RESUMEN
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.
RESUMEN
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.
Asunto(s)
Disolventes Eutécticos Profundos/química , Bebidas Fermentadas/análisis , Interacciones Hidrofóbicas e Hidrofílicas , Microextracción en Fase Líquida , Plásticos/análisis , Cromatografía Líquida de Alta Presión , Límite de Detección , Microextracción en Fase Líquida/métodos , Reproducibilidad de los Resultados , Espectrometría de Masas en TándemRESUMEN
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.
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Cromatografía Líquida de Alta Presión/métodos , Microextracción en Fase Líquida/métodos , Nanotecnología/métodos , Ácidos Ftálicos/análisis , Embalaje de Alimentos , Límite de Detección , Modelos Lineales , Reproducibilidad de los Resultados , Solventes/química , Vino/análisisRESUMEN
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.
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Bebidas Alcohólicas/análisis , Bebidas/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Plásticos/análisis , Espectrometría de Masas en Tándem/métodos , Límite de Detección , Reproducibilidad de los ResultadosRESUMEN
BACKGROUND: The technique used in the repair of a perineal injury resulting from childbirth could avoid discomfort and morbidity during the postpartum period. Recent studies show inconsistent results and support the need for new research with the inclusion of new health parameters not yet studied. Therefore, this study aims to evaluate if the suture technique (continuous or interrupted) has an effect on pain and other postpartum problems, incidence of incontinence (urinary and/or fecal), and the restart of sexual relations. METHODS: A single-blind randomized clinical trial was conducted in five hospitals in south-east Spain. The participants were primiparous women who had experienced a perineal injury during delivery (second-degree tear or episiotomy). Data was collected on sociodemographic variables, variables associated with pregnancy, labor and delivery, and the postpartum period, and outcomes during the 3 months after delivery: pain, incontinence, and restart of sexual relations. Odds ratios (OR) were calculated by binary logistic regression to assess the influence of the suture type on binary outcomes and t-test used for comparing continuous outcomes. Multivariate analyses (using logistic regression -adjusted (aOR)- and analysis of covariance) were carried out to adjust for unbalanced variables after randomization. RESULTS: A total of 70 women were included in the intervention group (continuous suture) and 64 in the reference group (interrupted sutures). A negative association was observed (aOR = 0.39; 95% CI = 0.18-0.86) between a continuous suture and the need for analgesia at 24 h postpartum. Pain experienced by the women at 24 h postpartum was assessed as 4.4 ± 0.3 compared with a score of 3.4 ± 0.3 in the group with continuous sutures (p = 0.011). At 15 days postpartum, women in the intervention group experienced less pain (aOR = 0.38; 95% CI = 0.18-0.80) (p = 0.019). Urinary sphincter incontinence was also evaluated at 15 days, with 4.3% (n = 3) of the women in the intervention group presenting with urinary incontinence compared with 18.8% (n = 12) in the control group (aOR = 0.11; 95% CI = 0.03-0.47) (P = 0.003). CONCLUSIONS: The women who had a continuous suture repair showed lower levels of pain from delivery to 3 months after delivery and had a lower incidence of urinary incontinence at 15 days postpartum. TRIAL REGISTRATION: ClinicalTrials.gov NCT03825211 posted January 31, 2019 (retrospectively registered).
Asunto(s)
Laceraciones/cirugía , Complicaciones del Trabajo de Parto/cirugía , Perineo/lesiones , Complicaciones Posoperatorias/etiología , Técnicas de Sutura/efectos adversos , Adulto , Parto Obstétrico/efectos adversos , Episiotomía/efectos adversos , Femenino , Humanos , Laceraciones/etiología , Perineo/cirugía , Periodo Posparto , Embarazo , Método Simple Ciego , España , Resultado del Tratamiento , Adulto JovenRESUMEN
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.
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Estrógenos/análisis , Indoles/química , Nanopartículas de Magnetita/química , Leche/química , Polímeros/química , Microextracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Animales , Bovinos , Cromatografía Líquida de Alta Presión/métodos , Cabras , Humanos , Límite de Detección , Leche Humana/química , OvinosRESUMEN
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.
Asunto(s)
Bebidas/análisis , Ácidos Ftálicos/análisis , Ácidos Ftálicos/aislamiento & purificación , Extracción en Fase Sólida/métodos , Cromatografía Líquida de Alta Presión , Contaminación de Alimentos/análisis , Espectrometría de Masas , Nanotubos de Carbono/química , Extracción en Fase Sólida/instrumentación , Agua/químicaRESUMEN
Within this study, a new method enabling monitoring of various estrogenic substances potentially occurring in milk and dairy products was proposed. Groups of compounds fairly differing in physico-chemical properties and biological activity were analyzed: four natural estrogens, four synthetic estrogens, five mycoestrogens, and nine phytoestrogens. Since they may pass into milk mainly in glucuronated and sulfated forms, an enzymatic hydrolysis was involved prior to the extraction based on the QuEChERS methodology. For the purification of the organic extract, a dispersive solid-phase extraction (d-SPE) with sorbent C18 was applied. The final analysis was performed by ultra-high-performance liquid chromatography (UHPLC) coupled with triple quadrupole tandem mass spectrometry (MS/MS). Method recovery ranged from 70 to 120% with a relative standard deviation (RSD) value lower than 20% and limits of quantification (LOQs) in the range of 0.02-0.60 µg/L (0.2-6.0 µg/kg dry weight) and 0.02-0.90 µg/kg (0.2-6.0 µg/kg dry weight) for milk and yogurt, respectively. The new procedure was applied for the investigation of estrogenic compounds in 11 milk samples and 13 yogurt samples from a Czech retail market. Mainly phytoestrogens were found in the studied samples. The most abundant compounds were equol and enterolactone representing 40-90% of all estrogens. The total content of phytoestrogens (free and bound) was in the range of 149-3870 µg/kg dry weight. This amount is approximately 20 times higher compared to non-bound estrogens.
Asunto(s)
Estrógenos/química , Leche/química , Fitoestrógenos/química , Esteroides/química , Yogur/análisis , Animales , Cromatografía Líquida de Alta Presión/métodos , Hongos , Reproducibilidad de los Resultados , Espectrometría de Masas en TándemRESUMEN
Nano-LC and CEC were coupled to MS through a nanospray or a pressurized liquid-junction interface for the simultaneous separation and determination of 11 estrogenic compounds. Different stationary phases, that is, phenyl, C18, and C18 bidentate silica hydrate, were studied. For both techniques, the phenyl stationary phase was the best option, considering separation efficiency, selectivity, and resolution. Under the optimized conditions, the baseline separation of the target compounds (including estradiol and zearalanol epimers) was achieved in less than 20 min in nano-LC-MS and less than 13 min in CEC-MS. Molecular imprinted polymer SPE was used for extracting the target compounds from mineral water samples with the analysis of nano-LC-MS. The whole molecular imprinted polymer SPE nano-LC-MS method was validated through a recovery study at two levels of concentration. Sensitivity was improved by on-column focusing technique obtaining LODs in the range 1.4-55.4 ng/L.
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Electrocromatografía Capilar/métodos , Estrógenos/análisis , Espectrometría de Masa por Ionización de Electrospray/métodos , Contaminantes Químicos del Agua/análisis , Cromatografía Liquida/métodos , Estrógenos/aislamiento & purificación , Límite de Detección , Nanotecnología/métodos , Agua/análisis , Contaminantes Químicos del Agua/aislamiento & purificaciónRESUMEN
In this work, a simple and environmental friendly methodology has been developed for the analysis of a group of six mycotoxins with estrogenic activity produced by Fusarium species (i.e. zearalanone, zearalenone, α-zearalanol, ß-zearalanol, α-zearalenol, and ß-zearalenol), using microdispersive SPE the symbol micro should de before dSPE with multiwalled carbon nanotubes as sorbent. Separation, determination, and quantification were achieved by HPLC coupled to ion trap MS with an ESI interface. Parameters affecting the extraction efficiency of µ-dSPE such as pH of the sample, amount of multiwalled carbon nanotubes, and type and volume of elution solvent, were studied and optimized. The methodology was validated for mineral, pond, and wastewater as well as for powdered infant milk using 17ß-estradiol-2,4,16,16,17-d5 (17ß-E2 -D5 ) as internal standard, obtaining recoveries ranging from 85 to 120% for the three types of water samples and from 77 to 115% for powdered infant milk. RSD values were lower than 10%. The LOQs achieved were in the range 0.05-2.90 µg/L for water samples and 2.02-31.9 µg/L for powdered infant milk samples.
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Fórmulas Infantiles/química , Aguas Minerales/análisis , Micotoxinas/aislamiento & purificación , Nanotubos de Carbono/química , Estanques/química , Extracción en Fase Sólida , Aguas Residuales/química , Cromatografía Líquida de Alta Presión , Límite de Detección , Espectrometría de Masas , Micotoxinas/análisis , Zearalenona/análisis , Zeranol/análogos & derivados , Zeranol/análisisRESUMEN
An environmentally friendly method based on hollow-fibre liquid-phase microextraction (HF-LPME) was developed for the extraction of selected estrogenic compounds (i.e. four natural sexual hormones: estrone, 17ß-estradiol, 17α-estradiol and estriol; two exoestrogens: 17α-ethynylestradiol and 2-methoxyestradiol; two synthetic stilbenes: dienestrol and hexestrol; and five resorcylic acid lactones: zearalenone, α-zearalanol, ß-zearalanol, α-zearalenol and ß-zearalenol), from whole cow and semi-skimmed goat milk and whole natural yogurt. After the optimization of the sample preparation procedure, spiked extracts were derivatized to their trimethylsilyl products using N,O-bis(trimethylsilyl)trifluoroacetamide reagent and then analyzed by gas chromatography-tandem mass spectrometry (GC-MS/MS). Once optimum extraction conditions were established (protein precipitation with acetonitrile, extraction and the back-extraction in acetonitrile following the HF-LPME procedure), the method was validated and the calibration range, precision and accuracy were studied. The RSD values for the intra- and inter-day precision of the peak areas were in the range 0.65-9.69 and 1.00-11.47 %, respectively. The determination coefficients were higher than 0.991 for method calibration curves while LOD and LOQ values were between 0.06-2.55 and 0.16-6.11 µg/L for whole cow milk, 0.04-1.70 and 0.11-4.86 µg/L for semi-skimmed goat milk and 0.07-3.73 and 0.23-9.81 µg/L for natural yogurt, respectively. Finally, the accuracy and precision of the method were evaluated, obtaining a value in the range 84 81-119 % and RSD values lower than 20 % in all cases.
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Estrógenos/análisis , Análisis de los Alimentos/métodos , Contaminación de Alimentos/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Leche/química , Yogur/análisis , Animales , Bovinos , Estrógenos/aislamiento & purificación , Cabras , Límite de Detección , Microextracción en Fase Líquida/métodosRESUMEN
In this work, the suitability of a methodology based on dispersive liquid-liquid microextraction (DLLME) has been evaluated for the extraction of four endoestrogens (estriol, 17α-estradiol, 17ß-estradiol, and estrone), an exoestrogen (17α-etynylestradiol), and a mycotoxin (zearalenone), together with some of their major metabolites (2-methoxyestradiol, α-zearalanol, ß-zearalanol, α-zearalenol, and ß-zearalenol) from different types of milk (whole and skimmed cow milk and semiskimmed goat milk) and whole natural yogurt. The methodology includes a previous protein precipitation with acidified ACN and a defatting step with n-hexane. Separation of the analytes, determination, and quantification were developed by MEKC coupled to ESI-MS using a BGE containing an aqueous solution of ammonium perfluorooctanoate as MS friendly surfactant. Calibration, precision, and accuracy studies of the described DLLME-MEKC-MS/MS method were evaluated obtaining a good linearity and LODs in the low micrograms per liter range.
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Cromatografía Capilar Electrocinética Micelar/métodos , Estrógenos/análisis , Microextracción en Fase Líquida/métodos , Leche/química , Yogur/análisis , Animales , Estrona/análisis , Análisis de los Alimentos/métodos , Contaminación de Alimentos/análisis , Límite de Detección , Espectrometría de Masas/métodos , Reproducibilidad de los Resultados , Zearalenona/análisis , Zeranol/análogos & derivados , Zeranol/análisisRESUMEN
In this work, we have compared the selectivity of two commercial molecularly imprinted polymers (AFFINIMIP®SPE Estrogens and AFFINIMIP®SPE Zearalenone) for the extraction of 12 estrogenic compounds of interest (i.e. 17α-estradiol, 17ß-estradiol, estrone, hexestrol, 17α-ethynylestradiol, diethylstibestrol, dienestrol, zearalenone, α-zearalanol, ß-zearalanol, α-zearalenol and ß-zearalenol) from different water samples. High-performance liquid chromatography coupled with ion trap mass spectrometry with electrospray ionization was used for their determination. Results showed that although both molecularly imprinted polymeric cartridges were specifically designed for different groups of analytes (natural estrogens like estradiol in the first case and zearalenone derivatives in the second) they nearly have the same extraction performance (with recovery values in the range 65-101%) for the same analytes in Milli-Q water because of the cross-reactivity of the polymer. However, when more complex water samples were analyzed, it was clear that the behavior was different and that the AFFINIMIP®SPE Estrogens showed less cross-reactivity than the other cartridge. Validation of the proposed methodology with both cartridges revealed that the extraction was reproducible and that the final limits of detection of the proposed method were in the low ng/L range.
RESUMEN
In this work, the potential of a symmetric dialkyl-substituted ionic liquid (IL), 1,3-dipenthylimidazolium hexafluorophosphate ([PPIm][PF6 ]), as extraction solvent in dispersive liquid-liquid microextraction (DLLME) has been studied for the analysis of a group of three natural (estriol, 17ß-estradiol, and 17α-estradiol) and four synthetic (17α-ethynylestradiol, diethylstibestrol, dienestrol, and hexestrol) estrogenic compounds as well as one mycotoxin with estrogenic activity (zearalenone) in different types of water samples (Milli-Q, mineral, and wastewater). Separation, determination, and quantification were developed by HPLC-DAD and a fluorescence detector (FD) connected in series. Factors influencing the IL-DLLME procedure (sample pH, amount of IL, type and volume of disperser solvent, ionic strength, and assistance of vortex agitation) were investigated and optimized by means of a step-by-step approach. Once the optimum extraction conditions were established (10 mL of water at pH 8, 60 mg of [PPIm][PF6 ], 500 µL of ACN as disperser solvent and vortex agitation for 1 min), the calibration curves of the whole method (IL-DLLME-HPLC-DAD/FD) were obtained and precision and accuracy were evaluated. It was demonstrated that the developed methodology was repeatable, accurate, and selective with limits of detection in the 0.30-0.57 µg/L and 13.8-37.1 µg/L range for FD and DAD, respectively. Relative recovery values were higher than 85% for the different types of water samples and the Student's t test demonstrated that there were not significant differences between the added and the found concentration.
Asunto(s)
Estrógenos/análisis , Imidazoles/química , Microextracción en Fase Líquida/métodos , Contaminantes Químicos del Agua/análisis , Cromatografía Líquida de Alta Presión , Estrógenos/química , Estrógenos/aislamiento & purificación , Concentración de Iones de Hidrógeno , Límite de Detección , Modelos Lineales , Reproducibilidad de los Resultados , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/aislamiento & purificaciónRESUMEN
In this manuscript, a dispersive SPE method based on the use of multiwalled carbon nanotubes has been developed for the determination of 15 organophosphorus pesticides residues including some of their metabolites (disulfoton sulfoxide, ethoprophos, cadusafos, dimethoate, terbufos, disulfoton, chlorpyrifos-methyl, malaoxon, fenitrothion, pirimiphos-methyl, malathion, chlorpyrifos, terbufos sulfone, disulfoton sulfone, and fensulfothion) from real environmental waters (run-off, mineral and tap water) by GC with nitrogen phosphorus detection. Factors that affect the enrichment efficiency such as sample volume, multiwalled carbon nanotubes amount, and volume of eluent were studied. The optimized method was validated in terms of matrix-matched calibration, recovery, precision, and accuracy for the three analyzed samples. In this last case, the developed Student's t test demonstrated that there were no significant differences between real and spiked concentrations. Optimum dispersive SPE conditions (extraction of 200 mL of water, pH 6.0, with 130 mg of multiwalled carbon nanotubes, elution with 25 mL of dichloromethane for run-off and tap water and 30 mL for mineral water) allowed the quantitative extraction of analytes at levels lower than the maximum residues limits legislated by the European Union, with LODs between 1.16 and 93.6 ng/L. Absolute recovery values achieved were in the range of 67-107% (RSD values <10.1%).
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Nanotubos de Carbono/química , Residuos de Plaguicidas/aislamiento & purificación , Extracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/aislamiento & purificación , Adsorción , Cromatografía de Gases , Residuos de Plaguicidas/análisis , Extracción en Fase Sólida/instrumentación , Contaminantes Químicos del Agua/análisisRESUMEN
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.
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Residuos de Plaguicidas , Cromatografía Líquida de Alta Presión/métodos , Grano Comestible/química , Contaminación de Alimentos/análisis , Humanos , Residuos de Plaguicidas/análisis , EspañaRESUMEN
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.
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Agua Potable , Microextracción en Fase Líquida , Plastificantes , Temperatura , Solventes , Adipatos/análisisRESUMEN
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.
Asunto(s)
Disruptores Endocrinos , Contaminantes Ambientales , Ácidos Ftálicos , Humanos , Solventes/química , Disolventes Eutécticos Profundos , Disruptores Endocrinos/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Contaminantes Ambientales/análisis , Ácidos Ftálicos/análisis , Agua/química , Adipatos/análisisRESUMEN
A new and simple method has been developed for the determination of a group of four benzimidazole pesticides (carbendazim/benomyl, thiabendazole, and fuberidazole), a carbamate (carbaryl), and an organophosphate (triazophos), together with two of their main metabolites (2-aminobenzimidazole, metabolite of carbendazim/benomyl, and 1-naphthol, metabolite of carbaryl) in soils. First, an ultrasound-assisted extraction (UAE) was performed, followed by evaporation and reconstitution in water. Then, extraction and preconcentration of the analytes was accomplished by two-phase hollow-fiber liquid-phase microextraction (HF-LPME) using 1-octanol as extraction solvent. Parameters that affect the extraction efficiency in HF-LPME technique (organic solvent, pH of the sample, extraction time, stirring speed, temperature, and ionic strength) were deeply investigated. Optimum HF-LPME conditions involved the use of a 2.0 cm polypropylene fiber filled with 1-octanol to extract 10 mL of an aqueous soil extract at pH 9.0 containing 20% (v/v) of NaCl for 30 min at 1440 rpm. Separation and quantification was achieved by HPLC with fluorescence detection (FD). The proposed optimum UAE-HF-LPME-HPLC-FD methodology provided good calibration, precision, and accuracy results for two soils of different physicochemical properties. LODs were in the range 0.001-6.94 ng/g (S/N = 3). With the aim of extending the validation, the HF-LPME method was also applied to different types of waters (Milli-Q, mineral and run-off), obtaining LODs in the range 0.0002-0.57 µg/L.
Asunto(s)
Bencimidazoles/aislamiento & purificación , Microextracción en Fase Líquida/métodos , Plaguicidas/aislamiento & purificación , Contaminantes del Suelo/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , 1-Octanol/química , Bencimidazoles/metabolismo , Cromatografía Líquida de Alta Presión/métodos , Límite de Detección , Plaguicidas/metabolismo , Suelo/análisis , Contaminantes del Suelo/metabolismo , Agua/análisis , Contaminantes Químicos del Agua/metabolismoRESUMEN
In this work, the use of the ionic liquid (IL) 1,3-dipentylimidazolium hexafluorophosphate ([PPIm][PF6]) as an alternative extractant for IL dispersive liquid-liquid microextraction (IL-DLLME) of a group of pesticides and metabolites (2-aminobenzimidazole, carbendazim/benomyl, thiabendazole, fuberidazole, carbaryl, 1-naphthol, and triazophos) from soils is described. After performing an initial ultrasound-assisted extraction (USE), the IL-DLLME procedure was applied for the extraction of these organic analytes from soil extracts. Separation and quantification was achieved by high-performance liquid chromatography (HPLC) with fluorescence detection (FD). Calibration, precision, and accuracy of the described USE-IL-DLLME-HPLC-FD method using [PPIm][PF6] as an alternative extractant was evaluated with two soils of different physicochemical properties. Accuracy percentages were in the range 93-118% with RSD values below 20%. A comparison of the performance of [PPIm][PF6] versus that of the so-common 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIm][PF6]) was accomplished. Results indicate a comparable extraction efficiency with both ILs, being slightly higher with [HMIm][PF6] for the metabolite 2-aminobenzimidazole, and slightly higher with [PPIm][PF6] for triazophos. In all cases, LODs were in the low ng/g range (0.02-14.2 ng/g for [HMIm][PF6] and 0.02-60.5 ng/g for [PPIm][PF6]). As a result, the current work constitutes a starting point for the use of the IL [PPIm][PF6] for further analytical approaches.