Trabajo presentado en el VII Congreso Argentino de la Sociedad de Toxicologia y Quimica Ambiental... more Trabajo presentado en el VII Congreso Argentino de la Sociedad de Toxicologia y Quimica Ambiental, celebrado en San Luis (Argentina), del 16 al 19 de octubre de 2018
Pharmaceuticals and personal care products (PPCPs) are abundantly used by people, and some of the... more Pharmaceuticals and personal care products (PPCPs) are abundantly used by people, and some of them are excreted unaltered or as metabolites through urine, with the sewage being the most important source to their release to the environment. These compounds are in almost all types of water (wastewater, surface water, groundwater, etc.) at concentrations ranging from ng/L to µg/L. The isolation and concentration of the PPCPs from water achieves the appropriate sensitivity. This step is mostly based on solid-phase extraction (SPE) but also includes other approaches (dispersive liquid-liquid microextraction (DLLME), buckypaper, SPE using multicartridges, etc.). In this review article, we aim to discuss the procedures employed to extract PPCPs from any type of water sample prior to their determination via an instrumental analytical technique. Furthermore, we put forward not only the merits of the different methods available but also a number of inconsistencies, divergences, weaknesses and...
Abstract Water bodies cover approximately 70 % of the earth´s surface, making them ecosystems wit... more Abstract Water bodies cover approximately 70 % of the earth´s surface, making them ecosystems with a high environmental value and the habitat for numerous species of flora and fauna. Emerging pollutants (EPs) are ubiquitous anthropogenic compounds of environmental concern that can be found at different concentration levels in matrices such as sediment, water and aquatic biota. In addition, EPs can be bioaccumulated and biomagnified, inducing adverse effects on biota, and posing a risk to humans when contaminated biota is consumed. Unlike abiotic matrices, the occurrence of EPs in aquatic biota has not been widely studied. This is probably because their complexity, due to the presence of lipids, proteins and other organic compounds, makes the extraction and analysis of EPs difficult. This review gathers the most relevant analytical methods published between 2014 and 2019, comparing them and evaluating their strengths and weaknesses. It is intended to provide a better understanding of the development of new and improved methods, and to be a reference for researchers who are looking for the best methodology for their studies.
Pest control in agriculture is mainly based on the application of insecticides, which may impact ... more Pest control in agriculture is mainly based on the application of insecticides, which may impact nontarget beneficial organisms leading to undesirable ecological effects. Neonicotinoids are among the most widely used insecticides. However, they have important negative side effects, especially for pollinators and other beneficial insects feeding on nectar. Here, we identify a more accessible exposure route: Neonicotinoids reach and kill beneficial insects that feed on the most abundant carbohydrate source for insects in agroecosystems, honeydew. Honeydew is the excretion product of phloem-feeding hemipteran insects such as aphids, mealybugs, whiteflies, and psyllids. We allowed parasitic wasps and pollinating hoverflies to feed on honeydew from hemipterans feeding on trees treated with thiamethoxam or imidacloprid, the most commonly used neonicotinoids. LC-MS/MS analyses demonstrated that both neonicotinoids were present in honeydew. Honeydew with thiamethoxam was highly toxic to bot...
The current literature about pharmaceutical and personal care compounds (PPCPs) focuses on identi... more The current literature about pharmaceutical and personal care compounds (PPCPs) focuses on identifying their concentration and toxicological risk both in surface water and in wastewater. However, the influence of urban areas (population ageing, income level, hospitals and others) has not yet been analysed. Knowing how a population (and its facilities) affects PPCPs' presence in wastewater is important to identify the conditions that are responsible for their presence. In this work, the influence of water consumption, population ageing, income level, hospitals and nursing homes on the anti-inflammatory concentration have been analysed. To fill the gap between the quantitative data on PPCPs' concentration and the qualitative reasoning of the influence of urban areas on the anti-inflammatory concentration, the use of fuzzy-set qualitative comparative analysis (fsQCA) is proposed. The fsQCA results are presented as recipes that show the different causal combinations of conditions that explain the presence of anti-inflammatories in wastewater. Using fsQCA for urban wastewater management with the aim of explaining the presence of anti-inflammatories in wastewater treatment plants (WWTPs) is a novelty in the literature. The results obtained here show the influence of water consumption (WATCON), hospitals (HOSP) and population ageing (POPAG) as the main conditions for the anti-inflammatory concentration in Valèncian wastewater. Specifically, these conditions are present in all the recipes obtained with consistency of 99%. Through the results obtained, it would be possible to identify that HOSP are the main facilities that discharge anti-inflammatories into urban wastewater. Hence, the necessity of preventive measures to avoid the anti-inflammatory discharge into water bodies has been showed. Furthermore, under a methodological point of view, this work highlights the eligibility of fsQCA as a wastewater cycle management tool.
A solid-liquid extraction method in combination with high-performance liquid chromatography and t... more A solid-liquid extraction method in combination with high-performance liquid chromatography and tandem mass spectrometry was developed and optimized for extraction and analysis of organophosphorus flame retardants in soil and fish. Methanol was chosen as the optimum extraction solvent, not only in terms of extraction efficiency, but also for its broader analyte coverage. The subsequent clean-up by solid-phase extraction is required to eliminate matrix coextractives and reduce matrix effects. Recoveries of the optimized method were 50-121% for soil and 47-123% for biota, both with high precision (RSDs <12% in soil and <23% in biota). The method limits of detection ranged from 0.06 to 0.20 ng/g dry weight and between 0.02 and 0.30 ng/g wet weight for soil and biota samples, respectively. However, samples with a high lipid content produce several problems as solid-phase extraction cartridge clogging that increase variability and analysis time. The method was successfully applied ...
The Science of the total environment, Jan 15, 2018
The presence of pharmaceutical and personal care products and drugs of abuse (PPCPs) in wastewate... more The presence of pharmaceutical and personal care products and drugs of abuse (PPCPs) in wastewater treatment plants (WWTPs) indicates discharge of the effluent may not be suitable for the ecological balance of water ecosystems, such as wetlands. These PPCPs degrade water quality, considered as an ecosystem service (ES), provoking serious environmental impacts. Assessing the monetary value of PPCPs can be used as a proxy for environmental status of the ES of water quality (ESWQ). Considering PPCPs as non-desirable outputs of WWTPs, the shadow prices methodology has been implemented using directional distance function to measure the environmental avoided cost of removing salicylic acid (SA), methylparaben (MP), and THCOOH from WWTPs effluents discharged to Albufera Natural Park (Spain). The SA shows the highest shadow price (138.16 €/μg), followed by THCOOH (48.15 €/μg), and MP (30.66 €/μg). These values are interpreted as the environmental cost that would be avoided if SA, MP, and TH...
Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association, Jan 3, 2017
The occurrence of pesticide residues in fruits was determined by a target method for 62 analytes ... more The occurrence of pesticide residues in fruits was determined by a target method for 62 analytes and a wide scope screening method against a database of 500 pesticides. Limits of quantification (LOQs) were from 0.5 to 6.3 μg kg(-1) for the target method and from 0.5 to 119 μg kg(-1) for the non-target. Thirty samples: dates, apples, oranges, tangerines, lemons and grapefruits were selected because their high consumption, except lemons and grapefruits that were to cover all citrus fruits. Using the target method, 15 compounds (mostly insecticides and fungicides) out of 62 pesticides (organophosphorus, carbamates, pyrethroids, chloroacetanilides, triazines, triazoles, imidazoles, etc.) were detected. Residues were in 100% of the samples, 80% contained at or below maximum residue limits (MRLs), and 20% above. Non-target method identified several additional pesticides (cypronil, fludioxonil, boscalid and pyraclostrobin in apples). The highest acute risk were for achrinathrin, chlorpyrif...
An analytical method using a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure ... more An analytical method using a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure for multi-residue determination of 52 pesticides in coffee leaf extractshas been developed and validated according to SANTE/11945/2015 guidelines. Different sorbent combinations for dispersive solid phase extraction (d-SPE) clean-up as well as dispersive liquid-liquid microextraction (DLLME) were tested. The relative standard deviations (RSDs) for the recovery of 87-94% of pesticides added to coffee leaf extracts,was ≤20% for samples spiked at concentrations up to 50ng*g depending on the clean-up procedures. However, samples spiked with a 100ng*g pesticide mixture gave RSDs&gt;20% for most pesticides when d-SPE was carried out adding Supelclean ENVI-Carb 120/400. To explain this fact,the secondary metabolic profile was analyzed in all the extraction and clean-up procedures. Only in the clean-up procedure with the addition of Supel QuE Z-Sep+, does caffeine show a constant adsorption between blank and spiked samples. In other clean-up procedures, the amount of caffeine was higher in those samples spiked with pesticides. This indicates competition between caffeine and pesticides for adsorption to the sorbent. Addition of Supel QuE Z-Sep+ to the procedure revealed only a 32% matrix effect, whereas using PSA+ C18 the matrix effect was close to 97%. The process efficiency is up to 54% with the addition of Supel QuE Z-Sep+ and just up to 7% for the other clean-up procedures. The method was successfully tested in coffee leaves from different types of cultivars. Pesticides were not detected in organic coffee leaf extracts, but thiametoxan was clearly detected in 50% of coffee leaf extracts harvested from coffee trees grown under traditional conditions as determined by UHPLC-TOFMSLC/QqTOF-MS/MS.
A combined methodology to identify and quantify farming chemicals in the entire Júcar River basin... more A combined methodology to identify and quantify farming chemicals in the entire Júcar River basin has been developed. The procedure consisted of the application of environmental forensic criteria associating laboratory analytical samples, cartographic analysis using Geographical Information Systems (GIS) and synthetic statistical analysis. Sampling involved the collection of 15 samples in surface waters distributed alongside the Júcar River and its two main tributaries (Cabriel and Magro Rivers). The analytical procedure involves generic sample extraction and selective determination of up to 50 target pesticides by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Geographical analysis was performed by mixing both sampling points with analytical results and land use-cover layers for the year 2011. PCA and descriptive statistical analysis was further performed combining land use/cover information and pesticides results to determine correlation between dominant agricultural practices (irrigation and rain fed farming) and location of sampling points. Out of 50 pesticides, 20 were identified and 18 presented concentrations higher than the limits of quantification in surface waters, with a large dispersion in concentrations: from 0.05ng/L (terbuthylazine-2 hydroxy) to 222.45ng/L (imazalil). Statistical analyses reveals that there is a correlation between the percentage of land devoted to irrigation farming, whereas correlations are weaker when analysing the relationship of pesticides in rain fed dominated areas.
HIGHLIGHTSMethod characterization for 47 organic contaminants in water, soil, sediment and fish.S... more HIGHLIGHTSMethod characterization for 47 organic contaminants in water, soil, sediment and fish.SLE with McIlvain‐EDTA (pH = 4.5) and methanol to extract the solid matrices.SPE to clean‐up the extract used also to extract different types of water samples.Contaminants widely distributed particularly in water but also in other matrices.Degree of contamination water >> sediment > soil > biota. ABSTRACT A sensitive and reliable method based on solid‐liquid extraction (SLE) using McIlvaine‐Na2EDTA buffer (pH = 4.5)‐methanol and solid‐phase extraction (SPE) clean up prior to ultra‐high‐performance liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS) was applied to determine 47 organic contaminants in fish, soil and sediments. The SPE procedure to clean‐up the extracts was also used as extraction method to determine these compounds in water. Recoveries ranged from 38 to 104% for all matrices with RSDs < 30%. Limits of Quantification for the target compounds were in the range of 10–50 ng/g for soil, 2–40 ng/g for sediment, 5–30 ng/g for fish and 0.3–26 ng/L for water. Furthermore, the proposed method was compared to QuEChERS (widely used for environmental matrices) that involves extraction with buffered acetonitrile (pH 5.5) and dispersive SPE clean‐up. The results obtained (recoveries>50% for 36 compounds in front of 9, matrix effect < 20% for 31 compounds against 21, and LOQs <25 ng g−1 for 38 compounds against 22) indicates that the proposed method is more efficient than QuEChERS, The method was applied to monitoring these compounds along the Turia River. In river waters, Paracetamol (175 ng L−1), ibuprofen (153 ng L−1) and bisphenol A (41 ng L−1) were the compounds most frequently detected while in sediments were vildagliptin (7 ng g−1) and metoprolol (31 ng g−1) and in fish, bisphenol A (33 ng g−1) or sulfamethoxazole (13 ng g−1).
A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method wa... more A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method was developed for simultaneous analysis of natural pyrethrins and synthetic pyrethroids residues in baby food. In this study, two sample preparation methods based on ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) and salting-out assisted liquid-liquid extraction (SALLE) were optimized, and then, compared regarding the performance criteria. Appropriate linearity in solvent and matrix-based calibrations, and suitable recoveries (75-120%) and precision (RSD values≤16%) were achieved for selected analytes by any of the sample preparation procedures. Both methods provided the analytical selectivity required for the monitoring of the insecticides in fruit-, cereal- and milk-based baby foods. SALLE, recognized by cost-effectiveness, and simple and fast execution, provided a lower enrichment factor, consequently, higher limits of quantification (LOQs) were obtained. Some o...
Monitoring of pesticides and veterinary drug residues is required to enforce legislation and guar... more Monitoring of pesticides and veterinary drug residues is required to enforce legislation and guarantee food safety. Liquid chromatography-mass spectrometry (LC-MS) is the prevailing technique for assessing both types of residues because LC offers a versatile and universal separation mechanism suitable for non-gas chromatography (GC) amenable and the majority of GC-amenable compounds. This characteristic becomes more relevant when LC is coupled to MS because the high sensitivity and specificity of the detector allows to apply generic sample preparation procedures, which simultaneously extract a wide variety of residues with different physico-chemical properties. Determination of metabolites and degradation products, non-target suspected screening of an increasing number of residues, and even unknowns identification are also becoming inherent LC-MS advantages thanks to the latest advances. For routine analysis and, in particular, for official surveillance purposes in food control, analytical methods properly validated following strict guidelines are needed. After a brief introduction and an outline of the legislation applicable around the world, aspects such as improvement of specificity of high-throughput methods, resolution and mass accuracy of identification strategies and quantitative accuracy are critically reviewed in this article. In them, extraction, separation and determination are emphasized. The main objective is to offer an assessment of the state of the art and identify research needs and future trends in determining pesticide and veterinary drug residues in food by LC-MS.
The Science of the total environment, Jan 25, 2015
The determination of the real toxicity of sediments in aquatic ecosystems is challenging and nece... more The determination of the real toxicity of sediments in aquatic ecosystems is challenging and necessary for an appropriate risk assessment. Different approaches have been developed and applied over the last several decades. Currently, the joint implementation of chemical, ecological and toxicological tools is recommended for an appropriate and successful toxicity risk assessment. We chose the combination of the toxic unit approach with acute pore water tests (Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna) and whole-sediment exposure tests (V. fischeri, Chironomus riparius), together with invertebrate community composition (multivariate analyses) to detect short and long-term responses of the organisms in four rivers of the Iberian Peninsula. High toxicity was detected in three sites (the downstream sites of the Llobregat and the Júcar, and the most upstream site of the Ebro). We identified organophosphate insecticides and metals as the main variables responsible ...
Trabajo presentado en el VII Congreso Argentino de la Sociedad de Toxicologia y Quimica Ambiental... more Trabajo presentado en el VII Congreso Argentino de la Sociedad de Toxicologia y Quimica Ambiental, celebrado en San Luis (Argentina), del 16 al 19 de octubre de 2018
Pharmaceuticals and personal care products (PPCPs) are abundantly used by people, and some of the... more Pharmaceuticals and personal care products (PPCPs) are abundantly used by people, and some of them are excreted unaltered or as metabolites through urine, with the sewage being the most important source to their release to the environment. These compounds are in almost all types of water (wastewater, surface water, groundwater, etc.) at concentrations ranging from ng/L to µg/L. The isolation and concentration of the PPCPs from water achieves the appropriate sensitivity. This step is mostly based on solid-phase extraction (SPE) but also includes other approaches (dispersive liquid-liquid microextraction (DLLME), buckypaper, SPE using multicartridges, etc.). In this review article, we aim to discuss the procedures employed to extract PPCPs from any type of water sample prior to their determination via an instrumental analytical technique. Furthermore, we put forward not only the merits of the different methods available but also a number of inconsistencies, divergences, weaknesses and...
Abstract Water bodies cover approximately 70 % of the earth´s surface, making them ecosystems wit... more Abstract Water bodies cover approximately 70 % of the earth´s surface, making them ecosystems with a high environmental value and the habitat for numerous species of flora and fauna. Emerging pollutants (EPs) are ubiquitous anthropogenic compounds of environmental concern that can be found at different concentration levels in matrices such as sediment, water and aquatic biota. In addition, EPs can be bioaccumulated and biomagnified, inducing adverse effects on biota, and posing a risk to humans when contaminated biota is consumed. Unlike abiotic matrices, the occurrence of EPs in aquatic biota has not been widely studied. This is probably because their complexity, due to the presence of lipids, proteins and other organic compounds, makes the extraction and analysis of EPs difficult. This review gathers the most relevant analytical methods published between 2014 and 2019, comparing them and evaluating their strengths and weaknesses. It is intended to provide a better understanding of the development of new and improved methods, and to be a reference for researchers who are looking for the best methodology for their studies.
Pest control in agriculture is mainly based on the application of insecticides, which may impact ... more Pest control in agriculture is mainly based on the application of insecticides, which may impact nontarget beneficial organisms leading to undesirable ecological effects. Neonicotinoids are among the most widely used insecticides. However, they have important negative side effects, especially for pollinators and other beneficial insects feeding on nectar. Here, we identify a more accessible exposure route: Neonicotinoids reach and kill beneficial insects that feed on the most abundant carbohydrate source for insects in agroecosystems, honeydew. Honeydew is the excretion product of phloem-feeding hemipteran insects such as aphids, mealybugs, whiteflies, and psyllids. We allowed parasitic wasps and pollinating hoverflies to feed on honeydew from hemipterans feeding on trees treated with thiamethoxam or imidacloprid, the most commonly used neonicotinoids. LC-MS/MS analyses demonstrated that both neonicotinoids were present in honeydew. Honeydew with thiamethoxam was highly toxic to bot...
The current literature about pharmaceutical and personal care compounds (PPCPs) focuses on identi... more The current literature about pharmaceutical and personal care compounds (PPCPs) focuses on identifying their concentration and toxicological risk both in surface water and in wastewater. However, the influence of urban areas (population ageing, income level, hospitals and others) has not yet been analysed. Knowing how a population (and its facilities) affects PPCPs' presence in wastewater is important to identify the conditions that are responsible for their presence. In this work, the influence of water consumption, population ageing, income level, hospitals and nursing homes on the anti-inflammatory concentration have been analysed. To fill the gap between the quantitative data on PPCPs' concentration and the qualitative reasoning of the influence of urban areas on the anti-inflammatory concentration, the use of fuzzy-set qualitative comparative analysis (fsQCA) is proposed. The fsQCA results are presented as recipes that show the different causal combinations of conditions that explain the presence of anti-inflammatories in wastewater. Using fsQCA for urban wastewater management with the aim of explaining the presence of anti-inflammatories in wastewater treatment plants (WWTPs) is a novelty in the literature. The results obtained here show the influence of water consumption (WATCON), hospitals (HOSP) and population ageing (POPAG) as the main conditions for the anti-inflammatory concentration in Valèncian wastewater. Specifically, these conditions are present in all the recipes obtained with consistency of 99%. Through the results obtained, it would be possible to identify that HOSP are the main facilities that discharge anti-inflammatories into urban wastewater. Hence, the necessity of preventive measures to avoid the anti-inflammatory discharge into water bodies has been showed. Furthermore, under a methodological point of view, this work highlights the eligibility of fsQCA as a wastewater cycle management tool.
A solid-liquid extraction method in combination with high-performance liquid chromatography and t... more A solid-liquid extraction method in combination with high-performance liquid chromatography and tandem mass spectrometry was developed and optimized for extraction and analysis of organophosphorus flame retardants in soil and fish. Methanol was chosen as the optimum extraction solvent, not only in terms of extraction efficiency, but also for its broader analyte coverage. The subsequent clean-up by solid-phase extraction is required to eliminate matrix coextractives and reduce matrix effects. Recoveries of the optimized method were 50-121% for soil and 47-123% for biota, both with high precision (RSDs <12% in soil and <23% in biota). The method limits of detection ranged from 0.06 to 0.20 ng/g dry weight and between 0.02 and 0.30 ng/g wet weight for soil and biota samples, respectively. However, samples with a high lipid content produce several problems as solid-phase extraction cartridge clogging that increase variability and analysis time. The method was successfully applied ...
The Science of the total environment, Jan 15, 2018
The presence of pharmaceutical and personal care products and drugs of abuse (PPCPs) in wastewate... more The presence of pharmaceutical and personal care products and drugs of abuse (PPCPs) in wastewater treatment plants (WWTPs) indicates discharge of the effluent may not be suitable for the ecological balance of water ecosystems, such as wetlands. These PPCPs degrade water quality, considered as an ecosystem service (ES), provoking serious environmental impacts. Assessing the monetary value of PPCPs can be used as a proxy for environmental status of the ES of water quality (ESWQ). Considering PPCPs as non-desirable outputs of WWTPs, the shadow prices methodology has been implemented using directional distance function to measure the environmental avoided cost of removing salicylic acid (SA), methylparaben (MP), and THCOOH from WWTPs effluents discharged to Albufera Natural Park (Spain). The SA shows the highest shadow price (138.16 €/μg), followed by THCOOH (48.15 €/μg), and MP (30.66 €/μg). These values are interpreted as the environmental cost that would be avoided if SA, MP, and TH...
Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association, Jan 3, 2017
The occurrence of pesticide residues in fruits was determined by a target method for 62 analytes ... more The occurrence of pesticide residues in fruits was determined by a target method for 62 analytes and a wide scope screening method against a database of 500 pesticides. Limits of quantification (LOQs) were from 0.5 to 6.3 μg kg(-1) for the target method and from 0.5 to 119 μg kg(-1) for the non-target. Thirty samples: dates, apples, oranges, tangerines, lemons and grapefruits were selected because their high consumption, except lemons and grapefruits that were to cover all citrus fruits. Using the target method, 15 compounds (mostly insecticides and fungicides) out of 62 pesticides (organophosphorus, carbamates, pyrethroids, chloroacetanilides, triazines, triazoles, imidazoles, etc.) were detected. Residues were in 100% of the samples, 80% contained at or below maximum residue limits (MRLs), and 20% above. Non-target method identified several additional pesticides (cypronil, fludioxonil, boscalid and pyraclostrobin in apples). The highest acute risk were for achrinathrin, chlorpyrif...
An analytical method using a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure ... more An analytical method using a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure for multi-residue determination of 52 pesticides in coffee leaf extractshas been developed and validated according to SANTE/11945/2015 guidelines. Different sorbent combinations for dispersive solid phase extraction (d-SPE) clean-up as well as dispersive liquid-liquid microextraction (DLLME) were tested. The relative standard deviations (RSDs) for the recovery of 87-94% of pesticides added to coffee leaf extracts,was ≤20% for samples spiked at concentrations up to 50ng*g depending on the clean-up procedures. However, samples spiked with a 100ng*g pesticide mixture gave RSDs&gt;20% for most pesticides when d-SPE was carried out adding Supelclean ENVI-Carb 120/400. To explain this fact,the secondary metabolic profile was analyzed in all the extraction and clean-up procedures. Only in the clean-up procedure with the addition of Supel QuE Z-Sep+, does caffeine show a constant adsorption between blank and spiked samples. In other clean-up procedures, the amount of caffeine was higher in those samples spiked with pesticides. This indicates competition between caffeine and pesticides for adsorption to the sorbent. Addition of Supel QuE Z-Sep+ to the procedure revealed only a 32% matrix effect, whereas using PSA+ C18 the matrix effect was close to 97%. The process efficiency is up to 54% with the addition of Supel QuE Z-Sep+ and just up to 7% for the other clean-up procedures. The method was successfully tested in coffee leaves from different types of cultivars. Pesticides were not detected in organic coffee leaf extracts, but thiametoxan was clearly detected in 50% of coffee leaf extracts harvested from coffee trees grown under traditional conditions as determined by UHPLC-TOFMSLC/QqTOF-MS/MS.
A combined methodology to identify and quantify farming chemicals in the entire Júcar River basin... more A combined methodology to identify and quantify farming chemicals in the entire Júcar River basin has been developed. The procedure consisted of the application of environmental forensic criteria associating laboratory analytical samples, cartographic analysis using Geographical Information Systems (GIS) and synthetic statistical analysis. Sampling involved the collection of 15 samples in surface waters distributed alongside the Júcar River and its two main tributaries (Cabriel and Magro Rivers). The analytical procedure involves generic sample extraction and selective determination of up to 50 target pesticides by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Geographical analysis was performed by mixing both sampling points with analytical results and land use-cover layers for the year 2011. PCA and descriptive statistical analysis was further performed combining land use/cover information and pesticides results to determine correlation between dominant agricultural practices (irrigation and rain fed farming) and location of sampling points. Out of 50 pesticides, 20 were identified and 18 presented concentrations higher than the limits of quantification in surface waters, with a large dispersion in concentrations: from 0.05ng/L (terbuthylazine-2 hydroxy) to 222.45ng/L (imazalil). Statistical analyses reveals that there is a correlation between the percentage of land devoted to irrigation farming, whereas correlations are weaker when analysing the relationship of pesticides in rain fed dominated areas.
HIGHLIGHTSMethod characterization for 47 organic contaminants in water, soil, sediment and fish.S... more HIGHLIGHTSMethod characterization for 47 organic contaminants in water, soil, sediment and fish.SLE with McIlvain‐EDTA (pH = 4.5) and methanol to extract the solid matrices.SPE to clean‐up the extract used also to extract different types of water samples.Contaminants widely distributed particularly in water but also in other matrices.Degree of contamination water >> sediment > soil > biota. ABSTRACT A sensitive and reliable method based on solid‐liquid extraction (SLE) using McIlvaine‐Na2EDTA buffer (pH = 4.5)‐methanol and solid‐phase extraction (SPE) clean up prior to ultra‐high‐performance liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS) was applied to determine 47 organic contaminants in fish, soil and sediments. The SPE procedure to clean‐up the extracts was also used as extraction method to determine these compounds in water. Recoveries ranged from 38 to 104% for all matrices with RSDs < 30%. Limits of Quantification for the target compounds were in the range of 10–50 ng/g for soil, 2–40 ng/g for sediment, 5–30 ng/g for fish and 0.3–26 ng/L for water. Furthermore, the proposed method was compared to QuEChERS (widely used for environmental matrices) that involves extraction with buffered acetonitrile (pH 5.5) and dispersive SPE clean‐up. The results obtained (recoveries>50% for 36 compounds in front of 9, matrix effect < 20% for 31 compounds against 21, and LOQs <25 ng g−1 for 38 compounds against 22) indicates that the proposed method is more efficient than QuEChERS, The method was applied to monitoring these compounds along the Turia River. In river waters, Paracetamol (175 ng L−1), ibuprofen (153 ng L−1) and bisphenol A (41 ng L−1) were the compounds most frequently detected while in sediments were vildagliptin (7 ng g−1) and metoprolol (31 ng g−1) and in fish, bisphenol A (33 ng g−1) or sulfamethoxazole (13 ng g−1).
A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method wa... more A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method was developed for simultaneous analysis of natural pyrethrins and synthetic pyrethroids residues in baby food. In this study, two sample preparation methods based on ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) and salting-out assisted liquid-liquid extraction (SALLE) were optimized, and then, compared regarding the performance criteria. Appropriate linearity in solvent and matrix-based calibrations, and suitable recoveries (75-120%) and precision (RSD values≤16%) were achieved for selected analytes by any of the sample preparation procedures. Both methods provided the analytical selectivity required for the monitoring of the insecticides in fruit-, cereal- and milk-based baby foods. SALLE, recognized by cost-effectiveness, and simple and fast execution, provided a lower enrichment factor, consequently, higher limits of quantification (LOQs) were obtained. Some o...
Monitoring of pesticides and veterinary drug residues is required to enforce legislation and guar... more Monitoring of pesticides and veterinary drug residues is required to enforce legislation and guarantee food safety. Liquid chromatography-mass spectrometry (LC-MS) is the prevailing technique for assessing both types of residues because LC offers a versatile and universal separation mechanism suitable for non-gas chromatography (GC) amenable and the majority of GC-amenable compounds. This characteristic becomes more relevant when LC is coupled to MS because the high sensitivity and specificity of the detector allows to apply generic sample preparation procedures, which simultaneously extract a wide variety of residues with different physico-chemical properties. Determination of metabolites and degradation products, non-target suspected screening of an increasing number of residues, and even unknowns identification are also becoming inherent LC-MS advantages thanks to the latest advances. For routine analysis and, in particular, for official surveillance purposes in food control, analytical methods properly validated following strict guidelines are needed. After a brief introduction and an outline of the legislation applicable around the world, aspects such as improvement of specificity of high-throughput methods, resolution and mass accuracy of identification strategies and quantitative accuracy are critically reviewed in this article. In them, extraction, separation and determination are emphasized. The main objective is to offer an assessment of the state of the art and identify research needs and future trends in determining pesticide and veterinary drug residues in food by LC-MS.
The Science of the total environment, Jan 25, 2015
The determination of the real toxicity of sediments in aquatic ecosystems is challenging and nece... more The determination of the real toxicity of sediments in aquatic ecosystems is challenging and necessary for an appropriate risk assessment. Different approaches have been developed and applied over the last several decades. Currently, the joint implementation of chemical, ecological and toxicological tools is recommended for an appropriate and successful toxicity risk assessment. We chose the combination of the toxic unit approach with acute pore water tests (Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna) and whole-sediment exposure tests (V. fischeri, Chironomus riparius), together with invertebrate community composition (multivariate analyses) to detect short and long-term responses of the organisms in four rivers of the Iberian Peninsula. High toxicity was detected in three sites (the downstream sites of the Llobregat and the Júcar, and the most upstream site of the Ebro). We identified organophosphate insecticides and metals as the main variables responsible ...
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Papers by Yolanda Picó