0000000000022290
AUTHOR
Damià Barceló
Analysis of microplastics and nanoplastics: How green are the methodologies used?
Microplastic (MP) and nanoplastic (NP) pollution is among the global environmental concerns of the 21st century owing to its transboundary distribution and persistence. The number of studies focused on the determination of MPs in air, water, sediment, soil, and biota of an important number of ecosystems has increased exponentially. However, the impact that the methodologies used to isolate and determine MPs and NPs have on the environment owing to the consumption of reagents and energy and the generation of waste is not yet studied. This review presents a critical overview of the analytical methodologies applied to determination of MPs and NPs assessing their greenness using the National En…
Identification of biomarkers in wastewater-based epidemiology: Main approaches and analytical methods
Wastewater-based epidemiology (WBE) has become popular to estimate the use of drugs of abuse and recently to establish the incidence of CoVID 19 in large cities. However, its possibilities have been expanded recently as a technique that allows to establish a fingerprint of the characteristics of a city, such as state of health/disease, healthy/unhealthy living habits, exposure to different types of contaminants, etc. with respect to other cities. This has been thanks to the identification of human biomarkers as well as to the fingerprinting and profiling of the characteristics of the wastewater catchment that determine these circumstances. The purpose of this review is to analyze the differ…
Distribution and fate of perfluoroalkyl substances in Mediterranean Spanish sewage treatment plants.
The concentrations of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylates, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in influent, effluent and sludge from 16 different sewage treatment plants (STPs) located in the Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (3) Rivers, in two consecutive years (2010 and 2011). The analytes were extracted by solid phase extraction (SPE) and determined by Liquid Chromatography triple Quadrupole Mass Spectrometer (LC-QqQ-MS). All samples, except two sludges from Guadalquivir River STPs, were contaminated with at least one PFAS. Perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (L-…
Prediction models based on soil properties for evaluating the uptake of eight heavy metals by tomato plant (Lycopersicon esculentum Mill.) grown in agricultural soils amended with sewage sludge
The aim of this study is to design de novo prediction models in order to gauge the likely uptake of eight heavy metals (Al, Cr, Cu, Fe, Mn, Ni, Pb and Zn) by Lycopersicon esculentum, the tomato plant. Uptake was assessed within the plant’s root, stem, leaf and fruit tissues, respectively. The plant was cultivated in soil amended by different application rates of sewage sludge, i.e. 0, 10, 20, 30 and 40 g/kg. The roots exhibited markedly elevated heavy metal concentrations compared to the above-ground plant components, with the exception of the quantity of Ni in the leaves. Apart from Al, Fe and Mn, a bioconcentration factor >1 was identified for all heavy metals. Excluding Ni in the leaves,…
Ecotoxicological Effects of Ibuprofen on Plant Growth of Vigna unguiculata L.
Despite the prevalence of the common pharmaceutical ibuprofen (IBU) in water and sediments worldwide, the effects of IBU on plants are largely unknown. This study was designed to assess the ecotoxicological effects of emerging pharmaceutical pollutant IBU on plant growth and development in a series of toxicity experiments using cowpea (Vigna unguiculata). Plant growth parameters (morphological and physicochemical) were investigated under a series of IBU concentrations (0, 400, 800, 1200, 1600, 2000 ppm IBU). IBU exposure reduced the shoot and root lengths, fresh and dry weights, leaf area, and chlorophyll a and b, carotenoid, total chlorophyll, mineral (K and Mg), glutathione reductase, and…
Shared effects of organic microcontaminants and environmental stressors on biofilms and invertebrates in impaired rivers
Land use type, physical and chemical stressors, and organic microcontaminants were investigated for their effects on the biological communities (biofilms and invertebrates) in several Mediterranean rivers. The diversity of invertebrates, and the scores of the first principal component of a PCA performed with the diatom communities were the best descriptors of the distribution patterns of the biological communities against the river stressors. These two metrics decreased according to the progressive site impairment (associated to higher area of agricultural and urban-industrial, high water conductivity, higher dissolved organic carbon and dissolved inorganic nitrogen concentrations, and high…
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…
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…
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…
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…
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 …
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…
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…
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…
Distribution of soil organic carbon in Wadi Al-Thulaima, Saudi Arabia: A hyper-arid habitat altered by wastewater reuse
The carbon cycle is being altered as a result of human-induced changes in the Earth's system. Therefore, ecosystems such as wetlands, authentic CO2 sinks, are becoming especially important. Little information exits on the soil organic carbon (SOC) stock for the middle east-countries man-made wetlands making wadis permanent with the outflow of wastewater treatment plants. This paper presents the vertical distribution of SOC content, soil bulk density (SBD) and SOC density in soil of vegetated and bare sites in Wadi Al-Thulaima, one of the artificial wetlands in central Saudi Arabia. The mean distribution of SBD in the vegetated and bare sites increased significantly with depth. Inversely, th…
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 …
Effect of the conversion of mangroves into shrimp farms on carbon stock in the sediment along the southern Red Sea coast, Saudi Arabia
The conservation of coastal ecosystems and specially mangroves ‘‘blue carbon’’ is receiving more attention as consequence of their recognition as high ecosystem carbon stocks and for the fact that these areas are undergoing land conversion. The aim of the present study is to evaluate the impact of land use changes due to conversion of mangroves to shrimp farms on the bulk density (SBD), organic carbon (SOC) concentration, and SOC stock in the sediments along the southern Saudi Arabian Red Sea coast. Shrimp farms and mangrove locations showed significant (P < 0.001) differences in SBD with high mean values in the sediments of shrimp farms. Shrimp farms and mangrove locations showed significa…
Pyrolysis gas chromatography-mass spectrometry in environmental analysis: Focus on organic matter and microplastic
Pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) has great potential within environmental analysis. This technique is mainly used for the chemical identification of macromolecules that cannot be characterized by either liquid or gas chromatography due to their big size. Through pyrolysis (controlled thermal degradation), these macromolecules are broken down into simpler molecules that can be separated by gas chromatography and detected by mass spectrometry. This technique has been traditionally used in environmental samples for the characterization of organic matter and humic substances, contaminants, lignins, etc. It attains the identification of the different types of chemical un…
Biomonitoring potential of the native aquatic plant Typha domingensis by predicting trace metals accumulation in the Egyptian Lake Burullus.
The ability of the native emergent macrophytes Typha domingensis for monitoring pollution with trace metals in Egyptian Lake Burullus was investigated through developing regression models for predicting their concentrations in the plant tissues. Plant samples (above-ground shoot and below-ground root and rhizome) as well as sediment samples were collected monthly during one growing season and analyzed. The association of trace metals concentration with several sediment characteristics (pH, organic matter, clay and silt) was also studied using the simple linear correlation coefficient (r). The concentration of some trace metals was significantly proportional to its values in the sediment suc…
Invertebrate community responses to emerging water pollutants in Iberian river basins
Abstract Chemical pollution is one of the greatest threats to freshwater ecosystems, especially in Mediterranean watersheds, characterized by periodical low flows that may exacerbate chemical exposure. Different groups of emerging pollutants have been detected in these basins during the last decade. This study aims to identify the relationships between the presence and levels of prioritary and emerging pollutants (pesticides, pharmaceutical active compounds—PhACs, Endocrine Disrupting Compounds EDCs and Perfluorinated Compounds—PFCs) and the invertebrate community in four Mediterranean basins: the Ebro, the Llobregat, the Jucar and the Guadalquivir. Structural (species composition and densi…
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…
Contaminants of emerging concern in freshwater fish from four Spanish Rivers.
This study investigated the occurrence of 135 contaminants of emerging concern (CECs) – pharmaceuticals, pesticides, a set of endocrine disrupting compounds (EDCs) (parabens, bisphenols, hormones, triazoles, organophosphorus flame retardants and triclosan), UV-filters, perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) – in 59 fish samples, collected in 2010 in 4 Spanish Rivers (Guadalquivir, Júcar, Ebro and Llobregat). Of the 135 CECs, 76 including 8 pharmaceuticals, 25 pesticides, 10 EDCs, 5 UV-filters, 15 PFASs and 13 HFRs were detected. Pharmaceuticals were the less frequently found and at lower concentrations. Pesticides, EDCs, UV-filters, PFASs and HFRs were det…
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…
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 …
Evaluation of a Multidimensional Solid-Phase Extraction Platform for Highly Selective On-Line Cleanup and High-Throughput LC−MS Analysis of Triazines in River Water Samples Using Molecularly Imprinted Polymers
A novel highly selective sample cleanup procedure based on the use of molecularly imprinted polymers (MIPs) as solid-phase extraction materials has been evaluated with respect to its applicability and routine use in environmental analysis. The method comprises the combination of a restricted access material (RAM) and a MIP allowing a selective sample preparation to be achieved in the online mode. This combination is called the size-selective sample separation and solvent switch (six-SPE). The RAM column combines size exclusion and adsorption chromatography, reducing the concentration of matrix molecules by a cutoff of 15 kDa. The MIP column selectively retains the triazine analytes whereas …
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…
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.
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…
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 …
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…
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…
Uptake prediction of nine heavy metals by Eichhornia crassipes grown in irrigation canals: A biomonitoring approach
The principal objective of this study is to generate mathematical regression equations that facilitate the estimation of the extent to which Eichhornia crassipes (C. Mart.) Solms, water hyacinth, absorbs heavy metals (HMs) into four plant organs (laminae, petioles, roots, and stolons). This study considers the absorption of nine HMs (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), and the E. crassipes evaluated in this study were located in three irrigation canals in the North Nile Delta in Egypt, with sampling being conducted in both monospecific and homogenous E. crassipes. Samples of both E. crassipes and water were collected on a monthly basis during one growing season. Analysis of the water s…
Selective trace enrichment of chlorotriazine pesticides from natural waters and sediment samples using terbuthylazine molecularly imprinted polymers
Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction…
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…
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 …
Case Studies of Macro-and Microplastics Pollution in Coastal Waters and Rivers: Is There a Solution With New Removal Technologies and Policy Actions?.
This opinion paper on microplastics pollution has selected different aspects and case studies of micro and macro-plastic litter pollution in coastal waters, and rivers. We point out a discussion on this topic and ask ourselves if there is a solution to the global problem by developing new microplastics removal technologies as well as policy actions. The first two case studies are related with macroplastics marine litter in beaches, a third report describes a new simple sampling device for microplastics in coastal and nearshore areas, five case study assess microplastics pollution in worldwide coastal environments, sediments and catchments (India, Mexico, Australia, Europe and the Nordic Sea…
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…
Perfluorinated Compounds’ Analysis, Environmental Fate and Occurrence: The Llobregat River as Case Study
Perfluorinated compounds are industrial chemicals widely used for more than 60 years. However, during the last decade, due to their high resistance to degradation, bioaccumulation attached to proteins, biomagnification to the food chain and their relation to toxicological effects of these compounds have gained scientific and regulatory attention.
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…
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…
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…
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 …
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…
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-…
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 …
Assessment of the mutagenic potency of sewage sludges contaminated with polycyclic aromatic hydrocarbons by an Ames sludges for fluctuation assay
9 pages, 1 figure, 6 tables.-- PMID: 14587895 [PubMed].