Prenatal Exposure to Herbicide 2,4-Dichlorophenoxyacetic Acid (2,4D) Exacerbates Zika Virus Neurotoxicity In Vitro and In Vivo.

Zika virus (ZIKV) infection during pregnancy can lead to a set of congenital malformations known as Congenital ZIKV syndrome (CZS), whose main feature is microcephaly. The geographic distribution of CZS in Brazil during the 2015-2017 outbreak was asymmetrical, with a higher prevalence in the Northeast and Central-West regions of the country, despite the ubiquitous distribution of the vector Aedes aegypti, indicating that environmental factors could influence ZIKV vertical transmission and/or severity. Here we investigate the involvement of the most used agrochemicals in Brazil with CZS. First, we exposed human neuroblastoma SK-N-AS cells to the 15 frequently used agrochemical molecules or derivative metabolites able to cross the blood-brain barrier. We found that a derived metabolite from a widely used herbicide in the Central-West region, 2,4-dichlorophenoxyacetic acid (2,4D), exacerbates ZIKV neurotoxic effects in vitro. We validate this observation by demonstrating vertical transmission leading to microcephaly in the offspring of immunocompetent C57BL/6J mice exposed to water contaminated with 0.025 mg/L of 2,4D. Newborn mice whose dams were exposed to 2,4D and infected with ZIKV presented a smaller brain area and cortical plate size compared to the control. Also, embryos from animals facing the co-insult of ZIKV and 2,4D exposition presented higher Caspase 3 positive cells in the cortex, fewer CTIP2+ neurons and proliferative cells at the ventricular zone, and a higher viral load. This phenotype is followed by placental alterations, such as vessel congestion, and apoptosis in the labyrinth and decidua. We also observed a mild spatial correlation between CZS prevalence and 2,4D use in Brazil's North and Central-West regions, with R2 = 0.4 and 0.46, respectively. Our results suggest that 2,4D exposition facilitates maternal vertical transmission of ZIKV, exacerbating CZS, possibly contributing to the high prevalence of this syndrome in Brazil's Central-West region compared to other regions.

Magnetic graphene derivates for efficient herbicide removal from aqueous solution through adsorption.

2,4-Dichlorophenoxyacetic acid (2,4-D) is an herbicide and is among the most widely distributed pollutant in the environment and wastewater. Herein is presented a complete comparison of adsorption performance between two different magnetic carbon nanomaterials: graphene oxide (GO) and its reduced form (rGO). Magnetic functionalization was performed employing a coprecipitation method, using only one source of Fe2+, requiring low energy, and potentially allowing the control of the amount of incorporated magnetite. For the first time in literature, a green reduction approach for GO with and without Fe3O4, maintaining the magnetic behavior after the reaction, and an adsorption performance comparison between both carbon nanomaterials are demonstrated. The nanoadsorbents were characterized by FTIR, XRD, Raman, VSM, XPS, and SEM analyses, which demonstrates the successful synthesis of graphene derivate, with different amounts of incorporate magnetite, resulting in distinct magnetization values. The reduction was confirmed by XPS and FTIR techniques. The type of adsorbent reveals that the amount of magnetite on nanomaterial surfaces has significant influence on adsorption capacity and removal efficiency. The procedure demonstrated that the best performance, for magnetic nanocomposites, was obtained by GO∙Fe3O4 1:1 and rGO∙Fe3O4 1:1, presenting values of removal percentage of 70.49 and 91.19%, respectively. The highest adsorption capacity was reached at pH 2.0 for GO∙Fe3O4 1:1 (69.98 mg g-1) and rGO∙Fe3O4 1:1 (89.27 mg g-1), through different interactions: π-π, cation-π, and hydrogen bonds. The adsorption phenomenon exhibited a high dependence on pH, initial concentration of adsorbate, and coexisting ions. Sips and PSO models demonstrate the best adjustment for experimental data, suggesting a heterogeneous surface and different energy sites, respectively. The thermodynamic parameters showed that the process was spontaneous and exothermic. Finally, the nanoadsorbents demonstrated a high efficiency in 2,4-D adsorption even after five adsorption/desorption cycles.

Herbicides in the initial growth and chlorophyll indices of sugarcane in pre-sprouted seedlings.

The aim of the present study was to assess the selectivity of herbicides applied in the pre and post-planting of pre-sprouted seedlings (PSS). The experiment was conducted in a greenhouse, using a completely randomized design, with nine treatments and four repetitions. The IACSP95-5000 cultivar was used. The treatments consisted of herbicides applied in five doses as follows: in pre-planting: sulfentrazone, diclosulam, imazapic, and imazapyr, in post-planting: ethoxysulfuron, halosulfuron, 2,4-D and MSMA, and a control treatment without herbicide. Injury symptoms were assessed at 7, 15, 30, 45, 60, 75, and 90 days after application (DAA), height, diameter, number of tillers, chlorophyll A, B, and total chlorophyll at 30, 60, and 90 DAA, leaf area, shoot and root dry mass at 90 DAA. The post-emergent herbicides were considered selective. Pre-planting herbicides reduced the variables assessed at 90 DAA, observed by linear regression for diclosulam and imazapic, and exponential regression for imazapyr. Treatments with sulfentrazone caused few injury symptoms, with subsequent recovery. In addition, all the variables analyzed were equal to control, with the sulfentrazone considered selective for the IACSP95-5000 cultivar.

Prenatal current-use pesticide exposure and children's neurodevelopment at one year of age in the Infants' Environmental Health (ISA) birth cohort, Costa Rica.

BACKGROUND: Pesticide exposure may affect young children's neurodevelopment, but only few cohort studies have addressed possible effects of non-organophosphate pesticides. OBJECTIVE: We evaluated associations between prenatal current-use pesticide exposure and neurodevelopmental outcomes among 1-year-old children from the Infants' Environmental Health (ISA) birth cohort. METHODS: To determine prenatal pesticide exposure, we measured biomarkers of pyrimethanil, chlorpyrifos, synthetic pyrethroids, and 2,4-D in urine samples among 355 women, 1-3 times during pregnancy. One-year post-partum, we evaluated children's neurodevelopment with the Bayley Scales of Infant and Toddler Development 3rd edition (BSID-III). We assessed associations between exposures and neurodevelopmental outcomes (composite and z-scores) using single-chemical linear regression models adjusted for possible confounders (maternal education, parity, sex, gestational age at birth, child age, HOME-score, location of assessment, biomarkers of mancozeb), and studied effect-modification by sex. We evaluated non-linear associations of multiple pesticide exposures with Bayesian kernel machine regression (BKMR). RESULTS: We found higher prenatal urinary 2,4-D concentrations were associated with lower language (ßper ten-fold increase = -2.0, 95 % confidence interval (CI) = -3.5, -0.5) and motor (ßper ten-fold increase = -2.2, 95 %CI = -4.2, -0.1) composite scores among all children. Also, higher chlorpyrifos exposure [measured as urinary 3,5,6-trichloro-2-pyridinol (TCPy)] was associated with lower cognitive composite scores (ßper ten-fold increase = -1.9, 95 %CI = -4.7, 0.8), and lower motor composite scores among boys (ßper ten-fold increase = -3.8, 95 % CI = -7.7, 0.1) but not girls (ßper ten-fold increase = 2.3, 95 %CI = -1.6, 6.3, pINT = 0.11). Finally, higher pyrimethanil was associated with lower language abilities among girls, but not boys. Pyrethroid metabolite concentrations did not explain variability in BSID-III composite scores. Associations were similar for BSID-III z-scores, and we found no evidence for non-linear associations or mixture effects. DISCUSSION: Prenatal exposure to common-use pesticides may affect children's neurodevelopment at 1-year of age, some effects may be sex-specific.

A mixture of glyphosate and 2,4-D herbicides enhances the deleterious reproductive outcomes induced by Western diet in obese male mice.

The consumption of Western diet (WD) - enriched in fats and sugars - is associated with overweight, obesity and male reproductive disorders. In addition to WD intake, crops and dairy products display residues of herbicides, including glyphosate and 2,4-D that are widely applied worldwide. The concomitant exposure to WD and herbicides - mimicking contemporary scenarios - is not fully investigated. Thus, we evaluated the effects of glyphosate and 2,4-D, alone or in mixture, on WD-induced alterations in the male genital system. Male C57BL6J mice were submitted to WD (chow containing 20% lard, 0.2% cholesterol, 20% sucrose, and high sugar solution with 23.1 and 18.9 g/L of D-fructose and D-glucose) for 6 months. Concomitantly to WD, the animals received glyphosate (0.05, 5, or 50 mg/kg/day), 2,4-D (0.02, 2 or 20 mg/kg/day) or their mixture (0, 05 + 0.02, 5 + 2, or 50 + 20 mg/kg/day) by intragastrical administration (5×/week). Doses were based on Acceptable Daily Intake (ADIs) or No Observed Adverse Effect Level (NOAEL) values. Herbicide exposure did not alter the WD-induced obesity, hypercholesterolemia and hyperglycemia. WD induced sperm cell abnormalities, reduced the number, volume and area of Leydig cells, enhanced the frequency of epididymal abnormalities, decreased the proliferation in both germinal and epididymal epithelia, and reduced the number of androgen receptor (AR) positive epididymal cells. Remarkably, the herbicide mixtures promoted such WD-induced effects: increased the frequency of sperm cell and epididymal abnormalities (absence of sperm, cytoplasmic vacuoles, and clear cell hypertrophy) (5 + 2 and 50 + 20 doses); decreased Leydig cell nuclei volume and area (5 + 2 and 50 + 20 doses), reduced epididymal cell proliferation (all mixtures), and AR expression (50 + 20 dose). In addition, herbicide mixtures reduced serum testosterone levels (5 + 2 and 50 + 20 doses). Our findings indicate that the mixture of glyphosate and 2,4-D herbicides, mimicking environmentally relevant scenarios, promotes WD-induced changes in the male genital system.

Phytotoxicity and cytogenotoxicity of pesticide mixtures: analysis of the effects of environmentally relevant concentrations on the aquatic environment.

In this study, we investigate the toxicity of commercial formulations based on glyphosate, 2,4-D, imidacloprid, and iprodione, in isolation and mixed, on Allium cepa. The mixtures consisted of combinations in the lowest (M1), intermediate (M2), and highest concentrations (M3) of each pesticide. We measured physiological (germination rate, germination speed, and radicular length) and cyto-genotoxic (mitotic index and frequency of aberrant cells) parameters. In addition, we analyzed the cell cycle progression and cell death induction by flow cytometry. When applied in isolation, the pesticides changed the parameters evaluated. M1 and M2 inhibited root length and increased the frequency of aberrant cells. Their genotoxic effect was equivalent to that of pesticides applied in isolation. Furthermore, M1 and M2 caused cell death and M2 changed the cell cycle progression. M3 had the greatest deleterious effect on A. cepa. This mixture inhibited root length and promoted an additive or synergistic effect on the mitotic index. In addition, M3 changed all parameters analyzed by flow cytometry. This research clearly demonstrates that the pesticides tested, and their mixtures, may pose a risk to non-target organisms.

Carbonaceous adsorbent as green silica by-product applied to the treatment of contaminated effluent by pesticide commonly sprayed on rice cultivation.

Grain cultivation and its impacts on the environment have been the focus of many studies, especially due to generated solid waste and the wide use of agrochemicals aiming for greater productivity. In this context, the present study proposes a new and consistent step in constructing self-sustainability in rice farming. The proposed stage includes reusing green silica waste as an adsorbent to treat effluents contaminated by pesticides directly applied to rice cultivation. After nano silica production through the rice husks burning, followed by basic leaching and acid precipitation, a carbonaceous material remains. This material, naturally impregnated by Na2SiO3, was washed and dried, characterized, and used to remove the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D). The adsorption essays were performed at 2,4-D at low concentrations (between 1 and 10 mg L-1) at different temperatures. The washed and dried porous carbon (WDPC) surface is irregular and presents slit-shaped channels. The FT-IR analysis identified the siloxane, carbonyl, carboxylate, and methylene functional groups available to interact with the pesticide molecules. The washing/drying process eliminated impurities, improving the surface area from 539.67 to 619.67 cm2 g-1 and pore volume from 0.29 to 0.44 cm3 g-1. Concerning the adsorption of 2,4-D on WDPC, the best pH was 6.0, where around 75% of the pesticide was removed from the water. The equilibrium isotherms presented an S-shaped form indicating a multilayer and cooperative adsorption, with maximum adsorption capacities of 7.504 and 7.736 mg g-1. The estimated ∆Gads, ΔHads, and ΔSads values suggested that pesticide adsorption was spontaneous, exothermic, and favorable. Finally, WDPC demonstrated a good potential to uptake 2,4-D from water, contributing to self-sustainability in rice farming.

Herbicides reduce the severity and sporulation of Phakopsora pachyrhizi in soybean with triple herbicide resistance.

BACKGROUND: Transgenic event DAS44406-6 (E3) makes soybeans that are herbicide [glyphosate (Gly), 2,4-dichlorophenoxyacetic acid (2,4-D) and glufosinate] and caterpillar resistant. The E3 soybean was commercially released for the 2021/2022 harvest in Brazil. We conducted this study to test whether Gly and 2,4-D applied alone and in a commercial mixture affect Asian soybean rust (ASR). Assays were conducted in detached leaves and in vivo, in a controlled environment using the herbicides Gly, 2,4-D and Gly + 2,4-D, and pathogen inoculation. Disease severity and spore production were evaluated. RESULTS: Only the herbicides Gly and Gly + 2,4-D inhibited ASR in detached leaves and in vivo. When applied preventively and curatively in vivo, these herbicides reduced the disease severity and spore production of the fungus. In vivo, inhibition of disease severity reached 87% for Gly + 2,4-D and 42% for Gly. A synergistic effect was observed with the commercial Gly + 2,4-D mixture. Application of 2,4-D alone in the in vivo assays did not reduce or increase disease severity. Gly and Gly + 2,4-D act residually in inhibiting the disease. Growing E3 soybeans may combine weed and caterpillar management benefits with ASR inhibition. CONCLUSION: Application of Gly and Gly + 2,4-D herbicides in resistant E3 soybean shows inhibitory activity for ASR. © 2023 Society of Chemical Industry.

Using mesocosms to evaluate the impacts of pasture intensification and pasture-sugarcane conversion on tadpoles in Brazil.

This study evaluated the effects of environmental contamination caused by pasture intensification and pasture-sugarcane conversion on oxidative stress, biotransformation, esterase enzymes, and development of Scinax fuscovarious and Physalaemus nattereri. Tadpoles were exposed in mesocosms allocated in three treatments: (1) untreated extensive pasture (EP); (2) intensive-pasture conversion (IP) (2,4-D herbicide + fertilizers); and (3) pasture-sugarcane conversion (SC) (fipronil + 2,4-D + fertilizers). After 7 days of exposure, IP reduced catalase (CAT) and increased malondialdehyde (MDA) levels in P. nattereri, while this treatment decreased glucose-6-phosphate dehydrogenase (G6PDH) and CAT activities in S. fuscovarious. SC decreased CAT, G6PDH, and glutathione S-transferase (GST) activities in P. nattereri. In S. fuscovarius, SC reduced G6PDH, acetylcholinesterase (AChE), and carboxylesterase (CbE) activities. MDA was raised in both tadpole species exposed to SC, evidencing oxidative stress. Integrated biomarker responses showed higher scores in both species exposed to SC. Our results warn that management practices currently applied to sugarcane cultivation in Brazil can negatively impact the functional responses of amphibians at natural systems.

Persistent and transgenerational effects of pesticide residues in zebrafish.

Highly toxic chemical compounds are present in rivers and lakes, endangering the survival of non-target species. To evaluate the effects of environmental contamination on non-target species, we used the zebrafish as an animal model. Environmental concentrations of the widely used pesticides, glyphosate (GBH) at 4.8 µg·L-1 and 2,4-dichlorophenoxyacetic acid (DBH) at 3.4 µg·L-1, were used. The animals were exposed during the entire period of organogenesis and evaluated in our previous study regarding initial developmental parameters. In the present study, we evaluate these fish when achieve the adult phase, using the novel tank test (NTT) and the aversivity test. In the second step, the animals were allowed to reproduce, and the initial parameters of development, behavioral parameters in the open field test (OFT) and in the aversivity test (AST), and biochemical biomarkers as acetylcholinesterase (AChE), catalase (CAT), and superoxide dismutase (SOD) in the F1 generation were studied. Fish exposed to GBH showed hypermobility, and their anti-predatory reaction was impaired during adulthood, indicating a persistent effect. We also showed that fish had impaired behavioral and survival changes in the F1 generation as well as effects on AChE activity and antioxidant enzymes, characterizing a transgenerational effect. The fish did not show persistent effects in adulthood due to DBH exposure; however, they were unable to reproduce. Our findings demonstrate the serious impact of pesticides on fish, where the effects of contamination can affect future generations and compromise the species' survival.

An eco-friendly and sustainable support of agave-fibers functionalized with graphene/TiO2:SnO2 for the photocatalytic degradation of the 2,4-D herbicide from the drinking water.

In this research, we evaluated the photocatalytic performance of biodegradable composites for the removal of the 2,4-Dichlorophenoxyacetic acid (2,4-D) herbicide. The composite was composed by agave fibers (AgF), graphene-microplates (GM) and titanium dioxide TiO2/SnO2 (TSn) nanoparticles (NPs) and was named TSn + AgF/GM. Both, the TSn NPs and the GM were deposited on the AgF using the Dip-coating method. According to the analysis by X-Ray Diffraction (XRD), the crystalline phase for the TiO2 and SnO2 was anatase and tetragonal-rutile, respectively. The Scanning Electron Microscopy (SEM) images demonstrated that the AgF were completely saturated by the GM (which had average dimensions of 15 µm × 22 µm) and by conglomerations of TSn NPs with average size of 642 nm. The TSn NPs and the TSn + AgF/GM composite were evaluated for the photocatalytic degradation of the 2,4-D herbicide under ultraviolet-visible (UV-Vis) light and found a maximum degradation of 98.4 and 93.7% (after 4 h) for the TSn NPs and the TSn + AgF/GM composite, respectively. Reuse cycles were also performed and the degradation percentage decreased by 13.1% and by 7.8% (after 3 cycles of reuse) when the TSn NPs and the TSn + AgF/GM composite are employed, respectively. Scavenger experiments were also carried out and found that the oxidizing agents are mainly produced in the order of: •OH>•O2- > h+; then, the main oxidizing agents generated during the photocatalytic reaction were the hydroxyl radicals. Thus, the photocatalytic system studied in this work for the degradation of 2,4-D could pave the way for the development of new eco-friendly/floatable photocatalysts, which can be applied in wastewater-treatment plants.

Removing 2,4-D micropollutant herbicide using powdered activated carbons: the influence of different aqueous systems on adsorption process.

The presence of microcontaminants in the water supply system offers adverse impacts. This study analyzed the performance of two powdered activated carbons (PAC1 and PAC2) in the removal of 2,4-D herbicide in ultrapure water (UW) and natural water (NW) to verify the influence of natural organic matter (NOM) on the adsorptive process. The properties of PAC1 and PAC2 were analyzed by textural analysis, FTIR, TG, pH, XDR, NMR. The specific surface area of PAC2 was lower than PAC1 and PAC2 showed better adsorption capacity in UW (37.04 mg.g-1) and in NW (8.06 mg.g-1). The results of experiments performed in natural water showed that both activated carbons had reduced 2,4-D adsorption capacity in the presence of NOM, since it may compete for the same adsorption sites or block the access of the 2,4-D molecule to the pores of the activated carbon. PAC2 showed a higher mesopores percentage, decreasing the effects caused by NOM in 2,4-D adsorption. The use of activated carbons with varying pore sizes for the removal of microcontaminants is recommended, especially in NW. This result contributes to the choice of the adsorbent type to be applied in water treatment plants.

The Genome Sequence of Brucella intermedia DF13, a 2,4-Dichlorophenoxyacetic Acid-Degrading Soil Bacterium Isolated in Brazil.

Brucella intermedia/Ochrobactrum intermedium strain DF13 was isolated from Brazilian soil and is able to degrade 2,4-dichlorophenoxyacetic acid (2,4-D). Here, we report on its genome sequence, with 4,570,268 bp and a 57.8% G+C content.

Synergistic effects of glyphosate- and 2,4-D-based pesticides mixtures on Rhinella arenarum larvae.

Glyphosate and 2,4-D are two herbicides commonly used together. Since there is little information about the interactions between these pesticides, the aim of this study was to evaluate the single and joint lethal toxicity of the glyphosate-based herbicide (GBH) ATANOR® (43.8% of glyphosate, isopropylamine salt) and the 2,4-D-based herbicide (2,4-DBH) Así Max 50® (602000 mg/L of 2,4-D) on Rhinella arenarum larvae. Equitoxic and non-equitoxic mixtures were prepared according to the recommendation for their combination and analyzed with a fixed ratio design at different exposure times and levels of lethality (LC10, LC50, and LC90). GBH (504h-LC50=38.67 mg ae/L) was significantly more toxic than 2,4-DBH (504h-LC50=250.31 mg ae/L) and their toxicity was time-dependent. At 48h, the equitoxic mixture toxicity was additive and from the 96h was antagonistic at LC10 and LC50 effect level. The non-equitoxic mixture toxicity was additive at LC10 effect level from the 48h to the 168h, and synergistic from the 240h. At LC50 and LC90 effect level, the mixture interaction resulted synergistic for all exposure times. This is the first study to report the synergistic interactions between GBH and 2,4-DBH on amphibians, alerting about its negative impact on aquatic ecosystems.

Riparian strips as attenuation zones for the toxicity of pesticides in agricultural surface runoff: Relative influence of herbaceous vegetation and terrain slope on toxicity attenuation of 2,4-D.

Pesticides reach aquatic ecosystems via surface runoff becoming one of the main contributors to their deterioration. Among the strategies to mitigate these impacts, the use of riparian strips is recommended, but the knowledge of how much each ecosystemic variable contributes to the process is still incipient. We analyzed the influence of terrain slope and vegetation in the attenuation of 2,4-Dichlorophenoxyacetic acid (2,4-D) toxicity in surface runoff using Lactuca sativa as a diagnostic organism. In addition, the differential effects of this herbicide were examined under laboratory conditions, with standardized water and ambient water as a dilution medium. The study was conducted in plots with different terrain slopes and presence/absence of vegetation. The herbicide was applied to each plot and rain was subsequently simulated. The runoff was collected at regular distances and the toxicity was measured. The runoff toxicity decreased with the distance from the application area in all plots, this reduction being greater in low-slope plots. No differences in attenuation of runoff toxicity were found between plots with and without vegetation. The data were incorporated into models to estimate the minimum widths of safety to reduce the toxicity of 2,4-D by 90% under these conditions, suggesting distances of 5 and 20 m for low-slope and high-slope zones, respectively. In laboratory experiments, lower relative toxicity of 2,4-D was detected when natural water was used as solvent. These results contribute to the design of sustainable agricultural practices.

One step acid modification of the residual bark from Campomanesia guazumifolia using H2SO4 and application in the removal of 2,4-dichlorophenoxyacetic from aqueous solution.

The residual bark of the tree species Campomanesia guazumifolia was successfully modified with H2SO4 and applied to remove the toxic herbicide 2.4-dichlorophenoxyacetic (2.4-D) from aqueous solutions. The characterization techniques made it possible to observe that the material maintained its amorphous structure; however, a new FTIR band emerged, indicating the interaction of the lignocellulosic matrix with sulfuric acid. Micrographs showed that the material maintained its irregular shape; however, new spaces and cavities appeared after the acidic modification. Regardless of the herbicide concentration, the system tended to equilibrium after 120 min. Using the best statistical coefficients, the Elovich model was the one that best fitted the kinetic data. The temperature increase in the system negatively influenced the adsorption of 2.4-D, reaching a maximum capacity of 312.81 mg g-1 at 298 K. The equilibrium curves showed a better fit to the Tóth model. Thermodynamic parameters confirmed the exothermic nature of the system (ΔH0 = -59.86 kJ mol-1). As a residue obtained from urban pruning, the bark of Campomanesia guazumifolia treated with sulfuric acid is a promising and highly efficient alternative for removing the widely used and toxic 2.4-D herbicide from aqueous solutions.

Insights into the Role of Transcriptional Gene Silencing in Response to Herbicide-Treatments in Arabidopsis thaliana.

Herbicide resistance is broadly recognized as the adaptive evolution of weed populations to the intense selection pressure imposed by the herbicide applications. Here, we tested whether transcriptional gene silencing (TGS) and RNA-directed DNA Methylation (RdDM) pathways modulate resistance to commonly applied herbicides. Using Arabidopsis thaliana wild-type plants exposed to sublethal doses of glyphosate, imazethapyr, and 2,4-D, we found a partial loss of TGS and increased susceptibility to herbicides in six out of 11 tested TGS/RdDM mutants. Mutation in REPRESSOR OF SILENCING 1 (ROS1), that plays an important role in DNA demethylation, leading to strongly increased susceptibility to all applied herbicides, and imazethapyr in particular. Transcriptomic analysis of the imazethapyr-treated wild type and ros1 plants revealed a relation of the herbicide upregulated genes to chemical stimulus, secondary metabolism, stress condition, flavonoid biosynthesis, and epigenetic processes. Hypersensitivity to imazethapyr of the flavonoid biosynthesis component TRANSPARENT TESTA 4 (TT4) mutant plants strongly suggests that ROS1-dependent accumulation of flavonoids is an important mechanism for herbicide stress response in A. thaliana. In summary, our study shows that herbicide treatment affects transcriptional gene silencing pathways and that misregulation of these pathways makes Arabidopsis plants more sensitive to herbicide treatment.

Three-bestseller pesticides in Brazil: Freshwater concentrations and potential environmental risks.

Agricultural production in Brazil is favored by weather conditions and by the large amount of available land. Therefore, currently, Brazil is the second largest exporter of agricultural products globally. Pesticides are widely used in Brazilian crops due to their high efficiency, their low cost, and permissive legislation. However, pesticides tend to reach water resources threatening organisms and the water quality. Thereby, we aimed to review the surface freshwater concentrations of the three-bestseller pesticides in Brazil (glyphosate, 2,4D, and atrazine), and discuss the results with sales, legislation, toxicity and potential risks. For that, we performed a systematic review of quantitative studies of glyphosate, atrazine, and 2,4D in Brazilian freshwater and included monitoring data provided by the Brazilian Ministry of Health in our analysis. Finally, we calculated the risk assessment for the three pesticides. Only a few scientific studies reported concentrations of either of the three-bestseller pesticides in Brazilian freshwaters. Between 2009 and 2018, an increase in the sales of 2,4D, atrazine, and glyphosate was observed. It was not possible to evaluate the relation between concentrations and sales, due to limited number of studies, lack of standard criteria for sampling, individual environmental properties, and type of pesticide. Atrazine showed a higher toxicity compared to 2,4D and glyphosate. Regarding the environmental risks, 65%, 72%, and 94% of the Brazilian states had a medium to high risk to 2,4D, atrazine, and glyphosate, respectively. Finally, 80% of the Brazilian states evaluated showed a high environmental risk considering a mixture of the three pesticides. Although most of the environmental concentrations registered were below the allowed limits according to the Brazilian legislation, they are already enough to pose a high risk for the aquatic ecosystems. We, therefore, strongly recommend a revaluation of the maximum allowed values in the national surface freshwater Brazilian legislation.

Adsorption investigation of 2,4-D herbicide on acid-treated peanut (Arachis hypogaea) skins.

In this work, peanut (Arachis hypogaea) skin, a by-product generated by the agricultural production of its seeds, was employed as a precursor in the preparation of an adsorbent for the 2,4-D removal in water. The skins were treated with sulfuric acid and characterized by different techniques. The adsorption was favored at acid pH = 2 with pHpzc = 6. The dosage of 0.9 g L-1 was considered ideal, obtaining satisfactory indications of removal and capacity. The kinetic curves were well represented by the general order model, with the equilibrium reached quickly in the first 30 min for all concentrations. Adsorption isotherm studies showed that the increase in temperature negatively affected the herbicide adsorption, obtaining a maximum capacity of 246.72 mg g-1, by the Langmuir isotherm at 298 K. The remarkable adsorption efficiency presented by the adsorbent can be associated with the presence of new functional groups on the adsorbent surface generated after the acid treatment. Thermodynamic parameters confirmed the exothermic nature of the adsorptive system. In the treatment of synthetic wastewater consisting of a mixture of herbicides and salts, a high removal efficiency (72%) of herbicides was obtained. Therefore, the development of an adsorbent derived from peanut (Arachis hypogaea) skin treated with sulfuric acid is an excellent alternative, generating remarkable removal results towards 2,4-D herbicide.

Importance of sequential herbicide application in the control of Elephantopus mollis / A importância da aplicação sequencial no controle de Elephantopus mollis

Popularmente conhecida como pata de elefante ou sussuaiá, Elephantopus mollis, é uma espécie que recentemente surgiu como uma planta daninha em lavouras de cultivos de grãos. Objetivou-se com este estudo avaliar a sensibilidade diferencial de biótipos de E. mollis oriundos de áreas agrícolas e não agrícolas e determinar as melhores combinações de herbicidas aplicados em diferentes estádios de desenvolvimento para o controle desta espécie. Foram realizados três experimentos. No experimento de sensibilidade diferencial foram utilizados dez herbicidas em dois biótipos em duas fases de desenvolvimento. O experimento de dose resposta foi conduzido com oito doses de sete herbicidas. O experimento a campo foi realizado em uma área que apresenta problemas com a planta daninha para validar os resultados dos experimentos anteriores. O biótipo oriundo de área agrícola apresentou menor sensibilidade aos herbicidas quando comparado ao biótipo oriundo de área não agrícola. Os herbicidas de contato inicialmente apresentam controle superior, mas logo a planta apresenta rebrote em função de gemas presentes no colo da planta. A aplicação isolada de 2,4-D com doses entre 1005 e 1675 g e.a ha-¹ possui controle de 25%. Quando o 2,4-D é seguido da aplicação de paraquat (400 g i.a ha-¹) o controle passa a ser entre 51 e 68%. O melhor tratamento para o controle de plantas desenvolvidas é a mistura de 2,4-D + glyphosate (1340 + 1080 g e.a ha-¹) com aplicação sequencial de paraquat.(AU)

Elephantopus mollis, popularly known as elephant paw or sussuaiá, is a species that has recently emerged as a weed affecting grain crops. This study aimed to evaluate the differential sensitivity of biotypes of E. mollis obtained from agricultural and nonagricultural areas and to determine the best combinations of herbicides applied at different stages of development for controlling this species. Three experiments were conducted. In the differential sensitivity experiment, 10 herbicides were used in 2 biotypes in 2 stages of development. The dose-response experiment was conducted using 8 doses of 7 herbicides. The field experiment was conducted in an area with weed issues to validate the results of previous experiments. The biotype from the agricultural area showed lower sensitivity to herbicides than the biotype from the nonagricultural area. The contact herbicides initially presented better control; however, the weed shortly showed re-growth due to the presence of buds in the plant crown. Isolated application of 2.4-D amine at doses between 1005 and 1675 g a.e. ha-¹ demonstrated 25% control. When 2,4-D amine was followed by paraquat application (400 g a.i. ha-¹), the control observed was between 51% and 68%. The best treatment for the control of completely developed weeds is 2,4-D amine + glyphosate mixture (1340 + 1080 g a.e. ha-¹), followed by sequential paraquat application.(AU)