Application of matrix solid phase dispersion to the determination of imidacloprid, carbaryl, aldicarb, and their main metabolites in honeybees by liquid chromatography–mass spectrometry detection

Abstract A method based on matrix solid phase dispersion (MSPD) using C18 as dispersant and dichloromethane–methanol as eluent and liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry (LC–APCI–MS) has been developed for the simultaneous determination of imidacloprid, 6-chloronicotinic acid, carbaryl, aldicarb, aldicarb sulfoxide, and aldicarb sulfone in honeybees. The proposed method was compared with liquid–liquid extraction (LLE) combined with LC–APCI–MS analysis. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. Recovery studies were performed at different fortification levels. Average re…

Analysis of thiabendazole and procymidone in fruits and vegetables by capillary electrophoresis–electrospray mass spectrometry

Abstract A capillary electrophoresis–mass spectrometry method for determining procymidone and thiabendazole in apples, grapes, oranges, pears, strawberries and tomatoes is described. Separation is achieved using a buffer of formic acid–ammonium formate at pH 3.5 with 2% of methanol. Fungicide residues present in the sample are preconcentrated by both solid-phase extraction and injection of large sample volumes into the capillary by a stacking technique, to obtain lower detection limits. Ionization is performed at atmospheric pressure in an electrospray type source and detection is carried out using positive ionization and selected ion monitoring modes. The quantitation limits are 0.005 and …

Occurrence of acidic pharmaceuticals and personal care products in Turia River Basin: From waste to drinking water

The occurrence of 21 acidic pharmaceuticals, including illicit drugs, and personal care products (PPCPs) in waste, surface and drinking water and in sediments of the Turia River Basin (Valencia, Spain) was studied. A liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed for the determination of these PPCPs with electrospray (ESI) in negative ionization (NI) mode. Ammonium fluoride in the mobile phase improved ionization efficiency by an average increase in peak area of 5 compared to ammonium formate or formic acid. All studied compounds were detected and their concentration was waste water>surface water>drinking water. PPCPs were in waste water treatment plants (WWT…

Improving the solid-phase extraction of “quat” pesticides from water samples

A novel strategy, based on the addition of a cationic surfactant, for preventing the interferences associated with a diminution in the efficacy of solid-phase extraction (SPE) with silica cartridges of diquat, paraquat and difenzoquat in water is developed. Conditions for extraction are optimised with respect to pH, cationic surfactant and its concentration. Humic acids, anionic surfactants, inorganic salts and other organic contaminants like pesticides, phenols, polycyclic aromatic hydrocarbons and polychlorinated biphenyls produce the studied interferences. The best performance is shown in the improvement of the "quats" recovery from waters with high levels of humic acids and anionic surf…

Evaluation of carbamazepine uptake and metabolization by Typha spp., a plant with potential use in phytotreatment

Abstract Phytoremediation technologies such as constructed wetlands have shown higher efficiencies in removal of pharmaceuticals from wastewaters than conventional wastewater treatment processes, and plants seem to have an important role in the removal of some of those compounds. In this context, a study was conducted to assess tolerance, uptake, and metabolism of the epilepsy drug, carbamazepine, by the macrophyte Typha spp. This evaluation was conducted in hydroponic solutions with 0.5–2.0 mg/L of this pharmaceutical for a maximum period of 21 days. The removal of carbamazepine from nutrient solutions by the plants reached values of 82% of the initial contents. Furthermore, a metabolite (…

Optimization of LC–MS/MS using triple quadrupole mass analyzer for the simultaneous analysis of carbosulfan and its main metabolites in oranges

This paper describes an analytical method involving a simple solvent extraction for the simultaneous liquid chromatography coupled to quadrupole tandem mass spectrometry (LC-MS/MS) determination of carbosulfan, its most toxic metabolite--carbofuran--, and its other main metabolites--3-hydroxycarbofuran, 3-ketocarbofuran, 3-hydroxy-7-phenolcarbofuran, 3-keto-7-phenolcarbofuran, 7-phenolcarbofuran and dibutylamine--in oranges. Chromatography was performed on a Zorbax Bonus-RP (150 mm x 2.1 mm, 5 microm). The mobile phase was a ternary gradient water-methanol-acetonitrile with 1.0 mM ammonium acetate at flow rate of 0.2 ml min(-1). The LC separation and MS/MS optimization were studied to selec…

Determination of organic pollutants in Anguilla anguilla by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS)

© 2021 The Authors.

Beeswax cleaning by solvent extraction of pesticides

We set out to test if the methodology used to clean sheep wool wax (Lanolin) from pesticides could be used to clean beeswax as well. We first made an aggregate sample of brood comb wax from three different US beekeepers. Sub-samples of these aggregate wax samples were analyzed for pesticide contamination. The remaining wax, was then dissolved into hexane solution and run through four N, N-Dimethylformamide (DMF) washes. During these extractions, the pesticides partitioned into the DMF, and so were removed from the beeswax. Following the solvent extractions, the beeswax was tested again for pesticides. An average of 95% of the pesticide contamination was removed by the chemical wash procedur…

Capillary electrophoresis for the determination of pesticide residues

Capillary electrophoresis (CE) is becoming an advantageous tool for determining pesticide residues in environmental matrices because of its simplicity and high separation efficiency. However, inadequate limits of detection (LODs) and a lack of selective detectors limit the technique. The present review gives an overview of current developments in off-column and on-column approaches to trace enrichment in analysing real samples, and summarises the determination of pesticides residues by conventional CE as well as by the emerging techniques, such as CE-mass spectrometry (MS). The usefulness of these approaches in environmental applications is documented.

An environmental forensic procedure to analyse anthropogenic pressures of urban origin on surface water of protected coastal agro-environmental wetlands (L'Albufera de Valencia Natural Park, Spain)

Detection and spatial distribution of 14 drugs of abuse and 17 pharmaceuticals in surface waters was investigated to determine transport hydrological connectivity between urban, agriculture and natural environments. Solid-phase extraction and liquid chromatography tandem mass spectrometry was applied to all samples. To determine spatial incidence of contaminants, analytical results of target compounds were georeferenced and integrated into a geographical information systems structure together with layers of municipal population, location of sewage water treatment plants and irrigation channels and sectors. The methodology was applied to L'Albufera Natural Park in Valencia (Spain). A total o…

Analysis of microplastics and nanoplastics: How green are the methodologies used?

Microplastic (MP) and nanoplastic (NP) pollution is among the global environmental concerns of the 21st century owing to its transboundary distribution and persistence. The number of studies focused on the determination of MPs in air, water, sediment, soil, and biota of an important number of ecosystems has increased exponentially. However, the impact that the methodologies used to isolate and determine MPs and NPs have on the environment owing to the consumption of reagents and energy and the generation of waste is not yet studied. This review presents a critical overview of the analytical methodologies applied to determination of MPs and NPs assessing their greenness using the National En…

Identification of biomarkers in wastewater-based epidemiology: Main approaches and analytical methods

Wastewater-based epidemiology (WBE) has become popular to estimate the use of drugs of abuse and recently to establish the incidence of CoVID 19 in large cities. However, its possibilities have been expanded recently as a technique that allows to establish a fingerprint of the characteristics of a city, such as state of health/disease, healthy/unhealthy living habits, exposure to different types of contaminants, etc. with respect to other cities. This has been thanks to the identification of human biomarkers as well as to the fingerprinting and profiling of the characteristics of the wastewater catchment that determine these circumstances. The purpose of this review is to analyze the differ…

Off-line solid-phase microextraction and capillary electrophoresis mass spectrometry to determine acidic pesticides in fruits.

A method based on solid-phase microextraction (SPME) and capillary electrophoresis/mass spectrometry (CE/ MS) is described for determining simultaneously five acidic pesticides (o-phenylphenol, ioxynil, haloxyfop, acifluorfen, picloram) in fruits. The CE device is coupled to an electrospray interface by a commercial sheath-flow adapter. Emphasis is placed on fulfillment of the speed and sensitivity requirements. The best separation is achieved using 32 mM ammonium formate/acid formic buffer at pH 3.1, with a working voltage of 25 kV. The MS detection of the five pesticides was performed in negative ionization mode. Full-scan spectra with base peaks corresponding to [M-H]- were obtained exce…

Determination of quinolone residues in chicken and fish by capillary electrophoresis-mass spectrometry

A specific pressure-assisted CE-MS method is described for the analysis of five quinolone residues. MS using a single quadrupole is compared with multiple-stage MS using a quadrupole IT (QIT-MS(n)). The procedure involves a common sample preparation by SPE on disposable cartridges. The most suitable electrolyte is 60 mM (NH(4))(2)CO(3) at pH 9.2. Single quadrupole does not provide enough fragmentation to confirm identities according to the current legislation. However, QIT-MS(n) achieves selective fragmentation. Using this method, danofloxacin, enrofloxacin, flumequine, ofloxacin, and pipemidic acid are analyzed in fortified samples of chicken and fish. Recoveries at levels of 50 ng/g were …

Distribution and fate of perfluoroalkyl substances in Mediterranean Spanish sewage treatment plants.

The concentrations of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylates, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in influent, effluent and sludge from 16 different sewage treatment plants (STPs) located in the Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (3) Rivers, in two consecutive years (2010 and 2011). The analytes were extracted by solid phase extraction (SPE) and determined by Liquid Chromatography triple Quadrupole Mass Spectrometer (LC-QqQ-MS). All samples, except two sludges from Guadalquivir River STPs, were contaminated with at least one PFAS. Perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (L-…

Solid-phase extraction on C18 in the trace determination of selected polychlorinated biphenyls in milk.

The utility of solid-phase extraction with octadecylsilica for determining fifteen polychlorinated biphenyl (PCB) congeners from milk samples was examined. Recoveries higher than 80% and relative standard deviations better than 10% were obtained for PCBs from different kinds of milk (whole, skimmed, 2%, powdered, breast and evaporated). A comparison with other procedures was made. The described method provides better detection limits than those attainable with the liquid-liquid extractions currently used as standard methods, when capillary gas-liquid chromatography is used for the final determination. A study of the separation was also performed using six different fused-silica capillary co…

Analysis of pyridoquinoline derivatives by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry

A method using liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (LC/APCI-MS) has been developed for the characterization and determination of pyridoquinoline derivatives 4,6-bis(dimethylaminoethylamino)-2,8,10-trimethylpyrido[3,2-g]quinoline, 4,6-bis(dimethylaminoethoxy)-2,8,10-trimethylpyrido[3,2-g]quinoline and 4,6-bis[(dimethylaminoethyl)thio]-2,8,10-trimethylpyrido[3,2-g] quinoline, all with potential antitumor properties. LC separation was performed on a conventional C18 column using a binary mobile phase composed of acetonitrile and 50 mM aqueous ammonium formate at pH 3. The APCI mass spectra obtained showed that proton addition giving [M + H]+ was the…

Procedures for Antibiotic Residues in Bovine Muscle Tissues

Abstract Acetonitrile extraction followed by primary-secondary amine dispersive SPE cleanup QuEChERS (quick, easy, cheap, effective, rugged, and safe), was compared to pressurized liquid extraction (PLE) using water at 70°C for 10 min at 1500 psi for the determination of 16 veterinary drugs in bovine muscle tissues by LC/MS/MS. PLE was significantly more effective for the extraction of veterinary drugs (ranging from 69 to 103% with RSD ≤ 18%) than QuEChERS (ranging from 19 to 89% with RSD ≤ 19%). Linearity of the calibration curves was obtained over the range considered (from 10 μg/kg or LOQ to 1000, μg/kg) with r2 ≥ 0.99 for all the analytes by both methods. Although an internal standard w…

The embodiment of wastewater data for the estimation of illicit drug consumption in Spain

Data obtained from wastewater analysis can provide rapid and complementary insights in illicit drug consumption at community level. Within Europe, Spain is an important country of transit of both cocaine and cannabis. The quantity of seized drugs and prevalence of their use rank Spain at the top of Europe. Hence, the implementation of a wastewater monitoring program at national level would help to get better understanding of spatial differences and trends in use of illicit drugs. In this study, a national wastewater campaign was performed for the first time to get more insight on the consumption of illicit drugs within Spain. The 13 Spanish cities monitored cover approximately 6 million inh…

Prediction models based on soil properties for evaluating the uptake of eight heavy metals by tomato plant (Lycopersicon esculentum Mill.) grown in agricultural soils amended with sewage sludge

The aim of this study is to design de novo prediction models in order to gauge the likely uptake of eight heavy metals (Al, Cr, Cu, Fe, Mn, Ni, Pb and Zn) by Lycopersicon esculentum, the tomato plant. Uptake was assessed within the plant’s root, stem, leaf and fruit tissues, respectively. The plant was cultivated in soil amended by different application rates of sewage sludge, i.e. 0, 10, 20, 30 and 40 g/kg. The roots exhibited markedly elevated heavy metal concentrations compared to the above-ground plant components, with the exception of the quantity of Ni in the leaves. Apart from Al, Fe and Mn, a bioconcentration factor >1 was identified for all heavy metals. Excluding Ni in the leaves,…

Evaluation of Organophosphorus Pesticide Residues in Citrus Fruits from the Valencian Community (Spain)

Abstract Approximately 200 citrus samples from markets of the Valencian Community (Spain) were analyzed to establish their residue levels in 12 organophosphorus pesticide residues during the 1994-1995 campaign. The organophosphorus pesticides carbophenothion, chlorpyriphos, chlorfenvinphos, diazinon, ethion, fenitrothion, malathion, methidation, methylparathion, phosmet, quinalphos, and tetradifon were simultaneously extracted by matrix solidphase dispersion and determined by gas chromatography- mass spectrometry using selected ion monitoring mode. A total of 32.25% contained pesticide residues and 6.9% exceeded the European Union Maximum Residue Levels (MRLs). The pesticides found in the s…

Total Sugar Intake and Macro and Micronutrients in Children Aged 6-8 Years: The Aniva Study

The objective of this study was to study the association between total sugar intake (TSI) levels of children aged 6-8 years old, nutrient intake and anthropometry. Food and beverage intakes were collected by a prospective three-day recall questionnaire. The 2237 children were distributed into three groups according to TSI percentiles. Mean TSI was 93.77 &plusmn

Multiple-stage mass spectrometric analysis of six pesticides in oranges by liquid chromatography–atmospheric pressure chemical ionization–ion trap mass spectrometry

Abstract Six pesticides were determined by liquid chromatography (LC) with positive ion (PI) atmospheric pressure chemical ionization quadrupole ion-trap tandem mass spectrometry (APCI–MS–MS). Ion fragmentation was studied by MS, MS 2 and MS 3 . Fragmentation of the pesticides produced ions formed by various losses from the side-chains and through heterocyclic ring opening, but without any common fragmentation pathway. Multiple reaction monitoring (MRM) of MS, MS 2 and MS 3 was used to identify and quantify the pesticides. The samples were extracted with ethyl acetate and dried over anhydrous sodium sulfate. Comparison of the three MS modes showed that MS 3 is slightly less sensitive but mu…

Capillary zone electrophoresis for the determination of thiabendazole, prochloraz and procymidone in grapes

Capillary zone electrophoresis with UV detection was applied to the simultaneous determination of thiabendazole, prochloraz and procymidone in grapes. Electrolyte conditions such as pH, composition and concentration of the buffer, addition of organic solvent and working voltage were checked to obtain a high-performance separation of the three fungicides (by measurement of separation efficiency and resolution). The most critical parameter was the pH of the running buffer. The best separation was achieved in 4 mM phosphate solution at pH 3.5. The repeatability of the migration times, expressed as RSD, was <0.44%. The three peaks were completely resolved with a separation efficiency up to 100 …

Risk assessment on the presence of pharmaceuticals in sediments, soils and waters of the Pego-Oliva Marshlands (Valencia, eastern Spain).

9 páginas, 3 figuras, 2 tablas.

Analytical method for simultaneous determination of pesticide and veterinary drug residues in milk by CE-MS

10 páginas, 2 figuras, 4 tablas.

Pressurized liquid extraction combined with capillary electrophoresis–mass spectrometry as an improved methodology for the determination of sulfonamide residues in meat

A new analytical method, based on capillary electrophoresis and tandem mass spectrometry (CE-MS2), is proposed and validated for the identification and simultaneous quantification of 12 sulfonamides (SAs) in pork meat. The studied SAs include sulfathiazole, sulfadiazine, sulfamethoxypyridazine, sulfaguanidine, sulfanilamide, sulfadimethoxyne, sulfapyridine, sulfachloropyridazine, sulfisoxazole, sulfasalazine, sulfabenzamide and sulfadimidine. Different parameters (i.e. separation buffer, sheath liquid, electrospray conditions) were optimized to obtain an adequate CE separation and high MS sensitivity. MS2 experiments using an ion trap as analyzer, operating in the selected reaction monitori…

Pesticide occurrence in the waters of Júcar River, Spain from different farming landscapes.

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). Geogra…

Comparison of microextraction procedures to determine pesticides in oranges by liquid chromatography-mass spectrometry.

A liquid chromatographic-mass spectrometric method has been developed for the determination of bitertanol, carbendazim, fenthion, flusilazole, hexythiazox, imidacloprid, methidathion, methiocarb, pyriproxyfen and trichlorfon. Two procedures, based on stir bar sorptive extraction (SBSE) and matrix solid-phase dispersion (MSPD), have been evaluated for the extraction of these compounds in oranges. Their respective advantages and disadvantages are also discussed. The recoveries obtained by MSPD ranged from 47 to 96% and the relative standard deviations (RSDs) ranged from 1 to 15%, whereas with the SBSE method the recoveries were between 8 and 84% and the RSDs between 4 and 16%. Although, the l…

Liquid chromatography-mass spectrometry in food safety.

Abstract The use of powerful mass spectrometric detectors in combination with liquid chromatography has played a vital role to solve many problems related to food safety. Since this technique is especially well suited for, but not restricted to the analysis of food contaminants within the food safety area, this review is focused on providing an insight into this field. The basic legislation in different parts of the world is discussed with a focus on the situation within the European Union (EU) and why it favors the use of liquid chromatography–mass spectrometry (LC–MS). Main attention in this review is on the achievements that have been possible because of the latest advances and novelties…

Combined use of liquid chromatography triple quadrupole mass spectrometry and liquid chromatography quadrupole time-of-flight mass spectrometry in systematic screening of pesticides and other contaminants in water samples

As a suitable way for routine screening of pesticides and control of other organic contaminants in water, the combination of liquid chromatography triple quadrupole tandem mass spectrometry (LC-QqQ-MS/MS) and liquid chromatography-hybrid quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) has been applied to the analysis of 63 surface and waste water samples after conventional solid-phase extraction (SPE). The extracts were screened for 43 pesticides or degradation products by LC-QqQ-MS/MS achieving limits of detection (LOD) ranged from 0.04 to 2 ng L(-1). Of the 43 selected pesticides, 33 were detected in water samples. The ESI-QTOF MS instrument was run using two simultaneous acquisi…

Pesticides and Herbicides: Residue Determination

Pesticide and herbicide residue determination in food is becoming an especially imperative and challenging issue. Commonly, it involves the simultaneous trace analysis of hundreds of compounds belonging to many chemical classes. This article provides a review of the current status of the routine methods in the monitoring and control of these residues and discusses the analytic problems arising at each stage of the procedure. The role of mass spectrometry in screening, identification, and confirmation of target and nontarget pesticides is highlighted. Consideration is given to new developments and future trends.

Comparison of solid-phase microextraction and stir bar sorptive extraction for determining six organophosphorus insecticides in honey by liquid chromatography-mass spectrometry.

Abstract Two approaches based on sorptive extraction, solid-phase microextraction (SPME) and stir bar sorptive extraction (SBSE), in combination with liquid chromatography (LC)–atmospheric pressure chemical ionization mass spectrometry (MS) have been assayed for analyzing chlorpyriphos methyl, diazinon, fonofos, phenthoate, phosalone, and pirimiphos ethyl in honey. In both, SPME and SBSE, enrichment was performed using a poly(dimethylsiloxane) coating. Significant parameters affecting sorption process such as sample volume, sorption and desorption times, ionic strength, elution solvent, and dilution (water/honey) proportion were optimized and discussed. Performance of both methods has been …

Ecotoxicological Effects of Ibuprofen on Plant Growth of Vigna unguiculata L.

Despite the prevalence of the common pharmaceutical ibuprofen (IBU) in water and sediments worldwide, the effects of IBU on plants are largely unknown. This study was designed to assess the ecotoxicological effects of emerging pharmaceutical pollutant IBU on plant growth and development in a series of toxicity experiments using cowpea (Vigna unguiculata). Plant growth parameters (morphological and physicochemical) were investigated under a series of IBU concentrations (0, 400, 800, 1200, 1600, 2000 ppm IBU). IBU exposure reduced the shoot and root lengths, fresh and dry weights, leaf area, and chlorophyll a and b, carotenoid, total chlorophyll, mineral (K and Mg), glutathione reductase, and…

Shared effects of organic microcontaminants and environmental stressors on biofilms and invertebrates in impaired rivers

Land use type, physical and chemical stressors, and organic microcontaminants were investigated for their effects on the biological communities (biofilms and invertebrates) in several Mediterranean rivers. The diversity of invertebrates, and the scores of the first principal component of a PCA performed with the diatom communities were the best descriptors of the distribution patterns of the biological communities against the river stressors. These two metrics decreased according to the progressive site impairment (associated to higher area of agricultural and urban-industrial, high water conductivity, higher dissolved organic carbon and dissolved inorganic nitrogen concentrations, and high…

Analysis of Fungicides in Fruits and Vegetables by Capillary Electrophoresis-Mass Spectrometry

On-line determination of bipyridylium herbicides in water by HPLC

Selective on-line solid phase extraction (SPE) and liquid chromatography determination (HPLC) of diquat, paraquat and difenzoquat from environmental water samples has been accomplished with Graphitized Carbon Black (GCB) as both extraction and analytical columns. The method involved passing of 50 mL of water through a cartridge filled with Carbograph. In the elution step, the herbicides were transferred from the cartridge to the analytical column (Hypercarb) by mean of a gradient of pH 3 aqueous solution of tetramethylammonium hydroxide (TMAOH) and ammonium sulphate and methanol. Hypercarb columns were found to give a low probability of false positives for bypiridylium herbicides and are ve…

Determination of pesticides and veterinary drug residues in food by liquid chromatography-mass spectrometry: A review

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 …

Nanoparticles in Foods, Determination of

This article discusses the state of the art in the identification and determination of nanoparticles in food. It is of utmost importance to determine, in addition to the particle-size distribution, the chemical composition as well as the physical and chemical properties of the nanomaterials within the sample. After a brief description of what nanomaterials are and how to classify them, sources and routes of nanomaterials to food are discussed. The article then follows the debate on legislative consideration, which has emerged very recently. Its main aim is to deliver information on how nanomaterials are determined in food because of the number of challenges that arise when analyzing food an…

Dataset of pharmaceuticals and personal care products in a Mediterranean coastal wetland

The dataset provides information on Pharmaceutical and Personal Care Products (PPCPs) detected in the Albufera Natural Park (Valencia, Spain), a typical Mediterranean coastal wetland. These PPCPs constitute an important group of organic pollutants highly representative of the human impact. The concentrations values measured in soil, sediment and water and the statistical relationship of contaminants between them and with the environmental parameters could help to understand their fate in different compartments. The data also reported the occurrence and removal efficiency (%) for each contaminant in ten wastewater treatment plants (WWTPs), located in the surrounding area. This dataset could …

Presence of illicit drugs in surface waters of protected natural wetlands connected to traditional irrigation systems and urban areas

Ponencia presentada en el I Simposio sobre Gestión del Agua en Espacios Protegidos celebrado en La Habana (Cuba) del 2 al 6 de noviembre de 2010

Pesticide contamination in water and sediment of the aquatic systems of the Natural Park of the Albufera of Valencia (Spain) during the rice cultivation period

The Natural Park of the Albufera (Valencia, Spain) is a Mediterranean wetland where rice cultivation dominates the agricultural activity. The purpose of this study was to offer broader information about the current state of the wetland assessing the contamination by pesticides in four aquatic habitats during the rice cultivation period in 2016. Liquid chromatography with tandem mass spectrometer (UHPLC-MS/MS) was used to determine the pesticides in water and sediment samples from the rice fields, Lake Albufera and irrigation and outlet channels. 21 pesticides were detected in our samples (seven already forbidden by European legislation). Higher values than 10000 ng L of accumulated pesticid…

Carbamazepine exposure in the sea anemones Anemonia sulcata and Actinia equina: Metabolite identification and physiological responses

Trabajo presentado en el 11º Congreso Ibérico, 8º Iberoamericano de Contaminación y Toxicología (CICTA 2018) celebrado en la Escuela Técnica Superior de Ingeniería de Montes, Forestal y del Medio Natural, Madrid del 11 al 13 de julio de 2018

Assessing alcohol consumption through wastewater-based epidemiology: Spain as a case study

Background In this study, an alternative and complementary method to those approaches currently used to estimate alcohol consumption by the population is described. This method, known as wastewater-based epidemiology (WBE), allows back-calculating the alcohol consumption rate in a given population from the concentrations of a selected biomarker measured in wastewater. Methods Composite (24-h) wastewater samples were collected at the inlet of 17 wastewater treatment plants located in 13 Spanish cities for seven consecutive days in 2018. The sampled area covered 12.8% of the Spanish population. Wastewater samples were analyzed to determine the concentration of ethyl sulfate, the biomarker use…

Toxicological Assessment of Recombinant Xylanase X22 in Wine

Toxicological evaluation of xylanase X(22) from Aspergillus nidulans expressed in a wine yeast strain was carried out. The safety of the X(22) intake was assessed by digestibility, bioinformatic, and mouse short-term repeated dosing studies, although X(22) shows resistance to proteolytic degradation in the gastrointestinal system, is a minority protein component (<0.5 10(-)(6) %) of the produced wine, and shows no significant amino acid sequence homology to any known food allergens. The 4-week oral toxicity study was performed in Swiss mice at a dose level of 0.01, 0.1, or 1 mg/kg/day (these dosages correlate to 8, 80, and 800 times, respectively, the enzyme amount contained in 250 mL of wi…

Distribution of soil organic carbon in Wadi Al-Thulaima, Saudi Arabia: A hyper-arid habitat altered by wastewater reuse

The carbon cycle is being altered as a result of human-induced changes in the Earth's system. Therefore, ecosystems such as wetlands, authentic CO2 sinks, are becoming especially important. Little information exits on the soil organic carbon (SOC) stock for the middle east-countries man-made wetlands making wadis permanent with the outflow of wastewater treatment plants. This paper presents the vertical distribution of SOC content, soil bulk density (SBD) and SOC density in soil of vegetated and bare sites in Wadi Al-Thulaima, one of the artificial wetlands in central Saudi Arabia. The mean distribution of SBD in the vegetated and bare sites increased significantly with depth. Inversely, th…

Wastewater-based epidemiology, a tool to bridge biomarkers of exposure, contaminants, and human health

The concept of wastewater-based epidemiology also known as sewage epidemiology was proposed by Daughton in 2001. Wastewater-based epidemiology has become now a reality that makes it possible to determine consumption or exposure to chemical substances or pathogens in a population by measuring certain compounds (drugs of abuse, metabolites, or biomarkers) or microorganisms (viruses, bacteria, and parasites) in wastewater. The first and most developed application is the estimation of illicit drug consumption in communities or populations, but it can be used to measure both consumption and exposure to a wide range of substances and pathogens. Its recent application to measure the severe acute r…

Effect of the conversion of mangroves into shrimp farms on carbon stock in the sediment along the southern Red Sea coast, Saudi Arabia

The conservation of coastal ecosystems and specially mangroves ‘‘blue carbon’’ is receiving more attention as consequence of their recognition as high ecosystem carbon stocks and for the fact that these areas are undergoing land conversion. The aim of the present study is to evaluate the impact of land use changes due to conversion of mangroves to shrimp farms on the bulk density (SBD), organic carbon (SOC) concentration, and SOC stock in the sediments along the southern Saudi Arabian Red Sea coast. Shrimp farms and mangrove locations showed significant (P < 0.001) differences in SBD with high mean values in the sediments of shrimp farms. Shrimp farms and mangrove locations showed significa…

Analysis of pesticide residues in fruit and vegetables by matrix solid phase dispersion (MSPD) and different gas chromatography element-selective detectors

A comparison between different element selective detectors for the determination of organophosphorus and organochlorine pesticide residues, from fruit and vegetables, was performed by capillary GC with electron capture detector (ECD), nitrogen phosphorus detector (NPD), flame photometric detector (FPD) in the sulphur and phosphorus modes, and mass spectrometry detector (MSD) in selected ion monitoring (SIM) mode. Pesticides were extracted from the different foodstuffs by Matrix Solid Phase Dispersion (MSPD). Recoveries of 41–108 % with relative standard deviation of 2–14 % in the concentration range 0.5–10 μg L−1 were obtained in oranges, lemons, grapefruit, pears, plums, lettuces and tomat…

Determination of fungicide residues in fruits and vegetables by liquid chromatography–atmospheric pressure chemical ionization mass spectrometry

Abstract A liquid chromatography (LC) method for the quantitative determination of five fungicide residues (dichloran, flutriafol, o -phenylphenol, prochloraz and tolclofos methyl) in oranges, lemons, bananas, peppers, chards and onions is described. The residues were extracted by matrix solid-phase dispersion (MSPD) using C 8 . Quantitative analysis was performed by isocratic LC coupled to quadrupole mass spectrometer using atmospheric pressure chemical ionization in the negative ionization mode. The limit of quantification was 0.01 mg kg −1 for flutriafol, o -phenylphenol and dichloran, and 0.1 mg kg −1 for prochloraz and tolclofos methyl. The MSPD method is also suitable for LC–UV analys…

Stereoisomeric profiling of drugs of abuse and pharmaceuticals in wastewaters of Valencia (Spain)

AbstractThe enantiomeric and diastereomeric profiling of chiral pharmaceuticals (ephedrine, norephedrine, atenolol and venlafaxine) and illicit drugs (amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA) and 3,4-methylenedioxy-N-ethylamphetamine (MDEA)) was undertaken over a period of fourteen consecutive days in three wastewater treatment plants (WWTPs) in the city of Valencia, Spain. Degradation efficiency of WWTPs was found to be compound and enantiomer dependent. Selective enantiomer enrichment was observed for several target analytes. Amphetamine and MDMA were enriched with R(−)-enantiomers. 1S,2S(+)-pseudoephedrine was found …

Detecting residues of urea and carbamate pesticides

Presence of pharmaceuticals and heavy metals in the waters of a Mediterranean coastal wetland: Potential interactions and the influence of the environment

The occurrence of 17 relevant pharmaceuticals and 7 heavy metals in the waters of the Pego-Oliva Marsh Natural Park (Valencia Community, Spain) were monitored. Thirty four zones (including the lagoon and the most important irrigation channels), covering the main land uses and water sources, were selected for sampling. Thirty three of them were contaminated with at least one pharmaceutical. Ibuprofen and codeine were the pharmaceuticals more frequently detected, in concentrations between 4.8 and 1.2 ng/L and a maximum of 59 ng/L and 63 ng/L, respectively.Regarding metals, Zn showed values under the detection limit in all the samples, while Cd, Co, Cr, Cu, Ni and Pb were detected at concentra…

Sample Preparation to Determine Pharmaceutical and Personal Care Products in an All-Water Matrix: Solid Phase Extraction

© 2020 by the authors.

Assessing population exposure to phthalate plasticizers in thirteen Spanish cities through the analysis of wastewater

Phthalates are widely used plasticizers that produce endocrine-disrupting disorders. Quantifying exposure is crucial to perform risk assessments and to develop proper health measures. Herein, a wastewater-based epidemiology approach has been applied to estimate human exposure to six of the mostly used phthalates within the Spanish population. Wastewater samples were collected over four weekdays from seventeen wastewater treatment plants serving thirteen cities and ca. 6 million people (12.8 % of the Spanish population). Phthalate metabolite loads in wastewater were transformed into metabolite concentrations in urine and into daily exposure levels to the parent phthalates. Considering all th…

Bioaccumulation of emerging contaminants in mussel (Mytilus galloprovincialis): Influence of microplastics

Coastal environments are heavily influenced by human activities. Chemical substances considered as emerging contaminants (ECs) are one of the most important indicators of the anthropic influence on the environment, and they have recently shown to interact with microplastics (MPs). Mussels are suitable for in-lab bioacumulation studies providing insight about the occurrence and fate of contaminants in the organisms. In this study, bioacummulation of 20 chemical substances catalogued as ECs, including pharmaceuticals and personal care products (PPCPs), pesticides, and perfluoroalkyl substances (PFASs) in Mytilus galloprovincialis was assessed, with or without the influence of the presence of …

Pyrolysis gas chromatography-mass spectrometry in environmental analysis: Focus on organic matter and microplastic

Pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) has great potential within environmental analysis. This technique is mainly used for the chemical identification of macromolecules that cannot be characterized by either liquid or gas chromatography due to their big size. Through pyrolysis (controlled thermal degradation), these macromolecules are broken down into simpler molecules that can be separated by gas chromatography and detected by mass spectrometry. This technique has been traditionally used in environmental samples for the characterization of organic matter and humic substances, contaminants, lignins, etc. It attains the identification of the different types of chemical un…

Wastewater-based epidemiology: current status and future prospects

Wastewater-based epidemiology (WBE) has been consolidated as a tool to provide real-time information on consumption of legal and illegal drugs of abuse by the population. However, WBE is expected to achieve more ambitious objectives such as establishing exposure to certain agents (pesticides, personal care products, persistent organic pollutants, and pathogens), incidence of specific diseases (diabetes, allergies, oxidative stress, and cancer), and determination of some lifestyle consequences (exposure to personal care products, consumption of doping substances or products for the treatment of erectile dysfunction) or environmental factors (increase in temperature) in populations. Herein, w…

Biomonitoring potential of the native aquatic plant Typha domingensis by predicting trace metals accumulation in the Egyptian Lake Burullus.

The ability of the native emergent macrophytes Typha domingensis for monitoring pollution with trace metals in Egyptian Lake Burullus was investigated through developing regression models for predicting their concentrations in the plant tissues. Plant samples (above-ground shoot and below-ground root and rhizome) as well as sediment samples were collected monthly during one growing season and analyzed. The association of trace metals concentration with several sediment characteristics (pH, organic matter, clay and silt) was also studied using the simple linear correlation coefficient (r). The concentration of some trace metals was significantly proportional to its values in the sediment suc…

Invertebrate community responses to emerging water pollutants in Iberian river basins

Abstract Chemical pollution is one of the greatest threats to freshwater ecosystems, especially in Mediterranean watersheds, characterized by periodical low flows that may exacerbate chemical exposure. Different groups of emerging pollutants have been detected in these basins during the last decade. This study aims to identify the relationships between the presence and levels of prioritary and emerging pollutants (pesticides, pharmaceutical active compounds—PhACs, Endocrine Disrupting Compounds EDCs and Perfluorinated Compounds—PFCs) and the invertebrate community in four Mediterranean basins: the Ebro, the Llobregat, the Jucar and the Guadalquivir. Structural (species composition and densi…

Critical review: Grand challenges in assessing the adverse effects of contaminants of emerging concern on aquatic food webs

Much progress has been made in the past few decades in understanding the sources, transport, fate, and biological effects of contaminants of emerging concern (CECs) in aquatic ecosystems. Despite these advancements, significant obstacles still prevent comprehensive assessments of the environmental risks associated with the presence of CECs. Many of these obstacles center around the extrapolation of effects of single chemicals observed in the laboratory or effects found in individual organisms or species in the field to impacts of multiple stressors on aquatic food webs. In the present review, we identify 5 challenges that must be addressed to promote studies of CECs from singular exposure e…

Analysis of post-harvest fungicides by micellar electrokinetic chromatography.

A method based on solid-phase extraction (SPE) and micellar electrokinetic chromatography (MEKC) was developed for the simultaneous determination of carbendazim, imazalil, methylthiophanate, O-phenylphenol, prochloraz, procimidone, thiabendazole and triadimefon residues in grape, lettuce, orange and tomato. Selectivity and resolution were studied changing the pH and the concentration of the buffer, the type and concentration of surfactant and the methanol content in the mobile phase. A buffer consisting of 4 mM borate with 75 mM sodium cholate (pH 9.2) gave the best results. The recoveries of the fungicides in spiked fruit and vegetable samples ranged from 30 to 105%, and the limits of dete…

Mycotoxins: Occurrence and Determination

Mycotoxins are toxic compounds produced by different types of fungi, belonging mainly to the Aspergillus , Penicillium , and Fusarium genera. This chapter presents a review of mycotoxins’ occurrence in food, and analytical methods proposed for their determination. Recent developments in sample preparation and chromatographic approaches for mycotoxins’ identification and quantification are highlighted. Current data on the occurrence of mycotoxins are also summarized. The chapter provides insight into the advances and progress in recent years and identifies remaining challenges.

Dietary administration of high doses of pterostilbene and quercetin to mice is not toxic.

The aim of this study is to evaluate possible harmful effects of high doses of t-pterostilbene (t-PTER) and quercetin (QUER) in Swiss mice. Mice were fed during 28 days at doses of 0, 30, 300, and 3000 mg/kg body weight/day of t-PTER, QUER, or a mixture of both, t-PTER + QUER, which are equivalent to 5, 50, and 500 times, respectively, the estimated mean human intake of these polyphenols (25 mg/day). Daily oral administration of QUER, t-PTER, or a mixture of both of them did not cause mortality during the experimental period. There were no differences in food and water consumption on sex. No significant body weight gain in the male or female groups was observed. Red blood cell number and th…

Rapid screening of organophosphorus pesticides in honey and bees by liquid chromatography—Mass spectrometry

Twenty-two organophosphorus pesticide residues were simultaneously determined in honey and honeybee samples by extraction procedures based on solid-phase and liquid chromatography-atmospheric pressure chemical ionization-mass in positive and negative ionization modes. Pesticides in honeybee samples were extracted by matrix solid phase dispersion with C18 silica and subsequently eluted with a mixture of dichloromethane-methanol (85∶15, v/v). The average recoveries from spiked honeybees (0.5–10 μg g−1) ranged from 76% for coumaphos to 100% for omethoate, with relative standard deviations between 3 and 17%. Limits of detection were ≤0.13 μg g−1 and limits of quantification were ≤0.43 μg g−1. H…

Analysis of Polychlorinated Biphenyls in Aqueous Samples Using C18 Glass Column Extraction

Abstract A method for polychlorinated biphenyl (PCB) trace extraction from contaminated water at the part-pertrillion levels is described. This procedure involves quantitative adsorption of PCBs on Cis glass microcolumns. PCBs are retained on the surface and subsequently eluted with n-hexane (5 mL) before gas chromatography. Recovery of water fortified with PCBs was 83.6-108.5%. Compared to liquid-liquid extraction methods, the Cis glass microcolumns give comparable results, lessen solvent costs, and are less time-consuming.

Contaminants of emerging concern in freshwater fish from four Spanish Rivers.

This study investigated the occurrence of 135 contaminants of emerging concern (CECs) – pharmaceuticals, pesticides, a set of endocrine disrupting compounds (EDCs) (parabens, bisphenols, hormones, triazoles, organophosphorus flame retardants and triclosan), UV-filters, perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) – in 59 fish samples, collected in 2010 in 4 Spanish Rivers (Guadalquivir, Júcar, Ebro and Llobregat). Of the 135 CECs, 76 including 8 pharmaceuticals, 25 pesticides, 10 EDCs, 5 UV-filters, 15 PFASs and 13 HFRs were detected. Pharmaceuticals were the less frequently found and at lower concentrations. Pesticides, EDCs, UV-filters, PFASs and HFRs were det…

Safety Assessment and Migration Tests

This chapter outlines (i) the advances to reduce the uncertainty in nanomaterials (NMs) determination; (ii) the results from migration experiments conducted with nano-clay, nanosilver, and other nanomaterial-containing polymers; and (iii) the different established protocols for risk assessment that ensure consumer's safety. The text starts highlighting the need of an understanding of potential exposure via migration into food and a deeper knowledge of the interaction of NMs with food constituents and their effects upon ingestion. The chapter covers the ability of the analytical techniques utilized to detect nanoparticles per se in food simulants. In addition, the results of the application …

Pharmaceuticals and personal care products in a Mediterranean coastal wetland: Impact of anthropogenic and spatial factors and environmental risk assessment

The present study focused on the occurrence, distribution and risk assessment of 32 pharmaceuticals and personal care products (PPCPs) in water and sediment, as well as the surrounding soil of the irrigation channels and lake of a Mediterranean coastal wetland, the Albufera Natural Park (Valencia, Spain). Moreover, the influent and effluent of ten wastewater treatment plants (WWTPs) that treat wastewater from Valencia and the surrounding areas were also studied. BPA, caffeine, diclofenac, ethyl paraben, methyl paraben, metformin, tramadol and salicylic acid were the predominant PPCPs detected in the channels and the lake, and are in good agreement with those detected in the effluent. Furthe…

Actigraphic Sleep and Dietary Macronutrient Intake in Children Aged 6–9 Years Old: A Pilot Study

The objective of this study was to examine the relationship between different sleep parameters and energy and macronutrient intake in school-aged children. A total of 203 children 6 to 9 years of age participated in this cross-sectional study. Anthropometric measurements were taken first. Diet was assessed with 3-day food logs and sleep was measured with a questionnaire on sleep quality and a wrist actigraph worn for at least 7 days. A decrease of 165.45 kcal was observed per each additional hour of sleep during the week (β (95% CI) = −165.45 (−274.01, −56.88)

Occurrence, distribution and behavior of emerging persistent organic pollutants (POPs) in a Mediterranean wetland protected area.

The analysis of perfluoroalkyl substances (PFASs) and organophosphate flame retardants (PFRs) in the different environmental compartments of a characteristic coastal wetland, the Albufera Natural Park (Valencia, Spain), is required for understanding the transport, accumulation and fate of these pollutants in an area under high anthropogenic pressure. Samples included 13 wastewater treatment plant influents, 13 effluents, 12 surface water, 19 sediment samples and 10 fish individuals from the Albufera Natural Park and the surrounding area. Tris(2-chloroisopropyl) phosphate (TCIPP) and perfluorooctane sulfonate (PFOS) were at the highest concentrations in water, 330.2 ng L−1 and 47.8 ng L−1, r…

Matrix solid-phase dispersion extraction procedure for multiresidue pesticide analysis in oranges.

A multiresidue extraction method based on matrix solid-phase dispersion (MSPD) is optimized for the extraction and gas chromatographic screening of eighteen insecticides (aldrin, carbophenothion, captafol, chlorpyriphos, chlorfenvinphos, diazinon, dicofol, alpha-endosulfan, beta-endosulfan, ethion, fenitrothion, folpet, methidathion, malathion, methyl-azinphos, methyl-parathion, phosmet, and tetradifon) from oranges. After optimization of different parameters, such as type of solid phase used and the amount of solid phase or eluent, recoveries ranged from 67 to 102% with relative standard deviations ranging from 2 to 10%. The limits of detection, calculated as 3 times the baseline noise ran…

Corrigendum to "Analysis of cannabinoids by liquid chromatography-mass spectrometry in milk, liver and hemp seed to ensure food safety" [Food Chem. 228 (2017) 177-185].

Multiresidue analysis of organic pollutants by in-tube solid phase microextraction coupled to ultra-high performance liquid chromatography-electrospray-tandem mass spectrometry.

In this work, in-tube solid phase microextraction (IT-SPME) coupling with ultra-high-pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) multiresidue analytical method has been proposed for the first time for on-line enrichment of 9 analytes included in Water Frame Directive 2000/60/EC (WFD). The device was equipped with a GC TRB-5 capillary column, used as pre-concentration loop, and two conventional six-port injection valves. Water sample and desorption solvent volumes were tested. The optimum conditions were 4mL of processed sample followed by elution with 40μL of methanol. The analytes were detected with a mass spectrometer after being ionized positively using an elect…

Determination of abamectin in citrus fruits by liquid chromatography-electrospray ionization mass spectrometry.

Liquid chromatography coupled to electrospray mass spectrometry (LC-ES-MS) with positive ion detection was used to determine abamectin in oranges. MS conditions were optimized to achieve maximum sensitivity. The main ion for abamectin was [M+Na]+ at a fragmentor voltage of 180 V. Abundant structural information can be obtained at different fragmentor voltages. The detection limit for the standard solution was 12 pg injected, and good linearity and reproducibility were observed. Abamectin residues were extracted using matrix solid-phase dispersion. Orange samples were homogenized with C18 bonded silica placed onto a glass column and eluted with dichloromethane. Recoveries of the abamectin fr…

Application of a low transition temperature mixture for the dispersive liquid–liquid microextraction of illicit drugs from urine samples

© 2021 by the authors.

First nation-wide estimation of tobacco consumption in Spain using wastewater-based epidemiology

Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3′-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine…

Monitoring of the pesticide levels in natural waters of the Valencia Community (Spain)

Nutrient Intake and Depression Symptoms in Spanish Children: The ANIVA Study

The aim of this study was to examine the relationship between nutritional intake and depressive symptoms in Valencian schoolchildren. The ANIVA (Antropometria y Nutricion Infantil de Valencia) study is a descriptive cross-sectional study. During academic year 2013–2014, 710 schoolchildren aged 6–9 years were selected from eleven primary schools in Valencia (Spain). Children’s dietary intake was measured on three-day food records, completed by parents/guardians; children completed the 20-item Center for Epidemiologic Studies Depression Scale for Children (CES-DC) Questionnaire to measure depressive symptoms. Weight, height, and body mass index (BMI), and z-scores were evaluated in all subjec…

Determination of Aldicarb, Aldicarb Sulfoxide, and Aldicarb Sulfone in Oranges by Simple Gas–Liquid Chromatography with Nitrogen–Phosphorus Detection

Abstract A reversed-phase liquid chromatographic method, using an acetonitrile–water gradient mobile phase, and a gas-liquid chromatographic method with nitrogen–phosphorus and flame photometric detection were compared for simultaneous and separate determinations of trace quantities of aldicarb and its metabolites aldicarb sulfone and aldicarb sulfoxide. One hundred gram samples of fortified oranges were extracted with water–acetone, water-acetonitrile, or water–methanol, and the extracts were partitioned with methylene chloride. Partitioning with other organic solvents such as chloroform, ethyl acetate, or methyl isobutyl ketone was also investigated. When performed under optimal condition…

Uptake prediction of nine heavy metals by Eichhornia crassipes grown in irrigation canals: A biomonitoring approach

The principal objective of this study is to generate mathematical regression equations that facilitate the estimation of the extent to which Eichhornia crassipes (C. Mart.) Solms, water hyacinth, absorbs heavy metals (HMs) into four plant organs (laminae, petioles, roots, and stolons). This study considers the absorption of nine HMs (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), and the E. crassipes evaluated in this study were located in three irrigation canals in the North Nile Delta in Egypt, with sampling being conducted in both monospecific and homogenous E. crassipes. Samples of both E. crassipes and water were collected on a monthly basis during one growing season. Analysis of the water s…

INGENIERÍA GENÉTICA E INDUSTRIA AGROALIMENTARIA: VENTAJAS E INCONVENIENTES GENETIC ENGINEERING AND FOOD INDUSTRY: ADVANTAGES AND INCONVENIENCES EXEÑERÍA XENÉTICA E INDUSTRIA AGROALIMENTARIA: VENTAXAS EINCONVINTES

Abstract Resumen Resumo Nowadays biotechnology allows to perform accurate changes on the genetic material of organisms, being a very important tool in food industry. However just a few recombinant products can be found in the market, as a result of the social repulse against these kind of foods. According to the Community Normative, it is necessary to evaluate the safety for human being and environment security previous to introducing a recombinant food into the market. In this work, the recommended protocols for several organisms to attend this evaluation on a rational way are reviewed. These protocols are fundamentally based on the SAFEST elements (Safety Assessment of Food by Equivalence…

Spatio‐temporal assessment of illicit drug use at large scale : evidence from 7 years of international wastewater monitoring

Background and aims Wastewater‐based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population‐normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4‐methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011–17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data. Design Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to…

IPM-recommended insecticides harm beneficial insects through contaminated honeydew

The use of some systemic insecticides has been banned in Europe because they are toxic to beneficial insects when these feed on nectar. A recent study shows that systemic insecticides can also kill beneficial insects when they feed on honeydew. Honeydew is the sugar-rich excretion of hemipterans and is the most abundant carbohydrate source for beneficial insects such as pollinators and biological control agents in agroecosystems. Here, we investigated whether the toxicity of contaminated honeydew depends on i) the hemipteran species that excretes the honeydew; ii) the active ingredient, and iii) the beneficial insect that feeds on it. HPLC-MS/MS analyses demonstrated that the systemic insec…

Chromatography-mass spectrometry: Recent evolution and current trends in environmental science

The coupling of chromatography to mass spectrometry has been a very important step in environmental science that has changed routine workflows opening a horizon of new and impressive possibilities. This hyphenated technique benefits from coupling as chromatography offers great separation power and comprises various techniques and mechanisms. In turn, chromatography exploits the identification capability of mass spectrometry and is able to provide nominal or exact mass charge ration (m/z) not only of the intact molecule but also of several characteristic fragments. The sensitivity, selectivity, specificity, and rapidity in chromatography–mass spectrometry make this technology highly powerful…

Case Studies of Macro-and Microplastics Pollution in Coastal Waters and Rivers: Is There a Solution With New Removal Technologies and Policy Actions?.

This opinion paper on microplastics pollution has selected different aspects and case studies of micro and macro-plastic litter pollution in coastal waters, and rivers. We point out a discussion on this topic and ask ourselves if there is a solution to the global problem by developing new microplastics removal technologies as well as policy actions. The first two case studies are related with macroplastics marine litter in beaches, a third report describes a new simple sampling device for microplastics in coastal and nearshore areas, five case study assess microplastics pollution in worldwide coastal environments, sediments and catchments (India, Mexico, Australia, Europe and the Nordic Sea…

Solid-phase microextraction-liquid chromatography-mass spectrometry applied to the analysis of insecticides in honey

An approach based on solid-phase microextraction-liquid chromatography-mass spectrometry (SPME-LC-MS) has been developed for determining 12 insecticides (bromophos ethyl, chlorpyrifos methyl, chlorpyrifos ethyl, diazinon, fenoxycarb, fonofos, phenthoate, phosalone, pirimiphos methyl, profenofos, pyrazophos, and temephos) in honey. The influence of several parameters on the efficiency of the SPME was systematically investigated. Under optimal conditions, the procedure provided excellent linearity (>0.990), detection and quantification limits (between 0.001 and 0.1 microg g(-1) and between 0.005 and 0.5 microg g(-1), respectively), and precision (<19% at the quantification limits and from 6 t…

Gas chromatography and mass spectroscopy techniques for the detection of chemical contaminants and residues in foods

Gas chromatography-mass spectrometry (GC-MS) is a cornerstone for qualitative and quantitative analysis of food contaminants and residues. It is fast and sensitive, provides a high peak capacity, and allows determination of thermally stable and volatile compounds. Recent research has resulted in better chromatographic columns and methods for sample preparation that enable a significant expansion of the application range of GC-MS, profiling strategies for sample characterization being identified as important future drivers. Newer detection/separation solutions, such as fast chromatography, comprehensive two-dimensional GC (GC × GC), triple quadrupole MS, time-of-flight MS or orbitrap, atmosp…

Pesticides (New Generation) and Related Compounds, Analysis of

Miscellaneous pesticides and related compounds comprise substances that can neither be included in the classical chemical category of pesticides nor classified by their mode of action. They are a heterogeneous group of substances, the most representative of which are macrocyclic lactones, chloronicotinyls, tetranortriterpenoids, ammonium quaternary salts, dinitroanilines, acetamides, oximes, triazoles, and pyridine-based molecules. The pesticides covered in this article have hardly changed in the last years. However, their analytical determination has undergone significant improvements. This article provides a well-defined and critical compilation of the sample treatment and clean-up proced…

Perfluorinated Compounds’ Analysis, Environmental Fate and Occurrence: The Llobregat River as Case Study

Perfluorinated compounds are industrial chemicals widely used for more than 60 years. However, during the last decade, due to their high resistance to degradation, bioaccumulation attached to proteins, biomagnification to the food chain and their relation to toxicological effects of these compounds have gained scientific and regulatory attention.

Determination of organochlorine pesticide residues in honey from the central zone of Portugal and the Valencian community of Spain

In this study nine organochlorine pesticide residues ([alpha]-, [beta]-, and [gamma]-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), aldrin, p,p'-DDE, p,p'-DDD, o,p'-DDT, and p,p'-DDT) in forty nine samples of honey collected from markets of Portugal and Spain during 2001 and 2002, respectively, were evaluated. For this evaluation, three analytical procedures were studied. The analytical procedure, based on LLE extraction with ethyl acetate followed by gas chromatography-electron-capture detection (GC-ECD) for quantification, and mass spectrometry (GC-MS) for confirmation, has been selected. Recoveries of spiked samples ranged from 68%, for [beta]-HCH, and 126% for p,p'-DDT, for forti…

Analysis of emerging and related pollutants in aquatic biota

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, prot…

Application of matrix solid-phase dispersion to the determination of a new generation of fungicides in fruits and vegetables.

A method based on matrix solid-phase dispersion (MSPD) and gas chromatography to determine eight fungicides in fruits and vegetables is described. Fungicide residues were identified and quantified using nitrogen-phosphorus detection and electron-capture detection connected in parallel and confirmed by mass spectrometric detection. The method required 0.5 g of sample, C18 bonded silica as dispersant sorbent, silica as clean-up sorbent and ethyl acetate as eluting solvent. Recoveries from spiked orange, apple, tomato, artichoke, carrot and courgette samples ranged from 62 to 102% and relative standard deviations were less than 15% in the concentration range 0.05-10 mg kg(-1). Detection and qu…

Anthropometric status and nutritional intake in children (6-9 years) in Valencia (Spain): The ANIVA study

The aim of our study was to assess nutritional intake and anthropometric statuses in schoolchildren to subsequently determine nutritional adequacy with Spanish Dietary Reference Intake (DRIs). The ANIVA study, a descriptive cross-sectional study, was conducted in 710 schoolchildren (6–9 years) in 2013–2014 in Valencia (Spain). Children’s dietary intake was measured using 3-day food records, completed by parents. Anthropometric measures (weight and height) were measured according to international standards, and BMI-for-age was calculated and converted into z-scores by WHO-Anthro for age and sex. Nutrient adequacy was assessed using DRI based on estimated average requirement (EAR) or adequate…

Determination of dithiocarbamates and metabolites in plants by liquid chromatography–mass spectrometry

Abstract A quantitative matrix solid-phase dispersion and liquid chromatography–atmospheric pressure chemical ionization mass spectrometry (LC–APCI–MS) method is outlined for the simultaneous analysis of dithiocarbamates (DTCs) and their degradation products in plants. Compounds analyzed are dazomet, disulfiram, thiram and the metabolites ethylenthiourea and propylenthiourea. The performance of two different sample preparation protocols, the proposed one and other based on solid-phase extraction, as well as, of both atmospheric pressure ionization sources, APCI and electrospray, were compared. The effect of several parameters on the extraction, separation and detection was studied. Dithioca…

Corrigendum to “Bioaccumulation of emerging contaminants in mussel (Mytilus galloprovincialis): Influence of microplastics” [Sci. Total Environ. 796 (2021) 149006]

Non-Occupational Exposure to Pesticides: Experimental Approaches and Analytical Techniques (from 2019)

© 2021 by the authors.

Determination of pesticide residues in fruit and vegetables.

A review concerning the determination of pesticide residues in fruit and vegetables is presented. The basic principles and recent developments in the extraction and quantitation of pesticides are discussed. Consideration is given to solid phase and supercritical extraction techniques, automation and robotic systems, and immunoassay procedures.

Identification of effective parameters for anti-inflammatory concentration in València City's wastewater using fuzzy-set qualitative comparative analysis

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' …

Analysis of organophosphorus pesticides in honeybee by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

Pesticides applied in extended agricultural fields may be controlled by means of bioindicators, such as honeybees, in which are the pesticides bioaccumulate. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) experiments with positive (PI) and negative (NI) ion modes were optimized for the analysis of 22 organophosphorus pesticides in honeybee samples. The extraction required 3 g of sample, which was extracted with acetone. The extract was purified with coagulating solution and reextracted with Cl(2)CH(2). Pesticides studied could be detected by both ionization modes except for parathion, parathion-methyl, and bromophos, which did not give signals …

Monetary valuation of salicylic acid, methylparaben and THCOOH in a Mediterranean coastal wetland through the shadow prices methodology

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), …

Sample Preparation to Determine Pharmaceutical and Personal Care Products in an All-Water Matrix: Solid Phase Extraction

© 2020 by the authors. 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 rev…

Evaluation of 10 pesticide residues in oranges and tangerines from Valencia (Spain)

Abstract One hundred and sixteen orange and tangerine samples from an agricultural cooperative of the Valencian Community (Spain) were analyzed for bitertanol, carbendazim, hexythiazox, imazalil, imidacloprid, methidathion, methiocarb, pyriproxyfen, thiabendazole, and trichlorfon by liquid chromatography–mass spectrometry (LC–MS) after a conventional multiresidue extraction procedure. Of 52 samples that contained pesticide residues, carbendazim was detected in 27 (51.9%) in the concentration range of 0.02–0.04 mg kg−1, hexythiazox in 22 (42.3%) in the concentration range of 0.02–0.05 mg kg−1, imazalil in 8 (15.0%) in the concentration range of 0.02–1.2 mg kg−1, imidacloprid in 5 (9.6%) in a…

Determination of organophosphate flame retardants in soil and fish using ultrasound-assisted extraction, solid-phase clean-up, and liquid chromatography with tandem mass spectrometry

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…

Liquid chromatographic–mass spectrometric determination of post-harvest fungicides in citrus fruits

Liquid chromatography (LC)-atmospheric pressure ionisation (API)-mass spectrometry (MS) has been used to determine residues of five fungicides in oranges with a minimum sample cleanup. Atmospheric pressure chemical ionisation (APCI) and electrospray (ES) were compared and both gave similar results in terms of sensitivity and structural information. The main ions were [M+H]+ for carbendazim, imazalil, thiophanate methyl and thiabendazole, and [M+H-C4H9NHCO]+ for benomyl. Samples were extracted with sodium sulphate and ethyl acetate. Although benomyl and thiophanate methyl were transformed through the extraction procedure to carbendazim, the method showed good precision (13%) and recovery (70…

Neonicotinoids in excretion product of phloem-feeding insects kill beneficial insects

Significance The use of insecticides in agriculture is one of the suggested causes of the decline in insect populations. Neonicotinoids are among the most widely used insecticides. However, they have important negative side effects, especially for pollinators and other beneficial insects feeding on floral nectar and pollen. We identified an exposure route: Neonicotinoids reach and kill beneficial insects when they 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, or psyllids. This route of exposure is likely to affect a much wider range of benefi…

Liquid chromatography/atmospheric pressure chemical ionization-mass spectrometric analysis of benzoylurea insecticides in citrus fruits.

A liquid chromatography (LC) method for the quantitative determination of three benzoylurea insecticide residues (diflubenzuron, flufenoxuron and hexaflumuron) in citrus fruits is described. Residues were successfully separated on a C18 column by methanol/water gradient elution. Detection was by negative-ion, selected-ion monitoring atmospheric pressure chemical ionization-mass spectrometry (APCI-MS); the main ions were [M - H]-, and the secondary fragment ions were [M - H - HF]-. Useful confirmatory information can thus be obtained at low extraction voltages from losses of HF. Detection limits for standard solutions were 10 fg injected and good linearity and reproducibility were obtained. …