RESUMO
In this study, the interaction of triazine herbicides with three kinds of different alkyl groups (simetryne, ametryn and terbutryn) with human serum albumin (HSA) are investigated through UV-vis, fluorescence, and circular dichroism (CD) spectra. The mechanisms on the fluorescence quenching of HSA initiated by triazine herbicides are obtained using Stern-Volmer, Lineweaver-Burk and Double logarithm equations. The quenching rate constant (Kq), Stern-Volmer quenching constant (Ksv), binding constant (KA), thermodynamic parameters such as enthalpy change (∆H), entropy change (∆S) and Gibbs free energy (∆G) and number of binding site (n) are calculated and compared. The variations in the microenvironment of amino acid residues are studied by synchronous fluorescence spectroscopy. The binding sites and subdomains are identified using warfarin and ibuprofen as site probes. The conformational changes of HSA are measured using CD spectra. The results reveal that the triazine herbicides with different alkyl groups can interact with HSA by static quenching. The combination of the three herbicides and HSA are equally proportional, and the binding processes are spontaneous. Hydrophobic interaction forces play important roles in simetryne-HSA and ametryn-HSA, while the interaction of terbutryn-HSA is Van der Waals forces and hydrogen bonding. Moreover, the three herbicides can bind to HSA at site I (sub-domain IIA) more than site II (subdomain IIIA), and combine with tryptophan (Trp) more easily than tyrosine (Tyr) residues, respectively. By comparison, the order of interaction strength is terbutryn-HSA > ametryn-HSA > simetryne-HSA. Terbutryn can destroy the secondary structure of HSA more than simetryne and ametryn, and the potential toxicity of terbutryn is higher. It is expected that the interactions of triazine herbicides with HSA via multi-spectral analysis can offer some valuable information for studying the toxicity and the harm of triazine herbicides on human health at molecular level in life science.
Assuntos
Herbicidas , Albumina Sérica Humana , Espectrometria de Fluorescência , Termodinâmica , Triazinas , Triazinas/química , Triazinas/metabolismo , Herbicidas/química , Herbicidas/metabolismo , Humanos , Albumina Sérica Humana/química , Albumina Sérica Humana/metabolismo , Dicroísmo Circular , Sítios de Ligação , Ligação Proteica , Interações Hidrofóbicas e HidrofílicasRESUMO
To obtain good control of wild poinsettia (Euphorbia heterophylla) in post-emergence in sugarcane crop, we evaluate the herbicides association on post-emergence of E. heterophylla and the ratoon cane selectivity. The experimental scheme was in randomized blocks with 6 treatments and 4 replications. The treatments were: control; ametryn + mesotrione + sulfentrazone (1,500 + 144 + 800 g i.a ha-1); ametryn + mesotrione + diclosulan (1,500 + 144 + 200 g i.a ha-1); ametryn + mesotrione (2,500 + 144 g i.a ha-1: Highest dose); ametryn + mesotrione (2,000 + 144 g i.a ha-1: Lowest dose) and ametryn + mesotrione + diuron (1,000 + 144 + 1,250 g i.a ha-1). The percentage of control, dry mass, height and percentage of germination of E. heterophylla and injury level, yield and technological quality of sugarcane were evaluated. The best control of E. heterophylla was: ametryn + mesotrione +sulfentrazone; ametryn + mesotrione + diclosulan and ametryn + mesotrione (Lowest dose). As for the ratoon cane selectivity the best yield was achieved with the association ametryn + mesotrione +diclosulan. An appropriate association of herbicide molecules provides successful control of E. heterophylla, especially the association of sulfentrazone or diclosulan together with ametryn and mesotrione.
Assuntos
Euphorbia , Herbicidas , Saccharum , Herbicidas/farmacologia , Herbicidas/análise , Grão Comestível/químicaRESUMO
It is highly desired to enhance charge separation and O2 adsorption of the pyropheophorbide-a (Ppa) to promote visible-light activity and stability. Herein, Ppa modified 001-facet-exposed TiO2 nanosheets (Ppa/001T) nanocomposites with different weight ratios were fabricated via the self-assembly approach by OH induced. Compared with the bare Ppa, the 8% amount optimized 8Ppa/001T sample displayed 41-fold enhanced activity for degradation of Ametryn (AME) under visible-light irradiation. The promoted photoactivities could be attributed to the accelerated charge carrier's separation by coupling TiO2 as thermodynamic platform for accepting the photoelectrons with high energy from Ppa and the promoted O2 adsorption because of the residual fluoride on TiO2. As for this, a distinctive two radicals (â¢O2- and â¢OH) involved pathway of AME degradation is carried out, which is different from the radical pathway dominated by â¢O2- for the bare Ppa. This work is of utmost importance since it gives us detailed information regarding the charge carrier's separation and the impact of the radical pathway that will pave a new approach toward the design of high activity visible-light driven photocatalysts.
RESUMO
The investigation reports the application of biogenic jarosite, an iron hydroxy sulfate mineral in Fenton's Oxidation process. Ametryn, a herbicide detrimental to aquatic life and also to human is treated by Fenton's oxidation process using synthesized iron mineral, jarosite. The jarosite synthesis was carried out by using an isolated Acidithiobacillus ferrooxidans bacterial strain with ferrous as an iron supplement. The isolated strain was characterized by molecular techniques and biooxidation activity to ferrous to ferric iron was checked. On Fenton's treatment ametryn degradation upto 84.9% and COD removal to the extent of 56.1% was observed within 2â¯h of treatment and the reaction follows the pseudo first order kinetics with the curve best fit. The slight increase in kinetic rate constant on jarosite loading rate increase from 0.1â¯g/L to 0.5â¯g/L with H2O2 dosage of 100â¯mg/L confirms that jarosite has a catalytic role in the removal of ametryn. Mass spectroscopy analysis of treated synthetic ametryn solution at various intervals reveal the degradation follows dealkylation and hydroxylation pathway with the formation of three major intermediate compounds discussed here.
Assuntos
Acidithiobacillus , Peróxido de Hidrogênio , Ferro , Oxirredução , TriazinasRESUMO
The present study was aimed to investigate biodegradation of 2-(ethylamino)-4-(isopropylamino)-6-(methylthio)-s-triazine (ametryn) in a laboratory-scale anaerobic sequential batch reactor (ASBR) and followed by aerobic post-treatment. Co-treatment of ametryn with starch is carried out at ambient environmental conditions. The treatment process lasted up to 150 days of operation at a constant hydraulic retention time (HRT) of 24â¯h and an organic loading rate (OLR) of 0.21-0.215â¯kg-COD/m3/d. Ametryn concentration of 4 and 6â¯mg/L was removed completely within 48-50 days of operation with chemical oxygen demand (COD) removal efficiencies >85% at optimum reactor conditions. Ametryn acted as a nutrient/carbon source rather causing toxicity and contributed to methane gas production and sludge granulation in the anaerobic reactor. Biotransformation products of ametryn to cyanuric acid, biuret, and their further conversion to ammonia nitrogen and CO2 are monitored during the study. Adsorption of ametryn on to reactor sludge was negligible, sludge granulation, presence of ANAMMOX bacteria, and low MLVSS/MLSS ratio between 0.68 and 0.72. The study revealed that ametryn removal occurred mainly due to biodegradation and co-metabolism processes. Aerobic post-treatment of anaerobic effluent was able to remove COD up to 95%. The results of this study exhibit that anaerobic-aerobic treatment is feasible due to easy operation, economic, and highly efficient.
Assuntos
Reatores Biológicos , Águas Residuárias , Anaerobiose , TriazinasRESUMO
Ametrym (AMT) is the most widely used herbicide and frequently detected in the aquatic environment. AMT also represent a potential health risk to aquatic organisms and animals, including humans. However, little data are available on their toxicity to zebrafish (Danio rerio). The aim of the present study was to evaluate the toxicological effects of AMT exposure on zebrafish embryos. In the acute toxicity test, 6 hpf embryos were exposed to various concentrations of AMT for 24 or 48 h. The results indicated that AMT induced malformation in larvae. To investigate the toxicological mechanism on the protein expression level. A proteomic approach was employed to investigate the proteome alterations of zebra fish embryos exposed to 20 mg/L AMT for 48 h. Among 2925 unique proteins identified, 298 differential proteins (> or <1.3-fold, P < 0.05) were detected in the treated embryos as compared to the corresponding proteins in the untreated embryos. Gene ontology analysis showed that these up-regulated proteins were most involved in glycolysis, lipid transport, protein polymerization, and nucleotide binding, and the down-regulated proteins were related to microtubule-based process, protein polymerization, oxygen transport. Moreover, KEGG pathway analysis indicated that tight junction, ribosome, and oxidative phosphorylation were inhibited in the treated embryos. These findings provide new insight into the mechanisms of toxicity induced by AMT.
Assuntos
Proteoma/efeitos dos fármacos , Triazinas/toxicidade , Poluentes Químicos da Água/toxicidade , Peixe-Zebra , Animais , Embrião não Mamífero/efeitos dos fármacos , Embrião não Mamífero/metabolismo , Herbicidas/toxicidade , Larva/efeitos dos fármacos , Larva/metabolismo , Redes e Vias Metabólicas/efeitos dos fármacos , Proteoma/análise , Proteoma/metabolismo , Proteômica/métodos , Testes de Toxicidade Aguda , Peixe-Zebra/embriologia , Peixe-Zebra/metabolismo , Proteínas de Peixe-Zebra/efeitos dos fármacos , Proteínas de Peixe-Zebra/metabolismoRESUMO
Ametryn is a selective herbicide belonging to the triazine family and widely used for killing annual grasses or weeds in China and other parts of the world. However, reports on its environmental risk assessment with regard to soil and crop contamination are limited. In this study, accumulation of ametryn in wheat, maize, ryegrass and alfalfa crops along with ametryn residues in the soil planted with the plants were comparatively investigated. Soil enzyme activities and low molecular weight organic acids (LMWOAs), as well as antioxidant and degradation enzyme activities in plant tissues were measured. The maximum accumulation of ametryn was found in shoots and roots of wheat and alfalfa. Ryegrass had the maximum ametryn translocation factor (TF) from roots to shoots, with more than three times over the other crops. The ametryn residue in ryegrass-planted soil was much lower than that in soil planted with others. The residual content of ametryn in crop-planted soils was ordered as rhizosphere soilAssuntos
Herbicidas/metabolismo
, Lolium/metabolismo
, Medicago sativa/metabolismo
, Triazinas/metabolismo
, Triticum/metabolismo
, Zea mays/metabolismo
, Biodegradação Ambiental
, China
, Glutationa Transferase/metabolismo
, Raízes de Plantas/metabolismo
, Rizosfera
, Solo/química
, Microbiologia do Solo
, Poluentes do Solo/análise
RESUMO
Herein, we report an in-situ mild and metal-free protocol for thiomethylation of heteroarenes in high yields. The thiomethylation of various chloropurines, nucleosides, and chloroheteroarenes has been accomplished offering easy access to agrochemicals and synthetic molecules useful for drug discovery.
RESUMO
Agrochemicals such as pesticide residues become environmental contaminants due to their ecotoxic risks to plant, animal and human health. Ametryn (AME) is a widely used farmland pesticide and its residues are widespread in soils, surface stream and groundwater. However, its toxicological and degradative mechanisms in plants and food crops are largely unknown. This study comprehensively investigated AME toxicology and degradation mechanisms in a paddy crop. AME was freely absorbed by rice roots, translocated to the above-ground and thus repressed plant elongation, and reduced dry weight and chlorophyll concentration, but increased oxidative injury and subcellular electrolyte permeability. Analysis of the transcriptome and metabolome revealed that exposure to AME evoked global AME-responsive genes and step-wise catabolism of AME. We detected 995 (roots) and 136 (shoots) upregulated and differentially expressed genes (DEGs) in response to AME. Metabolomic profiling revealed that many basal metabolites such as carbohydrates, amino acids, glutathione, hormones and phenylpropanoids involved in AME catabolism were accordingly accumulated in rice. Eight metabolites and twelve conjugates of AME were characterized by HPLC-Q-TOF-HRMS/MS. These AME metabolites and conjugates are closely related to DEGs, differentially accumulated metabolites (DAMs) and activities of antioxidative enzymes. Collectively, our work highlights the specific mechanisms for AME degradative metabolism through Phase I and II reactive pathways (e.g. hydroxylation and dealkylation), with will help develop genetically engineered rice used to bioremediate AME-contaminated paddy soils and minimize AME accumulation rice crops.
Assuntos
Oryza , Transcriptoma , Humanos , Oryza/genética , Oryza/metabolismo , Metaboloma , Solo , Regulação da Expressão Gênica de PlantasRESUMO
Pesticide residues in food crops are one of the seriously environmental contaminants that risk food safety and human health. Understanding the mechanism for pesticide catabolism is critical to develop effective biotechniques for rapid eliminating the residues in food crops. In this study we characterized a novel ABC transporter family gene ABCG52 (PDR18) in regulating rice response to pesticide ametryn (AME) widely used in the farmland. Efficient biodegradation of AME was evaluated by measuring its biotoxicity, accumulation, and metabolites in rice plants. OsPDR18 was localized to the plasma membrane and strongly induced under AME exposure. Transgenic rice overexpressing OsPDR18 (OE) conferred rice resistance and detoxification to AME by increasing chlorophyll contents, improving growth phenotypes, and reducing AME accumulation in plants. The AME concentrations in OE plants were only 71.8-78.1% (shoots) and 75.0-83.3% (roots) of the wild type. Mutation of OsPDR18 by CRISPR/Cas9 protocol led to the compromised growth and enhanced AME accumulation in rice. Five AME metabolites for Phase I and 13 conjugates for Phase II reactions in rice were characterized by HPLC/Q-TOF-HRMS/MS. Relative content analysis revealed that the AME metabolic products in OE plants were significantly reduced compared with wild-type. Importantly, the OE plants accumulated less AME metabolites and conjugates in rice grains, suggesting that OsPDR18 expression may actively facilitate the transport of AME for catabolism. These data unveil a AME catabolic mechanism by which OsPDR18 contributes to the AME detoxification and degradation in rice crops.
Assuntos
Oryza , Resíduos de Praguicidas , Praguicidas , Humanos , Oryza/metabolismo , Subfamília G de Transportadores de Cassetes de Ligação de ATP/genética , Praguicidas/metabolismo , Resíduos de Praguicidas/metabolismo , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Raízes de Plantas/metabolismo , Regulação da Expressão Gênica de PlantasRESUMO
Thyroid hormones (TH) are essential for the metamorphosis of amphibians and their production can be influenced by environmental stressors, such as temperature fluctuations, and exposure to aquatic pollutants, such as herbicides. In the present study we evaluated the influence of different temperatures (25 and 32 °C) on the effects of the herbicide ametryn (AMT, 0 - control, 10, 50 and 200 ng.L-1) for 16 days on thyroidogenesis of bullfrog tadpoles. Higher temperature and AMT exposure caused a delay in the development of tadpoles, despite no differences were noted in weight gain and total length of the animals. Levels of triiodothyronine (T3) and thyroxine (T4) were not altered neither by AMT nor by temperature, but the highest temperature caused a decrease in total area and number of follicles in the thyroid gland. Transcript levels of thyroid hormone receptors alpha and beta (TRα and TRß) and iodothyronine deiodinase 3 (DIO3) were lower at 32 °C, which is consistent with developmental delay at the higher temperature. Tadpoles exposed to 200 ng.L-1 of AMT at 25 °C also presented delayed development, which was consistent with lower TRα and DIO3 transcript levels. Lower levels of estradiol were noted in tadpoles exposed to AMT at the higher temperature, being also possibly related to a developmental delay. This study demonstrates that higher temperature and AMT exposure impair thyroidgenesis in bullfrog tadpoles, disrupting metamorphosis.
Assuntos
Herbicidas , Animais , Rana catesbeiana , Larva , Herbicidas/toxicidade , Temperatura , Metamorfose BiológicaRESUMO
The excessive use of pesticides and the demand for environmentally friendly compounds have driven the focus to detailed studies of the environmental destination of these compounds. Degradation by hydrolysis of pesticides, when released into the soil, can result in the formation of metabolites with potentially adverse effects on the environment. Moving in this direction, we investigated the mechanism of acid hydrolysis of the herbicide ametryn (AMT) and predicted the toxicities of metabolites through experimental and theoretical approaches. The formation of ionized hydroxyatrazine (HA) occurs with the release of the SCH3- group and the addition of H3O+ to the triazine ring. The tautomerization reactions privileged the conversion of AMT into HA. Furthermore, the ionized HA is stabilized by an intramolecular reaction that provides the molecule in two tautomeric states. Experimentally, the hydrolysis of AMT was obtained under acidic conditions and at room temperature with HA as the main product. HA was isolated in a solid state through its crystallization as organic counterions. The mechanism of conversion of AMT to HA and the experimental investigation of the reaction kinetics allowed us to determine the dissociation of CH3SH as the rate-controlling step in the degradation process that culminates in a half-life between 7 and 24 months under typical acid soil conditions of the Brazilian Midwest - region with strong agricultural and livestock vocation. The keto and hydroxy metabolites showed substantial thermodynamic stability and a decrease in toxicity compared to AMT. We hope that this comprehensive study will support the understanding of the degradation of s-triazine-based pesticides.
Assuntos
Herbicidas , Triazinas , Hidrólise , Estrutura Molecular , Cinética , Triazinas/química , Herbicidas/toxicidade , SoloRESUMO
The production of sugarcane bioethanol generates large volumes of vinasse, an effluent whose final disposal can produce an environmental impact that is of concern. The long-term disposal of vinasse in sugarcane fields could challenge crop management, such as the performance of traditional herbicides, by changing soil properties. This study aimed to evaluate the effect of long-term vinasse application on the field and the dissipation of atrazine and ametryn herbicides in a subtropical sugarcane agroecosystem, and to discuss the potential processes involved in it. Vinasse affected soil properties by increasing pH (12%), electrical conductivity (160%), and soil organic carbon (25%) at 0-10 cm depth of soil. Differences in the herbicide calculated sorption coefficient (Kd) varied according to the pedotransfer function applied and the herbicide type (atrazine or ametryn). During the first seven days after herbicide application, the soil underwent long-term vinasse application and increased atrazine and ametryn dissipation 45% and 33%, respectively, compared with the conventional fertilization scheme (control). The Pesticide Root Zone Model revealed that dissipation was mediated mainly by the degradation process rather than transport or other processes. The long-term application of vinasse in a typical sugarcane field of Tucumán, Argentina decreased the potential groundwater pollution of triazines and, adversely, reduced their bioavailability for weed control. For this, the present study presents original information about how long-term treatment with vinasse may require an adaptation of conventional management practices such as the application of herbicides in Argentina and other sugarcane-producing regions. Integr Environ Assess Manag 2023;00:1-12. © 2023 SETAC.
RESUMO
Ametryn (AME) is a triazine herbicide which is mainly used to kill unwanted herbs in crops. Despite its importance in agriculture, the usage of AME also poses a risk to humans and the ecosystem due to its toxicity. Hence, it is important to develop a method for the effective removal of AME from various water sources which is in the form of molecular imprinting polymer (MIP). In this study, MIP of AME was synthesized via precipitation polymerization using AME as the template molecule with three different functional monomers including methacrylic acid (MAA), acrylamide (AAm) and 2-vinylpyridine (2VP). The three different synthesized polymers namely MIP (MAA), MIP (AAm) and MIP (2VP) were characterized using Fourier Infra-red spectroscopy (FTIR) and Field Emission Electron Microscopy (FESEM). Then, the batch binding study was carried out using all three MIPs in which MIP (MAA) attained the highest rebinding efficiency (93.73%) among the synthesized polymers. The Energy-Dispersive X-ray spectroscopy (EDX) analysis, Brunauer-Emmett-Teller (BET) analysis and thermogravimetric analysis (TGA) were also conducted on the selected MIP (MAA). Adsorption studies including initial concentration, pH and polymer dosage were also conducted on MIP (MAA). In this study, the highest adsorption efficiency was attained at the optimum condition of 6 ppm of AME solution at pH 7 with 0.1 g of MIP (MAA). MIP (MAA) was successfully applied to remove AME from spiked distilled water, tap water and river water samples with removal efficiencies of 95.01%, 90.24% and 88.37%, respectively.
RESUMO
In marine aquaculture areas, herbicides have been used to inhibit the wild growth of seaweed, which may seriously affect the ecological environment and food safety. Here the commonly applied ametryn was used as the representative pollutant, and solar enhanced bio-electro-Fenton driven in situ by sediment microbial fuel cell (SMFC) was proposed to degrade ametryn in simulated seawater. SMFC with γ-FeOOH-coated carbon felt cathode was operated under the simulated solar light (γ-FeOOH-SMFC), where two-electron oxygen reduction and activation of H2O2 occurred to promote the production of hydroxyl radicals at the cathode. Hydroxyl radicals, photo-generated holes, and anodic microorganism worked together to degrade ametryn with an initial concentration of 2 mg/L in the self-driven system. The removal efficiency of ametryn in γ-FeOOH-SMFC was 98.7 % during the operation period of 49 days, which was 6 times higher than that under natural degradation condition. When γ-FeOOH-SMFC was in the steady phase, oxidative species were continuously and efficiently generated. The maximum power density (Pmax) of γ-FeOOH-SMFC was 44.6 W/m3. According to the intermediate products of ametryn degradation in γ-FeOOH-SMFC, four possible pathways of ametryn degradation were proposed. This study provides an effective, cost-saving, and in situ treatment for refractory organics in seawater.
Assuntos
Fontes de Energia Bioelétrica , Peróxido de Hidrogênio , Aquicultura , Radical Hidroxila , Água do MarRESUMO
In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HOâ), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23 ± 0.07) × 10-2 and (7.99 ± 1.61) × 10-3 mol Einstein-1, respectively. In contrast, reactions with HOâ radicals and 3CDOM* dominate their degradation, with 1O2 exhibiting rates three to five orders of magnitude lower. The values of kIMD,HOâ and kAMT,HOâ were (3.51 ± 0.06) × 109 and (4.97 ± 0.37) × 109 L mol-1 s-1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with kIMD,3AQ2S* = (1.02 ± 0.08) × 109 L mol-1 s-1 and kIMD,3CBBP* = (3.17 ± 0.14) × 108 L mol-1 s-1; on the contrary, the values found for AMT are close, kAMT,3AQ2S* = (8.13 ± 0.35) × 108 L mol-1 s-1 and kAMT,3CBBP* = (7.75 ± 0.80) × 108 L mol-1 s-1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO3-, NO2-, CO32-, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.
Assuntos
Praguicidas , Poluentes Químicos da Água , Brasil , Neonicotinoides , Nitrocompostos , Fotólise , Rios , Triazinas , Água , Poluentes Químicos da Água/análiseRESUMO
The S-triazine herbicide ametryn (AMT) is relatively low adsorbed in soils and has high solubility in water, thus believed to affect non-target aquatic organisms such as amphibians. Temperature increases can intensify the effects of herbicides, possibly increasing the susceptibility of amphibians to these compounds. The aim of this study was to evaluate the influence of temperature (25 and 32 °C) on the responses of biochemical biomarkers in bullfrog tadpoles (Lithobates catesbeianus) exposed to different concentrations of AMT (0, 10, 50 and 200 ng.L-1) for a period of 16 days. The antioxidant enzymes catalase (CAT) and superoxide dismutase (SOD) and the biotransformation enzyme glutathione S-transferase (GST) had their activity decreased at the highest temperature (32 °C). SOD activity was reduced at 200 ng.L-1 and 32 °C compared to the control at the same temperature. AMT exposure also decreased the activities of alanine aminotransferase and gamma glutamyl transferase. On the other hand, the activities of acetylcholinesterase, carboxylesterase, alkaline phosphatase, levels of lipid peroxidation and protein carbonyl, as well genotoxic markers (micronucleus and nuclear abnormalities frequencies) were unchanged. The evaluation of integrated biomarker response index (IBR) indicated highest variations at the concentration of 200 ng.L-1 at 32 °C, suggesting that the combination of high AMT concentrations and temperatures generate more pronounced negative effects to tadpoles.
Assuntos
Herbicidas , Poluentes Químicos da Água , Acetilcolinesterase/metabolismo , Alanina Transaminase/metabolismo , Fosfatase Alcalina/metabolismo , Animais , Antioxidantes/metabolismo , Biomarcadores/metabolismo , Catalase/metabolismo , Glutationa Transferase/metabolismo , Herbicidas/metabolismo , Larva , Rana catesbeiana/metabolismo , Solo , Superóxido Dismutase/metabolismo , Temperatura , Triazinas/metabolismo , Água/metabolismo , Poluentes Químicos da Água/metabolismoRESUMO
Ametryn (AMT), one of the most widely used herbicides in agriculture, has been frequently detected as a micropollutant in many aquatic environments. AMT residue not only pollutes water but also acts as a precursor for the production of disinfection by-products (DBPs). This study systematically investigated the fate of AMT during the UV/chlorine process. It was observed that the combination of UV irradiation and chlorination degraded AMT synergistically. The results of the radical quenching experiments suggested that AMT degradation by the UV/chlorine process involved the participation of UV photolysis, hydroxyl radical (OH) reactions, and reactive chlorine species (RCS) reactions, which accounted for 45.4%, 36.4%, and 14.5% of the degradation, respectively. Moreover, we found that Cl- 2 was an important reactive radical for AMT degradation. The chlorine dose, pH, coexisting anions (Cl- and HCO3-), and natural organic matter (NOM) were found to affect AMT degradation during the UV/chlorine process. Nineteen predominant intermediates/products of AMT degradation during UV/chlorine process were identified, including atrazine. Moreover, the corresponding transformation pathways were proposed, including electron transfer, bond cleavage (C-S, C-N), radical (OH, Cl and Cl- 2) reactions, and subsequent hydroxylation. The toxicity tests with Vibrio fischeri on AMT degradation suggested that more DBPs were generated by UV/chlorine-treated AMT, which possessed higher acute toxicity than AMT did. Although the UV/chlorine process evidently promoted the AMT degradation, optimization of process parameters may reduce the DBP production and merits further investigation.
Assuntos
Herbicidas/toxicidade , Triazinas/toxicidade , Poluentes Químicos da Água/toxicidade , Purificação da Água/métodos , Aliivibrio fischeri , Cloro/química , Desinfecção/métodos , Halogenação , Radical Hidroxila/química , Cinética , Fotólise , Raios Ultravioleta , Água , Poluentes Químicos da Água/análiseRESUMO
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.
Assuntos
Animais , Artrópodes , Poluentes Químicos da Água/toxicidade , Hemípteros , Herbicidas/toxicidade , Ecotoxicologia , GenitáliaRESUMO
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.