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A direct competitive impedimetric immunoassay for chlorpyrifos (CPF) was developed that is based on the specific affinity of immunoassay and the enzymatic biocatalytic precipitation amplification strategy. The CPF antibody (anti-CPF) was anchored onto an electro-deposited nanogold modified glassy carbon electrode surface by adsorption of the Au-NH 2 bond and Au-SH bond. This improved the electrode reactivity and the loading amount of anti-CPF. Abundant horseradish peroxidase (HRP) and bovine serum albumin-CPF (BSA-CPF) were anchored onto spherical gold nanoparticles (AuNPs, 16 ± 2 nm) to form HRP-AuNP-BSA-CPF (analyte competitor). CPF determination was achieved when the competitive immunoassay occurred between CPF and analyte competitor with anti-CPF. In the presence of H 2 O 2 and 4-chloro-1-naphthol, an enzyme-mediated biocatalytic precipitation process was triggered and produced an insoluble 4-chloro-1(4H)-naphthalenone. This insoluble substance increased the Faradaic impedance of the base electrode. The impedimetric signal was determined at the formal potential of 220 mV and alternating voltage of 10 mV. This signal decreased with increasing concentration of CPF over a linear range of 1.0 × 10 -3  ng mL -1 ~10 ng mL -1 with a detection limit of 0.070 pg mL -1 . The immunoassay has been tested for determination of chlorpyrifos in complex matrices such as artificially spiked vegetables with recoveries in the range 85 to 110%. The relative standard deviations were less than 7.5%. Graphical abstractSchematic representation of electrochemical impedimetric immunoassay for chlorpyrifos determination before enzymatic biocatalytic precipitation (BCP, red line) process and after BCP process (blue line).

A field study was conducted to further our understanding about the fate and transport of the organophosphate insecticide, chlorpyrifos, and its degradation product, chlorpyrifos oxon. Leaf, soil and air sampling was conducted for 21 days after chlorpyrifos application to a field of purple tansy (Phacelia tanacetifolia). Air samples were collected using a high-volume air sampler (HVAS) and seven battery-operated medium-volume active air samplers placed around the field and on a 500-m transect extending away from the field. Chlorpyrifos was detected every day of the sampling period in all matrices, with concentrations decreasing rapidly after application. Chlorpyrifos oxon was only detected in air samples collected with the HVAS during the first three days after application. Wind direction played a significant role in controlling the measured air concentrations in near-field samples. The SCREEN3 model and chlorpyrifos' Characteristic Travel Distance (CTD) were used to predict modelled chlorpyrifos concentrations in air along the transect. The concentration trend predicted by the SCREEN3 model was similar to that of measured concentrations whereas CTD-modelled concentrations decreased at a significantly slower rate, indicating that downwind chlorpyrifos concentrations in air were primarily controlled by air dispersion. The SCREEN3-predicted chlorpyrifos concentrations were >5 times higher than measured concentrations, indicating that simple approaches for calculating accurate pesticide volatilization fluxes from agricultural fields are still needed. Finally, we found that measured concentrations in air on Days 0-2 at locations up to 500 m from the field were at levels considered concerning for human health., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Pesticide loads and associated toxicity can be significantly reduced using integrated vegetated treatment systems, which remove moderately soluble and hydrophobic pesticides, but need a sorbent material to remove more soluble pesticides. Neonicotinoids such as imidacloprid are widely used insecticides, acutely toxic, and have been linked to a range of ecological effects. Laboratory experiments were conducted to test the sorptive capacity of granulated activated carbon and biochar for removing imidacloprid and the organophosphate insecticide chlorpyrifos in a scaled-down treatment system. Simulated irrigation water spiked with individual pesticides was treated with a bench-top system designed to mimic a 600 L carbon installation receiving 108,000 L of flow per day for sixteen days. Biochar reduced insecticides to less than detectable and non-toxic levels. Granulated activated carbon similarly reduced chlorpyrifos, but allowed increasing concentrations of imidacloprid to break through. Both media treated environmentally relevant concentrations, and would be effective if used under conditions with reduced particle loads.

A highly sensitive and convenient electrochemical sensor, based on surface molecularly imprinted polymers and multiwalled carbon nanotubes, was successfully developed to detect chlorpyrifos in real samples. In order to solve the problems like uneven shapes, poor size accessibility, and low imprinting capacity, the layer of the molecularly imprinted polymer was prepared on the surface of silica nanospheres. Moreover, the doping of multiwalled carbon nanotubes greatly improved the electrical properties of developed sensor. Under the optimal conductions, the electrochemical response of the sensor is linearly proportional to the concentration of chlorpyrifos in the range of 5.0 × 10 -12 -5.0 × 10 -8  mol/L with a low detection limit of 8.1 × 10 -13  mol/L. The prepared sensor exhibited multiple advantages such as low cost, simple preparation, convenient use, excellent selectivity, and good reproducibility. Finally, the prepared sensor was successfully used to detect chlorpyrifos in vegetable and fruit., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Organophosphorus pesticides (OPs) are harmful to people's health and d-amino acids (d-AAs) in the human body are closely related to various diseases. So, detection of OPs in foods and d-AAs in serum is important for food safety and clinical diagnosis. Herein, a long-lasting chemiluminescence (CL) imaging sensor was constructed for the detection of OPs and d-AAs. The method was based on N-(4-aminobutyl)-N-ethylisoluminol/Co2+/chitosan (ABEI/Co2+/CS) hydrogels, where metal organic framework materials (MOF-Pt) were selected as catalysts to improve the sensitivity greatly. Under the catalysis of acetylcholinesterase (AChE) and choline oxidase (CHO), H2O2 was produced by using acetylcholine chloride (ACh) as a substrate, which was sensitive to the proposed CL system. OPs inhibited the activity of AChE and decreased the production of H2O2, reducing CL intensity. The linear range of the method for chlorpyrifos was 0.5 ng mL-1-1.0 μg mL-1, with a limit of detection (LOD) of 0.21 ng mL-1. Seventeen kinds of OPs can be visually and simultaneously discerned by the CL imager. On the other hand, d-AAs were catalyzed and oxidized by d-α-amino oxidase (DAAO) to produce H2O2. Thus, d-Ala in serum was used as a model to be detected by the proposed method. The linear range for d-Ala was 1.0 μM-10 mM, with an LOD of 0.12 μM.

Conventional transverse relaxation time (T 2 )-mediated magnetic resonance sensors (MRS) that utilizing the target-induces state change of magnetic nanoparticles (MNPs) mainly suffer from low sensitivity. Recent T 2 -MRS that based on target-induced amount change of MNPs can achieve a higher sensitivity, but these sensors can hardly accommodate small molecules. We herein develop an ultrasensitive T 2 -MRS that enable the detection of small molecules based on cascade bioorthogonal reactions (BRs)-realized MNPs binding and assembly. Benefiting from rapid and highly selective cascade BRs, a single small molecule target can not only increase MNPs binding but also assembly MNPs, which greatly amplifies T 2 signal for sensing based on both the state and amount change of MNPs for the first time. Our strategy is capable of sensing chlorpyrifos with a liner range of 0.1 ng/mL to 1000 ng/mL. We justify the practicability of our assay by detecting chlorpyrifos in apple and cabbage samples, whose accuracy is higher than that of enzyme linked immunosorbent assay. Our assay provides a cascade BRs-mediated MRS that can greatly broaden the use of T 2 -based MRS for ultrasensitive sensing trace small molecules in complex samples.

Vernal pools are ephemeral wetlands that provide critical habitat to many listed species. Pesticide fate in vernal pools is poorly understood because of uncertainties in the amount of pesticide entering these ecosystems and their bioavailability throughout cycles of wet and dry periods. The Pesticide Water Calculator (PWC), a model used for the regulation of pesticides in the US, was used to predict surface water and sediment pore water pesticide concentrations in vernal pool habitats. The PWC model (version 1.59) was implemented with deterministic and probabilistic approaches and parameterized for three agricultural vernal pool watersheds located in the San Joaquin River basin in the Central Valley of California. Exposure concentrations for chlorpyrifos, diazinon and malathion were simulated. The deterministic approach used default values and professional judgment to calculate point values of estimated concentrations. In the probabilistic approach, Monte Carlo (MC) simulations were conducted across the full input parameter space with a sensitivity analysis that quantified the parameter contribution to model prediction uncertainty. Partial correlation coefficients were used as the primary sensitivity metric for analyzing model outputs. Conditioned daily sensitivity analysis indicates curve number (CN) and the universal soil loss equation (USLE) parameters as the most important environmental parameters. Therefore, exposure estimation can be improved efficiently by focusing parameterization efforts on these driving processes, and agricultural pesticide inputs in these critical habitats can be reduced by best management practices focused on runoff and sediment reductions., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A paper-based device (PBD) for the detection of chlorpyrifos pesticide at field application was fabricated based on the principles of enzyme inhibition and image processing. Rhizopus niveus lipase, p-nitrophenol palmitate and Whatman No.1 paper were used as an enzyme, substrate and support matrix, respectively. The performance of functionalized PBD was tested for lateral flow assay reaction in pure water (negative control), artificial pesticide water (positive control) and selected fruits and vegetables wash water (test). The digital image of the PBD after the test was captured using an android smartphone and analyzed in MATLAB software. Different colour space models such as, grey, RGB, HSV and YCbCr were studied and the Cb coordinate was chosen for its higher linearity (R 2  = 0.988) with pesticide concentration. Experimental variations such as paper length, relative concentration ratio of the substrate and enzyme were investigated to minimize the product cost and analysis time. The developed PBD showed a significant response over wide range of sample solution's pH and operational temperature. Further, a long-term storage stability was measured for developed PBD. The LOD and LOQ were found to be 0.065 mgL -1 and 0.198 mgL -1 . The results obtained from newly developed image processing method showed 92.8% accuracy with microtiter plate assay. Higher MRL was determined in the wash water of cauliflower, grapes, coriander leaves, brinjal and bitter guard. Overall, the developed paper biosensor was precise, cost effective and most suitable for field applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Background and Objective: Diagnosis of cholinesterase inhibitor insecticide ingestion is based on clinical suspicious and should be confirmed by cholinesterase essay. However, serum cholinesterase activity test requires specific instruments and procedure. This study aimed to develop simple colorimetric test to detect cholinesterase inhibitors in the gastric content, using phytoesterase and alpha naphthyl acetate as a chromogenic substrate., Materials and Methods: Methomyl and chlorpyrifos were selected for the phytoesterase enzyme inhibition assay. The experiment was conducted using pooled insecticide-free gastric content sample from ten cadavers. The gastric content samples were prepared by simple filtration procedure or liquid-liquid extraction procedure with dichloromethane or ethyl acetate. The inhibitor concentrations measured by the developed phytoesterase enzyme inhibition assay were compared with those analyzed by the LC-MS/MS and the GC-FPD., Results: Different sample preparation procedures, sensitivity and specificity and specificity of the test were investigated. Sample extracted with dichloromethane reduced the effect of matrix in gastric content as same as ethyl acetate. The developed color test method of detection showed 56.52% sensitivity and 100% specificity for methomyl, 100% sensitivity and 96.30% specificity for chlorpyrifos. The limit of detection of the assay was 422.6 ng mL-1 for methomyl and was 339.8 ng mL-1 for chlorpyrifos., Conclusion: This developed method could be used an alternative diagnostic test for methomyl and chlorpyrifos self-ingestion.

In the present work, an existing vegetation/air/litter/soil model (SoilPlusVeg) was modified to improve organic chemical fate description in terrestrial/aquatic ecosystems accounting for horizontal and vertical particulate organic carbon (POC) transport in soil. The model was applied to simulate the fate of three pesticides (terbuthylazine, chlorpyrifos and etofenprox), characterized by increasing hydrophobicity (log K OW from about 3 to 7), in the soil compartment and more specifically, their movement towards surface and groundwater through infiltration and runoff processes. The aim was to evaluate the role of dissolved organic carbon (DOC) and POC in the soil in influencing the peak exposure of pesticides in terrestrial/aquatic ecosystems. Simulation results showed that while terbuthylazine and chlorpyrifos dominated the free water phase (C W-FREE ) of soil, etofenprox was mainly present in soil porewater as POC associated chemical. This resulted in an increase of this highly hydrophobic chemical movement towards groundwater and surface water, up to a factor of 40. The present work highlighted the importance of DOC and POC as an enhancer of mobility in the water of poor or very little mobile chemicals. Further studies are necessary to evaluate the bioavailability change with time and parameterize this process in multimedia fate models.

In this study, new polymers containing amides ( TrisPS-Ntaa , and TrisPS-Ntaa-Fc ) were synthesized by condensation reaction for qualitative identification of insecticides. The synthesized polymers, including amides were investigated by infrared spectroscopy (IR), scanning electron microscopy-energy dispersion X- ray spectrometry (SEM-EDX), and gel permeation chromatography (GPC). Then, acetylcholinesterase enzyme (AChE) was covalently immobilized on these polymers to improve properties (including activity, reusability, and storage stability). Accordingly, organophosphate (malathion, acephate, chlorpyrifos methyl) and carbamate (carbofuran, methiocarb, methomyl), which are used to prevent harmful organisms in some agricultural products were enzymatically determined based on their inhibitory activity on AChE.

An in situ tracing study based on solid-phase microextraction (SPME) was conducted to investigate the uptake and elimination of organophosphorus pesticides in apples. A matrix-compatible polydimethylsiloxane/poly(styrene-co-divinylbenzene)/polydimethylsiloxane fiber was produced to meet the needs of in situ sampling. The fiber had high extraction ability, good sensitivity and accuracy with respect to the analytes in apple pulp, and could be used 85 times. Although the sampling rate was changing over time, quantification was still achieved by the sampling rate calibration method. Some factors that affect its applicability were studied. The limits of detection were 0.18 ng/g for diazinon and 0.20 ng/g for chlorpyrifos, rather lower than the maximum residue limits of the National Food Safety Standard of China (GB 2763-2016) and the European Commission (Reg.(EU) No 834/2013, 2018/686). The accuracy of in situ SPME quantification was verified by comparing with the results obtained by the traditional liquid-liquid extraction method. In this work, the in situ sampling method is developed using apples, diazinon, and chlorpyrifos as a model system; however, this method can be used for in vivo analysis of fruits and vegetables for nutrition and safety monitoring.

Persistent Organic Pollutants (POPs) are accumulated through time and can exert different effect on ecosystems. POPs and Chlorpyrifos, a current use pesticide, were assessed in body feathers of males and females of Black-browed albatross (Thalassarche melanophris, BBA) and Cape petrels (Daption capense, CAP) during their non-breeding seasons at the Patagonian Shelf, Argentina. Chlorpyrifos showed the highest values among all pollutants in both species (49.56-84.88 ng g -1 ), resulting from current agricultural practices. The pattern OCPs > PCBs > PBDEs was observed in both species, and CAP showed higher concentrations than BBA probably as a consequence of higher lipid mobilization and pollutants availability during dispersion. Non-significant differences between sexes about POPs levels were found; however a slight tendency was observed, females>males in CAP, and males>females in BBA. More attention and further studies are needed to understand seabirds' physiology and its relationship with the pollutants distribution in their tissues and considering breeding season., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Exploring the fabrication of an electrode with high photoelectric conversion efficiency and abundant functional groups for ideal photoelectrochemical (PEC) sensor development is highly urgent but faces a significant challenge. Herein we report an electropolymerization strategy for the preparation of phenothiazine polymeric film on an indium tin oxide (ITO) surface (PPT/ITO), within only a few seconds, and monomers. The fabricated PPT/ITO electrode possessed excellent stability and abundant quaternary ammonium salt groups for developing a highly sensitive PEC sensor through electrostatic binding with negatively charged materials. In this context, a CdS QDs-functionalized PPT/ITO electrode (CdS/PPT/ITO) was proposed and applied to the analysis of chlorpyrifos, used as a model target organophosphorous pesticide (OP). The thiocholine generated from acetylcholinesterase (AChE)-induced catalyzed hydrolysis of acetylthiocholine (ATCh) efficiently directed CdS QDs away from PPT/ITO via electrostatic repulsion, subsequently decreasing PEC current, whereas chlorpyrifos prohibited the generation of thiocholine through inhibiting AChE activity. As compared to the case where chlorpyrifos is absent, significantly enhanced PEC current is determined and is proportional to chlorpyrifos amounts. Thus, the developed CdS/PPT/ITO-based PEC sensor achieved excellent chlorpyrifos biosensing with improved sensitivity down to approximately ng/mL level with good specificity. We envision the proposed strategy will provide a new path to conveniently fabricate photoelectrodes possessing high performance, which will have more useful applications in PEC sensing.

New Zealand uses more than a ton of pesticides each year; many of these are mobile, relatively persistent, and can make their way into waterways. While considerable effort goes into monitoring nutrients in agricultural streams and programs exist to monitor pesticides in groundwater, very little is known about pesticide detection frequencies, concentrations, or their potential impacts in New Zealand streams. We used the 'Polar Organic Chemical Integrative Sampler' (POCIS) approach and grab water sampling to survey pesticide concentrations in 36 agricultural streams in Waikato, Canterbury, Otago and Southland during a period of stable stream flows in Austral summer 2017/18. We employed a new approach for calculating site-specific POCIS sampling rates. We also tested two novel passive samplers designed to reduce the effects of hydrodynamic conditions on sampling rates: the 'Organic-Diffusive Gradients in Thin Films' (o-DGT) aquatic passive sampler and microporous polyethylene tubes (MPTs) filled with Strata-X sorbent. Multiple pesticides were found at most sites; two or more were detected at 78% of sites, three or more at 69% of sites, and four or more at 39% of sites. Chlorpyrifos concentrations were the highest, with a maximum concentration of 180 ng/L. Concentrations of the other pesticides were generally below 20 ng/L. Mean concentrations of individual pesticides were not correlated with in-stream nutrient concentrations. The majority of pesticides were detected most frequently in POCIS, presumably due to its higher sampling rate and the relatively low concentrations of these pesticides. In contrast, chlorpyrifos was most frequently detected in grab samples. Chlorpyrifos concentrations at two sites were above the 21-day chronic 'No Observable Effect Concentration' (NOEC) values for fish and another two sites had concentrations greater than 50% of the NOEC. Otherwise, concentrations were well-below NOEC values, but close to the New Zealand Environmental Exposure Limits in several cases., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The composition of Atlantic salmon feed has changed considerably over the last two decades from being marine-based (fishmeal and fish oil) to mainly containing plant ingredients. Consequently, concern related to traditional persistent contaminants typically associated with fish-based feed has been replaced by other potential contaminants not previously associated with salmon farming. This is the case for many pesticides, which are used worldwide to increase food production, and may be present in plant ingredients. Earlier studies have identified two organophosphorus pesticides, chlorpyrifos-methyl and pirimiphos-methyl, in plant ingredients used for aquafeed production. In the present study, we developed a reliable and sensitive analytical method, based on liquid chromatography coupled to tandem mass spectrometry, for the determination of these pesticides and their main metabolites in warm water (zebrafish) and cold water (Atlantic salmon) species, where possible differences in metabolites could be expected. The method was tested in whole zebrafish and in different salmon tissues, such as muscle, bile, kidney, fat, and liver. The final objective of this work was to assess kinetics of chlorpyrifos-methyl and pirimiphos-methyl and their main metabolites in fish tissue, in order to fill the knowledge gaps on these metabolites in fish tissues when fed over prolonged time.

Surface-enhanced Raman spectroscopy (SERS) has the potential to detect pesticide residues in agricultural products. However, some systemic pesticides, such as chlorpyrifos, can enter the plant tissue, and not just stay on the surface. Consequently, many SERS studies halted at practical application because of its complexity. In this work, SERS technology was used to detect chlorpyrifos residues in tea products at the semiquantitative level. A simple pretreatment method effectively avoided interference of other fluorescent substances, and all major peaks could be distinguished on the basis of a novel substrate. A principal component analysis algorithm was applied to form a regression model, and a nanogram detection limit was obtained. Furthermore, chlorpyrifos residues in the same tea products were also measured by gas chromatography-mass spectrometry, and the results show a small range of errors. From the comparative study of the two detection methods, the results suggest the great promise of SERS technology for rapid inspection of agricultural products.

We develop an ultrasensitive T 2 -mediated immunosensor based on the coordination chemistry and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide andalkyne (CuAAC) and apply it for the detection of pesticide residues. We functionalize polyglutamic acid (PGA) on polystyrene to form a brush-like nanostructure that has a large loading capacity of Cu(II) through the coordination chemistry between PGA and Cu(II). Such a brush-like nanostructure could be used to chelate Cu(II) to modulate the CuAAC between azide-functionalized 1000 nm polystyrene (PS 1000 ) and alkyne-functionalized 30 nm magnetic nanoparticles (MNP 30 ), and the MNP 30 -PS 1000 conjugate as a product of CuAAC can act as a magnetic probe in this T 2 -based immunosensor. This click chemistry and coordination chemistry-mediated immunosensor allows for an ultrasensitive detection for chlorpyrifos residue (0.022 ng/mL), a 58-fold enhancement compared with that of enzyme-linked immunosorbent assay (1.28 ng/mL), providing a promising platform for detection of trace small molecules.

In this study, we report a direct surface plasmon resonance (SPR) biosensor based on an oriented assembly of antibody for the rapid detection of chlorpyrifos residue in agricultural samples. In this covalent-orientated strategy, staphylococcal protein A (SPA) was first covalently bound to the surface for monitoring chlorpyrifos residue, with subsequent binding of the antibody in an orientated fashion via its fragment crystallizable (Fc) region. Consequently, the SPA-modified biosensor exhibited a satisfactory specificity and a low detection limit of 0.056 ng mL -1 for chlorpyrifos, with a linear detection range of 0.25-50.0 ng mL -1 . Under optimal conditions, the sensor chip could be regenerated for at least 210 cycles. The results presented here indicate that the SPA-modified sensor chip can successfully improve the sensitivity and obviating the need of the modification of the antibody. The developed SPR biosensor method has the great potential for rapid, sensitive, and specific detection with broad applications in areas of environmental monitoring and food safety. Graphical abstract.

Current-use pesticides (CUPs) are widely applied in agriculture; however, little is known about their environmental behaviors, especially in the freshwater-seawater transitional zone. Water and sediment samples were collected in an intensively human impacted river (Xiaoqing River) from the headwaters to Laizhou Bay to investigate the distributions and environmental fates of four CUPs: trifluralin, chlorothalonil, chlorpyrifos, and dicofol. These CUPs were frequently detected in water and sediment samples. ∑CUPs in water and sediment samples ranged from 1.20 to 100.2 ng L -1 and 6.6-2972.5 ng g -1 dry weight (dw), respectively. Chlorpyrifos and chlorothalonil were the most abundant CUPs in water and sediment samples, respectively. Spatial distribution of CUPs in the Xiaoqing River aquatic ecosystem was mainly influenced by point sources, agricultural activities, the dilution effect by seawater, and environmental parameters. Field-based sediment water partitioning coefficients, normalized by organic carbon (log Koc), were calculated. Interestingly, temperature and salinity exhibited significant impacts on the distribution of log Koc of the four CUPs. The effect of temperature on the distribution of log Koc of the four CUPs varied between the CUPs. In most water samples, the levels of chlorpyrifos exceed the freshwater screening benchmarks. Hence, urgent control measures need to be devised and implemented., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The dissipation of three field-applied pesticides (chlorothalonil, chlorpyrifos, and malathion), on cultivated prickly pear ( Opuntia ficus-indica (L.) Mill.) pads was studied. The extraction of pesticides was carried out using the European quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique and detection was carried out using tandem liquid chromatography with mass spectrometry. At harvest, 15 days after application, pesticide dissipation was below the level of detectability. Dissipation curves for prickly pear pads fit to a first-order kinetic equation. Two initial concentration levels were used for each pesticide. The approximate dissipation time for all pesticides studied was similar (10 days) and the half-life time was around six days. Final concentrations for the three pesticides were below the reference maximum residue level (MRL) (0.01 mg/kg), which suggests that these products can be applied safely in the commercial production of prickly pear pads at the established concentrations.

The Pampa Húmeda region in Argentina is characterized by soybean, wheat, and maize production, with intensive application of agrochemicals such as herbicides and insecticides. We used a joint probabilistic approach to analyze the probabilities for environmental chlorpyrifos concentrations measured in the Pampa Húmeda to exceed acute or chronic hazardous concentration for 5% of the species (HC5) values estimated from species sensitivity distributions for aquatic species. Chlorpyrifos concentrations in water ranged from 0.0005 to 10.8 µg/L, with a median of 0.013 µg/L. The HC5 limits were 0.0637 µg/L for acute and 0.0007 µg/L for chronic effects. The probabilities for chlorpyrifos environmental concentrations to exceed the HC5 values ranged from 35% (acute effects) to 96% (chronic effects). Water quality criteria (WQC) for the protection of aquatic life were also frequently exceeded (by 48-87%) for both acute and chronic effects. Together with published threshold limit values from mesocosm studies, these data suggest that macroinvertebrate communities can be severely affected by the reported environmental concentrations of chlorpyrifos. Indeed, changes in the macroinvertebrate assemblage in the Pampa Húmeda have been correlated with chlorpyrifos levels in sediments. Nevertheless, the actual impact needs to be ascertained by assessing the recovery rate of macroinvertebrate populations in this region. Considering the HC5 for chronic effects and the threshold limits for macroinvertebrate community level effects, we propose 0.7 ng/L as a new WQC to effectively protect aquatic life from long-term exposure to chlorpyrifos. Environ Toxicol Chem 2019;38:1748-1755. © 2019 SETAC., (© 2019 SETAC.)

A method was developed for the determination of chlorpyrifos residues in paddy field aquatic products by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Samples were extracted with acetonitrile and purified by using 0.2 g primary secondary amine (PSA) sorbent and 1.2 g MgSO 4 . The target compound was separated on a Hypersil GOLD C 18 column (100 mm×2.1 mm, 5 μm), and was determined using a heated electrospray ionization (HESI) source in the positive ion selective reaction monitoring (SRM) mode. The analyte was quantified with external standard using the matrix-matched standard calibration curve method. The results showed that good linearities were obtained in the range of 0.5-100.0 μg/L, and the correlation coefficients were greater than 0.999. The spiked recoveries of chlorpyrifos ranged from 86.2% to 103.6% with RSDs of 3.5%-7.6% ( n =6). The limits of detection and quantification were 0.25 μg/kg and 0.5 μg/kg, respectively. This method is simple, quick, sensitive, and suitable for the rapid determination and analysis of chlorpyrifos residues in paddy field aquatic products.

Chlorpyrifos (CPF) is widely used in the prevention and control of crop pests and diseases in agriculture. However, the irrational utilization of pesticides not only causes environmental pollution but also threatens human health. Compared with the conventional techniques for the determination of pesticides in soil, surface-enhanced Raman spectroscopy (SERS) has shown great potential in ultrasensitive and chemical analysis. Therefore, this paper reported a simple method for synthesizing gold nanoparticles (AuNPs) with different sizes used as a SERS substrate for the determination of CPF residues in soil for the first time. The results showed that there was a good linear correlation between the SERS characteristic peak intensity of CPF and particle size of the AuNPs with an R 2 of 0.9973. Moreover, the prepared AuNPs performed great ultrasensitivity, reproducibility and chemical stability, and the limit of detection (LOD) of the CPF was found to be as low as 10 μg/L. Furthermore, the concentrations ranging from 0.01 to 10 mg/L were easily observed by SERS with the prepared AuNPs and the SERS intensity showed a good linear relationship with an R 2 of 0.985. The determination coefficient (Rp 2 ) reached 0.977 for CPF prediction using the partial least squares regression (PLSR) model and the LOD of CPF residues in soil was found to be as low as 0.025 mg/kg. The relative standard deviation (RSD) was less than 3.69% and the recovery ranged from 97.5 to 103.3%. In summary, this simple method for AuNPs fabrication with ultrasensitivity and reproducibility confirms that the SERS is highly promising for the determination of soil pesticide residues.

In Lebanon, apples are among the most consumed commodities; however, pesticide residues in apples have not been evaluated so far. Therefore, this study presents the occurrence of pesticide residues in apples produced in Lebanon during 2012-2016. A total of 212 samples were analysed for the presence of pesticides using the QuEChERS multi-residue extraction method, followed by GC-MS. Pesticide residues were not observed in 23% of the samples. Whereas pesticide residues were found in 77% of the samples, among them 61% exceeded the maximum residue limits (MRL) and 16% contained residues below the MRL. The most frequently detected pesticide residues were chlorpyrifos (n = 142), methidathion (n = 34), cypermethrin (n = 21), lambda-cyhalothrin (n = 16), myclobutanil (n = 13) and diazinon (n = 9). A preliminary long-term exposure assessment for the detected pesticides in apples showed that Hazard Quotient (HQ) was in the range of 0.1-8% of the ADI's, indicating no risk to human health.

Due to the concern over food safety, it is important to detect the pesticides residues in agricultural products. Here, a highly sensitive and low background fluorescent strategy for the detection of pesticides residues has been developed. The fluorescence intensity of N-methyl mesoporphyrin IX (NMM) binding G-quadruplex could be turn off because of inhibiting effect of the pesticides on the acetylcholinesterase (AChE) activity. For that, four single-stranded DNAs (named linker, trigger, H1 and H2, respectively) are rational designed and T-Hg-T mismatches duplex DNAs as a recognizer combined with the separation of magnetic beads. The design of hybridization chain reaction (HCR) amplification strategy assisted by magnetic separation has been adopted to improve the detection sensitivity. In the presence of pesticides, the amount of the thiol group generated by hydrolysis reaction of acetylcholine (ACh) is reduced, lead to release of less trigger DNA. Therefor subsequent HCR process is retarded with decreased fluorescence intensity. The reduced fluorescence intensity has a quantitative relationship with the pesticide concentration. The limit of detection of chlorpyrifos was estimated to be 2.0 ng ml -1 . It has been applied to detect the pesticides residues in real samples.

Only less than one percent applied pesticides reach the target pest, the remainder spread out into the environment, effecting on workers, bystanders, consumers and so on. Handlers with manual knapsack sprayer are completely exposed to the pesticide spray plume when they deal with the pesticides. Those kinds of sprayer are widely used in developing countries, more than 75% of farmers using hand-pumped knapsack sprayer in China, yet rarely systematic studies had been focused on the typical applying scenario. The occupational exposure of pesticide is highly correlated with the pesticide spray plume flying time in the air in this scenario. Our study aimed to compare the estimated exposure level of handlers to chlorpyrifos sprayed at three spraying direction using a lever-operated knapsack in small farms in five agro-climatic zones of China. Experiments were performed by 24 farms in each province with three different crop heights (< 80 cm, spraying downward; 80-130 cm, spraying horizontal; and > 130 cm, spraying upward; eight farms for every direction) under typical field conditions. Each farmer covered a uniform area of 667 m 2 . The whole body dosimetry method and a personal air sampler were used to monitor the dermal and inhalation exposure. The estimated dermal exposure of the three spraying direction was 629, 1580, and 2140 mg/kg, respectively. The results showed that the total dermal exposure level increased with the spraying direction from downward to upward. Furthermore, appropriate cotton coveralls could reduce more than 90% of the total dermal exposure., (Copyright © 2018 Elsevier Inc. All rights reserved.)

In this study, we investigated the degradation kinetics of chlorpyrifos, an organophosphorus (OP) compound, using ferrate(VI), and investigated the potential of this iron-based chemical oxidant on chlorpyrifos removal from water and wastewater treatments. A series of kinetic experiments were conducted to evaluate the influence of various environmental factors, such as pH, oxidant dosages, as well as the presence of anions, cations, humic acid (HA), and different water matrices. Chlorpyrifos was completely removed within 300 s under the following optimum conditions: [chlorpyrifos] 0 = 1 μM, [Fe(VI)] 0 :[chlorpyrifos] 0 = 100:1, T = 25 °C, and pH = 7.0. Anions such as Cl - , SO 4 2- , NO 3 - , and HCO 3 - and cations such as Fe 3+ , Cu 2+ , and NH 4 + did not appear to influence the removal of chlorpyrifos. However, the presence of Ca 2+ , Mg 2+ , and HA in water inhibited the degradation of chlorpyrifos. Experiments on removing chlorpyrifos from tap water, river water, and synthetic wastewater were performed to demonstrate the practical applications of Fe(VI). Ten oxidation products of chlorpyrifos were identified using liquid chromatography-quadrupole-time-of flight-mass spectrometry (LC-Q-TOF-MS), and their structures were further elucidated using MS/MS spectra. Then, two degradation pathways were preliminarily proposed including the oxidation of the P = S bond, cleavage of C-O bond, and hydroxyl substitution reaction. In general, Fe(VI) could be used as an efficient technology for chlorpyrifos removal from water and wastewater treatments., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Organophosphorus pesticide (OP) residues in agricultural products, herbal medicines and environment have attracted increasing concerns because they cause high healthy risk. Herein, a tyrosinase-mediated photoinduced electron transfer system was constructed for OPs analysis by using dopamine-functionalized upconversion nanoparticles (UCNPs) as fluorescent (FL) sensors. Dopamine quinone was produced by tyrosinase-mediated oxidation of dopamine on the surface of UCNPs, which acted as electron accepter to quench the FL emission of UCNPs. The FL quenching was inhibited by OP since it inhibited the activity of tyrosinase. Chlorpyrifos was used as a model analyte to investigate the feasibility of the FL sensor for the analysis of OPs. Under the optimal conditions, chlorpyrifos can be analysed in a wide range of 1.0 ‒ 1000 ng mL -1 , with a detection limit of 0.38 ng mL -1 (3σ). Some other groups pesticides, including organonitrogen pesticide, organochlorine pesticide and chloronicotinyl insecticide all showed negligible interference. The proposed sensor was successfully used to analyse chlorpyrifos spiked in Balloonflower and Angelica with acceptable recovery values of 95.4-120.0%, demonstrating its application potential for real samples. It exhibits some advantages like low cost, high sensitivity and free of autofluorescent interference and photobleaching., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Elevated levels of chlorpyrifos‑methyl have been detected in plant-based Atlantic salmon feeds. To evaluate the potential negative effects of long-term and continuous dietary exposure to chlorpyrifos‑methyl in fish, we fed juvenile Atlantic salmon three concentrations (0.1, 1.0 and 8.0 mg/kg) of the pesticide for about two months. Brain and liver tissues were collected after 30 and 67 days of exposure. Homogenized brain tissue was examined for effects on acetylcholinesterase, and brain and liver tissue from fish exposed to 8.0 mg/kg were used for transcriptional analysis (RNA-seq). The results showed a transient accumulation of chlorpyrifos‑methyl in the brain with lower levels after 67 days of exposure compared to after 30 days of exposure. In contrast, the liver showed a time-dependent accumulation pattern. No effect on acetylcholinesterase activity, the primary target of chlorpyrifos‑methyl, was seen in the brain. However, after 30 days of exposure, 98 significantly differentially expressed genes (DEGs) were found in brain tissue and 239 DEGs in liver tissue. After 67 days of exposure, two and 258 DEGs were found in brain and liver tissue, respectively. Continuous dietary exposure of chlorpyrifos‑methyl most profoundly affected mechanisms associated with protein degradation and lipid metabolism in both brain and liver. Specific for the brain, many of the significant DEGs encode proteins involved in neuron function. In conclusion, this study shows that chlorpyrifos‑methyl affects the transcription of genes involved in neurological function in Atlantic salmon brain, even at exposure concentrations below the threshold for systemic toxicity as seen from brain acetylcholinesterase inhibition., (Copyright © 2018 Elsevier Inc. All rights reserved.)

A liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously determine chlorpyrifos, imidacloprid, and imidacloprid metabolites in soil, wheat grain, and wheat straw matrices. Satisfactory linearity (R 2 ≥ 0.9965) of the method was obtained for all analytes. The ranges of limits of detection and limits of quantification for seven analytes in three matrices were 0.17-66.7 and 0.5-200 μg/kg, respectively. Average recoveries were 72.85-81.25% for chlorpyrifos, 78.54-84.70% for imidacloprid, 73.83-81.03% for imidacloprid olefin, 71.47-80.61% for 5-hydroxy imidacloprid, 71.79-81.32% for imidacloprid urea, 70.42-82.20% for imidacloprid nitroguanidine, and 70.91-82.46% for imidacloprid 6-chloronicotinic acid in soil, wheat grain, and wheat straw. The intra- and interday relative standard deviations were less than 8%. The established method was successfully applied for the residual analysis of chlorpyrifos, imidacloprid, and imidacloprid metabolites in actual soil, wheat grain, and wheat straw samples. The results indicated that the established method could be used to detect trace amounts of chlorpyrifos, imidacloprid, and imidacloprid metabolites in wheat and that the method might be able to provide some data on the detection of these seven compounds in other crops., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

As chlorpyrifos is used globally to control pests in sugarcane fields, analysis of its residues on food crops is essential to assess product safety for humans. In this study, chlorpyrifos content in sugarcane plants, soil and juice was determined using a gas chromatography with an electron capture detector. The limit of quantification was 0.01 mg/kg for plant and soil, and 0.01 mg/L for juice. The degradation and residual risk in sugarcane fields after applying chlorpyrifos to two sample sites (Changsha and Danzhou, China) were assessed. Chlorpyrifos concentrations in plants and soil decreased rapidly over time, reaching a degradation rate ranging from 98.82 to 99.25% on day 35. The half-life of chlorpyrifos in both plants and soil was only 5.97-6.12 days. Regardless of application dosage (standard or high) at a pre-harvest interval of 60 days, chlorpyrifos was undetectable in the harvested sugarcane. Risk assessment indicated that chlorpyrifos residue in sugarcane did not pose a health risk to humans., (© 2018 John Wiley & Sons, Ltd.)

Multi-component pesticide residues, especially pesticide residues with synergistic toxicity, are a serious threat to food safety. With risk assessment, we found that Chlorpyrifos (CPF) and Carbofuran (CBF) are 2 pesticide residues with highest risk for Actinidia chinensis planch. The results showed CPF and CBF have a synergistic neurotoxicity on neural cell SK-N-SH. The toxicity was partly depending on oxidative stress (OS) and had effects on cell apoptosis and cell cycle arrest. Furthermore, the toxicity remained on long-term low-dose condition., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Frequent and widespread pesticide use is a major concern for both human and environmental health. The aim of this study was to screen for 19 pesticides in rural rivers in Guangzhou, China, evaluating the potential impact of detected pesticides on the local ecosystem. Sampling was performed in rural rivers in three environment types: agricultural, industrial, and unpolluted, with sampling of water and sediments in both wet and dry seasons. A total of 11 pesticides were detected overall and their spatiotemporal distribution in water and ecological risk were assessed. Five pesticides were detected at concentrations above 100 ng L -1 , with the highest concentration pesticides being dimethoate (1318 ng L -1 ) in surface water and quinalphos (328 ng g -1 dry weight (dw)) in sediments. The most commonly detected pesticides were chlorpyrifos, acetochlor, and butachlor with detection frequencies of 50-57% and 29-43%, in water and sediments, respectively. Samples from the agricultural rural river contained the most pesticides and at higher concentrations, as compared to industrial and unpolluted areas, especially during the wet season. Ecotoxicological risk assessment through Risk Quotients (RQs) showed that chlorpyrifos and fenvalerate pose high ecological risks in water and therefore, reduction of the source input of these pesticides is essential.

The removal efficiency of the pesticide chlorpyrifos (50 and 500 μg L -1 ) by five wetland plant species (Cyperus alternifolius, Canna indica, Iris pseudacorus, Juncus effusus and Typha orientalis) was studied in recirculating vertical flow constructed wetland systems (RVFCWs). Results reveal that for chlorpyrifos at different concentrations, good removal efficiencies (94-98%) were observed using the same plant systems, while no significant differences in removal efficiencies were seen between the different plant systems. In addition, the chlorpyrifos removal efficiency of the planted systems increased significantly compared with the unplanted controls. The chlorpyrifos removal efficiency for wetland systems over time fit to the first-order kinetic model, with the first-order kinetic constant (k) ranging from 0.045 to 0.065 h -1 . The half-life of chlorpyrifos in the systems ranged from 10.66-15.43 h. The shortest chlorpyrifos half-life was detected in the wetland system containing C. indica, followed by that with C. alternifolius and I. pseudacorus. The main pathways to remove chlorpyrifos in these wetland systems were sorption (accounting for 64.6-86.4% of the total removal efficiency) and biodegradation (8.1-33.7%). Plants can enhance chlorpyrifos removal through enhanced biodegradation in the system. Plants with high biomass and transpiration were able to accelerate the removal of chlorpyrifos and conventional pollutants. Hence, C. indica, C. alternifolius and I. pseudacorus could be used as optimal plants for pesticide removal in wetland systems., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Agricultural farmers in developing countries are at high risk of pesticide exposure and adverse effects because of unsafe practices and inappropriate legislation. Biological monitoring is considered a useful tool for pesticide exposure assessment; however, its use is limited in developing countries due to a lack of techniques and resources such as laboratory analysis, trained staff and budgets. This study examines whether the World Health Organization predicted exposure assessment model (WHO-PEAM) is a suitable alternative tool for assessing insecticide exposure among agricultural farmers. WHO-PEAM was used to predict daily doses (PDD) of chlorpyrifos for a group of Vietnamese rice farmers using a set of exposure parameters obtained from a questionnaire survey of participant famers during a field study. These results were compared to absorbed daily doses (ADD) of chlorpyrifos for the farmers measured using a biological monitoring program, in which 24-h urine samples were collected and analysed for the chlorpyrifos metabolite, 3,5,6-trichloro-2-pyridinol (TCP) using LC/MS. Validation of the model results was tested using the Wilcoxon signed-rank test (WSR) and two-way mixed-model intraclass correlation coefficient (ICC). The mean of total ADD was 20 μg/kg/day while that of total PDD was 22 μg/kg/day. The WSR test revealed no statistically significant difference in the average values of ADD T and PDD T . ICC indicated substantial agreement for both single and average measures between ADD T and PDD T (ICC, 0.62 and 0.77, respectively). The results demonstrate that a refined WHO-PEAM model can be readily used as a field method, without biological monitoring, to evaluate chlorpyrifos exposure among agricultural farmers in Vietnam and similar developing countries.

Organic pollutants have attracted increasing attention due to their strong persistence and extensive diffusivity. Plasticizers (PAEs) and organophosphorus pesticides (OPs), as the vital part of organic pollutants, have made extensive damage to the environment with the rapid development of modern agriculture and industry. Therefore, we have, for the first time, carried out a quantitative analysis of the PAEs and OPs by fluorescence recognition. A series of isostructural lanthanide organic frameworks, [Ln(tftpa)1.5(2,2'-bpy)(H2O)] (Ln = Gd 1, Eu 2 and Tb 3, H2tftpa = tetrafluoroterephthalic acid), were hydrothermally synthesized, of which 3 exhibited excellent hydrolytic resistance to both boiling acidic and basic aqueous solutions. Moreover, luminescence investigations show that 3 can be used as a highly sensitive and recyclable luminescence sensor for the detection of DBP (di-n-butyl phthalate) in simulated seawater and chlorpyrifos in ethanol with the detection limits of 2.07 and 0.14 ppb, respectively.

Agricultural activities can involve the use of plant protection products (PPPs) and the use of such chemicals can occur near surface waters bodies, thus creating a potential for adverse effects on aquatic ecosystems. In mountain watersheds, where runoff fluxes are particularly rapid due to side slopes, exposure is generally characterized by short but intense concentration peaks. Monitoring campaigns are often inadequate or too expensive to be carried out and modelling tools are therefore vital for exposure assessment and their use is encouraged by current legislation. However, currently adopted models and scenarios (e.g., FOCUS for PPPs) are often too conservative and/or "static" to accurately capture exposure variability, and the need for more realistic and dynamic tools is now one of the major challenges for risk assessment. In a previous work, the new fate model DynAPlus was developed to improve pesticide fate predictions in cultivated mountain basins and was successfully evaluated against chlorpyrifos water concentrations measured in a mountain stream in Northern Italy. However, the need for some model improvements (e.g., the inclusion of dissolved organic matter and macrophytes in water) was highlighted. In this work, DynAPlus was improved by replacing the water-sediment unit with ChimERA fate, a recently-published model capable of predicting bioavailable chemical concentrations in shallow water environments accounting for the presence and temporal variations of particulate/dissolved organic carbon and primary producers. The model was applied to preliminarily characterize the risk associated to the use of four PPPs (two insecticides and two fungicides) in a sub-basin of the Adda River (Valtellina Valley, Northern Italy), surrounded by apple orchards. Results revealed the potential magnitude of exposure peaks for the four PPPs and suggested that monitoring campaigns should prioritize, in the selected case study, chlorpyrifos, etofenprox and fluazinam. The potential role of DynAPlus in providing more realistic exposure predictions for ecological risk assessment, as well as for planning efficient monitoring campaigns and help pesticide management practices, was also stressed., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In the last decades, research regarding the dynamics of pesticides has grown, even in remote regions. Due to long-range atmospheric transport, environmental persistence and toxicological potential of organochlorine pesticides (OCPs), similar characteristics of current-use pesticides (CUPs) and their massive use in Brazil, these contaminants have become a major concern for environmental and human life. Thus, this study aimed to evaluate subgroups or individual chemicals of OCPs and CUPs, which could have travelled over two Conservation Unit sites in the Rio de Janeiro state. The study was carried out for 24 months, (2013-2015), in Itatiaia National Park (INP) and in the Serra dos Órgãos National Park (SONP), at ∼2400 and ∼2200 meters above sea level, respectively. The study was based on atmospheric passive sampling (polyurethane foam disks). Target pesticides were detected by means of gas chromatography device coupled with mass spectrometry (GC-MS). Significantly higher concentrations were measured in SONP when compared to INP. However, in broad terms, the contamination profile was quite similar for both national parks: The highest concentrations of endosulfan (INP - 1275 pg m -3 and SONP - 3202 pg m -3 ) were followed by cypermethrin (INP - 148 pg m -3 and SONP - 881 pg m -3 ) and chlorpyrifos (INP - 67 pg m -3 and SONP - 270 pg m -3 ). In agreement with previous studies, the atmospheric concentrations of legacy OCPs showed background air levels. The decrease of endosulfan over the years was highlighted with a parallel increase of chlorpyrifos, suggesting a collateral effect of the national bias of permissive and massive use of agrochemicals. CUPs seemed to behave like pseudo-persistent pollutants (pseudo-POPs). This is the first report of atmospheric concentrations of pyrethroids in Brazilian mountain regions, and possibly the first to investigate them in the air in South America or in any mountain region in the world., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Chlorpyrifos (CPF) pollution has drawn widespread concerns in aquatic environments due to its risks to ecologic system, however, the response mechanisms of ciliates to CPF pollution were poorly studied. In our current work, the degradation of CPF by ciliates and the morphological changes of ciliates after CPF exposure were investigated. In addition, the transcriptomic profiles of the ciliate Uronema marinum, with and without exposure with CPF, were detected using digital gene expression technologies. De novo transcriptome assembly 166,829,634 reads produced from three groups (untreated, CPF treatment at 12 h and 24 h) by whole transcriptome sequencing (RNA-Seq). Gene ontology (GO) and Kyoto Encyclopaedia of Genes and Genomes (KEGG) pathways were analyzed in all unigenes and different expression genes to identify their biological functions and processes. Furthermore, the results indicated that genes related to the stress response, cytoskeleton and cell structure proteins, and antioxidant systems might play an important role in the resistance mechanism of ciliates. The enzyme activities of SOD and GST after CPF stress were also analyzed, and the result showed the good antioxidant capacity of SOD and GST in ciliates inferred from the increase of the activities of the two enzymes. The ciliate Uronema marinum showed a resistance response to chlorpyrifos stress at the transcriptomic level in the present work, which indicates that ciliates can be considered as a potential bioremediation agent.

This report describes levels of 170 pesticide residues in green pepper and cucumber marketed in Turkey. The report also comprises the outcome of the consumer risk assessment of selected pesticides. In total, 725 samples of vegetables were analysed for residues of 170 distinct pesticides by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The in-house validation data fulfilled the requirements of the European SANTE/11945/2015 Guideline. The limit of quantifications (LOQs) varied from 0.003 to 0.016 mg kg-1. Recoveries ranged between 80.5 and 118.2%, with inter-day precisions of 0.7-19% relative standard deviation (RSD). The expanded measurement uncertainty for individual pesticides ranged from 10.4 to 42.4%. Overall, 12.9% of green peppers and 13.5% of cucumbers contained at least one detectable residue, but the levels were below the EU legal limits. For adults, the Hazard Quotients (HQs) for identified pesticides in green peppers and cucumbers ranged from 0.0003 to 0.0143%, and from 0.0001 to 0.0103%, respectively. Propamocarb and chlorpyrifos were the major contributors to hazard index (HI) for green pepper and cucumber, respectively. The results showed that there is no reason to be concerned about cumulative exposure to residues from green pepper and cucumbers for Turkish population., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Chlorpyrifos (CP), an organophosphate insecticide is broadly used in the agricultural and industrial sectors to control a broad-spectrum of insects of economically important crops. CP detection has been gaining prominence due to its widespread contamination in different environmental matrices, high acute toxicity, and potential to cause long-term environmental and ecological damage even at trace levels. Traditional chromatographic methods for CP detection are complex and require sample preparation and highly skilled personnel for their operation. Over the past decades, electrochemical biosensors have emerged as a promising technology for CP detection as these circumvent deficiencies associated with classical chromatographic techniques. The advantageous features such as appreciable detection limit, miniaturization, sensitivity, low-cost and onsite detection potential are the propulsive force towards sustainable growth of electrochemical biosensing platforms. Recent development in enzyme immobilization methods, novel surface modifications, nanotechnology and fabrication techniques signify a foremost possibility for the design of electrochemical biosensing platforms with improved sensitivity and selectivity. The prime objective of this review is to accentuate the recent advances in the design of biosensing platforms based on diverse biomolecules and biomimetic molecules with unique properties, which would potentially fascinate their applicability for detection of CP residues in real samples. The review also covers the sensing principle of the prime biomolecule and biomimetic molecule based electrochemical biosensors along with their analytical performance, advantages and shortcomings. Present challenges and future outlooks in the field of electrochemical biosensors based CP detection are also discussed. This deep analysis of electrochemical biosensors will provide research directions for further approaching towards commercial development of the broad range of organophosphorus compounds., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper presents, for the first time, results for chlorpyrifos (CHLP) in Polish fruits and vegetables over the course of a long period of research, 2007-2016, with toxicological aspects. The challenge of this study was to re-evaluate the impact of chlorpyrifos residues in fruit and vegetables on health risk assessed via acute and chronic exposure based on old and new, lower, established values of: Average Daily Intakes (ADIs)/Acute Reference Doses (ARfDs) and Maximum Residue Levels (MRLs). A total of 3 530 samples were collected, and CHLP in the range of 0.005-1.514 mg/kg was present in 10.2% of all samples. The MRL was exceeded in 0.7% of all samples (MRL established in 2009-2015), and recalculation yielded a much greater number of violations for the new MRL (2016), which exceeded 2.9% of all samples. Acute exposure to CHLP calculated according to the old, higher toxicological data (0.10 mg/kg bw/day), does not exceed 14% of its respective ARfDs for adults and both groups of children, but when calculated for incidental cases according to the current value (ARfD 0.005 mg/kg bw) for infants and toddlers, was above 100% of its respective ARfDs in: white cabbage (263.65% and 108.24%), broccoli (216.80% and 194.72%) and apples (153.20% and 167.70%). The chronic exposure calculated for both newly established ADI values (0.001 mg/kg bw/day and 0.100 mg/kg bw/day) appears to be relatively low for adults and children., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The persistence of chlorpyrifos, fluopyram, and tebuconazole was estimated in green pods, matured seeds, and soil of French beans using dispersive QuEChERS. Three foliar applications each of chlorpyrifos and a combination fungicide fluopyram + tebuconazole (Luna experience, 400 SC) were applied at 600 and 125 + 125 as a standard dose and 1200 and 250 + 250 g a.i. ha -1 as a double dose, respectively, were applied at an interval of 10 days and treated pods were picked up at regular intervals. Dried mature seeds and soil were also monitored at harvest. The initial deposits of chlorpyrifos on bean pods were 3.083 and 6.017 mg kg -1 with a half-life of 1.86 and 2.29 days, at respective doses. Foliar application of a combi product Luna experience yielded 3.396 and 5.772 mg kg -1 residues of fluopyram and 3.613 and 5.887 mg kg -1 of tebuconazole in green pods at standard and double dose with almost same half-lives of 3.4 and 3.8-3.9 days. Residues declined below the limit of quantitation (LOQ) of 0.05 mg kg -1 in green beans after 15 and 25 days after the application of double dose of chlorpyrifos and Luna experience, respectively. However, the residues in dry bean seeds and soil reached below the LOQ of 0.05 mg kg -1 at the time of harvest. A pre-harvest interval of 5, 10, and 7 days has been proposed for chlorpyrifos, fluopyram, and tebuconazole, respectively, in beans. HQ < 1 and TMDI < MPI in all test chemicals. Hence, it was concluded that a waiting period of 5 days for chlorpyrifos and 7-10 days in Luna experience will be safer to consumers. This data generated will be useful for regulatory agency for fixing MRLs.

Climate change may increase the pest infestation leading to intensive use of insecticides. However, the effect of insecticide and climate factors on soil methane (CH 4 ) consumption is less understood. A laboratory experiment was carried out to evaluate the effect of temperature (15 °C, 35 °C, and 45 °C), moisture holding capacity (MHC) (60%, 100%), biochar (0%, 1%) and chlorpyrifos (0 ppm, 10 ppm) on CH 4 consumption and microbial abundance in a tropical Vertisol of central India. Methane consumption rate k (ng CH 4 consumed g -1 soil d -1 ) varied from 0.065 ± 0.005 to 0.608 ± 0.018. Lowest k was in 15 °C-60% moisture holding capacity (MHC)-no biochar and with 10 ppm chlorpyrifos. Highest k was in 35 °C-100% MHC-1% biochar and without (0 ppm) chlorpyrifos. Cumulative CO 2 production (ng CO 2 produced g -1 soil d -1 ) varied from 446 ± 15 to 1989 ± 116. Both CH 4 consumption and CO 2 production peaked in the treatment of 35 °C-100% MHC-1% biochar. Chlorpyrifos inhibited CH 4 consumption irrespective of treatments. Abundance of 16S rRNA of eubacteria (× 10 6 g -1 soil) varied from 2.33 ± 0.58 to 85.67 ± 7.00. Abundance of 16S rRNA genes representing Actinomycetes (× 10 4 g -1 soil) varied from 7.67 ± 1.53 and pmoA gene (Methanotrophs) (× 10 5 g -1 soil) varied from 1.23 ± 0.59 to 34.33 ± 6.51. Chlorpyrifos inhibited abundance of heterotrophic bacteria and methanotrophs but stimulated actinomycetes. Biochar stimulated the CH 4 consumption, CO 2 production and microbial abundance. Study highlighted that use of chlorpyrifos under climate change factors may inhibit CH 4 consumption but the use of biochar may alleviate the negative effect of the chlorpyrifos., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Bacterial cell immobilization offer considerable advantages over traditional biotreatment systems using free cells. Calcium alginate matrix usually used for bacterial immobilization is susceptible to biodegradation in harsh environment. Current study aimed to produce and characterize stable macrocapsules (MCs) of Chlorpyrifos (CP) degrading bacterial consortium using biocompatible calcium alginate matrix coupled with environmentally stable polysulfone. In current study bacterial consortium capable of CP biodegradation was immobilized using calcium alginate in a form of microcapsule (MC) reinforced by being coated with a synthetic polymer polysulfone (PSf) through phase inversion. Consortium comprised of five bacterial strains was immobilized using optimized concentration of sodium alginate (2.5gL -1 ), calcium chloride (6gL -1 ), biomass (600mgL -1 ) and polysulfone (10gL -1 ). It has been observed that MCs have high thermal, pH and chemical stability than CAMs. In synthetic media complete biodegradation of CP (100-600mgL -1 ) was achieved using macrocapsules (MCs) within 18h. CAMs could be reused effectively only upto 5cycles, contrary to this MCs could be used 13 times to achieve more than >96% CP degradation. Shelf life and reusability studies conducted for MCs indicated unaltered biomass retention and CP biodegradation activity (95%) over 16weeks of storage. MCs achieved complete biodegradation of CP (536mgL -1 ) in real industrial wastewater and reused several times effectively. Metabolites (3,5,6-trichloro-2-pyridinol (TCP), 3,5,6-trichloro-2-methoxypyridine (TMP) and diethyl-thiophosphate (DETP) were traced using GC-MS and possible metabolic pathway was constructed. Study indicated MCs could be used for cleanup of CP contaminated wastewater repeatedly, safely, efficiently for a longer period of time., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A biopurification system based on the adsorption and degradation capacity of a biomixture to degrade a mixture of pesticides (atrazine, chlorpyrifos, iprodione; 50 mg kg -1 each) in repeated applications (0, 30, and 60 days) was evaluated. Tanks of 1 m 3 packed with a biomixture (ρ 0.29 g mL -1 ) with and without vegetal cover were used. The biomixture contained soil, peat, and wheat straw in a proportion 1:1:2 by volume, respectively. Pesticide concentrations, biological activities (urease, phenoloxidase, and dehydrogenase), and microbial community changes (DGGE and qPCR) were evaluated periodically. Pesticide dissipation was higher in tanks with vegetal cover (> 95%) and no variation was observed after the three applications; contrarily, pesticide dissipation decreased in the tank without vegetal cover after each application. The presence of vegetal cover decreased the half-life of pesticides by at least twice. Biological activities were in general not affected by the application and reapplication of pesticides in the same treatment; however, they exhibited some differences between tanks containing and lacking the vegetal cover. High similarity between microbial groups (actinobacteria, bacteria, and fungi) was observed, suggesting no influence ascribable to the successive pesticide applications. The number of copies of bacteria and actinobacteria remained almost constant during the assay. However, the number of copies of fungi was significantly higher in the uncontaminated tank without vegetal cover.

A simple and effective method for the detection of three pesticides (chlorpyrifos, diazinon and cyprodinil) is developed using a polymer inclusion membrane (PIM) prior to gas chromatography and mass spectrometry detection (GC-MS). Analytes are extracted from natural water samples using a 3 cm 2 PIM made of the polymer, cellulose triacetate (CTA), and the plasticizer, nitrophenyl octyl ether (NPOE). Addition of the plasticizer to the CTA matrix is found to be necessary for the extraction of pesticides. After extraction, analytes are recovered from the membrane with 1 mL of acetonitrile and injected into the GC-MS system. The main factors affecting the extraction efficiency are evaluated, including membrane composition, stirring mode, extraction and elution time. Ultrasonic assisted elution of the extracted pesticides is accomplished after 15 min of contact. The PIM-assisted extraction method makes it possible for pesticides to be determined in the range of 50-1000 ng L -1 with good linearity (coefficient of determination ≥0.995) and suitable recoveries (85-119%) and precision (<21%, n = 3) using 100 mL of a water sample. This methodology is shown to be suitable for the detection of chlorpyrifos in local river waters., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A solid-phase microextraction probe was prepared on the surface of a stainless-steel wire through molecular sol-gel imprinting technology using chlorpyrifos as a template molecule, tetraethoxysilane as a sol-gel precursor, and acrylamide and β-cyclodextrin as functional monomers. The polymer was characterized by infrared spectrometry and scanning electron microscopy. Moreover, the selectivity and the parameters including the type and volume of the extraction solvents, ionic strength, pH, temperature, extraction time, stirring speed, and desorption time affecting extraction performance were evaluated. Under the optimum solid-phase microextraction and gas chromatography conditions, the linear ranges were 0.25-25.0 μg/L for chlorpyrifos, quinalphos, triazophos, pirimiphos-methyl, and chlorpyrifos-methyl with the correlation coefficient above 0.99. The detection limits (S/N = 3) were in the range of 0.02-0.07 μg/L and the RSDs were <7.3%. The developed method was successfully used to determine the multi-residues of chlorpyrifos, quinalphos, triazophos, pirimiphos-methyl, and chlorpyrifos-methyl in green peppers and cinnamon with satisfactory recoveries., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon-silica hybrid nanofibers as high performance coatings for solid-phase microextraction fibers were used for analyzing some pesticides by using gas chromatography-corona discharge ion mobility spectrometry. To that end, the fibers were prepared by carbonizing sol-gel based on electrospun polyacrylonitrile and tetraethyl orthosilicate nanofibers as carbon and silica precursors, respectively. Different parameters affecting the electrospinning and the extraction processes including spinning distance, voltage, feeding rate, stirring rate, salt concentration, temperature and extraction time were optimized by response surface methodology. The method involved deionized water samples spiked with pesticides at different concentration levels. The calibration curves were linear in the ranges of 0.1-20 and 0.05-20 μg L -1 with determination coefficients (R 2 ) of 0.9976 and 0.9928 for malathion and chlorpyrifos, respectively. The limits of detection of 0.032 and 0.019 μg L -1 and the limits of quantification of 0.1 and 0.05 μg L -1 were found for malathion and chlorpyrifos, respectively. Acceptable reproducibility values were obtained with relative standard deviations (RSD, n = 3) lower than 6 and 15%, for intra-day and inter-day precision, respectively. Finally, the relative recoveries of the proposed method were calculated in the range of 80-111% for real samples., (Copyright © 2018 Elsevier B.V. All rights reserved.)