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Microplastics (MP) are spread into all ecosystems and represent a threat to the equilibrium of the environment and human health, not only due to their intrinsic characteristics but also to their action as effective carriers of contaminants, such as pesticides, pharmaceuticals, polychlorinated biphenyls and polycyclic aromatic hydrocarbons. The pesticide α-endosulfan is persistent and spread in the environment. The MP are another possible way of dissemination to be considered in the fate of this pesticide. The adsorption dynamics of α-endosulfan by six different MP (low-density polyethylene—LDPE, polyethylene-co-vinyl acetate, unplasticized polyvinyl chloride, polyamide 6, polystyrene granule, polypropylene granule) with different sizes/shapes and chemical compositions were evaluated. The most critical situation was identified for the system LDPE (particle size < 300 μm). Equilibrium studies (48 h equilibrium time) were performed for distilled, tap and filtered river water. Based on the Langmuir model parameters, the highest maximum adsorption capacity was obtained for distilled water, followed by filtered river and tap waters (i.e., 366 ± 39, 247 ± 38, 157 ± 22 μg/g). The obtained results demonstrate the important role that microplastics may have in the fate and transport of pesticides and their potentially harmful effect on the environment, which requires further investigation. [ABSTRACT FROM AUTHOR]

A multiresidue analytical methodology based on a solid-phase microextraction (SPME), followed by gas chromatography-ion trap mass spectrometry (GC-IT/MS), has been developed for trace analysis of 20 known or suspected endocrine-disrupting pesticides. The SPME conditions are optimized considering several key parameters to obtain the maximum sensitivity. After the optimization, the method validation is performed, and the limits of detection (ranged from 2-150 ng/L) and the coefficient of determination (above 0.990) of studied compounds are determined for all the analytes. A robust sampling of twenty sampling points of surface water samples from the north and center of Portugal is performed, and the validated methodology is applied. In total, 20 compounds from four chemical families (13 organochlorine, 1 organophosphorus, 2 dicarboximide, and 4 pyrethroids) are studied, and the pesticides most frequently detected are eight organochlorine pesticides (α-, β-HCHs, lindane, HCB, o,p'-DDT, p,p'-DDE, p,p'-DDD, α-endosulfan), cypermethrin, and vinclozolin. [ABSTRACT FROM AUTHOR]

Abstract Synthetic pyrethroids (SPs) are one of the most common pesticides used worldwide. Their use has greatly increased in the last decades and its' continuous application lead to added pesticides concentration in soil. Consequently, SPs may enter the food chain, affecting the environment and human health. The degradation over time of the pyrethroid pesticide deltamethrin applied to cabbages was monitored. The evolution was followed both on cabbages and the surrounding soils, and the soil microbial community characterized by next-generation sequencing of the 16S rRNA gene. The main shift in the microbial community structure was observed during the first 30 days after pesticides' application. The modification in the microbial community composition, where an increased abundance of Nocardioides sp. and Sphingomonas sp. were observed, was correlated respectively with the conversions of deltamethrin and its metabolite, 3-phenoxybenzoic acid (3-PBA). Although deltamethrin was not found in any of the tested samples (soil and cabbage) after 180 days, it caused an environmental impact much further than the 7 days security interval. These findings suggest that deltamethrin application can disturb soil microbial community and that natural biodegradation can have an important part in pesticides soil decontamination. Graphical abstract Image 1 Highlights • Monitoring of deltamethrin on the applied cabbage and soils over time. • NGS as a tool to understand how microbial communities responded to deltamethrin application. • Natural microbial community potentially biodegrades deltamethrin and 3-PBA. • Shifts in soil microbial community structure after 30 days of pesticide application. [ABSTRACT FROM AUTHOR]

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM. [ABSTRACT FROM PUBLISHER]

A novel enzymatic biosensor for carbamate pesticides detection was developed through the direct immobilization of Trametes versicolor laccase on graphene doped carbon paste electrode functionalized with Prussian blue films (LACC/PB/GPE). Graphene was prepared by graphite sonication-assisted exfoliation and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The Prussian blue film electrodeposited onto graphene doped carbon paste electrode allowed considerable reduction of the charge transfer resistance and of the capacitance of the device. The combined effects of pH, enzyme concentration and incubation time on biosensor response were optimized using a 23 full-factorial statistical design and response surface methodology. Based on the inhibition of laccase activity and using 4-aminophenol as redox mediator at pH 5.0, LACC/PB/GPE exhibited suitable characteristics in terms of sensitivity, intra- and inter-day repeatability (1.8–3.8% RSD), reproducibility (4.1 and 6.3% RSD), selectivity (13.2% bias at the higher interference:substrate ratios tested), accuracy and stability (ca. twenty days) for quantification of five carbamates widely applied on tomato and potato crops. The attained detection limits ranged between 5.2×10−9 molL−1 (0.002mgkg−1 w/w for ziram) and 1.0×10−7 molL−1 (0.022mgkg−1 w/w for carbofuran). Recovery values for the two tested spiking levels ranged from 90.2±0.1 (carbofuran) to 101.1±0.3% (ziram) for tomato and from 91.0±0.1% (formetanate) to 100.8±0.1% (ziram) for potato samples. The proposed methodology is appropriate to enable testing pesticide levels in food samples to fit with regulations and food inspections. [ABSTRACT FROM AUTHOR]

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multi-walled carbon nanotubes (MWCNTs) paste electrode modified by dispersion of laccase (3%, w/w) within the optimum composite matrix (60:40%, w/w, MWCNTs and paraffin binder) showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate 4-aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90×10−7 to 1.15×10−5 molL−1 using 4-aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%). The limit of detection obtained was 1.8×10−7 molL−1 (0.04mgkg−1 on a fresh weight vegetable basis). The high activity and catalytic properties of the laccase-based biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.0±0.1% to 101.0±0.3% were attained. No significant effects in the pirimicarb electroanalysis were observed by the presence of pro-vitamin A, vitamins B1 and C, and glucose in the vegetable extracts. The proposed biosensor-based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs. [ABSTRACT FROM AUTHOR]

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1-14.3 µg/L and 0.2-43.3 µg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed. [ABSTRACT FROM AUTHOR]

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography-photodiode array (LC-PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250-403 µg kg-1 in each pesticide. The pesticide residues were extracted using 20 mL acetonitrile at 60°C, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µg kg-1 for carbaryl to 12.3 µg kg-1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds. [ABSTRACT FROM AUTHOR]

Seven pyrethroids (bifenthrin, fenpropathrin, λ-cyhalothrin, permethrin, α-cypermethrin, fenvalerate, and deltamethrin) were extracted from water using C18 solid-phase extraction disks, followed by gas chromatography with an electron capture detector (GC-ECD) analysis. The limits of detection in water samples ranged from 0.5 ng L-1 (fenpropathrin) to 110 ng L-1 (permethrin), applying the calibration graph. The effects of different numbers of (re)utilizations of the same disks (up to four times with several concentrations) on the recoveries of the pyrethroids were considered. The recoveries were all between 70 and 120% after four utilizations of the same disk. There was no difference between these recoveries at a confidence level of 95%. [ABSTRACT FROM AUTHOR]

An analytical method, based on microwave-assisted extraction and liquid chromatography with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20 mL acetonitrile, for 10 minutes, at 60°C), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSDs < 7%). Quantification limits between 6.5 and 39.6 µg/kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS. [ABSTRACT FROM AUTHOR]

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron, metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0±0.46% and 120±2.9% except for ethiofencarb (46.4±4.4% to 105±1.6%) and butylate (22.1±7.6% to 49.2±11%). Soil samples from five locations of Portugal were analysed. [ABSTRACT FROM AUTHOR]

A simple, rapid, and precise amperometric method for quantification of N-methylcarbamate pesticides in water samples and phytopharmaceuticals is presented. Carbofuran and fenobucarb are the target analytes. The method is developed in flow conditions providing the anodic oxidation of phenolic-based compounds formed after alkaline hydrolysis. Optimization of instrumental and chemical variables is presented. Under the optimal conditions, the amperometric signal is linear for carbofuran and fenobucarb concentrations over the range of 1.0 × 10-7 to 1.0 × 10-5 mol L-1, with a detection limit of about 2 ng mL-1. The amperometric method is successfully applied to the analysis of spiked environmental waters and commercial formulations. The proposed method allows 90 samples to be analysed per hour, using 500 µL of sample, and producing wastewaters of low toxicity. The proposed method permits determinations at the µg L-1 level and offers advantages of simplicity, accuracy, precision, and applicability to coloured and turbid samples, and automation feasibility. [ABSTRACT FROM AUTHOR]

The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MT aqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L−1. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10−1 to 1.0 mg L−1 using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min−1. Real samples were analysed via calibration curves over the concentration range 1.3×10−2 to 1.3 mg L−1. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L−1), and the value obtained was 1.5%. [ABSTRACT FROM AUTHOR]

The work presented describes the development and evaluation of two flow-injection analysis (FIA) systems for the automated determination of carbaryl in spiked natural waters and commercial formulations. Samples are injected directly into the system where they are subjected to alkaline hydrolysis thus forming 1-naphthol. This product is readily oxidised at a glassy carbon electrode. The electrochemical behaviour of 1-naphthol allows the development of an FIA system with an amperometric detector in which 1-naphthol determination, and thus measurement of carbaryl concentration, can be performed. Linear response over the range 1.0×10-7 to 1.0×10-5 mol L-1, with a sampling rate of 80 samples h-1, was recorded. The detection limit was 1.0×10-8 mol L-1. Another FIA manifold was constructed but this used a colorimetric detector. The methodology was based on the coupling of 1-naphthol with phenylhydrazine hydrochloride to produce a red complex which has maximum absorbance at 495 nm. The response was linear from 1.0×10-5 to 1.5×10-3 mol L-1 with a detection limit of 1.0×10-6 mol L-1. Sample-throughput was about 60 samples h-1. Validation of the results provided by the two FIA methodologies was performed by comparing them with results from a standard HPLC–UV technique. The relative deviation was <5%. Recovery trials were also carried out and the values obtained ranged from 97.0 to 102.0% for both methods. The repeatability (RSD, %) of 12 consecutive injections of one sample was 0.8% and 1.6% for the amperometric and colorimetric systems, respectively. [ABSTRACT FROM AUTHOR]

The ever-increasing presence of contaminants in environmental waters is an alarming issue, not only because of their harmful effects in the environment but also because of their risk to human health. Pharmaceuticals and pesticides, among other compounds of daily use, such as personal care products or plasticisers, are being released into water bodies. This release mainly occurs through wastewater since the treatments applied in many wastewater treatment plants are not able to completely remove these substances. Therefore, the analysis of these contaminants is essential but this is difficult due to the great variety of contaminating substances. Facing this analytical challenge, electrochemical sensing based on molecularly imprinted polymers (MIPs) has become an interesting field for environmental monitoring. Benefiting from their superior chemical and physical stability, low-cost production, high selectivity and rapid response, MIPs combined with miniaturized electrochemical transducers offer the possibility to detect target analytes in-situ. In most reports, the construction of these sensors include nanomaterials to improve their analytical characteristics, especially their sensitivity. Moreover, these sensors have been successfully applied in real water samples without the need of laborious pre-treatment steps. This review provides a general overview of electrochemical MIP-based sensors that have been reported for the detection of pharmaceuticals, pesticides, heavy metals and other contaminants in water samples in the past decade. Special attention is given to the construction of the sensors, including different functional monomers, sensing platforms and materials employed to achieve the best sensitivity. Additionally, several parameters, such as the limit of detection, the linear concentration range and the type of water samples that were analysed are compiled. Image 1 • Contaminant analysis faces great challenges because of their variety and levels. • Advantages of MIPs as recognition elements: low-cost, robustness, reusability. • Main inconvenient of MIP-based sensors for environmental analysis: sensitivity. • Discussion of MIP-based electrochemical sensors for environmental analysis. • Discussion of advances and trends in MIP-based electrochemical sensors. [ABSTRACT FROM AUTHOR]