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The photocatalytic conversion in aqueous media of phenol and guaiacol as a lignin model compound using Nb2O5 with different crystal phases was studied. Nb2O5 particles were synthesized using hydrothermal methods, where it was observed that changes in the solvent control their morphology and crystal phase. Different photocatalytic behavior of Nb2O5 was observed with the selected model compounds, indicating that its selection directly impacts the resulting conversion and selectivity rates as well as the reaction pathway, highlighting the relevance of model molecule selection. Photocatalytic conversion of phenol showed conversion rate (C%) up to 25 % after 2â h irradiation and high selectivity (S%) to pyrogallol (up to 50 %). Orthorhombic Nb2O5 spheres favored conversion through free hydroxyl radicals while monoclinic rods did not convert phenol. Guaiacol photocatalytic oxidation showed high conversion rate but lower selectivity. Orthorhombic and monoclinic Nb2O5 favored the formation of resorcinol with S % ~0.43 % (C % ~33 %) and ~13 % (C % ~27 %) respectively. The mixture of both phases enhanced the guaiacol conversion rate to ~55 % with ~17 % of selectivity to salicylaldehyde. The use of radical scavengers provided information to elucidate the reaction pathway for these model compounds, showing that different reaction pathways may be obtained for the same photocatalyst if the model compound is changed.
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In the last decade, the application of nanoscale zero-valent iron (nZVI) has garnered great attention as an adsorbent due to its low cost, non-toxicity, high porosity, and BET-specific surface area. In particular, the immobilization of nZVI particles onto inorganic and organic substrates (nanocomposites) decreased its agglomeration, allowing them to be effective and achieve greater adsorption of pollutants than pristine nanoparticles (NPs). Although nZVI began to be used around 2004 to remove pollutants, there are no comprehensive review studies about phosphate removal from aquatic systems to date. For this reason, this study will show different types of nZVI, pristine nZVI, and its nanocomposites, that exist on the market, how factors such as pH solution, oxygen, temperature, doses of adsorbent, initial phosphate concentration, and interferents affect phosphate adsorption capacity, and mechanisms involved in phosphate removal. We determined that nanocomposites did not always have higher phosphate adsorption than pristine nZVI particles. Moreover, phosphate can be removed by nZVI-based nanoadsorbents through electrostatic attraction, ion exchange, chemisorption, reduction, complexation, hydrogen bonding, and precipitation mechanisms. Using the partition coefficient (PC) values, we found that sepiolite-nZVI is the most effective nanoadsorbent that exists to remove phosphate from aqueous systems. We suggest future studies need to quantify the PC values for nZVI-based nanoadsorbents as well as ought to investigate their phosphate removal efficiency under natural environmental conditions.
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In recent years, the release of metal and metallic oxide engineered nanoparticles (ENPs) into the environment has generated an increase in their accumulation in agricultural soils, which is a serious risk to the ecosystem and soil health. Here, we show the impact of ENPs on the physical and chemical properties of soils. A literature search was performed in the Scopus database using the keywords ENPs, plus soil physical properties or soil chemical properties, and elements availability. In general, we found that the presence of metal and metallic oxide ENPs in soils can increase hydraulic conductivity and soil porosity and reduce the distance between soil particles, as well as causing a variation in pH, cation exchange capacity (CEC), electrical conductivity (EC), redox potential (Eh), and soil organic matter (SOM) content. Furthermore, ENPs or the metal cations released from them in soils can interact with nutrients like phosphorus (P) forming complexes or precipitates, decreasing their bioavailability in the soil solution. The results depend on the soil properties and the doses, exposure duration, concentrations, and type of ENPs. Therefore, we suggest that particular attention should be paid to every kind of metal and metallic oxide ENPs deposited into the soil.
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Currently, the human species has been recognized as the primary species responsible for Earth's biodiversity decline. Contamination by different chemical compounds, such as pesticides, is among the main causes of population decreases and species extinction. Insects are key for ecosystem maintenance; unfortunately, their populations are being drastically affected by human-derived disturbances. Pesticides, applied in agricultural and urban environments, are capable of polluting soil and water sources, reaching non-target organisms (native and introduced). Pesticides alter insect's development, physiology, and inheritance. Recently, a link between pesticide effects on insects and their epigenetic molecular mechanisms (EMMs) has been demonstrated. EMMs are capable of regulating gene expression without modifying genetic sequences, resulting in the expression of different stress responses as well as compensatory mechanisms. In this work, we review the main anthropogenic contaminants capable of affecting insect biology and of triggering EMMs. EMMs are involved in the development of several diseases in native insects affected by pesticides (e.g., anomalous teratogenic reactions). Additionally, EMMs also may allow for the survival of some species (mainly pests) under contamination-derived habitats; this may lead to biodiversity decline and further biotic homogenization. We illustrate these patterns by reviewing the effect of neonicotinoid insecticides, insect EMMs, and their ecological consequences.
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The sorption behavior of 2,4-dichlorophenoxyacetic acid (2,4-D) in the abundant agricultural volcanic ash-derived soils (VADS) is not well understood despite being widely used throughout the world, causing effects to the environment and human health. The environmental behavior and risk assessment of groundwater pollution by pesticides can be evaluated through kinetic models. This study evaluated the sorption kinetics and 2,4-D sorption-desorption in ten VADS through batch sorption experiments. Differences in the sorption extent for the fast and slow phases was observed through the IPD model where 2,4-D sorption kinetics was controlled by external mass transfer and intra organic matter diffusion in Andisols (C1 ≠ 0). We confirmed from the spectroscopic analysis that the carboxylate group directly drives the interaction of 2,4-D on Andisol soil. The MLR model showed that IEP, FeDCB, and pH×Silt are important soil descriptors in the 2,4-D sorption in VADS. The Freundlich model accurately represented sorption equilibrium data in all cases (Kf values between 1.1 and 24.1 µg1-1/n mL1/ng-1) with comparatively higher sorption capacity on Andisols, where the highest hysteresis was observed in soils that presented the highest and lowest OC content (H close to 0).
Assuntos
Herbicidas , Poluentes do Solo , Ácido 2,4-Diclorofenoxiacético , Adsorção , Herbicidas/análise , Humanos , Cinética , Solo , Poluentes do Solo/análiseRESUMO
American trypanosomiasis or Chagas disease caused by the protozoan Trypanosoma cruzi (T. cruzi) is an important endemic trypanosomiasis in Central and South America. This disease was considered to be a priority in the global plan to combat neglected tropical diseases, 2008-2015, which indicates that there is an urgent need to develop more effective drugs. The development of new chemotherapeutic agents against Chagas disease can be related to an important biochemical feature of T. cruzi: its redox defense system. This system is based on trypanothione ([Formula: see text],[Formula: see text]-bis(glutathyonil)spermidine) and trypanothione reductase (TR), which are rather unique to trypanosomes and completely absent in mammalian cells. In this regard, tricyclic compounds have been studied extensively due to their ability to inhibit the T. cruzi TR. However, synthetic derivatives of natural products, such as [Formula: see text]-carboline derivatives ([Formula: see text]-CDs), as potential TR inhibitors, has received little attention. This study presents an analysis of the structural and physicochemical properties of commercially available [Formula: see text]-CDs in relation to compounds tested against T. cruzi in previously reported enzymatic assays and shows that [Formula: see text]-CDs cover chemical space that has not been considered for the design of TR inhibitors. Moreover, this study presents a ligand-based approach to discover potential TR inhibitors among commercially available [Formula: see text]-CDs, which could lead to the generation of promising [Formula: see text]-CD candidates.