Solid-phase extraction in multi-residue pesticide analysis of water

The determination of pesticides in water is fundamental to the solution of environmental problems as natural waters are usually contaminated with a large number of pesticides. The selection of an isolation and/or concentration technique depends largely on the class of pesticides to be determined. It is often necessary to determine simultaneously a wide variety of compounds in a water sample. Application of solid-phase extraction techniques offers a solution. The mechanisms of solid-phase extraction, types of sorbents and their application to multi-residue pesticide analysis are reviewed.

The Use of Chromatographic Methods Coupled to Mass Spectrometry for the Study of Emerging Pollutants in the Environment.

The consumption of compounds that improve the human health and wellness is increasing, and as a result, the residues of these substances reach the environment or food chain. For this reason, the scientific community is looking for new analytical methods that are more accurate and can detect the greatest number of compounds in different matrices. This manuscript compares different studies in abiotic and biotic matrices, where most of them (92%) uses Liquid Chromatography to separate the compounds. For the detection, most of the studies for both matrices uses, coupled to the chromatograph, a triple quadrupole mass spectrometer (50%) due to the precision to quantify the concentration of these …

Multiple-stressor effects on river biofilms under different hydrological conditions

Summary We studied the relative importance of environmental factors (river flow, nutrients, dissolved organic matter) and organic micro-pollutants [herbicides, insecticides, industrial organic compounds, personal care products, antibiotics and pharmaceuticals, (PhCs)] to the structure and function of epilithic biofilms under various hydrological conditions and land uses. Biofilms from four river basins in the Iberian Peninsula (Llobregat, Ebro, Jucar and Guadalquivir) were analysed in summer–autumn during a wet period and base-flow conditions. The sites experienced different levels of pollution. We used variance partitioning (Redundancy Detrended Analysis, RDA) to link environmental stresso…

Determination of urea-derived pesticides in fruits and vegetables by solid-phase preconcentration and capillary electrophoresis

A multiresidue analytical method based on solid-phase extraction (SPE) enrichment combined with capillary electrophoresis (CE), using micellar electrokinetic capillary chromatography (MEKC), was developed to determine ten substituted urea pesticides in orange and tomato samples. Several factors such as pH, composition and concentration of the buffer, concentration of surfactant, addition of organic solvent, and working voltage were optimized to obtain the best compound separation in the shortest time. Separation can be achieved in 7 min using a micellar aqueous pH 9 buffer composed of 4 mM borate and 35 mM sodium dodecyl sulfate. After an SPE procedure, which provided a 10-fold enrichment, …

Target vs non-target analysis to determine pesticide residues in fruits from Saudi Arabia and influence in potential risk associated with exposure

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 detec…

Nanoelectrospray with ion-trap mass spectrometry for the determination of beta-casomorphins in derived milk products.

Beta-casomorphins (b-CMs) are bioactive peptides derived from casein with opioid agonist effects similar to morphine. The use of electrospray (ESI) with quadrupole ion-trap mass spectrometry (QIT-MS) for these compounds in two matrices, cheese and milk, was examined. It was compared to a liquid chromatography (LC) coupled to mass spectrometry (LC-MS), and a "soft" ionisation technique, NanoMate, with selected ion monitoring (SIM), which are unreliable for the determination of trace casomorphins in derived milk products. b-CM mass fragmentation pathways were done for the four most common b-CMs: beta-casomorphin (1-5) bovine (b-CM-5), beta-casomorphin (1-7) bovine (b-CM-7), [D-Ala2, D-Pro4,Ty…

Direct Peel Monitoring of Xenobiotics in Fruit by Direct Analysis in Real Time Coupled to a Linear Quadrupole Ion Trap–Orbitrap Mass Spectrometer

Study of xenobiotics present in fruit peel by exposing it (without any pretreatment) to direct analysis in real time coupled to a high-resolution orbitrap mass spectrometer (DART-HRMS) is reported for the first time. Variables such as DART gas heater temperature and pressure, source-to-MS distance, and sample velocity are investigated. The analysis of one sample by DART-MS lasts ca. 1 min, and the benefits of both high-resolution and tandem mass spectrometry to elucidate nontarget or unknown compounds are combined. Identification of postharvest fungicides, antioxidants, and sugars in fruit peel is performed in the positive ion mode. A possible elemental formula is suggested for marker compo…

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 …

Universal method to determine acidic licit and illicit drugs and personal care products in water by liquid chromatography quadrupole time-of-flight

Graphical abstract

Capabilities of different liquid chromatography tandem mass spectrometry systems in determining pesticide residues in food

Abstract Three different liquid chromatography–mass spectrometry (LC–MS) instruments equipped with triple quadrupole (QqQ), quadrupole ion trap (QIT) and quadrupole-time-of-flight (QqTOF), suitable to carry out tandem mass spectrometry, were examined to determine pesticide residues in food. Twelve pesticides (acrinathrin, bupirimate, buprofezin, cyproconazole, λ-cyhalothrin, fluvalinate, hexaflumuron, kresoxim-methyl, propanil, pyrifenox, pyriproxyfen and tebufenpyrad) and six matrices (oranges, strawberries, cherries, peaches, apricots and pears) were taken as model. The comparison was focused on two aspects: the quantitative, covering sensitivity, precision and accuracy as well as the qua…

Analysis of emerging contaminants and nanomaterials in plant materials following uptake from soils

The reuse of treated wastewater or wastewater-impacted river water is growing, particularly in arid areas, due to the climate change. As well, the disposal of sludges, biosolids or biochar as soil amendments to improve agricultural output is widely implemented in the EU. These practices can be a source of emerging contaminants and engineering nanomaterials (ENMs) to the environment and condition their incorporation to food chain that could affect human beings. This review covers current analytical techniques, instruments and methodologies used to determine emerging contaminants and ENMs from irrigation water and/or soil amendments in plants. Trends regarding sample treatment, separation and…

Liquid chromatography–electrospray quadrupole ion-trap mass spectrometry of nine pesticides in fruits

A liquid chromatographic method, with electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS), has been developed for determining acrinathrin, carbosulfan, cyproconazole, lambda-cyhalothrin, kresoxim methyl, pyrifenox, pyriproxyfen, propanil, and tebufenpyrad in fruits. The ions prominent in ESI spectra were [M + H]+ and [M + Na]+. In the mass analyzer, collision-induced dissociation fragmentation involved common pathways, for example, product ions of [M + H]+ resulted from the cleavage of the carbamic group or an oxygen bound. The utility of the method is demonstrated by the analysis of crude extracts obtained by matrix solid-phase dispersion (MSPD) using C18 as dispersant and dich…

Nano- and microplastic analysis: Focus on their occurrence in freshwater ecosystems and remediation technologies

Plastic pollution is a global problem since 2016 when its production reached 322 million tonnes, excluding fibers. Daily discharges of microplastics (MPs, defined as <5 mm in size) are estimated in the range of 50,000 up to 15 million particles, whereas no information on nanoplastic (NP, <100 nm) release is available yet. Different processes further degraded these materials producing more MPs and NPs. This review attempts to fill the void of information on the state-of-art analysis of MPs and NPs (recently identified as emerging contaminants) and provides a critical overview on modern instrumentation, newly developed workflows, and promising techniques for their characterization (Raman and …

Application of capillary electrophoresis-mass spectrometry for determining organic food contaminants and residues.

Food contamination continues to be a serious problem around the world. Surveillance of chemical contaminants in foods is important not only for public health but also because of the negative economic impact of contamination. From the analytical perspective, analysis of contaminants in food is an extremely challenging area. There is a wide variety of questions, ranging from the quantification of extremely low levels of individual components to the detailed assessment and evaluation of the analytical technique possibilities. This review considers the applications of CE coupled to MS detection (CE-MS) for the analysis of organic contaminants in food. Analytical information on sample concentrat…

APPLICATION OF REAL-TIME POLYMERASE CHAIN REACTION FOR RAPID DETERMINATION OFSALMONELLAIN RESTAURANT FOODS

Several foods have been identified as frequently or occasionally contaminated with Salmonella, such as eggs, raw milk and all raw foods of animal origin that may carry salmonella and other bacteria. Salmonellosis is the most common food-borne illness, but it is usually preventable according to the implementation of a food safety system that includes Hazard Analysis and Critical Control Point. In this study, 96 food samples of the University restaurant of Valencia (Spain) were divided into four groups: first course; main course; accompaniment; and dessert, and were analyzed simultaneously with classical and fluorogenic polymerase chain reaction microbiological analysis. Neither of the proced…

Comparison of four mass analyzers for determining carbosulfan and its metabolites in citrus by liquid chromatography/mass spectrometry

Four liquid chromatography/mass spectrometry (LC/MS) systems, equipped with single quadrupole, triple quadrupole (QqQ), quadrupole ion trap (QIT) and quadrupole time-of-flight (QqTOF) mass analyzers, were evaluated for the analysis of carbosulfan and its main transformation products. The comparison of quantitative aspects (sensitivity, precision and accuracy) was emphasized. Results showed that the triple quadrupole instrument reaches at least 20-fold higher sensitivity (LOD from 0.04 to 0.4 microg kg(-1)) compared to the single quadrupole (4-70 microg kg(-1)), the QIT (4-25 microg kg(-1)) and the QqTOF (4-23 microg kg(-1)) instruments. Recoveries were over 70% for all the analytes, except …

Current trends in solid-phase-based extraction techniques for the determination of pesticides in food and environment

Solid-phase extraction (SPE) procedures for pesticide residues in food and environment are reviewed and discussed. The use of these procedures, which include several approaches such as: matrix solid-phase dispersion (MSPD), solid-phase micro-extraction (SPME) and stir-bar sorptive extraction (SBSE), represents an opportunity to reduce analysis time, solvent consumption, and overall cost. SPE techniques differ from solvent extraction depending on the interactions between a sorbent and the pesticide. This interaction may be specific for a particular pesticide, as in the interaction with an immunosorbent, or non-specific, as in the way a number of different pesticides are adsorbed on apolar or…

Rapid and sensitive ultra-high-pressure liquid chromatography-quadrupole time-of-flight mass spectrometry for the quantification of amitraz and identification of its degradation products in fruits.

Liquid chromatography under high pressure in combination with quadrupole time-of-flight mass spectrometry (QqTOF-MS and MS/MS) has been used to detect amitraz degradation products in pears, to characterize their structures, and to evaluate their occurrences in samples of different origins. Using the proposed approach, the parent pesticide and four degradation products were identified. To this end, pear samples were extracted with ethyl acetate and anhydrous sodium sulphate. Amitraz was found to be rapidly decomposed into four related compounds, of which N-(2,4-dimethylphenyl)formamidine (DMPF) was the most abundant and persistent. N,N'-bisdimethylphenylformamidine (BDMPF), 2,4-dimethylforma…

Liquid Chromatography Quadrupole Time-of-Flight Mass Spectrometry Analysis of Carbosulfan, Carbofuran, 3-Hydroxycarbofuran, and Other Metabolites in Food

The potential of liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS) to identify and confirm carbosulfan and seven of its main metabolites (carbofuran, 3-hydroxycarbofuran, 3-ketocarbofuran, 3-hydroxy-7-phenol carbofuran, 3-keto-7-phenolcarbofuran, 7-phenolcarbofuran, dibutylamine) at trace levels from food is explored for the first time. The analytical method developed consists of pressurized liquid extraction (PLE) and LC-QqTOF-MS in positive ion mode, which attains unequivocal identification and quantification of the studied compounds in food, at levels well below of those of concern (0.05 mg/kg for the sum of carbosulfan, carbofuran, and 3-hydroxycarbofuran).…

Perfluoroalkyl substances in the Ebro and Guadalquivir river basins (Spain).

Mediterranean rivers are characteristically irregular with changes in flow and located in high population density areas. This affects the concentration of pollutants in the aquatic environments. In this study, the occurrence and sources of 21 perfluoroalkyl substances (PFASs) were determined in water, sediment and biota of the Ebro and Guadalquivir river basins (Spain). In water samples, of 21 analytes screened, 11 were found in Ebro and 9 in Guadalquivir. In both basins, the most frequents were PFBA, PFPeA and PFOA. Maximum concentration was detected for PFBA, up to 251.3ngL-1 in Ebro and 742.9ngL-1 in Guadalquivir. Regarding the sediments, 8 PFASs were detected in the samples from Ebro an…

SOLID-PHASE EXTRACTION OF PESTICIDES FROM WATER SAMPLES

Sample preparation methods for the determination of pesticides in foods using CE-UV/MS.

Much progress has been made in pesticide analysis over the past decade, during this time hyphenated techniques involving highly efficient separation with sensitive detection have become the techniques of choice. Among these, methods based on separation with mass spectrometric detection have resulted in greater likelihood of identification and are acknowledged to be extremely useful and authoritative methods for the determination of pesticide residues but the inherent advantages of the use of CE as a separation technique are well-known and can be summarized as high separation efficiency, low analysis time, high resolution power, and low consumption of samples and reagents. Although UV is the…

Advances in the analysis of legal and illegal drugs in the aquatic environment

We review the current methods developed for the analysis of legal and illegal drugs (LIDs) and their metabolites in environmental samples. We discuss the advantages and the pitfalls of multi-class methods with emphasis on new strategies for sample preparation and recent technical developments. Finally, we present the applicability of these methods to the analysis of LIDs in protected environmental areas.

Quantitative determination of octylphenol, nonylphenol, alkylphenol ethoxylates and alcohol ethoxylates by pressurized liquid extraction and liquid chromatography-mass spectrometry in soils treated with sewage sludges.

6 páginas, 1 figura, 2 tablas.

Analytical challenges to determine emerging persistent organic pollutants in aquatic ecosystems

Emerging persistent organic pollutants (ePOPs) include polybrominated diphenyl ethers (PBDEs) and perfluorooctane sulfonyl fluoride/perfluorooctane sulfonate (POSF/PFOS), which are newly listed in the Stockholm Convention. Other ePOPs, which have not been regulated, include organophosphate flame retardants (PFRs), novel brominated flame retardants (NBFRs) and other perfluoroalkyl substances (PFASs). Often ePOPs data related to occurrence, toxicity, impact or environmental behavior are insufficient or inadequate because of the lack of proper analytical methods to obtain them. Thus, a critical review of the analytical procedures proposed in the last six years (2011–2017) for determining ePOPs…

Estimating population size in wastewater-based epidemiology. Valencia metropolitan area as a case study.

Wastewater can provide a wealth of epidemiologic data on common drugs consumed and on health and nutritional problems based on the biomarkers excreted into community sewage systems. One of the biggest uncertainties of these studies is the estimation of the number of inhabitants served by the treatment plants. Twelve human urine biomarkers —5-hydroxyindoleacetic acid (5-HIAA), acesulfame, atenolol, caffeine, carbamazepine, codeine, cotinine, creatinine, hydrochlorothiazide (HCTZ), naproxen, salicylic acid (SA) and hydroxycotinine (OHCOT)— were determined by liquid chromatography-tandem mass spectrometry (LC–MS/MS) to estimate population size. The results reveal that populations calculated fr…

Volatile dimethylsiloxanes in market seafood and freshwater fish from the Xúquer River, Spain

Abstract Volatile dimethylsiloxanes are a family of synthetic organosilicon-compounds, which have received rising attention because of their widespread use and occurrence in the environment. In the present work, an analytical method based on ultrasound-assisted solid–liquid extraction (USAE) followed by gas chromatography coupled to tandem mass spectrometry (GC–MS/MS) has been optimized and applied to assess the presence of eight volatile dimethyl siloxanes (VMS) (hexamethylcyclotrisiloxane (D3), octamethylcyclotetra-siloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), octamethyltrisiloxane (MDM), decamethyltetrasiloxane (MD2M) and dodecamethylpentasiloxane …

Mass Spectrometry in Wastewater-Based Epidemiology for the Determination of Small and Large Molecules as Biomarkers of Exposure: Toward a Global View of Environment and Human Health under the COVID-19 Outbreak

Wastewater-based epidemiology (WBE) estimates collective consumption or exposure to chemicals or pathogens by monitoring the substances excreted in the population’s wastewater. Advances in mass spectrometry (MS) and the application of some clinical diagnostic tools and proteomics to wastewater fingerprinting have been linked to the discovery of new biomarkers and indicators of population health and are broadening the scope of WBE that nowadays cover not only small molecule biomarkers but also genetic biomarkers, large molecules, viruses, infection diseases, resistance, etc. This mini-review highlights recent WBE advances using MS and how this progress can create a fingerprint of a city’s he…

Pesticide analysis in coffee leaves using a quick, easy, cheap, effective, rugged and safe approach and liquid chromatography tandem mass spectrometry: Optimization of the clean-up step.

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-1 depending on the clean-up procedures. However, samples spiked with a 100ng*g-1 pesticide mixture gave RSDs>20% for most pest…

Solid-phase extraction of quaternary ammonium herbicides

This paper highlights recent advances in the solid-phase extraction (SPE) of quaternary ammonium herbicides in water, soil, plant and biological samples. After a brief introduction summarizing the properties of quaternary ammonium herbicides and the difficulties involved in measuring them, attention is paid primarily to solid supports used for isolation and concentration, pre-treatments required for the different matrices, and eluents applied for quantitative desorption of these analytes. The determination techniques used after SPE and applications of the proposed SPE methodology are also briefly discussed.

Simultaneous determination of imidacloprid, carbendazim, methiocarb and hexythiazox in peaches and nectarines by liquid chromatography–mass spectrometry

Abstract A liquid chromatographic (LC) atmospheric pressure chemical ionization mass spectrometric (MS) method is described for determining imidacloprid, carbendazim, methiocarb and hexythiazox in peaches and nectarines. The samples were extracted with ethyl acetate and anhydrous sodium sulfate. Recoveries yield for spiking samples were ranged from 64±9% (R.S.D) for carbendazim to 108±14% (R.S.D.) for hexythiazox at the concentration of 0.1 mg kg−1 (n=5). The correlation coefficients were greater than 0.998 over the range between 0.02 and 2 mg kg−1. The limits of quantitation (LOQ) were 0.02 mg kg−1 for all the pesticides. The applicability of the method to detect and quantify imidacloprid,…

Patterns of presence and concentration of pesticides in fish and waters of the Júcar River (Eastern Spain).

The Jucar River, in a typical Mediterranean Basin, is expected to suffer a decline in water quality and quantity as a consequence of the climate change. This study is focused on the presence and distribution of pesticides in water and fish, using the first extensive optimization and application of the QuEChERS method to determine pesticides in freshwater fish. Majority pesticides in water - in terms of presence and concentration - were dichlofenthion, chlorfenvinphos, imazalil, pyriproxyfen and prochloraz (associated with a frequent use in farming activities), as well as buprofezin, chlorpyriphos and hexythiazox. In fish, the main compounds were azinphos-ethyl, chlorpyriphos, diazinon, dime…

Pressurised liquid extraction and capillary electrophoresis–mass spectrometry for the analysis of pesticide residues in fruits from Valencian markets, Spain

Abstract A procedure based in capillary electrophoresis–mass spectrometry (CE–MS) for the analysis of seven pesticides (flutolanil, simazine, haloxyfop, acifluorfen, dinoseb, picloram, and ioxynil) in four Mediterranean summer fruits with high water content (peaches, melon, watermelon, and apricot) is developed. Several conditions were studied for the optimisation of both, the separation and the electrospray (ESI) connection. The best results were obtained using 35 mM ammonium formiate (pH 9.7) as separation buffer, 20 °C as capillary temperature and 23 kV as applied voltage in an uncoated fused-silica capillary with 50 cm total length, 25 cm thermostated length, 25 cm at room temperature l…

Determination of benzoylurea insecticides in food by pressurized liquid extraction and LC-MS

A method based on pressurized liquid extraction and LC-MS/MS has been developed for determining nine benzoylureas (BUs) in fruit, vegetable, cereals, and animal products. Samples (5 g) were homogenized with diatomaceous earth and extracted in a 22 mL cell with 22 mL of ethyl acetate at 80 degrees C and 1500 psi. After solvent concentration and exchange to methanol, BUs were analyzed by LC-MS/MS using an IT mass analyzer, which achieved several transitions of precursor ions that increase selectivity providing identification. LOQs were between 0.002 and 0.01 mg/kg, which are equal or lower than maximum residue limits established by the Codex Alimentarius. Excellent linearity was achieved over…

Direct analysis in real-time high-resolution mass spectrometry as a valuable tool for polyphenols profiling in olive oil

A fast and reliable method to characterize the polyphenolic compound profiles in extra virgin olive oil (EVOO) has been developed using direct analysis in real time (DART) and linear ion-trap Orbitrap mass spectrometry (LTQ-Orbitrap-MS). Hydroalcoholic extraction increased speed and reduced matrix effects, and DART-MS/MS ensured accurate analysis. Characterization of polyphenol fingerprinting in EVOO samples takes 2 min. This method exhibited proper linearity (R2 ≥ 0.99) in the range of 5–2500 μg g−1, limit of detection (LOD) of 1.5 μg g−1 (signal-to noise S/N = 3), and limits of quantitation (LOQs) of 5 μg g−1 (S/N = 10) for resveratrol (a polyphenol not detected in olive oil). Six spiked …

Determining nanomaterials in food

Abstract Nanotechnology has emerged as one of the most innovative technologies and has the potential to improve food quality and safety. However, there are a few studies demonstrating that nanomaterials (NMs) are not inherently benign. This review highlights some current applications of NMs in food, food additives and food-contact materials, and reviews analytical approaches suitable to address food-safety issues related to nanotechnology. We start with a preliminary discussion on the current regulatory situation with respect to nanotechnology in relation to foods. We cover sample preparation, imaging techniques (e.g., electron microscopy, scanning electron microscopy and X-ray microscopy),…

Assessing drugs of abuse distribution in Turia River based on geographic information system and liquid chromatography mass spectrometry

Drugs of abuse are continuously discharged into wastewaters as part of their elimination process. Pollution at very low concentrations appears to be broad in environmental compartments near populated areas. A total of 42 drugs of abuse and metabolites were analysed in surface water samples collected in 2012 and 2013 by solid phase extraction and liquid chromatography coupled to mass spectrometry. Analytical results of target compounds were georeferenced and integrated into a geographical information systems (GIS). Ecotoxicological risk of drugs of abuse detected in the Turia River was evaluated in this study by calculating risk quotient (RQ). In 2012, 6 compounds were detected in a total of…

On-line preconcentration strategies for analyzing pesticides in fruits and vegetables by micellar electrokinetic chromatography.

Five pesticides (fludioxonil, procymidone, pyriproxyfen, dinoseb and carbendazim) were separated in reversed migration micellar electrokinetic chromatography (RM-MEKC) using 20 mmol l(-1) phosphate buffer at pH 2.3, containing 25 mmol l(-1) sodium dodecylsulfate and 10% methanol. Three on-line concentration strategies, sweeping (SW), normal stacking with reversed migration and a water plug (SRW) and stacking with reverse migration and removal of sample matrix using polarity switching (SRMM), were compared. About 10-, 30- and 50-fold increases in detection sensitivity, compared with standard hydrodynamic injection (5 s at 0.5 psi), were observed with SW, SRW and SRMM, respectively. Limits of…

Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds

Exposure assessments conducted using a personal sampler include the contribution of human activities to exposure that is neglected when using a stationary air sampler. This study evaluated the uptake characteristics and application of the polydimethylsiloxane (PDMS or silicone rubber) brooch as a personal passive air sampler (PPAS) for measuring concentrations of two groups of semi-volatile organic compounds (SVOCs), namely phthalates and organophosphate esters (OPEs), indoors in proximity to the breathing zone. Uptake rates of the PDMS brooch were calibrated against a personal low volume active air sampler (PLV-AAS) co-deployed on each of five study participants working in offices for 8 hs…

Effect of methylparaben in Artemia franciscana.

In this study, the toxicity of methylparaben (MeP) an emerging contaminant, was analysed in the sexual species Artemia franciscana, due to its presence in coastal areas and marine saltworks in the Mediterranean region. The acute toxicity (24 h-LC50) of MeP in nauplii was tested and its chronic effect (9 days) evaluated by measuring survival and growth under two sublethal concentrations (0.0085 and 0.017 mg/L). Also, the effect on several key enzymes involved in: antioxidant defences (catalase (CAT) and gluthathion-S-transferase (GST)), neural activity (cholinesterase (ChE)) and xenobiotic biotransformation (carboxylesterase (CbE), was assessed after 48 h under sublethal exposure. The result…

Suspected-screening assessment of the occurrence of organic compounds in sewage sludge

The profiling of emerging organic pollutants present in sludge and generated during wastewater treatment is much more limited than in water. This is mainly due to the difficulty of sludge analysis because of its high content of organic matter and interfering compounds. In this study, a generic extraction method using a mixture of buffered water (pH 4.1) and solid phase extraction (SPE) clean-up was applied to samples of sludge obtained in different treatment plants. This extraction was followed by determination of the contaminants by ultra-high performance liquid chromatography coupled to high resolution mass spectrometry (UHPLC-HRMS), using suspected screening to detect the most relevant o…

Challenges in the determination of engineered nanomaterials in foods

Detection, characterization, and quantification of engineering nanomaterials (ENMs) in foods is still a pending issue that needs to be tackle to protect consumers and to fix some related aspects (e.g. labelling or control). The global challenge for the analytical sciences is that ENMs are a new sort of analytes, involving both chemical (composition, mass and number concentration) and physical information (e.g. size, shape, aggregation). In this critical review, we evaluate and compare the procedures involved in the analytical methods and studies developed thus far for the identification and quantification of ENMs in food. We discuss advantages and limitation as well as prospects. We pointed…

Occurrence and removal of drugs of abuse in Wastewater Treatment Plants of Valencia (Spain)

The occurrence of 8 drugs of abuse and metabolites in the influent and effluent of the 3 Wastewater Treatment Plants (WWTP) that treat wastewater from Valencia was studied in 2011, 2012 and 2013. Target drugs except 6-monoacetylmorphine (6-ACMOR) were detected in 100% of the influents. The WWTPs eliminate cocaine (COC), amphetamine (AMP), methamphetamine (MAMP) and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH). Benzoylecgonine (BECG) was also efficiently eliminated (93-98%), whereas 3,4-methylenedioxymethamphetamine (MDMA) presented removal rates of 32-57% and ketamine (KET) was not eliminated. The most consumed illicit drugs, according to the estimated concentrations of each compound…

Screening of currently used pesticides in water, sediments and biota of the Guadalquivir River Basin (Spain)

The occurrence of 50 currently used pesticides and their transformation products in surface and waste waters, sediment and fish in the Guadalquivir River Basin was determined in 2010 and 2011. After selective sample extraction, pesticides were identified and quantified by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The contamination profile in water and sediments is marked by the presence of organophosphorus and triazines. Transformation products were even at higher concentrations than parent pesticides. A wider range of pesticides was present in water than in sediments but none of them were detected in fish. The mean concentrations ranged from 0.2 to 13.0 ng/L in …

Pressurized liquid extraction of organic contaminants in environmental and food samples

Pressurized liquid extraction (PLE) is an automated technique that uses elevated temperature and pressure to achieve exhaustive extraction from solid matrices, so reducing solvent consumption and enhancing sample throughput when compared with traditional procedures. Hence, it can be considered an environment-friendly technique, generating small volumes of waste and reducing costs and time. This review focuses on application of this green technique to the analysis of organic contaminants in food and environmental matrices for monitoring purposes. We examine fundamentals and key aspects of the development of a PLE method, including pressurized hot-water extraction, together with some relevant…

Determination of microcystins in biological samples by matrix solid-phase dispersion and liquid chromatography–mass spectrometry

A method for the detection and quantification of the microcystins (MCs)-MC-LR, MC-RR and MC-YR-in biological samples by matrix solid-phase dispersion (MSPD) has been developed. The optimum extraction conditions were 500 mg of liver or kidney, C18 bonded silica as dispersant, and a mixture methanol-water (70:30) as eluent. The MCs were determined by liquid chromatography electrospray mass spectrometry (LC/ES/MS). Recoveries of biological extracts at three different spiked levels (1-10 mg kg(-1)) ranged from 40.5 to 87.0% in liver, and from 52.5 to 74.5 in kidney. R.S.D.s were < 15.6% and < 10.6%, respectively. The detection and quantification limits were 0.05 and 0.5 mg kg(-1), for all MCs. …

Progress in analysis of residual antibacterials in food

Abstract Residual antibacterials in food constitute a risk to human health. Although epidemiological data on the real magnitude of their adverse effects are very scarce, they indicate that food could be an important avenue for evolution and dissemination of antibiotic-resistant bacteria. Analysis of these residues plays a key role in ensuring food safety, to the point that the European Union has not only established maximum residue limits but also requirements concerning the performance of analytical methods and the interpretation of the results. These specifications have had a great influence on protocols and techniques applied. In this review, we discuss the progress of rapid screening me…

Determination of pesticides and their degradation products in soil: critical review and comparison of methods

18 páginas, 5 figuras, 5 tablas.

Multi-class determination of antimicrobials in meat by pressurized liquid extraction and liquid chromatography–tandem mass spectrometry

A multi-residue method using pressurized liquid extraction (PLE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for determining trace levels of 31 antimicrobials, including beta-lactams, lincosamides, macrolides, quinolones, sulfonamides, tetracyclines, nitroimidazoles and trimethoprim. The extraction method required pre-homogeneization of the meat with EDTA-washed sand and subsequent one-static-cycle extraction for 10 min with 40 ml of water at 1500 psi and 70 degrees C. The effect of operation temperature, pressure, flush volume, and static cycles on PLE performance was studied. Average recoveries ranged from 75 to 99% with relative standard deviations <1…

Assessment of two extraction methods to determine pesticides in soils, sediments and sludges. Application to the Túria River Basin.

Pressurized liquid extraction (PLE) and Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction methods were optimized for the simultaneous determination of 50 pesticides in sediment, soils and sewage sludge. For QuEChERS development, several buffers and dispersive solid-phase extraction clean-up (dSPE) sorbents were tested. In the PLE method, several parameters affecting the extraction efficiency, such as organic solvent, amount of sample, cell size, temperature, pressure, static time, number of cycles and % of flush, as well as sorbent used for the on-line clean up, were also evaluated. PLE and QuEChERS were assessed and compared in obtained recoveries (33-89% versus 25-120%)…

Analytical Methods for Pesticide Residue Determination in Bee Products

Monitoring pesticide residues in honey, wax, and bees helps to assess the potential risk of these products to consumer health and gives information on the pesticide treatments that have been used on the field crops surrounding the hives. The present review seeks to discuss the basic principles and recent developments in pesticide analysis in bee products and their application in monitoring programs. Consideration is given to extraction, cleanup, chromatographic separation, and detection techniques.

Nanosensors and other techniques for detecting nanoparticles in the environment

Abstract: Detecting nanomaterials in the environment is a demanding task, not only because of the extremely small size of the particles and their potential sequestration and agglomeration, but also because of their unique physical and chemical characteristics. The aim of this review is to recommend a way forward on tackling the challenge of engineered nanomaterial detection in the environment. An overview will be presented of the available analytical techniques used for the detection and characterization of nanoparticles in environmental matrices including particle-size analysis, particle-fraction concentration counts, surface-area analysis, morphology, and particle chemical composition ana…

Emerging Contaminants

Brominated flame retardants (BFRs), compounds formed during food processing, mycotoxins, perfluoroalkyl substances (PFASs), pesticides, phycotoxins, polycyclic aromatic hydrocarbons (PAHs), and veterinary drugs are considered environmental emerging contaminants of particular concern. This chapter reviews the most important groups of emerging contaminants as well as the analytical platforms based on mass spectrometry (MS) developed to determine their presence in food. MS instruments utilize many different types of mass analyzers to improve selectivity and also confidence in assigning the identity of these emerging pollutants. Current analytical approaches are discussed together with the majo…

Occurrence and removal efficiency of pesticides in sewage treatment plants of four Mediterranean River Basins.

Removal of contaminants in the sewage treatment plants (STPs) can be incomplete causing their release to the environment. In this paper, the results of an extensive survey on more than 40 pesticides carried out in 2010 and 2011 in 16 STPs of Ebro, Guadalquivir, Jucar and Llobregat Rivers (Spain) are presented. In 2010, of 43 analytes screened, 29 were detected in influent and 28 in effluent samples, meanwhile in 2011, of 50 analytes, 33 and 34 were detected, respectively. Pesticides were in the range of 0.33 ng L(-1) (terbumeton, 2011)-2526.05 ng L(-1) (diuron, 2010) for influent and 0.25 ng L(-1) (terbumeton, 2011)-2821.12 ng L(-1) (carbendazim, 2011) for effluent. Regarding the sludge sam…

Pesticide monitoring in the basin of Llobregat River (Catalonia, Spain) and comparison with historical data.

Through an extensive sampling in the Llobregat River basin, the presence of 50 currently used pesticides in water, sediment, and biota was assessed. Pesticides were detected primarily in water (up to 56% of the analytes), whereas their presence in sediments was more intermittent, and in biota was scarce. Those at high concentrations in water were the benzimidazoles (carbendazim in 22% of the samples up to 697ngL-1), the organophosphorus (malathion in 54% of the samples up to 320ngL-1), and the ureas (diuron in 54% of the samples up to 159ngL-1). However, this pattern differed in sediments and biota, which were contaminated primarily with organophosphorus (higher Kow) (chlorpyrifos 93% of se…

Comparison of gas and liquid chromatography coupled to mass spectrometry for the residue analysis of pesticides in organges

Liquid chromatography-mass spectrometry (LC-MS) with atmospheric pressure chemical ionization (APCI), and gas chromatography-mass spectrometry (GC-MS) with electron impact ionization (EI), are compared for the determination of eight pesticides in oranges. Seven of the selected pesticides, chlorpyriphos, chlorpyriphos-methyl, imazalil, α and β-endosulfan, endosulfan sulphate and dicofol, are commonly determined by GC whereas one, thiabendazole, can only be directly determined by LC. Primary ions [M-H]− or [M-Cl+O]− are obtained using LC-APCI-MS in negative ionization (NI) mode. In contrast, a high degree of fragmentation is reported with GC-MS. Both techniques were applied to oranges, which …

Sequential window acquisition of all theoretical fragments versus information dependent acquisition for suspected-screening of pharmaceuticals in sediments and mussels by ultra-high pressure liquid chromatography-quadrupole time-of-flight-mass spectrometry

The aquatic ecosystems are dynamic environments often affected directly or indirectly by a myriad of anthropogenic contaminants that need to be properly identified. In this study, liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS) suspected-screening was applied to mussels and riverine sediment both, non-spiked and spiked with a mixture of 32 pharmaceuticals. Three data acquisition methods –sequential window acquisition of all theoretical fragment-ion spectra (SWATH), in fix (FSWATH) and variable (VSWATH) window modes and Information Dependent Acquisition (IDA)– were compared to determine the most suitable acquisition technique. The results obtained in the spike…

Current anthropogenic pressures on agro-ecological protected coastal wetlands

Coastal wetlands are areas that suffer from great pressure. Much of it is due to the rapid development of the surrounding artificial landscapes, where socio-economic factors lead to alterations in the nearby environment, affecting the quality of natural and agricultural systems. This work analyses interconnections among landscapes under the hypothesis that urban-artificial impacts could be detected on soils and waters of an agro-ecological protected area, L'Albufera de Valencia Natural Park, located in the vicinity of the City of Valencia, Spain. The methodological framework developed addresses two types of anthropogenic pressure: (1) direct, due to artificialisation of soil covers that cau…

Evaluation of solid-phase extraction and stir-bar sorptive extraction for the determination of fungicide residues at low-microg kg(-1) levels in grapes by liquid chromatography-mass spectrometry.

Abstract A liquid chromatography–mass spectrometry method has been developed for determining bitertanol, carboxin, flutriafol, pyrimethanil, tebuconazole and triadimefon. The evaluation of both atmospheric pressure interfaces (API), atmospheric pressure chemical ionization (APCI) and electrospray (ESI) using positive and negative ionization modes, clearly shows that the studied pesticides are more sensitive using APCI in positive mode. Two procedures based on solid-phase extraction (SPE) and stir-bar sorptive extraction (SBSE) have been assessed for extracting these compounds in grape. The recoveries obtained by SPE in samples spiked at the limit of quantification (LOQ) level ranged from 60…

Monitoring of five postharvest fungicides in fruit and vegetables by matrix solid-phase dispersion and liquid chromatography/mass spectrometry

Abstract A method was developed for monitoring dichloran, flutriafol, o-phenylphenol, prochloraz, and tolclofos-methyl in fruits and vegetables, using matrix solid-phase dispersion and liquid chromatography with mass spectrometry detection. The method was used to determine fungicide content in 200 samples of chards, onions, peppers, bananas, lemons, and oranges. Of the samples examined, 54% contained o-phenylphenol with concentrations ranging from 0.005 to 3.34 mg/kg and 35% showed prochloraz in the range of 0.06–1.95 mg/kg. Dichloran, flutriafol, and tolclofos-methyl were detected only occasionally. Only 4% of the samples exceeded the European Union maximum residue limits. The pesticides i…

Simultaneous determination of different classes of antibiotics in fish and livestock by CE-MS

A specific CE-MS method was developed for the simultaneous determination of 12 antibacterial residues (four sulfonamides: sulfamethazine, sulfathiazole, sulfadiazine, and sulfachlorpyridazine; four beta-lactams: amoxicillin, ampicillin, oxacillin, and penicillin V, and four quinolones: danofloxacin, enrofloxacin, ofloxacin, and flumequine) in fish and livestock. Separation conditions, sheath liquid composition and electrospray parameters were optimized to obtain adequate CE separation and a high sensitivity. CE employed a 75 cm long fused-silica capillary (50 cm thermostated plus 25 cm at room temperature) 75 microm id and a 60 mM ammonium acetate separation buffer at pH 8 with 10% of metha…

Capillary electrophoresis for analyzing pesticides in fruits and vegetables using solid-phase extraction and stir-bar sorptive extraction.

Two procedures based on solid-phase extraction (SPE) and stir-bar sorptive extraction (SBSE) in combination with micellar electrokinetic chromatography (MEKC)--diode array detection (DAD) were compared for the simultaneous extraction of acrinathrin, bitertanol, cyproconazole, fludioxonil, flutriafol, myclobutanil, pyriproxyfen, and tebuconazole in lettuce, tomato, grape, and strawberry. Selectivity and resolution of the MEKC procedure were studied changing the pH and the molarity of the buffer, the type and the concentration of surfactant, and the methanol content in the mobile phase. A buffer consisting of 6 mM sodium tetraborate decahydrate with 75 mM of cholic acid sodium solution (pH 9.…

Determination of five pesticide residues in oranges by matrix solid-phase dispersion and liquid chromatography to estimate daily intake of consumers.

Abstract Residues of benzoylphenylurea insecticides (diflubenzuron, hexaflumuron, and flufenuxuron), carboxamide acaricides (hexythiazox), and carbamate insecticides (benfuracarb) were determined in 150 orange fruit samples from September 1998 to June 1999, to estimate exposure of the Valencian population to oranges contaminated with these newly developed pesticides. The method for monitoring these residues is based on matrix solid-phase dispersion and liquid chromatography with UV or atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) detection. Orange samples representing 11 varieties were collected from an agricultural cooperative and examined for the 5 pesticides. In 74…

The expanding role of LC-MS in analyzing metabolites and degradation products of food contaminants

Abstract Liquid chromatography-mass spectrometry (LC-MS) has contributed significantly in advancing research in the analysis of metabolites and degradation products of food contaminants. Of particular interest is the comprehensive application of LC-MS to discovery of degradation products and metabolites. This review, covering research published between 2003 and 2008, describes how LC-MS has been used in this field, with the majority of work dealing with target-metabolite analysis and only a small fraction using LC-MS comprehensively. In considering the significance of this topic and the potential interest in it, we briefly describe state-of-the art mass analyzers applied for it (QtrAP, QqTO…

Suspect, non-target and target screening of emerging pollutants using data independent acquisition: Assessment of a Mediterranean River basin

A single workflow based on three approaches (target, suspected and non-target screening) using liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS) in data independent acquisition mode (DIA) was developed to assess the presence of emerging pollutants (EPs) in water and sediments from a Mediterranean River Basin. Identification of potential contaminants was based on mass accuracy, isotopic ratio pattern, theoretical fragmentation, and retention time using Waters UNIFI software. In the suspect screening against a library containing 2200 components, 68 contaminants were tentatively identified, 6 of which were confirmed and quantified with analytical standar…

Analysis of perfluoroalkyl substances in waters from Germany and Spain

Water has been identified as one of the main routes of human exposure to perfluoroalkyl substances (PFASs). This work assessed the presence of 21 PFASs along the whole water cycle using a new fast and cost effective analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated for different types of matrices (ultrapure water, tap water and treated wastewater). The quality parameters for the 21 selected compounds presented good limits of detection (LOD) and quantification (LOQ) ranging, in general, from 0.83-10 ng/L to 2.8-50 ng/L, respectively. The method was applied to assess the occurrence …

Determination of organic contaminants in food by capillary electrophoresis

This review addresses recent advances in the analysis of organic contaminants, such as antibiotics, pesticides, biological toxins, and food-borne pathogens, in foods by capillary electrophoresis (CE). Special attention is paid to those aspects that increase sensitivity and/or selectivity, such as sample extraction and concentration, on-line preconcentration techniques (stacking), affinity capillaries or/and specific detectors (laser induced fluorescence (LIF), mass spectrometry (MS)). The various CE modes used to separate the compounds and the quantification strategies are also examined. As a result, this work presents an updated overview on the principal applications of CE, together with a…

Control of pesticide residues by liquid chromatography-mass spectrometry to ensure food safety.

Liquid chromatography-mass spectrometry (LC-MS) has become an invaluable technique for the control of pesticide residues to ensure food safety. After an introduction about the regulations that highlights its importance to meet the official requirements on analytical performance, the different mass spectrometers used in this field of research, as well as the LC-MS interfaces and the difficulties associated with quantitative LC-MS determination, are discussed. The ability to use practical data for quantifying pesticides together with the option of obtaining structural information to identify target and non-target parent compounds and metabolites are discussed. Special attention is paid to the…

Evaluation of a solid-phase extraction system for determining pesticide residues in milk.

Abstract A simple and rapid procedure based on reversed solid-phase extraction with octadecylsilica was developed for determining chlorinated pesticide residues in milk. The need for an agent that breaks the fat globules was first investigated and the method variables were optimized on whole homogenized milk (3.6% fat content). Recovery experiments performed for 26 organochlorine pesticides at levels of 3–40 μg/l gave > 80% recoveries for all the compounds. The method was validated and evaluated by comparison with two widely used liquid-liquid extraction methods. The performance was checked by analysis of a certified standard with natural low endogenous levels (CMR 187) and different kinds …

Analysis of psychoactive substances in water by information dependent acquisition on a hybrid quadrupole time-of-flight mass spectrometer.

Emerging drugs of abuse, belonging to many different chemical classes, are attracting users with promises of “legal” highs and easy access via internet. Prevalence of their consumption and abuse through wastewater-based epidemiology can only be realized if a suitable analytical screening procedure exists to detect and quantify them in water. Solid-phase extraction and ultra-high performance liquid chromatography quadrupole time-of-flight-mass spectrometry (UHPLC–QqTOF–MS/MS) was applied for rapid suspect screening as well as for the quantitative determination of 42 illicit drugs and metabolites in water. Using this platform, we were able to identify amphetamines, tryptamines, piperazines, p…

Development and validation of a pressurized liquid extraction liquid chromatography–tandem mass spectrometry method for perfluorinated compounds determination in fish

Abstract This paper describes the development and validation of an analytical methodology to determine eight perfluorinated compounds (PFCs) in edible fish using pressurized liquid extraction (PLE) with water and solid-phase extraction (SPE) with an ion-exchanger as extraction and pre-concentration procedures, followed by liquid chromatography–quadrupole-linear ion trap mass spectrometry (LC–QqLIT–MS). The rapidity and effectiveness of the proposed extraction procedure were compared with those most commonly used to isolate PFCs from fish (ion-pairing and alkaline digestion). The average recoveries of the different fish samples, spiked with the eight PFCs at three levels (the LOQ, 10 and 100…

Recent Advances in Sample Preparation for Pesticide Analysis

Much progress has been made in pesticide analysis in the past decade. During this time, hyphenated techniques involving highly efficient separation with sensitive mass spectrometric detection have become the methods of choice. Even with such powerful instrumental techniques, a demanding task in pesticide residue analysis is the development of multiresidue methods for the determination of pesticides in air, water, soil, sediment, biota, and food. This chapter summarizes the analytical characteristics of the different methods of sample preparation for the determination of pesticide residues in a variety of food matrices, and surveys their recent applications in combination with gas chromatogr…

Advanced Sample Preparation Techniques for MS Analysis

Pesticide residues in honey bees, pollen and beeswax: Assessing beehive exposure

In order to study the distribution of pesticide residues in beekeeping matrices, samples of live in-hive worker honey bees (Apis mellifera), fresh stored pollen and beeswax were collected during 2016–2017 from 45 apiaries located in different landscape contexts in Spain. A total of 133 samples were screened for 63 pesticides or their degradation products to estimate the pesticide exposure to honey bee health through the calculation of the hazard quotient (HQ). The influence of the surrounding environment on the content of pesticides in pollen was assessed by comparing the concentrations of pesticide residues found in apiaries from intensive farming landscapes to those found in apiaries loca…

Efficiency of QuEChERS approach for determining 52 pesticide residues in honey and honey bees

A comparison between QuEChERS and other pesticide extraction procedures for honey and honey bee matrices is discussed. Honey bee matrix was extracted by solvent based procedure whereas solid phase extraction was the protocol for the honey matrix. The citrate buffered QuEChERS method was used for both matrices. The methods were evaluated regarding cost (equipment and reagents), time, accuracy, precision, sensitivity and versatility. The results proved that the QuEChERS protocol was the most efficient method for the extraction of the selected pesticides in both matrices. QuEChERS is the most economical and less time-consuming procedure.SPE and solvent-based extraction procedures show equivale…

Last trends in pesticide residue determination by liquid chromatography–mass spectrometry

Liquid chromatography–mass spectrometry (LC–MS) is as an excellent analytical tool in the determination of pesticides. Multiresidue analysis of these compounds at trace levels is one of the oldest analytical schemes within environmental and food safety. However, the issue of “pesticide residue determination” is still a hot topic for the analytical community. This review discusses current approaches and recent advances in using LC–MS for pesticide identification and quantification. We outline how MS has influenced the sample preparation process. We critically assess and compare various mass spectrometers, highlighting their strengths and limitations. We, then, review the main applications of…

Dietary Calcium Intake and Adherence to the Mediterranean Diet in Spanish Children: The ANIVA Study

The aim of this study was to evaluate the relationship of dietary calcium intake with anthropometric measures, physical activity and adherence to the Mediterranean diet (MedDiet) in 1176 Spanish children aged 6–9 years. Data were obtained from “Antropometría y Nutrición Infantil de Valencia” (ANIVA), a cross-sectional study of a representative sample. Dietary calcium intake assessed from three-day food records was compared to recommended daily intakes in Spain. Anthropometric measures (weight and height) were measured according to international standards and adherence to the MedDiet was evaluated using the Mediterranean Diet Quality Index (KIDMED) test. For the total sample of children, 25.…

Spatial differences and temporal changes in illicit drug use in Europe quantified by wastewater analysis

Aims To perform wastewater analyses to assess spatial differences and temporal changes of illicit drug use in a large European population. Design Analyses of raw wastewater over a 1-week period in 2012 and 2013. Setting and Participants Catchment areas of wastewater treatment plants (WWTPs) across Europe, as follows: 2012: 25 WWTPs in 11 countries (23 cities, total population 11.50 million); 2013: 47 WWTPs in 21 countries (42 cities, total population 24.74 million). Measurements Excretion products of five illicit drugs (cocaine, amphetamine, ecstasy, methamphetamine, cannabis) were quantified in wastewater samples using methods based on liquid chromatography coupled to mass spectrom…

Analysis and Prevention of Microplastics Pollution in Water: Current Perspectives and Future Directions

The analysis, prevention, and removal of microplastics (MPs) pollution in water is identified as one major problem the world is currently facing. MPs can be directly released to water or formed by the degradation of bigger plastics. Nowadays, it is estimated that annually between 4 and 12 million tonnes of plastic go into the seas and oceans-with a forecast for them to outweigh the amount of fish in 2050. Based on the existing studies, the characterization of MPs in waters is still one of the remaining challenges because they can be easily confused with organic or other types of matter. Consequently, there is an urgent necessity to establish pathways for the chemical identification of the M…

Confirmation of Fenthion Metabolites in Oranges by IT-MS and QqTOF-MS

14 pages, 4 figures, 4 tables.-- PMID: 18020315 [PubMed].-- Printed version published Dec 15, 2007.

Determination of carbamate residues in fruits and vegetables by matrix solid-phase dispersion and liquid chromatography-mass spectrometry.

Abstract Thirteen carbamates were analysed in orange, grape, onion and tomatoes by matrix solid-phase dispersion (MSPD) followed by liquid chromatography–mass spectrometry (LC–MS). Electrospray (ES) and atmospheric pressure chemical ionisation (APCI) were compared and both gave similar results in terms of sensitivity and structural information because at 20 V fragmentor voltages the fragmentation is minimal. The efficiency of different solid-phases (C18, C8, cyano, amine and phenyl) for the MSPD was compared. Mean recoveries using C8 varied from 64 to 106% with relative standard deviations of 5–15% in the concentration range of 0.01–10 mg kg−1. Matrix constituents did not interfere signific…

Development of an improved method for trace analysis of quinolones in eggs of laying hens and wildlife species using molecularly imprinted polymers.

A sensitive, selective, and efficient method was developed for simultaneous determination of 11 fluoroquinolones (FQs), ciprofloxacin, danofloxacin, difloxacin, enrofloxacin, flumequine, marbofloxacin, norfloxacin, ofloxacin, oxolinic acid, pipemidic acid, and sarafloxacin, in eggs by molecularly imprinted polymer (MIP) and column liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). Samples were diluted with 50 mM sodium dihydrogen phosphate at pH 7.4, followed by purification with a commercial MIP (SupelMIP SPE-Fluoroquinolones). Recoveries for the 11 quinolones were in the range of 90-106% with intra- and interday relative standard deviation ranging from …

Microplastics in the global aquatic environment: Analysis, effects, remediation and policy solutions

This opinion paper reports on Microplastics (MPs) pollution in the aquatic environment. MPs are a global problem being detected everywhere: marine environment, wastewaters, surface waters, soils, sediments, food and air. MPs can also absorb organic contaminants, and can be ingested by organisms and introduced into the food web. MPs can be a vector as well of pathogens whereas airborne fibrous MPs may enter our respiratory system with risk to the environment and humans. Main issues and gaps related to MPs on-going and future research are highlighted: chemical analysis, fate in wastewater and drinking water treatment plants, environmental and human health effects as well as remediation strate…

The Role of the Liquid Chromatography-Mass Spectrometry in Pesticide Residue Determination in Food

The use of liquid chromatography (LC) in pesticide residue determination was usually limited to groups of compounds or single compounds for which no suitable gas chromatographic (GC) conditions were available. However, recent developments have significantly enlarged the LC scope in this field of analysis. One of the most important advances was the on-line coupling of efficient LC separation with mass spectrometry detectors (LC-MS and LC-MS/MS) that makes this technique an excellent method for the determination of pesticides and their transformation products in complex matrices such as food. This review considers the application of LC-MS/MS in this field. Emphasis is placed on the tandem MS …

Solid-Phase Microextraction Liquid Chromatography/Tandem Mass Spectrometry To Determine Postharvest Fungicides in Fruits

A method to determine five postharvest fungicides (dichloran, flutriafol, o-phenylphenol, prochloraz, tolclofos methyl) in fruits (cherries, lemons, oranges, peaches) has been developed using solid-phase microextraction (SPME) coupled to liquid chromatography (LC) with photodiode array (DAD), mass spectrometry (MS), or tandem mass spectrometry (MS/MS) with ion trap detection. Extraction involved sample homogenization with an acetone/water solution (5:1), filtration, and acetone evaporation prior to fiber extraction. The pesticides were isolated with a fused-silica fiber coated with 50-microm Carbowax/template resin. The effects of pH, ion strength, sample volume, and extraction time were in…

Determination of amitraz and its transformation products in pears by ethyl acetate extraction and liquid chromatography-tandem mass spectrometry.

A method has been developed for identification and quantification of the acaricide amitraz and its transformation products, 2,4-dimethylaniline (DMA), 2,4-dimethylformamidine (DMF) and N-2,4-dimethylphenyl-N-methylformamidine (DMPF) in pears. The analytes were extracted using ethyl acetate and anhydrous sodium sulphate. Analysis was performed by liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) in the positive ion mode using a triple quadrupole (QqQ) instrument. Two precursor-product ion transitions were monitored for each compound in the selected reaction monitoring (SRM) mode. The method was validated with pears taken from the orchard before the amitraz treatment …

Multi-residue determination of 47 organic compounds in water, soil, sediment and fish—Turia River as case study

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 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 mor…

Application of ultra-high pressure liquid chromatography linear ion-trap orbitrap to qualitative and quantitative assessment of pesticide residues

Abstract The analysis of pesticides residues using a last generation high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometer (LTQ-Orbitrap-MS) was explored. Pesticides were extracted from fruits, fish, bees and sediments by QuEChERS and from water by solid-phase with Oasis HLB cartridges. Ultra-high pressure liquid chromatography (UHPLC)–LTQ-Orbitrap mass spectrometer acquired full scan MS data for quantification, and data dependent (dd) MS 2 and MS 3 product ion spectra for identification and/or confirmation. The regression coefficients ( r 2 ) for the calibration curves (two order of magnitude up to the lowest calibration level) in the study were ≥0.99. Th…

Pesticides in the Ebro River basin: Occurrence and risk assessment

In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 2…

Real-time quantitative PCR of Staphylococcus aureus and application in restaurant meals.

Staphylococcus aureus is considered the second most common pathogen to cause outbreaks of food poisoning, exceeded only by Campylobacter. Consumption of foods containing this microorganism is often identified as the cause of illness. In this study, a rapid, reliable, and sensitive real-time quantitative PCR was developed and compared with conventional culture methods. Real-time quantitative PCR was carried out by purifying DNA extracts of S. aureus with a Staphylococcus sample preparation kit and quantifying it in the LightCycler system with hybridization probes. The assay was linear from a range of 10 to 10(6) S. aureus cells (r2 > 0.997). The PCR reaction presented an efficiency of >85%. …

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…

Analysis of pesticides in fruits by pressurized liquid extraction and liquid chromatography-ion trap-triple stage mass spectrometry.

A multi-residue method using pressurized liquid extraction (PLE) and liquid chromatography-quadrupole ion trap-triple stage mass spectrometry (LC-IT-MS(3)) has been developed for determining trace levels of pesticides in fruits. The selected pesticides can be distinguished in: benzimidazoles and azoles, organophosphorus, carbamates, neonicotinoids, and acaricides. PLE has been optimized to extract these pesticide residues from oranges and peaches by studying the effect of experimental variables on PLE efficiency. Samples were extracted at high temperature and pressure (75 degrees C and 1500psi) using ethyl acetate as extraction solvent and acidic alumina as drying agent. The recoveries obta…

Determination of carbosulfan and its metabolites in oranges by liquid chromatography ion-trap triple-stage mass spectrometry.

Liquid chromatography ion-trap mass spectrometry LC-MSn has been successfully applied to identify and confirm carbosulfan and seven of its metabolites in oranges after pressurized liquid extraction (PLE) with dichloromethane. Mass spectra of carbosulfan and its metabolites were investigated using multiple stages of mass spectrometry. Although interpretation of the fragmentation pathways, based on mass spectra, enables structural elucidation and identification of these compounds, the proposed fragmentation pathways and ion structures need verification by exact mass measurements. The analytical method--PLE and LC-MS3 --was validated: limits of quantification (LOQ) ranged from 0.01 to 0.07 mg …

Micro(Nano)plastic analysis: a green and sustainable perspective

Within the last years aspects such as green, eco-friendly and sustainable are making their way into analytical chemistry. The field has changed with the introduction of these concepts. Information on the consumption of toxic solvents and energy is now a part of everyday life. This green analytical chemistry could be playing a pioneering role in the analysis of micro(nano)plastics in the environment. We discuss the roles of green analytical and sustainability within micro(nano) plastics determination and its possible applications. We explain its many advantages, like their function to preserve the environment and operator health or their role in the so-called eco-friendly methodologies, but …

Infant exposure of perfluorinated compounds: Levels in breast milk and commercial baby food

In this study, an analytical method to determine six previous termperfluorinatednext term compounds (PFCs) based on alkaline digestion and solid phase extraction (SPE) followed by liquid chromatography-quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS) was validated for the analysis of human breast milk, milk previous terminfantnext term formulas and cereals baby food. The average recoveries of the different matrices were in general higher than 70% with a relative standard deviation (RSD) lower than 21% and method limits of detection (MLOD) ranging from 1.2 to 362 ng/L for the different compounds and matrices. The method was applied to investigate the occurrence of PFCs in 20 sample…

Advanced Mass Spectrometry

Abstract Until recently, analytical methods for food safety and quality control had mainly been focused on restricted lists of well-known analytes. Nowadays, in addition to these classical methods, comprehensive analysis attains authentication as well as the detection of hazardous or safety-relevant manipulations and violations of the laws (e.g., addition of nonauthorized substances or application of technological processes prohibited is of urgent need in food control). This chapter shows that high resolution mass spectrometry (HRMS) associated with the data mining tools developed for metabolomics can address this issue by enabling (1) targeted analyses, (2) detection of untargeted and unkn…

Nanomaterials in Food, Which Way Forward?

Abstract Nanotechnology has emerged as one of the most innovative technologies occurred in decades and has the potential to improve food quality and safety. At present, there are also a few studies demonstrating that nanomaterials (NMs) are not inherently benign. This chapter highlights some current applications of NMs in food, food additives and food contact materials and reviews analytical approaches suitable to address food safety-related issues of nanotechnology. As starting point, discussion on the current regulatory situation of nanotechnology in relation to food is addressed, followed by a detailed description of sample preparation aspects, separation methods (e.g. field-flow fractio…

Perfluoroalkyl substances in Breast milk, infant formula and baby food from Valencian Community (Spain)

Environmental and human exposures to perfluoroalkyl substances (PFASs) are of emerging concern since they are persistent and bioaccumulative. The present study reports PFASs levels in human milk, infant formulas and baby food (dry cereals and pots) from the Valencian Community (Spain) in order to evaluate the infant exposure to these substances through the diet. The results show that perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA) were in all the samples of the four selected matrices (except PFOA in one sample of dry cereal baby food). Perfluoroheptanoic acid (PFHpA) and perfluorodecanoic acid (PFDA) were also detected in 70% of the breast milk samples. In infant formulas, P…

Evaluation of the Fate of Aldicarb and Its Metabolites in Oranges

Abstract The accumulation, persistence and fate of systemic pesticide aldicarb was melencholy evaluated in orange crops. The concentration of this pesticide and its two toxic metabolites, aldicarb sulfoxide and aldicarb sulfone was determined in leaves, rind and pulp of three orange varieties (Satsuma, Navelina and Clemetina de Nules) and in the top soil of the orange groves. The groves were located in two different places in the Valencia Community (Spain). The analysis showed that the aldicarb concentration was lower than those of aldicarb sulfoxide and aldicarb sulfone. In all cases, the residues persisted at least 160 days in vegetable samples and between 157 and 227 days in soil samples…

Emerging contaminants related to the occurrence of forest fires in the Spanish Mediterranean

Forest fires can be a source of contamination because, among others, of the use of chemicals to their extinction (flame retardants, FRs), or by the production of Polycyclic Aromatic Hydrocarbons (PAHs) derived from high temperature alteration of organic matter. Up to our knowledge, this study is the first to assess the direct (PAHs 16 on the USA EPA's priority list), and indirect [tri- to hepta- brominated diphenyl ethers (PBDEs), organophosphorus flame retardants (PFRs) and perfluoroalkyl substances (PFASs)] contamination related to forest fires. The abundance and distribution of these contaminants were monitored on two Mediterranean hillslopes, one burned and one unburned, near Azuébar (S…

Analysis of 18 perfluorinated compounds in river waters: Comparison of high performance liquid chromatography–tandem mass spectrometry, ultra-high-performance liquid chromatography–tandem mass spectrometry and capillary liquid chromatography–mass spectrometry

In this work, the performance of ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) and capillary liquid chromatography-mass spectrometry (CLC-MS) has been studied for the analysis of eighteen perfluorinated compounds in water samples. UHPLC-MS/MS and CLC-MS analysis were carried out using a Zorbax C-18 column (50 mm × 2.1 mm, 1.8 μm) and a Zorbax SB-C18 column (150 mm × 0.5 mm, 3.5 μm), respectively, in gradient elution mode with a mobile phase of ammonium formate and methanol. Both techniques were compared with conventional LC-MS/MS in terms of speed, sensitivity, selectivity and resolution. Water samples were extracted by solid phase extraction (SPE). Mea…

Profiling of compounds and degradation products from the postharvest treatment of pears and apples by ultra-high pressure liquid chromatography quadrupole-time-of-flight mass spectrometry

This study deals with a simple strategy to pinpoint potential unknown compounds in full scan mass spectrometry (MS) experiments. Forty samples of apples and pears intended for human consumption were analyzed by ultra-high performance liquid chromatography quadrupole-time-of-flight (UPLC–QqTOF-MS), after extraction of the possible contaminants by rinsing the peel of the fruit with ethyl acetate. The peaks were visually recognized in the total ion chromatogram (TIC). Two major types of postharvest treatments were detected in this set of samples: imazalil (IMZ)/ethoxyquin (EQ) and thiabendazole (TBZ)/diphenylamine (DPA). The present work also describes the metabolites formed by degradation of …

Prospects for combining chemical and biological methods for integrated environmental assessment

Abstract Inherently interdisciplinary, environmental assessment applied to contamination is evolving rapidly, despite associated uncertainties in methodologies and data limitations. Mixtures of known and unknown pollutants can cause toxic effects in the environment. Besides deploying a chemicals-driven strategy for the ecological risk assessment of the pollutants, it is necessary to apply and to explore biological strategies. Consequently, bioassays, biosensors and effect-directed analysis (EDA) to identify pollutants responsible of particular effects have become increasingly important. We give a broad overview of how to assess biological monitoring of ecosystems and chemical monitoring of …

Ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry to identify contaminants in water: an insight on environmental forensics.

Ultra-high pressure liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QqTOF-MS) acquiring full scan MS data for quantification, and automatic data dependent information product ion spectra (IDA-MS/MS) without any predefinition of the ions by the user was checked for identifying organic contaminants in water samples. The use of a database with more than 2000 compounds achieved high confidence results for a wide number of contaminants based upon retention time, accurate mass, isotopic pattern and MS/MS library searching. More than 20 contaminants, mostly pharmaceuticals, but also mycotoxins and polyphenols were unambiguously identified. Furthermore, the combination of s…

Determination of pharmaceuticals in soils and sediments by pressurized liquid extraction and liquid chromatography tandem mass spectrometry

13 páginas, 4 figuras, 6 tablas.

Analytical utility of quadrupole time-of-flight mass spectrometry for the determination of pesticide residues in comparison with an optimized column high-performance liquid chromatography/tandem mass spectrometry method.

Abstract A multiresidue method for the analysis of 30 pesticides with different physicochemical properties in fruits and vegetables was developed. The method involves a rapid and small-scale extraction procedure based on matrix solid-phase dispersion using octadecylsilyl (C18) as the dispersant and dichloromethane as the eluent. The target pesticides were determined using column high-performance liquid chromatography/triple quadrupole-tandem mass spectrometry (LC/QqQ-MS/MS). The method was validated for sensitivity, linearity, reproducibility, and accuracy. A recovery study was conducted at 3 different levels, and the average ranged from 74 to 99 for all of the studied compounds, with relat…

Liquid chromatography-mass spectrometry

Can a healthy life prevent us from post-menopausal osteoporosis? Myths and truths

Abstract Postmenopausal osteoporosis is related to unmodifiable risk factors (genetics, race, gender and age). However, other controllable factors such as activity, body mass, hormone and calcium levels and dietary habits can reduce fracture risk. For example, significant increases in bone mass density have been linked to physical activity in children, supplements of Vitamin C taken for more than 10 years, or high consumption of fish, olive oil or dried plums. This review establishes the scientific basis behind these non-pharmaceutical practices and summarizes a number of basic studies and clinical trials involving them as well as discusses their potential for the osteoporosis treatment. A …

Solid phase techniques in the extraction of pesticides and related compounds from foods and soils

The application of SPE technology to the isolation of pesticides and related compounds from food and soils has grown enormously in the last decade. Much of this growth has been due to the relative ease of sample handling and the wide range of solid supports currently available for a variety of applications. The aim of this review is to present the methods for solid phase extraction (SPE) of pesticide residues from soils and foods. There are three main areas according to the type of approach used to handle the sample: solid phase extraction, solid phase clean-up (SPC), and matrix solid phase dispersion (MSPD). This review covers milk products, fatty foods, fruits, vegetables, and soils. Soli…

Comparison of different removal techniques for selected pharmaceuticals

[EN] Recently, there is an emergence of endocrine-disrupting compounds, pharmaceuticals, and personal care products (EDC/PPCPs) as important pollutants to remove from drinking water and reclaimed wastewater. In this work, the efficiency of removing pharmaceuticals (PCs) from model aqueous solutions and raw wastewater with ultrafiltration (UF), nanofiltration (NF), activated carbon adsorption (AC), biological methods (SBR) and oxidation with ClO2 was investigated. Some treatments have also been used as combined processes: UF + NF, UF +AC, SBR + ClO2. Ibuprofen, Acetaminophen, Diclofenac, Sulfamethoxazole, Clonazepam, and Diazepam were selected as model compounds. In order to evaluate their r…

Perfluorinated Compounds in Food: A Global Perspective

Perfluorinated compounds (PFCs) are resistant to breakdown and are turning up in unexpected places around the world, becoming emerging food contaminants. Although these chemicals have been used in countless products since the 1950s, they have been subject to little control until now. There is still an insufficient knowledge of their sources, occurrence, and hazards for food safety decision making. This article provides a comprehensive review of the food contamination levels and dietary intake risks posed by PFCs, as well as the specific methods developed for their determination. It is based on the evaluation of the published literature between 2004 and the beginning of 2010, with special em…

Quantification of Listeria monocytogenes in salads by real time quantitative PCR

Abstract A real time quantitative PCR (RTQ-PCR) was carried out purifying DNA extracts of Listeria monocytogenes using a High Pure Listeria Sample Preparation Kit and quantifying in a LightCycler system with hybridisation probes. A standard curve was constructed with serial dilutions. A range linear relationship, from 10 to 10 5 L. monocytogenes colony forming units (CFU), was observed between threshold cycle ( C t ) and logarithmic concentration of the serial dilutions. The assay was linear in a range from 10 to 10 5 L. monocytogenes CFU and the coefficient of determination ( r 2 ) was > 0.98. RTQ-PCR presented an efficiency of > 85%. The accuracy of the PCR-based assay, expressed as % bia…

Analytical strategies to determine quinolone residues in food and the environment

23 páginas, 5 figuras, 5 tablas.

Analysis of the presence of perfluoroalkyl substances in water, sediment and biota of the Jucar River (E Spain). Sources, partitioning and relationships with water physical characteristics.

The presence, sources and partitioning of 21 perfluoroalkyl substances (PFASs: C4–C14, C16, C18 carboxylate, C4, C6–C10 sulfonates and C8 sulfonamide) were assessed in water, sediment, and biota of the Jucar River basin (E Spain). Considering the three matrices, perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (PFOS) were the most frequent compounds, being remarkable the high occurrence of short-chain PFASs (C≤8), which are intended to replace the long-chain ones in several industrial and commercial applications. In general, all samples were contaminated with at least one PFAS, with the exception of three fish samples. Mean concentrations detected in sediments (0.22–11.5 ng g−1) an…

Analysis of insecticides in honey by liquid chromatography–ion trap-mass spectrometry: Comparison of different extraction procedures

The feasibility of different extraction procedures was tested and compared for the determination of 12 organophosphorus and carbamates insecticides in honey samples. In this sense, once the samples were pre-treated - essentially dissolved in hot water by stirring - and before they could be analyzed by liquid chromatography-ion trap-second stage mass spectrometry (LC-MS(2)), four different approaches were studied for the extraction step: QuEChERS, solid-phase extraction (SPE), pressurized liquid extraction (PLE) and solid-phase microextraction (SPME). The main aim of this work was to maximise the sensitivity of pesticides and to minimise the presence of interfering compounds in the extract. …

Treatments for post-menopausal osteoporotic women, what's new? How can we manage long-term treatment?

Since the mid-1980s, postmenopausal osteoporosis (PMO) has been considered a serious public health concern because of the associated fractures. Pharmacological therapies that effectively reduce the number of fractures by improving bone mass have been and are being developed continuously. Most current agents inhibit bone loss by reducing bone resorption, but emerging therapies may increase bone mass by stimulating bone formation. Furthermore, nowadays, the most representative pharmaceuticals have been prescribed long enough to include the reporting of some adverse effects. This review discusses osteoporotic drugs that are approved or are under investigation for the treatment of post-menopaus…

Mass Spectrometry in Food Quality and Safety

Abstract In recent years, mass spectrometry has gained a wide recognition as a selective and fast technique for the analysis and assessment of a wide range of food products. The state of the art in the determination of safety and quality of food is presented to illustrate the capability of this technique for classification and grading, defect and disease detection, distribution and visualization of chemical attributes, and evaluations of overall quality of meat, fish, fruits, vegetables, and other food products. The features of mass spectrometry for each category were summarized in the aspects of the investigated quality and safety attributes, the used systems (triple quadrupole, quadrupole…

Estimation of alcohol consumption during >Fallas> festivity in the wastewater of Valencia city (Spain) using ethyl sulfate as a biomarker

Alcohol consumption has been increasing in the last years and it has become a sociological problem due its derived health and safety problems. Ethyl sulfate is a secondary metabolite of the alcohol degradation that is excreted through the urine (0.010-0.016%) after alcohol ingestion and it is quite stable in water. In this study, a new methodology to determine ethyl sulfate by ion-pair liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. Different ion-pairs and additives were tested directly in the sample extracts or in the mobile phase. The best ion-pair was set up adding 0.5M of tributylamine and 0.1% of formic acid to the sample. The limit of quantification was 0.3μgL…

Transcriptomic, biochemical and individual markers in transplanted Daphnia magna to characterize impacts in the field

Daphnia magna individuals were transplanted across 12 sites from three Spanish river basins (Llobregat, Ebro, Jucar) showing different sources of pollution. Gene transcription, feeding and biochemical responses in the field were assessed and compared with those obtained in re-constituted water treatments spiked with organic eluates obtained from water samples collected at the same locations and sampling periods. Up to 166 trace contaminants were detected in water and classified by their mode of action into 45 groups that included metals, pharmaceuticals, pesticides, illicit drugs, and other industrial compounds. Physicochemical water parameters differentiated the three river basins with Llo…

Liquid chromatography–mass spectrometry as a tool for wastewater-based epidemiology: Assessing new psychoactive substances and other human biomarkers

Wastewater-based epidemiology (WBE) started to develop significantly in the last 8 years due, in part, to the advance of liquid chromatography–mass spectrometry (LC–MS). Its initial objective ― to estimate the consumption of illicit drugs ― has been expanded to new psychoactive substances (NPS) and other human biomarkers of health, lifestyle and disease. The purpose of this review is to introduce recent methods and outstanding challenges in the application of LC–MS to these new targets, including target, suspect and non-target screening and, outline the workflows developed for discovering metabolites of NPS and biomarkers. Further, we discuss a number of specific methodological challenges t…

Determination of microcystins in fish by solvent extraction and liquid chromatography

A liquid chromatography electrospray mass spectrometry (LC/ESI/MS) method has been developed to identify and quantify microcystins in fish liver and intestine. Microcystins (MCs) were extracted from 500 mg sample with methanol-water (85:25, v/v) and the extracts concentrated to 250 microl. The parameters were optimized by a full factorial 2(3) design. Neither laborious pre-treatment nor clean up were necessary. MCs were separated using conventional C18 column and an acetonitrile-acidified water (pH 3) gradient. Negative samples (without MCs) were discriminated by liquid chromatography diode array detection (LC/DAD). The limits of detection (LOD) and the limits of quantification (LOQ) result…

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…

Identification of unknown pesticides in fruits using ultra-performance liquid chromatography–quadrupole time-of-flight mass spectrometry

Abstract Ultra-high-performance liquid chromatography–quadrupole time-of-flight mass spectrometry (UPLC-QqTOF-MS) is an emerging technique offering more rapid and efficient separation, as well as the possibility to obtain accurate mass measurement and tandem mass spectrometry (MS/MS). This paper deals with the use of UPLC-QqTOF-MS to identify the pesticide residues present in complex pear extracts. Carbendazim, imazalil, and ethoxyquin were successfully identified because of the accurate mass determination of their protonated molecule and their major fragments in the product ion mass spectra. A few plastic and latex additives were also found, most of them probably coming from the packaging …

Environmental and food applications of LC-tandem mass spectrometry in pesticide-residue analysis: An overview

An overview is given on pesticide-residue determination in environmental and food samples by liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS). Pesticides comprise a large number of substances that belong to many completely different chemical groups, the only common characteristic is that they are effective against pests. They still constitute a challenge in MS because there is no collective pathway for fragmentation. A brief introduction to the theory of tandem MS permits a discussion of which parameters influence the ionization efficiency when the ions are subjected to different actions. Emphasis is placed on the different tandem MS instruments: triple and ion-trap quad…

Multi‐residue extraction to determine organic pollutants in mussel hemolymph

This study assesses the extraction of eleven pharmaceuticals, five pesticides, five perfluoroalkyl substances, and two illicit drugs in hemolymph from (Mytilus Galloprovincialis). Four extraction procedures using Phree™ Phospholipid Removal cartridges were tested using different volumes of methanol (400 and 600 μL) and acetonitrile (300 and 450 μL). The pollutants were determined by high-performance liquid chromatography–tandem mass spectrometry. The use of methanol gave several problems during the extraction procedure, such as longer times and sample loss. Three methods (acetonitrile 300 and 450 μL; and methanol 600 μL) were validated. Recoveries at three concentration levels (5, 50, and 1…

Analysis of perfluorinated compounds in sewage sludge by pressurized solvent extraction followed by liquid chromatography–mass spectrometry

Perfluorinated compounds (PFCs) are widely used in everyday life and one of the main recipients of these compounds is waste water treatment plants (WWTPs). Due to the structure and physicochemical properties of PFCs, these compounds could be redistributed from influent water to sludge. This work reports a new validated protocol for the analysis of 13 perfluorinated acids, 4 perfluorosulfonates and the perfluorooctanesulfonamide. The present work has been focused to develop a sensitive and robust method for the analysis of 18 PFCs in sewage sludge, based on pressurized solvent extraction (PSE) followed by solid phase extraction (SPE) clean-up, analytes separation by liquid chromatography and…

Pesticide residue determination in fruit and vegetables by liquid chromatography–mass spectrometry

An overview is given of pesticide residue determination in fruit and vegetables by liquid chromatography-mass spectrometry (LC-MS). Emphasis is placed on the thermospray, particle beam and atmospheric pressure ionization interfaces including advantages and drawbacks and typical detection limits. The capacity of each interface to provide useful data for identification/confirmation of analytes and the possibility of obtaining structural information for the identification of target and non-target compounds is discussed. Finally, sample preparation techniques are dealt with in relation to their influence on further LC-MS determination.

Occurrence of pesticide residues in Spanish beeswax

Beeswax from Spain was collected during 2016 to determine pesticide residues incidence. The 35 samples were divided in foundation, old combs, cappings or virgin beeswax to compare pesticide content between groups. Wax was screened for 58 pesticides or their degradation products by QuEChERS extraction and liquid chromatography mass spectrometry (LC-MS/MS). Beeswax was uniformly contaminated with acaricides and, to a much lesser extent, with insecticide and fungicide residues. Virgin followed by cappings were less contaminated than foundation and old combs beeswax. The miticides applied in-hive had a contribution to average pesticide load higher than 95%. Compounds widely used as acaricides, …

Comparison of green sample preparation techniques in the analysis of pyrethrins and pyrethroids in baby food by liquid chromatography–tandem mass spectrometry

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…

Ecotoxicity of sediments in rivers: Invertebrate community, toxicity bioassays and the toxic unit approach as complementary assessment tools

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-…

Low-Intensity Ultrasounds

Ultrasonics, showing increasing use in the food industry for both the analysis and modification of food products, is a rapidly growing field of research. The sound ranges employed can be divided into high-frequency, low-energy diagnostic ultrasounds and low-frequency, high-energy power ultrasounds. The former is usually used as a nondestructive, rapid, easy-to-automate, and relatively inexpensive analytical technique for quality assurance and process control with particular reference to physicochemical properties, such as composition, structure, and physical state of foods. Nowadays, power ultrasound is considered to be an emerging and promising technology for industrial food processing. Th…

Determination of triazines and organophosphorus pesticides in water samples using solid-phase extraction.

Abstract Octadecyl (C 18 )-bonded porous silica was evaluated for the extraction of triazine and organophosphorus pesticides from natural water. The extraction results showed an effective performance when 1 l of water was passed through small glass columns containing 500 mg of 50–100-μm C 18 bonded porous silica. The absorbed compounds were removed with ethyl acetate, evaporated to 200 μl and determined by gas chromatography. The overall average recoveries were greater than 85% except for dimethoate and trichlorfon. Application of this procedure to the analysis of natural water samples gave results that agree well with those obtained by solvent extraction methods.

Influence of pesticide use in fruit orchards during blooming on honeybee mortality in 4 experimental apiaries

Samples of dead honey bees (Apis mellifera L.) were collected periodically from 4 different locations during citrus and stone fruit trees blooming season to evaluate the potential impact of agrochemicals on honey bee death rate. For the determination of mortality, dead honey bee traps were placed in front of the experimental hives entrance located in areas of intensive agriculture in Valencian Community (Spain). A total of 34 bee samples, obtained along the monitoring period, were analyzed by means of QuEChERS extraction method and screened for 58 pesticides or their degradation products by LC-MS/MS. An average of four pesticides per honey bee sample was detected. Coumaphos, an organophosph…

Optimization of experimental conditions for the identification of pesticide mixtures on six GLC columns

Quantitative analysis of six pesticides in fruits by capillary electrophoresis-electrospray-mass spectrometry.

A method to identify and quantify six pesticide residues - dinoseb, pirimicarb, procymidone, pyrifenox, pyrimethanil, and thiabendazole - in peaches and nectarines using capillary electrophoresis-electrospray ionization-quadrupole ion trap-tandem mass spectrometry (CE-ESI-MS/MS) is described. Separation was carried out using a buffer of 0.3 M ammonium acetate at pH 4 with 10% methanol. Pesticide residues present in peach and nectarine samples were preconcentrated by solid-phase extraction using C(18), eluted with CH(2)Cl(2), concentrated to dryness, and redissolved in buffer to obtain lower detection limits. The recoveries of the analytes ranged from 58 to 99% and the relative standard devi…

Ultra-high-pressure liquid chromatography tandem mass spectrometry method for the determination of 9 organophosphate flame retardants in water samples

Few methods are available for comprehensive organophosphate flame retardants (PFRs) detection in water and wastewater. Gas chromatography has been employed previously, but this approach is less selective, not amenable for use with deuterated standards and can suffer unfavorable fragmentation. Ultra-high-pressure liquid chromatography tandem mass spectrometry (UHPLC-QqQ-MS/MS) has become the most promising platform, already applied successfully for analysis of selected PFRs in some environmental matrices like water and wastewater. However, the presence of some interferences from the dissolvent, the equipment and the used materials should be taken into account. The procedure involves: The fir…

Assessment of Pesticide Residues in Honey Samples from Portugal and Spain

Fifty samples of honey collected from local markets of Portugal and Spain during year 2002 were analyzed for 42 organochlorine, carbamate, and organophosphorus pesticide residues. An analytical procedure based on solid-phase extraction with octadecyl sorbent followed by gas chromatography-mass spectrometry (GC-MS), for organochlorines, and by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), for organophosphorus and carbamates, has been developed. Recoveries of spiked samples ranged from 73 to 98%, except for dimethoate (40%), with relative standard deviations from 3 to16% in terms of repeatability, and from 6 to 19% in terms of reproducibility. …

Organochlorine residue analysis of commercial milks by capillary gas chromatography

The determination of organochlorine pesticides and polychlorinated biphenyls in milks requires the use of efficient extraction methods. A rapid procedure has been developed, based on extraction of organochlorine residues from milk on to octadecylsilica solid phase extraction cartridges and elution with hexane. The addition of different organic solvents to the milk before solid phase extraction has been studied. The use of methanol to disrupt the fat globules enables almost complete recovery of the residues with minimum extraction of fatty substances. Recovery experiments were performed for eighteen compounds present at ppb levels in whole, two per cent, and skimmed milks. The average recove…

Recent trends in liquid chromatography-tandem mass spectrometry to determine pesticides and their metabolites in food

Abstract The applications of liquid chromatography-mass spectrometry (LC-MS) have exploded in innumerable analytical fields, including pesticide-residue determination. There is no doubt that LC-MS is currently competing with gas chromatography (GC)-MS for the status of ‘reference’ analytical technique to determine pesticide residues and that its ever-increasing application is bound to the evolution of modern instruments and their growing performance qualities. We highlight the large number and variety of pesticides that can be readily determined using such instruments, the respective merits of the different mass analyzers, and the improvements brought about by tandem MS (MS 2 ). We also dis…

Pesticide residues in oranges from Valencia (Spain)

One hundred and fifty citrus samples from an agricultural co-operative of the Valencian Community (Spain) were analysed for pre- and post-harvest pesticide residues using high performance liquid chromatography and gas chromatography. Among the residues from post-harvest treatments, imazalil was detected in 112 (74.7%) samples at a mean level of 1.2 mg/kg, thiabendazole in 21 (14.0%) samples at a mean level of 0.47 mg/kg and carbendazim in 5 (3.3%) samples at a mean level of 1.05 mg/kg. Among the residues from pre-harvest treatment, dicofol was detected in 28 (18.7%) samples at a mean level of .28 mg/kg chlorpyriphos in 19 (12.7% samples at a mean level of 0.16 mg/kg and endosulfan in 11 (7.…

Multi-residue determination of organic micro-pollutants in river sediment by stir-disc solid phase extraction based on oxidized buckypaper

This paper describes a procedure for the isolation of 20 organic micro-pollutants among pesticides, drugs, recreational drugs, flame retardants from river sediments. After a solid-liquid extraction with a methanol:water (50:50, v/v) solution, the supernatant was diluted with water and cleaned up by stir-disc solid-phase extraction (SPE). The disc was made of buckypaper, a self-supporting entangled assembly of carbon nanotubes, which was used as a highly porous, two-sided, sorbent membrane. In the preliminary activation step, the membrane was oxidised for 2-hours with nitric acid to extend its extraction capability also to more polar compounds. All extracts were analysed by ultra-high-perfor…

Routine application using single quadrupole liquid chromatography-mass spectrometry to pesticides analysis in citrus fruits.

Abstract A rapid and sensitive liquid chromatography–electrospray ionization–mass spectrometry method has been developed for the routine analysis of buprofezin, bupirimate, hexaflumuron, tebufenpyrad, fluvalinate and pyriproxyfen in citrus fruits. Extracts were obtained by matrix solid-phase dispersion (MSPD) using C 18 as dispersant and dichloromethane-methanol (80:20, v/v) as eluent. Matrix effects were tested for all matrices by addition of standard to sample blank extracts (samples containing no detectable residues). Mean recoveries obtained at fortification levels between 0.01 and 5 mg kg −1 were 57–97% with relative standard deviations (RSDs) from 5 to 19%. The limits of quantificatio…

Comparing illicit drug use in 19 European cities through sewage analysis

Abstract: The analysis of sewage for urinary biomarkers of illicit drugs is a promising and complementary approach for estimating the use of these substances in the general population. For the first time, this approach was simultaneously applied in 19 European cities, making it possible to directly compare illicit drug loads in Europe over a 1-week period. An inter-laboratory comparison study was performed to evaluate the analytical performance of the participating laboratories. Raw 24-hour composite sewage samples were collected from 19 European cities during a single week in March 2011 and analyzed for the urinary biomarkers of cocaine, amphetamine, ecstasy, methamphetamine and cannabis u…

Aldicarb residues in citrus soil, leaves and fruits

Aldicarb was applied to the soil of Late Valencia orange field plots. A comparative study between four analytical methods is reported, the NPD-gas chromatography method being the best choice. The work also reports the study of accumulation and persistence of aldicarb and its biologically active metabolites in the soil, leaves and fruits (rind and pulp, separately). Residue content, at the ppb level, was found in the order leaves much greater than rind greater than pulp. Carbamate was found to accumulate mainly in its oxidized forms. Residues had reached a maximum level in about 90 days after application.

Determination of tetracyclines in multi-specie animal tissues by pressurized liquid extraction and liquid chromatography–tandem mass spectrometry

Abstract A specific, sensitive and robust pressurized liquid extraction (PLE) and liquid chromatography tandem mass spectrometry (LC–MS/MS) method for determining tetracycline, chlortetracycline, oxytetracycline and doxycycline in bovine, swine, poultry and lamb muscle tissues is presented. PLE was performed using an ASE ® 200 from Dionex and water as extractant, followed by solid-phase extraction (SPE) using an Oasis HLB cartridge. The method was validated for beef, chicken, pork and lamb meat in compliance with the requirements set by Commission Decision, 2002/657/EC [Commission Decision 2002/657/EC (2002). Implementing Council Directive 96/23/EC concerning the performance of analytical m…

Simultaneous determination of traditional and emerging illicit drugs in sediments, sludges and particulate matter

An analytical method for determining traditional and emerging drugs of abuse in particulate matter, sewage sludge and sediment has been developed and validated. A total of 41 drugs of abuse and metabolites including cocainics, tryptamines, amphetamines, arylcyclohexylamines, cathinones, morphine derivatives, pyrrolidifenones derivatives, entactogens, piperazines and other psychostimulants were selected. Samples were ultrasound extracted with McIlvaine buffer and methanol, and the extracts were cleaned up by solid phase extraction (SPE) using Strata-X cartridges. Drugs were eluted using methanol and methanol-dichloromethane and determined by liquid chromatography tandem mass spectrometry. Th…

A two-year monitoring of pesticide hazard in-hive: High honey bee mortality rates during insecticide poisoning episodes in apiaries located near agricultural settings.

Pesticide residues in beebread, live and dead honey bees, together with honey bee death rate were monitored from June 2016 to June 2018 in three apiaries, located near agricultural settings and in wildlands. Dead honey bees were only collected and analyzed when significant mortality episodes occurred and pesticide content in beeswax of each experimental apiary was evaluated at the beginning of the study. Samples were extracted by a modified QuEChERS procedure and screened for pesticides residues by liquid chromatography mass spectrometry (LC-MS/MS). Pesticide hazard in the samples was evaluated through the hazard quotient approach (HQ). Beebread was widely contaminated with coumaphos and am…

Analysis of carbamate and phenylurea pesticide residues in fruit juices by solid-phase microextraction and liquid chromatography–mass spectrometry

A new analysis method to detect carbamates and phenylurea pesticide residues in fruit juices was developed using solid-phase microextraction (SPME) coupled with liquid chromatography-single quadrupole mass spectrometry (LC/MS) and liquid chromatography-quadrupole ion trap mass spectrometry (LC/QIT-MS). The pesticide residues present in watery matrices as fruit juices were extracted using three types of fibers: 50-microm Carbowax/templated resin (CW/TPR), 60-mum poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB) and 85-microm polyacrylate. The different extraction conditions were evaluated choosing as the best parameters 90 min (time), 20 degrees C (temperature) and 1 ml (volume). After extrac…

Perfluoroalkyl substance contamination of the Llobregat River ecosystem (Mediterranean area, NE Spain).

The occurrence and sources of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylate, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in water, sediment, and biota of the Llobregat River basin (NE Spain). Analytes were extracted by solid phase extraction (SPE) and determined by liquid chromatography triple quadrupole mass spectrometer (LC-QqQ-MS). All samples were contaminated with at least one PFAS, being the most frequently found perfluorobutanoate (PFBA), perfluorooctanoate (PFOA) and perfluorooctane sulfonate (L-PFOS). In general, mean PFAS concentrations measured in sediments (0.01-3.67 ng g(-1)) and biota (0.79-431 μg kg(-1)) samples were higher than those …

Analysis of cannabinoids by liquid chromatography–mass spectrometry in milk, liver and hemp seed to ensure food safety

A method for determining cannabinoids, Δ9-tetrahidrocannabinol (THC), 11-nor-9-carboxy-Δ9-THC (THC-COOH) and 11-hidroxy-Δ9-THC (THC-OH) in milk, liver and hemp seeds based on liquid chromatography tandem mass spectrometry has been optimized and validated. Analytes were extracted with methanol and the extracts cleaned-up by solid-phase extraction using Oasis HLB (60 mg). The developed method was validated according to the Commission Decision 2002/657/EC. The decision limit (CCα) and detection capability (CCβ) ranged from 3.10–10.5 ng g−1 and 3.52–11.5 ng g−1, the recoveries were 76–118% and matrix effect ranged from −17.8% to 19.9% in the three matrices studied. The method was applied to foo…

Ultrasound-assisted extraction for food and environmental samples

Abstract In recent years, ultrasound-assisted extraction (UAE) has attracted growing interest, as it is an effective method for the rapid extraction of a number of compounds from food and environmental samples, with extraction efficiency comparable to that of classical techniques. In particular, recently, numerous analytical applications of this technique dealt with the extraction of natural compounds and pollutants from food and environmental samples. This review gives a brief presentation of the theory of UAE, discusses recent advances that influence its efficiency, and summarizes the main results in selected applications published in the period 2010–12. There is discussion of the advanta…

Comparison of liquid chromatography using triple quadrupole and quadrupole ion trap mass analyzers to determine pesticide residues in oranges.

Liquid chromatography-triple quadrupole/mass spectrometry (LC-TQ/MS) and liquid chromatography-quadrupole ion trap/mass spectrometry (LC-QIT/MS) for determining bupirimate, hexaflumuron, tebufenpyrad, buprofezin, pyriproxyfen, and fluvalinate in fruits have been compared. The differences in the mass spectra obtained by triple and ion trap quadrupoles are discussed, showing how both of them provide interesting features. The evaluation of the two instruments was carried out by ethyl acetate extraction of oranges spiked with the studied pesticides at LOQ and 10 times the LOQ. Results obtained by LC-TQ/MS correlated well with those obtained by LC-QIT/MS. Recoveries were 70-94% by LC-TQ/MS and 7…