Uptake and Biotransformation of Guvermectin in Three Crops after In Vivo and In Vitro Exposure.

Guvermectin, as a novel nucleoside-like biopesticide, could increase the rice yield excellently, but the potential environmental behaviors remain unclear, which pose potential health risks. Therefore, the uptake and biotransformation of guvermectin in three types of crops (rice, lettuce, and carrot) were first evaluated with a hydroponic system. Guvermectin could be rapidly absorbed and reached equilibrium in roots (12-36 h) and shoots (24-60 h) in three plants, and guvermectin was also vulnerable to dissipation in roots (t1/2 1.02-3.65 h) and shoots (t1/2 9.30-17.91 h). In addition, 8 phase I and 2 phase II metabolites, transformed from guvermectin degradation in vivo and in vitro exposure, were identified, and one was confirmed as psicofuranine, which had antibacterial and antitumor properties; other metabolites were nucleoside-like chemicals. Molecular simulation and quantitative polymerase chain reaction further demonstrated that guvermectin was metabolized by the catabolism pathway of an endogenous nucleotide. Guvermectin had similar metabolites in three plants, but the biotransformation ability had a strong species dependence. In addition, all the metabolites exhibit neglectable toxicities (bioconcentration factor <2000 L/kg b.w., LC50,rat > 5000 mg/kg b.w.) by prediction. The study provided valuable evidence for the application of guvermectin and a better understanding of the biological behavior of nucleoside-like pesticides.

A sensitive fluoroimmunoassay for quantitative detection of imidacloprid based on quantum dot-streptavidin conjugate.

Imidacloprid (IMI), the most commonly used neonicotinoid, is widely present in both the environment and agro-products due to extensive and prolonged application, posing potential risks to ecological security and human health. This study introduced a sensitive and rapid fluorescence-linked immunosorbent assay, employing Quantum Dot-Streptavidin conjugate (QDs-SA-FLISA), for efficient monitoring of IMI residues in agro-products. Under optimized conditions, the QDs-SA-FLISA exhibited a half-maximal inhibition concentration (IC50) of 1.70 ng/mL and a limit of detection (LOD, IC20) of 0.5 ng/mL. Investigation into the sensitivity enhancement effect of the QDs-SA revealed that the sensitivity (IC50) of the QDs-SA-FLISA was 7.3 times higher than that of ELISA. The recoveries and relative standard deviation (RSD) ranged from 81.7 to 118.1 % and 0.5-9.4 %, respectively, for IMI in brown rice, tomato and pear. There was no significant difference in IMI residues obtained between QDs-SA-FLISA and UHPLC-MS/MS. Thus, the QDs-SA-FLISA represents a reliable approach for the quantitative determination of IMI in agro-products.

From Water to Water: Insight into the Translocation of Pesticides from Plant Rhizosphere Solution to Leaf Guttation and the Associated Ecological Risks.

Plant guttation is an important source of water/nutrients for many beneficial insects, while the presence of pesticides in guttation has been considered as a new exposure route for nontarget insects. This study aimed to elucidate how 15 diverse pesticides are translocated from growth media to guttation by maize plants through a hydroponic experiment. All pesticides were effectively translocated from the growth solution to maize guttation and reached a steady state within 5 days. The strong positive correlation (R2 = 0.43-0.84) between the concentrations of pesticides in guttation and in xylem sap demonstrated that xylem sap was a major source of pesticides in guttation. The relationship between the bioaccumulation of pesticides in guttation (BCFguttation) and the chemical Kow was split into two distinct patterns: for pesticides with log Kow > 3, we identified a good negative linear correlation between log BCFguttation and log Kow (R2 = 0.71); however, for pesticides with log Kow < 3, all data fall close to a horizontal line of BCFguttation ≅ 1, indicating that hydrophilic pesticides can easily pass through the plants from rhizosphere solution to leaf guttation and reach saturation status. Besides, after feeding with pesticide-contaminated guttation, the mortality of honeybees was significantly impacted, even at very low levels (e.g., ∑600 µg/L with a mortality of 93%). Our results provide essential information for predicting the contamination of plant guttation with pesticides and associated ecological risks.

Comparative uptake, translocation and metabolism of phenamacril in crops under hydroponic and soil cultivation conditions.

Many studies investigate the plant uptake and metabolism of xenobiotics by hydroponic experiments, however, plants grown in different conditions (hydroponic vs. soil) may result in different behaviors. To explore the potential differences, a comparative study on the uptake, translocation and metabolism of the fungicide phenamacril in crops (wheat/rice) under hydroponic and soil cultivation conditions was conducted. During 7-14 days of exposure, the translocation factors (TFs) of phenamacril were greatly overestimated in hydroponic-wheat (3.6-5.2) than those in soil-wheat systems (1.1-2.0), with up to 3.3 times of difference between the two cultivation systems, implying it should be cautious to extrapolate the results obtained from hydroponic to field conditions. M-144 was formed in soil pore water (19.1-29.9 µg/L) in soil-wheat systems but not in the hydroponic solution in hydroponics; M-232 was only formed in wheat shoots (89.7-103.0 µg/kg) under soil cultivation conditions, however, it was detected in hydroponic solution (20.1-21.2 µg/L), wheat roots (146.8-166.0 µg/kg), and shoots (239.2-348.1 µg/kg) under hydroponic conditions. The root concentration factors (RCFs) and TFs of phenamacril in rice were up to 2.4 and 3.6 times higher than that in wheat for 28 days of the hydroponic exposure, respectively. These results highlighted that cultivation conditions and plant species could influence the fate of pesticides in crops, which should be considered to better assess the potential accumulation and transformation of pesticides in crops.

Pesticides in Greenhouse Airborne Particulate Matter: Occurrence, Distribution, Transformation Products, and Potential Human Exposure Risks.

Pesticides are frequently sprayed in greenhouses to ensure crop yields, where airborne particulate matter (PM) may serve as a carrier in depositing and transporting pesticides. However, little is known about the occurrence and fate of PM-borne pesticides in greenhouses. Herein, we examined the distribution, dissipation, and transformation of six commonly used pesticides (imidacloprid, acetamiprid, prochloraz, triadimefon, hexaconazole, and tebuconazole) in greenhouse PM (PM1, PM2.5, and PM10) after application as well as the associated human exposure risks via inhalation. During 35 days of experiment, the six pesticides were detected in all PM samples, and exhibited size- and time-dependent distribution characteristics, with the majority of them (>64.6%) accumulated in PM1. About 1.0-16.4% of initially measured pesticides in PM remained after 35 days, and a total of 12 major transformation products were elucidated, with six of them newly identified. The inhalation of PM could be an important route of human exposure to pesticides in the greenhouse, where the estimated average daily human inhalation dose (ADDinh) of the six individual pesticides was 2.1-1.2 × 104 pg/kg day-1 after application (1-35 days). Our findings highlight the occurrence of pesticides/transformation products in greenhouse PM, and their potential inhalation risks should be further concerned.

Simultaneous determination of 27 pesticides in corn and cow matrices by ultra-performance liquid chromatography-tandem mass spectrometry.

In this paper, we developed a sensitive UPLC-MS/MS method to determine pesticide residues in plant matrices (corn, fresh corn, fresh corn stover, old corn stover, and corn silage) and animal matrices (beef, fat, milk, milk fat, kidney, liver, and cow stomach) quantitatively. Twenty-seven pesticides were extracted with acetonitrile from all plant and animal matrices separately and purified with a mixture of primary secondary amine (PSA) and graphitized carbon black (GCB) or octadecylsilane (C18). The average recoveries of these compounds ranged from 60.7% to 118.2%, and the relative standard deviations were less than 20.0%. The limit of quantitation for all compounds was 0.01 mg kg-1 (for cyhalothrin and beta cypermethrin the LOQ was 0.02 mg kg-1). The establishment of multi-residue analysis methods for a variety of matrices can be used as a database for future method research. The results of this study are essential for calculating the transfer of pesticide residues from feed to animal products and for monitoring food safety, which will protect people's health and safety.

The fate of mycotoxins in oranges during storage and processing.

To evaluate the safety of orange consumption induced by mycotoxins, 'Newhall' navel oranges were artificially inoculated with P. expansum and A. tenuissima, followed by an evaluation of the distribution and migration patterns of corresponding mycotoxins (patulin [PAT], tentoxin [Ten], altenuene [ALT], alternariol monomethyl ether [AME], alternariol [AOH] and tenuazonic acid [TeA]) during orange storage and processing. The concentration of mycotoxins decreased as the increase of distance from the lesion, and mycotoxins could be detected throughout the orange when the lesion extended to 8 mm in diameter. AOH and AME pose the primary source of dietary risk with high concentrations and low thresholds of toxicological concern. Orange juice and pectin processing could remove 43.4-98.7% of mycotoxins, while tangerine peelprocessing might lead to significant enrichment of mycotoxins with the processing factors (PFs) of 2.8-3.5. The findings may offer scientific insights into mitigating the dietary risk of mycotoxin exposure from oranges and their derivatives.

Rational understanding of chiral fungicide penthiopyrad stereoselectivity: Bioactivity, aquatic toxicity and cytotoxicity.

Penthiopyrad is a novel chiral succinate dehydrogenase inhibitor (SDHI) fungicide with two enantiomers. However, enantioselective information on the biological activity, nontarget organisms and human health risk of penthiopyrad is not comprehensive, which may cause inaccurate risk assessment. In this study, the enantioselective bioactivity to three kinds of phytopathogens (Rhizoctonia solani, Botrytis cinerea and Sclerotinia sclerotiorum) was first disclosed, and the antifungal activity of S-(+)-penthiopyrad was higher than that of R-(-)-penthiopyrad by 12-37 times. Moreover, its enantioselective toxicity to Raphidocelis subcapitata and Daphnia magna was also clarified, and the order of toxicity was S-(+)-penthiopyrad > rac-penthiopyrad >R-(-)-penthiopyrad, with 1.8- and 5.3-fold differences between the two enantiomers. Furthermore, the enantioselectivity of penthiopyrad on HepG2 cytotoxicity was studied. The data showed that the cytotoxicity of S-(+)-penthiopyrad was 1.8 times higher than that of R-(-)-penthiopyrad, and S-(+)-penthiopyrad had a stronger impact on cell proliferation, oxidative stress and lipid peroxidation. In summary, due to the enantioselectivity of the activity and toxicity of the chiral pesticide, the efficacy and risk evaluation of penthiopyrad should be considered at the enantiomer level.

Toxicity assessment of a novel biopesticide guvermectin and identification of its transformation products in soils.

Guvermectin is a novel biopesticide often used as seed soaking to promote the rice yield. However, its biotoxicity and degradation behavior in soils were still not disclosed, which posed a knowledge gap to guide its rational application. Therefore, the degradation behaviors of guvermectin in four typical soils under aerobic and anaerobic conditions were investigated in the laboratory. The results showed that guvermectin was degraded fast with DT50 ranging from 0.95 to 10.10 d, and the degradation rate was higher in aerobic condition than that in anaerobic condition. Eight transformation products were screened using UPLC-QTOF/MS. The acute toxicities tests of guvermectin to Coturnix coturnix japonica and Apis mellifera were measured by biological laboratory experiments, and the acute and chronic toxicities of transformation products to Danio rerio, Daphnia magna Straus and Green algae were predicted by ECOSAR software. The results showed that guvermectin has low toxic to quail and honeybee (LD50 2000 mg a.i./kg body weight, LD50 Ëƒ 100 µg a.i./bee), and its transformation products were also low toxic class to Danio rerio, Daphnia magna Straus and Green algae (LC50/EC50 > 100 mg a.i./L). However, the nucleoside-like metabolites may pose a potential risk due to their similarity to genetic material, which should be concerned. The findings provided important environmental risk assessment data for the rational use of guvermectin.

Insight into the Long-Lasting Control Efficacy of Neonicotinoid Imidacloprid against Wheat Aphids during the Entire Growth Period.

Understanding the mechanism of long-lasting control efficacy of pesticides is important for developing sustainable high-efficacy pesticides, decreasing pesticide-use frequency and environmental input. This study investigates the long-term control mechanism of imidacloprid against wheat aphids under seed treatment. The concentrations of imidacloprid and its metabolites were 2.2-69.6 times lower than their individual LC50 after 238 days of treatment, and the control efficacy was still higher than 94.6%. The mixed bioactivity tests demonstrated that the insecticidal activity of the mixture of imidacloprid and its bioactive metabolites was approximately 1.5-189.7 times greater than that of a single compound against wheat aphids. The concentrations of imidacloprid, 5-hydroxy imidacloprid, and imidacloprid olefin in top flag leaves were 0.022, 0.084, and 0.034 mg/kg, respectively, during the aphid flourishing period, which were higher than the LC50 of the mixture (0.011 mg/kg), therefore providing long-lasting control efficacy. The study provides a first insight into the synergistic effects between a pesticide and its bioactive metabolites in ensuring long-term control performance.

Assessment on the stereoselective behavior of cyflumetofen to earthworms (Eisenia foetida): Degradation, bioaccumulation, toxicity mechanism, and metabolites.

In this study, environmental behavior and toxicity of cyflumetofen (CYF) enantiomers were evaluated comprehensively in a soil-earthworm system. In the earthworm (Eisenia foetida), (+)-CYF was preferentially accumulated, and acute toxicity of Rac-CYF was greater than that of (+)-CYF and (-)-CYF, indicating that the combination of CYF enantiomers increased the toxicity. As a measure of chronic toxicity, compared with (-)-CYF-treated earthworms, malondialdehyde accumulation was higher in (+)-CYF-treated earthworms, indicating a more severe oxidative stress response. In a DNA comet plot, the trailing distance in the (+)-CYF treatment was 1.97 times greater than that in the (-)-CYF-treated, revealing more severe genotoxicity with (+)-CYF. However, (-)-CYF was more likely than (+)-CYF to activate the earthworm detoxification enzyme pathway. With (+)-CYF treatment, the number of differentially expressed genes (DEGs) involved in the pathogenic pathway increased significantly, whereas with (-)-CYF-treatment, more DEGs were involved in P450 and glutathione S-transferase (GST) detoxification metabolic pathways, including high expression of the genes chi-III, GST-S-1, and GST-alpha-5. The main metabolites of the CYF enantiomers were A-2, A-12, B-1, AB-1, AB-7, and B-3, which exhibited potential ecotoxicity. In general, CYF was stereoselective in the soil-earthworm ecosystem, with (+)-CYF causing a higher genotoxicity risk than that of (-)-CYF. The study provides insight into the selective toxicity mechanisms of chiral CYF and contributes to a theoretical basis for risk assessment of low-risk pesticides.

Occurrence and impact of carbendazim and hymexazol residues on yeast growth and ochratoxin A contamination during wine production.

BACKGROUND: Grapes are highly vulnerable to infection by carbon black aspergilli, which produce ochratoxin A (OTA), a mycotoxin. Carbendazim and hymexazol are widely applied to control grape diseases. Howerver, fungicides, toxigenic fungi, and OTA can be transferred from grapes to wine causing potential safety issues. The impact of these residues on fungal populations and OTA during vinification are currently unclear. Here we investigated the effects of carbendazim and hymexazol on the viability of Aspergillus carbonarius and OTA contamination during an indoor wine-processing experiment. RESULTS: The population size of A. carbonarius substantially increased at 24 h followed by a significantly decreased at 72 h after destemming and crushing. However, carbendazim and hymexazol notably inhibited the growth of A. carbonarius in must samples. In addition, yeast growth was substantially deleyed by carbendazim, hymexazol, and OTA during the first 3 days in compared with the control. Carbendazim, hymexazol, and OTA residues declined over time, and the processing factors (PFs) for carbendazim and hymexazol throughout vinification were 0.164, 0.074, and 0.185-0.476, respectively. Carbendazim and hymexazol each reduced OTA concentrations. However, there was no significant difference after 48 h. Addition of carbendazim or hymexazol significantly reduced the level of A. carbonarius but had no significant effect on the final concentration of OTA in mature wine. CONCLUSION: The wine-making process can reduce the residues of OTA, carbendazim, and hymexazol in grapes, but it is recommended that grapes chosen to make wine should be free of A. carbonarius contamination. © 2023 Society of Chemical Industry.

Highly-Selective Analytical Strategy for 90 Pesticides and Metabolites Residues in Fish and Shrimp Samples.

The analysis of pesticide residues in aquatic products is challenging due to low residue levels and the complex matrix interference. In this study, we developed a simple, fast method for the trace analysis of 90 pesticides and metabolites in aquatic products. The analytes covered a wide polarity range with log Kow (log octanol-water partition coefficient) ranging from -1.2 to 6.37. Grass carp (Ctenopharyngodon idellus) and prawn (Penaeus chinensis) samples were chosen to validate the quantification method. The samples were extracted by 0.2% formic-acetonitrile, cleaned by solid-phase extraction (PRiME HLB), and analyzed by high performance liquid chromatography-tandem mass spectrometry. The results showed good linearities for the analytes and were observed in the range of 0.05-50 µg/L. The recoveries of the method were within 50.4-118.6%, with the relative standard deviations being lower than 20%. The limits of quantifications (LOQs) of the method were in the range of 0.05-5.0 µg/kg, which were superior to values compared with other research. The developed method was applied to detect pesticide residues in prawn samples from eastern coastal areas of China. Three herbicide residues of diuron, prometryn, and atrazine were detected in prawn samples. The method was sensitive and efficient, which is of significance in expanding the screening scope and improving the quantitative analysis efficiency in aquatic products.

The interaction effects of pesticides with Saccharomyces cerevisiae and their fate during wine-making process.

Pesticide residues in grapes could be transferred to fermentation system during the wine-making process, which may interfere the normal proliferation of Saccharomyces cerevisiae and subsequently affect the safety and quality of wine products. However, the interaction between pesticides and Saccharomyces cerevisiae is still poorly understood. Herein, the fate, distribution and interaction effect with Saccharomyces cerevisiae of five commonly-used pesticides during the wine-making process were evaluated. The five pesticides exerted varied inhibition on the proliferation of Saccharomyces cerevisiae, and the order of inhibition intensity was difenoconazole > tebuconazole > pyraclostrobin > azoxystrobin > thiamethoxam. Compared with the other three pesticides, triazole fungicides difenoconazole and tebuconazole showed stronger inhibition and played a major role in binary exposure. The mode of action, lipophilicity and exposure concentration were important factors in the inhibition of pesticides. Saccharomyces cerevisiae had no obvious impacts on the degradation of target pesticides in the simulated fermentation experiment. However, the levels of target pesticides and their metabolite were significantly reduced during the wine-making process, with the processing factors ranged from 0.030 to 0.236 (or 0.032 to 0.257) during spontaneous (or inoculated) wine-making process. As a result, these pesticides were significantly enriched in the pomace and lees, and showed a positive correlation (R2 ≥ 0.536, n = 12, P < 0.05) between the hydrophobicity of pesticides and distribution coefficients in the solid-liquid distribution system. The findings provide important information for rational selection of pesticides on wine grapes and facilitate more accurate risk assessments of pesticides for grape processing products.

Systematic assessment of cyflumetofen toxicity in soil-earthworm (Eisenia fetida) microcosms.

Cyflumetofen was widely applied in agriculture with its excellent acaricidal effect. However, the impact of cyflumetofen on the soil non-target organism earthworm (Eisenia fetida) is unclear. This study aimed to elucidate the bioaccumulation of cyflumetofen in soil-earthworm systems and the ecotoxicity of earthworms. The highest concentration of cyflumetofen enriched by earthworms was found on the 7th day. Long-term exposure of earthworms to the cyflumetofen (10 mg/kg) could suppress protein content and increases Malondialdehyde content leading to severe peroxidation. Transcriptome sequencing analysis demonstrated that catalase and superoxide-dismutase activities were significantly activated while genes involved in related signaling pathways were significantly upregulated. In terms of detoxification metabolic pathways, high concentrations of cyflumetofen stimulated the number of Differentially-Expressed-Genes involved in the detoxification pathway of the metabolism of glutathione. Identification of three detoxification genes (LOC100376457, LOC114329378, and JGIBGZA-33J12) had synergistic detoxification. Additionally, cyflumetofen promoted disease-related signaling pathways leading to higher disease risk, affecting the transmembrane capacity and cell membrane composition, ultimately causing cytotoxicity. Superoxide-Dismutase in oxidative stress enzyme activity contributed more to detoxification. Carboxylesterase and glutathione-S-transferase activation play a major detoxification role in high-concentration treatment. Altogether, these results contribute to a better understanding of toxicity and defense mechanisms involved in long-term cyflumetofen exposure in earthworms.

Photodegradation of the Novel Herbicide Pyraquinate in Aqueous Solution: Kinetics, Photoproducts, Mechanisms, and Toxicity Assessment.

Pyraquinate, a newly developed 4-hydroxyphenylpyruvate dioxygenase class herbicide, has shown excellent control of resistant weeds in paddy fields. However, its environmental degradation products and corresponding ecotoxicological risks after field application remain ambiguous. In this study, we systematically investigate the photolytic behaviors of pyraquinate in aqueous solutions and in response to xenon lamp irradiation. The degradation follows first-order kinetics, and its rate depends on pH and the amount of organic matter. No vulnerability to light radiation is indicated. Ultrahigh-performance liquid chromatography with quadrupole-time-of-flight mass spectrometry and UNIFI software analysis reveals six photoproducts generated by methyl oxidation, demethylation, oxidative dechlorination, and ester hydrolysis. Gaussian calculation suggests that activities due to hydroxyl radicals or aquatic oxygen atoms caused these reactions on the premise of obeying thermodynamic criteria. Practical toxicity test results show that the toxicity of pyraquinate to zebrafish embryos is low but increases when the compound is combined with its photoproducts.

Effective photodegradation of antibiotics by guest-host synergy between photosensitizer and bismuth vanadate: Underlying mechanism and toxicity assessment.

The removal of antibiotics in wastewater has attracted increasing attention. Herein, a superior photosensitized photocatalytic system was developed with acetophenone (ACP) as the guest photosensitizer, bismuth vanadate (BiVO4) as the host catalyst and poly dimethyl diallyl ammonium chloride (PDDA) as the bridging complex, and used for the removal of sulfamerazine (SMR), sulfadiazine (SDZ) and sulfamethazine (SMZ) in water under simulated visible light (λ > 420 nm). The obtained ACP-PDDA-BiVO4 nanoplates attained a removal efficiency of 88.9%-98.2% for SMR, SDZ and SMZ after 60 min reaction and achieved kinetic rate constant approximately 10, 4.7 and 13 times of BiVO4, PDDA-BiVO4 and ACP-BiVO4, respectively, for SMZ degradation. In the guest-host photocatalytic system, ACP photosensitizer was found to have a great superiority in enhancing the light absorption, promoting the surface charge separation-transfer and efficient generation of holes (h+) and superoxide radical (·O2-), greatly contributing to the photoactivity. The SMZ degradation pathways were proposed based on the identified degradation intermediates, involving three main pathways of rearrangement, desulfonation and oxidation. The toxicity of intermediates was evaluated and the results demonstrated that the overall toxicity was reduced compared with parent SMZ. This catalyst maintained 92% photocatalytic oxidation performance after five cyclic experiments and displayed a co-photodegradation ability to others antibiotics (e.g., roxithromycin, ciprofloxacin et al.) in effluent water. Therefore, this work provides a facile photosensitized strategy for developing guest-host photocatalysts, which enabling the simultaneous antibiotics removal and effectively reduce the ecological risks in wastewater.

Distribution, migration and changes of typical chemical preservatives on orange during storage and processing.

To evaluate the safety of orange treated with preservatives, we analyzed the distribution, migration and changes of the three most common preservatives (prochloraz, imazalil, and thiophanate-methyl) during orange storage and processing. After treatment, preservatives entered orange rapidly within 2 h, and with the greatest levels being in the outer yellow peel, followed by the stem, middle white peel, and finally pulp. The intra-fruit migration ability of the three preservatives correlated inversely with their octanol/water partition coefficients. Residual preservatives and their metabolites in orange pulp were less than 0.84 mg/kg in storage duration. Orange juice and pectin processing could effectively remove the residues, with processing factors (PFs) of 0.159-0.446 and 0.014-0.059. For tangerine peel, however, the process increased the levels of residual preservatives with PFs of 2.964-6.004. Therefore, concern is warranted with regard to the risk of dietary exposure to tangerine peel and essential oil.

Characterization and catalytic mechanism of a direct demethylsulfide hydrolase for catabolism of the methylthiol-s-triazine prometryn.

Demethylthio is one of the most important ways for microorganisms to metabolize triazine herbicides. Previous studies have found that the initial reaction of prometryn catabolism in Leucobacter triazinivorans JW-1 was the hydroxylation of its methylthio group, however, the corresponding functional enzyme was not yet clear. In this study, the gene proA was responsible for the initial step of prometryn catabolism from the strain JW-1 was cloned and expressed, and the purified amidohydrolases ProA have the ability to transform prometryn to 2-hydroxypropazine and methanethiol. The optimized reaction temperature and pH of ProA were 45 °C and 7.0, respectively, and the kinetic constants Km and Vmax of ProA for the catalysis of prometryn were 32.6 µM and 0.09 µmol/min/mg, respectively. Molecular docking analyses revealed that different catalysis efficiency of ProA and TrzN (Nocardioides sp. C190) for prometryn and atrazine was due to non-covalent changes in amino acid residues. Our findings provide new insights into the understanding of s-triazine catabolism at the molecular level.

The long-acting herbicide mesosulfuron-methyl inhibits soil microbial community assembly mediating nitrogen cycling.

Mesosulfuron-methyl is a widely used herbicide in wheat fields. We previously reported that mesosulfuron-methyl alters the bacterial/fungal community structure in experimental indoor microcosms, ultimately affecting NO3--N and NH4+-N contents in soil nitrogen (N) cycling. However, how mesosulfuron-methyl application alter soil N cycling by changing microbial community assembly is unknown. Here, we designed an outdoor experiment comprising 2-month periods to investigate changes in soil N-cycle functional genes and structural shifts in the microbial community assembly in response to mesosulfuron-methyl applied at 11.25 and 112.5 g a.i. hm-2. Results showed that high mesosulfuron-methyl input significantly decreased AOA amoA and nirK abundances within the initial 15 days, but increased AOB amoA on day 60. The nifH abundance displayed a stimulation-inhibition trend. Moreover, high mesosulfuron-methyl input decreased the network's complexity, and newly formed multiple network modules exhibited strong negative associations with nifH, AOB amoA, nirK and nirS. Further structural equation model demonstrated that mesosulfuron-methyl did reveal strong direct inhibition of nirK, and it indirectly affected nirK by changing nifH abundance and Planomicrobium. Thus mesosulfuron-methyl perturbs N-cycling processes by reshaping bacterial community assembly. Taken together, our study provides theoretical support for determining the microbiological mechanism by which mesosulfuron-methyl affects soil N cycling.