Understanding the responses of tillering to 2,4-D isooctyl ester in Setaria viridis L.

BACKGROUND: Green foxtail [Setaria viridis (L.)] is one of the most abundant and troublesome annual grass weeds in alfalfa fields in Northeast China. Synthetic auxin herbicide is widely used in agriculture, while how auxin herbicide affects tillering on perennial grass weeds is still unclear. A greenhouse experiment was conducted to examine the effects of auxin herbicide 2,4-D on green foxtail growth, especially on tillers. RESULTS: In the study, 2,4-D isooctyl ester was used. There was an inhibition of plant height and fresh weight on green foxtail after application. The photosynthetic rate of the leaves was dramatically reduced and there was an accumulation of malondialdehyde (MDA) content. Moreover, applying 2,4-D isooctyl ester significantly reduced the tillering buds at rates between 2100 and 8400 ga. i. /ha. Transcriptome results showed that applying 2,4-D isooctyl ester on leaves affected the phytohormone signal transduction pathways in plant tillers. Among them, there were significant effects on auxin, cytokinin, abscisic acid (ABA), gibberellin (GA), and brassinosteroid signaling. Indeed, external ABA and GA on leaves also limited tillering in green foxtail. CONCLUSIONS: These data will be helpful to further understand the responses of green foxtail to 2, 4-D isooctyl ester, which may provide a unique perspective for the development and identification of new target compounds that are effective against this weed species.

Photocatalytic degradation of 2,4-dichlorophenoxyacetic acid by electrospun TiO2 nanofibres synthesised from two different titanium molecular precursors.

The evaluation of the photocatalytic properties of electrospun TiO2 nanofibres (TiO2-NFs) synthesised in the same experimental conditions using two distinct precursors, tetraisopropyl orthotitanate (TTIP) and tetrabutyl orthotitanate (TNBT), with morphology and crystalline structure controlled by annealing at 460 °C for 3 h is presented. The presence of circular-shaped TiO2-NFs was corroborated by scanning electron microscopy (SEM). By using X-ray photoelectron spectroscopy (XPS), the chemical binding energies and their interactions of the TiO2 with the different incorporated impurities were determined; the most intense photoelectronic transitions of Ti 2p3/2 (458.39 eV), O 1 s (529.65 eV) and C 1 s (284.51 eV) were detected for TTIP and slightly blue-shifted for TNBT. By using energy-dispersive X-ray spectroscopy (EDS), the chemical element percentages in TiO2 were determined. Using X-ray diffraction, it was found that the annealed electrospun TiO2-NFs presented the anatase crystalline phase and confirmed by Raman scattering. Bandgap energies were determined by diffuse reflectance spectroscopy at room temperature. The photocatalytic degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide under exposure to ultraviolet light was studied using the TiO2-NFs obtained with the two molecular precursors. The results showed that the catalyst, prepared with the TTIP precursor, turned out to be the one that presented the highest photocatalytic activity with a half-life time (t1/2) of 28 min and a degradation percentage of 93%. The total organic carbon (TOC) in the solutions resulting from the 2,4-D degradation by the TiO2-NFs was measured, which showed a TOC removal of 50.67% for the TTIP sample and 36.14% for the TNBT sample. Finally, by using FTIR spectroscopy, the final chemical compounds of the degradation were identified as H2O and CO2.

Synergistic degradation of 2,4-dichlorophenoxyacetic acid in water by interfacial pre-reduction enhanced peroxymonosulfate activation derived from novel zero-valent iron/biochar.

Iron-based biochar exhibits great potential in degrading emerging pollutants and remediation of water environments. In this study, a highly efficient catalytic Fe0/biochar (MZB-800) was synthesized by the co-pyrolysis of poplar sawdust and K2FeO4 at 800 °C. A novel water purification technology of pre-reduction followed by PMS activation for MZB-800 was proposed to degrade the refractory 2,4-dichlorophenoxyacetic acid (2,4-D) pesticide. The corrosive effect of the strong oxidizing potassium salt endowed the MZB-800 surface with more Fe0 and porous structure, achieving greater 2,4-D adsorption binding energy. The removal efficiency of MZB-800 on 2,4-D was greater than that of biochar (BC) and conventional Fe0/biochar (Fe-BC) prepared by FeCl3·6 H2O as the precursor. The proposed novel water purification technology showed the synergistic effect between the interfacial pre-reduction and the PMS activation derived by MZB-800. Regarding 2,4-D degradation and dechlorination performance, the synergistic coefficient between pre-reduction and subsequent PMS activation for MZB-800 were 2 and 1.4 respectively. Based on the normalized kinetic analysis and the Langmuir-Hinshelwood model, we proposed the underlying mechanism of MZB-800 interfacial pre-reduction and subsequent PMS activation for synergistic removal of 2,4-D. The large amount of Fe2+ and hydroxyl density accumulated by the Fe0 and hydroquinone structures on the MZB-800 surface during the pre-reduction stage provided abundant active sites for the subsequent activation of PMS. The improved activation reaction rate generated more reactive oxygen species, further strengthening the removal efficiency of 2,4-D. This work manifested that the novel water purification technology of pre-reduction/PMS activation of iron-based biochar is feasible for removing emerging pollutants in the water environment. ENVIRONMENTAL IMPLICATION: Extensive abuse of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide with high solubility and refractory degradation has caused environmental pollution and ecological deterioration. This manuscript described a novel water purification technology, centered on high-efficiency Fe0/biochar and utilizing pre-reduction and PMS reactivation strategies to synergistically degrade 2,4-D, which had strong environmental relevance. By elucidating the synergistic removal mechanism, the research provided valuable insights into removing emerging pollutants, thus promoting environmental sustainability and safeguarding ecosystem health. Overall, it is of high importance to provide a feasible and efficient method for removing hazardous 2,4-D from water environments, which contributes to addressing pressing environmental problems.

Histological, biochemical and immunohistochemical assessments of Roundup®, atrazine, and 2,4-D mixtures on tissue architecture, body fluid conditions, nitrotyrosine protein and Na+/K+-ATPase expressions in the American oyster, Crassostera virginica.

Pesticides are widely used to control weeds and pests in agricultural settings but harm non-target aquatic organisms. In this study, our objective was to evaluate the effect of short-term exposure (one week) to environmentally relevant concentrations of pesticides mixture (low concentration: 0.4 µg/l atrazine, 0.5 µg/l Roundup®, and 0.5 µg/l 2,4-D; high concentration: 0.8 µg/l atrazine, 1 µg/l Roundup®, and 1 µg/l 2,4-D) on tissue architecture, body fluid conditions, and 3-nitrotyrosine protein (NTP) and Na+/K+-ATPase, expressions in tissues of American oyster (Crassostrea virginica) under controlled laboratory conditions. Histological analysis demonstrated the atrophy in the gills and digestive glands of oysters exposed to pesticides mixture. Periodic acid-Schiff (PAS) staining showed the number of hemocytes in connective tissue increased in low- and high-concentration pesticides exposure groups. However, pesticides treatment significantly (P < 0.05) decreased the amount of mucous secretion in the gills and digestive glands of oysters. The extrapallial fluid (i.e., body fluid) protein concentrations and glucose levels were dropped significantly (P < 0.05) in oysters exposed to high-concentration pesticides exposure groups. Moreover, immunohistochemical analysis showed significant upregulations of NTP and Na+/K+-ATPase expressions in the gills and digestive glands in pesticides exposure groups. Our results suggest that exposure to environmentally relevant pesticides mixture causes morphological changes in tissues and alters body fluid conditions and NTP and Na+/K+-ATPase expressions in tissues, which may lead to impaired physiological functions in oysters.

Assessment of the effects of 2,4-D-dichlorophenoxyacetic acid-based herbicide exposure in eggs and embryos of golden apple snails using OCT.

This study aimed to evaluate the effects of herbicide 2, 4-D-dichlorophenoxy acetic acid on golden apple snail eggs and embryos. Additionally, the study assessed the applicability of optical coherence tomography (OCT), a non-invasive depth cross-sectional microscopic imaging technique, as a novel method, to the best of our knowledge, for studying morphological changes in golden apple snail eggs and embryos, in comparison to the conventional approach of using white light microscopy. The study revealed that the herbicide 2,4-D-dichlorophenoxy acetic acid affected the hatchery rate and morphological changes of the eggs and embryos. The lethal concentration (LC50), representing the concentration of a substance that is expected to cause death in half of the population being studied, of the golden apple eggs and embryos increased with longer exposure time and higher concentrations. The estimated median effective concentration (EC50), which denotes the concentration producing the desired effect in 50% of the exposed golden apple embryos, exhibited a similar trend of change as the LC50. When compared to the microscopic study, it was observed that OCT could be employed to investigate morphological changes of golden apple snail eggs and embryos, enabling evaluation of alterations in both 2D and 3D structures.

Efficient adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) using biomass derived magnetic activated carbon nanocomposite in synthetic and simulated agricultural runoff water.

This study focused on evaluating the efficacy of a magnetic activated carbon material (CPAC@Fe3O4) derived from pods of copper pod tree in adsorbing the toxic herbicide, 2,4- (2,4-D) from aqueous solutions. The synthesized CPAC@Fe3O4 adsorbent, underwent various characterization techniques. FESEM images indicated a rough surface, incorporating iron oxide nanoparticles, while EDS analysis confirmed the presence of elements like Fe, O, and C. Notably, the CPAC@Fe3O4 exhibited high surface area (749.10 m2/g) and pore volume (0.5351 cm³/g), confirming its mesoporous nature. XRD investigations identified distinct signals associated with graphitic carbon and magnetite nanoparticles, while VSM analysis verified its magnetic properties with a high magnetic saturation value (2.72 emu/g). The adsorption process was exothermic, with a decrease in adsorption capacity at higher temperatures. Freundlich isotherm provided the best fit for the adsorption, and the pseudo-second-order equation effectively described the kinetics. Remarkably, the maximum adsorption capacity ranged from 246.43 to 261.03 mg/g, surpassing previously reported values. The ΔH° value (-8.67 kJ/mol) suggested a physisorption mechanism, and the negative ΔG° values established the spontaneous nature. Furthermore, the synthesized adsorbent demonstrated exceptional reusability, allowing for up to five cycles of adsorption-desorption operations. When applied to simulated agricultural runoff, CPAC@Fe3O4 showcased a significant adsorption capacity of 160.71 mg/g for 50 mg/L 2,4-D, using a 0.2 g/L dosage at pH 2. This study showcased the transformation of copper pod biomass into a valuable magnetic nanoadsorbent capable of efficiently eliminating the noxious 2,4-D pollutant from aqueous environments.

Chiral Herbicide 2,4-D Ethylhexyl Ester: Absolute Configuration, Stereoselective Herbicidal Activity, Crop Safety, and Metabolic Behavior on Maize and Flixweed.

This study represents the initial examination of the herbicidal efficacy, crop safety, and degradation patterns of 2,4-D ethylhexyl ester (2,4-D EHE) at the enantiomeric level. Baseline separation of 2,4-D EHE enantiomers was achieved using a superchiral R-AD column, with their absolute configurations determined through chemical reaction techniques. Evaluation of weed control efficacy against sensitive species such as sun spurge and flixweed demonstrated significantly higher inhibition rates for S-2,4-D EHE compared to R-2,4-D EHE. Conversely, no stereoselectivity was observed in the fresh-weight inhibition rates of both enantiomers on crops or nonsensitive weeds. A sensitive HPLC-MS/MS method was developed to simultaneously detect two enantiomers and the metabolite 2,4-D in plants. Investigation into degradation kinetics revealed no substantial difference in the half-lives of R- and S-2,4-D EHE in maize and flixweed. Notably, the metabolite 2,4-D exhibited prolonged persistence at elevated levels on flixweed, while it degraded rapidly on maize.

Association between pesticide exposure and thyroid function: analysis of Chinese and NHANES databases.

Background: Pesticides are widely used in agricultural activities. Although pesticide use is known to cause damage to the human body, its relationship with thyroid function remains unclear. Therefore, this study aimed to investigate the association between pesticide exposure and thyroid function. Methods: The Chinese database used included 60 patients with pyrethroid poisoning and 60 participants who underwent health checkups between June 2022 and June 2023. The NHANES database included 1,315 adults enrolled from 2007 to 2012. The assessed pesticide and their metabolites included 2,4-dichlorophenoxyacetic acid (2,4-D), 4-fluoro-3-phenoxybenzoic acid (4F3PB), para-nitrophenol (PN), 3-phenoxybenzoic acid (3P), and trans-dichlorovinyl-dimethylcyclopropane carboxylic acid (TDDC). The evaluated indicators of thyroid function were measured by the blood from the included population. The relationship between pesticide exposure and thyroid function indexes was investigated using linear regression, Bayesian kernel machine regression (BKMR), restricted cubic spline (RCS), and weighted quantile sum (WQS) models. Results: The Chinese data showed that pesticide exposure was negatively correlated with the thyroid function indicators FT4, TT4, TgAb, and TPOAb (all p < 0.05). The BKMR model analysis of the NHANES data showed that the metabolic mixture of multiple pesticides was negatively associated with FT4, TSH, and Tg, similar to the Chinese database findings. Additionally, linear regression analysis demonstrated positive correlations between 2,4-D and FT3 (p = 0.041) and 4F3PB and FT4 (p = 0.003), whereas negative associations were observed between 4F3PB and Tg (p = 0.001), 4F3PB and TgAb (p = 0.006), 3P and TgAB (p = 0.006), 3P and TPOAb (p = 0.03), PN and TSH (p = 0.003), PN and TT4 (p = 0.031), and TDDC and TPOAb (p < 0.001). RCS curves highlighted that most pesticide metabolites were negatively correlated with thyroid function indicators. Finally, WQS model analysis revealed significant differences in the weights of different pesticide metabolites on the thyroid function indexes. Conclusion: There is a significant negative correlation between pesticide metabolites and thyroid function indicators, and the influence weights of different pesticide metabolites on thyroid function indicators are significantly different. More research is needed to further validate the association between different pesticide metabolites and thyroid disease.

Computational design and preparation of water-compatible noncovalent imprinted microspheres.

Herein, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model template in a rational design strategy to produce water-compatible noncovalent imprinted microspheres. The proposed approach involved computational modelling for screening functional monomers and a simple method for preparing monodisperse and highly cross-linked microspheres. The fabricated non-imprinted polymer (NIP) and 2,4-d-imprinted polymer (2,4-d-MIP) were characterised, and their adsorption capabilities in an aqueous environment were evaluated. Results reveal that the pseudo-second-order kinetics model was appropriate for representing the adsorption of 2,4-D on NIP and 2,4-d-MIP, with R2 values of 0.97 and 0.99, respectively. The amount of 2,4-D adsorbed on 2,4-d-MIP (97.75 mg g-1) was considerably higher than those of phenoxyacetic acid (35.77 mg g-1), chlorogenic acid (9.72 mg g-1), spiramycin (1.56 mg g-1) and tylosin (1.67 mg g-1). Furthermore, it exhibited strong resistance to protein adsorption in an aqueous medium. These findings confirmed the feasibility of the proposed approach, providing a reference for the development of water-compatible noncovalent imprinted polymers.

Adsorption simulation of 2,4-D pesticide on novel zinc-based 2-amino-4-(1H-1,2,4-triazole-4-yl)benzoic acid coordination complexes using machine learning approach.

The capacity of zinc-based 2-amino-4-(1H-1,2,4-triazole-4-yl)benzoic acid coordination complex (Zn(NH2-TBA)2) and modified Zn(NH-TBA)2COMe complex for removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solutions was investigated through adsorption modeling and artificial intelligence tools. Analyzing the adsorption characteristics of pesticides helps in studying the groundwater pollution by pesticides in agriculture area.In this study, Zn(NH2-TBA)2 was synthesized using Schiff base and its surface was modified using acetic anhydride group and their physical characteristics were identified using proton NMR, FTIR, and XRD. NMR results showed maximum modification yield obtained was 65% after 5 days. The porous structure and surface area monitored using nitrogen isotherm and BET surface area analysis presented relatively less surface area and porosity after modification. Adsorption modelling indicated that Toth model with a maximum adsorption capacity of 150.8 mg/g and 100.7 mg/g represents the homogenous adsorption systems which satisfy both low- and high-end boundary of adsorbate concentration in all settings according to the optimum point, while the kinetics and rate of 2,4-D adsorption follow the pseudo-first-order kinetic model in all situations. Artificial neural network (ANN), support vector regression, and particle swarm optimized least squares-support vector regression (PSO-LSSVR) were used for the optimization and modelling of adsorbent mass, adsorbate concentration, contact time, and temperature to develop predictive equations for the simulation of the adsorption efficiency of 2,4-D pesticide. The obtained results exhibited the better performance of ANN and PSO-LSSVR for prediction of adsorption results. The mean square error values of ANN (0.001, 0.012) and PSO-LSSVR (0.121, 0.105) were obtained for Zn(NH2-TBA)2 and Zn(NH-TBA)2COMe, respectively, while their respective coefficient of determination (R2) obtained were 0.999 and 0.988 for ANN and 0.980 and 0.825 for PSO-LSSVR. The study specified that machine learning predictive behavior performed better for Zn(NH2-TBA)2 compared to Zn(NH-TBA)2COMe that is also supported by theoretical kinetics and isotherm models. The research concludes that artificial intelligence models are the most efficient tools for studying the predictive behavior of adsorption data.

The effects of commercial 2,4-D herbicide on game fish species: Natural lake water vs. laboratory system water.

Aquatic herbicides with active ingredient 2,4-dichlorophenoxyacteic acid (2,4-D) are commonly used to control and combat aquatic non-native species that cause detrimental impacts including habitat destruction, strained resources among biota, and biodiversity loss. While many (eco)toxicology studies are performed in the laboratory under highly controlled circumstances, these studies may disregard the nuances and disorder that come with the complexity of natural aquatic ecosystems. Therefore, we conducted a series of laboratory experiments using laboratory system water, different lake waters, and different water parameters to determine the effects of ecologically relevant concentrations of 2,4-D (0.00-4.00 ppm a.e.) on the development and survival of two freshwater game species (Sander vitreus and Esox lucius). For 2,4-D exposures using different water sources, there were significant main effects of 2,4-D concentration and water source on walleye embryo and larval survival, however, there was no significant interaction between 2,4-D exposure and water source. For 2,4-D exposures and pH (5-9 pH), there were significant main effects of 2,4-D concentration and pH on walleye and northern pike embryo survival and a significant interaction between 2,4-D exposure and pH. Our results indicate that 2,4-D exposures in controlled laboratory system water can predict similar outcomes as 2,4-D exposures in natural lake water. Moreover, individual water parameters, such as pH, play a significant role in the toxicity of 2,4-D. Taken together, these results suggest that highly controlled laboratory studies are a useful tool for predicting impacts on survival of non-target fish in natural waters, but it is crucial for management agencies to consider individual water sources and specific lake water parameters in herbicide risk assessments to minimize the impacts to non-target organism.

Biogenic magnetic nanocomposite of hydroxyapatite and dextran: synthesis, characterization, and enhanced removal of 2,4-D from aqueous environment.

In this study, a biogenic magnetic nanocomposite, HAP@DEX@MNP, using hydroxyapatite from eggshell waste and dextran was developed to efficiently remove 2,4-D from aqueous solutions. The magnetic nano biocomposite underwent rigorous characterization using a comprehensive suite of analytical techniques, including FTIR, XRD, FESEM, EDX, TEM, and VSM. FTIR analysis was used to validate the existence of pivotal functional groups, such as phosphate, carbonyl, hydroxyl, and iron oxide. XRD analysis verified both the crystalline nature of hydroxyapatite and the successful integration of dextran and hematite within the composite structure. FESEM and EDX examinations provided valuable insights into the surface morphology and elemental composition. TEM observations elucidated the existence of nano-sized particles underscoring the unique structural characteristics of the nanocomposite. Batch adsorption experiments were conducted under optimized conditions, highlighting the critical role of pH 2 for efficient 2,4-D removal. The mechanisms driving the binding of 2,4-D to HAP@DEX@MNP were found to encompass diverse interactions, encompassing electrostatic forces, hydrogen bonding, π-π interactions, and van der Waals forces. Adsorption isotherm studies revealed both monolayer and multilayer adsorption, with the Langmuir and Freundlich models fitting well, indicating a maximal adsorption capacity of 217.39 µg/g at 25 °C. Kinetic investigations supported the pseudo-second-order model for efficient adsorption dynamics, and thermodynamic analysis emphasized the versatility of HAP@DEX@MNP across different temperatures. Importantly, the study highlighted the remarkable regenerative capacity of the nanocomposite using a 0.1 M NaOH solution, positioning it as an environmentally friendly option for water treatment. In conclusion, HAP@DEX@MNP holds significant potential for diverse applications in addressing global water treatment and environmental challenges.

Agent orange exposure and prostate cancer risk in the million veteran program.

BACKGROUND: The US government considers veterans to have been exposed to Agent Orange if they served in Vietnam while the carcinogen was in use, and these veterans are often deemed at high risk of prostate cancer (PCa). Here, we assess whether presumed Agent Orange exposure is independently associated with increased risk of any metastatic or fatal PCa in a diverse Veteran cohort still alive in the modern era (at least 2011), when accounting for race/ethnicity, family history, and genetic risk. PATIENTS AND METHODS: Participants in the Million Veteran Program (MVP; enrollment began in 2011) who were on active duty during the Vietnam War era (August 1964-April 1975) were included (n = 301,470). Agent Orange exposure was determined using the US government definition. Genetic risk was assessed via a validated polygenic hazard score. Associations with age at diagnosis of any PCa, metastatic PCa, and death from PCa were assessed via Cox proportional hazards models. RESULTS AND INTERPRETATION: On univariable analysis, exposure to Agent Orange was not associated with increased PCa (hazard ratio [HR]: 1.02, 95% confidence interval [CI]: 1.00-1.04, p = 0.06), metastatic PCa (HR: 0.98, 95% CI: 0.91-1.05, p = 0.55), or fatal PCa (HR: 0.94, 95% CI: 0.79-1.09, p = 0.41). When accounting for race/ethnicity and family history, Agent Orange exposure was independently associated with slightly increased risk of PCa (HR: 1.06, 95% CI: 1.04-1.09, <10-6) but not with metastatic PCa (HR: 1.07, 95% CI: 0.98-1.15, p = 0.10) or PCa death (HR: 1.02, 95% CI: 0.83-1.23, p = 0.09). Similar results were found when accounting for genetic risk. Agent Orange exposure history may not improve modern PCa risk stratification.

CdIn2Se4@chitosan heterojunction nanocomposite with ultrahigh photocatalytic activity under sunlight driven photodegradation of organic pollutants.

This research focused on synthesizing a CdIn2Se4@Ch nanocomposite by doping CdIn2Se4 into chitosan using a photolysis assisted ultrasonic process. The aim was to enhance the photodegradation efficiency of ofloxacin and 2,4-dichlorophenoxyacetic acid under sunlight. The synthesized CdIn2Se4@Ch nanocomposite was investigated via different techniques, including XRD, XPS, FTIR, TEM, DSC, TGA, UV-Vis and PL. The study also investigated the influence of various reaction parameters, including the effects of inorganic and organic ions. The synthesized nanocomposite demonstrated exceptional efficiency, achieving 86 % and 95 % removal rates, with corresponding rate constants of 0.025 and 0.047 min-1. This performance surpasses that of CdIn2Se4 by approximately 1.35 and 2.25 times, respectively. The values of COD were decreased to 78 and 86 % for ofloxacin and 2,4-dichlorophenoxyacetic, while the TOC values decreased to 71 and 84 %, respectively, from their premier values. The improvement in performance is associated with the introduction of CdIn2Se4 into chitosan, resulting in the self-integration of Cd into the catalyst. This creates a localized accumulation point for electrons, enhancing the efficiency of charge separation and further reducing the surface charge of chitosan. Experimental evidence suggests that superoxide and hydroxyl radicals play a significant role in the photodegradation of pollutants. Additionally, the nanocomposite exhibits excellent stability and can be reused up to five times, indicating remarkable stability and reusability of the developed photocatalyst.

Dual C-Cl isotope fractionation offers potential to assess biodegradation of 1,2-dichloropropane and 1,2,3-trichloropropane by Dehalogenimonas cultures.

1,2-dichloropropane (1,2-DCP) and 1,2,3-trichloropropane (1,2,3-TCP) are hazardous chemicals frequently detected in groundwater near agricultural zones due to their historical use in chlorinated fumigant formulations. In this study, we show that the organohalide-respiring bacterium Dehalogenimonas alkenigignens strain BRE15 M can grow during the dihaloelimination of 1,2-DCP and 1,2,3-TCP to propene and allyl chloride, respectively. Our work also provides the first application of dual isotope approach to investigate the anaerobic reductive dechlorination of 1,2-DCP and 1,2,3-TCP. Stable carbon and chlorine isotope fractionation values for 1,2-DCP (ƐC = -13.6 ± 1.4 ‰ and ƐCl = -27.4 ± 5.2 ‰) and 1,2,3-TCP (ƐC = -3.8 ± 0.6 ‰ and ƐCl = -0.8 ± 0.5 ‰) were obtained resulting in distinct dual isotope slopes (Λ12DCP = 0.5 ± 0.1, Λ123TCP = 4 ± 2). However direct comparison of ΛC-Cl among different substrates is not possible and investigation of the C and Cl apparent kinetic isotope effects lead to the hypothesis that concerted dichloroelimination mechanism is more likely for both compounds. In fact, whole cell activity assays using cells suspensions of the Dehalogenimonas-containing culture grown with 1,2-DCP and methyl viologen as electron donor suggest that the same set of reductive dehalogenases was involved in the transformation of 1,2-DCP and 1,2,3-TCP. This study opens the door to the application of isotope techniques for evaluating biodegradation of 1,2-DCP and 1,2,3-TCP, which often co-occur in groundwaters near agricultural fields.

Biostimulation with oxygen and electron donors supports micropollutant biodegradation in an experimentally simulated nitrate-reducing aquifer.

The availability of suitable electron donors and acceptors limits micropollutant natural attenuation in oligotrophic groundwater. This study investigated how electron donors with different biodegradability (humics, dextran, acetate, and ammonium), and different oxygen concentrations affect the biodegradation of 15 micropollutants (initial concentration of each micropollutant = 50 µg/L) in simulated nitrate reducing aquifers. Tests mimicking nitrate reducing field conditions showed no micropollutant biodegradation, even with electron donor amendment. However, 2,4-dichlorophenoxyacetic acid and mecoprop were biodegraded under (micro)aerobic conditions with and without electron donor addition. The highest 2,4-dichlorophenoxyacetic acid and mecoprop biodegradation rates and removal efficiencies were obtained under fully aerobic conditions with amendment of an easily biodegradable electron donor. Under microaerobic conditions, however, amendment with easily biodegradable dissolved organic carbon (DOC) inhibited micropollutant biodegradation due to competition between micropollutants and DOC for the limited oxygen available. Microbial community composition was dictated by electron acceptor availability and electron donor amendment, not by micropollutant biodegradation. Low microbial community richness and diversity led to the absence of biodegradation of the other 13 micropollutants (such as bentazon, chloridazon, and carbamazepine). Finally, adaptation and potential growth of biofilms interactively determined the location of the micropollutant removal zone relative to the point of amendment. This study provides new insight on how to stimulate in situ micropollutant biodegradation to remediate oligotrophic groundwaters as well as possible limitations of this process.

ESR2-HDA6 complex negatively regulates auxin biosynthesis to delay callus initiation in Arabidopsis leaf explants during tissue culture.

Plants exhibit an astonishing ability to regulate organ regeneration upon wounding. Excision of leaf explants promotes the biosynthesis of indole-3-acetic acid (IAA), which is polar-transported to excised regions, where cell fate transition leads to root founder cell specification to induce de novo root regeneration. The regeneration capacity of plants has been utilized to develop in vitro tissue culture technologies. Here, we report that IAA accumulation near the wounded site of leaf explants is essential for callus formation on 2,4-dichlorophenoxyacetic acid (2,4-D)-rich callus-inducing medium (CIM). Notably, a high concentration of 2,4-D does not compensate for the action of IAA because of its limited efflux; rather, it lowers IAA biosynthesis via a negative feedback mechanism at an early stage of in vitro tissue culture, delaying callus initiation. The auxin negative feedback loop in CIM-cultured leaf explants is mediated by an auxin-inducible APETALA2 transcription factor, ENHANCER OF SHOOT REGENERATION 2 (ESR2), along with its interacting partner HISTONE DEACETYLASE 6 (HDA6). The ESR2-HDA6 complex binds directly to, and removes the H3ac mark from, the YUCCA1 (YUC1), YUC7, and YUC9 loci, consequently repressing auxin biosynthesis and inhibiting cell fate transition on 2,4-D-rich CIM. These findings indicate that negative feedback regulation of auxin biosynthesis by ESR2 and HDA6 interferes with proper cell fate transition and callus initiation.

Synthetic auxin herbicide 2,4-D and its influence on a model BY-2 suspension.

2,4-D is a broadly used auxin herbicide. The presence of the 2,4-D synthetic auxin in the medium is imperative for long-term BY-2 tobacco suspension viability. The precise mechanism of this symbiosis of the suspension and the synthetic auxin remains unclear. Our goal was to study the hormonal regulation of the growth of the cell suspension; and to describe the experiments clarifying the interaction between the chosen growth regulators and phytohormones on the cellular level, specifically between the 2,4-D synthetic auxin and the native stress phytohormone - ethylene. This study examined the influence of low 2,4-D concentrations stimulating cell growth in vitro as well as the influence of high herbicide concentrations on the model tobacco BY-2 suspension. The culture took 6 days. Different parameters were evaluated, including the influence of different 2,4-D concentrations on the production of the phytohormone ethylene and its precursor 1-Aminocyclopropane-1-carboxylic acid (ACC) in the tobacco cells. The content of 2,4-D in the cells and the medium was established. The observations of the morphological changes showed that a heavy impregnation of the cell walls taking place depending on the concentration of 2,4-D. A dramatic increase in protective polysaccharides and a remodulation of the cell walls by the formation of a pectin shield in artificial conditions were expected and observed. At the same time, massive production of the stress phytohormone ethylene took place, and, because of that, plant mutagenicity, anomalous tumour-type proliferation growth, and the production of supercells were observed. The hypothesis of the protective shield is discussed.

Meta-analytical review of antioxidant mechanisms responses in animals exposed to herbicide 2,4-D herbicide.

The 2,4-Dichlorophenoxyacetic acid (2,4-D) is a low-cost herbicide to eradicate broadleaf weeds. Since the development of 2,4-D resistant transgenic crops, it has been described as one of the most widely distributed pollutants in the world, increasing concern about its environmental impacts. This study aimed to elucidate the antioxidant system response in animals exposed to 2,4-D by different routes of exposure. It focused on determining if tissue, phylogenetic group, and herbicide formulation would influence the antioxidant mechanisms. A careful literature search of Scopus, WoS, and Science Direct retrieved 6983, 24,098, and 20,616 articles, respectively. The dataset comprised 390 control-treatment comparisons and included three routes of exposure: transgenerational, oral, and topical. The data set for transgenerational and oral exposure revealed oxidative stress through a decrease in enzymatic activities and the level of molecules of the antioxidant system. In contrast, topical exposure increased the oxidative stress. Tissue-specific analyses revealed that the transgenerational effects reduced hepatic catalase (CAT) activity. Oral exposure caused a variety of effects, including increased CAT activity in the prostate and decreased activity in various tissues. Mammals predominate in the transgenerational and oral groups, showing a significantly reduced activity of the antioxidant system. In contrast, in the topical exposure, an increased activity of oxidative stress biomarkers was observed in fish, earthworms, and mollusks. The effects of the 2,4-D formulation on oxidative stress responses showed significant differences between pure and commercial formulations, with oral exposure resulting in decreased activity and topical exposure increasing responses. In summary, orally exposed animals exhibited a clear decrease in enzyme activities, transgenerational exposure elicited tissue-specific prompted biochemical reductions, and topical exposure induced increased responses, emphasizing the need for unbiased exploration of the effects of 2,4-D on biomarkers of oxidative stress while addressing publication bias in oral and topical datasets.

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.