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Precisely detecting organophosphorus pesticides (OPs) is paramount in upholding human safety and environmental preservation, especially in food safety. Herein, an electrochemical acetylcholinesterase (AChE) sensing platform entrapped in chitosan (Chit) on the glassy carbon electrodes (GCEs) decorated with Pt/MoS 2 /Ti 3 C 2 MXene (Pt/MoS 2 /TM) was constructed for the detection of chlorpyrifos. It is worth noting that Pt/MoS 2 /TM possesses good biocompatibility, remarkable electrical conductivity, environmental stability and large specific surface area. Besides, the heterostructure formed by the composite of TM and MoS 2 improves the conductivity and maintains the original structure, which is conducive to improving the electrochemical property. The coordination effect between the individual components enables the even distribution of functional components and enhances the electrochemical performance of the biosensor (AChE-Chit/Pt/MoS 2 /TM). Under optimal efficiency and sensitivity, the AChE-Chit/Pt/MoS 2 /TM/GCE sensing platform exerts comparable analytical performance and a wide concentration range of chlorpyrifos from 10 -12 to 10 -6  M as well as a low limit of detection (4.71 × 10 -13  M). Furthermore, the biosensor is utilized to detect OPs concerning three kinds of fruits and vegetables with good feasibility and recoveries (94.81% to 104.0%). This work would provide a new scheme to develop high-sensitivity sensors based on the two-dimensional nanosheet/laminar hybrid structure for practical applications in environmental monitoring and agricultural product detection., Competing Interests: Declaration of competing interest There is no conflict of interest in this manuscript, and the work described is original research., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Enzyme-inhibited electrochemical sensor is a promising strategy for detecting organophosphorus pesticides (OPs). However, the poor stability of enzymes and the high oxidation potential of thiocholine signal probe limit their potential applications. To address this issue, an indirect strategy was proposed for highly sensitive and reliable detection of chlorpyrifos by integrating homogeneous reaction and heterogeneous catalysis. In the homogeneous reaction, Hg 2+ with low oxidation potential was employed as signal probe for chlorpyrifos detection since its electroactivity can be inhibited by thiocholine, which was the hydrolysate of acetylthiocholine catalyzed by acetylcholinesterase. Additionally, Co,N-doped hollow porous carbon nanocage@carbon nanotubes (Co,N-HPNC@CNT) derived from ZIF-8@ZIF-67 was utilized as high-performance electrode material to amplify the stripping voltammetry signal of Hg 2+ . Thanks to their synergistic effect, the sensor exhibited outstanding sensing performance, excellent stability and good anti-interference ability. This strategy paves the way for the development of high-performance OP sensors and their application in food safety., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Implementation of cost-effective, reliable, and efficient technologies for the sensitive, rapid, and accurate detection of pesticide residues in agriproducts presents a promising solution to the escalating food safety concerns. Herein, a high-performance surface-enhanced Raman scattering (SERS) aptasensor based on nanotag (AuNS@4-MBN@Ag-aptamer) was introduced for ultrasensitive, reliable, and interference-free detection of chlorpyrifos (CPF). This aptasensor featured star-shaped bimetallic nanotag as the principal Raman signal enhancement material and 4-mercaptobenzonitrile (4-MBN) as "biological-silent"-window reporter (at 2228 cm -1 ). Moreover, cDNA-linked Fe 3 O 4 @AuNPs (FA-cDNA) served as magnetic substrates to simplify the separation process of FA-cDNA-combined nanotags. In the aptasensor, the formation of FA-cDNA-aptamer-AuNS@4-MBN@Ag hybrids was hindered by CPF, and its Raman intensity decreased with increasing CPF concentration. Under optimal SERS conditions, the aptasensor exhibited a broad linear detection range from 2.5 × 10 2 to 5.0 × 10 4  pg⋅mL -1 , with an impressively low limit of detection of 220.35 pg⋅mL -1 (signal-to-noise ratio = 3). The selectivity and reproducibility assessments highlighted its exceptional sensitivity and interference-free capabilities. Furthermore, practical applications on wheat and apples demonstrated satisfactory spiked recovery rates, ranging from 89.61% to 107.33% (relative standard deviation ≤ 14.55%). Consequently, the high-performance "biological-silent"-window nanotag-based aptasensor is a promising tool for monitoring trace CPF in complex matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pesticides are chemicals used to enhance crop production. However, their residues can persist and accumulate in various environmental settings. This study assessed the occurrence of pesticide residues and ecological risks in surface water and sediment from the Libga and Builpela dams in northern Ghana. A total of 42 pesticides were analysed. Toxic units were used to assess the acute risk to sediment-dwelling organisms and aquatic biota. Risk quotients were employed to assess the chronic risk to aquatic organisms. Chlorpyrifos, atrazine, profenofos, and chlorfenvinphos were the main chemicals found in surface water. The concentrations were highest near the Builpela dam (0.413μg/L, 2.927μg/L, 0.304μg/L, 0.692μg/L, 0.073μg/L, 0.290μg/L, 0.06μg/L, and absent in the Libga dam). In the sediment, the organophosphates pyrimiphos-methyl and chlorpyrifos were found at high concentrations. They were found in higher quantities in the Libga dam (0.554mg/kg and 0.052mg/kg, respectively) and Builpela dam (0.051mg/kg and 0.043mg/kg, respectively). For organochlorines, p,p'-DDE and p,p'-DDD were the main residues detected at high concentrations. However, concentrations were higher for p,p'-DDD at Builpela than for p,p'-DDE. Additionally, high concentrations of atrazine were detected in this study. The toxic units showed a high acute risk for organisms that live in sediment as a result of chlorpyrifosfos and chlorfenvinphos residues. Similarly, pirimiphos-methyl and chlorfenvinphos, followed by chlorpyrifos, contributed to high acute risk in aquatic invertebrates. Risk quotients showed that both dams had a high long-term risk for aquatic life; however, the risk was higher at the Builpela dam due to Pirimiphos-methyl and Chlorfenvinphos. Ghana's pesticide regulations are less comprehensive and enforcement is often weaker in protecting aquatic organisms. It is recommended to enforce strict limits on pesticide residues. Additionally, there is a need to regularly review and update these regulations based on new scientific data to protect aquatic ecosystems., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Orou-Seko et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

A metal-organic-framework (MOF) fluorescent sensor is reported based on NH 2 -MIL-101(Fe) propelled pesticide and alkaline phosphatase (ALP) catalytic reaction. Different from previous reports, a cascade reaction system combined with MOF structural changes to generate fluorescence was employed. The rationale is that ALP can hydrolyze L-ascorbic acid 2-phosphate (AAP) into L-ascorbic acid (AA), which can reduce Fe 3+ to decompose structurally NH 2 -MIL-101(Fe), resulting in 2-aminoterephthalic acid (NH 2 -BDC) with intense fluorescence. The  fluorescence can be decreased to different degrees due to inhibition of organophosphate pesticides (OPPs) on the activity of ALP. By taking chlorpyrifos (CPY) as the model compound of an OPP pesticide and adding ALP and CPY into the NH 2 -MIL-101(Fe) framework, the resulting cascade reaction fluorescence sensors exhibit a good sensitivity for CPY and ALP sensing. The working ranges are  0.02-2 μg/L and 0.2-20 mU/mL with detection limits (LOD) of 5.31 ng/L and 0.05 mU/mL, respectively. The proposed sensor has been actually applied to satisfactory detection of CPY and ALP in food and serum samples. This fluorescence-based assay may extend the application of MOF-based biosensors., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

This study investigates the behaviour of gold nanoparticles (AuNPs) when exposed to chlorpyrifos, an agricultural pesticide, and its application in detecting the pesticide via surface-enhanced Raman spectroscopy (SERS). Under synergistic addition of NaCl, AuNPs undergo agglomeration at lower chlorpyrifos concentrations but aggregation at higher concentrations, resulting in a distinctive nonlinear SERS response. A linear relationship is obtained between 0.001 and 1 ppm with detection limit (LOD) of 0.009 ppm, while an inverse response is observed at higher concentrations (1-1000 ppm) with a LOD of 1 ppm. Combining the colorimetric response of AuNP solutions, their absorbance spectra, and principal component analysis can improve detection reliability. The assay, coupled with a simple recovery method using acetonitrile swabbing, achieves high reproducibility in detecting chlorpyrifos in cucumber, even at concentrations as low as 0.11 ppm. This approach can be tailored for various chlorpyrifos concentrations not only in cucumbers but also in different food matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Organophosphorus pesticides (OPPs) constitute the most widely employed class of pesticides. However, the prevalent use of OPPs, while advantageous, raises concerns due to their toxicity, posing serious threats to food safety. Chemical sensors utilizing quantum dots (QDs) demonstrate promising applications in rapidly detecting OPPs residues, thereby facilitating efficient inspection of agricultural products. In this study, we employ an aqueous synthesis approach to prepare low toxic CdTe@ZnS QDs with stable fluorescence properties. To mitigate the risk of imprecise measurements stemming from the inherent susceptibility of fluorescence to quenching, we have adopted the principle of fluorescence resonance energy transfer (FRET) for the construction of the turn-on quantum dot sensor. With a detection limit for chlorpyrifos as low as 10 ppb (10 μg/L), the QDs sensor exhibits notable resistance to interference from various pesticides. Application of this system to detect organophosphorothioate pesticides in apples produced results consistent with those obtained from high-performance liquid chromatography (HPLC) detection, affirming the promising application prospects of this sensing system for the rapid detection of OPPs residues., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study evaluated the presence of the three pesticides methomyl (MET), carbendazim (CBZ) and chlorpyrifos-ethyl (CPE), as well as the degradation product of CPE (3,5,6-trichloro-2-pyridinol; TCP), in 44 honey samples from all 12 regions of Morocco. With a validated HPLC-UV method occurrence frequencies of 63.6% for MET, 54.5% for CBZ, 95.1% for CPE and 34.1% for TCP were obtained, even at concentrations higher than the maximum residue limits for MET, CPE and TCP. Based on the predominant pesticide, principal component analysis separated sampling regions into three groups. Risk assessment indicated that ingestion of these pesticides, alone or in combination, in honey did not pose a risk to consumers (HQ and HI < 1).

The apple (Malus domestica), a cultivated fruit extensively grown in temperate regions worldwide, is abundant in nutrients and phytochemicals that promote health. However, the application of pesticides in apple cultivation raises significant concern regarding their influence on food safety. This study investigated the dynamic behavior of five pesticides, including chlorpyrifos, imidacloprid, acetamiprid, carbendazim, prochloraz, in apple trees, utilizing both field experiments and predictive modeling to analyze their distribution, transfer, and degradation patterns. Results from the field experiment revealed that at harvest, the residue levels of the five pesticides on apple were below international and national maximum residue limits. The dynamiCROP modeling results, corresponding to the field trial findings, demonstrated that these pesticides exhibited comparable dissipation patterns across various environmental compartments. The primary sources of pesticides in apples were the air and the fruit surface up to 10 days after application, while the soil and leaf surface became the main sources over time. The transferred pesticides adhered to the apple fruits at varying rates and persist therein. Choosing pesticides with lower impact scores helped reduce the impacts on human health and the environment. The assessment of health risks associated with consuming apples containing pesticide residues suggested that the impact on human health is acceptable. These findings were crucial for apple producers, as they enable the optimization of pesticide application timing to ensure compliance with food safety standards and help improve pesticide management strategies in agriculture. This study is essential for minimizing the environmental impact of pesticides and enhancing sustainable agricultural practices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Exploring efficient photoactive material presents an intriguing opportunity to enhance the analytical performance of photoelectrochemical (PEC) sensor in the environmental analysis. In this work, a sandwich-structured multi-interface Co 9 S 8 @ZnIn 2 S 4 /CdSe QDs dual Z-Scheme heterojunction, derived from metal-organic framework (MOF), was synthesized as a sensing platform for chlorpyrifos detection, by integrating with enzyme-induced in situ insoluble precipitates strategy. The meticulously designed Co 9 S 8 @ZnIn 2 S 4 /CdSe QDs exhibited enhanced charge separation efficiency and was proved to be a highly effective sensing platform for the immobilization of biomolecules, attributing to the intrinsic dual Z-Scheme heterojunction and the distinctive hollow structure. The proposed PEC sensing platform combined with enzyme-induced in situ precipitate signal amplification strategy achieved superior performance for sensing of chlorpyrifos (CPF), showing in wide linear range (1.0 pg mL -1 -100 ng mL -1 ), with a limit of detection (0.6 pg mL -1 ), excellent selectivity, and stability. This work offers valuable insights for the design of novel advanced photoactive materials aimed at detecting environmental pollutants with low level concentration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Chlorpyrifos (CPS) is widely found in food and water sources due to agricultural use, posing health and environmental risks. Therefore, this work introduces a fluorescent sensor design of silver nanoparticle-embedded nano zirconium-based metal-organic frameworks (UiO-66-NH 2 @AgNPs) for accurate examination of CPS. Briefly, UiO-66-NH 2 was synthesized hydrothermally, exhibiting weak luminescence owed to ligand-to-metal charge transfer (LMCT). Here, it limits its direct utility in fluorescence-based detection. To address this limitation, silver nanoparticles (AgNPs) were introduced into UiO-66-NH 2 , enhancing fluorescence via the metal-enhanced fluorescence (MEF) effect. Briefly, a comprehensive spectral analysis such as XPS, SEM, TEM, PXRD, etc., was performed to validate the synthesis of UiO-66-NH 2 @AgNPs. Subsequent evaluation revealed that CPS effectively quenched the luminescence intensity of UiO-66-NH 2 @AgNPs through a static quenching mechanism. The fluorescence intensity exhibited good linearity with CPS concentration in the span of 10 to 1,000 ng/mL, with a recognition limit of 191.5 ng/mL(S/N = 3). The interaction involved Ag-S bond formation and electrostatic interactions, reducing fluorescence intensity. The method was confirmed through successful CPS detection in fruit samples. The UiO-66-NH 2 @AgNPs nanoprobe offers a simple, sensitive, and accurate platform for CPS sensing, with potential for future use in detecting CPS in fruits and vegetables., (© 2024 John Wiley & Sons Ltd.)

Elasmobranchs are good indicators of marine pollution as they accumulate pollutants from water and food, and occupy different trophic levels. Concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and chlorpyrifos were quantified in muscle, liver, gonads, gills, and brain in both sexes and maturity stages of the Southern Eagle Ray, Myliobatis goodei, captured in Argentine coastal waters. Moreover, possible histological alterations in the liver and gonads were analyzed. Pollutant concentrations were pervasive across all tissues, with PCBs > OCPs > chlorpyrifos. Elevated pollutant levels were notably found in the liver and gills. We identified thirty-six PCB congeners in tissues, with low-chlorine congeners prevailing. Among OCPs, ∑DDT and ∑endosulfan were predominant. Females exhibited higher pollutant levels in most tissues compared to males, except in the gonads, and adults generally displayed elevated pollutant levels. Histological analysis revealed the presence of atretic follicles and melanomacrophages (MM). Continuous monitoring of pollutant levels, alongside their effects on physiological and ecological traits, is imperative for effective management and conservation efforts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of pesticides in water and sediments of two protected areas namely Doñana Natural Park (DNP) and Tablas de Daimiel National Park (TDNP) performing an environmental risk assessment in order to highlight potential risks to living organisms derived from pesticide burden. Higher pesticide load was found in DNP than TDNP with similar distribution profiles, with pyrethroid insecticides (PYRs) the main detected class. Particularly problematic are two PYRs, cyhalothrin and fenvalerate, which were detected at high concentrations that can pose a high risk to aquatic organisms. In addition, despite being detected at lower concentrations, the presence of chlorpyrifos, cypermethrin, and permethrin in water, and of chlorpyrifos, dicofol, and diflufenican in sediments, must be taken into account due to their potential risks for aquatic organisms. Moreover, some banned pesticides such as dimethoate, terbutryn, diazinon, and tricyclazol were detected in water at levels which deserve further investigation to assess their potential sources, including potential illegal practices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Background: The Centers for Disease Control and Prevention (CDC) bottle bioassay is a commonly used susceptibility test for measuring insect response to insecticide exposure. However, inconsistencies and high variability in insect response when conducting CDC bottle bioassays have been reported in previous publications. We hypothesized that the CDC bottle bioassay results may be compromised when expected and actual insecticide concentrations in the bottles are not equivalent and that inadequate bottle cleaning and/or loss during insecticide introduction and bottle storage steps could be responsible. We explored this hypothesis by quantifying insecticides using gas chromatography tandem mass spectrometry (GC-MS/MS) in bottles that had been cleaned, prepared, and stored according to the CDC guidelines., Methods: We investigated the bottle cleaning, preparation, and storage methods outlined in the CDC bottle bioassay procedure to identify sources of irreproducibility. We also investigated the effectiveness of cleaning bottles by autoclaving because this method is commonly used in insecticide assessment laboratories. The two insecticides used in this study were chlorpyrifos and lambda-cyhalothrin (λ-cyhalothrin). Insecticides were removed from glass bioassay bottles by rinsing with ethyl-acetate and n-hexane and then quantified using GC-MS/MS., Results: The CDC bottle bioassay cleaning methods did not sufficiently remove both insecticides from the glass bottles. The cleaning methods removed chlorpyrifos, which has higher water solubility, more effectively than λ-cyhalothrin. Chlorpyrifos experienced significant loss during the bottle-coating process whereas λ-cyhalothrin did not. As for bottle storage, no significant decreases in insecticide concentrations were observed for 6 h following the initial drying period for either insecticide., Conclusions: The CDC bottle bioassay protocol is susceptible to producing inaccurate results since its recommended bottle cleaning method is not sufficient and semi-volatile insecticides can volatilize from the bottle during the coating process. This can lead to the CDC bottle bioassay producing erroneous LC 50 values. High levels of random variation were also observed in our experiments, as others have previously reported. We have outlined several steps that CDC bottle bioassay users could consider that would lead to improved accuracy and reproducibility when acquiring toxicity data., (© 2024. The Author(s).)

Chlorpyrifos (CPF) residues in food pose a serious threat to ecosystems and human health. Herein, we propose a three-dimensional folded paper-based microfluidic analysis device (3D-μPAD) based on multifunctional metal-organic frameworks, which can achieve rapid quantitative detection of CPF by fluorescence-colorimetric dual-mode readout. Upconversion nanomaterials were first coupled with a bimetal organic framework possessing peroxidase activity to create a fluorescence-quenched nanoprobe. After that, the 3D-μPAD was finished by loading the nanoprobe onto the paper-based detection zone and spraying it with a color-developing solution. With CPF present, the fluorescence intensity of the detection zone gradually recovers, the color changes from colorless to blue. This showed a good linear relationship with the concentration of CPF, and the limits of detection were 0.028 (fluorescence) and 0.043 (colorimetric) ng/mL, respectively. Moreover, the 3D-μPAD was well applied in detecting real samples with no significant difference compared with the high-performance liquid chromatography method. We believe it has huge potential for application in the on-site detection of food hazardous substance residues.

The development of advanced biosensors for tracking chemical residues and detecting environmental pollution is of great significance. Insect chemical sensory proteins, including chemosensory proteins (CSPs), are easy to synthesize and purify and have been used to design proteins for specific biosensor applications. Chlorpyrifos is one of the most commonly used chemicals for controlling insect pests in agriculture. This organophosphate is harmful to aquatic species and has long-term negative consequences for the ecosystem. CSPs can bind and carry a variety of environmental chemicals, including insecticides. However, the mechanism by which CSPs bind to insecticides in aphids has not been clarified. In this study, we discovered that RpCSP1 from Rhopalosiphum padi has a higher affinity for chlorpyrifos, with a K i value of 4.763 ± 0.491 μM. Multispectral analysis revealed the physicochemical binding mechanism between RpCSP1 and chlorpyrifos. Computational simulation analysis demonstrated that the main factor promoting the development of the RpCSP1-chlorpyrifos complex is polar solvation energy. Four residues (Arg33, Glu94, Gln145, Lys153) were essential in facilitating the interaction between RpCSP1 and chlorpyrifos. Our research has improved knowledge of the relationship between CSPs and organophosphorus pesticides. This knowledge contributes to the advancement of biosensor chips for tracking chemical residues and detecting environmental pollution through the use of CSPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pesticides are used in vegetable farming to control pests and diseases, reduce crop losses and improve yield. The study examined pesticide residues in irrigation waters and leafy green vegetables grown in some farming areas in Accra, Ghana. Three types of irrigation water sources ( n  = 23) and two exotic and four indigenous Ghanaian leafy vegetables ( n  = 34) from 10 farming areas in Accra, Ghana were collected and examined for 15 organochlorines, 13 organophosphorus and 9 synthetic pyrethroids pesticide residues using the modified QuEChERS procedure. Pesticide residues were detected on 50% (17/34) of the leafy vegetable and 52% (12/23) of the irrigation water samples analysed. Chlorpyrifos and deltamethrin were the most detected pesticide residues in the vegetables and irrigation water. About 26.5% of the vegetables contained pesticide residues exceeding the EU maximum residue limits, so vegetable farmers should be encouraged to comply with appropriate measures on pesticide use to enhance food safety.

Argentina is a leading honey producer and honey bees are also critical for pollination services and wild plants. At the same time, it is a major crop producer with significant use of insecticides, posing risks to bees. Therefore, the presence of the highly toxic insecticide chlorpyrifos, and forbidden contaminants (organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)) was investigated in honey bee, beebread, wax and honey samples in apiaries from three contrasting regions of Argentina. Chlorpyrifos was detected in all samples with higher levels during period 1 (spring) in contrast to period 2 (fall), agreeing with its season-wise use in different crops, reaching 3.05 ng/g in honey bees. A subsequent first-tier pesticide hazard analysis revealed that it was relevant to honey bee health, mainly due to the high concentrations found in wax samples from two sites, reaching 132.4 ng/g. In addition, wax was found to be the most contaminated matrix with a prevalence of OCPs (∑OCPs 58.23-172.99 ng/g). Beebread samples showed the highest concentrations and diversity of pesticide residues during period 1 (higher temperatures). A predominance of the endosulfan group was registered in most samples, consistent with its intensive past use, especially in Central Patagonia before its prohibition. Among the industrial compounds, lighter PCB congeners dominated, suggesting the importance of atmospheric transport. The spatio-temporal distribution of pesticides shows a congruence with the environmental characteristics of the areas where the fields are located (i.e., land use, type of productive activities and climatic conditions). Sustained monitoring of different pollutants in beekeeping matrices is recommended to characterize chemical risks, assess the health status of honey bee hives and the pollution levels of different agroecosystems. This knowledge will set a precedent for South America and be helpful for actions focused on the conservation of pollination services, apiculture and ecosystems in Argentina., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Evaluating biomarkers of stress in amphibians is critical to conservation, yet current techniques are often destructive and/or time-consuming, which limits ease of use. In the present study, we validate the use of dermal swabs in spotted salamanders (Ambystoma maculatum) for biochemical profiling, as well as glutathione (GSH) stress response following pesticide exposure. Thirty-three purchased spotted salamanders were acclimated to laboratory conditions at Washington College (Chestertown, MD, USA) for 4 weeks. Following acclimation, salamanders were randomly sorted into three groups for an 8-h pesticide exposure on soil: control with no pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), or chlorpyrifos. Before and after exposure, mucus samples were obtained by gently rubbing a polyester-tipped swab 50 times across the ventral and dorsal surfaces. Salamanders were humanely euthanized and dissected to remove the brain for acetylcholinesterase and liver for GSH and hepatic metabolome analyses, and a whole-body tissue homogenate was used for pesticide quantification. Levels of GSH were present in lower quantities on dermal swabs relative to liver tissues for chlorpyrifos, 2,4-D, and control treatments. However, 2,4-D exposures demonstrated a large effect size increase for GSH levels in livers (Cohen's d = 0.925, p = 0.036). Other GSH increases were statistically insignificant, and effect sizes were characterized as small for 2,4-D mucosal swabs (d = 0.36), medium for chlorpyrifos mucosal swabs (d = 0.713), and negligible for chlorpyrifos liver levels (d = 0.012). The metabolomics analyses indicated that the urea cycle, alanine, and glutamate metabolism biological pathways were perturbed by both sets of pesticide exposures. Obtaining mucus samples through dermal swabbing in amphibians is a viable technique for evaluating health in these imperiled taxa. Environ Toxicol Chem 2024;43:1126-1137. © 2024 SETAC., (© 2024 SETAC.)

Bioaccumulation of Chlorpyrifos (CP) as pesticides due to their aggrandized use in agriculture has raised serious concern on the health of ecosystem and human beings. Moreover, their degraded products like 3,5,6-trichloro-2-pyridinol (TCP) has enhanced the distress due to their unpredictable biotoxicity. This study evaluates and deduce the comparative in vivo mechanistic biotoxicity of CP and TCP with zebrafish embryos through experimental and computational approach. Experimental cellular and molecular analysis showed higher induction of morphological abnormalities, oxidative stress and apoptosis in TCP exposed embryos compared to CP exposure due to upregulation of metabolic enzymes like Zhe1a, Sod1 and p53. Computational analysis excavated the differential discrepancies in intrinsic atomic interaction as a reason of disparity in biotoxicity of CP and TCP. The mechanistic differences were deduced due to the differential accumulation and internalisation leading to variable interaction with metabolic enzymes for oxidative stress and apoptosis causing physiological and morphological abnormalities. The study unravelled the information of in vivo toxicity at cellular and molecular level to advocate the attention of taking measures for management of CP as well as TCP for environmental and human health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

An enzymatic electrochemical biosensor was built for the indirect detection of organophosphates (OPs), based on acetylcholinesterase inhibition. The biosensor was fabricated for enhanced performance on a screen-printed carbon electrode (SPCE), modified with copper nanowires (CuNWs) composited with reduced graphene oxide (rGO). The oxidation current was measured using the cyclic voltammogram (CV) method, as generated by the enzymatic interaction between acetylcholinesterase (AChE) and its substrate, acetylthiocholine (ATCh). The biosensing response is the reduction in signal caused by the inhibition of acetylcholinesterase in the presence of an organophosphate inhibitor. Benchmarking shows that the CuNWs/rGO nanocomposite enhanced the signal current considerably and decreased the oxidation potential for electrochemical detection of the OP chlorpyrifos, exhibiting a wide linear detection rangefrom 10 µg/L-200 µg/L, with a limit of detection of 3.1 µg/L and limit of quantification of 12.5 µg/L. This sensor is useful for the analysis of chlorpyrifosin drinking water and orange juice, with high recovery rates and no interference effects., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Introduction: Erectile dysfunction (ED) poses a significant disease morbidity and contributor to male infertility, where an estimated 20-40% of men are affected annually. While several risk factors have been identified in the etiology of ED (e.g., aging, heart disease, diabetes, and obesity), the complete pathogenesis remains to be elucidated. Over the last few decades, the contribution of environmental exposures to the pathogenesis of ED has gained some attention, though population studies are limited and results are mixed. Among environmental contaminants, organophosphate (OP) insecticides represent one of the largest chemical classes, and chlorpyrifos is the most commonly used OP in the U.S. OP exposure has been implicated in driving biological processes, including inflammation, reactive oxygen species production, and endocrine and metabolism disruption, which have been demonstrated to adversely affect the hypothalamus and testes and may contribute to ED. Currently, studies evaluating the association between OPs and ED within the U.S. general population are sparse., Methods: Data were leveraged from the National Health and Nutrition Examination Survey (NHANES), which is an annually conducted, population-based cross-sectional study. Urinary levels of 3,5,6-trichloro-2-pyridinol (TCPy), a specific metabolite of the most pervasive OP insecticide chlorpyrifos, were quantified as measures of OP exposure. ED was defined by responses to questionnaire data, where individuals who replied "sometimes able" or "never able" to achieve an erection were classified as ED. Chi-square, analysis of variance (ANOVA), and multivariable, weighted linear and logistic regression analyses were used to compare sociodemographic variables between quartiles of TCPy exposure, identify risk factors for TCPy exposure and ED, and to analyze the relationship between TCPy and ED., Results: A total of 671 adult men were included in final analyses, representing 28,949,379 adults after survey weighting. Approximately 37% of our cohort had ED. Smoking, diabetes, aging, Mexican-American self-identification, and physical inactivity were associated with higher ED prevalence. Analysis of TCPy modeled as a continuous variable revealed nonsignificant associations with ED (OR = 1.02 95% CI [0.95, 1.09]). Stratification of total TCPy into quartiles revealed increased odds of ED among adults in the second and fourth quartiles, using the first quartile as the reference (OR = 2.04 95% CI [1.11, 3.72], OR = 1.51 95% CI [0.58, 3.93], OR = 2.62 95% CI [1.18, 5.79], for quartiles 2, 3, and 4, respectively)., Conclusions: The results of our study suggest a potential role for chlorpyrifos and other OPs the pathogenesis of ED. Future studies are warranted to validate these findings, determine clinical significance, and to investigate potential mechanisms underlying these associations., (© 2023. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

The use of pesticides plays an essential role in improving crop quality and yield, however, it causes air, water, and soil pollution and the residue of these pesticides in agricultural products threatens the ecosystem and human life. Therefore, it is highly desirable to develop rapid, simple, and cost-effective methods for regular monitoring of pesticide residues in agricultural products especially strawberry that is consumed fresh and unpeeled. In this study, gold nanoparticles (AuNPs) of varying sizes have been exploited as sensing units to design a non-enzymatic colorimetric sensor array for the detection and discrimination of various pesticides including; bifenazate (BF), paraquat (PQ), diazinon (DZ), thiometon (TM), and carbendazim (CD) and chlorpyrifos (CP). Because of their strong size- and environmentally-dependent properties, AuNPs with different sizes produced distinguished plasmonic patterns in the presence of pesticides at a vast range of concentrations (25-800 ng mL -1 ). Plasmonic patterns of sensor units have been analyzed by various data visualization (bar plots and heat maps) and pattern recognition methods (linear discriminant analysis (LDA)). The multivariate calibrations showed linear responses ranging from 50 to 800 ng mL -1 for carbendazim, chlorpyrifos, paraquat, and bifenazate and 25-800 ng mL -1 for diazinon and thiometon. The limit of detection (LOD) was calculated to be 17.7, 22.8, 22.4, 9.7, 7.4, and 23.8 ng mL -1 for carbendazim, chlorpyrifos, paraquat, diazinon, thiometon, and bifenazate respectively. Finally, the applicability of the designed sensor was evaluated in real samples comprising tap water, well water, soil, and fruit, leave, drainage water, and culture substrate of strawberry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Chlorpyrifos (CP) is an extensively used organophosphate (OP) pesticide that inhibits the biogeochemical cycle with subsequent loss of soil fertility. In this view, indigenous soil bacteria with significant CP degradation capacity were identified as Pseudomonas aeruginosa RNC3 and Stenotrophomonas maltophilia RNC7 through 16 S rRNA. The optimum values of independent variables for CP degradation were found to be 30 ℃, pH 7, 100 mgL -1 of CP, and 1 OD 600 cell culture . RNC3 and RNC7 showed 82.5 mgL -1 and 77.1 mgL -1 CP degradation within 5 days. A Michaelis-Menten kinetic model estimated the degradation rate (V max ) and substrate binding affinity (K s ) for RNC3 were 1.23 mgL -1 h -1 and 123 mgL -1 whereas for RNC7 as 1.19 mgL -1 h -1 and 124.3 mgL -1 , respectively. The major metabolites 3,5,6-trichloro-2-pyridinol (TCP) and 2-hydroxy pyridine were identified during CP degradation by RNC3 whereas, only TCP by RNC7 using GC-MS. Key enzymes encoded by opd and opch2 genes were annotated in the genomes of RNC3 and RNC7 along with the set of putative degradation genes (tcp, yieH, pho, prp). Protein-ligand docking between OPCH2 and CP found - 7.9 kcal mol -1 as a high binding affinity with the conserved catalytic triad (Ser 155 -Asp 251 -His 281 ) in the active site. The study suggests that RNC3 can completely mineralize CP, whereas both strains have shown robust degradation ability of OP group of pesticides. The potential of rapid acclimatization to natural soil environment and non-virulent nature of the selected strains are beneficial for in situ application. Thus, selected indigenous strains can be applied for the bioremediation of OP-contaminated soil., Competing Interests: Declaration of Competing Interest The authors declare that they have no known conflict of interest or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Free enzymes cause difficulties in many applications due to their insufficient stability, loss of activity in a short time, and most importantly, although they are costly, they are used only once in reactions, lose their effect and cannot be recovered from the environment. Magnetic nanoparticles coated with biocompatible polymeric material are potential candidates for promising enzyme carriers due to their multifunctional pore surfaces, easy removal from the environment provided by the magnetization, ability to main stability under various harsh conditions. This study prepared a biosensor candidate based on the inhibiting acetylcholinesterase enzyme by organophosphate pesticides from chitosan-coated magnetic nanoparticles doped with gold. Transmission electron microscopy, scanning electron microscopy, X-ray diffraction diffractometry, and Fourier transform infrared spectroscopy analysis confirmed the structure of synthesized nanocomposites. Magnetic characteristics of the nanocomposites were assessed using VSM. Bio-nanocomposite (Fe 3 O 4 @Cht/Au/AChE) was used to determine environmental pollutants qualitatively. Remediation of organophosphate-containing wastewater is an essential issue for environmental sustainability. In this work, Dichlorvos and Chlorpyrifos were selected as organic pollutants to assess the enzymatic activity of immobilized Fe 3 O 4 @Cht/Au/AChE. Optimum conditions for AChE enzyme were immobilized nanostructures (Fe 3 O 4 @Cht/Au/AChE) were determined. The optimum pH for the immobilized enzyme was found to be 8, and the optimum temperature was found to be 60 °C. Retained immobilized enzyme activity is found to be around 50% for the 20th reuse. In the presence of 150 µL pesticide, retained immobilized enzyme activity is found to be around 25%. Method validation was performed for pesticides. When using immobilized AChE, the LOD (limit of detection)-LOQ (limit of quantitation) values for Dichlorovos and Chlorpyrifos was obtained in the range of 0.0087-0.029 nM and 0.0014-0.0046 nM, respectively. The relative standard deviation (RSD%) values, which are indicators of precision, were found to be below 2%.

Throughout this research, a new magnetic molecularly imprinted polymer on fibrous silica nanosphere was prepared through self-polycondensation. The selective extraction of chlorpyrifos was performed by the synthesized sorbent and as a determination system, a gas chromatography-electron capture was applied. The formation of sorbent was confirmed through the use of Fourier transform infrared spectroscopy and field emission scanning electron microscopy techniques. The parameters affecting the extraction efficacy of the proposed method were scrutinized in an optimized way. The linear range and the detection limit of the studied method were 0.003-0.3 and 0.001 ng mL -1 , respectively. The relative standard deviations were 4.1-5.2 and 5.6-7.6 % for intra- and inter-day (n = 3), respectively. To assess the performance of the proposed method, some water and fruit samples were analyzed and the extraction recoveries of 83-109 % were obtained. These results revealed the method's performance in the analysis of chlorpyrifos in real samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The study was designed to test the feasibility of using 3D-printed pollen traps for long-term monitoring of Bombus terrestris colonies' exposure to pesticide residues in pollen loads collected by them, along with an assessment of the resulting risks to the bumblebee's adults, larvae, and queens. Bumblebee colonies were placed in the vicinity of flowering orchards, winter oilseed rape, allotments, or home gardens for 6 weeks of the experiment. Pollen traps printed in 3D technology were installed in the hive inlets. The weight of bumblebee pollen loads obtained using pollen traps was in the range of 0.036-5.83 g. Pollen load samples were analyzed for residues of up to 261 pesticides and their metabolites by liquid and gas chromatography techniques coupled to tandem mass spectrometry (LC-MS/MS and GC-MS/MS). Residues of 18 fungicides, 12 herbicides, 6 insecticides, and an acaricide were detected. Herbicide - pendimethalin, fungicide - thiophanate-methyl, and insecticide - chlorpyrifos-ethyl were the most commonly detected pesticides. Chlorpyrifos and thiacloprid residues were detected in pollen load samples in the next year after their ban from use as plant protection products in the European Union. The risk of acute or chronic effects was assessed as negligible or low, although the chronic risk of bumblebee queens to insecticide chlorpyrifos and the acute risk of larvae exposed to acaricide fenpyroximate could be interpreted as moderate. The risk of sublethal effects related to chronic exposure of adult bumblebees and queens to pollen loads contaminated by chlorpyrifos-ethyl and cypermethrin cannot be excluded. The risk of chronic toxicity or sublethal effects may be particularly relevant for bumblebee queens, especially during their foraging in the initial period of establishing a new colony., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Mancozeb residue estimation was done using second derivative ultraviolet spectroscopy by Shimadzu ultraviolet-visible spectrophotometer, and chlorpyrifos was estimated by QuEChERS technique using GC-FPD. The persistence for chlorpyrifos was carried out at two locations, and for mancozeb, persistence studies were carried out at four locations. Initial deposits of mancozeb on apple fruits ranged from 1.33 to 1.63 mg/kg at the recommended dose and from 2.55 to 3.26 mg/kg at double the recommended dose at all four locations. Chlorpyrifos residues in apple fruits had an initial deposit of 0.94-0.99 mg/kg at recommended dose and 1.75-1.92 mg/kg at double the recommended dose. Mancozeb residues in apple fruit were below the detection limit (BDL) after 20 days at recommended dose and after 25 days at double the recommended dose at two locations, while mancozeb residue at the other two locations and the residues of chlorpyrifos at all locations reached BDL after 15 and 20 days at recommended and double the recommended doses, respectively. Half-life of mancozeb varied from 3.07 to 4.02 days at recommended dose and from 3.30 to 4.32 days at double the recommended dose, whereas chlorpyrifos residues dissipated to half their initial concentration on 2.33-2.35 days at recommended dose and 2.89-2.90 days at double the recommended dose. The soil samples showed no presence of residues of chlorpyrifos and mancozeb at harvest. The risk assessment revealed that hazard quotient for the intake of mancozeb was in the range of 0.06-0.13% and 0.20-0.44% for rural and urban population, while for the intake of chlorpyrifos, hazard quotient was in the range of 0.10-0.12% for rural population and 0.33-0.38% for urban population, and theoretical maximum dietary intake (9.67 × 10 -5  mg/person and 3.18 × 10 -4  mg/person for rural population and urban population in case of mancozeb and 3.22 × 10 -5  mg/person and 1.06 × 10 -4  mg/person for rural population and urban population in case of chlorpyrifos) was also found to be less than maximum permissible intake (1.38 mg/kg for mancozeb and 0.60 mg/kg for chlorpyrifos). The results of risk assessment thereby indicated that apple consumption does not pose a risk to human health., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

The surface-enhanced Raman spectroscopy (SERS) technique is being increasingly used for the detection of pesticide residues in agricultural products. However, there are large amounts of fluorescence-producing substances in agricultural products, which seriously affect the Raman signal of the analyte. In this paper, the QuEChERS method was used to remove interfering fluorescent substances in the analyte, and the purification effects of different doses of nano bamboo charcoal (NBC) and Fe 3 O 4 magnetic nanoparticle (Fe 3 O 4 MNP) adsorbents were studied. Meanwhile, the Raman spectral acquisition conditions (AuNPs, test solution, and NaCl) were optimized based on the orthogonal test method. The results showed that 300 µL AuNPs, 40 µL test solution, and 100 µL 1.5% NaCl gave the best SERS response effect. 12.5 mg NBC combined with 10 mg Fe 3 O 4 MNPs could effectively remove the interfering substances from citrus. The Raman spectra of chlorpyrifos molecules were theoretically modeled using density-functional theory (DFT). By comparing the DFT results with the actual tests, five feature peaks, at 338, 522, 558, 672, and 1600 cm -1 , were obtained for the detection of chlorpyrifos pesticide residues in citrus. Based on the Raman feature peak intensity at 672 cm -1 , the concentration of chlorpyrifos in citrus showed a good linear relationship ( R 2 = 0.9979) in the concentration range of 3-20 mg kg -1 . The recovery rate was 92.12% to 98.38%, and the relative standard deviation (RSD) was 1.77% to 5.29%. The lowest detection concentration was about 3 mg kg -1 , and the detection time of a single sample could be completed within 15 min. This study showed that the combination of SERS and QuEChERS preprocessing methods could achieve rapid detection of chlorpyrifos pesticide residues in citrus.

To improve farming productivity, a large number of pesticides have been used worldwide in recent decades, leading to the pollution of soil, agri-products, and water, directly/indirectly affecting human health. In this regard, many studies were conducted in different countries on residual pesticides in the environment. In the current study, residual pesticides including chlorpyrifos, cypermethrin, diazinon, malathion, and metalaxyl in tomatoes were meta-analyzed and health risk of consumers was estimated. For this purpose, based on a systematic review, data from 47 studies were extracted and meta-analyzed, and the health impact of pooled concentrations was assessed via a health risk method. According to the results, metalaxyl had the most concentration followed by malathion, cypermethrin, diazinon, and chlorpyrifos, respectively. The non-carcinogenic risk (n-CR) was calculated from crop consumption also showed that exposure to malathion has the most risk. Among the investigated communities, Iranian consumers were in considerable health risk (THQ > 1). Considering that the potential for the use of pesticides will increase with the need for food in the future, hence, governments must manage the usage by governments via alternative methods such as cultural, biological, physical, and genetic modifications., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Cantaloupe is a popular agricultural product in the hot season of Iran. On the other hand, the frequent use of pesticides in cantaloupe fields is the most important threat to the health of farmers and consumers. Therefore, the present study aims to measure the concentration of diazinon (DZN), chlorpyrifos (CPF), and malathion (MLT) in cantaloupe cultivated in Kashan and Aran-Bidgol (Iran) and to estimate the possible oral and dermal risk of these pesticides by Monte Carlo simulation (MCS). 36 cantaloupe samples, 18 samples before, and 18 samples after the latent period were collected from different places of cantaloupe cultivation from April to May 2021. After measuring the pesticides using the QuEChERS approach, oral and dermal risk assessments were calculated.The mean and standard deviation of the concentrations of chlorpyrifos, malathion, and diazinon in 18 cantaloupe samples, after the latent period, were (30.39 ± 13.85), (18.361 ± 1.8), and (21.97 ± 0.86) μg kg- 1 , respectively. Concentration of Malathion, diazinon, and Chlorpyrifos in the soil were 0.22, 0.25, and 0.3 mg kg- 1 , respectively, and pesticide cumulative risk assessment in soil was obtained 0.011 for Malathion, 0.05 for diazinon and 0.03 for Chlorpyrifos. Target Hazard Quotient (THQ) according to the cantaloupe consumption and dermal exposure in children and adults, was safe range. Although non-cancerous dermal and oral risk of cantaloupe is low, constant exposure can be harmful. Therefore, the findings of this study play an important role in increasing the understanding of the negative health consequences of pesticide contamination in cantaloupe for consumers, especially local residents, and can help by adopting remedial strategies to reduce environmental concerns., Competing Interests: Declaration of Competing Interest The authors of this article declare that they have no conflict of interests., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

In this study, we propose an interference-free SERS-based aptasensor for trace detection of chlorpyrifos (CPF) in real samples. In the aptasensor, gold nanoparticles coated with Prussian blue (Au@PB NPs) were employed as SERS tags to provide a sole and intense Raman emission at 2160 cm -1 , which could avoid overlapping with the Raman spectrum of the real samples in 600-1800 cm -1 to improve the anti-matrix effect ability of the aptasensor. Under the optimum conditions, this aptasensor displayed a linear response for CPF detection in the range of 0.1-316 ng mL -1 with a low detection limit of 0.066 ng mL -1 . In addition, the prepared aptasensor shows excellent application to determine CPF in cucumber, pear and river water samples. The recovery rates were highly correlated with high-performance liquid chromatography‒mass spectrometry (HPLC‒MS/MS). This aptasensor shows interference-free, specific and sensitive detection for CPF and offers an effective strategy for other pesticide residue detection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Pesticide residues in fruits and vegetables cause serious health issues, especially among children. This research was carried out to monitor and evaluate the risks of organophosphate pesticide residues in Maragheh County apple products from 2020. The Monte Carlo Simulation approach (MCS) was used to evaluate the non-cancerous effects of exposure to pesticide residues in adults and children. Apple samples were taken every two weeks at the Maragheh central market during the summer and fall months. In this study, seventeen pesticide residues in 30 apple samples were estimated using a modified QuECheRS extraction technique coupled with GC/MS. Of the seventeen organophosphate pesticides, thirteen were identified as pesticide residues (76.47%). The highest concentration found in the apple samples was associated with chlorpyrifos pesticide at 1.05 mg/kg. Pesticide residues exceeding the maximum residue limits (MRLs) were found in 100% of apple specimens, and more than 75% of the samples contained ten or more pesticide residues. Approximately 45%-80% of pesticide residues on apple samples were removed after washing and peeling. Chlorpyrifos pesticide had the highest health quotient (HQ) for men, women, and children with values of 0.046, 0.054, and 0.23, respectively. Cumulative risk assessment (CRA) of non-carcinogenic effects indicates that there is no significant health risk in the adult age group from apple consumption (HI < 1). Nevertheless, children are at high non-cancer risk from eating unwashed apples (HI = 1.3). This finding shows that high levels of pesticide residues in apple samples, especially unwashed apples, can be a serious concern for the health of children. To better protect consumer health, continuous and regular monitoring, strict regulations, training, and awareness of farmers, especially control pre-harvest interval (PHI) is recommended.

Intrauterine environment is the first chemical exposure scenario in life, through transplacental transfer. In this study, the aim was to determine concentrations of organochlorine pesticides (OCPs) and selected current use pesticides in the placentas of pregnant women from Argentina. Socio-demographic information, the mother's lifestyle and neonatal characteristics were also analysed and related to pesticides residue concentrations. Thus, 85 placentas were collected at birth, from an area of intensive fruit production for the international market, in Patagonia Argentina. Concentrations of 23 pesticides including, trifluralin (herbicide), the fungicides chlorothalonil and HCB, and the insecticides chlorpyrifos, HCHs, endosulfans, DDTs, chlordanes, heptachlors, drins and metoxichlor, were determined by GC-ECD and GC-MS. Results were first analysed all together and then grouped by their residential settings, in urban and rural groups. Total mean pesticide concentration was 582.6 ± 1034.4 ng/g lw, where DDTs (325.9 ± 950.3 ng/g lw) and chlorpyrifos (188.4 ± 365.4 ng/g lw) showed a high contribution. Pesticide levels found exceeded those reported in low, middle and high income countries from Europe, Asia and Africa. In general, pesticides concentrations were not associated with neonatal anthropometric parameters. When the results were analysed by residence place, significantly higher concentrations of total pesticides and chlorpyrifos (Mann Whitney test p = 0.0003 and p = 0.032, respectively) were observed in placentas collected from mothers living in rural settings compared to urban areas. Rural pregnant women presented the highest pesticide burden (5.9 μg), where DDTs and chlorpyrifos were the major constituents. These results suggested that all pregnant women are highly exposed to complex pesticide mixtures, including banned OCPs and the widely used chlorpyrifos. Based on the pesticide concentrations found, our results warn of possible health impacts from prenatal exposure through transplacental transfer. This is one of the first reports of both chlorpyrifos and chlorothalonil concentrations in placental tissue, and contributes to the knowledge of current pesticide exposure in Argentina., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Pesticide residues in soils can cause negative impacts on soil health as well as soil biota. However, research related to the toxicity and exposure risks of pesticides to soil biota are scarce, especially in the North China Plain (NCP) where pesticides are intensively applied. In this study, the occurrence and distribution of 15 commonly used pesticides in 41 fields in Quzhou county in the NCP were determined during the growing season in 2020. The ecological risks of pesticides to the soil biota, including earthworms, enchytraeids, springtails, mites and nitrogen mineralization microorganisms, were assessed using toxicity exposure ratios (TERs) and risk quotient (RQ) methods. Based on pesticide detection rates and RQs, pesticide hazards were ranked using the Hasse diagram. The results showed that pesticides were concentrated in the 0-2 cm soil depth. Chlorantraniliprole was the most frequently detected pesticide with a detection rate of 37%, while the highest concentration of 1.85 mg kg -1 was found for carbendazim in apple orchards. Chlorpyrifos, carbendazim and imidacloprid posed a chronic exposure risk to E. fetida, F. candida and E. crypticus with the TERs exceeding the trigger value. Pesticide mixtures posed ecological risks to soil biota in 70% of the investigated sites. 47.5% of samples were ranked as high-risk, with the maximum RQ exceeding 490. According to the Hasse diagram, abamectin, tebuconazole, chlorantraniliprole and chlorpyrifos were ranked as the most hazardous pesticides for soil biota in the study region, indicating that alternative methods of pest management need to be considered. Therefore, practical risk mitigation solutions are recommended, in which the use of hazardous pesticides would be replaced with low-risk pesticides with similar functions from the Hasse diagram, or with biopesticides., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Chlorpyrifos is an organophosphate and the cypermethrin is type 2 pyrethroid insecticide that are used for indoor and outdoor pest control. The present study aimed to investigate differential transcriptional profiling to identify the candidate gene associated with lung injury following exposure to chlorpyrifos and/or cypermethrin in a mouse model system. Swiss male albino mice ( n  = 24) were divided into three treatment groups ( n  = 6 each) that were given chlorpyrifos (2.76 mg kg -1 body weight), cypermethrin (2 mg kg -1 body weight) and the combination of both pesticides orally dissolved in corn oil and one control group ( n  = 6) that received corn oil for 90 days. The pulmonary expression of the Apaf1 was observed using RT2 Profiler PCR Array. The results showed that chronic exposure to chlorpyrifos, cypermethrin and their combination downregulated (67, 63 and 66 genes) and upregulated (4, 2 and 2 genes), respectively. The pulmonary expression of Apaf1 that plays important role in apoptosis was found to be downregulated. The immunohistochemistry depicted reduced expression of Apaf1 in both airway epithelium and alveolar septa following exposure to chlorpyrifos and/or cypermethrin. In conclusion, results demonstrated that exposure to chlorpyrifos, cypermethrin and their combination cause lung damage by the dysregulation of Apaf1 gene expression.

Researchers are continually seeking potential alternatives to develop water quality sensors with higher selectivity to obtain the desired performance during real-time deployment. Quantification technologies involving interface materials of distinguishing capacity at elevated matrix complexity are desirable. However, there remains a challenge in designing suitable techniques, methodologies, and appropriate validations to support the grounds for the selection of interface materials of enhanced selectivity. The ability to monitor chlorpyrifos in analytical and commercial grade compounds and in the water matrix using an interface material of suitable states is the focus of this work. Herein, N-(2-hydroxyethyl) ethylenediamine triacetic acid trisodium (N-(2-C 2 H 5 O) ED(CH 3 COONa) 3 ) incorporated with functionalized multiwalled carbon nanotube (f-MWCNT) is reported to provide thermodynamically favorable charge transfer for the quantification of chlorpyrifos residues under varying internal and external conditions with appropriate validations using density functional theory (DFT) and high-performance liquid chromatography (HPLC). The sensor exhibited excellent figures of merit such as limit of detection (LOD) and limit of quantitation (LOQ) of 9.7 pM and 29.4 pM, respectively.

This study uses repeated measures to document the pesticide exposure of rural and urban Latinx children (age eight at baseline), and to compare these children in terms of the frequency and concentration of their exposure to a large set of pesticides, accounting for season. We used silicone wristbands worn for one week up to ten times at quarterly intervals from 2018 to 2022 to assess pesticide exposure in children from rural farmworker ( n = 75) and urban non-farmworker ( n = 61) families. We determined the detection and concentrations (ng/g) of 72 pesticides and pesticide degradation products in the wristbands using gas chromatography electron capture detection and gas chromatography mass spectrometry. The most frequently detected pesticide classes were organochlorines, pyrethroids, and organophosphates. Controlling for season, organochlorine or phenylpyrazole detections were less likely for rural children than for urban children. Detections of organochlorines, pyrethroids, or organophosphates were lower in spring and summer versus winter. Controlling for season, urban children had greater concentrations of organochlorines, while rural children had greater concentrations of pyrethroids and Chlorpyrifos. Pesticide concentrations were lower in winter and spring compared with summer and fall. These results further document that pesticides are ubiquitous in the living environment for children in vulnerable, immigrant communities.

Pesticides are a large group of pristine organic contaminants, which are widely discharged into environmental water due to agricultural activities. Hence, extraction, determination, and removal of pesticides from water resources are necessary for human health. In this study, novel adsorbent was developed based on three-dimensional magnetic graphene coated with gold nanoparticles (3D-MG@AuNPs) for extraction of chlorpyrifos, dicrotophos, fenitrothion, and piperophos as four specific organophosphorus pesticides (OPPs) from wastewater and tap water samples. The proposed nanocomposite was characterized; FTIR and EDX are performed for the expected functional groups and elemental analysis, SEM showed the unique and spherical AuNPs are well dispersed over graphene sheets. In this investigation, the important parameters that have effect on the extraction efficiency, including the desorbing solvent, desorbing solvent volume, vortex time, the extraction time, adsorbent dosage, pH of sample solutions, and salt effect were evaluated. In conclusion, the measured amounts of the chosen OPPs were determined using the gas chromatography microelectron capture (μECD-GC) method. Limits of quantification (S/N ratio of 10) and detection (S/N ratio of 3) were attained at concentrations of 0.26-0.43 μg.L -1 and 0.08-0.14 μg.L -1 , respectively. According to the results of the investigations, the synthesized 3D-MG@AuNPs did not require any complicated sample preparation methods; therefore, it is a very good choice for solid magnetic phase extraction studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The abuse of chlorpyrifos (CHP), a commonly used organophosphorus pesticide, has caused many environmental pollution problems, especially its toxicological effects on non-target organisms. First, CHP enriched on the surface of plants enters ecosystem circulation along the food chain. Second, direct inflow of CHP into the water environment under the action of rainwater runoff inevitably causes toxicity to non-target organisms. Therefore, we used rats as a model to establish a CHP exposure toxicity model and studied the effects of CHP in rats. In addition, to alleviate and remove the injuries caused by residual chlorpyrifos in vivo, we explored the alleviation effect of chitosan oligosaccharide (COS) on CHP toxicity in rats by exploiting its high water solubility and natural biological activity. The results showed that CHP can induce the toxicological effects of intestinal antioxidant changes, inflammation, apoptosis, intestinal barrier damage, and metabolic dysfunction in rats, and COS has excellent removal and mitigation effects on the toxic damage caused by residual CHP in the environment. In summary, COS showed significant biological effects in removing and mitigating blood biochemistry, antioxidants, inflammation, apoptosis, gut barrier structure, and metabolic function changes induced by residual CHP in the environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

On-field detection of pesticide residue in complex-food matrices is a challenge when it comes to analytical detection involving multistep extraction and purification. In this study, we test the feasibility of an electrochemical portable device for detection of spiked pesticides Glyphosate (Glyp) and Chlorpyrifos (Chlp) in low-fat and high-fat food matrix. The immunoassay based two-plex sensing platform was fabricated using respective antibody glyphosate on one side and chlorpyrifos antibody on other side. The sensor response was tested using non-faradaic electrochemical impedance spectroscopy (EIS), which showed a linear response in Glyp/Chlp concentrations from 0.3 ng/mL to 243 ng/mL with limit of detection 1 ng/mL for low fat and 1 ng/mL to 243 ng/mL with LOD 1 ng/mL for high-fat matrix respectively. The laboratory-based benchtop data was then compared with portable device for feasibility of application as portable device. Such electrochemical portable sensing approach can be a future commercial field testing tool., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Shalini Prasad and Sriram Muthukumar have a significant interest in Enlisense LLC, a company that may have a commercial interest in the results of this research and technology. The potential individual conflict of interest has been reviewed and managed by The University of Texas at Dallas, and played no role in the study design; in the collection, analysis, and interpretation of data; in the writing of the report, or in the decision to submit the report for publication., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Chlorpyrifos (CPF) is the most frequently found organophosphate pesticide residue in solid food samples and can cause increasing public concerns about potential risks to human health. Traditional detection signals of such small molecules are mostly generated by target-mediated indirect conversion, which tends to be detrimental to sensitivity and accuracy. Herein, a novel magnetic relaxation switching detection platform was developed for target-mediated direct and sensitive detection of CPF with a controllable aggregation strategy based on a bioorthogonal ligation reaction between tetrazine (Tz) and trans-cyclooctene (TCO) ligands. Under optimal conditions, this sensor can achieve a detection limit of 37 pg/mL with a broad linear range of 0.1-500 ng/mL in 45 min, which is approximately 51-fold lower than that of the gas chromatography analysis and 13-fold lower than that of the enzyme-linked immunosorbent assay. The proposed click chemistry-mediated controllable aggregation strategy is direct, rapid, and sensitive, indicating great potential for residue screening in food matrices.

Organophosphorus compounds such as chlorpyrifos (CPS) are causing serious environmental problems worldwide. Efficient monitoring of the CPS levels in water resources demands portable devices for on-field testing. Here we report the development of a CPS sensor coupled with smartphones for automated reading and data analysis. The sensing mechanism makes use of gold nanoparticles stabilized by a CPS-specific aptamer, where colloidal destabilization occurs in presence of competing CPS molecules. In particular, an innovative readout is proposed: quantitative analysis of the stain patterns left by evaporating drops of the test solutions. We have found that the CPS-induced destabilization suppresses the typical coffee-ring stain of the colloidal gold, and then exploited the phenomenon to quantitatively determine the CPS concentration in water samples. A strong correlation between CPS level in samples and the alteration of the stain patterns was established for a wide range of CPS concentrations (0.048 μM-482 μM). The limit of detection of the sensor was 0.2 μM. The assay was implemented on Whatman filter paper cards that were specially patterned by wax-printing. A smartphone-based Python program was written for fully automated image capture and processing. Notably, as we analyze the spatial configuration of the stains, the reading system is independent of external illumination. The system also enables data management and traceability, which are highly desirable attributes for environmental monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Several organophosphorus compounds such as organophosphate pesticides (OPPs) and trialkylphosphates (TAPs) are suspected to inhibit cholinesterase activities, to affect endocrine systems or to possibly be carcinogenic. To evaluate their adverse effects on health with chronic exposure in the general population, especially in children, we measured the household exposure to OPPs and TAPs by Japanese children via all exposure pathways and the contribution of indoor air quality. First-morning void urine was collected from subjects aged 6 to 15 years (n = 132), and airborne organophosphorus compounds were sampled in the subject's bedroom for 24 h. Airborne levels of nine OPPs and three TAPs and their urinary metabolites were determined. No significant correlations were detected for any compounds between their airborne concentrations and the urinary excretion amounts of their corresponding metabolites. The estimated daily intakes were as follows (median, μg/kg b.w./d): chlorpyrifos, 0.042; diazinon, 0.067; tri-n-butylphosphate, 0.094. The 95th percentiles of the intakes for fenthion, fenitrothion and the above three compounds did not exceed their reference limit values, although one subject had a daily intake of tri-n-butylphosphate that was about twice its reference limit value. The concentration levels of the urinary metabolite of tri-n-butylphosphate in our subjects tended to be higher than those for children in many other countries. The fractions of the amounts absorbed by inhalation to the amounts absorbed via all of the exposure pathways was only 2.3 % (median) for tri-n-butylphosphate. Inhalation did not seem to contribute very much as an absorption pathway of the organophosphorus compounds in these Japanese children while they were at home. The exposure amounts of OPPs were not suggested to be high enough to adversely affect the health of these children at present on the basis of their daily intakes compared to their reference limit values., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Background: Ultrasound has the potential to increase microbial metabolic activity, so this study explored the stimulatory effect of ultrasound pre-treatment on the degradation of four common pesticides (fenitrothion, chlorpyrifos, profenofos, and dimethoate) during milk fermentation by Lactobacillus plantarum and its effect on yogurt quality., Results: Appropriate ultrasound pretreatment significantly enhanced the growth of L. plantarum. The degradation percentages of pesticides increased by 19-38% under ultrasound treatment. Ultrasonic intensity, pulse duty cycle, and duration time were key factors affecting microbial growth and pesticide degradation. Under optimal ultrasonic pre-treatment conditions, the degradation rate constants of four pesticides were at least 3.4 times higher than those without sonication. In addition, such ultrasound pretreatment significantly shortened yogurt fermentation time, increased the water holding capacity, hardness and antioxidant activity of the yogurt, and improved the flavor quality of the yogurt., Conclusion: Ultrasonic pretreatment significantly accelerated the degradation of the four pesticides during yogurt fermentation. In addition, such ultrasound pretreatment increased the efficiency of yogurt making and improved the quality of yogurt in terms of water holding capacity, firmness, antioxidant activity, and flavor. These findings provide a basis for the application of ultrasound to the removal of pesticide residues and quality improvement of yogurt. © 2022 Society of Chemical Industry., (© 2022 Society of Chemical Industry.)

Lanolin, also known as wool wax, is derived from sheep and has diverse applications in food, cosmetic, textile and lubricant industries. Owing to its direct contact with human, there is a need of studying pesticide residues as contaminants in lanolin. The present study describes a single novel hyphenated gas chromatography-tandem mass spectrometry (GC-MS/MS) technique for the quantification of 14 organophosphorus (OP) pesticides (tecnazene, propetamphos, diazinon, dichlofenthion, chlorpyrifos methyl, fenchlorphos, malathion, chlorpyrifos, pirimiphos ethyl, bromophos ethyl, tetrachlorvinphos, ethion, phosalone, and coumaphos) in lanolin using electrospray ionization (EI) with multiple reaction monitoring (MRM) acquisition mode. The method is simple in terms of sample preparation steps based on matrix solid-phase dispersion (MSPD). The method was found to be linear over the analytical range of 0.05-2.0 μg/g, with acceptable coefficient of determination (r 2  ≥ 0.99) for all the 14 pesticides. The limit of detection (LOD) and limit of quantification (LOQ) of the method were found to be less than 0.05 and 0.1 μg/g, respectively, for all the 14 OP pesticide residues. The precision and accuracy of the method were found to be within the acceptable limits, that is, recoveries in the range of 83.5%-104.1% with less than 12.5% of relative standard deviation for all the pesticides. The multiresidue method for estimating pesticide residues employing GC-MS/MS technique will be useful for OP pesticide levels in large number of lanolin samples., (© 2022 John Wiley & Sons Ltd.)

The present research is an attempt to expand the recently reported microextraction on screw method. For this purpose, polyacrylonitrile/calcined ZnMgAl-LDH nanofiber was fabricated by the electrospinning technique on the surface of a screw. It was applied to the extraction of organophosphorus pesticides (OPP) from agricultural samples. The separation and determination of OPPs were carried out by gas chromatography-mass spectrometry. The characterization of the fabricated nanofiber was performed utilizing Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction instruments. Effective parameters on the extraction efficiency of the analytes including sample pH, ionic strength, sample flow rate and number of cycles, type, volume, and flow rate of desorption solvent were optimized by one-variable-at-a-time method. Under optimized conditions, the limits of detection were 0.03 and 0.07 μg L -1 for diazinon and chlorpyrifos, respectively. This method showed wide linearity in the range 0.10-1000 μg L -1 for diazinon and 0.25-1000 μg L -1 for chlorpyrifos with R 2  > 0.996. The intra- and inter-day precisions (RSD%, n = 3) were ≤ 6.4% and ≤ 7.7%, respectively. Also, RSD% values less than 11.1% were obtained for screw-to-screw reproducibility. The applicability of the method for the extraction and determination of the analytes in complex agricultural environments such as cabbage, potato, tomato, cucumber, and beetroot was investigated. The results led to acceptable relative recoveries in the range 81.0-108.2%., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

This study aimed to assess the levels of selected pesticides residues in harvested tomatoes and their associated dietary risks to consumers at Makambako Town in Njombe region, Tanzania. Forty-two fresh tomatoes were sampled among tomato farmers during harvesting season and extraction of analytes was done using QuEChERS method and analysed by Gas Chromatography-Mass Spectrometer. Residues of chlorpyrifos, profenofos, gamma cyhalothrin and cypermethrin were alternatingly detected in 78.51% of samples. The average concentrations of residues were 0.014, 0.056, 0.003 and 0.2 mg/kg for chlorpyrifos, profenofos, gamma cyhalothrin and cypermethrin and were all below their respective Codex MRLs. The highest concentration was 0.718 mg/kg for cypermethrin, above the Codex MRL of 0.2 mg/kg. The hazard indexes indicate no potential health hazards to the general population due to the lifetime consumption of fresh tomatoes from the study area. Periodic monitoring of residue levels of pesticides in vegetable fruits, including tomatoes, is recommended.

A combination of modified quick easy cheap effective rugged and safe extraction approach with carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction was developed for the extraction of several pesticides (diazinon, chlorpyrifos, tebuconazole, deltamethrin, permethrin, haloxyfop-methyl, penconazole, and cyhalothrin) from grape before their analysis by gas chromatography-flame ionization detection. In the extraction approach, an aliquot of grape sample is chopped and after separating its juice, the pesticides that remained in the refuse are extracted by the quick, easy, cheap, effective, rugged, and safe extraction method. The obtained acetonitrile phase is mixed with juice and the analytes are extracted by the carbon nano-onions-based dispersive solid-phase extraction. The analytes are concentrated using the microextraction procedure to obtain high enrichment factors. The results showed low limits of detection (0.5-1.6 ng/g) and quantification (1.8-5.4 ng/g) with satisfactory linearity of the calibration curves (determination coefficient, r 2 ≥ 0.994). The precision of the developed method expressed as relative standard deviations was good (≤7.2%). The method provided high enrichment factors (350-410) and extraction recoveries (70-82%). Finally, seven grape samples were analyzed successfully., (© 2022 Wiley-VCH GmbH.)

This work presents, for the first time, a fast and highly sensitive electrochemical method for determination of three organophosphorus compounds (OPs), diazinon (DZN), malathion (MLT), and chlorpyrifos (CLPF), using a modified pyrolytic graphite electrode (PGE) coupled to batch injection analysis system with multiple pulse amperometric detection (BIA-MPA). The PGE was modified by a nanocomposite based on functionalized carbon nanotubes (CNTf) and silver nanoparticles (AgNPs). The OPs samples were directly analyzed on the modified working electrode surface by BIA-MPA system in Britton-Robinson (BR) buffer 0.15 mol L -1  at pH 6.0. The MPA detection of DZN, MLT and CLPF was performed using two potential pulses, which were sequentially applied on modified PGE at -1.3 V (100 ms) and +0.8 V (100 ms) for selective determination of these three OPs and working electrode cleaning, respectively. Under optimized conditions, the sensor presented a linear range of 0.1-20 μmol L -1 for DZN, 1.0-30 μmol L -1 for MLT and from 0.25 to 50 μmol L -1 for CLPF. The limits of detection (LOD) and quantification (LOQ) of 0.35 and 1.18 μmol L -1 for DZN, 0.89 and 2.98 μmol L -1 for MLT, and 0.53 and 1.78 μmol L -1 for CLPF were obtained. The proposed method exhibited high sensitivity of 0.068, 0.030 and 0.043 mA L μmol -1 for DZN, MLT and CLPF detection, respectively. Furthermore, the BIA-MPA system provided an analytical frequency of 71 determinations per hour for direct determination of these OPs in water and food samples. The modified PGE coupled to BIA-MPA system showed a high stability of electrochemical response for OPs detection with relative standard deviation (RSD) of 1.60% (n = 20). The addition-recovery studies of the proposed method were carried out in tap water, orange juice, and apple fruit real samples, which showed suitable recovery values between 77 and 124%. The analytical performance of the developed sensor provides an attractive alternative method for OPs determination with great potential for a fast and sensitive application in contaminated samples with these pesticides., (Copyright © 2022 Elsevier B.V. All rights reserved.)