Occurrence and toxicological relevance of pesticides and trace metals in agricultural soils, sediments, and water of the Sogamoso River basin, Colombia.

Historical pesticide use in agriculture and trace metal accumulation have long term impact on soil, sediment, and water quality. This research quantifies legacy and current-use pesticides and trace metals, assessing their occurrence and toxicological implications on a watershed scale in the Sogamoso River basin, tributary of the Magdalena River in Colombia. Organochlorine pesticides (22), organophosphates (7), and azole fungicides (5), as well as trace metals cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb), and zinc (Zn) were analyzed in croplands and along the river. Toxic units (TU) and hazard quotients (HQ) were calculated to assess the mixture toxicity. Organochlorines were detected in 84% of soils, 100% of sediments, and 80% of water samples. Organophosphates were found in 100% of soil and sediment samples, as well as in 70% of water samples. Azole fungicides were present in 79% of soils, 60% of sediments, and in 10% of water samples. Total pesticide concentrations ranged from 214.2 to 8497.7 µg/kg in soils, 569.6-12768.2 µg/kg in sediments, and 0.2-4.1 µg/L in water. In addition, the use of partition coefficient (Kd) and organic carbon fraction (foc) allowed the distribution analysis for most of the pesticides in sediments, suspended particulate matter (SPM), and water systems, but not for soils. Concentrations of trace metals Cu, Zn, Pb, and Zn exceeded international quality guidelines for agricultural soils in 16% of the samples. Furthermore, Cu and Zn concentrations exceeded sediment quality guidelines in 50 and 90% of the samples, respectively. These findings demonstrate the broad distribution of complex mixtures of trace metals, legacy organochlorines, and current-use pesticides across the basin, indicating that conventional agriculture is a significant source of diffuse pollution. Sustainable agricultural practices are needed to mitigate adverse impacts on ecosystems and human health.

Impact of landscape composition on honey bee pollen contamination by pesticides: A multi-residue analysis.

The honey bee is the most common and important managed pollinator of crops. In recent years, honey bee colonies faced high mortality for multiple causes, including land-use change and the use of plant protection products (hereafter pesticides). This work aimed to explore how contamination by pesticides of pollen collected by honey bees was modulated by landscape composition and seasonality. We placed two honey bee colonies in 13 locations in Northern Italy in contrasting landscapes, from which we collected pollen samples monthly during the whole flowering season in 2019 and 2020. We searched for almost 400 compounds, including fungicides, herbicides, insecticides, and acaricides. We then calculated for each pollen sample the Pollen Hazard Quotient (PHQ), an index that provides a measure of multi-residue toxicity of contaminated pollen. Almost all pollen samples were contaminated by at least one compound. We detected 97 compounds, mainly fungicides, but insecticides and acaricides showed the highest toxicity. Fifteen % of the pollen samples had medium-high or high levels of PHQ, which could pose serious threats to honey bees. Fungicides showed a nearly constant PHQ throughout the season, while herbicides and insecticides and acaricides showed higher PHQ values in spring and early summer. Also, PHQ increased with increasing cover of agricultural and urban areas from April to July, while it was low and independent of landscape composition at the end of the season. The cover of perennial crops, i.e., fruit trees and vineyards, but not of annual crops, increased PHQ of pollen samples. Our work highlighted that the potential toxicity of pollen collected by honey bees was modulated by complex interactions among pesticide category, seasonality, and landscape composition. Due to the large number of compounds detected, our study should be complemented with additional experimental research on the potential interactive effects of multiple compounds on honey bee health.

Low concentrations of ethylene bisdithiocarbamate pesticides maneb and mancozeb impair manganese and zinc homeostasis to induce oxidative stress and caspase-dependent apoptosis in human hepatocytes.

The worldwide and intensive use of phytosanitary compounds results in environmental and food contamination by chemical residues. Human exposure to multiple pesticide residues is a major health issue. Considering that the liver is not only the main organ for metabolizing pesticides but also a major target of toxicities induced by xenobiotics, we studied the effects of a mixture of 7 pesticides (chlorpyrifos-ethyl, dimethoate, diazinon, iprodione, imazalil, maneb, mancozeb) often detected in food samples. Effects of the mixture was investigated using metabolically competent HepaRG cells and human hepatocytes in primary culture. We report the strong cytotoxicity of the pesticide mixture towards hepatocytes-like HepaRG cells and human hepatocytes upon acute and chronic exposures at low concentrations extrapolated from the Acceptable Daily Intake (ADI) of each compound. Unexpectedly, we demonstrated that the manganese (Mn)-containing dithiocarbamates (DTCs) maneb and mancozeb were solely responsible for the cytotoxicity induced by the mixture. The mechanism of cell death involved the induction of oxidative stress, which led to cell death by intrinsic apoptosis involving caspases 3 and 9. Importantly, this cytotoxic effect was found only in cells metabolizing these pesticides. Herein, we unveil a novel mechanism of toxicity of the Mn-containing DTCs maneb and mancozeb through their metabolization in hepatocytes generating the main metabolite ethylene thiourea (ETU) and the release of Mn leading to intracellular Mn overload and depletion in zinc (Zn). Alteration of the Mn and Zn homeostasis provokes the oxidative stress and the induction of apoptosis, which can be prevented by Zn supplementation. Our data demonstrate the hepatotoxicity of Mn-containing fungicides at very low doses and unveil their adverse effect in disrupting Mn and Zn homeostasis and triggering oxidative stress in human hepatocytes.

Occurrence, distribution, and risk assessment of pesticides in surface water and sediment in Jiangsu Province, China.

The occurrence and distribution of 157 pesticides were investigated in surface water and sediment in Jiangsu Province, China. Gas chromatography-mass spectrometry was used to analyze and quantify these pesticides, and the risk quotient method was used to evaluate their respective environmental risk. The results showed that 91 pesticides were detected in surface water. The organophosphates (OPPs), fungicides, and amide herbicides were predominant. The total concentration in surface water ranged from 63.7 to 22,463 ng/L, 3.90 to 7262 ng/L, and ND to 34,120 ng/L, respectively. The mean concentration was 3479 ng/L, 1644 ng/L, and 1878 ng/L, respectively. The concentration range of detected pesticides in the Yangtze River Basin was generally lower than that in the Huai River Basin. In sediment samples, a total of 63 pesticides were detected. OPPs and amide herbicides were also ranked highest; the total concentration in sediment samples ranged from 2951 to 47,739 ng/g and 106 to 12,996 ng/g, respectively. And the mean concentrations was 6971 ng/g and 5130 ng/g, respectively. Suqian City had the highest concentration for OPPs and amide herbicides in the Huai River Basin, followed by Huai'an City, while Nanjing City and Yangzhou City ranked highest in the Yangtze River Basin. The spatial distribution of pesticides in Jiangsu Province indicated a concentration significantly higher in the western and northern regions than in the eastern and southern regions, and a concentration generally higher in lakes than in rivers. The risk assessment results showed that OPPs, fungicides, amide herbicides, organochlorines, and triazine herbicides in most surface water samples posed a high risk and had regional pollution characteristics. In sediment samples, organochlorines, carbamates, other herbicides, and other insecticides posed a high risk in northern Jiangsu Province, whereas OPPs, amide herbicides, and triazine herbicides posed high risks everywhere in Jiangsu Province.

Additive and synergistic antifungal effects of copper and phenolic extracts from grape cane and apples.

BACKGROUND: Organic viticulture seeks sustainable alternatives for eco-toxic copper fungicides to control downy mildew caused by Plasmopara viticola. (Poly)phenol-rich extracts of agricultural byproducts are known to possess antifungal activity, but high production costs often limit their actual implementation. RESULTS: We developed and produced novel ligninsulfonate-based grape cane extract (GCE) formulations and an apple extract on a pilot plant scale, including a detailed (poly)phenol characterization by high-performance liquid chromatography photodiode array mass spectrometry (HPLC-PDA-MS). Our GCE formulations alone reduced downy mildew disease severity in greenhouse trials by 29%-69% in a dose-dependent manner, whereas a standard application of the copper-based agent alone reached ~56%. When applied together, disease severity was diminished by 78%-92%, revealing a synergistic effect that depended on the mixture ratio. Combining GCE formulations with the apple extract, additive effects were found (80% disease severity reduction). CONCLUSION: The studied plant extracts are proposed to both substitute for and synergistically reinforce copper fungicides in grapevine downy mildew control. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Review of Characteristics and Analytical Methods for Determination of Thiabendazole.

Thiabendazole (TBZ) is a fungicide and anthelmintic drug commonly found in food products. Due to its toxicity and potential carcinogenicity, its determination in various samples is important for public health. Different analytical methods can be used to determine the presence and concentration of TBZ in samples. Liquid chromatography (LC) and its subtypes, high-performance liquid chromatography (HPLC) and ultra-high-performance liquid chromatography (UHPLC), are the most commonly used methods for TBZ determination representing 19%, 18%, and 18% of the described methods, respectively. Surface-enhanced Raman spectroscopy (SERS) and fluorimetry are two more methods widely used for TBZ determination, representing 13% and 12% of the described methods, respectively. In this review, a number of methods for TBZ determination are described, but due to their limitations, there is a high potential for the further improvement and development of each method in order to obtain a simple, precise, and accurate method that can be used for routine analysis.

The metabolic processes of selected pesticides and their influence on plant metabolism. A case study of two field-cultivated wheat varieties.

Pesticides that are absorbed by plants undergo biotransformation and might affect plant metabolic processes. The metabolisms of two cultivated wheat varieties, Fidelius and Tobak, treated with commercially available fungicides (fluodioxonil, fluxapyroxad, and triticonazole) and herbicides (diflufenican, florasulam, and penoxsulam) were studied under field conditions. The results provide novel insights regarding the effects of these pesticides on plant metabolic processes. Plants (roots and shoots) were sampled six times during the six-week experiment. Pesticides and pesticide metabolites were identified using GC-MS/MS, LC-MS/MS, and LC-HRMS, while root and shoot metabolic fingerprints were determined using non-targeted analysis. Fungicide dissipation kinetics were analyzed according to the quadratic mechanism (R2: 0.8522-0.9164) for Fidelius roots, and zero-order for Tobak roots (R2: 0.8455-0.9194); shoot dissipation kinetics were analyzed according to first-order (R2: 0.9593-0.9807) and quadratic (R2: 0.8415-0.9487) mechanisms for Fidelius and Tobak, respectively. The fungicide degradation kinetics were different compared to reported literature values, most likely due to differences in pesticide application methods. The following metabolites were respectively identified in shoot extracts of both wheat varieties for fluxapyroxad, triticonazole, and penoxsulam: 3-(difluoromethyl)-N-(3',4',5'-trifluorobiphenyl-2-yl)-1H pyrazole-4-carboxamide, 2-chloro-5-{(E)-[2-hydroxy-3,3-dimethyl-2-(1H-1,2,4-triazol-1-ylmethyl)-cyclopentylidene]-methyl}phenol, and N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)-2,4-dihydroxy-6 (trifluoromethyl)benzene sulfonamide. Metabolite dissipation kinetics varied depending on the wheat variety. These compounds were more persistent than parent compounds. Despite having the same cultivation conditions, the two wheat varieties varied in their metabolic fingerprints. The study revealed that pesticide metabolism has a greater dependence on plant variety and method of administration compared to the physicochemical properties of the active substance. This highlights the necessity of conducting research on pesticide metabolism under field conditions.

Separation and determination of triadimefon and its metabolites triadimenol enantiomers in fruit puree by supercritical fluid chromatography.

A method was established for the separation and determination of triadimefon and its metabolite triadimenol enantiomer residues in major complementary fruit puree for infants and young children (banana puree, pineapple puree, and grape puree) by supercritical fluid chromatography. After the samples were extracted with acetonitrile and purified with a solid phase extraction cartridge, Acquity Trefoil CEL2 chiral chromatographic column was adopted for separation, and gradient elution was conducted at the flow rate of 1.0 ml/min under the mobile phase of supercritical carbon dioxide - 0.5% ammonia methanol, the detection wavelength was 220 nm and quantification was conducted with the external standard method. The limits of quantitation of triadimefon and triadimenol enantiomers were both 0.05 mg/kg, the linear ranges were 0.5-50 mg/L, and the linear correlation coefficients were greater than 0.9993. The recoveries in the spiked samples at 0.05, 0.2, and 3.0 mg/kg were from 80.1 to 106%, and the relative standard deviation reached 3.3-7.6%. The method is efficient, rapid, reproducible, and environmentally friendly, enabling accurate analysis of pesticide enantiomers, which can detect the enantiomer residues of triadimefon and its metabolite triadimenol in major complementary fruit puree for infants and young children.

Combination of switchable hydrophilic solvent liquid-liquid microextraction with QuEChERS for trace determination of triazole fungicide pesticides by GC-MS.

This work first proposed a novel green and efficient method based on Quick, Easy, Cheap, Efficient, Rugged, and Safe pretreatment (QuEChERS) combined with switchable hydrophilic solvent homogeneous liquid-liquid microextraction (SHS-HLLME) for trace determination of triazole fungicides (TFs) in agricultural products such as vegetables and fruits by gas chromatography-mass spectrometry (GC-MS). N,N-Dimethyl benzylamine was used for the synthesis of SHS. Box-Behnken design was applied for the optimization of extraction conditions and a mathematical model was obtained. Ultimately, 0.50 mL SHS, 1.0 mL 10 mol L-1 sodium hydroxide, and 45 s ultrasonic time were determined as optimal conditions for the SHS-HLLME method. The limit of detection and limit of quantification determined using the optimal method (SHS-HLLME/GC-MS) were 0.13-0.27 ng mL-1 and 0.43-0.90 ng mL-1, respectively. In addition, the SHS-HLLME method under optimal conditions was combined with the traditional QuEChERS method to realize the advancement of the SHS-HLLME method from simple to complex matrix analysis, and the QuEChERS-SHS-HLLME method was successfully applied to the analysis of TFs in cucumbers, tomatoes, watermelon and grapes in agricultural products. Matrix-matched calibration standards were used to improve the accuracy of TFs in spiked cucumber samples to obtain recovery results close to 100%. It was shown that the new method is green and rapid, enabling fast and inexpensive sample pretreatment with up to 100-fold enrichment factor and low detection limit compared with the original QuEChERS method.

Occurrence, spatial distribution, and potential risks of organic micropollutants in urban surface waters from qinghai, northwest China.

Lack of knowledge on the destiny of organic micropollutants (OMPs) in the Tibetan Plateau region of China prevents the public from being aware of the need for protecting these unique aquatic ecosystems that are precious water resources and source areas of the Yellow River. To address this knowledge gap, this study systematically investigated the multi-residue analysis, distribution, and potential risks of six types of OMPs, namely, neonicotinoid pesticides (NEOs), fungicides, organophosphate esters (OPEs), organophosphorus pesticides (OPPs), psychoactive substances (PSs), and antidepressants (ADs), in surface waters of major cities in Qinghai. A total of 31 compounds, consisting of 8 NEOs, 1 fungicide, 12 OPEs, 2 OPPs, 5 PSs, and 3 ADs, were detected in >50% of the sites, showing their ubiquitous nature in the study area. Results showed that the total OMP concentration in surface water was 28.3-908 ng/L, and OPEs were the dominant composition (48.6%-97.4%). The risk quotient values of the detected diazinon and dursban regularly exceeded 1 for aquatic organisms at all sampling sites, indicating moderate-high chronic ecological risk. The joint probability curves showed that dursban and NEOs have higher risk levels than other OMPs. Although the results of the non-carcinogenic total hazard quotient of the OMPs in the surface water was less than 1 in all age groups and the carcinogenic risk was lower than the negligible risk level, the potential risks to children and infants were considerably greater and should not be underestimated. In addition to pollutant concentration and exposure duration, ingestion rate and body weight (BW) are also important factors affecting health risk, with BW having a negative effect. To the best of the authors' knowledge, this report is the first to describe OMP pollution in Qinghai, and the results provide new insight into the ecological security of the water resources of the Tibetan Plateau.

Wild Bee Exposure to Pesticides in Conservation Grasslands Increases along an Agricultural Gradient: A Tale of Two Sample Types.

Conservation efforts have been implemented in agroecosystems to enhance pollinator diversity by creating grassland habitat, but little is known about the exposure of bees to pesticides while foraging in these grassland fields. Pesticide exposure was assessed in 24 conservation grassland fields along an agricultural gradient at two time points (July and August) using silicone band passive samplers (nonlethal) and bee tissues (lethal). Overall, 46 pesticides were detected including 9 herbicides, 19 insecticides, 17 fungicides, and a plant growth regulator. For the bands, there were more frequent/higher concentrations of herbicides in July (maximum: 1600 ng/band in July; 570 ng/band in August), while insecticides and fungicides had more frequent/higher concentrations in August (maximum: 110 and 65 ng/band in July; 1500 and 1700 ng/band in August). Pesticide concentrations in bands increased 16% with every 10% increase in cultivated crops. The bee tissues showed no difference in detection frequency, and concentrations were similar among months; maximum concentrations of herbicides, insecticides, and fungicides in July and August were 17, 27, and 180 and 19, 120, and 170 ng/g, respectively. Pesticide residues in bands and bee tissues did not always show the same patterns; of the 20 compounds observed in both media, six (primarily fungicides) showed a detection-concentration relationship between the two media. Together, the band and bee residue data can provide a more complete understanding of pesticide exposure and accumulation in conserved grasslands.

A review of modeling pesticides in freshwaters: Current status, progress achieved and desirable improvements.

This study comprises a critical review of modeling of pesticides in surface waters. The aim was to update the status of the use of models to simulate the fate of pesticides from diffuse sources. ISI papers were selected on Scopus and the information concerning the study areas, type of pesticides (herbicides, fungicides and insecticides), the model, and the methodology adopted (i.e., calibration and/or validation, spatial and temporal scales) were analyzed. The studies were carried out in Europe (55.5%), North America (22.3%), Asia (13.9%) and South America (8.3%). The Soil and Water Assessment Tool proved to be the most used model (45.95%). Herbicides were the most modeled pesticides (71.4%), followed by insecticides (18.2%) and fungicides (10.4%). The main herbicides modeled were atrazine, metolachlor, isoproturon, glyphosate, and acetochlor. Insecticides such as chlorpyrifos and metaldehyde. Chlorothalonil, and fungicides (i.e., tebuconazole) were the most widely investigated. Based on published studies, it was found that modeling approaches for assessing the fate of pesticides are constantly evolving and the model algorithms work well with diverse watershed conditions, management strategies, and pesticide properties. Several papers reported concentrations of pesticides exceeding ecotoxicological thresholds revealing that water contamination with pesticides used in agriculture and urban areas is a priority issue of current global concern.

Exposure assessment for pesticide residues in agricultural products consumed in the Republic of Korea during 2016-2020.

Pesticide residues in food comprise compounds such as insecticides, fungicides, herbicides, miticides, and plant activators. The insecticides diazinon (O, O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate) and malathion (O, O-dimethyl dithiophosphate of diethyl-mercaptosuccinate) are classified as probably carcinogenic (Group 2A) and the fungicides chlorothalonil (2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile) and hexachlorobenzene (pentachlophenyl chloride) as possibly carcinogenic to humans (Group 2B) by the International Agency for Research on Cancer under the World Health Organization. In this study, gas chromatographic and gas chromatography-tandem mass spectrometric analyses were used to determine the concentrations of pesticide residues in agricultural products and assess the effects of chronic human exposure to pesticide residues through the consumption of agricultural products during 2018-2020. Food consumption data were obtained from the Korea National Health and Nutrition Examination Survey of 2016-2018. The chronic exposures determined using mean consumption data for the whole population and mean concentrations of the pesticide residues were 5.15E-11 to 2.08E-05 [lower bound (LB)] and 2.41E-07 to 4.69E-05 mg/kg bw/day [upper bound (UB)], corresponding to 0.00012-2.16% of the hazard index (HA). Exposures to pesticide residues, calculated using the 95th percentile of the consumption data, were 0-8.76E-05 (LB) and 9.26E-07 to 1.56E-04 mg/kg bw/day (UB), corresponding to 0.00045-9.41% of the HA. Based on the result of current exposure assessment, it could be considered that the pesticide residues in agricultural products are properly controlled by the regulatory authorities.

Pesticide drift mitigation measures appear to reduce contamination of non-agricultural areas, but hazards to humans and the environment remain.

Pesticide drift onto non-agricultural land is a common problem in intensively farmed regions, and national action plans have been established across Europe to prevent it. Here, we analyzed official data on pesticide residues in grass samples collected over six years to determine whether implemented measures to reduce pesticide drift were effective. We used 306 samples collected between 2014 and 2020 on non-agricultural land in one of the most intensively managed apple and wine growing regions in Europe, the Autonomous Province of Bolzano-South Tyrol, Italy. Samples were analyzed for up to 314 substances by gas chromatography and mass spectrometry. Percentage of sites with multiple pesticides and number of pesticides decreased between 2014 and 2020. Fungicides were most often detected, with fluazinam found on 74 % and captan on 60 % of the contaminated sites (53 sites out of a total of 88 sites were contaminated). The most frequently found insecticide, phosmet, was detected in 49 % of the contaminated sites. Only one herbicide, oxadiazon, was detected in <1 % of the sites; glyphosate was not analyzed. The percentage of residues with human hazard properties increased significantly across years regarding reproductive toxicity (from 21 % of the detected substances in 2014 to 88 % in 2020) and specific target organ toxicity (0 % in 2014 to 21 % in 2020). Percentages of substances associated with endocrine-disruption (89 % of substances across years) or carcinogenic properties (45 % of substances across years) remained constant. The percentage of sites where concentrations in grass samples exceeded the surrogate maximum residue levels (MRLs) for lettuce also remained constant. Potential ecotoxicological hazards of detected residues regarding acute contact toxicity to honeybees remained high over the study years, while the acute and chronic toxicity to earthworms decreased. Our results suggest that while drift mitigation measures contributed some reduction in pesticide contamination, they were not sufficient to eliminate substantial risks to human health and the environment in nontarget areas.

[Simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts by QuEChERS-high performance liquid chromatography-tandem mass spectrometry].

Chromatography combined with mass spectrometry is the most commonly used detection technology, and it offers the advantages of high sensitivity and high selectivity. The quick, easy, inexpensive, effective, rugged, and safe (QuEChERS) method is low-cost, effective, and time efficient. The application of the QuEChERS has now been extended to the analysis of contaminants in food samples. The aim of the study was to identify different concentration levels of multiple harmful drug residues in bean sprouts. In this study, QuEChERS coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established for the simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts. In the HPLC-MS/MS experiment, gibberellic acid, 4-fluorophenoxyacetic acid, chloramphenicol, N6-(δ2-isopentenyl)-adenine, 6-benzylaminopurine, 4-chlorophenoxyacetic acid, and 2,4-dichlorophenoxyacetic acid (2,4-D) were analyzed by MS/MS with negative electrospray ionization (ESI-). The other 33 target analytes (chlormequat, ronidazole, metronidazole, pymetrozine, dimetridazole, methomyl, carbendazim, enoxacin, levofloxacin, pefloxacin mesylate, norfloxacin, ciprofloxacin, enrofloxacin, thiabendazole, lomefloxacin, chlorpyrifos, sarafloxacin, imidacloprid, etc.) were analyzed by MS/MS with positive electrospray ionization (ESI+). Sensitive MS conditions were realized by optimizing the instrumental parameters such as the desolvent temperature, collision energy, spraying needle position, precursor ions, and product ions. Then, the optimal pretreatment method was determined by comparing the recovery rates of the 40 drugs obtained with different extraction solvents (methanol, acetonitrile, acetonitrile containing 0.1% ammonia, acetonitrile with 1% acetic acid), different extraction methods (ultrasonic extraction, shaking extraction), and purification with primary secondary amine (PSA) and C18. In this study, the bean sprouts samples were extracted twice by 10 mL acetonitrile with 1% acetic acid, and extracted under ultrasonic conditions. Then, the extracting solution was only cleaned with 100 mg C18. The chromatographic separation of the 40 compounds was accomplished on a Waters ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm) with gradient elution. Methanol and 0.01% formic acid aqueous solution were used as the mobile phases. The 40 compounds were analyzed in the multiple reaction monitoring (MRM) mode. The matrix matching external standard method was used for quantitative determination. The results showed that the 40 compounds could be analyzed within 15 min. Under the optimized conditions, the calibration curves showed good linearities for the 40 compounds, and the coefficients of determination (r2) were greater than 0.99 in the range of 2-200 µg/L. The limits of detection (LODs) and limits of quantification (LOQs) were in the range of 0.1-3 µg/kg and 0.3-9 µg/kg, respectively. Using negative bean sprouts as the substrates, the recovery tests were carried out at three spiked levels of 5, 10, and 50 µg/kg. The average recoveries of the 40 drugs were 78.5% to 115.3%, and the corresponding relative standard deviations (RSDs) were 1.3% to 9.7% (n=6). This method was successfully applied to the analysis of the 40 drug residues in 21 batches of local bean sprouts in Handan city. The results revealed the presence of extensive drug residues in the bean sprouts. The 26 batches were detected to varying degrees, among which 4-chlorophenoxyacetic acid, carbendazim, 6-benzyladenine, 2,4-D, enrofloxacin, and metronidazole were detected at high rates. The detection rates of 4-chlorophenoxyacetic acid, 6-benzyladenine, carbendazim, 2,4-D, gibberellic acid, and enrofloxacin were 28.6%, 19.0%, 9.5%, 9.5%, 4.8%, and 4.8%, respectively. The contents ranged from 37.5-352.4, 32.4-273.1, 28.8-38.7, 316.1-20.2, 19.9 and 13.6 µg/kg, respectively. Given its advantages of simplicity, rapidness, and high sensitivity, the developed method can be used for the rapid and accurate determination of trace levels of the 40 drug residues in large quantities of bean sprouts.

Residue analysis and dietary risk assessment of tebuconazole in loquat and sugarcane after open-field application in China.

Tebuconazole is an effective but potentially carcinogenic fungicide. Tebuconazole residues in loquat and sugarcane were investigated, together with an analysis of their dietary risk. Solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry showed fortified recoveries of 87% to 98%, with standard deviations ≤ 6.4%. The tebuconazole residues were below 6.34 mg kg-1 for whole loquat and 0.80 mg kg-1 for sugarcane. Based on the final residue test, the chronic hazard index was 90.74% in whole loquat and sugarcane, while the acute hazard index ranged from 66.32% to 109.49% for loquat and 33.37% to 76.93% for sugarcane. The assessment of potential dietary risk showed that while loquats may represent an acute risk to human health, whereas sugarcane consumption was safe. A 21-day pre-harvest interval is proposed to comply with maximum residue limit regulations and the observed risks when using 430 g/L tebuconazole for treating sugarcane. These findings offer guidance for tebuconazole formulation and use.

Pesticides in ambient air, influenced by surrounding land use and weather, pose a potential threat to biodiversity and humans.

Little is known about (i) how numbers and concentrations of airborne pesticide residues are influenced by land use, interactions with meteorological parameters, or by substance-specific chemo-physical properties, and (ii) what potential toxicological hazards this could pose to non-target organisms including humans. We installed passive air samplers (polyurethane PUF and polyester PEF filter matrices) in 15 regions with different land uses in eastern Austria for up to 8 months. Samples were analyzed for 566 substances by gas-chromatography/mass-spectrometry. We analyzed relationships between frequency and concentrations of pesticides, land use, meteorological parameters, substance properties, and season. We found totally 67 pesticide active ingredients (24 herbicides, 30 fungicides, 13 insecticides) with 10-53 pesticides per site. Herbicides metolachlor, pendimethalin, prosulfocarb, terbuthylazine, and the fungicide HCB were found in all PUF samplers, and glyphosate in all PEF samplers; chlorpyrifos-ethyl was the most abundant insecticide found in 93% of the samplers. Highest concentrations showed the herbicide prosulfocarb (725 ± 1218 ng sample-1), the fungicide folpet (412 ± 465 ng sample-1), and the insecticide chlorpyrifos-ethyl (110 ± 98 ng sample-1). Pesticide numbers and concentrations increased with increasing proportions of arable land in the surroundings. However, pesticides were also found in two National Parks (10 and 33 pesticides) or a city center (17 pesticides). Pesticide numbers and concentrations changed between seasons and correlated with land use, temperature, radiation, and wind, but were unaffected by substance volatility. Potential ecotoxicological exposure of mammals, birds, earthworms, fish, and honeybees increased with increasing pesticide numbers and concentrations. Human toxicity potential of detected pesticides was high, with averaged 54% being acutely toxic, 39% reproduction toxic, 24% cancerogenic, and 10% endocrine disrupting. This widespread pesticide air pollution indicates that current environmental risk assessments, field application techniques, protective measures, and regulations are inadequate to protect the environment and humans from potentially harmful exposure.

Integrating high-throughput sequencing and metabolomics to investigate the stereoselective responses of soil microorganisms to chiral fungicide cis-epoxiconazole.

The use of the chiral triazole fungicide cis-epoxiconazole in agricultural production continues to increase; however, little is known about the stereoselective and toxic responses of soil microorganisms to cis-epoxiconazole in the soil microenvironment. High-throughput sequencing and metabolomics were integrated to investigate the stereoselective response of soil microbial community structure, metabolic profile to cis-epoxiconazole exposure, and the correlation between the microbiomes and different metabolites. Soil microbial community structure and soil metabolic profile were significantly altered and exhibited significant enantioselectivity. The alpha diversity (Chao, Shannon, and Simpson diversity) of bacterial and fungus was not significantly affected, whereas the beta diversity (Bray-Curtis dissimilarity and PLS-DA) of bacterial and fungus was significantly altered in treatment of cis-epoxiconazole and its enantiomers (p-value < 0.05). The variation in bacterial and fungus community structure was the highest under (+)-enantiomer exposure, followed by exposure to racemate and (-)-enantiomer. Soil metabolomic analysis revealed that exposure to high or low doses of cis-epoxiconazole and its enantiomers resulted in different degrees of reprogramming of the soil metabolic pool. The 39 significantly changed metabolites mainly included small molecular organic acids, amino acids and their intermediates, and purine and adenosine intermediates. Six metabolic pathways were significantly disrupted. Different correlation patterns were observed between the significantly altered metabolites and microbes (p-value < 0.05) by Pearson correlation-based analysis. In conclusion, as xenobiotic pollutant, epoxiconazole altered the structure and metabolism of soil microorganisms with significant stereoselectivity mainly driven by 2R, 3S-(+)-cis-epoxiconazole. This study provided a more robust assessment of the risks of epoxiconazole exposure to soil microorganisms. Given the importance of the soil environment in agricultural production, characterization of the soil microbiome and metabolome can provide new insights into the ecological risks posed by exposure to the chiral triazole pesticide cis-epoxiconazole and its enantiomers.

Spectral responses at visible and near-infrared wavelengths of soybean plants to fungicides / Respostas espectrais em comprimentos de onda visível e infravermelho-próximo de plantas de soja a fungicidas

The study evaluated the efficacy and soybean spectral responses to fifteen foliar fungicide mixtures labeled to control Asian soybean rust. Canopy level reflectance was measured using a multispectral camera onboard a multirotor drone before and two hours after each spray. The third application of fungicides improved control of soybean rust and increased yield. Nevertheless, up to three consecutive foliar fungicides applications did not affect the reflectance of soybean plants at visible and infrared wavelengths. Thus, drones can be a viable strategy for data acquisition regardless of the application of the fungicides.

Esse estudo avaliou a eficácia e as respostas espectrais de plantas de soja a quinze misturas de fungicidas utilizados no controle da ferrugem asiática da soja (FAS). A refletância do nível do dossel foi medida usando uma câmera multiespectral a bordo de um drone multirotor antes e duas horas após cada pulverização. A terceira aplicação de fungicidas melhorou o controle de FAS e aumentou a produtividade. Porém, três aplicações foliares consecutivas de fungicidas não afetaram a refletância de plantas de soja nos comprimentos de onda visível e infravermelho. Assim, drones podem ser uma estratégia viável para aquisição de dados independentemente da aplicação de fungicidas.

COMPARATIVE HYGIENIC ASSESSMENT OF WORKING CONDITIONS AND OCCUPATIONAL RISK IN THE APPLICATION OF PESTICIDES (ON THE EXAMPLE OF FUNGICIDE AMISTAR EXTRA 280, SC) USING DIFFERENT TYPES OF SPRAYERS.

OBJECTIVE: The aim: Was a comparative hygienic assessment of working conditions and occupational risk in the application of fungicide Amistar Extra 280, SC using slotted and injector sprayers. PATIENTS AND METHODS: Materials and methods: Sprayers Super Poly 110-04 (variant №1) and Guardian Air GA110-04 (variant № 2), and certified equipment were used. The occupational risk was assessed in accordance with the methodological recommendations proposed by the L.I. Medvedia Scientific Center for Preventive Toxicology, Food and Chemical Safety specialists. RESULTS: Results: When using the slotted sprayer Super Poly 110-04 in the air of the working zone of the tractor driver the content of azoxystrobin was 0.0015 ± 0.0001 mg/m3, cyproconazole - 0.085 ± 0.002 mg/m3, at a distance of 10 m from the edge of the field on the leeward side - 0.003 ± 0.001 and 0.11 ± 0.02 mg/m3, respectively. Visual analysis of water-sensitive cards after using slotted sprayers showed the presence of single drops of pesticide working solution in the wear zone. When applying the pesticide using a Guardian Air GA110-04 injector sprayer in the air of the working zone of the tractor driver, areas of possible wear (10 and 100 m), theconcentration of the active substances of Amistar Extra 280, SC formulation was below the limit of quantification of the method. When assessing the complex risk for tractor drivers, a statistically significant difference was found for azoxystrobin (p = 0.002) and cyproconazole (p = 0.001) when using a slotted sprayer Super Poly 110-04 and injector Guardian Air GA110-04. CONCLUSION: Conclusions: Values of the combined complex risk of application of the Amistar Extra 280, SC formulation for tractor drivers of variant №2 application were significantly lower than those for tractor drivers of variant №1.