Annually, the Mediterranean region attracts around one-third of the global coastal tourism, which is acknowledged as a substantial contributor to plastic pollution. Coastal municipalities mitigate ...this through periodic sand and shore cleaning. However, the efficacy of these measures remains uncertain. In this study, the occurrence of MPs (10 μm-5 mm) in sand from seven different, regularly cleaned, touristic beaches of the coastline of Valencia province (E Spain) was assessed. Two different sampling campaigns were performed in winter and in summer (2022) to compare the results and understand the influence of the high touristic activity, as well as, the efficiency of the measures taken against MPs pollution. The methodology used was designed specifically for the matrix and employed density separation using a Sediment Microplastic Isolation (SMI) Unit. In addition to conventional visual inspection and ATR-FTIR, automatic quantification and identification of the polymers of lower size was performed by μFTIR. The average MPs concentration in the summer (339 ± 92 MP kg−1 by stereomicroscopy and 339 ± 189 MP kg−1 by μFTIR) was significantly higher than in the winter (71 ± 92 MP kg−1 and 143 ± 85 MP kg−1) (p < 0.05). The combination of these analytical tools provides comprehensive information about the MPs present in beach sand. Fibers were the most abundant form of MPs, while most of the polymers analyzed were polyethylene (PE) and halogenated polystyrene (Cl-PS and Br-PS) with food packaging, swimming equipment and fishing nets being their most probable sources. Ecological risk assessment was performed through the Pollution Load Index (PLI), the Hazardous Index (HI) and the Risk Quotient (RQ), with the results indicating potential risk that ranges from moderate to high depending on the applied approach.
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•7 regularly cleaned tourist beaches of Valencia province (E Spain) were studied in 2022.•MPs concentration was found to be double in the summer than in the winter.•μFTIR detects <50 μm MP yielding, in some cases, higher amounts than stereomicroscopy.•PE and halogenated PS were the most abundant polymer types.•Valencia beaches show potential ecological risk due to MPs' chemical composition.
•SWATH is able to provide MS/MS of more compounds than IDA.•The quality of the MS/MS spectra is lower in SWATH than in IDA.•No significant differences between FSWATH and VSWATH were ...appreciated.•Several pharmaceuticals were detected in mussel samples.•Several pesticides, pharmaceuticals and PCPs were detected in sediment samples.
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 spiked samples showed that the two SWATH modes enable to obtain the MS/MS spectrum of a higher number of compounds (up to 27 with FSWATH and 25 with VSWATH) than IDA (up to 19) in sediment and mussel. The different data acquisition modes were also tested in non-spiked samples to verify the results obtained in the spiked ones. Importantly, all the methods are able to detect the MS/MS spectrum of several contaminants in the samples when analysed against a database of >600 compounds. Up to 7 contaminants were tentatively detected with IDA, 15 with FSWATH and 17 with VSWATH. Most pollutants were pesticides and pharmaceuticals, being of particular interest the presence of ibuprofen and acetaminophen in mussels.
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), separation methods (e.g., field-flow fractionation and chromatographic techniques) and detection or characterization techniques (e.g., light scattering, Raman spectroscopy and mass spectrometry). We also show the first applications of the analysis of NMs in food matrices.
•PLE and QuEChERS were compared to extract 50 pesticides in soil, sediment and sludge.•The two methods were able to extract the selected pesticides.•QuEChERS with dSPE using PSA and C18 was the best ...method.•Pesticide residues occurred in the three types of samples along 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%), number of pesticides for which recoveries are in the range of 80–100% (up to 13 versus up to 35) and cost of the approach. QuEChERS procedure was faster, cheaper and easier to perform. Recoveries were around 80% (at 50ngg−1 d.w.) and the matrix effect was less than −20% using matrix-matched standard calibration curve for most of the analytes. The limits of quantification were between 0.1 and 10ngg−1 (d.w.) except for alachlor and acetochlor. Repeatability and reproducibility were lower than 28% (%RSD, n=5). Soil, sediment and sludge samples, taken from the Túria River Basin, were analyzed by QuEChERS to determine pesticides. Chlorpyrifos (up to 65.3ngg−1 d.w.) was the most frequent and at higher concentrations. Thiabendazole, imazalil, diazinon, pyriproxyfen, hexythiazox, carbofuran, isoproturon, terbuthylazine and terbumeton were also found in some samples.
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•Dilute and shoot or SPE followed by LC–MS/MS to analyze 10 human biomarkers.•Population served by WWTP estimated from these biomarkers.•Comparison to population estimates based on ...WWTP capacity, COD, BOD, N and P.•Consumption of several drugs calculated using these biomarkers.
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 from cotinine, 5-HIAA and caffeine are commonly in agreement with those calculated by the hydrochemical parameters. Creatinine is too unstable to be applicable. HCTZ, naproxen, codeine, OHCOT and carbamazepine, under or overestimate the population compared to the hydrochemical population estimates but showed constant results through the weekdays. The consumption of cannabis, cocaine, heroin and bufotenine in Valencia was estimated for a week using different population calculations.
Two solid-phase extraction methods were systematically studied to determine 32 pharmaceuticals and personal care products in water and sediments by ultrahigh-performance liquid chromatography–tandem ...mass spectrometry. One involves HLB cartridges activated with sodium dodecyl sulfate before the passage of the sample to form an ion pair with cationic analytes, and the other uses mixed HLB–cation exchange cartridges. The accuracy of the sodium dodecyl sulfate method was good for most compounds (recoveries of 61–120% with relative standard deviation less than 23%). However, the recoveries for atorvastatin, codeine, paracetamol, flufenamic acid, and salicylic acid were approximately 50% and for omeprazole and triclocarban were even lower (from 0 to 12%). The detection limits were 1.65–25 ng L
-1
in water and 0.33–4.00 ng g
-1
(dry weight) in sediment. The recoveries for the mixed-mode cartridge (Strata-X-CW) method ranged from 57% to 120% with relative standard deviation less than 21%, with the exception of codeine 25% (water), metformin 11% (sediment), paracetamol 48% (sediment), and salicylic acid 32% (sediment). The detection limits were 1.65–38.35 ng L
-1
in water and 0.33–10 ng g
-1
(dry weight) in sediment. Both methods followed the same pattern when applied to water. For sediments, the recoveries, which offer good performance, were not very high, although 60% of the compounds had recoveries greater 80%. The methods were applied to the analysis of surface water and sediments from the Albufera Natural Park (Spain). Twenty-seven of 32 analytes were detected in the samples analyzed.
Microplastics (MPs) are in all environmental compartments, including atmosphere, terrestrial, and aquatic environments as well as in marine organisms, foods, drinking water, and indoor and outdoor ...environments. MPs can enter the human body through the food chain and contaminated environment. Ingestion, inhalation, and dermal contact are the routes of their entry into the human body. Recent studies reporting the detection of MPs within the human body have raised concern among the scientific community as the knowledge about human exposure is still very limited and their impact on health is not well-understood yet. In this review article, we briefly cover the reports evidencing MP detection within the human body, e.g., stool, placenta, lungs, liver, sputum, breast milk, and blood. A concise synopsis of sample preparation and analysis of such human matrices is also provided. This article also presents a summary of the effect of MPs on human cell lines and human health.
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•Ingestion and inhalation are the main routes for exposure to MPs.•MPs have been found in placenta, feces, colon, lungs, sputum, liver, breast milk, and blood.•Utmost care is required while sample treatment and analysis to avoid contamination.•Some diseases appear to correlate with the presence of MPs.•Human cell line studies and health effects of MPs are briefly presented.
Pest control in agriculture is mainly based on the application of insecticides, which may impact nontarget beneficial organisms leading to undesirable ecological effects. Neonicotinoids are among the ...most widely used insecticides. However, they have important negative side effects, especially for pollinators and other beneficial insects feeding on nectar. Here, we identify a more accessible exposure route: Neonicotinoids reach and kill beneficial insects that feed on the most abundant carbohydrate source for insects in agroecosystems, honeydew. Honeydew is the excretion product of phloem-feeding hemipteran insects such as aphids, mealybugs, whiteflies, and psyllids. We allowed parasitic wasps and pollinating hoverflies to feed on honeydew from hemipterans feeding on trees treated with thiamethoxam or imidacloprid, the most commonly used neonicotinoids. LC-MS/MS analyses demonstrated that both neonicotinoids were present in honeydew. Honeydew with thiamethoxam was highly toxic to both species of beneficial insects, and honeydew with imidacloprid was moderately toxic to hoverflies. Collectively, our data provide strong evidence for honeydew as a route of insecticide exposure that may cause acute or chronic deleterious effects on nontarget organisms. This route should be considered in future environmental risk assessments of neonicotinoid applications.
Identification of degradation products of the organophophorous pesticide fenthion formed in two orange varieties, Valencia Navel and Navel Late, under field conditions has been assessed using liquid ...chromatography quadrupole time-of-flight mass spectrometry and ion trap mass spectrometry. The structural elucidation of the metabolites was accomplished by the accurate mass measurements provided by the quadrupole time-of-flight mass spectrometer in MS and MS/MS modes. This instrument achieved elemental composition diagnosis for the precursor and product ions with absolute mass error of <5 ppm, which unambiguously establishes the identity of the metabolites even at low concentration. The presence of these compounds was also confirmed by electrospray ionization-ion trap mass spectrometry, performing successive fragmentation steps (MS n ). Once identified, each molecule was confirmed by comparison with its analytical standard, also used to explore the quantitative capabilities of both mass analyzers. The extraction method was evaluated because it predetermines the metabolites that can be found (e.g., according to their polarity). Recoveries ranged from 70% for fenoxon sulfoxide (the most polar) to 101% for fenthion (the most apolar), which also indicates the method's facility to extract other more polar metabolites if present. Satisfactory linear range (r > 0.99) of more than 2 orders of magnitude was obtained with both analyzers for standards prepared in methanol and in untreated orange extracts. However, the matrix-matched standards showed suppression of the mass signal due to the matrix effect, especially for fenoxon sulfoxide and sulfone. The limits of quantification ranged from 0.005 to 0.015 mg/kg. The QqTOF-MS provided better quantification limits for fenthion and its sulfoxide and sulfone than the IT-MS. The resulting fenthion degration curves in oranges indicated that it was mainly degraded by sunlight photolysis to its sulfoxide and sulfone. However, hydrolysis was also observed by the appearance of fenoxon, fenoxon sulfoxide, and fenoxon sulfone, but always in low concentrations, which can be related to the rain events.
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 detection approaches are addressed. Special emphasis is placed on in-situ characterization of ENMs (e.g. particle size distribution, shape, aggregation state, etc.). We also discuss the advantages and disadvantages of the analytical methods and techniques for determining emerging contaminants and fully ENMs characterization, and cover promising future prospects.
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•Advances in the analysis of emerging contaminants and ENMs in plants displayed.•Sample treatment, separation and determination considered.•Lessons from ENMs location and characterization in plant tissues presented.•Fundamentals, shortcomings and advantages of each technique discussed.•Challenges outlined in detail and future prospects envisaged.
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