Assessment of endocrine disruptor pollutants and their metabolites in environmental water samples using a sustainable natural deep eutectic solvent-based analytical methodology.

In this work, an evaluation of the occurrence of fifteen phthalates, four metabolites and one adipate in different groundwater, seawater and wastewater samples has been carried out due to their relevance on human health as they act as endocrine disruptors. For this purpose, a sustainable, fast and easy-handling vortex-assisted liquid-liquid microextraction method using a natural hydrophobic deep eutectic solvent based on menthol and carvacrol as extraction agent, combined with ultra-high performance liquid chromatography-mass spectrometry technique, has been developed and applied for the first time. An optimization was performed to evaluate four important factors affecting the extraction performance, and an analytical validation was carried out in terms of matrix effect, linearity, extraction efficiency, and sensitivity. Recovery values were obtained in the range 72-119% for all analytes (except for monoethyl phthalate: 61.1-72.3%) with relative standard deviation values lower than 17%. Limits of quantification were found between 0.91 and 8.09 µg L-1. As a result of the assessment of 31 different environmental water samples, monoethyl phthalate, diethyl phthalate, dibutyl phthalate and bis (2-ethylhexyl) phthalate were detected and quantified at different concentrations in the range 2.59-21.17 µg L-1 in 6 samples, and diallyl phthalate, butyl benzyl phthalate, dipentyl phthalate, dicyclohexyl phthalate, dihexyl phthalate and bis (2-ethylhexyl) adipate were detected in 20 more, showing the exposition of the population to these hazardous substances.

Monitoring of the presence of plasticizers and effect of temperature and storage time in bottled water using a green liquid-liquid microextraction method.

In this work, a natural deep eutectic solvent was used for the liquid-liquid microextraction of fourteen phthalates and one adipate from bottled waters. The methodology was validated in terms of matrix effect, linearity, recovery, and limits of quantification (LOQs). Optimum extraction conditions (10 mL of water at pH 8.0 with 100 µL of thymol: menthol 2:1 (n/n) as solvent) provided satisfactory determination coefficients (≥ 0.9977), recovery values (82-127%), and LOQs (0.018-0.523 µg/L). The effects of temperature and storage time on plasticizer presence were studied for 36 different brands stored at 4 °C, room temperature, and 45 °C, and analyzed at 0, 24, 48, 72 h, and 1 week. Only diethyl-, dibutyl-, bis-(2-ethylhexyl) phthalates, and bis-(2-ethylhexyl) adipate were detected. The results showed that there is no relationship between the storage conditions, the bottle material or water carbonation, and the occurrence of these plasticizers, suggesting that residues are introduced during production or by the water supply. The estimated daily intake was lower than the total daily intake set by the European Food Safety Authority.

Assessment of pesticide residues contamination in cereals and pseudo-cereals marketed in the Canary Islands.

In this work, the development of an analytical method for the evaluation of a wide variety of pesticide residues in cereals and pseudo-cereals widely consumed has been carried out. A QuEChERS method was used as extraction and clean-up procedure prior to separation and quantification of the target analytes by ultra-high performance liquid chromatography coupled to mass spectrometry using a single quadrupole-time-of-flight analyser. The methodology was validated for oat, rye, spelt, barley and quinoa matrices, following the European Commission guidelines (SANTE/11312/2021), achieving good absolute recovery values in the range 60-124% with relative standard deviation values lower than 20% and providing limits of quantification of the method in the low mg/kg range, in accordance with the maximum residue limits established by European policies. Finally, considering the importance of cereals in general population diet, the analysis of 60 samples was carried out in order to assure their safe consumption.

Application of polyaniline-based magnetic-dispersive-solid-phase microextraction combined with liquid chromatography tandem mass spectrometry for the evaluation of plastic migrants in food matrices.

Magnetic nanoparticles of Fe3O4 coated with polyaniline have been synthesised through chemical co-precipitation, and successfully characterised using different techniques such as FT-IR and X-ray diffraction. Such nanocomposite was applied as sorbent for a new magnetic micro-dispersive solid phase extraction procedure for the extraction of seven plastic migrants in jelly samples, followed by determination using ultra-high performance liquid chromatography-tandem mass spectrometry. Optimisation of several parameters that could affect extraction efficiency has been performed both by a conventional one-step-at-a-time approach and the use of a Box Behnken experimental design. The developed method was successfully validated obtaining recovery values in the range 70-124% with relative standard deviations lower than 20%, limits of quantification in the range 0.0106-0.0171 µg/L, and R2 values higher than 0.9915 for all the analytes. The greenness of the procedure was also evaluated using the AGREE calculator. Finally, the developed method was applied for the determination of plastic migrants in a group of 11 commercial jellies acquired in local stores. Results showed the presence of BBP in almost all the samples and DCHP in three of them, as well as DEHA, which was detected in another three commercial samples and quantified at a concentration of 2.17 µg/L in another one.

Safety assessment of citrus and olive by-products using a sustainable methodology based on natural deep eutectic solvents.

In this work, the application of betaine-based hydrophilic natural deep eutectic solvents (NADESs) as green extraction solvents was proposed for the first time for the evaluation of twelve pesticides in citrus and olive by-products intended to be applied as potential sources of compounds with neuroprotective activity against Alzheimer Disease. Ultrasound-assisted extraction of selected pesticides was followed by separation and determination using gas chromatography coupled to single quadrupole mass spectrometry. Eight NADESs were tested using different hydrogen bond donors (i.e. citric and lactic acid, fructose, glucose, glycerol, propylene glycol, propionic and butanoic acid). Other factors affecting extraction efficiency were also evaluated using a step-by-step approach. Eight mL of a mixture composed of 60% betaine:propylene glycol NADES at a molar ratio 1:4 and 40% of water, as well as 30 min of ultrasound-assisted extraction were selected as the most adequate conditions. The methodology was validated prior to its application in citrus and olive by-products. Recovery values were between 73 and 115% (RSD% < 20%), while limits of quantification of the method were in the range 8.5-128.8 µg/kg, which demonstrates the suitability of the procedure to determine the selected group of pesticides, usually applied in citrus and olive crops, at the legislated levels. The greenness of the procedure was also evaluated using AGREE calculator. Finally, the whole method was applied for the safety assessment of seven olive leaf samples and seven citrus by-products produced in Spain, finding the presence of several of the evaluated compounds at concentrations higher than the established limits for similar products.

Analysis of alkylphenols, bisphenols and alkylphenol ethoxylates in microbial-fermented functional beverages and bottled water: Optimization of a dispersive liquid-liquid microextraction protocol based on natural hydrophobic deep eutectic solvents.

In this work, the analysis of alkylphenols, bisphenols and alkylphenol ethoxylates in bottled waters, kombuchas and water kefir was performed through a vortex-assisted dispersive liquid-liquid microextraction method based on a natural hydrophobic eutectic solvent. For this purpose, mixtures of monoterpenes and fatty acids were employed. Different factors affecting extraction were optimized and the method was validated in terms of matrix effect, linearity, limits of detection and recovery. Recovery values varied between 70.0 and 124.3% (except for 4-tert-butylphenol: 67.0% and 4-n-nonylphenol: 60.8% in water kefir) and limits of detection were in the range 0.10 ng/L - 2.99 µg/L. Finally, 8 bottled waters, 8 kombuchas and 4 water kefirs were analyzed and 4-tert-octylphenol monoethoxylate was detected in water (20.28 ± 0.99 - 62.08 ± 3.63 µg/L). This is the first application analyzing xenobiotic contaminants in kombucha and water kefir and the first time in which the three types of compounds are simultaneously extracted by dispersive liquid-liquid microextraction.

Quality assessment of environmental water by a simple and fast non-ionic hydrophobic natural deep eutectic solvent-based extraction procedure combined with liquid chromatography tandem mass spectrometry for the determination of plastic migrants.

A non-ionic hydrophobic natural deep eutectic solvent (HNADES) based on thymol and menthol was proposed for the liquid-liquid microextraction of fourteen phthalates and one adipate from environmental water samples. Separation, identification, and quantification were achieved by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. The main factors affecting the extraction efficiency were thoroughly studied. Sample pH of 8 and 100 µL of thymol:menthol at molar ratio 2:1 were selected as the best conditions, while ionic strength and type of dispersant solvent were not relevant for the extraction of the target compounds. The whole methodology was validated for treated wastewater, runoff, and pond water matrices, using di-n-butyl phthalate-3,4,5,6-d4 and dihexyl phthalate-3,4,5,6-d4 as surrogates. Recovery ranged from 70 to 127% with relative standard deviation values lower than 14%. Limits of quantification of the method were in the range 0.042-0.425 µg/L for treated wastewater, 0.015-0.386 µg/L for runoff, and 0.013-0.376 µg/L for pond water. The methodology was applied for the analysis of real treated wastewater, runoff, and pond water samples from different places of Tenerife and Gran Canaria (Canary Islands) finding the presence of diethyl phthalate, diallyl phthalate, dipropyl phthalate, benzylbutyl phthalate, di-n-butyl phthalate, bis-(2-n-butoxyethyl) phthalate, di-n-pentyl phthalate, dicyclohexyl phthalate, and bis-(2-ethylhexyl) phthalate at concentrations between 105.2 and 3414 ng/L.

Sustainable polypyrrole-based magnetic-microextraction of phthalates from jellies and apple-based beverages prior to tandem mass spectrometry analysis.

Synthesised polypyrrole-coated Fe3O4 magnetic nanoparticles have been successfully characterised and applied as sorbent for the magnetic-micro-dispersive solid-phase extraction of eleven phthalic acid esters from jelly and apple-based beverage matrices widely consumed by the population and, especially, by children. Sorbent was synthesised through chemical coprecipitation and subsequently characterised by different techniques. The influence of several parameters on the extraction efficiency was exhaustively evaluated using a step-by-step strategy. The separation and quantification of the selected phthalates were performed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry. The validation of the methodology was carried out for jellies and apple-based beverages, employing dihexyl phthalate-3,4,5,6-d4 as the surrogate standard. Relative recovery values were in the range 70-114% for both matrices and relative standard deviations below 20% were obtained. The limits of quantification of the method were found in the range 0.147-0.416 µg/L. Feasibility of the developed methodology was proved by the analysis of commercialised jelly and apple-based beverage products.

Application of a Liquid-Liquid Microextraction Method Based on a Natural Hydrophobic Deep Eutectic Solvent for the Extraction of Plastic Migrants from Kombuchas.

A vortex-assisted liquid-liquid microextraction, based on a natural hydrophobic deep eutectic solvent made from the monoterpene thymol and octanoic fatty acid, was employed for the analysis of 11 phthalate esters and one adipate in kombucha (a tea-based fermented beverage). Separation and determination were performed using an ultra-high performance liquid chromatography (UHPLC) system coupled to a single quadrupole mass spectrometer. Confirmatory analyses were carried out through UHPLC tandem mass spectrometry. The full method was validated in terms of matrix effect, matrix-matched calibration, sensitivity, recovery, limits of detection and quantification and repeatability. Satisfactory determination coefficients for quadratic calibration curves (≥0.9938), recovery values (67-120%) and limits of detection (0.07-5.45 µg/L) were obtained. Analysis of 26 kombucha samples reported concentrations for dibutyl phthalate and dimethyl phthalate in the range between the limit of quantification (LOQ) and 16.18 ± 1.14 µg/L, although these phthalates were also detected under the LOQ in some of the analyzed samples. Only one of the samples bottled in plastic containers (7) did not present residues while only five of the 19 samples in glass bottles contained any plasticizer. However, the highest concentration was found in a kombucha bottled in food-grade glass. This work represents the first application in which phthalates and adipates are analyzed in kombuchas.

Comparison of Pesticide Residue Levels in Red Wines from Canary Islands, Iberian Peninsula, and Cape Verde.

In this work, the QuEChERS method coupled to liquid chromatography-time-of flight-mass spectrometry and gas chromatography-triple quadrupole-mass spectrometry were applied for the evaluation of pesticide residues and risk assessment in red wines. The methodologies were successfully validated for 173 pesticides. Recovery values were in the range 75-100% for almost all pesticides and limits of quantification were between 2.60 and 21.39 µg/kg, which are in good agreement with the maximum residue limits (MRLs) established by the European Commission for pesticides in wine grapes. Finally, the analysis of 84 red wine samples from the Canary Islands, the Iberian Peninsula, and Cape Verde was carried out, which found the presence of 31 pesticide residues. However, the risk assessment disclosed that despite the large number of pesticides and the concentrations found, which in some cases exceeded the MRLs, the consumption of these wines, without considering a possible cumulative effect, does not entail a risk to the consumers.

Critical review and re-assessment of analyte protectants in gas chromatography.

Despite nearly 80 years of advancements in gas chromatography (GC), indirect chemical matrix effects (MEs), known as the matrix-induced response enhancement effect, still occur to cause a high bias in the GC analysis of susceptible analytes, unless precautions are taken. Matrix-matched calibration is one common option used in GC to compensate for the MEs, but this approach is usually inconvenient, imprecise, and inefficient. Other options, such as the method of standard additions, surface deactivation techniques, chemical derivatizations, priming the GC, and/or use of internal standards, also have flaws in practice. When methods are accommodating, the use of analyte protectants (APs) can provide the best practical solution to not only overcome MEs, but also to maximize analyte signal by increasing chromatographic and detection efficiencies for the analytes. APs address the source of MEs in every injection by filling active sites in the GC inlet, column, and detector, particularly in GC-MS, rather than the analytes that would otherwise undergo degradation, peak tailing, and/or diminished response due to interactions with the active sites. The addition of an adequate amount of APs (e.g. sugar derivatives) to all calibration standards and final extracts alike often leads to lower detection limits, better accuracy, narrower peaks, and greater robustness than the other options to compensate for MEs in GC. This article consists of a critical review of the scientific literature, proposal of mechanisms and theory, and re-evaluation studies involving APs for the first time in GC-orbitrap and GC-MS/MS with a high-efficiency ion source design. The findings showed that 1 µg each of co-injected shikimic acid and sorbitol in the former case, and 1 µg shikimic acid alone in the latter case, led to high quality results in multi-residue analysis of pesticides and environmental contaminants.

Nano-liquid chromatography combined with a sustainable microextraction based on natural deep eutectic solvents for analysis of phthalate esters.

The separation of 11 phthalic acid ester (PAEs) was carried out by nano-liquid chromatography coupled to ultraviolet and MS detection. Preliminary experiments were achieved in order to select suitable stationary phases and chromatographic conditions. The baseline separation was obtained, for all compounds, with an XBridgeTM C18 column in less than 15 min, working in step gradient mode. The sensitivity of the method was improved by on-column focusing. PAEs were extracted from alcoholic and nonalcoholic beverages using vortex-assisted emulsification dispersive liquid-liquid microextration and natural deep eutectic solvents. The whole method was validated in terms of linearity, sensitivity, precision, recovery, and repeatability. Combination of both off-line sample preparation preconcentration and large injection volume led to obtain LOQs in the range 5-47 ng/mL. The developed nano-LC-UV method was extended to MS detection to confirm the presence of PAEs in some beverages commercialized in different types of packaging.

A simple, fast and easy methodology for the monitoring of plastic migrants in alcoholic and non-alcoholic beverages using the QuEChERS method prior to gas chromatography tandem mass spectrometry.

In this work, the development of a simple, fast and reliable method for the evaluation of a group of twelve plastic migrants in alcoholic and non-alcoholic beverages widely consumed by the population has been carried out. For that, a modified QuEChERS method for the extraction and preconcentration of the target compounds has been used prior to their separation and quantification by gas chromatography coupled to triple quadrupole tandem mass spectrometry. The whole methodology was validated for beer, cider and grape juice matrices, using dibutyl phthalate-3,4,5,6-d4 as surrogate. Recovery ranged from 75 to 120% for all matrices with relative standard deviation values lower than 20%, and the limits of quantification of the method were achieved in the range 0.034-1.415 µg/L. Finally, the analysis of different beer, cider and grape juice samples commercialised in different supermarkets of Tenerife was carried out, finding the presence of four of the evaluated phthalates in the range 0.14-1.1 µg/L in some of the evaluated beers, six of them in several cider samples, in the range 0.3-2.1 µg/L, and one in the range 1.2-1.5 µg/L in three of the analysed grape juices.

A green and simple procedure based on deep eutectic solvents for the extraction of phthalates from beverages.

In this work, a green, inexpensive, simple and fast deep eutectic solvent (DES)-based dispersive liquid-liquid microextraction was evaluated, for the first time, for the extraction of phthalates (i.e. benzylbutyl phthalate, diisobutyl phthalate, diisopentyl phthalate, di-n-pentyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate) from different beverages. Separation and determination were achieved by high performance liquid chromatography-diode-array detection while confirmation was carried out by tandem mass spectrometry. The main factors affecting the extraction such as type and volume of DES and emulsifier, pH and ionic strength, were optimised. Choline chloride:phenol-based DES showed the best results. The methodology was validated for tea, apple-based beverage and pineapple juice. Recovery values ranged from 84 to 120% with relative standard deviation values lower than 11%. Limits of detection of the method were in the range 5.1-14.2 µg L-1 for tea, 5.3-17.8 µg L-1 for apple beverages and 5.9-15.6 µg L-1 for pineapple juices.

Nanomaterials as alternative dispersants for the multiresidue analysis of phthalates in soil samples using matrix solid phase dispersion prior to ultra-high performance liquid chromatography tandem mass spectrometry.

In this study, the application of different nanomaterials as dispersants in matrix solid phase dispersion has been evaluated for the extraction of fifteen phthalates from different environmental samples prior to their separation and quantification by ultra-high performance liquid chromatography coupled to triple quadrupole mass spectrometry. Within the evaluated nanomaterials, including graphene oxide, multi-walled carbon nanotubes and iron 1,3,5-benzenetricarboxylate metal-organic framework, the last one showed the best results in terms of extraction capacity and sample clean-up. The effects of the different parameters affecting the sample pretreatment efficiency were exhaustively evaluated. The whole methodology was validated for agricultural soil and sand, using dibutyl phthalate-3,4,5,6-d4 as surrogate. Recovery values ranged from 70 to 120% for both matrices with RSD values lower than 20% and the limits of quantification of the method achieved were in the range 0.14-2.7 µg/kg dry weight. Finally, the analysis of soil samples from different locations of Tenerife (Canary Islands, Spain) was carried out finding the presence of BBP, DIBP and DBP in the range 5-52 µg/kg dry weight in agricultural soils, and DIPP, DNOP and DINP in the range 2-101 µg/kg dry weight in sand samples.

Use of Basolite® F300 metal-organic framework for the dispersive solid-phase extraction of phthalic acid esters from water samples prior to LC-MS determination.

In the present work, a commercial metal-organic framework (Basolite® F300) has been applied for the first time as dispersive solid-phase extraction (dSPE) sorbent of eight phthalic acid esters (PAEs) (butyl benzyl phthalate, bis-2-n-butoxyethyl phthalate, bis-isopentyl phthalate, bis-n-pentyl phthalate, dicyclohexyl phthalate, di-(2-ethylhexyl) phthalate -DEHP-, di-n-octyl phthalate and diisononyl phthalate) and an adipate (bis (2-ethylhexyl) adipate), which is utilized as a PAE substitutive. Milli-Q, pond, tap and waste water were selected as samples. Dihexyl phthalate-3,4,5,6-d4 was used as procedural internal standard. High-performance liquid chromatography mass spectrometry was used for the determination of the target compounds. Optimum dSPE conditions were the following: 50 mL of the water sample (pH 6.0), 120 mg of sorbent and 15 mL of ACN as elution solvent. For the validation of the method, matrix-matched calibration and trueness of the method were addressed, obtaining determination coefficients (R2) higher than 0.9905 and relative recovery values between 70 and 118 % (RSDs < 20 %). The limits of quantification of the method were in the range 22-69 ng/L. Matrix effects were also studied. Different real samples were analysed, finding DEHP in all of them at the low µg/L level.

Reduced graphene oxide-coated magnetic-nanoparticles as sorbent for the determination of phthalates in environmental samples by micro-dispersive solid-phase extraction followed by ultra-high-performance liquid chromatography tandem mass spectrometry.

In this work, the suitability of Fe3O4 nanoparticles coated with reduced-graphene oxide as sorbent was evaluated for the extraction of a group of fourteen phthalic acid esters (i.e. benzylbutyl phthalate (BBP), bis-2-n-butoxyethyl phthalate (DBEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), bis-2-ethoxyethyl phthalate (DEEP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), bis-isopentyl phthalate (DIPP), bis-(2-methoxyethyl) phthalate (DMEP), dimethyl phthalate (DMP), di-n-octyl phthalate (DNOP), bis-n-pentyl phthalate (DNPP), dipropyl phthalate (DPP)) from environmental samples. Extraction was carried out using magnetic-micro dispersive solid-phase extraction while separation, identification and quantification of the target analytes were achieved by ultra-high-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry. The methodology was validated for three different types of water samples using dibutyl phthalate-3,4,5,6-d4 as internal standard for all of them. Recovery values ranged from 70 to 120% for the three matrices with relative standard deviation values lower than 20%. Limits of quantification of the method achieved were in the range 6-178 ng/L for all samples and analytes. The methodology was applied for the evaluation of real samples finding the presence of DMP, DPP, BBP, DIBP and DBP in some of the analysed matrices.

Determination of phthalates in beverages using multiwalled carbon nanotubes dispersive solid-phase extraction before HPLC-MS.

A microdispersive solid-phase extraction method has been developed using multiwalled carbon nanotubes of 110-170 nm diameter and 5-9 µm length for the extraction of a group of nine phthalic acid esters (i.e., bis(2-methoxyethyl) phthalate, bis-2-ethoxyethyl phthalate, dipropyl phthalate, butylbenzyl phthalate, bis-2-n-butoxyethyl phthalate, bis-isopentyl phthalate, bis-n-pentyl phthalate, dicyclohexyl phthalate, and di-n-octyl phthalate) from tap water as well as from different beverages commercialized in plastic bottles (mineral water, lemon- and apple-flavored mineral water, and an isotonic drink). Determination was carried out by high-performance liquid chromatography coupled to mass spectrometry. The extraction procedure was optimized following a step-by-step approach, being the optimum extraction conditions: 50 mL of each sample at pH 6.0, 80 mg of sorbent, and 25 mL of acetonitrile as elution solvent. To validate the methodology, matrix-matched calibration and a recovery study were developed, obtaining determination coefficients >0.9906 and absolute recovery values between 70 and 117% (with relative standard deviations < 17%) in all cases. The limits of quantification of the method were between 0.173 and 1.45 µg/L. After the evaluation of the matrix effects, real samples were also analyzed, finding butylbenzyl phthalate in all samples (except in apple-flavored mineral water), though at concentrations below its limit of quantification of the method.

Determination of phthalic acid esters in water samples by hollow fiber liquid-phase microextraction prior to gas chromatography tandem mass spectrometry.

A new hollow fiber liquid-phase microextraction (HF-LPME) method has been developed for the extraction of a group of phthalic acid esters (PAEs) of interest from different water samples prior to gas chromatography tandem mass spectrometry analysis. HF-LPME was carried out using 1-octanol as extraction solvent followed by a back extraction step with cyclohexane. The different parameters that affect HF-LPME such as sample pH, ionic strength, extraction time, stirring rate, extraction temperature and back extraction conditions were investigated. The optimized conditions involved the extraction of 10 mL of sample without pH adjustment or addition of salt during 75 min under a stirring of 850 rpm at 60 °C and subsequent desorption with 200 µL of cyclohexane for 10 min in an ultrasonic bath. The method was validated in terms of calibration and recovery studies using dibutyl phthalate-d4 as internal standard. The developed procedure gave satisfactory recovery (74-120%) and relative standard deviation values (<20%) for the studied PAEs in mineral, tap, pond and waste water samples.

Multiresidue analysis of oestrogenic compounds in cow, goat, sheep and human milk using core-shell polydopamine coated magnetic nanoparticles as extraction sorbent in micro-dispersive solid-phase extraction followed by ultra-high-performance liquid chromatography tandem mass spectrometry.

In this work, the suitability of Fe3O4 nanoparticles coated with polydopamine was evaluated as sorbent for the extraction of a group of 21 compounds with oestrogenic activity including seven phytoestrogens, six mycotoxins as well as four synthetic and four natural oestrogens from different types of milk, including sheep milk, in which the evaluation of oestrogenic compounds have never been developed before. Extraction was carried out using magnetic micro-dispersive solid-phase extraction after a previous deproteinisation step. Separation, determination and quantification of the target analytes were achieved by ultra-high-performance liquid chromatography coupled to triple quadrupole-tandem mass spectrometry. The methodology was validated for five milk samples using 17ß-estradiol-2,4,16,16,17-d5 as internal standard for natural and synthetic oestrogens, ß-zearalanol-10,10,11,12,12-d5 for mycotoxins and prunetin for phytoestrogens. Recovery values ranged from 70 to 120% for the five types of matrices with relative standard deviation values lower than 18%. Limits of quantification of the method were in the range 0.55-11.8 µg L-1 for all samples. Graphical abstract General scheme of the multiresidue analysis of oestrogenic compounds in milk using core-shell polydopamine coated magnetic nanoparticles as extraction sorbent in µ-dSPE.