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.

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.

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.

Detection and Evaluation of Lipid Classes and Other Hydrophobic Compounds Using a Laser Desorption/Plasma Ionization Interface.

Ionization mechanisms of different lipid classes and other hydrophobic compounds have been evaluated in an ambient air laser-desorption flexible microtube plasma ionization (LD-FµTPi) setup, without sample manipulation. Lipids require a minimum laser fluency of 27 W/mm2 for efficient desorption and detection, providing the possibility for temperature-programmed laser desorption of different lipid classes. The flexible microtube plasma (FµTP) produces oxygen addition to double bonds, even to polyunsaturated molecules. The characteristic fragmentation pattern of phospholipids consisting of the neutral loss of the phosphocholine head group was verified. The formation of dimers due to hydrogen bonding and dispersion forces was observed as well. In this sense, soft ionization capabilities of the FµTP were proven in both ion modes. Ambient air mass spectrometry methods often suffer from decreased reproducibility, for instance, due to changing atmospheric conditions or sensitive positioning of the ion source. It was shown that neutrals become increasingly unstable above a distance of 7 ± 1 mm to the spectrometer's inlet, providing estimates for the free volume in LD-FµTPi MS. In this sense, no guided transport is required. The ion plume ejected from the plasma can be altered by applying a bias voltage to the copper substrate. Ions can be detected at -950 V, 300 V (negative ion mode) and -400 V, 900 V (positive ion mode), respectively. The ions are guided through an internal electric field gradient of the FµTP that arises from charged capillary walls, ideal for ion detection. In conclusion, this makes the method fast, robust, and flexible.

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.

Exploring the Microalga Euglena cantabrica by Pressurized Liquid Extraction to Obtain Bioactive Compounds.

In the present study, the chemical composition of the microalga Euglena cantabrica was investigated. The extraction of bioactive compounds was done using pressurized liquid extraction (PLE) at different temperatures (40-180 °C) and using green solvents (ethanol-water mixtures). A statistical design of experiments was used to optimize the maximum antioxidant capacity of the extracts by response surface methodology. The antioxidant capacity was determined through the inhibition of 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals, while the chemical analyses of the extracts were carried out using different chromatographic techniques. Chlorophylls and carotenoids were analyzed by high-performance liquid chromatography coupled to a diode array detector and mass spectrometry (HPLC-DAD-MS/MS) and carbohydrates by gas chromatography with flame ionization detection (GC-FID) and high-pressure size-exclusion chromatography coupled to an evaporative light-scattering detector (HPSEC-ELSD). The results showed different possibilities for the extraction conditions, depending on the desired bioactivity or chemical composition. Briefly, (i) mixtures of ethanol-water containing around 40% ethanol at 180 °C gave the best antioxidant capacity, (ii) mixtures containing around 50% ethanol at 110 °C gave the best yield of ß-glucan paramylon, and (iii) the use of pure ethanol at a low temperature (40 °C) is the best choice for the recovery of carotenoids such as diatoxanthin. Summing up, E. cantabrica seems to be a good candidate to be used in biorefinery to obtain different bioactive compounds.

Standardization of Sandwich-Structured Cu-Glass Substrates Embedded in a Flexible Diode Laser-Plasma Interface for the Detection of Cholesterol.

This study introduced sandwich-structured copper-glass substrates for standardization of laser desorption and plasma ionization. For standardized quantitative analysis, cavities were constructed which allow better reproducibility in droplet deposition and for laser application. Applying the diode laser, molten substrate material is incorporated into the glass, being trapped inside. Therefore, this method can be separated from laser ablation, achieving high ion signals without ablating material from the surface. Flexible microtube plasma (FµTP) was selected as the ionization source, this being the first time that laser desorption and FµTP ionization are coupled. This laser-plasma interface was applied to the detection of cholesterol, which showed a significantly improved limit of detection of 0.46 ng and linear dynamic range of 3 orders of magnitude in positive ion mode compared to other (ambient air mass spectrometry) methods. The main reason was the change of phase on the copper surface. The dehydrated molecule [M-H2O+H]+ was the base peak of the spectrum and no further dissociation or fragmentation was observed. Blood plasma was spiked with cholesterol. In a 1:100 chloroform dilution, the presence of the plasma was neglectable and led to the same detection limits and linear dynamic range as in the cholesterol standard. No sample preparation or internal standards were needed for calibration. The physical effects of the surface modification were investigated, including the calculation of the laser beam waist to simplify the comparison and reproducibility of results.

Synthesis and Structural Characterization of a Ubiquitous Transformation Product (BTS 40348) of Fungicide Prochloraz.

Prochloraz is a widely used imidazole fungicide that has to be analyzed together with its metabolites or transformation products for food safety monitoring purposes in the European Union. Although the focus in food of plant origin has been set on metabolites BTS 44595 and BTS 44596, we consider relevant the study of BTS 40348 metabolite, too, because it has been detected in both raw and processed foods based on citrus fruits in the EU. Metabolite BTS 40348 should be monitored in surface water due to its ecotoxicological effects. In this work, the synthesis and structural characterization of BTS 40348 metabolite of fungicide prochloraz is presented, because the structure is closely related to the chemistry and biological activity of the substance. Characterization using 13C and 1H NMR, infrared (IR), and Raman spectroscopy is detailed, together with confirmation by electrospray mass spectrometry analysis.

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.

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.

Development of green extraction processes for Nannochloropsis gaditana biomass valorization.

In the present work, the valorization of Nannochloropsis gaditana biomass is proposed within the concept of biorefinery. To this aim, high-pressure homogenization (HPH) was used to break down the strong cell wall and supercritical fluid extraction (SFE) with pure CO2 was applied as a first step to extract valuable compounds (such as non-polar lipids and pigments). Extraction of the remaining residue for the recovery of bioactive compounds was studied by means of an experimental design based on response surface methodology (RSM) employing pressurized liquid extraction (PLE) with green solvents such as water and ethanol. Optimum extract was achieved with pure ethanol at 170°C for 20 min, providing an important antioxidant capacity (0.72 ± 0.03 mmol trolox eq g-1 extract). Complete chemical characterization of the optimum extract was carried out by using different chromatographic methods such as reverse-phase high-performance liquid chromatography with diode array detection (RP-HPLC-DAD), normal-phase HPLC with evaporative light scattering detection (NP-HPLC-ELSD) and gas chromatography coupled to mass spectrometry detection (GC-MS); carotenoids (e.g. violaxanthin), chlorophylls and polar lipids were the main compounds observed while palmitoleic, palmitic, myristic acids and the polyunsaturated eicosapentanoic (EPA) acid were the predominant fatty acids in all PLE extracts.

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.

Optimization of pressurized liquid extraction by response surface methodology of Goji berry (Lycium barbarum L.) phenolic bioactive compounds.

Pressurized liquid extraction (PLE) has been used for the first time in this work to extract phenolic compounds from Goji berries according to a multilevel factorial design using response surface methodology. The global yield (% w/dw, weight/dry-weight), total phenolic content (TPC), total flavonoid (TF) and antioxidant activity (determined via ABTS assay, expressed as TEAC value) were used as response variables to study the effects of temperature (50-180°C) and green solvent composition (mixtures of ethanol/water). Phenolic compounds characterization was performed by high performance liquid chromatography-diode array detector-tandem mass spectrometry (HPLC-DAD-MS/MS). The optimum PLE conditions predicted by the model were as follows: 180°C and 86% ethanol in water with a good desirability value of 0.815. The predicted conditions were confirmed experimentally and once the experimental design was validated for commercial fruit samples, the PLE extraction of phenolic compounds from three different varieties of fruit samples (Selvatico mongolo, Bigol, and Polonia) was performed. Nine phenolic compounds were tentatively identified in these extracts, including phenolic acids and their derivatives, and flavonols. The optimized PLE conditions were compared to a conventional solid-liquid extraction, demonstrating that PLE is a useful alternative to extract phenolic compounds from Goji berry.

Phenolic Compounds from Edible Algae: Bioactivity and Health Benefits.

Algae have been consumed for many years in Asian countries; at present, its consumption around the world either as food ingredient or directly as food commodity has increased considerably mainly due to the Asian influence and its cuisine, but also because of the growing interest in the beneficial health effects of algae. Although several biological activities have been attributed to different algae compounds such as pigments, lipids, polysaccharides, fiber, proteins or vitamins, in the present review we will highlight the different phenolic compounds present on seaweeds and their important role in the functional and health effects, paying special attention to the antioxidant, anti-proliferative, anti-obesity and antidiabetic activities.

Experimental and theoretical determination of pesticide processing factors to model their behavior during virgin olive oil production.

The purpose of the present work was the experimental evaluation of pesticides transfer to virgin olive oil during the production step and prediction of their processing factors, which could be eventually used for the calculation of maximum residue limits (MRLs) in olive oil from the MRLs set in olives. A laboratory-scale Abencor system was used for the production of olive oil from olives spiked with the 104 pesticides studied, three different chromatographic methods being used for the analysis of raw olives and the obtained olive oil: (i) gas chromatography-tandem mass spectrometry (GC-MS/MS) for GC-amenable pesticides; (ii) hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) for polar pesticides, and; (iii) reversed-phase liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for low to medium polarity pesticides. Processing factors experimentally calculated were correlated to their octanol-water partitioning coefficient (logKow), enabling the calculation of the equivalent MRLs in olive oil from the MRLs in olives, considering the percentage of oil extracted (oil yield) and the log Kow of each pesticide.