VLC-PUFAs as ω3 or ω6 compounds. VLC-PUFAs spectra found in biological samples were compared to those obtained from corresponding peaks found in heterologous expression experiments of fish's Elovl4.

Comprehensive investigation of pesticides in Brazilian surface water by high resolution mass spectrometry screening and gas chromatography-mass spectrometry quantitative analysis.

In this work, a comprehensive investigation on the occurrence of pesticides in the Paraná 3 hydrographic basin of Paraná State, Brazil, was made by application of wide-scope screening based on ultra-high performance liquid chromatography (LC) and gas chromatography (GC) both coupled to quadrupole time-of-flight mass spectrometry (QTOF MS). The use of two complementary techniques, such as GC-QTOF MS and LC-QTOF MS, allowed screening a large number of compounds with different polarity and volatility. This screening approach was applied to 17 samples, enabling the detection of fifty-two pesticides and six metabolites. In a second step, an specific research was made on the herbicide atrazine, one of the most frequent compounds in samples, and its major transformation products (TPs), which were quantitatively analyzed by dispersive liquid-liquid microextraction (DLLME) followed by GC-MS measurement. Twenty-one agricultural streams from the Paraná 3 hydrographic basin were sampled twice in 2017, each time along six successive weeks. Additional samples were also collected after rain events exceeding 10 mm. In total, 407 samples were quantitatively analyzed by DLLME/GC-MS. Atrazine concentrations did not exceed the maximum permitted concentration of 2 µg L-1 according to Brazilian legislation, and only one surface water sample, collected after precipitation events, was slightly above this value (2.89 µg L-1). The maximum concentrations for the TPs desethylatrazine and deisopropylatrazine were 0.80 and 1.22 µg L-1, respectively. Based on the quantification results, a map was produced showing the occurrence of atrazine and its TPs in the area under study. This is the first time that the presence of agrochemicals is evaluated in the Paraná 3 hydrographic basin.

Multi-class determination of undesirables in aquaculture samples by gas chromatography/tandem mass spectrometry with atmospheric pressure chemical ionization: A novel approach for polycyclic aromatic hydrocarbons.

In this work, a method for the analysis of 24 PAHs in 19 different matrices, including fish tissues, feeds and feed ingredients, has been developed using gas chromatography coupled to triple quadrupole tandem mass spectrometry with atmospheric pressure chemical ionization source (GC-APCI-MS/MS). The method is based on a modification of the unbuffered QuEChERS method, using freezing as an additional clean-up step and applying a 20-fold dilution factor to the final extract. The procedure was also tested for 15 pesticides and 7 polychlorinated biphenyl (PCB) congeners in order to widen the scope of the method. The excellent sensitivity and selectivity provided by GC-APCI-MS/MS allowed the dilution of the sample extracts and quantification using calibration with standards in solvent for all the 19 matrices tested. The developed method was evaluated at 2, 5 and 50ngg-1 spiking levels. LOQs were 2ngg-1 for most compounds, and LODs ranged from 0.5 to 2ngg-1. Analysis of real-world samples revealed the presence of naphthalene, fluorene, phenanthrene, fluoranthene and pyrene at concentration levels ranging from 4.8 to 187ngg-1. No PCBs, DDTs and pesticides were found in fillets from salmon and sea bream.

Quality classification of Spanish olive oils by untargeted gas chromatography coupled to hybrid quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization and metabolomics-based statistical approach.

The novel atmospheric pressure chemical ionization (APCI) source has been used in combination with gas chromatography (GC) coupled to hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) for determination of volatile components of olive oil, enhancing its potential for classification of olive oil samples according to their quality using a metabolomics-based approach. The full-spectrum acquisition has allowed the detection of volatile organic compounds (VOCs) in olive oil samples, including Extra Virgin, Virgin and Lampante qualities. A dynamic headspace extraction with cartridge solvent elution was applied. The metabolomics strategy consisted of three different steps: a full mass spectral alignment of GC-MS data using MzMine 2.0, a multivariate analysis using Ez-Info and the creation of the statistical model with combinations of responses for molecular fragments. The model was finally validated using blind samples, obtaining an accuracy in oil classification of 70%, taking the official established method, "PANEL TEST", as reference.

Analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in stack gas emissions by gas chromatography-atmospheric pressure chemical ionization-triple-quadrupole mass spectrometry.

A gas chromatography coupled to triple-quadrupole mass spectrometry (GC-(QqQ)MS/MS) including a soft-ionization through an atmospheric pressure chemical ionization (APCI) source based method was compared with the high resolution mass spectrometry (HRMS) standard reference method EN1948, for the analysis of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in stack gas emissions. The stack emission samples were collected, both, by manual method sampling (from 6 to 8h) and by long-term sampling systems (sampling time of several weeks). This work presents the first comparison of GC-(QqQ)MS/MS with APCI source with the European Standard EN1948 technique for stack gas emissions. Sample concentrations ranged from 0.5 to 596pg I-TEQ/Nm3. Comparative results in all investigated samples showed relative errors that were within ±15%. These results make GC-(QqQ)MS/MS with APCI suitable for the quantitative analysis of dioxins in the studied samples and create a real alternative tool to the reference sector GC-HRMS instruments.

Comprehensive strategy for pesticide residue analysis through the production cycle of gilthead sea bream and Atlantic salmon.

Plant ingredients and processed animal proteins are alternative feedstuffs for fish feeds in aquaculture. However, their use can introduce contaminants like pesticides that are not previously associated with marine Atlantic salmon and gilthead sea bream farming. This study covers the screening of around 800 pesticides by gas chromatography (GC) and liquid chromatography (LC) coupled to high resolution time-of-flight mass spectrometry in matrices throughout the entire marine food production chain. Prior to analysis of real-world samples, the screening methodology was validated for 252 pesticides to establish the screening detection limit. This was 0.01 mg kg-1 for 113 pesticides (45%), 0.05 mg kg-1 for 73 pesticides (29%) and >0.05 mg kg-1 for 66 pesticides (26%). After that, a quantitative methodology based on GC coupled to tandem mass spectrometry with atmospheric pressure chemical ionization source (GC-APCI-MS/MS) was optimized for the pesticides found in the screening. Although several polar pesticides, of which pirimiphos methyl and chlorpyriphos-methyl were most dominant, were found in plant material and feeds based on these ingredients, none of them were observed in fillets of Atlantic salmon and gilthead sea bream fed on these feeds.

Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg µL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices.

Potential of atmospheric pressure chemical ionization source in gas chromatography tandem mass spectrometry for the screening of urinary exogenous androgenic anabolic steroids.

The atmospheric pressure chemical ionization (APCI) source for gas chromatography-mass spectrometry analysis has been evaluated for the screening of 16 exogenous androgenic anabolic steroids (AAS) in urine. The sample treatment is based on the strategy currently applied in doping control laboratories i.e. enzymatic hydrolysis, liquid-liquid extraction (LLE) and derivatization to form the trimethylsilyl ether-trimethylsilyl enol ether (TMS) derivatives. These TMS derivatives are then analyzed by gas chromatography tandem mass spectrometry using a triple quadrupole instrument (GC-QqQ MS/MS) under selected reaction monitoring (SRM) mode. The APCI promotes soft ionization with very little fragmentation resulting, in most cases, in abundant [M + H](+) or [M + H-2TMSOH](+) ions, which can be chosen as precursor ions for the SRM transitions, improving in this way the selectivity and sensitivity of the method. Specificity of the transitions is also of great relevance, as the presence of endogenous compounds can affect the measurements when using the most abundant ions. The method has been qualitatively validated by spiking six different urine samples at two concentration levels each. Precision was generally satisfactory with RSD values below 25 and 15% at the low and high concentration level, respectively. Most the limits of detection (LOD) were below 0.5 ng mL(-1). Validation results were compared with the commonly used method based on the electron ionization (EI) source. EI analysis was found to be slightly more repeatable whereas lower LODs were found for APCI. In addition, the applicability of the developed method has been tested in samples collected after the administration of 4-chloromethandienone. The highest sensitivity of the APCI method for this compound, allowed to increase the period in which its administration can be detected.

Fast gas chromatographic residue analysis in animal feed using split injection and atmospheric pressure chemical ionisation tandem mass spectrometry.

Significant speed improvement for instrumental runtime would make GC­MS much more attractive for determination of pesticides and contaminants and as complementary technique to LC­MS. This was the trigger to develop a fast method (time between injections less than 10 min) for the determination of pesticides and PCBs that are not (or less) amenable to LC­MS. A key factor in achieving shorter analysis time was the use of split injection (1:10) which allowed the use of a much higher initial GC oven temperature. A shorter column (15 m), higher temperature ramp, and higher carrier gas flow rate (6 mL/min) further contributed to analysis-time reduction. Chromatographic resolution was slightly compromised but still well fit-for-purpose. Due to the high sensitivity of the technique used (GC­APCI-triple quadrupole MS/MS), quantification and identification were still possible down to the 10 µg/kg level, which was demonstrated by successful validation of the method for complex feed matrices according to EU guidelines. Other advantages of the method included a better compatibility of acetonitrile extracts (e.g. QuEChERS) with GC, and a reduced transfer of co-extractants into the GC column and mass spectrometer.

Analytical strategy based on the combination of gas chromatography coupled to time-of-flight and hybrid quadrupole time-of-flight mass analyzers for non-target analysis in food packaging.

The potential of an advanced analytical strategy based on the use of gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS) with two different analyzers and ionization sources has been investigated and applied to the non-target analysis of food packaging contaminants. Initially, the approach based on GC-time-of-flight (TOF) MS with electron ionization (EI) source allowed performing a library search and mass accurate measurements of selected ions. Then, a second analysis was performed using hybrid quadrupole (Q) TOF MS with an atmospheric pressure chemical ionization (APCI) source in order to search for the molecular ion or the protonated molecule and study the fragmentation behavior. This analytical strategy was applied to the analysis of four polypropylene/ethylene vinyl alcohol/polypropylene (PP/EVOH/PP) multilayer trays and one PP/Al foil/PP film, each one subjected to migration assays with the food simulants isooctane and Tenax®, in order to investigate its potential on the determination of migrant substances.

Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization.

A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS(E)). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20mg kg(-1). For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01mg kg(-1) level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01mg kg(-1) for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01mg kg(-1) level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20mg kg(-1) level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios.

Mass spectrometric behavior of anabolic androgenic steroids using gas chromatography coupled to atmospheric pressure chemical ionization source. Part I: ionization.

The detection of anabolic androgenic steroids (AAS) is one of the most important topics in doping control analysis. Gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)) with electron ionization and liquid chromatography coupled to tandem mass spectrometry have been traditionally applied for this purpose. However, both approaches still have important limitations, and, therefore, detection of all AAS is currently afforded by the combination of these strategies. Alternative ionization techniques can minimize these drawbacks and help in the implementation of a single method for the detection of AAS. In the present work, a new atmospheric pressure chemical ionization (APCI) source commercialized for gas chromatography coupled to a quadrupole time-of-flight analyzer has been tested to evaluate the ionization of 60 model AAS. Underivatized and trimethylsylil (TMS)-derivatized compounds have been investigated. The use of GC-APCI-MS allowed for the ionization of all AAS assayed irrespective of their structure. The presence of water in the source as modifier promoted the formation of protonated molecules ([M+H](+)), becoming the base peak of the spectrum for the majority of studied compounds. Under these conditions, [M+H](+), [M+H-H2O](+) and [M+H-2·H2O](+) for underivatized AAS and [M+H](+), [M+H-TMSOH](+) and [M+H-2·TMSOH](+) for TMS-derivatized AAS were observed as main ions in the spectra. The formed ions preserve the intact steroid skeleton, and, therefore, they might be used as specific precursors in MS/MS-based methods. Additionally, a relationship between the relative abundance of these ions and the AAS structure has been established. This relationship might be useful in the structural elucidation of unknown metabolites.

Application of gas chromatography time-of-flight mass spectrometry for target and non-target analysis of pesticide residues in fruits and vegetables.

In this work, the capability of gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF MS) for quantitative analysis of pesticide residues has been evaluated. A multiclass method for rapid screening of pesticides (insecticides, acaricides, herbicides and fungicides) in fruit and vegetable matrices has been developed and validated, including detection, identification and quantification of the analytes. To this aim, several food matrices were selected: high water content (apples, tomatoes and carrots), high acid content (oranges) and high oil content (olives) samples. The well known QuEChERS procedure was applied for extraction of pesticides, and matrix-matched calibration using relative responses versus internal standard was used for quantification. The sample extracts were analyzed by GC-TOF MS. Up to five ions using narrow window (0.02 Da)-extracted ion chromatograms at the expected retention time were monitored using a target processing method. The most abundant ion was used for quantification while the remaining ones were used for confirmation of the analyte identity. Method validation was carried out for 55 analytes in the five sample matrices tested at three concentrations (0.01, 0.05 and 0.5 mg/kg). Most recoveries were between 70% and 120% with relative standard deviations (RSDs) lower than 20% at 0.05 and 0.5mg/kg. At 0.01 mg/kg, roughly half of the pesticides could be satisfactorily validated due to sensitivity limitations of GC-TOF MS, which probably affected the ion ratios used for confirmation of identity. In the case of olive samples, results were not satisfactory due to the high complexity of the matrix. An advantage of TOF MS is the possibility to perform a non-target investigation in the samples by application of a deconvolution software, without any additional injection being required. Accurate-mass full-spectrum acquisition in TOF MS provides useful information for analytes identification, and has made feasible in this work the discovery of non-target imazalil, fluoranthene and pyrene in some of the samples analyzed.