Occurrence and risk assessment of pesticides and their transformation products related to olive groves in surface waters of the Guadalquivir river basin.

Pesticides are considered one of the main sources of contamination of surface waters, especially in rural areas highly influenced by traditional agricultural practices. The objective of this work was to evaluate the impact caused by pesticides and their transformation products (TPs) related to olive groves in surface waters with strong agricultural pressure. 11 streams were monitored during four sampling campaigns over 2 years. A solid-phase extraction, followed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) analysis was used in the quantitative target approach, with more than 70 validated compounds. Target method was combined with a suspect screening strategy involving more than 500 pesticides and TPs, using ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) to identify additional pesticides and TPs out of the scope of analysis. A total of 43 different compounds were detected with the target method. The herbicide MCPA was present in all samples and at the highest concentration (1260 ng L-1), followed by the fungicide carbendazim (1110 ng L-1), and the herbicide chlorotoluron (706 ng L-1). The suspect screening strategy revealed the presence of 7 compounds out of the target analysis (1 pesticide and 6 TPs). 6 analytes were confirmed with the analytical standards. Semi-quantification results revealed that TPs exhibited higher concentrations than their corresponding parent compounds, indicating higher persistency. Some small streams showed a comparable number of pesticides and concentrations to the most polluted large river. The determined pesticide and TPs concentrations represented an estimated environmental hazard in almost all sampling sites under study. This work underscores the importance of including pesticide TPs and small streams impacted by extensive agricultural activities in water quality monitoring programs.

Miniaturized flexible micro-tube plasma ionization source for the effective ionization of non-easily ionizable pesticides in food with liquid chromatography/mass spectrometry.

In this article, we have studied the potential of flexible microtube plasma (FµTP) as ionization source for the liquid chromatography high-resolution mass spectrometry detection of non-easily ionizable pesticides (viz. nonpolar and non-ionizable by acid/basic moieties). Phthalimide-related compounds such as dicofol, dinocap, o-phenylphenol, captan, captafol, folpet and their metabolites were studied. Dielectric barrier discharge ionization (DBDI) was examined using two electrode configurations, including the miniaturized one based on a single high-voltage (HV) electrode and a virtual ground electrode configuration (FµTP), and also the two-ring electrode DBDI configuration. Different ionization pathways were observed to ionize these challenging, non-easily ionizable nonpolar compounds, involving nucleophilic substitutions and proton abstraction, with subtle differences in the spectra obtained compared with APCI. An average sensitivity increase of 5-fold was attained compared with the standard APCI source. In addition, more tolerance with matrix effects was observed in both DBDI sources. The importance of the data reported is not just limited to the sensitivity enhancement compared to APCI, but, more notably, to the ability to effectively ionize nonpolar, late-eluting (in reverse-phase chromatography) non-ionizable compounds. Besides o-phenylphenol ([M - H]-), all the parent species were efficiently ionized through different mechanisms involving bond cleavages through the effect of plasma reagent species or its combination with thermal degradation and subsequent ionization. This tool can be used to figure out overlooked nonpolar compounds in different environmental samples of societal interest through non-target screening (NTS) strategies.

Ion Heating in Advanced Dielectric Barrier Discharge Ion Sources for Ambient Mass Spectrometry.

Dielectric barrier discharges (DBD) are highly versatile plasma sources for forming ions at atmospheric pressure and near ambient temperatures for the rapid, direct, and sensitive analysis of molecules by mass spectrometry (MS). Ambient ion sources should ideally form intact ions, as in-source fragmentation can limit sensitivity, increase spectral complexity, and hinder interpretation. Here, we report the measurement of ion internal energy distributions for the four primary classes of DBD-based ion sources, specifically DBD ionization (DBDI), low-temperature plasma (LTP), flexible microtube plasma (FµTP), and active capillary plasma ionization (ACaPI), in addition to atmospheric pressure chemical ionization (APCI) using para-substituted benzylammonium thermometer ions. Surprisingly, the average extent of energy deposited by the use of ACaPI (90.6 kJ mol-1) was ∼40 kJ mol-1 lower than the other ion sources (DBDI, LTP, FµTP, and APCI; 130.2 to 134.1 kJ mol-1) in their conventional configurations, and slightly higher than electrospray ionization (80.8 kJ mol-1). The internal energy distributions did not depend strongly on the sample introduction conditions (i.e., the use of different solvents and sample vaporization temperatures) or the DBD plasma conditions (i.e., maximum applied voltage). By positioning the DBDI, LTP, and FµTP plasma jets on axis with the capillary entrance to the mass spectrometer, the extent of internal energy deposition could be reduced by up to 20 kJ mol-1, although at the expense of sensitivity. Overall, the use of an active capillary-based DBD can result in substantially less fragmentation of ions with labile bonds than alternate DBD sources and APCI with comparably high sensitivity.

Comprehensive and heart-cutting multidimensional liquid chromatography-mass spectrometry and its applications in food analysis.

In food analysis, conventional one-dimensional liquid chromatography methods sometimes lack sufficient separation power due to the complexity and heterogeneity of the analysed matrices. Therefore, the use of two-dimensional liquid chromatography (2D-LC) turns out to be a powerful tool to consider, especially when coupled to mass spectrometry (MS). This review presents the most remarkable 2D-LC-MS food applications reported in the last 10 years, including a critical discussion of the multiple approaches, modulation strategies as well as the importance of the optimisation of the different analytical aspects that will condition the 2D-LC-MS performance. The presence of contaminants in food (food safety), the food quality and authenticity or the relationship between the beneficial effects of food and human health are some of the fields in which most of the 2D-LC-MS applications are mainly focused. Both heart-cutting and comprehensive applications are described and discussed in this review, highlighting the potential of 2D-LC-MS for the analysis of such complex samples.

Comprehensive and heart-cutting multidimensional liquid chromatography-mass spectrometry and its applications in food analysis.

In food analysis, conventional one-dimensional liquid chromatography methods sometimes lack sufficient separation power due to the complexity and heterogeneity of the analyzed matrices. Therefore, the use of two-dimensional liquid chromatography (2D-LC) turns out to be a powerful tool to consider, especially when coupled to mass spectrometry (MS). This review presents the most remarkable 2D-LC-MS food applications reported in the last 10 years, including a critical discussion of the multiple approaches, modulation strategies as well as the importance of the optimization of the different analytical aspects that will condition the 2D-LC-MS performance. The presence of contaminants in food (food safety), the food quality, and authenticity or the relationship between the beneficial effects of food and human health are some of the fields in which most of the 2D-LC-MS applications are mainly focused. Both heart-cutting and comprehensive applications are described and discussed in this review, highlighting the potential of 2D-LC-MS for the analysis of such complex samples.

Dielectric Barrier Discharge Ionization Mechanisms: Polycyclic Aromatic Hydrocarbons as a Case of Study.

Dielectric barrier discharge ionization (DBDI) is a versatile tool for small-molecule mass spectrometry applications, helping cover from polar to low polar molecules. However, the plasma gas-phase interactions are highly complex and have been scarcely investigated. The ionization mechanisms of plasmas have long been assumed to be somewhat similar to atmospheric pressure chemical ionization (APCI). Here, we evaluated the ionization mechanisms of a two-ring DBDI ion source, using different discharge gases to analyze vaporized liquid samples. Polycyclic aromatic hydrocarbons (PAHs) were used as model analytes to assess the mechanisms' dominance: protonation, [M + H]+, or radical ion species formation, [M]·+. In the present work, two different ionization trends were observed for APCI and DBDI during the PAH analysis; the compounds with proton affinities (PA) over 856 kJ/mol were detected as [M + H]+ when APCI was used as ionization source. Meanwhile, independently of the PA, DBDI showed the prevalence of charge exchange reactions. The addition of dopants in the gas-phase region shifted the ionization mechanisms toward charge exchange reactions, facilitating the formation of [M]·+ ion species, showing anisole a significant boost of the PAH radical ion species signals, over nine times for Ar-Prop-DBDI analysis. The presence of high-energy metastable atoms (e.g., HeM) with high ionization potentials (IE = 19.80 eV) did not show boosted PAH abundances or extensive molecule fragmentation. Moreover, other species in the plasma jet region with closer and more appropriate IE, such as N2 B3Πg excited molecules, are likely responsible for PAH Penning ionization.

Liquid chromatography-dielectric barrier discharge ionization mass spectrometry for the analysis of neutral lipids of archaeological interest.

Dielectric barrier discharge ionization has gained attention in the last few years due to its versatility and the vast array of molecules that can be ionized. In this study, we report on the assessment of liquid chromatography coupled to dielectric barrier discharge ionization with mass spectrometry for neutral lipid analysis. A set of different neutral lipid subclasses (triacylglycerides, diacylglycerides, and sterols) were selected for the study. The main species detected from our ionization source were [M-H2 O+H]+ , [M+H]+ or [M-R-H2 O+H]+ , attributed to sterol dehydration, protonation or the fragmentation of an acyl chain accompanied by a water loss of the glycerolipids, respectively. In terms of sensitivity, the dielectric barrier discharge displayed overall improved abundances and comparable or better limits of quantitation than atmospheric pressure chemical ionization for both acylglycerols and sterols. As a case study, different archaeological samples with variable content in neutral lipids, particularly triacylglycerides, were studied. The identification was carried out by combining accurate mass and the tentative formula associated with the exact mass, retention time matching with standards, and additional structural information from in-source fragmentation. The high degree of unsaturation and the presence of sterols revealed the potential vegetal origin of the material stored in the analyzed samples.

Evaluation of a novel controlled-atmosphere flexible microtube plasma soft ionization source for the determination of BTEX in olive oil by headspace-gas chromatography/mass spectrometry.

Although electron impact ionization (EI) remains the standard ionization source for GC-MS, it presents extensive fragmentation as its main limitation. The potential of a novel plasma-based soft ionization source named controlled-atmosphere flexible microtube plasma (CA-FµTP) has been evaluated in this work for the determination of monoaromatic volatile BTEX group (namely benzene, toluene, ethylbenzene, and o-, m- and p-xylenes) in olive oil, based on headspace technique. The obtained results show an attractive advantage over EI due to no fragmentation was observed. A nitrosated ion [M + NO]+ is obtained as the most abundant species. Thus, the BTEX mass spectrum identification can be carried out without major effort. In general, the sensitivity for CA-FµTP was comparable to those obtained by EI, achieving LODs ranged from 0.6 to 1.0 µg kg-1. The potential usefulness of GC-CA-FµTP-MS for the detection of BTEX was demonstrated by analyzing olive oil samples and identifying traces of these compounds in one sample. Therefore, the proposed plasma-based soft ionization is suitable for BTEX analysis in fatty complex matrixes as olive oil.

Worldwide survey of pesticide residues in citrus-flavored soft drinks.

After more than ten years since pesticide residues were detected in citrus-flavored soft drinks, this study reveals that the situation has not changed. A new sensitive multiresidue UHPLC-MS/MS method has been validated for 88 pesticides, which was used to analyze 200 samples manufactured in 67 countries, 80% corresponding to fruit-based soft drinks. The results show that 98% of the samples collected worldwide contained at least one pesticide, and 85% of them contained more than 4 pesticides. 40 out of 88 target compounds were quantified among the screened samples. Europe was the world region with the highest total amount of pesticides, probably due to the higher content of juice concentrate in samples, which may be the main source of the pesticide residues. Nevertheless, residues were also found in samples with no juice, so water quality also plays an important role as the main ingredient of citrus-flavored soft drinks.

Determination of atropine and scopolamine in spinach-based products contaminated with genus Datura by UHPLC-MS/MS.

Datura species are well known because of their high concentration of tropane alkaloids, which has led to poisoning episodes when Datura is accidentally mixed with edible crops. Therefore, the European Union has set a maximum level in cereal-based infant food products of 1 µg kg-1 for atropine and scopolamine. However, the occurrence of these compounds in other commodities has become a global concern. Spinach and derived products can be contaminated with Datura innoxia leaves. In this study, we tested frozen spinachs and spinach-based infant food products. The determination was carried out by UHPLC-MS/MS after applying the QuEChERS method as sample treatment. The LOQs were below 0.016 µg kg-1, achieving satisfactory results in terms of precision, accuracy, and matrix effects. The obtained results (ranging between 0.02 and 8.19 µg kg-1) were close to the maximum level set by the European Union for 24% of the samples tested.

Ambient (desorption/ionization) mass spectrometry methods for pesticide testing in food: a review.

Ambient mass spectrometry refers to the family of techniques that allows ions to be generated from condensed phase samples under ambient conditions and then, collected and analysed by mass spectrometry. One of their key advantages relies on their ability to allow the analysis of samples with minimal to no sample workup. This feature maps well to the requirements of food safety testing, in particular, those related to the fast determination of pesticide residues in foods. This review discusses the application of different ambient ionization methods for the qualitative and (semi)quantitative determination of pesticides in foods, with the focus on different specific methods used and their ionization mechanisms. More popular techniques used are those commercially available including desorption electrospray ionization (DESI-MS), direct analysis on real time (DART-MS), paper spray (PS-MS) and low-temperature plasma (LTP-MS). Several applications described with ambient MS have reported limits of quantitation approaching those of reference methods, typically based on LC-MS and generic sample extraction procedures. Some of them have been combined with portable mass spectrometers thus allowing "in situ" analysis. In addition, these techniques have the ability to map surfaces (ambient MS imaging) to unravel the distribution of agrochemicals on crops.

Endogenous Biosynthesis of S-Nitrosoglutathione From Nitro-Fatty Acids in Plants.

Nitro-fatty acids (NO2-FAs) are novel molecules resulting from the interaction of unsaturated fatty acids and nitric oxide (NO) or NO-related molecules. In plants, it has recently been described that NO2-FAs trigger an antioxidant and a defence response against stressful situations. Among the properties of NO2-FAs highlight the ability to release NO therefore modulating specific protein targets through post-translational modifications (NO-PTMs). Thus, based on the capacity of NO2-FAs to act as physiological NO donors and using high-accuracy mass-spectrometric approaches, herein, we show that endogenous nitro-linolenic acid (NO2-Ln) can modulate S-nitrosoglutathione (GSNO) biosynthesis in Arabidopsis. The incubation of NO2-Ln with GSH was analyzed by LC-MS/MS and the in vitro synthesis of GSNO was noted. The in vivo confirmation of this behavior was carried out by incubating Arabidopsis plants with 15N-labeled NO2-Ln throughout the roots, and 15N-labeled GSNO (GS15NO) was detected in the leaves. With the aim to go in depth in the relation of NO2-FA and GSNO in plants, Arabidopsis alkenal reductase mutants (aer mutants) which modulate NO2-FAs levels were used. Our results constitute the first evidence of the modulation of a key NO biological reservoir in plants (GSNO) by these novel NO2-FAs, increasing knowledge about S-nitrosothiols and GSNO-signaling pathways in plants.

Quantitative determination of pesticide residues in specific parts of bee specimens by nanoflow liquid chromatography high resolution mass spectrometry.

The presence of pesticide residues in bees is of great interest, given the central role of bees as indicators for environmental assessment. The goal of this article is to propose a method to capture enhanced chemical information for these central environmental indicators. Most of the methods rely on the analysis of pooled samples rather than individual specimens due to practical sample preparation method considerations and limitations in sensitivity. This leads to miss information on the mapping of pesticides and actual amount of pesticide per specimen. In this article, a nanoflow liquid chromatography system coupled to high resolution mass spectrometry (using a hybrid quadrupole-Orbitrap instrument) has been applied for the development of a multiresidue pesticide method for the determination of 162 multiclass pesticides in specific part of honeybee samples (ca. abdomen, head or thorax). The reduced flow rate provided an enhancement in sensitivity and a strong reduction of matrix effects, thus only a quick and simple ultrasound assisted extraction using minute amount of sample was required. Satisfactory results were obtained for all tested analytes with concentration levels detected lower than 0.5 ng g-1 in all cases, thus being acceptable for monitoring purposes. Matrix effect was negligible for 94% of compounds. Extraction recoveries ranged from 70% to 105%, being within SANTE guidelines. Finally, the applicability of the method was demonstrated, by successful application to the analysis of contaminated honeybee samples, extracting useful information from specific bee parts of single specimens, thus, enabling pseudo spatially resolved chemical information.

Basin-scale monitoring and risk assessment of emerging contaminants in South American Atlantic coastal lagoons.

Emerging contaminants (ECs) such as pharmaceuticals, personal care products, drugs of abuse and polar pesticides are under particular attention due to their high consumption, frequent detection in the environment and reported ecotoxicological risk. This study investigates the occurrence and distribution of multiclass of ECs in surface waters at basin scale of two Atlantic coastal lagoons of Uruguay, South America. For this purpose, a target screening approach covering up to 362 compounds was employed using nanoflow liquid chromatography - high resolution mass spectrometry (nanoLC/HRMS). 56 compounds were identified including five banned pesticides in the European Union: atrazine, carbendazim, chlorpyrifos ethyl, diazinon, and ethion. Pharmaceuticals, hormones and drugs of abuse showed maximum detection frequencies and concentrations downstream cities. The highest occurrence of pesticides was found in lagoons and streams with neighboring agricultural activity. ECs were also found in coastal sea. Environmental risk assessment revealed that the hormones 17α-ethinylestradiol and 17-ß-estradiol showed the highest risk to aquatic organisms in these basins. This study represents the first basin- scale monitoring of ECs in superficial waters encompassing streams, lagoons, and coastal seas in Uruguay, South America.

Detection of multiclass explosives and related compounds in soil and water by liquid chromatography-dielectric barrier discharge ionization-mass spectrometry.

In this work, the multiclass detection of explosives and related compounds has been studied by liquid chromatography-high-resolution mass spectrometry by means of a time-of-flight mass spectrometer (TOFMS) operated in the negative ion mode, using dielectric barrier discharge ionization (DBDI). Reversed-phase high-performance liquid chromatography (HPLC) separation was performed using water-methanol mobile phase without any modifier, although the effect of ammonium acetate was studied. DBD plasma was generated by applying a square wave voltage of 2.5 kV to a 100-mL min-1 He flow. The DBDI probe was adjusted to fit the commercial API source housing so that the HPLC eluent was nebulized and vaporized in the same manner as for atmospheric-pressure chemical ionization (APCI). The ionization process was affected by the temperature of the two nitrogen streams used to vaporize the solvent and the analytes, particularly for RDX and HMX, which are thermolabile compounds. The best approach in terms of sensitivity for all the studied compounds was the use of a gradient of temperatures in the ionization source, starting at 225/200 °C (vaporizer/drying gas temp) for nitramines and ending at 350/325 °C for nitroaromatic compounds. High-resolution full-scan spectra of individual selected compounds were recorded by LC-DBDI-TOFMS, and the results were compared to LC-APCI-TOFMS. A better sensitivity (slope of calibration curve) was obtained by DBDI for more than 70% of the studied compounds in both wastewater and soil extracts. Graphical abstract ᅟ.

Critical assessment of two sample treatment methods for multiresidue determination of veterinary drugs in milk by UHPLC-MS/MS.

In this work, two sample treatment procedures have been evaluated for the determination of veterinary drug residues in milk. In order to cover a wide range of polarities, a total of 66 veterinary drugs with log Kow ranging from - 1 to 5 were selected. Two sample cleanup steps, (i) dispersive solid-phase extraction (dSPE) using enhanced matrix removal lipid as sorbent and (ii) solid-phase extraction (in pass-through mode) using Oasis HLB PRiME cartridges, were critically assessed in terms of sample throughput, recovery, matrix effect, cleanliness of extracts, limit of quantification, and repeatability. The veterinary drugs tested (viz. benzimidazoles, cephalosporins, imidazothiazoles, macrolides, NSAIDs, penicillins, quinolones, steroids, sulfonamides, and ß-agonists) were analyzed by ultra-high-performance liquid chromatography tandem mass spectrometry. According to the results, both methods exhibited similar recovery rates between 70 and 120% for most of compounds tested. Matrix effects were satisfactory for both methodologies, although the tolerance to matrix effects was slightly higher with HLB PRiME with nearly negligible matrix effects in most cases. Limits of quantitation were also well below the current maximum residue levels established by the European Union. Notably, sample throughput was higher in the case of HLB PRiME, since this pass-through SPE cleanup approach involved fewer steps than the EMR-Lipid dSPE approach. The results in terms of analysis time, sensitivity, precision, cleanliness of extracts, and matrix effect showed the suitability of both procedures for the monitoring of veterinary drugs residues in milk samples in a single run. Graphical abstract.

Use of a modified QuEChERS method for the determination of mycotoxin residues in edible nuts by nano flow liquid chromatography high resolution mass spectrometry.

A nanoflow liquid chromatography high resolution mass spectrometry method for the quantification of mycotoxins in nuts has been developed. Two strategies based on QuEChERS methodology were evaluated. Thus, EMR-lipid was compared with a conventional mixture of PSA and C18 dispersive solid phase extraction sorbents which have been commonly used in this type of matrices as sample clean-up. The results showed that the use of EMR-lipid reduced more effectively matrix components, achieving a negligible matrix effect for all mycotoxins studied in peanut, pistachio and almond. The proposed method was validated in line with SANTE guidelines using EMR-Lipid as dispersive solid phase extraction sorbent. The lowest concentration level were between 0.05 and 5 µg kg-1, being lower than the maximum levels established by the current legislation. Recovery rates ranged from 75% to 98% was obtained in all sample studied, achieving also satisfactory precision with RSD values lower than 19% in all cases.

Use of dielectric barrier discharge ionization to minimize matrix effects and expand coverage in pesticide residue analysis by liquid chromatography-mass spectrometry.

Although electrospray ionization (ESI) remains the gold standard ionization source for LC-MS, it exhibits two main limitations: the occurrence of matrix effects and the limited ionization coverage towards nonpolar compounds. Dielectric barrier discharge ionization (DBDI) has gained attraction in recent years as a versatile ionization method in different applications and formats. Here, we report a thorough evaluation of DBDI as ionization interface for LC-MS, which reveals attractive advantages over ESI and atmospheric pressure chemical ionization (APCI) provided its singular ionization mechanism versatility. A suite of 80 pesticides across a wide range of physicochemical properties were selected and the results were compared with both ESI and APCI sources. Using a helium plasma operated in homogeneous regime with square-wave AC waveform and relatively low voltages (2.5 kV), not only DBDI was able to ionize compounds only amenable so far by GC-MS (eg. organochlorine species), but also offered a competitive performance in terms of sensitivity when contrasted with the commercial electrospray ionization source under equivalent conditions. Unlike ESI, DBDI mechanism occurs in the gas-phase, so the method is less affected by liquid-phase surface phenomena that yield ion suppression in ESI. Data collected in the positive ion mode revealed negligible matrix effect values (<10% suppression) for most of the studied compounds in different complex matrix extracts such as wastewater, orange or olive oil. This is also consistent with the absence of adduct formation whereas with ESI source, Na adduct formation is quite common with these species. In general, both sensitivity and average limits of quantitation for DBDI were similar to those obtained by ESI and better than APCI. Results showed that analyte coverage with DBDI is enhanced with respect to ESI and APCI sources being able to effectively analyze organochlorine compounds.

Renewable chemiluminescence optosensors based on implementation of bead injection principle with multicommutation.

In this work, the implementation of Bead Injection with multicommutation-based flow systems is reported. A surface renewable chemiluminescence (CL) flow sensor is presented based on the use of CL reaction of luminol with H2O2. Dowex 1 × 8 beads with immobilized luminol onto them were injected in the flow system by means of a six-port rotary valve and were accommodated into a 1 mm optical glass flow cell placed just in front of the rectangular photosensor window with the same size than the cell wall. Automatic computer-controlled manipulation of both reagents and sample solutions was undertaken using a multicommutated flow system which comprises five three-way solenoid valves, a home-made electronic interface and a Java-written software. Once the chemiluminescence signal was registered, sensing beads were automatically discarded out with a six-port rotary valve without needing to reverse or stop the flow. As a proof of concept and example, the enhancement of the chemiluminescence signal produced by Co(II) on the luminol-H2O2 reaction in alkaline medium was used for illustrating this implementation determining vitamin B12 in pharmaceutical preparations (after mineralization for releasing Co(II)). The analytical performance of the approach was satisfactory, showing a linear dynamic range from 1.7 to 50 µg L-1, a detection limit of 0.5 µg L-1, RSD (%) of 5.3%, with a sampling frequency of 11 h-1. The proposed approach was applied to different samples and the results were consistent with those obtained with a reference method based on ICP-MS. Based on the same reaction (or re-configuring the system to accommodate it to reaction requirements) the approach can also be applied to the determination of other metal ions such as Cr(III) and Fe(II) and appropriately extended to molecules of bioanalytical interest based e.g. in CL immunoassays, given its versatility.

Direct olive oil analysis by mass spectrometry: A comparison of different ambient ionization methods.

Analytical methods based on ambient ionization mass spectrometry (AIMS) combine the classic outstanding performance of mass spectrometry in terms of sensitivity and selectivity along with convenient features related to the lack of sample workup required. In this work, the performance of different mass spectrometry-based methods has been assessed for the direct analyses of virgin olive oil for quality purposes. Two sets of experiments have been setup: (1) direct analysis of untreated olive oil using AIMS methods such as Low-Temperature Plasma Mass Spectrometry (LTP-MS) or paper spray mass spectrometry (PS-MS); or alternatively (2) the use of atmospheric pressure ionization (API) mass spectrometry by direct infusion of a diluted sample through either atmospheric pressure chemical ionization (APCI) or electrospray (ESI) ionization sources. The second strategy involved a minimum sample work-up consisting of a simple olive oil dilution (from 1:10 to 1:1000) with appropriate solvents, which originated critical carry over effects in ESI, making unreliable its use in routine; thus, ESI required the use of a liquid-liquid extraction to shift the measurement towards a specific part of the composition of the edible oil (i.e. polyphenol rich fraction or lipid/fatty acid profile). On the other hand, LTP-MS enabled direct undiluted mass analysis of olive oil. The use of PS-MS provided additional advantages such as an extended ionization coverage/molecular weight range (compared to LTP-MS) and the possibility to increase the ionization efficiency towards nonpolar compounds such as squalene through the formation of Ag+ adducts with carbon-carbon double bounds, an attractive feature to discriminate between oils with different degree of unsaturation.