Our study investigated the effects of terbuthylazine (TBA) and metribuzin (MT) on rice and radish at field application concentrations. Both herbicides induced oxidative stress and severely inhibited growth in the two crops. However, the radish cultivar T-33 exhibited significantly lower stress levels compared to the sensitive cultivar S-24, suggesting its higher tolerance to TBA and MT. To explore the potential role of metabolism in this tolerance, we developed a novel HPLC-Q-TOF-MS method, which demonstrated excellent performance and identified 18 TBA and 20 MT metabolites, most of which were discovered in plants for the first time. The results revealed significantly higher accumulation of both herbicides in rice compared to radish, especially in the aerial parts, with increasing translocation in rice and the opposite trend in radish. Quantitative analysis revealed significantly higher levels of glycosylated MT products and amino acid conjugates in T-33 compared to S-24, suggesting their crucial role in detoxification and tolerance mechanisms. Our findings have significant implications for food safety, crop protection, and sustainable agricultural practices in regions employing vegetable-crop rotation systems.

Untreated plant waste of the Mediterranean region as bioadsorbent of persistent organic pollutants

Pharmacotherapeutic potential of pratensein to avert metribuzin instigated hepatotoxicity via regulating TGF-β1, PI3K/Akt, Nrf-2/Keap-1 and NF-κB pathway

Plasmonic Metribuzin Sensor by using synthesized CuO NPs decorated graphene oxide nanocomposite

Abstract. Fouad MR, El-Aswad AF, Aly MI, Badawy ME-T. 2024. Environmental impact of biochar and wheat straw on mobility of dinotefuran and metribuzin into soils. Asian J Agric 8: 57-63. The environmental effect of 5% biochar and wheat straw on the mobility of dinotefuran (DNF) and metribuzin (MBZ) in alluvial soil (A) and calcareous soil (B) was studied. The breakthrough (BTC) curves of DNF and MBZ were delayed in soil columns compared to that of iodide. The amendment of soil A or B columns with biochar and wheat straw increased the leaching of DNF collected in leachates, consequently reducing the breakthrough time. Biochar amendment increased the leaching of MBZ in soil A, whereas it significantly reduced the leaching of MBZ in soil B. Wheat straw amendment also significantly reduced the MBZ cumulative percentage. It is indicated that the downward of DNF in soil A is more rapid than that in soil B, while MBZ was faster in soil B compared to soil A; the leaching rate of MBZ is higher than DNF in all soil columns. The calculated GUS indices of DNF and MBZ were lower than 2.8, which means these pesticides are non-lechers. DNF required more water to leach from soil B than from soil A. In contrast more water was needed to leach MBZ from soil A compared to soil B. In addition, the DNF required more water for leaching from soil A or B than MBZ.

The efficiency of different sorbents (bulk soil, sand, silt, clay and humic acid-HA) for chlorantraniliprole (CAP), dinotefuran (DNF), bispyribac-sodium (BPS), and metribuzin (MBZ) adsorption was described and compared. The adsorption of CAP, DNF, BPS and MBZ were significantly greater on clay and HA fractions than the bulk soils. Also, the tested pesticides sorption was greater on HA fraction compared to clay fraction except in the case of BPS. The mass unit of bulk soil adsorbed of CAP, DNF, BPS and MBZ approximately 15, 20, 10 and 5 % of the same of HA and 40, 60, 95 and 35 % of that of clay fraction, respectively. The actual amounts adsorbed on bulk soil ranged from (88.63 to 93.93 %) of the calculated amounts adsorbed on all soil components indicating high efficiency of the tested soils to adsorb tested pesticides. All adsorption data fitted well to the linear Freundlich equation. The adsorption of tested pesticides in soil and their different constituents is S-type according to 1/n (except some cases).

Accelerated degradation of micro-pollutant by combined UV and chlorine dioxide: Unexpected inhibition of chlorite formation

The use of zinc oxide nanoparticles (ZnO NPs), applied as a possible micronutrient source, in conjunction with organic pesticides in agricultural soils has the potential to alter the environmental behavior and toxicity of these chemicals to soil biota. This research examines the joint effects of ZnO NPs and the herbicide metribuzin (MTZ) on phytotoxicity to plants, toxicity to soil microorganisms, and the accumulation of Zn and MTZ in plants. After 23 days, effects on growth, photosynthetic pigment content, and oxidative stress biomarkers in bean plants (Phaseolus vulgaris) and soil enzymatic activities were evaluated. Additionally, the amounts of Zn and MTZ (and the latter’s main metabolites) in soil and plant tissues were quantified. ZnO NPs reduced ammonium oxidase activity and growth among MTZ-stressed plants while reducing photosynthetic pigment levels and enhancing antioxidant enzymatic activities. MTZ had a marginal impact on the availability and accumulation of Zn in plant tissues, although significant effects were observed in some specific cases. In turn, ZnO NPs drastically affected MTZ degradation in soil and influenced MTZ accumulation/metabolization in the bean plants. Our findings indicate that the indirect effects of ZnO NPs, through their interaction with commonly used organic pesticides, may be relevant and should be taken into account in agricultural soils.

Adsorption of pesticides using graphene oxide through computational and experimental approach

Metribuzin (MB), a triazinone herbicide is extensively sprayed for weed control in agriculture, has been reported to contaminate soil, groundwater, and surface waters. In soil, MB residues can negatively affect not only the germination of subsequent crops but also disturb soil bacterial community. The present study describes the use of biochar as a carrier material to immobilize MB-degrading bacterial consortium, for remediation of MB-contaminated soil and restoration of soil bacterial community in soil microcosms. The bacterial consortium (MB3R) comprised four bacterial strains, i.e., Rhodococcus rhodochrous AQ1, Bacillus tequilensis AQ2, Bacillus aryabhattai AQ3, and Bacillus safensis AQ4. Significantly higher MB remediation was observed in soil augmented with bacterial consortium immobilized on biochar compared to the soil augmented with un-immobilized bacterial consortium. Immobilization of MB3R on biochar resulted in higher MB degradation rate (0.017 Kd-1) and reduced half-life (40 days) compared to 0.010 Kd-1 degradation rate and 68 day half-life in treatments where un-immobilized bacterial consortium was employed. It is worth mentioning that the MB degradation products metribuzin-desamino (DA), metribuzin-diketo (DK), and metribuzin desamino-diketo (DADK) were detected in the treatments where MB3R was inoculated either alone or in combination with biochar. MB contamination significantly altered the composition of soil bacteria. However, soil bacterial community was conserved in response to augmentation with MB3R immobilized on biochar. Immobilization of the bacterial consortium MB3R on biochar can potentially be exploited for remediation of MB-contaminated soil and protecting its microbiota.

Abstract An effective nano‐adsorbent has been synthesized by the modification of magnetite nanoparticles with ionic‐liquid modified calix[4]arene through covalent linkage. This nanocomposite was used for the removal of amino‐functionalized nitrogenous pesticides, metribuzin (MET), and dicloran (DIC) from an aqueous solution through adsorption. The adsorption studies showed that the synthesized nanomaterial was effective in removing these pollutants from an aqueous solution. The maximum adsorption capacity for MET and DIC were 5.88 and 1.94 mg g −1 , respectively. The effect of various factors, such as dosage, pH, and temperature, were studied on the adsorptive removal of MET and DIC. The adsorption was observed to follow Freundlich isotherm and pseudo‐second‐order kinetics for MET and DIC. The nano‐adsorbent was stable and reusable even after the third cycle. The present studies will lead to the development of an ultimate tool for attempting to the problem of water pollution.

The dissipation and side-effect of metribuzin (MBZ) were studied with various factors; two soil types (clay loam and sandy loam), soil amendment (wheat straw and without amendment), two temperature levels (25 and 50°C), sterilization (sterilized and unsterilized soil) and time of incubation (15 and 30 days) and designed by Windows version of MINITAB software package to reduce the time and the cost as well as increased the precision. Determination of MBZ by HPLC with recoveries ranged from 50.85 to 108.09%. The MBZ residues were detected in all samples up to 60 days of storage, respectively with decline in their concentrations with the time of incubation. The clay loam soil showed higher dissipation than the sandy loam soil. The different factors in the present study confirmed that the wheat straw amendment, non-sterilization and incubation at 50°C caused higher dissipation of MBZ than without wheat straw, sterilization and incubation at 25°C. The dissipation was described mathematically by a first order equation with t0.5 was ranged from 9.62 to 16.82 days in clay loam soil and from 10.01 to 16.04 days in sandy loam soil. The side-effect of MBZ was tested on soil dehydrogenase activity that can be considered as an indicator of the biological activity and microbial degradation. The result proved that the enzyme activity was significantly decreased in all treatments compared with the controls at 1 and 3 days of incubation then it was gradually increased at 7, 10, 15 and 30 days of incubation. Treatments of wheat straw, non-sterilized and incubated at 25°C or 50°C showed the lowest enzyme inhibition among all treatments.

Metribuzin and metamitron degradation using catalytic ozonation over tourmaline: Kinetics, degradation pathway, and toxicity

Efficient micropollutants degradation by ferrate(VI)-Ti/Zn LDH composite under visible light: Activation of ferrate(VI) and self-formation of Fe(III)-LDH heterojunction

Application of molecularly imprinted electrochemical sensor for trace analysis of Metribuzin herbicide in food samples

Effect of the Ni3TeO6 phase in a Ni2Te3O8/expanded graphite composite on the electrochemical monitoring of metribuzin residue in soil and water samples

Anaerobic digestion of biomass has increasing implementation for bioenergy production. The solid by-product of this technology, i.e., the digestate, has relevant potential in agricultural and environmental applications. This study explored the capacity of a digestate from mixed feedstock to remove from water four endocrine-disrupting chemicals, namely the pesticides metribuzin (MET) and boscalid (BOS) and the xenoestrogens bisphenol A (BPA) and 4-tert-octylphenol (OP). The surface micromorphology and functional groups of the digestate were investigated using scanning electron microscopy (SEM) and Fourier-transform infrared (FTIR) spectroscopy, respectively. Results of sorption kinetics showed that all compounds reached the steady state in a few hours according to a pseudo-first-order model in the cases of MET and OP, a pseudo-second-order model for BOS and both models in the case of BPA. Data of adsorption isotherms were fitted to the Henry, Freundlich, Langmuir and Temkin equations. The adsorption of MET preferentially followed the non-linear Freundlich model, whereas the adsorption of the other compounds was properly described by both the linear and Freundlich models. The organic carbon partition coefficients, KOC, were 170, 1066, 256 and 2180 L kg−1 for MET, BOS, BPA and OP, respectively. The desorption of BOS, BPA and OP was slow and incomplete, indicating a phenomenon of hysteresis. In conclusion, the digestate showed a remarkable efficiency in the removal of the compounds, especially those with high hydrophobicity, thus behaving as a promising biosorbent for environmental remediation.

Abstract In this work, a comparative study of three frequently employed modification techniques to g‐C 3 N 4 (CN) nanosheets for the photocatalytic degradation of metribuzin (MET) under visible‐light irradiation has been carried out in detail. The modification methods were coupling TiO 2 nanoparticles (TO) as electron acceptors, nano‐sized Fe 2 O 3 (FO) to construct a Z‐scheme nanocomposite, and phosphate (HP) modification to promote O 2 adsorption. The steady‐state and transient‐state surface photovoltage spectra and transient photoluminescence (PL) spectra confirmed that all the three modification techniques enhanced the charge separation with prolonged lifetimes and presented degradation activities in the order of TO/CN > FO/CN > HP/CN. The TO/CN nanocomposite showed the highest photocatalytic activity for MET degradation, with a sixfold higher rate than bulk CN. Liquid chromatography–tandem mass spectrometry and radical trapping experiments indicated that the increased activity was related to the synergetic effect of two radicals (·O 2 − and ·OH) involved in the photocatalytic degradation pathway, which was different from the ·OH radical‐dominated pathway of bulk CN. This work reveals the importance of charge separation and the influence of the radical pathway and provides guidance for the design of high‐efficiency photocatalysts.

Abstract The wide use of pesticides in agriculture has caused uncontrolled distribution of these chemicals in the environment, calling for the development and investigation of new environmentally friendly formulations, which would reduce human impact on nature. In the present study, the metribuzin (MET), tribenuron‐methyl (TBM), and fenoxaprop‐P‐ethyl (FPE) herbicides were encapsulated in microparticles of degradable microbial polymers – polyhydroxyalkanoates (PHAs) – of two types – poly‐3‐hydroxybutyrate [P(3HB)] and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate [P(3HB/3HV)]. The use of P(3HB) resulted in higher yields of microparticles (63% to 79%) and larger sizes of the particles, whose average diameter was 0.60 ± 0.06–0.75 ± 0.11 μm, while the average diameter of copolymer particles varied between 0.43 ± 0.12 and 0.55 ± 0.05 μm. Encapsulation efficiency was rather determined by the type of herbicide and its solubility, varying from 24.7% to 48.2%. In vitro herbicide release from microparticles to water was affected by herbicide solubility and PHA chemical composition. The readily soluble MET showed the highest release rate, and over 30 days, 64% and 78% of the encapsulated amounts were released from P(3HB) and P(3HB/3HV) microparticles, respectively. High herbicidal activity of microparticles loaded with metribuzin and tribenuron‐methyl was demonstrated in the laboratory stands of the Elsholtzia ciliata weed plant.

ABSTRACT Solar heating techniques were tested to enhance the dissipation of eight herbicides belonging to four different chemical families (phenylurea, triazine, dinitroaniline and diphenylether derivatives). Guano, vermicompost, green manure, and goat manure were used as biofumigants for biosolarization. In all experiments, the soil was covered with high-density polyethylene (HDPE) film along 60 d after treatment and the results were compared with control plots. A significant increase in the soil temperature from 2 to 6 °C was detected in solarized soils as compared to control plots being probably the direct hydrothermal effect the most important factor on herbicide degradation. The behaviour of herbicides in mulched soils presents a faster phase of disappearance (15 d) followed by a slower phase (15–60 d). The mean half-lives ranged from 98 d in control plots to 17 d in the solarized soil amended with goat excrements manure being isoproturon and trifluralin the more and the less persistent herbicides, respectively. In all cases, significant differences (p < 0.05) in the persistence were observed between control soil and solarized soils for all herbicides. Therefore, the use of solar heating techniques, especially biosolarization can be considered as an environmentally friendly tool to enhance herbicide disappearance from the soil. Abbreviations: Aclonifen (AF); Biosolarized soil (BS); Chlorotoluron (CL); Control soil (CS); Goat manure (GTM); Green manure (GRM); Guano (GAN); Half-life time (t½); High-density polyethylene (HDPE); Isoproturon (IR); Metribuzin (MZ); Organic amendment (OA); Organic matter (OM); Organisation for Economic Co-operation and Development (OECD); Oxyfluorfen (OF); Pendimethalin (PL); Relative humidity (RH); Single first-order (SFO); Solarized soil (SS); Terbuthylazine (TZ); Trifluralin (TL); Vermicompost (VRC).