Evaluating the spatiotemporal variation of Ba River water quality in the agricultural and urban watershed in the highland of Vietnam.

The Ba River in Vietnam has been facing pollution due to waste generation from agricultural and urban areas. This study focuses on evaluating the spatiotemporal variations in river water quality based on physicochemical characteristics and pesticide parameters for different seasons in 2022-2023. The results indicate that the concentrations of most parameters in the rainy season were higher than those in the early-dry and dry seasons due to the non-point sources in agricultural areas. Notably, the analysis of pesticide residue in both the rainy and dry seasons revealed low levels of chlorpyrifos (ethyl), and deltamethrin was detected in the only rainy season. The results from the hierarchical cluster analysis and water quality index show that the water quality at Ben Mong, An Khe, and Ba River Bridges was classified as moderately to highly polluted. These areas should focus on regular water quality monitoring and appropriate pollution source management. PRACTITIONER POINTS: Agriculture activities strongly affected the water quality of the Highland Ba River of Vietnam. Chlorpyrifos and deltamethrin pesticides (0.0074-0.0218 µg/L) were detected in Ba River. Non-point pollution sources significantly influenced water quality in the Ba River. Variations in river water quality mainly depend on seasons and locations. Water quality index values in rainy seasons (26-88) are lower than that in dry season (37-92).

Dissipation behaviour and dietary risk evaluation of pesticides on cucumber.

Cucumber (Cucumis sativus L.) is the world's most widely consumed salad vegetable, and it is frequently treated with pesticides to prevent pest and disease outbreaks. Pesticide residues in food commodities impede trade and pose a major health risk. Prior to residue estimation, the QuEChERS approach was validated utilising criteria such as limit of detection, limit of quantitation, linearity, accuracy, and precision. The residues of carbendazim, cypermethrin, ethion, profenofos, quinalphos, and triazophos were examined using a Gas Chromatograph equipped with an Electron Capture Detector or a Flame Photometric Detector and a high-performance liquid chromatography coupled to a photo diode array. The initial deposits of carbendazim, cypermethrin, ethion, profenofos, quinalphos, and triazophos at the prescribed dose were 1.235, 0.407, 0.817, 0.960, 0.628, and 0.985 mg/kg, respectively, with a pre-harvest interval of 5.58-11.30 days. According to the consumer risk evaluation data, the Hazard Quotient is less than one, and the Theoretical Maximum Dietary Intake is less than the Maximum Permissible Intake and Maximum Residue Limit, both of which are considered safe for human consumption at the authorised dose.

Risk assessment of multiple pesticide residues in Agrocybe aegerita: Based on a 3-year monitoring survey.

The presence of pesticide residues in Agrocybe aegerita has raised an extensive concern. In this paper, based on a 3-year monitoring survey, the dietary exposure risks through A. aegerita consumption for different population subgroups were assessed using both deterministic and semi-probabilistic approaches under the best-case and the worst-case scenarios. Among the 52 targeted pesticides, 28 different compounds were identified in the concentration range of 0.005-3.610 mg/kg, and 87.4 % of samples contained one or more pesticide residues. The most frequently detected pesticide was chlormequat, followed by chlorfenapyr and cyhalothrin. The overall risk assessment results indicated extremely low chronic, acute, and cumulative dietary exposure risks for consumers. Using the ranking matrix, intake risks of pesticides were ranked, revealing endsoluran, chlorpyrifos, and methamidophos to be in the high-risk group. Finally, considering various factors such as the toxicity and risk assessment outcomes of each positive pesticide, use suggestions were proposed for A. aegerita cultivation.

Development and Validation of a High-Performance Liquid Chromatography Diode Array Detector Method to Measure Seven Neonicotinoids in Wheat.

Neonicotinoids (NEOs), used as insecticides against aphids, whiteflies, lepidopterans, and beetles, have numerous detrimental impacts on human health, including chronic illnesses, cancer, infertility, and birth anomalies. Monitoring the residues in food products is necessary to guarantee public health and ecological balance. The present work validated a new method to measure seven neonicotinoid insecticides (acetamiprid ACT, clothianidin CLT, dinotefuran DNT, imidacloprid IMD, nitenpyram NTP, thiacloprid TCP, and thiamethoxan THT) in wheat. The analytical procedure was based on simple and fast wheat sample cleanup using solid-phase extraction (SPE) to remove interferents and enrich the NEOs, alongside the NEOs' separation and quantification by reverse-phase chromatography coupled with a diode array detector (DAD). The validation process was validated using the accuracy profile strategy, a straightforward decision tool based on the measure of the total error (bias plus standard deviation) of the method. Our results proved that, in the future, at least 95% of the results obtained with the proposed method would fall within the ±15% acceptance limits. The test's cost-effectiveness, rapidity, and simplicity suggest its use for determining the levels of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam in routine analyses of wheat.

Development of bio-composite mulch film from cotton gin wastes: Study of pesticide residue and outdoor stability and degradation.

Non-degradable plastic mulch films used in agriculture are polluting the environment by leaving residues and microplastics in the soil. They are also difficult to recycle due to contamination during their use. Biodegradable mulch films are needed as alternatives so that they can be used effectively during the growing season and later be ploughed to be degraded in soil. However, market-available so-called biodegradable mulch films are very slow to degrade in the natural environment and thus do not fit with crop rotation demands or annual cultivation. In this study, we have developed mulch films from cotton gin trash (CGT) and/or gin motes (GM) in combination with biodegradable polycaprolactone and demonstrated their effectiveness over 3 months in outdoor conditions. Both the stability and degradation behaviours of mulch film samples were observed when they were placed on top of the soil and buried in the soil, respectively. Pesticide residue analysis also was carried out on CGT powder to identify and quantify individual pesticides against a matrix of known pesticides. The mulch films prepared in this study showed comparable and stable mechanical properties compared to commercial biodegradable mulch film, though were much quicker to degrade when buried in the soil. No pesticides were detected in the CGT samples. The films produced were vapour-permeable and may be useful in practical agricultural settings by being able to maintain consistent soil moisture and allowing precipitation to penetrate gradually. The lab-scale production cost for the film was 98.8 AUD/kg, which could be lowered by integrating a continuous film line in large-scale production.

Silver coated PS microsphere array SERS microfluidic chip for pesticide detection.

Carbendazim and acetamidine are pesticides that widely used to control pests and diseases in oilseed rape. In this paper, a rapid, accurate and reliable method was proposed for the detection of carbendazim and acetamidine with SERS microfluidic chip technology. Ag-ps(Polystyrene microspheres) microsphere SERS substrate was prepared by spin coating and magnetron sputtering deposition of Ag. The enhancement factor of prepared SERS substrate was 2.4 × 1010. The SERS detection working curves were well fitted and the linear parameters R2 were 0.987 and 0.994, respectively. The limit of detection was 0.01 mg/mL. The use of SERS microfluidic chip to detect carbendazim and acetamidine is expected to provide a way for the detection of pesticide residues in crops, which has broad application prospects in the field of food safety.

Monitoring of Pesticide Residues in Chili Peppers Using International Pesticide Monitoring Data for Safety Management.

Repeated pesticide residue detection in chili peppers in the Republic of Korea has become a serious health concern. Thus, monitoring domestically grown and imported chili peppers for pesticide residues is of great significance. Here, we investigated pesticide residues detected in imported and domestically grown chili peppers using global pesticide residue monitoring data. Our analysis involved organizing inspection and detection data from different sources. Global pesticide residue monitoring data for chili peppers revealed 139 pesticide types, 43,532 inspections, and 3966 detections (detection rate, 9.11%). Peppers from Mexico were sampled the most (39,927 inspections) and showed the highest number of detected cases (2998 cases). Globally, the top 10 most frequently detected pesticides were clothianidin, imidacloprid, thiamethoxam, chlorpyrifos, thiacloprid, metalaxyl, myclobutanil, azoxystrobin, carbendazim, and cyhalothrin, with detection rates in the range of 10.52-28.66%. Furthermore, domestic chili pepper pesticide residue monitoring revealed 73 pesticide types, 3535 inspections, and 332 detected cases (detection rate, 9.39%), and the top 10 most frequently detected pesticides were chlorfenapyr, tebuconazole, flonicamid, dinotefuran, boscalid, pyraclostrobin, fluxametamide, thiamethoxam, pyridaben, and azoxystrobin, with detection rates in the range of 13.89-32.58%. These findings may serve as fundamental data for safety management related to chili pepper pesticide residues in the Republic of Korea.

Fabrication of versatile Fe3O4/GO/Au composite nanomaterial as SERS-active substrate for detection of pesticide residue.

Highly active Fe3O4/GO/Au composite nanomaterial was fabricated as a substrate of surface-enhanced Raman spectroscopy (SERS) and applied for pesticide residue detection. The three-layer multifunctional Fe3O4/GO/Au nanoparticles (NPs) were designed by facile method, with high hotspots, and were characterized by various techniques, including ultraviolet spectrophotometry (UV), X-ray diffraction (XRD), infrared absorption spectrometer (IR), and transmission electron microscopy (TEM). The performance of Fe3O4/GO/Au was evaluated by Raman spectroscopy with R6G as a probe molecule to verify its enhancement effect. It exhibited a strong Raman signal with 10-6 M of R6G. Furthermore, the presence of Fe3O4/GO/Au nanohybrid enabled the SERS-based method to detect mancozeb and showed an excellent linear relationship in the range of 0.25-25 ppm, with a low limit of detection (0.077 ppm), satisfactory EF, stability, and repeatability. In addition, the mechanism of SERS enhancement with electromagnetic mechanism (EM) and chemical mechanism (CM) was discussed in detail. Therefore, the proposed SERS approach holds promise as an auxiliary technique for screening contaminated agricultural products, environmental sample, and food in the future.

Ornamental plants as vectors of pesticide exposure and potential threat to biodiversity and human health.

The production of conventional ornamental plants is pesticide-intensive. We investigated whether pesticide active ingredients (AIs) are still present in ornamentals at the time of purchase and assessed their potential ecotoxicity to non-target organisms. We purchased 1000 pot plants and 237 cut flowers of different species from garden centers in Austria and Germany between 2011 and 2021 and analyzed them for up to 646 AIs. Ecotoxicological risks of AIs were assessed by calculating toxic loads for honeybees (Apis mellifera), earthworms (Eisenia fetida), birds (Passer domesticus), and mammals (Rattus norvegicus) based on the LD50 values of the detected AIs. Human health risks of AIs were assessed on the basis of the hazard statements of the Globally Harmonized System. Over the years, a total of 202 AIs were detected in pot plants and 128 AIs in cut flowers. Pesticide residues were found in 94% of pot plants and 97% of cut flowers, with cut flowers containing about twice as many AIs (11.0 ± 6.2 AIs) as pot plants (5.8 ± 4.0 AIs). Fungicides and insecticides were found most frequently. The ecotoxicity assessment showed that 47% of the AIs in pot plants and 63% of the AIs in cut flowers were moderately toxic to the considered non-target organisms. AIs found were mainly toxic to honeybees; their toxicity to earthworms, birds, and mammals was about 105 times lower. Remarkably, 39% of the plants labeled as "bee-friendly" contained AIs that were toxic to bees. More than 40% of pot plants and 72% of cut flowers contained AIs classified as harmful to human health. These results suggest that ornamental plants are vectors for potential pesticide exposure of consumers and non-target organisms in home gardens.

Developing a Multi-Spectral NIR LED-Based Instrument for the Detection of Pesticide Residues Containing Chlorpyrifos-Methyl in Rough, Brown, and Milled Rice.

A recent study showed the potential of the DA Perten 7200 NIR Spectrometer in detecting chlorpyrifos-methyl pesticide residue in rough, brown, and milled rice. However, this instrument is still lab-based and generally suited for point-of-sale testing. To provide a field-deployable version of this technique, an existing light emitting diode (LED)-based instrument that provides discrete NIR wavelength illumination and reflectance spectra over the range of 850-1550 nm was tested. Spectra were collected from rough, brown, and milled rice at different pesticide concentrations and analyzed for quantitative and qualitative measurement using partial least squares regression (PLS) and discriminant analysis (DA). Simulations for two LED-based instruments were also evaluated using corresponding segments of spectra from the DA7200 to represent LED illumination. For the simulation of the existing LED-based instrument (LEDPrototype1) fitted with 850, 910, 940, 970, 1070, 1200, 1300, 1450, and 1550 nm LED wavelengths, resulting R2 ranged from 0.52 to 0.71, and the correct classification was 70.4% to 100%. The simulation of a second LED instrument (LEDPrototype2) fitted with 980, 1050, 1200, 1300, 1450, 1550, 1600, and 1650 nm LED wavelengths showed R2 of 0.59 to 0.82 and correct classifications of 66% to 100%. These LED wavelengths were selected based on the significant wavelength regions from the PLS regression coefficients of DA7200 and the commercial availability of LED wavelengths. Results showed that it is possible to use a multi-spectral LED-based instrument to detect varying levels of chlorpyrifos-methyl pesticide residue in rough, brown, and milled rice.

Pesticide residues in vegetables from Gansu province, China and risk assessment by Monte Carlo simulation.

To assess the dietary exposure risks of pesticide residues in vegetables for the general population, the presence of 39 pesticides was determined in 70 samples, of which 13 were detected. The most frequently detected pesticide was bifenthrin, with a detection rate of 35.7%, mainly found in gingers, followed by isoprocarb and acephate (11.4%) and dimethoate (8.6%). In 17.1% of the samples two or more pesticide residues were found. Acute, chronic and chronic cumulative dietary exposure risk was assessed. Chronic exposure risks were determined by Monte Carlo Simulation (MCS). Estimated chronic exposure to carbofuran, omethoate, disulfoton and dimethoate of approximately 49%, 52%, 40% and 3%, respectively, were at non-carcinogenic human risk. Acute exposure risk to acephate was considered to be of concern due to the high acute hazard quotient (aHQ).

A SERS-based point-of-care testing approach for efficient determination of diquat and paraquat residues using a flexible silver flower-coated melamine sponge.

Diquat (DQ) and paraquat (PQ) residues in food are potential hazards to consumers' health. Point-of-care testing (POCT) of them remains challenging. Based on surface-enhanced Raman spectroscopy (SERS) technology, we developed a POCT strategy for DQ and PQ on apple surface and in apple juice. A point-of-use composite was fabricated using a piece of porous melamine sponge (MS) modified with silver nanoflowers (AgNFs), combining the specificity of the SERS fingerprint and the excellent adsorption capacity of MS. Using this dual-functional AgNFs@MS, the on-site determination of the DQ and PQ residues was completed within 3 min without pretreatment. Clear trends were observed between SERS intensity and logarithmic concentrations, with r values from 0.962 to 0.984. The limit of detection of DQ and PQ were 0.14-0.70 ppb in apple juice and on apple surface. This study provides a new point-of-use alternative for rapidly detecting DQ and PQ residues in nonlaboratory settings.

Deciphering the key factors affecting pesticide residue risk in vegetable ecosystem.

Soil contamination, particularly from pesticide residues, presents a significant challenge to the sustainable development of agricultural ecosystems. Identifying the key factors influencing soil pesticide residue risk and implementing effective measures to mitigate their risks at the source are essential. Here, we collected soil samples and conducted a comprehensive survey among local farmers in the Three Gorges Reserve Area, a major agricultural production region in Southwest China. Subsequently, employing a dual analytical approach combining structural equation modeling (SEM) and random forest modeling (RFM), we examined the effects of various factors on pesticide residue accumulation in vegetable ecosystems. Our SEM analysis revealed that soil characteristics (path coefficient 0.85) and cultivation factor (path coefficient 0.84) had the most significant effect on pesticide residue risk, while the farmer factors indirectly influenced pesticide residues by impacting both cultivation factors and soil characteristics. Further exploration using RFM identified the three most influential factors contributing to pesticide residue risk as cation exchange capacity (CEC) (account for 18.84%), cultivation area (account for 14.12%), and clay content (account for 13.01%). Based on these findings, we carried out experimental trials utilizing Integrated Pest Management (IPM) technology, resulting in a significant reduction in soil pesticide residues and notable improvements in crop yields. Therefore, it is recommended that governmental efforts should prioritize enhanced training for vegetable farmers, promotion of eco-friendly plant protection methods, and regulation of agricultural environments to ensure sustainable development.

Investigation of variability in the matrix effect on stable isotope-labeled internal standards in liquid chromatography-tandem mass spectrometry analysis of 25 pesticides in vegetables.

The matrix effects (ME) in simultaneous analysis of pesticide residue using liquid chromatography-tandem mass spectrometry (LC-MS/MS) were evaluated by comparing the slopes of matrix-matched and reagent-only calibrations of four types of vegetable samples. Both the sampling and measurement variances of the ME were also determined using one-way analysis of variance. Substantial ion suppression (ME<-20%) was observed in komatsuna, spinach, and tomato when a modified Japanese official method was implemented. The ME magnitude varied significantly due to sample variability for some pesticides, but it varied by no more than 4% as a result of analytical procedure variance. This study also showed that the addition of stable isotope-labeled internal standards at low concentrations improved the recovery of pesticides from samples at various residue levels. The findings of this study highlight the importance and practical application of internal standards and the matrix-matched calibration method in residue analysis using LC-MS/MS.

Development of a Portable Cell-Based Biosensor for the Ultra-Rapid Screening for Boscalid Residues in Lettuce.

Fungal plant pathogens have posed a significant threat to crop production. However, the large-scale application of pesticides is associated with possible risks for human health and the environment. Boscalid is a widely used fungicide, consistently implemented for the management of significant plant pathogens. Conventionally, the detection and determination of boscalid residues is based on chromatographic separations. In the present study, a Bioelectric Recognition Assay (BERA)-based experimental approach combined with MIME technology was used, where changes in the electric properties of the membrane-engineering cells with anti-boscalid antibodies were recorded in response to the presence of boscalid at different concentrations based on the maximum residue level (MRL) for lettuce. The membrane-engineering Vero cells with 0.5 µg/mL of antibody in their surface were selected as the best cell line in combination with the lowest antibody concentration. Furthermore, the biosensor was tested against another fungicide in order to prove its selectivity. Finally, the BERA cell-based biosensor was able to detect the boscalid residue, below and above the MRL, in spiked lettuce leaf extracts in an entirely distinct and reproducible manner. This study indicates that the BERA-based biosensor, after further development and optimization, could be used for the routine, high-throughput detection of boscalid residue in lettuce, and not only that.

Quantitative determination of residue amounts of pesticide active ingredients used in grapes by LC-MS/MS and GC-MS/MS devices and evaluation of these pesticides in terms of public health.

The aim of this study was to quantitatively determine pesticide residues in grapes, one of the most produced and consumed fruits in Turkey and in the world. A total of 226 active ingredients were analyzed in 21 samples collected from Southeastern and Eastern Anatolia regions using QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and multiple residue analysis technique and LC-MS/MS and GC-MS/MS devices. In 11 out of 21 samples (52.4%), no active ingredient was detected, while at least one active ingredient was detected in 10 samples (47.6%). Thirteen different active substances (Ametoctradin, Azoxystrobin, Boscalid, Diphenoconazole, Dimethomorph, Fenhexamid, Fluopyram, Flutriafol, Metalaxyl- Metalaxyl-M, Metrafenone, Tebuconazole, Trifloxystrobin) were detected in the samples. The top 3 most detected active substances were Boscalid-Azoxystrobin and Fluopyram, respectively. The active ingredients were found between 0.015 and 0.499 mg kg-1 values.

Dissipation pattern of tetraniliprole in/on green chilies.

Field and lab experiments explored tetraniliprole dissipation in chili plants. A supervised trial in Devarayapuram village, Coimbatore, assessed the CO2 chili variety (December-March 2018-2019). Using the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method and ultra-high-performance liquid chromatography (UHPLC), samples were collected up to 15 d post-application. Initial tetraniliprole deposits on chili fruits, 1-h post-spray, were 0.898 and 1.271 µg g-1 at single and double doses. Over 80% dissipated within 5 d, reaching below detection limits by day 7 and 10 for single and double doses, respectively. Transformation analysis favored first-order kinetics. Tetraniliprole half-life on chili fruit was 1.49 and 1.53 d at recommended and double doses. The safe waiting period was 4.16 and 5.04 d for 60 and 120 g a.i ha-1. This study provides insights into tetraniliprole dynamics in chili plants, crucial for effective pesticide management.

In situ mass spectrometry imaging reveals pesticide residues and key metabolic pathways throughout the entire cowpea growth process.

Cowpea plants, renowned for their high edibility, pose a significant risk of pesticide residue contamination. Elucidating the behavior of pesticide residues and their key metabolic pathways is critical for ensuring cowpea safety and human health. This study investigated the migration of pesticide residues and their key metabolic pathways in pods throughout the growth process of cowpea plants via in situ mass spectrometry. To this end, four pesticides--including systemic (thiram), and nonsystemic (fluopyram, pyriproxyfen, and cyromazine) pesticides--were selected. The results indicate the direct upward and downward transmission of pesticides in cowpea stems and pods. Systemic pesticides gradually migrate to the core of cowpea plants, whereas nonsystemic pesticides remain on the surface of cowpea peels. The migration rate is influenced by the cowpea maturity, logarithmic octanol-water partition coefficient (log Kow) value, and molecular weight of the pesticide. Further, 20 types of key metabolites related to glycolysis, tricarboxylic acid cycle, and flavonoid synthesis were found in cowpea pods after pesticide treatment. These findings afford insights into improving cowpea quality and ensuring the safe use of pesticides.

A molecularly imprinted electrochemical sensor MIP/Cu-MOF/rGO/AuNPs/GCE for highly sensitive detection of electroneutral organophosphorus pesticide residues.

A novel electrochemical sensor, MIP/Cu-MOF/rGO/AuNPs/GCE, was developed by depositing gold nanoparticles, coating Cu-MOF/GO on the surface of glassy carbon electrode (GCE) before electroreducing graphene oxide (GO) to rGO and covering molecularly imprinted membrane by electropolymerization for highly sensitive detection of electroneutral organophosphorus pesticide residues in agricultural product. Cyclic voltammetry, differential pulse voltametry, scanning electron microscopy, energy-dispersive spectroscopy, and atomic force microscopy were used to characterize the imprinted sensor. Several key factors such as chitosan concentration, suspension volume, pH of polymerization solution, and polymerization scanning rate during preparation of the imprinted sensor were optimized in detail. When electroneutral phosmet was used as a template, the linear range of MIP/Cu-MOF/rGO/AuNPs/GCE for detecting phosmet was 1.00 × 10-14-5.00 × 10-7 mol/L with the limit of detection of 7.20 × 10-15 mol/L at working potentials of - 0.2 to 0.6 V. The selectivity, reproducibility, and repeatability of MIP/Cu-MOF/rGO/AuNPs/GCE were all acceptable. The recoveries of this method for determining phosmet in real samples ranged from 94.2 to 106.5%. The MIP/Cu-MOF/rGO/AuNPs/GCE sensor could be applied to detect electroneutral pesticide residues in organisms and agricultural products.

Simultaneous Analysis of 272 Pesticides in Agricultural Products by the QuEChERS Method and Gas Chromatography with Tandem Mass Spectrometry.

The aim of this study is to develop a rapid and accurate method for simultaneous analysis of multi-residue pesticides and conduct pesticide monitoring in agricultural products produced by the production and distribution stage in Korea. The representative agricultural products were selected as brown rice, soybean, potato, mandarin, and green pepper and developed using gas chromatography with tandem mass (GC-MS/MS) for the analysis of 272 pesticide residues. The experimental samples were extracted by the QuEChERS-EN method and then cleaned up by using d-SPE, including MgSO4 and primary secondary amine (PSA) sorbents. The established method was validated in accordance with Codex CAC-GL/40, and the limit of quantitation (LOQ) was determined to be 0.01 mg/kg. A total of 243 pesticides satisfied the guidelines in five samples at three levels with values of 60 to 120% (recovery) and ≤45% (coefficient of variation, CV). The remaining 29 pesticides did not satisfy the guidelines, and these pesticides are expected to be used as a screening method for the routine inspection of agricultural products. As a result of analyzing 223 agricultural products in South Korea by applying the simultaneous analysis method, none of the detected levels in the samples exceeded the standard values based on maximum residue limits (MRLs). The developed method in this study will be used to inspect residual pesticides in agricultural products, and it is anticipated to contribute to the distribution of safe agricultural products to consumers.