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Enantioselective antibodies have emerged as great potential biomaterials in the fields of immunoassays and chiral separation. However, cross-reactivity of antibodies to the distomer may severely restrict the application. Comprehending the interaction mechanism between antibodies and enantiomers could be beneficial to produce superior enantioselective antibodies. In this study, a pair of recombinant antibodies (RAbs) against metolachlor enantiomers at chiral carbon (αSS-MET and αSR-MET) were generated and characterized. The αSS-MET-RAb and αSR-MET-RAb showed comparable sensitivity and specificity to the parental monoclonal antibodies by icELISA, with IC 50 values of 3.45 and 223.77 ng/mL, respectively. Moreover, the complex structures of RAbs and corresponding eutomer were constructed and analyzed, and site-specific mutagenesis was utilized to verify the reliability of the enantioselective mechanism elucidated. It demonstrated that the strength of the interaction between the chiral center region of eutomer and the antibody was the key factor for the enantioselectivity of antibody. Increasing this interaction could limit the conformational adjustment of the distomer in a specific chiral recognition cavity, thus decreasing the affinity of the antibody to the distomer. This work provided the in-depth analysis of enantioselective mechanism for two RAbs and paved the way to regulate antibody enantioselective performance for immunoassays of chiral compounds., Competing Interests: Declaration of competing interest The authors declare that they have no financial and personal relationships with other people or organizations that can inappropriately influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Enantioselective antibodies have emerged as efficient tools in the field of chiral chemical detection and separation. However, it is complicated to obtain a highly stereoselective antibody due to the unclear recognition mechanism. In this study, the hapten of metolachlor was synthesized and enantio-separated. The absolute configuration of the four haptens obtained was identified by the computed and experimental electronic circular dichroism comparison. Five polyclonal antibodies against the Rac-metolachlor and its enantiomers were generated by immunization. The cross-activity of all the 5 antibodies with 44 structural analogues, including metolachlor enantiomers, was tested. It demonstrated that antibodies have higher specificity to recognize central chirality than axial chirality. Especially, αRR-MET-Ab exhibited excellent specificity and stereoselectivity. Accordingly, 3D-QSAR models were constructed and revealed that paired stereoisomers exhibited opposite interactions with the antibodies. It is the first time that the antibodies against four stereoisomers were prepared and analyzed, which will be conducive to the rational design of the stereoselective antibodies.

The extensive use of herbicides has raised concerns about crop damage, necessitating the development of effective herbicide safeners. Fluxofenim has emerged as a promising herbicide safener; however, it's underlying mechanism remains unclear. Here, we screened two inbred lines 407B and HYZ to investigate the detoxication of fluxofenim in mitigating metolachlor damage in sorghum. Metolachlor inhibited seedling growth in both 407B and HYZ, while, fluxofenim could significantly restore the growth of 407B, but not effectively complement the growth of HYZ. Fluxofenim significantly increased the activities of glutathione-S-transferase (GST) to decrease metolachlor residue in 407B, but not in HYZ. This implys that fluxofenim may reduce metolachlor toxicity by regulating its metabolism. Furthermore, metolachlor suppressed AUX-related and JA-related genes expression, while up-regulated the expression of SA-related genes. Fluxofenim also restored the expression of AUX-related and JA-related genes inhibited by metolachlor and further increased expression of SA-related genes. Moreover, we noted a significant increase in the content of trans-zeatin O-glucoside (tZOG) and Gibberellin1 (GA1) after the fluxofenim treatment. In conclusion, fluxofenim may reduce the injury of herbicide by affecting herbicide metabolism and regulating hormone signaling pathway., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2023. Published by Elsevier Inc.)

Although it is known that microplastics (MPs) in soils cause a threat to this complex environment, the actual effects of MPs on soil microorganisms and their catabolic activities, particularly with the biodegradation of herbicides, remain unclear. Hence, the objective of this study was to investigate the effects of a simultaneous presence of metolachlor and low-density polyethylene (LDPE) microplastics on growth inhibition and adaptive responses of Trichoderma harzianum in soil microcosms. Using ergosterol content as an indicator of fungal biomass, it was observed that MPs alone had a marginal inhibitory effect on the growth of the fungus, whereas MET exhibited a dose-dependent inhibitory effect on T. harzianum. However, the presence of MPs did not influence the fungal transforming activity toward the herbicide. Conversely, analysis of lipid profiles in the presence of MPs and herbicides revealed a reduction in the overall fluidity of phospholipid fatty acids, primarily attributed to an increase in lysophospholipids. The activities of six extracellular enzymes in the soil, measured using methylumbelliferone-linked substrates, were significantly enhanced in the presence of MET. These findings contribute to a broader understanding of the alterations in fungal activity in soil resulting from the influence of MPs and MET., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Pesticides and climate change are both thought to contribute to the global amphibian decline, yet their combined effects are still poorly understood. Metolachlor is a widespread herbicide applied across North America, but little is known about its effects on amphibians. We used a replicated mesocosm experimental design with different levels of drying (i.e., no drying and medium and rapid drying) and metolachlor concentrations (0, 0.8, 8, and 80 µg/L) to assess their respective and combined effects on wood frog (Lithobates sylvaticus) larvae throughout metamorphosis. Metolachlor had no significant effect on survival and development of tadpoles. However, metolachlor significantly interacted with drying levels to reduce the growth of tadpoles, which was mainly due to a difference detected among metolachlor concentrations under the rapid drying treatment. Drying also directly reduced growth and body mass at metamorphosis. Our results suggest that environmental stressors, such as drying, should be considered in toxicological experiments to provide relevant exposure conditions to pesticides for ephemeral pond species in the context of global climate change. Environ Toxicol Chem 2023;42:1772-1781. © 2023 SETAC., (© 2023 SETAC.)

Glyphosate, the most heavily used herbicide world-wide, is applied to plants in complex formulations that promote absorption. The National Toxicology Program reported in 1992 that glyphosate, administered to rats and mice at doses up to 50,000 ppm in feed for 13 weeks, showed little evidence of toxicity, and no induction of micronuclei was observed in the mice in this study. Subsequently, mechanistic studies of glyphosate and glyphosate-based formulations (GBFs) that have focused on DNA damage and oxidative stress suggest that glyphosate may have genotoxic potential. However, few of these studies directly compared glyphosate to GBFs, or effects among GBFs. To address these data gaps, we tested glyphosate, glyphosate isopropylamine (IPA), and (aminomethyl)phosphonic acid (AMPA, a microbial metabolite of glyphosate), 9 high-use agricultural GBFs, 4 residential-use GBFs, and additional herbicides (metolachlor, mesotrione, and diquat dibromide) present in some of the GBFs in bacterial mutagenicity tests, and in human TK6 cells using a micronucleus assay and a multiplexed DNA damage assay. Our results showed no genotoxicity or notable cytotoxicity for glyphosate or AMPA at concentrations up to 10 mM, while all GBFs and herbicides other than glyphosate were cytotoxic, and some showed genotoxic activity. An in vitro to in vivo extrapolation of results for glyphosate suggests that it is of low toxicological concern for humans. In conclusion, these results demonstrate a lack of genotoxicity for glyphosate, consistent with observations in the NTP in vivo study, and suggest that toxicity associated with GBFs may be related to other components of these formulations., (© 2023 Integrated Laboratory systems, LLC. Environmental and Molecular Mutagenesis published by Wiley Periodicals LLC on behalf of Environmental Mutagen Society. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.)

Background: The adverse effects of pesticides has led to a series of ecological, environmental and public health issues. Amide herbicides are an important agrochemical, yet many are prone to leach and pollute the environment, which limits their further application. In this study, metolachlor (METO) was selected as a model pesticide and a controlled released nanoparticle (NP) system was constructed employing a zeolitic imidazolate framework-8 hybrid inorganic-organic porous material (METO@ZIF-8)., Results: The synthesis parameters of METO@ZIF-8 were optimized, and the loading content of METO@ZIF-8 was maximized by a central composite design of response surface test. The NPs were regular dodecahedron with uniform size (mostly 54.3 nm diameter). METO@ZIF-8 had high specific surface area and good dispersal in water. Moreover, it endowed the active ingredient with a pH-responsive release property. The nanocarrier effectively improved the adsorption capacity of METO in soil and reduce the leaching by 10.3-21.7%. Pot experiments suggested that the control effect of METO@ZIF-8 was 16.6 and 48.4% higher than that of METO emulsifiable concentrate (EC) and METO technical concentration (TC) at the recommended dose. Based on the excellent controlled release profiles, METO@ZIF-8 did not affect corn plant growth and significantly reduced the risk of phytotoxicity induced by METO. METO@ZIF-8 effectively reduced acute toxicity in zebrafish compared with METO EC., Conclusion: This study explored the fabrication of a nanocarrier for improving the efficacy and promoting the environmental safety of leachable amide herbicides. © 2022 Society of Chemical Industry., (© 2022 Society of Chemical Industry.)

Pesticides applied to agricultural land can enter aquatic ecosystems through runoff or leaching during precipitation events. In a lotic system, these events result in a pulse of exposure to biota living in these systems. The concentration of pesticide increases, peaks, and then gradually declines, and this pulsed exposure may occur multiple times over the course of a growing season. The dynamic nature of exposure to pesticides in the environment is not often mimicked in the laboratory testing of the toxicity of pesticides. The present study investigated the potential latent effects of a 24-h pulsed exposure of metolachlor, metribuzin, MCPA (2-methyl-4-chlorophenoxyacetic acid), MCPP (methylchlorophenoxypropionic acid or mecoprop), dicamba, and 2,4-D to the aquatic macrophyte Lemna minor followed by a 5-day recovery period. The relative sensitivity of L. minor to the herbicides were, in this decreasing order: metolachlor > metribuzin >2,4-D > MCPA > MCPP > dicamba. This study also investigated the effects of short-term exposures of the diamide insecticides cyantraniliprole and chlorantraniliprole on the survival of the larvae of the parthenogenetic mayfly Neocloeon triangulifer. The median lethal concentrations (96-h LC50s) for cyantraniliprole and chlorantraniliprole were 8.60 and 2.92 μg/L, respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

We previously discovered a method to estimate the groundwater mean residence time using the changes in the enantiomeric ratio of metolachlor ethanesulfonic acid (MESA), (2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid), a metabolite of the herbicide metolachlor. However, many grab samples would be needed for each watershed over an extended period, and this is not practical. Thus, we examined the use of a polar organic chemical integrative sampler (POCIS) deployed for 28 days combined with a modified liquid chromatography-mass spectrometry LC-MS/MS method to provide a time-weighted average of the MESA enantiomeric ratio. POCISs equipped with hydrophilic-lipophilic-balanced (HLB) discs were deployed at five sites across the United States where metolachlor was used before and after 1999 and compared the effectiveness of the POCIS to capture MESA versus grab samples. In addition, an in situ POCIS sampling rate ( R ) for MESA was calculated (0.15 L/day), the precision of MESA extraction from stored POCIS discs was determined, and the effectiveness of HLB to extract MESA was examined. Finally, using molecular modeling, the influence of the asymmetric carbon of metolachlor degradation on the MESA enantiomeric ratio was predicted to be negligible. Results of this work will be used in projects to discern the groundwater mean residence times, to evaluate the delivery of nitrate-N from groundwater to surface waters under various soil, agronomic, and land use conditions, and to examine the effectiveness of conservation practices.s ) for MESA was calculated (0.15 L/day), the precision of MESA extraction from stored POCIS discs was determined, and the effectiveness of HLB to extract MESA was examined. Finally, using molecular modeling, the influence of the asymmetric carbon of metolachlor degradation on the MESA enantiomeric ratio was predicted to be negligible. Results of this work will be used in projects to discern the groundwater mean residence times, to evaluate the delivery of nitrate-N from groundwater to surface waters under various soil, agronomic, and land use conditions, and to examine the effectiveness of conservation practices.

Due to the increasing use of chlorinated organic compounds, environmental pollution is a key issue in agricultural and industrial areas. In this study, biodegradation of chloroacetanilide herbicides, such as alachlor and metolachlor, by eight fungal strains of Trichoderma spp. originating from different microorganism collections was investigated. The tested fungi converted 80-99% of alachlor and 40-79% of metolachlor after 7 days of incubation. Biotransformation of herbicides was performed mainly by dechlorination and hydroxylation reactions. Eight alachlor metabolites and four byproducts of metolachlor conversion were detected in Trichoderma cultures, including two metolachlor intermediates for the first time identified in fungi. Moreover, in the cultures of six Trichoderma strains supplemented with chloroacetanilides, a decrease in toxicity was observed toward tested Artemia franciscana crustaceans. Simultaneously, 7 days after the application of the spores of T. koningii IM 0956, T. citrinoviride IM 6325, T. harzianum KKP 534, T. viride KKP 792 and T. virens DSM 1963 the length of roots and shoots of rapeseed seedlings treated with alachlor or metolachlor significantly increased. All tested strains exhibited plant growth-promoting traits, such as siderophore production, 1-aminocyclopropane-1-carboxylate deaminase (ACCD) activity, and phosphate solubilization, even in the presence of chloroacetanilide herbicides., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Agricultural chemicals are normally used as mixtures of several isomers, e.g., enantiomers. In theory, in order to minimize the pesticides dose, it is desirable to use the most target-active isomer. Metolachlor is a typical multichiral herbicide belonging to amide herbicides. An asymmetric carbon atom and a chiral axis yield four stereoisomers. In this study, a novel laboratory method was developed to prepare the S-metolachlor and the four stereoisomers using high performance liquid chromatography. The separated isomers had a purity of >99%, with their absolute configurations assigned by electronic circular dichroism. The enantioseparation by ultra performance convergence chromatography tandem mass spectrometry was also performed for the rapid and sensitive detection of metolachlor stereoisomers. The enantioselective herbicidal activity toward the target weed (Echinochloa crusgalli) was systematically assessed for the first time by measuring the morphology of the weed after treatment with rac-, S-metolachlor and the four stereoisomers, respectively. Among the commercial pesticides, S-metolachlor was more effective in weed inhibition than rac-metolachlor, and to the four stereoisomers, the herbicidal activities were ranked as: SS > SR ≫ RS > RR, and the RR-isomer even had some stimulative effect to the weed growth at lower concentration (1 ppm). Thus, we concluded that in these cases, the chiral carbon feature played a major role in herbicidal activity rather than the chiral axis feature, and the higher bioactivity of the S-isomers was confirmed by more effective uptake and stronger interaction with target enzymes that were involved in the gibberellic acid biosynthesis. Although the SS-isomer shows the highest herbicidal activity, controlling the major chiral feature is still much easier and more economical than controlling two chiral features., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Degradation of metolachlor in surface soil is extremely important to its potential mobility and overall persistence. In this study, the effects of earthworms (Eisenia fetida) on the degradation of metolachlor at two concentration levels (5 and 20 mg kg -1 ) in soil were investigated via the column experiment. The degradation kinetics of metolachlor indicate that addition of earthworms enhances metolachlor degradation significantly (P < 0.05), with the enhanced degradation rate of 30% and 63% in the low and high concentration treatments at the 15th day, respectively. Fungi rather than bacteria are primarily responsible for metolachlor degradation in soil, and earthworms stimulate metolachlor degradation mainly by stimulating the metolachlor-degrading functional microorganisms and improving fungal community structure. Earthworms prefer to promote the possible fungal degraders like order Sordariales, Microascales, Hypocreales and Mortierellales and the possible bacteria genus Rubritalea and strengthen the relationships between these primary fungi. Two metabolites metolachlor oxanilic (MOXA) and moetolachlor ethanesulfonic acid (MESA) are detected in soil and earthworms in the high concentration treatments. Earthworms stimulate the formation of MOXA and yet inhibit the formation of MESA in soil. Another metabolite metolachlor-2-hydroxy (M2H) is also detected in earthworms, which is reported firstly. The study provides an important information for the remediation of metolachlor-polluted soil., (Copyright © 2019. Published by Elsevier Ltd.)

The unfounded use of chiral pesticides has caused widespread concern. In this study, the enantioselective effects of S- and racemic (Rac)-metolachlor on the oxidative stress of wheat seedlings was determined based on physiological and gene transcription differences. Growth inhibition increased with increasing concentrations of tested metolachlor, and S-metolachlor had a stronger inhibitory effect than did Rac-metolachlor. Root growth was also significantly inhibited, but no enantioselective effects from the tested concentrations of the metolachlor enantiomers were observed. At a concentration of 5 mg L -1 , the maximal fresh weight inhibition reached 63.7% and 53.8% for S-metolachlor and Rac-metolachlor, respectively. In response to the S-metolachlor treatment, the maximum level of superoxide anions and malondialdehyde (MDA) increased to 1.73 and 2.55 times that in response to the control treatment, both of which were greater than those in response to the Rac-metolachlor treatment. The activity of superoxide dismutase (SOD) also increased in response to the S-metolachlor treatment, but the activity of peroxidase (POD) decreased. Real-time polymerase chain reaction (PCR) revealed that, compared with the Rac-metolachlor treatment, the S-metolachlor treatment attenuated the expression of several antioxidant genes. Together, these results demonstrate that S-metolachlor has a greater effect than does Rac-metolachlor on wheat seedlings.

The enantioselective effects of chiral herbicides on aquatic organisms have received increasing attention. As one kind of freshwater algae responsible for most algal blooms, Microcystis aeruginosa can produce hepatotoxic microcystin and cause serious health concerns for drinking water. Thus, the effects of chiral herbicides on M. aeruginosa are of vital significance but poorly understood, especially as the structures of chiral herbicides become more complex. In this study, the enantioselective effects of four metolachlor enantiomers based on carbon center and axis chirality on M. aeruginosa were investigated for the first time at an enantiomeric level. The results of the investigation into algal growth inhibition, chlorophyll a content, and cell integrity indicated that ( S)-metolachlor [( S)-Met] was significantly more toxic than any other isomer. The toxicity ranking of different enantiomers at the highest concentration (15 mg/L) against M. aeruginosa was ( S)-Met > (α R,1' S)-Met > (α S,1' S)-Met > (α S,1' R)-Met > (α R,1' R)-Met, with (α S,1' S)-Met and (α R,1' S)-Met displaying a synergistic effect. Additionally, the Fe distribution in M. aeruginosa presented distinct enantioselectivity, which may contribute to the enantioselective toxicity of metolachlor. Furthermore, metolachlor upregulated the expression of genes mcyD and mcyH in an enantioselective manner, indicating that this herbicide can potentially promote the synthesis and efflux of microcystin, thus aggravating agricultural water contamination to different extents. Overall, this study will help to understand the ecotoxicity of metolachlor at a deeper level and provide theoretical insights into the enantioselective behaviors of metolachlor.

This work explores the role of electrode material and the oxidation ability of electrochemical advanced oxidation processes (EAOPs), such as electro-oxidation (EO) with or without H 2 O 2 production, electro-Fenton (EF), and UVA photoelectron-Fenton (PEF), in the degradation of metolachlor. The performance of the EAOPs using Boron-doped diamond (BDD) or Pt as anode has been compared from the analysis of decay kinetics, mineralization profile, and energy consumption using small undivided batch cell. Metolachlor concentration always decays following a pseudo-first-order kinetics. Using the Pt anode, none of the processes reaches 30% mineralization, including PEF. In contrast, the BDD anode showed a higher mineralization rate allowing almost total mineralization in PEF due to the synergetic action of UVA light and oxidant hydroxyl radicals formed in the bulk from Fenton's reaction, as well as in the BDD, which has large reactivity to oxidize the pollutants. The increase in current density and decrease in metolachlor concentration accelerated the mineralization in PEF, although lower current efficiency and higher energy consumption was obtained. The GC-MS and HPLC analysis allowed the identification of up to 17 aromatics intermediates and 7 short-chain carboxylic acids. Finally, a reaction pathway for metolachlor mineralization by EAOPs is proposed. PEF with BDD allowed total removal of the herbicide in real water matrix and a high mineralization (83.82%).

Glutathione S-transferases (GSTs) have been widely studied in relation to their role in herbicide tolerance and detoxification. However, a detailed characterization of GSTs from herbicide tolerant and sensitive maize cultivars is still lacking. In this study, we determined the mechanism of differential tolerance between two maize cultivars which had 4-fold difference tolerance to metolachlor. The metabolism rate of metolachlor was more rapid in the tolerant cultivar (Zea mays L. cv Nongda86) than the susceptible one (Zea mays L. cv Zhengda958). Addition of the GST inhibitor ethacrynic acid reduced the metabolism of metolachlor indicating the involvement of GSTs in the differential detoxification of metolachlor. The expression profiles of 32 GST isozymes were measured using quantitative RT-PCR. The results showed the expression of GST genes were slightly up-regulated in Nongda86, but severely inhibited in Zhengdan958 24h after metolachlor treatment. The genes GSTI, GSTIII, GSTIV, GST5, GST6 and GST7, which can detoxify chloroacetanilide herbicides, were all expressed higher in Nongda86 compared to Zhendgan958. The result of GST activity was consistent with the gene expression profiles. Collectively, higher-level expression of GST genes, leading to higher GST activity and faster herbicide detoxification, appears to be responsible for the difference in tolerance to metolachlor in two maize cultivars., (Copyright © 2016. Published by Elsevier Inc.)

Rice husk biochar (RHBC) was prepared for use as adsorbents for the herbicide metolachlor. The characteristics and sorption properties of metolachlor adsorbed by the RHBC prepared at different pyrolysis temperatures were determined by analysis of physico-chemical characteristics, Fourier transform infrared spectroscopy (FTIR), Boehm titration, scanning electron microscopy (SEM), and thermodynamics and kinetics adsorption. With increasing pyrolysis temperature, the RHBC surface area greatly increased (from 2.57 to 53.08 m 2  g -1 ). RHBC produced at the highest temperature (750 °C) had the greatest surface area; SEM also showed the formation of a porous surface on RH-750 biochar. The sorption capacity of RHBC also increased significantly with increasing pyrolysis temperature and was characterized by the Freundlich constant K f for the adsorption capacity increasing from 125.17-269.46 (pyrolysis at 300 °C) to 339.94-765.24 (pyrolysis at 750 °C). The results indicated that the surface area and pore diameter of RHBC produced with high pyrolysis temperature (i.e., 750 °C) had the greatest impact on the adsorption of metolachlor. The FTIR, Boehm titration, and SEM analysis showed that the greatest number of surface groups were on RHBC produced at the lowest temperature (300 °C). The biochars produced at different pyrolysis temperatures had different mechanisms of adsorbing metolachlor, which exhibited a transition from hydrogen bonds dominant at low pyrolytic temperature to pore-filling dominant at higher pyrolytic temperature.

Glutathione S-transferases (GSTs) play important roles in herbicide tolerance. However, studies on GST function in herbicide tolerance among plant tissues are still lacking. To explore the mechanism of metolachlor tolerance difference between maize shoots and roots, the effects of metolachlor on growth, GST activity, and the expression of the entire GST gene family were investigated. It was found that this differential tolerance to metolachlor was correlated with contrasting GST activity between the two tissues and can be eliminated by a GST inhibitor. An in vitro metolachlor-glutathione conjugation assay confirmed that the transformation of metolachlor is 2-fold faster in roots than in shoots. The expression analysis of the GST gene family revealed that most GST genes are expressed much higher in roots than shoots, both in control and in metolachlor-treated plants. Taken together, higher level expression of most GST genes, leading to higher GST activity and faster herbicide transformation, appears to be responsible for the higher tolerance to metolachlor of maize roots than shoots.

The study reports the effect of Inderprastha (IP) and Badarpur (BP) fly ashes on degradation of metolachlor and atrazine in Inceptisol and Alfisol soils. Metolachlor dissipated at faster rate in Alfisol (t1/2 8.2-8.6 days) than in Inceptisol (t1/2 13.2-14.3 days). The fly ashes enhanced the persistence of metolachlor in both the soils; however, the extent of effect was more in Inceptisol (t1/2 16.6-33.8 days) than Alfisol (t1/2 8.4-12 days) and effect increased with fly ash dose. 2-Ethyl-6-methylacetanilide was detected as the only metabolite of metolachlor. Atrazine was more persistent in flooded soils (t1/2 10.8-20.3 days) than nonflooded soils (t1/2 3.7-12.6 days) and fly ash increased its persistence, but effect was more pronounced in the flooded Inceptisol (t1/2 23.7-31 days) and nonflooded Alfisol (t1/2 6.3-10.1 days). Increased herbicide sorption in the fly ash-amended soils might have contributed to the increased pesticide persistence. The IP fly ash inhibited microbial biomass carbon at 5 % amendment levels in both the soils, while BP fly ash slightly increased microbial biomass carbon (MBC) content. Dehydrogenase activity was inhibited by both fly ashes in both the soils with maximum inhibition observed in the IP fly ash-amended Alfisol. No significant effect of fly ash amendment was observed on the fluorescein diacetate activity.

Herbicide runoff from cropping fields has been identified as a threat to the Great Barrier Reef ecosystem. A field investigation was carried out to monitor the changes in runoff water quality resulting from four different sugarcane cropping systems that included different herbicides and contrasting tillage and trash management practices. These include (i) Conventional - Tillage (beds and inter-rows) with residual herbicides used; (ii) Improved - only the beds were tilled (zonal) with reduced residual herbicides used; (iii) Aspirational - minimum tillage (one pass of a single tine ripper before planting) with trash mulch, no residual herbicides and a legume intercrop after cane establishment; and (iv) New Farming System (NFS) - minimum tillage as in Aspirational practice with a grain legume rotation and a combination of residual and knockdown herbicides. Results suggest soil and trash management had a larger effect on the herbicide losses in runoff than the physico-chemical properties of herbicides. Improved practices with 30% lower atrazine application rates than used in conventional systems produced reduced runoff volumes by 40% and atrazine loss by 62%. There were a 2-fold variation in atrazine and >10-fold variation in metribuzin loads in runoff water between reduced tillage systems differing in soil disturbance and surface residue cover from the previous rotation crops, despite the same herbicide application rates. The elevated risk of offsite losses from herbicides was illustrated by the high concentrations of diuron (14μgL(-1)) recorded in runoff that occurred >2.5months after herbicide application in a 1(st) ratoon crop. A cropping system employing less persistent non-selective herbicides and an inter-row soybean mulch resulted in no residual herbicide contamination in runoff water, but recorded 12.3% lower yield compared to Conventional practice. These findings reveal a trade-off between achieving good water quality with minimal herbicide contamination and maintaining farm profitability with good weed control., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Background: Crop residue removal for bioenergy production can alter soil hydrologic properties and the movement of agrochemicals to subsurface drains. The Root Zone Water Quality Model (RZWQM), previously calibrated using measured flow and atrazine concentrations in drainage from a 0.4 ha chisel-tilled plot, was used to investigate effects of 50 and 100% corn (Zea mays L.) stover harvest and the accompanying reductions in soil crust hydraulic conductivity and total macroporosity on transport of atrazine, metolachlor and metolachlor oxanilic acid (OXA)., Results: The model accurately simulated field-measured metolachlor transport in drainage. A 3 year simulation indicated that 50% residue removal reduced subsurface drainage by 31% and increased atrazine and metolachlor transport in drainage 4-5-fold when surface crust conductivity and macroporosity were reduced by 25%. Based on its measured sorption coefficient, approximately twofold reductions in OXA losses were simulated with residue removal., Conclusion: The RZWQM indicated that, if corn stover harvest reduces crust conductivity and soil macroporosity, losses of atrazine and metolachlor in subsurface drainage will increase owing to reduced sorption related to more water moving through fewer macropores. Losses of the metolachlor degradation product OXA will decrease as a result of the more rapid movement of the parent compound into the soil. Published 2015. This article is a U.S. Government work and is in the public domain in the USA., (Published 2015. This article is a U.S. Government work and is in the public domain in the USA.)

Herbicides are often applied to crop residues, but their fate has not been well studied. We measured herbicide washoff from sugar cane trash during simulated rainfall, at 1, 8, and 40 days after spraying (DAS), to provide insight into herbicide fate and for use in modeling. Herbicides included are commonly used in the sugar industry, either in Australia or in Brazil. Concentrations of all herbicides and applied Br tracer in washoff declined exponentially over time. The rate of washoff during rainfall declined with increasing DAS. Cumulative washoff as a function of rainfall was similar for most herbicides, although the most soluble herbicides did have more rapid washoff. Some but not all herbicides became more resistant to washoff with increasing DAS. Of the total mass washed off, 80% washed off in the first 30 mm (∼40 min) of rainfall for most herbicides. Little herbicide remained on the trash after rainfall, implying nearly complete washoff.

Addition of organic amendments such as biochar to soils can influence pesticide sorption-desorption processes and, in turn, the amount of pesticide readily availability for transport and biodegradation. Sorption-desorption processes are affected by both the physical and chemical properties of soils and pesticides, as well as soil-pesticide contact time, or aging. Changes in sorption-desorption of metolachlor with aging in soil amended with three macadamia nut shell biochars aged 0 (BCmac-fr), 1 year (BCmac-1yr), and 2 years (BCmac-2yr) and two wood biochars aged 0 (BCwood-fr) and 5 years (BCwood-5yr) were determined. Apparent sorption coefficient (Kd-app) values increased with incubation time to a greater extent in amended soil as compared to unamended soils; Kd-app increased by 1.2-fold for the unamended soil, 2.0-fold for BCwood-fr, 1.4-fold for BCwood-5yr, 2.4-fold for BCmac-fr, 2.5-fold for BCmac-1yr, and 1.9-fold for BCmac-4yr. The increase in calculated Kd-app value was the result of a 15% decrease in the metolachlor solution concentration extractable with CaCl2 solution with incubation time in soil as compared to a 50% decrease in amended soil with very little change in the sorbed concentration. Differences could possibly be due to diffusion to less accessible or stronger binding sites with time, a faster rate of degradation (in solution and on labile sites) than desorption, or a combination of the two in the amended soils. These data show that transport models would overpredict the depth of movement of metolachlor in soil if effects of aging or biochar amendments are not considered.

Laboratory and field trials evaluated the efficacy of three methods of detecting aquatic pesticide concentrations. Currently used pesticides: atrazine, metolachlor, and diazinon and legacy pesticide dieldrin were targeted. Pesticides were extracted using solid-phase extraction (SPE) of water samples, titanium plate passive samplers coated in ethylene vinyl acetate (EVA) and eastern oysters (Crassostrea viginica) as biosamplers. A laboratory study assessed the extraction efficiencies and precision of each method. Passive samplers yielded the highest precision of the three methods (RSD: 3-14% EVA plates; 19-60% oysters; and 25-56% water samples). Equilibrium partition coefficients were derived. A significant relationship was found between the concentration in oyster tissue and the ambient aquatic concentration. In the field (Housatonic River, CT (U.S.)) water sampling (n = 5) detected atrazine at 1.61-7.31 μg L(-1), oyster sampling (n = 2×15) detected dieldrin at n.d.-0.096 μg L(-1) SW and the passive samplers (n = 5×3) detected atrazine at 0.97-3.78 μg L(-1) SW and dieldrin at n.d.-0.68 μg L(-1) SW., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Background: Complex environmental models are frequently extrapolated to overcome data limitations in space and time, but quantifying data worth to such models is rarely attempted. The authors determined which field observations most informed the parameters of agricultural system models applied to field sites in Nebraska (NE) and Maryland (MD), and identified parameters and observations that most influenced prediction uncertainty., Results: The standard error of regression of the calibrated models was about the same at both NE (0.59) and MD (0.58), and overall reductions in prediction uncertainties of metolachlor and metolachlor ethane sulfonic acid concentrations were 98.0 and 98.6% respectively. Observation data groups reduced the prediction uncertainty by 55-90% at NE and by 28-96% at MD. Soil hydraulic parameters were well informed by the observed data at both sites, but pesticide and macropore properties had comparatively larger contributions after model calibration., Conclusions: Although the observed data were sparse, they substantially reduced prediction uncertainty in unsampled regions of pesticide breakthrough curves. Nitrate evidently functioned as a surrogate for soil hydraulic data in well-drained loam soils conducive to conservative transport of nitrogen. Pesticide properties and macropore parameters could most benefit from improved characterization further to reduce model misfit and prediction uncertainty., (Published 2014. This article is a U.S. Government work and is in the public domain in the USA.)

Peanut (Arachis hypogaea) is produced intensively in the southern Atlantic Coastal Plain of the eastern USA. To effectively protect the region's water quality data are needed which quantify runoff of pesticides used to protect these crops. Fungicides are used intensively yet there is little published data which describe their potential for loss in surface runoff. This study compared runoff of a fungicide, tebuconazole (α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol), and an herbicide, metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide) from 0.2 ha fields in strip (ST), a commonly used conservation-tillage practice, and conventional tillage (CT) near Tifton, GA (USA). Following their first application, metolachlor and tebuconazole were detected at high frequency in runoff. Concentrations and their annual losses increased with application frequency and runoff event timing and frequency with respect to applications, and when fields were positioned at the top of the slope and CT was practiced. Runoff one day after treatment (DAT) contributed to high tebuconazole runoff loss, up to 9.8% of the amount applied on an annual basis. In all cases, metolachlor loss was more than 10 times less even though total application was 45% higher. This was linked to the fact that the one metolachlor application to each crop was in May, one of the region's driest months. In sum, studies showed that fungicide runoff rates may be relatively high and emphasize the need to focus on these products in future studies on peanut and other crops. The study also showed that peanut farmers should be encouraged to use conservation tillage practices like ST which can substantially reduce pesticide runoff., (Published by Elsevier B.V.)

Szechuan peppers are extensively used as a spice and in traditional medicine in Asia, primarily because of its active compounds, sanshools (S). However, there is only limited mention in agriculture, and there are no papers reporting its use as an herbicide safener. In this study, we provide the first evidence that S can effectively alleviate rice-seedling injury from metolachlor (M). We observed that the M-treated (0.25 μM) rice seedlings, which were 56.0%, 66.0%, and 57.0% of the non-treated control in shoot height, root length, and fresh biomass, respectively, were recovered by S to 93.1%, 97.6%, and 94.8%, respectively. The emergence rate was enhanced to over 80% in the M+S treatment, whereas it was below 60% in the M treatment. This M+S mixture elevated the rice-seedling root activity to higher than 87.0% of the value for the non-treated control. The activity of glutathione transferases in the combined treatments approximately doubles that of the M treatment and quadruples that of the non-treated controls. This effect was positively correlated with the induced expression of OsGSTU3. Our results suggest that S may represent a new group of safeners and enable the possibility of using these compounds for improving plant production or protecting rice from the phytotoxicity of metolachlor., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Aiming to reduce herbicide leaching, "in situ" adsorption of herbicide-micelle formulations to soils was explored. Sulfentrazone or metolachlor were solubilized in cationic micelles, and these herbicide-micelle formulations were applied to sandy and alluvial soils. Sulfentrazone adsorption to the soils was negligible; however, its adsorption via its solubilization in micelles and their adsorption to the soil was significant and in good agreement with the Freundlich and Langmuir models. Adsorption of solubilized herbicide to the sandy soil was higher than to the alluvial soil. The low ratio between the surfactant concentration and the cation exchange capacity (CEC) of the alluvial soil brought upon micelle decomposition and reduction in herbicide adsorption. Therefore, an optimized ratio between surfactant and soil CEC was chosen to maximize herbicide retention. Even upon adding relatively low loadings of surfactant (0.075-0.3% w/w soil), herbicide leaching through the soils was significantly reduced (2-5-fold) in comparison with the commercial formulations.

This study analyses the floristic composition of field weeds recorded at the University of Ilorin Teaching and Research Farm (008° 27' 23.9'N and 004° 39' 42.9'E) in the southern Guinea savannah of Nigeria during the 2019 - 2021 growing seasons. The area is characterized by a bimodal rainfall pattern with an average annual rainfall of 1227.85 mm and sandy loam soil (plinthustaffs). The experiment was set up as a randomized complete block design and repeated three times in a field that had been continuously maize-cropped for 10 years. Treatments were preemergence applications of atrazine, metolachlor, and primextra at the rate of 1.5, 2.5, and 3.5 kg a.i.ha-1 and Weedy Check. Maize was sown and maintained using the recommended agronomic practices for ecology. Weed species composition was estimated using four continuous sample quadrats (0.5 m²) at 3, 6, 9, and 12 weeks after sowing. The weed flora consisted of 48% broadleaves, grasses 45%, and 7% sedges. Between 2019 and 2021 there was a gradual shift from the predominant annual broadleaves to induced annual grasses and a reduction in the floristic composition of the weed community by approximately 2 - 28%. Fifteen (15) weed species were predominant and the most stable weed species were Richardia scabra, Digitaria horizontalis and Digitaria sanguinalis. This requires finding an ideal weed control option that controls the negative impact of agricultural weeds on crop after yield while maintaining a diverse weed community. [ABSTRACT FROM AUTHOR]

An efficient synthesis of a well known chiral herbicide, (S)-metolachlor has been described using 2-methoxymethylaziridine ring formation and reductive ring opening as key steps using commercially available (R)-epichlorohydrin. The present protocol delivers the required enantiomer of metolachlor in overall yield of 50.8% and high enantiopurity (>99%). [ABSTRACT FROM AUTHOR]

The effects of many pesticides on aquatic ecosystems remain poorly understood, especially in naturalistic communities in which organisms are connected by a complex array of direct and indirect interactions. Moreover, multiple stressors can interact, and the addition of apex predators, such as fish, may introduce additional ecosystem changes that exacerbate or mitigate pesticide effects. Despite being both common and environmentally persistent, the effects of the herbicide metolachlor on realistic aquatic communities have received insufficient research attention. We tested the effects of metolachlor on pond mesocosms at three concentrations (0, 20, and 80 ppb), along with the presence vs. absence of fish (black crappie, Pomoxis nigromaculatus) to determine the independent and combined effects of these two environmental changes. We found both metolachlor and fish altered the pond mesocosms, but their effects did not interact. Metolachlor reduced phytoplankton as expected, but had nonlinear effects on dissolved oxygen. Metolachlor also altered tadpole behavior, making them less prone to hiding. Fish presence increased periphyton and decreased snail counts, as well as changing the behavior of tadpoles, reducing their hiding behavior. This work demonstrates previously undocumented effects of metolachlor in the presence and absence of fish and suggests future avenues of investigation. [ABSTRACT FROM AUTHOR]

Featured Application: The use of pre-emergent (or residual) herbicides like metolachlor has increased dramatically worldwide as an option to manage herbicide-resistant biotypes, as they suppress weed seed emergence from the soil. Hence, there is an emerging interest in comprehending its persistence and fate in cropping systems. Recurring flooding events and the consequent anoxic conditions in agro-ecosystems are ubiquitously present and inevitable. However, much less is known about the environmental fate of a popular herbicide like metolachlor in such soil environmental conditions. Hence, in this paper, we explored the impacts of the aerobic and anaerobic soil conditions of the environmental fate of 14C-labeled metolachlor by using radioactive analytical techniques. This article contributes to better understanding the behavior of a globally utilized plant protection chemical like metolachlor in soils. The information generated could be applied for the efficacious and judicious use of metolachlor or similar herbicides in crop production systems. The impact of the aeration status of soils on the environmental fate of the soil-applied pre-emergent herbicide metolachlor is of significance to sustainable agriculture practices and has not been investigated thoroughly by existing research works. To address this knowledge gap, we examined the adsorption, desorption, degradation, and mineralization of radioactively labeled [14C] metolachlor in Catlin, Flanagan, and Drummer soils under aerobic and anaerobic conditions. Based on our findings, anaerobic conditions in the soil significantly reduced the adsorption of 14C-metolachlor while also promoting its desorption, thereby potentially releasing a greater amount of herbicide from the soil after a field application. The first-order degradation and mineralization kinetics of 14C-metolachlor were distinctively enhanced by anaerobic conditions in all the soils tested. Furthermore, the degradation and mineralization rates of 14C-metolachlor in non-sterilized versus sterilized soil microcosms clearly indicated microbial activity in the degradation of metolachlor in soil. The results from this study suggest that soil redox conditions could impact the bioavailability and environmental fate of herbicide metolachlor and should be taken into consideration as part of sustainable weed management programs. [ABSTRACT FROM AUTHOR]

Three activated carbons from lignocellulosic residues and a commercial carbon have been tested for the removal of the herbicide metolachlor and its two degradation transformation products, named ESA and OXA, in aqueous solutions. The kinetics and equilibrium adsorption were studied for the four materials, showing higher adsorption capacities for the three molecules on the carbon materials chemically activated by potassium carbonate, mainly associated with its greater porous development, especially in the range of microporosity. Additionally, the chemical composition of the adsorbents also highlighted their important influence on the ESA and OXA adsorption process. The efficient adsorption of both compounds—even at low initial concentrations—allows a removal efficiency of up to 80% to be reached, revealing promising perspectives for the use of biomass-derived carbon materials for the elimination of not only the herbicide metolachlor, but also its degradation compounds from contaminated wastewater. [ABSTRACT FROM AUTHOR]

Atrazine is a foundational herbicide in corn (Zea mays L.) because of its broad‐spectrum weed control and utility for pre‐emergence or postemergence applications. Extensive atrazine use has led to traces in groundwater, surface water, and aquifers. This research explored corn herbicide regimes with little or no atrazine. Pre‐emergence herbicide treatments [S‐metolachlor (0.955 lb acre–1); saflufenacil (0.054 oz acre–1) plus dimethenamid‐P (0.473 lb acre–1)] and postemergence herbicide mixtures [bicyclopyrone (0.040 lb acre–1) plus mesotrione (0.161 lb acre–1) plus S‐metolachlor (1.429 lb acre–1); thiencarbazone‐methyl (0.013 lb acre–1) plus tembotrione (0.067 lb acre–1), thiencarbazone‐methyl (0.033 lb acre–1) plus isoxaflutole (0.082 lb acre–1); acetochlor (0.964 lb acre–1) plus mesotrione (0.103 lb acre–1) plus clopyralid (0.065 lb acre–1)] were applied alone or combined with atrazine at 0.50 lb acre–1 to glyphosate‐ or glufosinate‐resistant corn. All postemergence applications contained glyphosate (1.125 lb acre–1) plus glufosinate (0.402 lb acre–1). Palmer amaranth [Amaranthus palmeri (S.) Watson], broadleaf signalgrass [Urochloa platyphylla (Munro ex C. Wright) Nash], and pitted morningglory (Ipomoea lacunosa L.) control were always greater than 95%. Saflufenacil plus dimethenamid‐P injured corn 8 and 5% more than S‐metolachlor 21 d after pre‐emergence application. Averaged over pre‐emergence herbicide and atrazine rate, thiencarbazone‐methyl plus isoxaflutole injured corn by 21% in 2017. The addition of atrazine did not improve corn yield in 7 of 16 instances. According to this research, the weeds assessed at these densities can be controlled without atrazine by some programs. Core Ideas: Weed control programs with and without postemergence atrazine were examined.Corn exhibited adequate tolerance to the herbicide programs evaluated.Effective herbicide programs were identified in the absence of atrazine.Several herbicide programs without atrazine allowed corn yields comparable with its use. [ABSTRACT FROM AUTHOR]

Metolachlor (MET) is a widely used herbicide that can adversely affect phytoplanktonic non-target organisms, such as cyanobacteria. Chytrids are zoosporic fungi ubiquitous in aquatic environments that parasitize cyanobacteria and can keep their proliferation in check. However, the influence of organic pollutants on the interaction between species, including parasitism, and the associated ecological processes remain poorly understood. Using the host-parasite system consisting of the toxigenic cyanobacterium Planktothrix agardhii and its chytrid parasite Rhizophydium megarrhizum , we investigated the effects of environmentally relevant concentrations of MET on host-parasite interactions under i) continuous exposure of chytrids and cyanobacteria, and ii) pre-exposure of chytrids. During a continuous exposure, the infection prevalence and intensity were not affected, but chytrid reproductive structures were smaller at the highest tested MET concentration. In the parasite's absence, MET promoted cyanobacteria growth possibly due to a hormesis effect. In the pre-exposure assay, MET caused multi- and transgenerational detrimental effects on parasite fitness. Chytrids pre-exposed to MET showed reduced infectivity, intensity, and prevalence of the infection, and their sporangia size was reduced. Thus, pre-exposure of the parasite to MET resulted in a delayed decline of the cyanobacterial cultures upon infection. After several parasite generations without MET exposure, the parasite recovered its initial fitness, indicating that detrimental effects are transient. This study demonstrates that widely used herbicides, such as MET, could favor cyanobacterial bloom formation both directly, by promoting cyanobacteria growth, and indirectly, by inhibiting their chytrid parasites, which are known to play a key role as top-down regulators of cyanobacteria. In addition, we evidence the relevance of addressing multi-organism systems, such as host-parasite interactions, in toxicity assays. This approach offers a more comprehensive understanding of the effects of pollutants on aquatic ecosystems. [Display omitted] • Continuous exposure to MET stimulated cyanobacterial growth. • Infection prevalence and intensity were not affected by continuous exposure to MET. • Pre-exposure of chytrids to MET delayed cyanobacterial decline. • MET decreases disease spread over multiple parasite generations. [ABSTRACT FROM AUTHOR]

A green, sensitive and accurate dispersive liquid–liquid microextraction (DLLME) method was used to preconcentrate four selected pesticides in dam lake water samples for determination by gas chromatography–mass spectrometry (GC–MS). Conditions of the DLLME method were comprehensively investigated and optimized according to type/volume of extraction solvent, type/volume of dispersive solvent, and type/period of mixing. The developed method was validated according to the limits of detection and quantitation, accuracy, precision and linearity. Under the optimum conditions, limit of detection values calculated for alachlor, acetochlor, metolachlor and fenthion were 1.7, 1.7, 0.2 and 7.8 µg/kg (mass based), respectively. The method recorded 202, 104, 275 and 165 folds improvement in detection power values for acetochlor, alachlor, metolachlor and fenthion, respectively, when compared with direct GC–MS measurements. In order to evaluate the accuracy of the developed method, real sample application with spiking experiments was performed on dam lake water samples, and satisfactory percent recovery results in the range of 81%–120% were obtained. [ABSTRACT FROM AUTHOR]

Electronic structure calculations have been performed to determine the thermochemistry and kinetics of the reaction between OH and the radicals of the S enantiomer of the herbicide Metolachlor, 2-chloro-N-(2-methyl-6-ethylphenyl)-N(2-methoxy-1-methylethyl) acetamide (MC), produced by photoinduced breaking of the C–Cl bond. Both density functional and ab initio composite methods were employed to calculate the structure of reactants, intermediates, transition states and products, in gas phase and in aqueous solution. The expected relative abundance of each product was calculated and compared to the experimentally observed concentrations. It is shown that a combination of thermodynamic and kinetic characteristics interplay to produce the expected theoretical abundances, which turn out to be in agreement with the experimentally observed distribution of products. [ABSTRACT FROM AUTHOR]

• R. subcapitata present palmelloid-like phenotype in presence of pollutants. • Palmelloid phenotype is characterized by multinucleated cells and lipids accumulation. • Palmelloid formation is dependent on pollutant, its concentration and exposure time. • Palmelloid is a transitory state being reverted to a single-nucleus state after stress release. • Palmelloid phenotype is not a generalized defense response against stress. This work focuses on the formation of palmelloid-like phenotype in the freshwater alga Raphidocelis subcapitata (formerly known as Pseudokirchneriella subcapitata and Selenastrum capricornutum) , when exposed to adverse conditions generated by the presence of organic [the antibiotic erythromycin (ERY) and the herbicide metolachlor (MET)] or inorganic [the heavy metals, cadmium (Cd) and zinc (Zn)] pollutants, at environmentally relevant concentrations. This alga in absence of stress or when exposed to ERY or Zn, up to 200 µg/L, essentially showed a single-nucleus state, although algal growth was reduced or stopped. R. subcapitata "switched" to a multinucleated state (palmelloid-like morphology) and accumulated energy-reserve compounds (neutral lipids) when stressed by 100–200 µg/L MET or 200 µg/L Cd; at these concentrations of pollutants, growth was arrested, however, the majority of the algal population (≥83 %) was alive. The formation of palmelloid-like phenotype, at sub-lethal concentrations of pollutants, was dependent on the pollutant, its concentration and exposure time. The multinucleated structure is a transitory phenotype since R. subcapitata population was able to revert to a single-nucleus state, with normal cell size, within 24–96 h (depending on the impact of the toxic in the alga), after being transferred to fresh OECD medium, without pollutants. The obtained results indicate that the formation of a palmelloid-like phenotype in R. subcapitata is dependent on the mode of action of toxics and their concentration, not constituting a generalized defense mechanism against stress. The observations here shown contribute to understanding the different strategies used by the unicellular alga R. subcapitata to cope with severe stress imposed by organic and inorganic pollutants. [ABSTRACT FROM AUTHOR]

• DBD in air achieves complete mineralization of herbicides in water. • Mechanisms of mesotrione and metolachlor advanced oxidation by non-thermal plasma. • No reciprocal influence of mesotrione and metolachlor in atmospheric plasma treatment. The goals of this research were to i) test the ability of air non-thermal plasma to promote the degradation in water of two widespread herbicides, mesotrione and metolachlor, ii) determine the process efficiency and products for each herbicide treated individually, iii) detect and investigate any possible reciprocal effects when the two herbicides, which are often used in combination, are treated together in the same solution. The experiments were carried out using a dielectric barrier discharge (DBD) reactor to generate a strongly oxidizing non-thermal plasma above the liquid surface and induce the advanced oxidation of dissolved organic chemicals. The results of extensive HPLC (UV, MS and MS/MS) and TOC analyses show that air non-thermal plasma efficiently decomposes both herbicides, that mesotrione is considerably more reactive than metolachlor and that complete mineralization of both is achieved at sufficiently long treatment times. Treatment of metolachlor was also performed in tap water, a closer model for environmental systems, achieving the same results as found in deionized water. Detailed product and kinetic studies failed to reveal any effect attributable to reciprocal influence of mesotrione and metolachlor when treated together in the same solution. [ABSTRACT FROM AUTHOR]

The combination of pre- and post-emergence herbicides may affect their selectivity to soybean plants, especially to short-cycle cultivars. The objective of this work was to evaluate the selectivity of pre- and post-emergence herbicides to very-early maturing soybean cultivars. Two field experiments were conducted, one in Mandaguaçu, Paraná (E1) and other in Rio Verde, Goiás (E2), Brazil, using a 4×7 factorial arrangement. The treatments consisted of four pre-emergence herbicide managements (S-metolachlor at 1440 g ha-1, diclosulam at 25.2 g ha-1, sulfentrazone at 300 g ha-1, and no herbicide application); and seven post-emergence herbicide managements (lactofen at 120 g ha-1, chlorimuron-ethyl at 12.5 g ha-1, bentazon at 720 g ha-1, lactofen at 120 g ha-1 + chlorimuron-ethyl at 12.5 g ha-1, glyphosate at 900 g a. e. ha-1, two sequential glyphosate applications at 720 g a. e. ha-1 each, and no herbicide application). The early-maturing soybean cultivars evaluated showed sensitivity to the herbicides used. The combined use of pre- and post-emergence herbicides increased the occurrence of injuries in the plants. Diclosulam and sulfentrazone were the least selective pre-emergence herbicides. All herbicide combinations used affected soybean grain yield in E1; lactofen, chlorimuron, and bentazon presented the least selectivity in E2. [ABSTRACT FROM AUTHOR]

This study evaluates the dissipation of terbuthylazine, metolachlor, and mesotrione at different depths in soils with contrasting texture. The field trial was conducted at the Padua University Experimental Farm, north-east Italy. The persistence of three herbicides was studied in three different soil textures (clay soil, sandy soil, and loamy soil) at two depths (0-5 and 5-15 cm). Soil organic carbon content was highest in the clay (1.10%) followed by loam (0.67%) and sandy soil (0.24%); the pH of soils was sub-alkaline. Terbuthylazine, metolachlor, and mesotrione were applied on maize as a formulated product (Lumax®) at a dose of 3.5 L ha−1. Their dissipation in the treated plots was followed for 2 months after application. The concentrations of herbicides were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine, metolachlor, and mesotrione could be described by a pseudo first-order kinetics. Terbuthylazine showed the highest DT50, followed by metolachlor and mesotrione. Considering the tested soil, the highest DT50 value was found in clay soil for terbuthylazine and metolachlor, whereas for mesotrione there was no difference among soils. Significant differences were found between the two soil depths for terbuthylazine and metolachlor, whereas none were found for mesotrione. These results suggest that soil texture and depth have a strong influence on the dissipation of terbuthylazine and metolachlor, whereas no influence was observed on mesotrione because of its chemical and physical properties. [ABSTRACT FROM AUTHOR]

The prediction of chemical mixture toxicity is a major concern regarding unintentional mixture of pesticides from agricultural lands treated with various such compounds. We focused our work on a mixture of three herbicides commonly applied on maize crops within a fortnight, namely mesotrione (β-triketone), nicosulfuron (sulfonylurea) and S-metolachlor (chloroacetanilide). The metabolic pathways of mesotrione and nicosulfuron were qualitatively and quantitatively determined with a bacterial strain ( Bacillus megaterium Mes11). This strain was isolated from an agricultural soil and able to biotransform both these herbicides. Although these pathways were unaffected in the case of binary or ternary herbicide mixtures, kinetics of nicosulfuron disappearance and also of mesotrione and nicosulfuron metabolite formation was strongly modulated. The toxicity of the parent compounds and metabolites was evaluated for individual compounds and mixtures with the standardized Microtox® test. Synergistic interactions were evidenced for all the parent compound mixtures. Synergistic, antagonistic or additive toxicity was obtained depending on the metabolite mixture. Overall, these results emphasize the need to take into account the active ingredient and metabolites all together for the determination of environmental fate and toxicity of pesticide mixtures. [ABSTRACT FROM AUTHOR]

Growth chamber experiments were conducted to evaluate the response of sesame to PRE and POST applications of soil residual herbicides. PRE applications of acetochlor and S-metolachlor at 1.26 and 1.43 kg ai·ha−1 showed little or no sesame injury (0 to 1%) 4 wks after herbicide treatments (WAT). POST treatments of acetochlor and trifluralin made 3 wks after planting (WAP) resulted in greater sesame injury (40%) compared to applications at bloom (18%). Field studies were conducted in Texas and Oklahoma during the 2014 and 2015 growing seasons to determine sesame response to clethodim, diuron, fluometuron, ethalfluralin, quizalofop-P, pendimethalin, pyroxasulfone, trifluralin, and trifloxysulfuron-sodium applied 2, 3, or 4 weeks after planting (WAP). Late-season sesame injury with the dinitroaniline herbicides consisted of a proliferation of primary branching at the upper nodes of the sesame plant (in the shape/form of a broom). Ethalfluralin and trifluralin caused more “brooming” effect than pendimethalin. Some yield reductions were noted with the dinitroaniline herbicides. Trifloxysulfuron-sodium caused the greatest injury (up to 97%) and resulted in yield reductions from the untreated check. Early-season diuron injury (leaf chlorosis and necrosis) decreased as application timing was delayed, and late-season injury was virtually nonexistent with only slight chlorosis (<4%) still apparent on the lower leaves. Sesame yield was not consistently affected by the diuron treatments. Fluometuron caused early-season injury (stunting/chlorosis), and a reduction of yield was observed at one location. Pyroxasulfone applied 2 WAP caused up to 25% sesame injury (stunting) but did not result in a yield reduction. Quizalofop-P caused slight injury (<5%) and no reduction in yield. [ABSTRACT FROM AUTHOR]

An ever-increasing diversity of potentially toxic chemical compounds are being developed and released into the environment as a result of human activities (e.g. agriculture, drugs, and cosmetics). Among these, pesticides have been shown to affect non-targeted wildlife since the 1960s. A range of ecotoxicological tests are used to assess the toxicity of pesticides on various model organisms. However most model organisms are metazoans, while the majority of Eukaryotes are unicellular microorganisms known as protists. Protists are ubiquitous organisms of key functional roles in all ecosystems but are so far little studied with respect to pesticide impact. To fill this gap, we developed a new ecotoxicological test based on Euglypha rotunda , a common soil amoeba, grown in culture flask with Escherichia coli as sole food source. We tested this assay with the herbicide S -metolachlor, which is known to affect cell division in seedling shoots and roots of weeds. Reproducible growth conditions were obtained for E. rotunda . The growth of E. coli was not affected by the herbicide. The growth of E. rotunda was affected by the herbicide in a non-linear way, growth being significantly reduced at ca. 15 μg/L, but not at 150 μg/L. Our results show the potential for using soil protists in ecotoxicology and adds to the growing body of evidence for non-linear impacts of pesticides on non-target organisms. With the acquisition of additional data, the protocol should be suitable for standard ecotoxicological tests. [ABSTRACT FROM AUTHOR]

The aim of the study was to evaluate the effect of the active substance of diflufenican and its combination with s-metolachlor or metribuzin, applied to yellow lupine, on the nitrogenase activity, the population size of selected groups of microorganisms, the activity of soil enzymes and their sensitivity to the tested preparations. All analysed preparations caused a reduction in the total number of bacteria and the number of actinobacteria and oligotrophic bacteria at the beginning of the vegetation period of yellow lupine. In the combination where diflufenican was used separately a stimulatory effect on nitrogenase activity was observed. The research revealed very high sensitivity of dehydrogenases and acid phosphatase to the soil contamination caused by application of all the tested herbicides. The dehydrogenases activity values were closely correlated with reduced populations of the groups of microorganisms. Diflufenican applied separately caused a relatively small negative effect on biological soil properties and consequently could have a smaller negative effect on soil environment contamination in comparison to other variants. [ABSTRACT FROM AUTHOR]

Variations in soil properties with depth strongly influence the degradation and persistence of herbicides, underlining the importance of studying these processes in soil horizons with distinctively different properties. The persistence of the herbicides acetochlor, atrazine, and S-metolachlor was measured in samples of the A, B, and C horizons of 2 Typic Argiudolls from Argentina under no-till management. The soils studied differed in soil organic carbon (OC) content, pH, particle size distribution, and structure. Quantification of herbicides in soil was done through high-performance liquid chromatography with diode array detector. There were interactions of herbicide × horizon ( p < 0.01) that resulted in degradation rates ( k) of all herbicides decreasing, and their corresponding dissipation half-life (DT50) values increasing, with soil depth. Herbicide persistence across all soils and horizons ranged from 15 to 73 d for acetochlor, 13 to 29 d for atrazine, and 82 to 141 d for S-metolachlor, which had significantly ( p < 0.01) greater persistence than atrazine and acetochlor. The DT50 values of herbicides were negatively correlated with the contents of OC (correlation coefficients ranging from -0.496 to -0.773), phosphorus (-0.427 to -0.564), and nitrogen-nitrate (-0.507 to -0.662), and with microbial activity (-0.454 to -0.687) and the adsorption coefficient (-0.530 to -0.595); DT50s were positively correlated with pH (0.366 to 0.648). Adsorption was likely the most influential process in determining persistence of these herbicides in surface and subsurface horizons. The present study can potentially improve the prediction of the fate of acetochlor, atrazine, and S-metolachlor in soils because it includes much needed information on the degradation of the herbicides in subsurface horizons. Environ Toxicol Chem 2017;36:3065-3073. © 2017 SETAC [ABSTRACT FROM AUTHOR]

A leaching experiment focusing on atrazine and metolachlor was conducted using a soil column with prescribed hydrological conditions. The transport parameters determined the concentrations in the soil depth. Atrazine and metolachlor were applied at the surface of the soil column at the average concentrations of 2.23±0.04 and 2.15±0.02 mg kg-1, for atrazine and metolachlor, respectively. At the end of the experiment, the concentrations of atrazine and metolachlor in the soil surface were 0.0068±0.0015 and 0.0013±0.0012 mg kg-1, respectively. The concentrations in atrazine and metolachlor in the water percolating at the bottom of the column were 0.14±0.03 mg kg-1 and 0.21±0.01 mg kg-1, respectively. The computed dissipation rate constants ranged from 0.014 to 0.036 day-1 for atrazine and from 0.010 to 0.028 day-1 for metolachlor. The corresponding half-lives were 23.5 days and 24.7 days for atrazine and metolachlor, respectively. There were no significant differences in leaching nor in the dissipation behaviors between atrazine and metolachlor (Student' s t-test, α = 0.05). The HYDRUS-1D simulated herbicide concentrations had fair accuracy, and the RMSE values between the simulated results and observed data were about 0.25 mg.L-1 for atrazine and 0.29 mg.L-1 for metolachlor. At the middle of the soil column, the soil water concentrations increased to maximum values of 2.24 and 2.98 mg. L-1 at 28 and 24 min and decreased to 0.31 and 0.36 mg.L-1 at the final time for atrazine and metolachlor, respectively. This result may be due to the very similar physicochemical properties of atrazine and metolachlo. [ABSTRACT FROM AUTHOR]