Ecotoxicological effects of commercial herbicides on the reproductive system of aquatic arthropod Limnocoris submontandoni (Hemiptera: Naucoridae) / Efeitos ecotoxicológicos de herbicidas comerciais no sistema reprodutivo do artrópode aquático Limnocoris submontandoni (Hemiptera: Naucoridae)

Abstract Worldwide, conventional agriculture makes extensive use of pesticides. Although the effects of herbicides are relatively well known in terms of environmental impacts on non-target organisms, there is very little scientific evidence regarding the impacts of herbicide residues on aquatic arthropods from tropical conservation areas. This study evaluates for the first time the toxicity of the herbicides ametryn, atrazine, and clomazone on the aquatic insect Limnocoris submontandoni (Hemiptera: Naucoridae). The lethal concentration (LC50) of herbicides was evaluated for these insects, as well as the effect of the herbicides on the insects' tissues and testicles. The estimated LC50 was 1012.41, 192.42, and 46.09 mg/L for clomazone, atrazine, and ametryn, respectively. Spermatocyte and spermatid changes were observed under the effect of atrazine, and effects on spermatogenesis were observed for some concentrations of clomazone, with apparent recovery after a short time. Our results provide useful information on the effects of herbicide residues in aquatic systems. This information can help minimize the risk of long-term reproductive effects in non-target species that have been previously overlooked in ecotoxicology studies.

Resumo Em todo o mundo, a agricultura convencional faz uso extensivo de pesticidas. Embora os efeitos dos herbicidas sejam relativamente bem conhecidos em termos de impactos ambientais em organismos não-alvo, há pouca evidência científica sobre os impactos de resíduos de herbicidas em artrópodes aquáticos de áreas de conservação tropicais. Este estudo avalia pela primeira vez a toxicidade dos herbicidas ametryn, atrazine e clomazone sobre o inseto aquático Limnocoris submontandoni (Hemiptera: Naucoridae). A concentração letal (LC50) de herbicidas foi avaliada para esses insetos, bem como o efeito dos herbicidas nos tecidos e testículos dos insetos. A LC50 estimada foi de 1012,41, 192,42 e 46,09 mg/L para clomazone, atrazine e ametryn, respectivamente. Alterações nos espermatócitos e espermátides foram observadas sob o efeito de atrazine, e efeitos na espermatogênese foram observados para algumas concentrações de clomazone, com aparente recuperação após um curto período de tempo. Nossos resultados fornecem informações úteis sobre os efeitos de resíduos de herbicidas em sistemas aquáticos. Essas informações podem ajudar a minimizar o risco de efeitos reprodutivos de longo prazo em espécies não-alvo que foram negligenciadas anteriormente em estudos de ecotoxicologia.

Phytotoxic and cytogenotoxic assessment of glyphosate on Lactuca sativa L / Avaliação fitotóxica e citogenotóxica do glifosato em Lactuca sativa L

The active ingredient glyphosate is the most commercialized herbicide on the world market due to its capability in eliminating weeds. However, it can harm the development of non-target organisms and threaten environmental quality. This study analyzed the effects of potentially toxic concentrations of glyphosate on germination, growth, cell cycle and genomic stability of Lactuca sativa L., and identified the most sensitive variables for assessing the toxicity of this herbicide to this biomonitor. Seeds of L. sativa were germinated in Petri dishes containing a sheet of filter paper moistened with 5 mL of a concentration of glyphosate (1.34, 3.35, 6.70, 10.05, 13.40 mg L-1). Controls consisted of distilled water (negative) and 3 mg L-1 CuSO4 (positive). Macroscopic and microscopic variables were analyzed. The germination of L. sativa was not affected by the concentrations of glyphosate. Root length and shoot height of the plants and the mitotic index decreased from the lowest concentration tested on. The chromosomal anomaly index and frequency of micronuclei increased by 3.2 and 22 times, respectively, with the presence of the lowest concentration of glyphosate compared to the negative control. The observed phytotoxic and cytogenotoxic effects demonstrate the negative influence that glyphosate has on the development of L. sativa. Root length and microscopic variables showed the highest sensitivity. This study warns of the possible harmful effects that glyphosate can have on non-target organisms and suggests greater control over the use of this herbicide to mitigate its environmental impact.

O ingrediente ativo glifosato é o herbicida mais comercializado do mercado mundial, pela sua capacidade de eliminar as plantas daninhas. No entanto, ele pode prejudicar o desenvolvimento dos organismos não-alvo e ameaçar a qualidade do ambiente. O estudo teve como objetivo analisar os efeitos de concentrações potencialmente tóxicas de glifosato sobre a germinação, o crescimento, o ciclo celular e a estabilidade genômica de Lactuca sativa L., e identificar as variáveis mais sensíveis para avaliar a toxicidade deste herbicida ao biomonitor. Sementes de L. sativa foram germinadas em placas de Petri contendo uma folha de papel-filtro umedecida com 5 mL das concentrações de glifosato (1,34, 3,35, 6,70, 10,05, 13,40 mg L-1). Os controles consistiram em água destilada (negativo) e 3 mg L-1 de CuSO4 (positivo). Variáveis macroscópicas e microscópicas foram analisadas. A germinação de L. sativa não foi afetada pelas concentrações de glifosato. O comprimento da raiz e a altura da parte aérea das plantas e o índice mitótico reduziram desde a menor concentração testada. O índice de anomalias cromossômicas e a frequência de micronúcleos aumentaram, respectivamente, 3,2 e 22 vezes na presença da menor concentração de glifosato em comparação ao controle negativo. Os efeitos fitotóxicos e citogenotóxicos observados demonstram a interferência negativa do herbicida no desenvolvimento de L. sativa. O comprimento da raiz e as variáveis microscópicas foram as que apresentaram maior sensibilidade. Este estudo alerta sobre os possíveis efeitos prejudiciais que o glifosato pode provocar nos organismos não-alvo, sugerindo um maior controle quanto à utilização deste herbicida, a fim de mitigar o seu impacto ambiental.

Improved Chromatography and MS-Based Detection of Glyphosate and Aminomethylphosphonic Acid Using iTrEnDi.

Glyphosate (GLY), a synthetic, nonselective systemic herbicide that is particularly effective against perennial weeds, is the most used weedkiller in the world. There are growing concerns over GLY accumulation in the environment and the attendant human health-associated risks, and despite increased attention in the media, GLY and its breakdown product aminomethylphosphonic acid (AMPA) remain elusive to many analytical strategies. Chemical derivatization coupled with high-performance liquid chromatography-mass spectrometry (HPLC-MS) addresses the challenge of quantifying low levels of GLY and AMPA in complex samples. Here we demonstrate the use of in situ trimethylation enhancement using diazomethane (iTrEnDi) to derivatize GLY and AMPA into permethylated products ([GLYTr]+ and [AMPATr]+, respectively) prior to analysis via HPLC-MS. iTrEnDi produced quantitative yields and resulted in a 12-340-fold increases in HPLC-MS-based sensitivity for [GLYTr]+ and [AMPATr]+, respectively, compared with underivatized counterparts. The limits of detection of derivatized compounds were found to be 0.99 ng/L for [GLYTr]+ and 1.30 ng/L for [AMPATr]+, demonstrating significant sensitivity improvements compared to previously established derivatization techniques. iTrEnDi is compatible with the direct derivatization of Roundup formulations. Finally, as proof of principle, a simple aqueous extraction followed by iTrEnDi enabled the detection of [GLYTr]+ and [AMPATr]+ on the exterior of field-grown soybeans that were sprayed with Roundup. Overall, iTrEnDi ameliorates issues relating to low proton affinity and chromatographic retention, boosting HPLC-MS-based sensitivity and enabling the elucidation of elusive analytes such as GLY and AMPA within agricultural systems.

Potential Role of EPSPS Mutations in the Resistance of Eleusine indica to Glyphosate.

Gene mutation is a basic evolutionary mechanism in plants under selection pressure of herbicides. Such mutation has pleiotropic effects on plant growth. We systemically investigated the effects of Pro106Leu (P106L), Pro106Ser (P106S), and Thr102Ile + Pro106Ser (TIPS) mutations on EPSPS functionality and fitness traits in Eleusine indica at the biochemical and physiological levels. The affinity of natural EPSPS for glyphosate was 53.8 times higher than that for phosphoenolpyruvate (PEP), as revealed by the dissociation constant; the constant decreased in both the P106L (39.9-fold) and P106S (46.9-fold) mutants but increased in the TIPS (87.5-fold) mutant. The Km (PEP) values of the P106L, P106S, and TIPS mutants were 2.4-, 0.7-, and 4.1-fold higher than that of natural EPSPS, corresponding to resistance levels of 2.5, 1.9, and 11.4, respectively. The catalytic efficiency values (maximum reaction rates) were 0.89-, 0.94-, and 0.26-fold higher than that of natural EPSPS. The levels of metabolites related to amino acids and nucleotides were significantly reduced in the mutated plants. The fitness costs were substantial for the biomass, total leaf area, seed number, and seedling emergence throughout the growth period in the plants with P106L and TIPS mutations. These results provide insights into EPSPS kinetics and their effect on plant growth.

Towards Protection of Nucleic Acids from Herbicide Attack: Self-Assembly of Betaines Based on Pillar[5]arene with Glyphosate and DNA.

Herbicides are one of the main parts of pesticides used today. Due to the high efficiency and widespread use of glyphosate-based herbicides, the search for substances reducing their genotoxicity is an important interdisciplinary task. One possible approach for solving the problem of herbicide toxicity is to use compounds that can protect DNA from damage by glyphosate derivatives. For the first time, a method for developing DNA-protecting measures against glyphosate isopropylamine salt (GIS) damage was presented and realized, based on low-toxicity water-soluble pillar[5]arene derivatives. Two- and three-component systems based on pillar[5]arene derivatives, GIS, and model DNA from salmon sperm, as well as their cytotoxicity, were studied. The synthesized pillar[5]arene derivatives do not interact with GIS, while GIS is able to bind DNA from salmon sperm with lgKa = 4.92. The pillar[5]arene betaine derivative containing fragments of L-phenylalanine and the ester derivative with diglycine fragments bind DNA with lgKa = 5.24 and lgKa = 4.88, respectively. The study of the associates (pillar[5]arene-DNA) with GIS showed that the interaction of GIS with DNA is inhibited only by the betaine pillar[5]arene containing fragments of L-Phe (lgKa = 3.60). This study has shown a possible application of betaine pillar[5]arene derivatives for nucleic acid protection according to its competitive binding with biomacromolecules.

Coconut shell biochar application in liquid-solid microextraction of triazine herbicides from multi-media environmental samples.

A rapid, fast, widely applicable liquid-solid microextraction and purification method of triazine herbicides (TRZHs) in muti-media samples using salting-out assisted liquid-liquid extraction (SALLE) combined with self-assembled monolithic spin columns-solid phase micro extraction (MSC-SPME) was developed. Environmentally friendly coconut shell biochar (CSB) was used as the adsorbents of MSC-SPME. Ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was the separation and determination method. The adsorption kinetics and isotherms were investigated to indicate the interaction between CSB and TRZHs. Several parameters influencing the liquid-solid microextraction efficiency, such as sample pH, salting-out solution volume and pH, sample loading speed, elution speed, elution ratio and volume of eluent were systematically investigated with the aid of orthogonal design. The whole extraction process was operated within 10 min. Under the optimum extraction and determination conditions, good linearities for three TRZHs were obtained in a range of 0.10-200.00 ng mL-1, with linear coefficients (R2) greater than 0.999. The limits of detection (LODs) and limits of quantification (LOQs) were in the range of 6.99-11.00 ng L-1 and 23.33-36.68 ng L-1, respectively. The recoveries of the three TRZHs in multi-media environmental samples were ranged from 69.00% to 124.72%, with relative standard deviations (RSDs) lower than 0.43%. This SALLE-MSC-SPME-UPLC-MS/MS method was successfully applied to the determination of TRZHs in environmental and food samples and exhibited the advantages of high efficiency and sensitivity, low cost, and environmental friendliness. Compared with the methods published before, CSB-MSC was green, rapid, easy-operated, and reduced the whole cost of the experiment; SALLE combined MSC-SPME eliminated the matrix references effectively; what's more, the SALLE-MSC-SPME-UPLC-MS/MS method could be applied to various sample without complicated sample pretreatment procedure.

Effect of soil amendments on the sorption behavior of atrazine in sandy loam soil.

The sorption behavior of pesticides applied during cultivation of crops is affected by amendments such as farm yard manure (FYM) and vermicompost (VC) during land preparation. Among pesticides, atrazine, a widely used herbicide in many crops, was analyzed for its kinetics and sorption behavior through the addition of FYM and VC in sandy loam soil. The pseudo-second-order (PSO) model best fit the kinetics results in the recommended dose of FYM and VC mixed soil. More atrazine was sorbed onto VC mixed soil than FYM mixed soil. In comparison to control (no amendment), both FYM and VC (1, 1.5, and 2%) increased atrazine adsorption, but the effect varied with dosage and type of amendment. The Freundlich adsorption isotherm adequately explained atrazine adsorption in soil/soil + (FYM/VC) mixtures, and the adsorption was highly nonlinear. The values of Gibb's free energy change (ΔG) were negative for both adsorption and desorption in soil/soil + (FYM/VC) mixtures, suggesting sorption was exothermic and spontaneous in nature. The results revealed that the application of amendments used by farmers interferes the availability, mobility, and infiltration of atrazine in the soil. Therefore, the findings of this study suggest that amendments such as FYM and VC can be effectively used to minimize the residual toxicity of atrazine-treated ago-ecosystems in tropical and sub-tropical regions.

Selected herbicides screened for toxicity and analysed as inhibitors of both cholinesterases.

Sets of 346 herbicides in use and 163 no longer in use were collected from open access online sources and compared in silico with cholinesterases inhibitors (ChI) and drugs in terms of physicochemical profile and estimated toxic effects on human health. The screening revealed at least one potential adverse consequence for each herbicide class assigned according to their mode of action on weeds. The classes with most toxic warnings were K1, K3/N, F1 and E. The selection of 11 commercial herbicides for in vitro biological tests on human acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), the enzymes involved in neurotoxicity and detoxification of various xenobiotics, respectively, was based mainly on the structural similarity with inhibitors of cholinesterases. Organophosphate anilofos and oxyacetanilide flufenacet were the most potent inhibitors of AChE (25 µM) and BChE (6.4 µM), respectively. Glyphosate, oxadiazon, tembotrione and terbuthylazine were poor inhibitors with an estimated IC50 above 100 µM, while for glyphosate the IC50 was above 1 mM. Generally, all of the selected herbicides inhibited with a slight preference towards BChE. Cytotoxicity assays showed that anilofos, bensulide, butamifos, piperophos and oxadiazon were cytotoxic for hepatocytes (HepG2) and neuroblastoma cell line (SH-SY5Y). Time-independent cytotoxicity accompanied with induction of reactive oxygen species indicated rapid cell death in few hours. Our results based on in silico and in vitro analyses give insight into the potential toxic outcome of herbicides in use and can be applied in the design of new molecules with a less impact on humans and the environment.

Glyphosate Interference in Follicular Organization in the Wall Lizard Podarcis siculus.

Glyphosate (Gly) is a broad-spectrum herbicide widely used thanks to its high efficiency and low toxicity. However, evidence exists of its toxic effects on non-target organisms. Among these, the animals inhabiting agricultural fields are particularly threatened. Recent studies demonstrated that exposure to Gly markedly affected the morphophysiology of the liver and testis of the Italian field lizard Podarcis siculus. The present study aimed to investigate the effects of the herbicide on the female reproductive system of this lizard in order to have a full picture of Gly-induced reproductive impairment. The animals were exposed to 0.05 and 0.5 µg/kg of pure Gly by gavage for 3 weeks. The results demonstrated that Gly, at both doses tested, profoundly interfered with ovarian function. It induced germ cells' recruitment and altered follicular anatomy by anticipating apoptotic regression of the pyriform cells. It also induced thecal fibrosis and affected oocyte cytoplasm and zona pellucida organizations. At the functional levels, Gly stimulated the synthesis of estrogen receptors, suggesting a serious endocrine-disrupting effect. Overall, the follicular alterations, combined with those found at the level of the seminiferous tubules in males, suggest serious damage to the reproductive fitness of these non-target organisms, which over time could lead to a decline in survival.

Spatial and seasonal distribution of pesticides in the waters of Azagny area (Grand Lahou, Cote d'Ivoire).

This study provides comprehensive data on the seasonal variation and distribution of pesticides in the waters bordering Azagny National Park (ANP). Forty-six (46) samples of water from the Azagny area were analyzed using high-performance liquid chromatography (HPLC) coupled with a UV/visible detector to assess the level of thirty-one pesticide molecules divided into six families. These include triazines, phenylureas, organophosphates, carbamates, chloroacetanilides, dicarboximides, and crimidine, which are regularly used in this area. The respective average concentrations of pesticides are 54.54 µg//L, 20.93 µg/L, 18.24 µg/L, 3.06 µg/L, and 16.52 µg/L in the Bandama, Azagny Canal, ANP, mangroves, and estuarine environment. The analyses also showed that herbicides were the most abundant pesticides in the three waters, Bandama, Azagny Canal, and Azagny Park, with levels of 100%, 63%, and 59%, respectively, followed by insecticides with a levels of 0%, 37%, and 41%, respectively. However, rodenticides (76%) were more frequently detected than herbicides (24% in the mangroves). Regarding seasonal variation, high levels of pesticides were detected in the Bandama River, the Azagny Canal, and the mangroves during the dry season, while multiple pesticide residues were detected during the rainy season. The waters bordering Azagny National Park (ANP) are contaminated with pesticide residues (triazines, phenylureas, organophosphates, carbamates, and chloroacetanilides). As a result, policymakers should implement measures to regularly monitor pesticide levels in plantations surrounding the Azagny region's waters in order to better preserve biodiversity.

Discovery of novel HPPD inhibitors: Virtual screening, molecular design, structure modification and biological evaluation.

4-Hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD, a Fe(II)/α-ketoglutarate dependent oxygenases), is a popular herbicide target. In this work, two pharmacophore models based on common molecular characteristics (HipHop) and receptor-ligand complex (CBP) were generated for virtual screening for HPPD inhibitors. About 1,000,000 molecules containing diketone structure from PubChem were filtered by Lipinski's rules to build a 3D database. Then the database was screened through combining HipHop model, CBP model, ADMET (absorption, distribution, metabolism, excretion and toxicity) prediction and molecular docking. Subsequently, based on the specific binding mode and affinity of HPPD inhibitors, 4 molecules with high -CDOCKER energy, good aqueous solubility and human safety predicative properties values were screened. From the screening results and combined with previous work, three novel HPPD inhibitors were designed and synthesized through fragment splicing and bioisosterism strategies. Compound IV-a exhibited similar inhibition of Arabidopsis thaliana HPPD (AtHPPD) and herbicidal activity as mesotrione. Crop selectivity showed that compound IV-a had better crop safety than mesotrione. Comparing the molecular properties, ADMET and molecular docking studies indicated that compounds IV-a exhibited better properties than mesotrione, which could be further modified as novel HPPD inhibitor herbicides.

Tolerance of microorganisms to residual herbicides found in eucalyptus plantations.

Competition with weeds is one of the main factors that limit the development of forest species. Some herbicides used to control these plants have a residual effect on the soil. Bioremediation is an alternative to decontaminate these areas. The aim of this study was to evaluate the tolerance of Aspergillus niger, Penicillium pinophilum and Trichoderma sp. and its degrading potential on residual effect herbicides. The tolerance of Bacillus subtilis, Pseudomonas sp. and Azospirillum brasilense to herbicides was also evaluated. The herbicides used in this study were indaziflam, sulfentrazone, sulfentrazone + diuron, clomazone and glyphosate + s-metolachlor. The analysis of the tolerance and degradation potential of fungi was carried out in Czapek Dox medium and the growth was evaluated by determining the biomass. Bacterial tolerance analysis was performed in Luria Bertani medium and growth monitored by optical density. The data were applied to the Gompertz model to evaluate the behavior of bacteria. Bacterial growth parameters were not influenced by the presence of herbicides. All fungi were tolerant to the herbicides tested and there was an increase in the growth of Trichoderma sp. Thus, the analysis of the degrading potential was performed only for Trichoderma sp. in the presence of herbicides that potentiated its growth. In this analysis, there was no effect of herbicides on fungal growth; the fungus was unable to use the carbon present in the herbicide to enhance its growth; and there was no significant effect of nitrogen in the presence of the herbicide. It is concluded, therefore, that the tested residual herbicides do not interfere with the development of the evaluated microorganisms.

Hazardous impacts of glyphosate on human and environment health: Occurrence and detection in food.

With the ever-increasing human population, farming lands are decreasing every year, therefore, for effective crop management; agricultural scientists are continually developing new strategies. However, small plants and herbs always impart a much loss in the yields of the crop and farmers are using tons of herbicides to eradicate that problem. Across the world, several herbicides are available in the market for effective crop management, however, scientists observed various environmental and health effects of the herbicides. Over the past 40 years, the herbicide glyphosate has been used extensively with the assumption of negligible effects on the environment and human health. However, in recent years, concerns have increased globally about the potential direct and indirect effects on human health due to the excessive use of glyphosate. As well, the toxicity on ecosystems and the possible effects on all living creatures have long been at the center of a complex discrepancy about the authorization for its use. The World Health Organization also further classified glyphosate as a carcinogenic toxic component and it was banned in 2017 due to numerous life-threatening side effects on human health. In the present era, the residues of banned glyphosate are more prevalent in agricultural and environmental samples which are directly affecting human health. Various reports revealed the detailed extraction process of glyphosate from different categories of the food matrix. Therefore, in the present review, to reveal the importance of glyphosate monitoring in the food matrix, we discussed the environmental and health effects of glyphosate with acute toxicity levels. Also, the effect of glyphosate on aquatic life is discussed in detail and various detection methods such as fluorescence, chromatography, and colorimetric techniques from different food samples with a limit of detection values are revealed. Overall, this review will give an in-depth insight into the various toxicological aspects and detection of glyphosate from food matrix using various advanced analytical techniques.

Design, Synthesis, and Biological Activities of Novel 2-Cyanoacrylate Compounds Containing Substituted Pyrazolyl or 1,2,3-Triazolyl Moiety.

To develop novel 2-cyanoacrylate derivatives with potential bioactivity, a number of 2-cyanoacrylate compounds, including substituted pyrazole or 1,2,3-triazole ring, were designed, prepared, and structurally detected by 1H NMR, 13C NMR, and elemental analysis. The biological assessment displayed that some designed compounds had significant herbicidal activities against Brassica juncea, Chenopodium serotinum, Rumex acetosa, Alopecurus aequalis, Polypogon fugax, and Poa annua at a dosage of 1500 g/ha. Furthermore, some derivatives still expressed satisfactory herbicidal activities against Brassica juncea, Chenopodium serotinum, and Rumex acetosa when the dosage was lowered to 150 g/ha, especially the inhibitory effects of compounds 9a, 9d, 9f, 9i, 10a, 10b, 10e, and 10n against Brassica juncea were all over 80%, compounds 9d, 9f, 9g, 9h, 9i, 10h, 10i, 10m, 10n, and 10o possessed more than 70% inhibition rates against Chenopodium serotinum, and compound 9d indicated 70% herbicidal activity against Rumex acetosa. These results provided an important basis for further design and discovery of biologically active 2-cyanoacrylate compounds.

[Research Progress on the Remediation Technology of Herbicide Contamination in Agricultural Soils].

Asthe most-used pesticides in the agricultural production process, herbicides are mainly applied to protect crops from weeds. However, with the increased global demand for food, the dosage of herbicides is rising annually, and the efficacy of herbicides is getting stronger, which can cause some environmental issues including the accumulation, migration and transformation, and toxic effects of herbicides in agricultural soils. According to the characteristics of herbicide contamination and regional agricultural production, developing green and low-carbon technologies to reduce the ecological risks of herbicides to the soil-crop systems is a current concern in the ecological environment field. In this paper, relevant studies in recent years on herbicide pollution management in agricultural soils were identified and reviewed, the research progress and application cases of remediation technologies for herbicide pollution was analyzed and demonstrated, and future research and development tendency regarding the remediation of herbicides pollution was also prospected. Current remediation technologies for herbicides mainly include bioremediation technologies (e.g., microbial remediation, enzyme remediation, and phytoremediation), adsorption, and immobilization technologies (e.g., biochar-based materials). The bioremediation technologieswere rather mature and had been applied to the herbicide-contaminated soil in fields. Additionally, many successful bioremediation cases have been reported. Moreover, in order to enhance the remediation effect on herbicide pollution in agriculture soils, remediation technologies have been gradually developed from a single model to a coupled model with physical,chemical, and biological technology, which can maximize the synergy of the multi-technology application.

Biomineralization of pretilachlor by free and immobilized fungal strains isolated from paddy field.

The excessive use of pretilachlor (a chloroacetamide herbicide) has raised concern throughout the world as it has been reported as highly toxic. The present study deals with isolating and screening pretilachlor degrading fungal strains. The strains Aspergillus ficuum (AJN2) and Aspergillus sp. (PDF1) isolated using enrichment technique were able to degrade 79% and 73% of pretilachlor respectively as analyzed using HPLC. Further, the immobilization technique was used in the study the pretilachlor degradation ability of the isolated strains. The immobilized spores of the strains AJN2 and PDF1 mineralized 84% and 95% of pretilachlor respectively. The degradation dynamics study revealed that the DT50 value of the herbicide was reduced to 2.4 d in aqueous medium due to the enhanced enzymatic activity. The enzymatic study showed high lignin peroxidase and manganese peroxidase activity by the strains AJN2 and PDF1 respectively. The study confirmed the efficient degradation of pretilachlor by Aspergillus ficuum (AJN2).

Glyphosate and Aminomethylphosphonic Acid (AMPA) Modulate Glutathione S-Transferase in Non-Tumorigenic Prostate Cells.

Glyphosate (GLY) was developed in the early 1970s and has become the most used broad-spectrum herbicide in the world so far. Its main metabolite is aminomethylphosphonic acid (AMPA), and the accumulation of GLY and its derivative compounds raises some concerns regarding possible health outcomes. In this study, we aimed to evaluate the effects of GLY and AMPA on prostate cell lines by evaluating cell viability, proliferation, gene and protein expression, and cellular pathways involved in the response to oxidative stress. Our results indicated that GLY and AMPA reduced the cell viability of tumorigenic and non-tumorigenic prostate cell lines only at higher concentrations (10 mM GLY and 20 mM AMPA). In contrast, both compounds increased the clonogenicity of non-tumorigenic PNT2 cells, mainly at concentrations below the IC50 (5 mM GLY and 10 mM AMPA). Moreover, treatment of non-tumorigenic cells with low concentrations of GLY or AMPA for 48 h increased GSTM3 expression at both mRNA and protein levels. In contrast, the treatments decrease the GST activity and induced an increase in oxidative stress, mainly at lower concentrations. Therefore, both compounds can cause cellular damage even at lower concentrations in non-tumorigenic PNT2 cells, mainly affecting cell proliferation and oxidative stress.

Green construction of hydroxyl-functionalized magnetic porous organic framework for effective extraction of triazine herbicides from environmental water and watermelon juice samples.

Triazine herbicides have been widely detected in water resources and food, which poses a potential hazard to both ecosystem and human health. Due to their high polarity, conventional adsorbents have limitations for their extractions. Herein, for the effective magnetic extraction of triazine herbicides, a novel and effective magnetic adsorbent was prepared with a satisfactory extraction performance. In the experiments, five porous organic frameworks (POFs) with hydroxyl functional groups were synthesized by diazo-coupling reactions in aqueous solution with ß-cyclodextrin (ß-CD) as a green monomer. After evaluation of the five POFs, the DDM-CD-POF, which was synthesized with 4'4-diaminodiphenylmethane (DDM) and ß-CD, showed the largest specific surface area and the best adsorption capacity for the five triazine herbicides. Then, it was magnetized by introducing Fe3O4@SiO2 into it to prepare a magnetic adsorbent (M-DDM-CD-POF) to facilitate separation and recycling. Finally, the M-DDM-CD-POF-based magnetic solid-phase extraction in combination with high performance liquid chromatographic detection method was established for the quantitative determination of the triazine herbicides in environmental water and watermelon juice samples. The current strategy showed low limits of detection of 0.03-0.11 ng mL-1 for environmental water and 0.07-0.22 ng mL-1 for watermelon juice sample. The method recoveries for spiked samples ranged from 84.0% to 113.0% with the relative standard deviations ≤8.8%. This work provides a new approach for the detection of the triazine herbicides with good application prospect.

Cover crop termination options and application of remote sensing for evaluating termination efficiency.

Efficient termination of cover crops is an important component of cover crop management. Information on termination efficiency can help in devising management plans but estimating herbicide efficacy is a tedious task and potential remote sensing technologies and vegetative indices (VIs) have not been explored for this purpose. This study was designed to evaluate potential herbicide options for the termination of wheat (Triticum aestivum L.), cereal rye (Secale cereale L.), hairy vetch (Vicia villosa Roth.), and rapeseed (Brassica napus L.), and to correlate different VIs with visible termination efficiency. Nine herbicides and one roller-crimping treatment were applied to each cover crop. Among different herbicides used, glyphosate, glyphosate + glufosinate, paraquat, and paraquat + metribuzin provided more than 95% termination for both wheat and cereal rye 28 days after treatment (DAT). For hairy vetch, 2,4-D + glufosinate and glyphosate + glufosinate, resulted in 99 and 98% termination efficiency, respectively, followed by 2,4-D + glyphosate and paraquat with 92% termination efficiency 28 DAT. No herbicide provided more than 90% termination of rapeseed and highest control was provided by paraquat (86%), 2,4-D + glufosinate (85%), and 2,4-D + glyphosate (85%). Roller-crimping (without herbicide application) did not provide effective termination of any cover crop with 41, 61, 49, and 43% termination for wheat, cereal rye, hairy vetch, and rapeseed, respectively. Among the VIs, Green Leaf Index had the highest Pearson correlation coefficient for wheat (r = -0.786, p = <0.0001) and cereal rye (r = -0.804, p = <0.0001) with visible termination efficiency rating. Whereas for rapeseed, the Normalized Difference Vegetation Index (NDVI) had the highest correlation coefficient (r = -0.655, p = <0.0001). The study highlighted the need for tankmixing 2,4-D or glufosinate with glyphosate for termination instead of blanket application of glyphosate alone for all crops including rapeseed and other broadleaf cover crops.