Comparative catalytic degradation of a metabolite 3,5-dichloroaniline derived from dicarboximide fungicide by laccase and MnO2 mediators.

A ternary catalysis system was investigated to evaluate the comparative degradation of toxic fungicide metabolite 3,5-dichloroaniline (3,5-DCA) by laccase and MnO2 with mediators. In this study, copper based fungal enzyme laccase (Trametes versicolor origin) and metal catalyst MnO2 with various combinations of phenolic mediators (catechol, syringaldehyde, syringic acid, caffeic acid and gallic acid) were monitored to optimize and screen the better one for 3,5-DCA degradation assay. Catechol showed better potentiality in reduction of 3,5-DCA among the studied mediators. Catechol (2mM) showed the highest reduction rate (99-100%) followed by syringaldehyde (40.51%) with 2U/mL of laccase at 25 °C within 24 h reaction time. Similarly, complete degradation of 3,5-DCA was obtained by catechol (2mM) with 2 mg/mL of MnO2 in MnO2-mediator assay. The notable finding of current study indicated the triggering of catechol for better 3,5-DCA degradation at higher pH condition but inertness in laccase-mediator assay due to laccase destabilization. The reaction pathways of optimized mediator-based catalysis for laccase and MnO2 were proposed. Finally, the optimized laccase-catechol based degradation was considered as a pioneer green catalysis approach to reduce the toxic metabolite 3,5-DCA concentrations in aqueous medium as compared to MnO2-catechol catalysis.

Residue Monitoring and Risk Assessment of Cyazofamid and Its Metabolite in Korean Cabbage Under Greenhouse Conditions.

The residual characteristics and risk assessment with respect to cyazofamid and its metabolite 4-chloro-5-p-tolylimidazole-2-carbonitrile were monitored in case of Korean cabbage at different preharvest intervals during a greenhouse trial. The 0.02 kg a.i/ha of cyazofamid was sprayed twice on seven-day intervals (i.e., on day 0, 7, 14, and 21 before harvest). The liquid chromatography-tandem mass spectrometry analysis was used to monitor the residual amount of fungicide. The matrix-matched calibration curves with respect to the cyazofamid in Korean cabbage exhibited good linearity (R2 ≥ 0.999) and acceptable recoveries of 84.1%-114.9%. The biological half-life of cyazofamid in Korean cabbage was 3.18 days. During the treatment, the preharvest residue of cyazofamid in Korean cabbage 14 days before harvest (0.80 mg/kg) was lower than that specified by the MFDS-MRL (Ministry of Food and Drug Safety-Maximum Residue Limit, 2.0 mg/kg) and should be recommended as the safe preharvest-interval application limit. The hazard quotient showed low toxicity (70.58%) during the risk assessment study of cyazofamid.

Improved dissipation kinetic model to estimate permissible pre-harvest residue levels of pesticides in apples.

Prediction of residual concentrations of applied pesticides during the pre-harvest period may be required to ensure the safety of agricultural products. In this study, time-dependent dissipation trends of carbaryl (CB), kresoxim-methyl (KM), flubendiamide (FB), flufenoxuron (FN), bitertanol (BT), and chlorantraniliprole (CN) applied to apples at recommended and threefold greater doses were modeled to estimate pre-harvest residue limit concentrations (CPHRL) indicating permissible pesticide concentrations during the pre-harvest period. Double-exponential (DE) model results best fit the dissipation trends of all tested pesticides (correlation coefficients of 0.91-0.99) compared to zero-, first-, and second-order models. Among the pesticides examined, CB half-lives in apples of 2.9 and 6.6 days were the shortest, while those of FN (21.1-32.7 days) were the longest. The CPHRL values for each pesticide in apples were estimated with DE model parameter values and could be used to determine harvest dates for safe apples with pesticide concentrations below their maximum residue limits. Application of the DE model for CPHRL calculation provides more accurate information for farmers to produce agricultural products safe from pesticide residues.

Development of a single-run analytical method for the detection of ten multiclass emerging contaminants in agricultural soil using an acetate-buffered QuEChERS method coupled with LC-MS/MS.

This study was undertaken to develop and validate a single multiresidue method for the monitoring of ten multiclass emerging contaminants, viz. ceftiofur, clopidol, florfenicol, monensin, salinomycin, sulfamethazine, sulfathiazole, sulfamethoxazole, tiamulin, and tylosin in agricultural soil. Samples were extracted using an acetate-buffered, modified quick, easy, cheap, effective, rugged, and safe method followed by liquid chromatography with tandem mass spectrometric analysis in positive ion mode. Separation on an Eclipse Plus C18 column was conducted in gradient elution mode using a mobile phase of methanol (A) and distilled water (B), each containing 0.1% formic acid and 5 mM ammonium formate. The linearity of the matrix-matched calibrations, expressed as determination coefficients, was good, with R2 ≥ 0.9908. The limits of quantification were in the range 0.05-10 µg/kg. Blank soil samples spiked with 4 × and 20 × the limit of quantification provided recovery rates of 60.2-120.3% (except sulfamethoxazole spiked at 4 × the limit of quantification, which gave 131.9%) with a relative standard deviation < 13% (except clopidol spiked at 20 × the limit of quantification, which gave 25.2%). This method was successfully applied to the monitoring of 51 field-incurred agricultural loamy-sand soil samples collected from 17 provincial areas throughout the Korean Peninsula. The detected and quantified drugs were clopidol (≤ 4.8 µg/kg), sulfathiazole (≤ 7.7 µg/kg), sulfamethazine (≤ 6.6 µg/kg), tiamulin (≤ 10.0 µg/kg), and tylosin (≤ 5.3 µg/kg). The developed method is simple and versatile, and can be used to monitor various classes of veterinary drugs in soil.

Interpretation and estimation for dynamic mobility of chlorpyrifos in soils containing different organic matters.

The adsorption and removal behaviors of the organophosphate insecticide chlorpyrifos in two soils (AS and GW soils) with different organic matter contents were investigated to predict the dynamic residues in the soil environment. The adsorption test showed that the chlorpyrifos adsorptive power for the AS soil containing high organic matter content was greater than that for the GW soil. The extent of the time-dependent removal of chlorpyrifos in the tested soils was not significantly different except at 90 days after the treatment. The availability of a chemical-specific residue model developed in this study was statistically assessed to estimate the chlorpyrifos residue in soil solutions that could be absorbed into plants. The values modeled using the soil experimental data were satisfactory, having a mean deviation of 32% from the measured data. The correlation between the modeled and measured data was acceptable, with mean coefficients of correlation (R(2)) of 0.89. Furthermore, the average of the residual error was low at 0.43, which corresponded to a mean factor of -1.9. The developed model could be used as a critical tool to predict the subsequent plant uptake of chlorpyrifos.

A pilot lab trial for enhanced oxidative transformation of procymidone fungicide and its aniline metabolite using heterogeneous MnO2 catalysts.

In this study, the feasibility of two heterogeneous catalysis (non-Fenton heterogeneous catalysis and catalytic ozonation) was evaluated for the oxidative transformation of the fungicide procymidone and its major metabolite (3,5-dichloroaniline; 3,5-DCA) under a pilot lab experiment. Among the studied treatments, only H2O2 or O3 significantly oxidized procymidone and 3,5-DCA. However, heterogeneous catalysis used with various types of MnO2 catalysts was found to be an effective rapid strategy for transformation of procymidone and its aniline metabolite. Among the studied catalysts, δ-MnO2 performed well in the enhanced oxidative transformation of procymidone and 3,5-DCA in MnO2-mediator system assay. The optimal reaction parameters, such as reaction pH, and initial catalyst concentration were comparatively evaluated. However, heterogeneous catalysis and catalytic ozonation were revealed as the rapid strategy for oxidative transformation of investigated procymidone and 3,5-DCA as compared to single oxidation by peroxide/ozone. Finally, as a novel insight of this investigation, a postulated reaction mechanism underlying the accelerated transformation of aniline metabolites via heterogeneous catalysis was explored. The findings of this study will open new avenues for evaluating heterogeneous catalysis during oxidative transformation of non-phenolic pollutants in both lab trial and field applications. This study can be expanded for use in actual field settings, using environmental samples from contaminated areas exposed to non-phenolic pesticides and their metabolites.

Uptake and translocation of fungicide picarbutrazox in greenhouse cabbage: the significance of translocation factors and home processing.

This study evaluated the uptake and translocation of the fungicide picarbutrazox (PBZ) and its isomer in greenhouse cabbage. Two distinct treatments, including foliar spray and soil application of PBZ, were used in this study. In the foliar application, the fungicide was sprayed thrice at intervals of 7 days from 30, 21, and 14 days before harvest following the OECD guidelines of fungicides in crops, whereas in soil treatment, PBZ was applied for one time at concentrations of 2 and 10 mg/kg, and cabbage was cultivated for 68 days. Additionally, the role of root and translocation factors during residual fungicide distribution was demonstrated. The quality control of the analytical study exhibited excellent linearity (R2 ≥ 0.99), the limit of quantification (LOQ 0.005 mg/kg), accuracy (recovery within the range of 70-120%), and precision (relative coefficient within 0.3-13.8%) for studied PBZ and its metabolites. In the foliar application, initially higher amount of residual PBZ was evident in the outermost leaf of the cabbage, whereas in soil treatment, the highest residual PBZ was observed in the soil and roots. Therefore, the application method of picarbutrazox is a critical factor for defining the initial entry route of pesticides and the subsequent translocations through the investigated crops.

Development of a method for analysis and risk assessment of residual pesticides in ginseng using liquid and gas chromatography-tandem mass spectrometry.

In this study, we developed a method for detecting 335 pesticides in ginseng using liquid chromatography quadrupole mass spectrometry (LC-MS/MS) and gas chromatography quadrupole mass spectrometry (GC-MS/MS). Additionally, the linearity, sensitivity, selectivity, accuracy, and precision of the method was validated. The limits of detection (LOD) and limits of quantification (LOQ) for the instrument used in these experiments was 0.1-5.8 µg/kg and 0.3-17.5 µg/kg, respectively. The average recovery was 71.6-113.4%. From 2016 to 2019, 467 ginseng samples were analyzed, of which 304 samples detected pesticide residues, but most of them were below the standard. It can be observed that the hazard quotient (HQ) of ginseng for detected pesticides was less than 1, thus implying that the risk was low. Hence, in this study, we developed a specific, reliable, and suitable method for a fast and simultaneous analysis of 335 pesticides in ginseng.

A pilot study for enhanced transformation of a metabolite 3,5-dichloroaniline derived from dicarboximide fungicides through immobilized laccase mediator system.

This pilot investigation aimed to evaluate the removal efficiency and the underlying biocatalytic pathways of immobilized fungal laccase during the oxidative biotransformation of a non-phenolic metabolite, 3,5-dichloroaniline (3,5-DCA) derived from dicarboximide fungicides. The maximum loading of laccase on the microporous support surfaces could reach 36.4 mg/g. The immobilized laccase on the microporous support surfaces exhibited excellent thermal stability, pH adaptability, storage stability, and reusability compared to free laccase. The ILMS assay indicated that the immobilized laccase efficiently removed studied 3,5-DCA (99-100%) in the aqueous medium, within 72 h in the presence of catechol. In this study, we identified three coupling reaction products during the removal of 3,5-DCA through an ILMS assay. Based on the identified coupling reaction products, we proposed the reaction pathway for the biotransformation of 3,5-DCA by immobilized laccase, which was shown to be potentially useful in the sustainable environmental remediation of aniline metabolite (i.e., 3,5-DCA) derived from dicarboximide fungicides.

Uptake of endosulfan isomers from soils by leafy vegetable lettuce: A comparative study between model-predicted and field-experimented results.

The organochlorine insecticide endosulfan has been classified as a persistent organic pollutant due to its long persistence and high toxicity, and banned in most countries. However, endosulfan residues are still detected in various environmental sites (even in non-agricultural areas) and have a likelihood to return to agricultural soils through various routes. In this study, time-dependent uptake of α- and ß-isomers of endosulfan by lettuce from soils was estimated using theoretical models which include parameters describing sorption/dissipation in soil and plants, plant transpiration, root-soil transfer, and plant growth. A chemical-specific residue (CSR) model developed in a previous study was used as a sub-model to estimate the portion of endosulfan residues in soils ready to be absorbed by lettuce, and the accuracy of the CSR model was verified by properly estimating concentrations of endosulfan isomers in soils with different organic matters; a low mean deviation (18.8 %) was observed between the modeled and measured values. Modeled results of ß-endosulfan using a soil-lettuce uptake model satisfactorily matched the experimentally measured results, with a moderate correlation (R2 > 0.79) and a low residual error (0.42) against a mean factor of -1.04. However, the uptake model showed the low potential to predict the soil-lettuce uptake of α-endosulfan (176.3 % mean deviation), probably due to not considering an intrinsic trait of ß-isomer converting to α-isomer. Although the improvement with more sophisticated parameters is needed, the plant uptake model developed in this study could be utilized to predict soil-lettuce uptake of at least ß-endosulfan and as a model template that may apply for other types of plants and contaminants.

In-House Validation of an Efficient and Rapid Procedure for the Simultaneous Determination and Monitoring of 23 Mycotoxins in Grains in Korea.

A high-performance liquid chromatography tandem mass spectrometry method is described for the simultaneous determination of mycotoxins, including Ergot alkaloids (EAs), in 3 types of grains. The extraction of 23 mycotoxins was evaluated and performed by using a modified QuEChERS-based sample preparation procedure. The proposed method was fully validated on spiked grain samples (barley, wheat and oat) to assess the linearity, limit of detection (LOD) and limit of quantitation (LOQ), matrix effects, precision and recovery. After validation, this method was applied to 143 samples of various types of 3 grains from the Republic of Korea to survey the level of mycotoxin contamination in Republic of Korean grains. A total of 42 grain samples (29%) were contaminated with at least one of these mycotoxins at levels higher than the LOQ. The results demonstrated that the procedure was suitable for simultaneously determining these mycotoxins in cereals and could be performed for their routine analysis in mycotoxin laboratories.

Optimization of a Multi-Residue Analytical Method during Determination of Pesticides in Meat Products by GC-MS/MS.

In this study, a multi-residue analysis was developed for 32 compounds, including pesticides and metabolites, in five meat products using gas chromatography-tandem mass spectrometry (GC-MS/MS). The validation of the developed analytical method was also evaluated in accordance with Codex Alimentarius guidelines. Aminopropyl (NH2), C18, and florisil solid phase extraction (SPE) cartridges were used to evaluate and optimize the cleanup procedure of the tested samples prior to GC-MS/MS analysis. Based on the analytical performance, the C18 SPE cartridge was deemed to be the most suitable among the examined SPE cartridges. The optimized method demonstrated that 29 out of 32 tested compounds acquired good linearity (R2 ≥ 0.99), and 25 tested compounds displayed the method limit of quantification (MLOQ) ≤ 0.01 mg/kg. Out of the 32 tested compounds, only 21 compounds met the acceptable analytical criteria for the lard and tallow samples, compared to 27 compounds in the beef, pork, and chicken samples that falls within the acceptable standards for recovery (70-120%) and analytical precision (relative standard deviation RSD ≤ 20%). The average matrix effect was widely varied (20.1-64.8%) in the studied meat samples that were affected by either ion enhancement or suppression. In particular, in the lard sample, 13 compounds showed poor recovery and analytical precision due to ion suppression. Thus, the matrix effect (ME) was considered a critical factor during multi-residue pesticide analysis in different meat products. In conclusion, this developed analytical method can be used as a routine monitoring system for residual pesticide analysis in livestock products with acceptable analytical standards. Further meticulous analytical studies should be optimized and validated for multi-residue pesticide analysis in diversified meat products.

Heavy metals contamination and associated health risks in food webs-a review focuses on food safety and environmental sustainability in Bangladesh.

Heavy metals occur naturally in very small amounts in living organisms, but exposure to their higher concentrations is hazardous. Heavy metals at hazardous levels are commonly found in foodstuffs of Bangladesh, mainly due to the lack of safety guidelines and poor management of industrial effluents. Several lines of evidence suggest that the level of heavy metals in foodstuffs of Bangladesh is higher than the acceptable limits set by World Health Organization/Food and Agriculture Organization. Literature survey revealed that the sources and transport pathways of heavy metals in the ecosystem and the abundance of heavy metals in the food products of Bangladesh are potential threats to food safety. However, an extensive assessment of the toxicity of heavy metals in food webs is lacking. Although widespread heavy metal contamination in various foodstuffs and environmental matrices have been summarized in some reports, a critical evaluation regarding multi-trophic transfer and the health risk of heavy metal exposure through food chain toxicity in Bangladesh has not been performed. This systematic review critically discussed heavy metal contamination, exposure toxicity, research gaps, existing legislation, and sustainable remediation strategies to enhance Bangladesh's food safety. In particular, this study for the first time explored the potential multi-trophic transfer of heavy metals via food webs in Bangladesh. Furthermore, we recommended a conceptual policy framework to combat heavy metal contaminations in Bangladesh.

Dissipation characteristics of spirotetramat and its metabolites in two phenotypically different Korean vegetables under greenhouse conditions.

This study involved analysis and method validation of spirotetramat applied to two phenotypically different Korean vegetables (e.g. Korean cabbage and shallots) to determine the safe pre-harvest residue limit (PHRL) and comparative dissipation patterns. Two steps of the investigation involved greenhouse monitoring during crop cultivation followed by LC-MS/MS analysis. Commercial spirotetramat was sprayed twice with seven-day intervals according to the spray schedule (0, 3, 7, 10, 14, and 21 days before harvest) at the dose recommended by the Ministry of Food and Drug Safety (MFDS), Korea. During the validation of the analytical method, good linearity, specificity, and acceptable recoveries (82%-114% for Korean cabbage and 82%-111% for shallot) were established for spirotetramat and its four metabolites. The calculated biological half-life derived from the first-order reaction (t1/2) of spirotetramat was 4.8 days for Korean cabbage and 4.0 days for shallot, respectively. The safe PHRL for Korean cabbage was suggested at 7 days, due to permissible spirotetramat concentration in terms of an acceptable MRL. The findings of the study will be used as the analytical reference point for developing spirotetramat safety guidelines for use in the vegetables investigated.

Removal of organochlorine insecticide endosulfan in water and soil by Fenton reaction with ascorbic acid and various iron resources.

An assortment of Fenton (or Fenton-like) reaction treatment systems using various iron resources such as ferrous sulfate, ferric nitrate, commercial zerovalent iron (mZVI), or self-made ZVI (Fe-nanowire) were evaluated to effectively remove α- and ß-isomers of endosulfan (ED) from contaminated water and soil. Ascorbic acid (AA) was added as a chelation reagent to maintain the aqueous reaction of soluble iron. In the aqueous experiment, a combined treatment of 1% mZVI, 0.01 M AA, and 0.1 M H2O2 was determined to be the most effective method, showing 98-100% of ED removal within 24 h. The mZVI/AA/H2O2 treatment method was finally applied to ED-contaminated soil samples, and the application removed significant ED residues from both soil slurries (65-73%) and immobile soils containing small amount of moisture (64-66.2%). Overall results showed that the mZVI/AA/H2O2 treatment can be utilized as a potential technique to remediate both water and soil contaminated with ED.

Uncertainty of pesticides in foodstuffs, associated environmental and health risks to humans-a critical case of Bangladesh with respect to global food policy.

The uncertain fate and transport pathways of applied pesticides are the key hidden threats with respect to the safety and quality evaluation of foodstuffs in Bangladesh. The risk assessment of and uncertainty about applied pesticides are poorly explored due to weak regulatory systems, farmer ignorance, intensive agricultural practices, and lack of available research data on improper handling of pesticides on farming lands with poor phytosanitary management. However, increasing evidence suggests that the prevalence of pesticides in common foodstuffs is due to their uptake by crops and improper management of crop protection practices. Besides, the biotransformation of pesticides in common Bangladeshi food products is poorly understood. Several studies have reported higher concentrations of pesticides than allowed by European Union guidelines in Bangladeshi foodstuffs. However, to date, no systematic review with critical discussion on current research findings and knowledge gaps concerning fate, uncertainty, and health risks of pesticides in the foodstuffs of Bangladesh is published. Therefore, this review summarizes the findings of existing literature on pesticide residue in foodstuffs and points out the weaknesses in the regulatory system and risk assessments for highlighting the critical challenges to food safety in Bangladesh as compared to global food policy. In addition, strategies for the sustainable management of residual pesticides are also discussed.

Accumulation characteristics of endosulfan soil residues in soybean and reduction in their phytoavailability by treatment with powdered activated carbon.

Powdered activated carbon (PAC) has been utilized for sorptive remediation of environmental sites contaminated with various organic chemicals. In the present study, time-dependent sorption/desorption characteristics of the α- and ß-isomers and a sulfate-metabolite of endosulfan (ED) were investigated in PAC-amended soils to determine the optimal PAC amendment dosage. Subsequently, ED phytoavailability to soybean (Glycine max Merr.) plants were examined in the presence or absence of PAC under restricted laboratory conditions. Based on the results of sorption/desorption tests, the optimal dosage of PAC amendment for ED-contaminated soils was determined as 1% (w/w), and at this dosage, all ED residues were sorbed completely onto the PAC-amended soils without any desorption. In soil amended with 1% PAC, the extents of ED accumulated by soybean plants were reduced by 89.4-100.0% within 20 days compared to those extents observed in unamended controls. Moreover, PAC treatment precluded the formation of the toxic metabolite ED-sulfate in either the soil or soybean plants. Therefore, PAC amendment in ED-contaminated soils could be highly effective for limiting uptake of ED into plants from contaminated soil and may be useful as an alternative method to produce safe food resources from contaminated arable soils.

Evaluating cytotoxicity of methyl benzoate in vitro.

Methyl benzoate (MB) is a small, hydrophobic organic compound that is isolated from the freshwater fern, Salvinia molesta. Because of its pleasant odor, it has been used as a fragrance and flavor enhancer. In addition, it is used to attract orchid bees for pollination in the farm and has been tested for its potential to be developed as a green pesticide targeting a diverse group of insects. In spite of its wide applications, the safety of MB to humans remains poorly understood. In this study, we tested the cytotoxicity of MB against cultured human cells, including kidney, colon, and neuronal cells. Furthermore, other natural and synthetic benzoic acids such as ethyl benzoate (EB) and vinyl benzoate (VB) were compared with MB for their similarity and broad commercial and industrial applications. We found that MB and VB have the least and most overall toxicity to the tested human cells, respectively. In addition, the expression of some genes involved in cell cycle, protein quality control, and neurotransmission such as cyclin D1, HSP70, and ACHE genes was differentially expressed in the presence of these chemicals, most noticeably in treatment of VB. Our study provided the LC50 values of these benzoic acids for human cells in vitro and suggested their mild toxicity that should be considered in the industrial and agricultural applications to be within safe limits.

A review of microplastics pollution in the soil and terrestrial ecosystems: A global and Bangladesh perspective.

Microplastics (MP) are a persistent and silent threat to the environment and are already considered a significant problem in aquatic environments. However, the presence of MP in soils and terrestrial ecosystems has been largely unexplored. Recent research has identified the risk of MP transfer from terrestrial agriculture to the human food chain. Thus, MP should be treated as a future threat to food safety and sustainable agriculture. Several reviews have focused on MP effects within global environmental matrices. However, scant investigations on the disposition, ecological impact and remediation strategies of MP have been reported in case of unexplored soil ecosystems as compared to aquatic ecosystems. Therefore, this review focuses on the contemporary global MP research with respect to research opportunities and related challenges of MP for the soil and terrestrial ecosystem from a Bangladesh perspective.

Microbial biodegradation and toxicity of vinclozolin and its toxic metabolite 3,5-dichloroaniline.

Vinclozolin, an endocrine disrupting chemical, is a chlorinated fungicide widely used to control fungal diseases. However, its metabolite 3,5-dichloroaniline is more toxic and persistent than the parent vinclozolin. For the biodegradation of vinclozolin, vinclozolin- and/or 3,5-dichloroaniline-degrading bacteria were isolated from pesticide-polluted agriculture soil. Among the isolated bacteria, a Rhodococcus sp. was identified from a 16S rDNA sequence analysis and named Rhodococcus sp. T1-1. The degradation ratios for vinclozolin or 3,5- dichloroaniline in a minimal medium containing vinclozolin (200 microg/ml) or 3,5-dichloroaniline (120 microg/ml) were 90% and 84.1%, respectively. Moreover, Rhodococcus sp. T1-1 also showed an effective capability to biodegrade dichloroaniline isomers on enrichment cultures in which they were contained. Therefore, these results suggest that Rhodococcus sp. T1-1 can bioremediate vinclozolin as well as 3,5-dichloroaniline.