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Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

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The increase in prices of fertilizers, energy and other materials necessary for the industry triggered a global economic crisis. Reason that was investigated on the biological and chemical characteristics in relation to the yield of radish nourished with humus from plant residue. The objective was to determine the appropriate dose of humus to obtain greater yield and its relationship with the chemical and biological characteristics of the radish. It is based on applied methodology with an experimental approach; Therefore, the Completely Random Block Design model was used, which consisted of 3 blocks and 5 treatments that were T1 with 0, T2 with 4, T3 with 6, T4 with 8 and T5 with 10 t/ha of humus and They applied 15 days after sowing. The physical characteristics of the radish were evaluated and processed using analysis of variance and Duncan. Concentration of elements in leaves and stomatal density were also analyzed. It was determined that T5 stood out in total plant length with 28.95 cm, plant weight with 76.87 g, equatorial diameter with 4,404 cm and commercial yield with 20,296 t/ha. Nitrogen consumption in relation to yield with 247.44 kg/ha. Stomatal density 459 stomata/mm2 and profitability with 150% and nutrient concentration in leaves highlighted T4 with N, K, Ca, Mg, Mo and Zn. It concludes that T5 stood out with 20,296 t/ha, which differed by 26.04% in relation to the control (T1) with 15,011 t/ha. Therefore, this dose added nutrients to the soil that improved the availability for plant absorption and this influenced the concentration of nutrients in leaves such as N, P and Fe and stomatal density with 459 stomata/mm2, which had a response in good development, strengthening against environmental stress and therefore greater performance.

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Tetracycline (TC) is a widely used antibiotic, and evaluating its interaction with humic substances (HS) that act as a complexing agent in the environment is essential to understanding the availability of this contaminant in the environment. This study evaluated the interaction between HS and TC using different spectroscopic techniques, theoretical studies, and biological assays simulating environmental conditions. TC interacts with HS, preferably by electrostatic forces, with a binding constant of 9.2 × 103 M-1 (30 °C). This process induces conformational changes in the superstructure, preferably in the HS, like protein fraction. Besides, studies using the 8-anilino-1-naphthalene sulfonate (ANS) probe indicated that the antibiotic alters the hydrophobicity degree on HS's surface. Synchronized fluorescence shows that the TC interaction occurs preferentially with the protein-like fraction of soil organic matter (KSV = 26.28 ± 1.03 M-1). The TC epitope was evaluated by 1H NMR and varied according to the pH (4.8 and 9.0) of the medium, as well as the main forces responsible for the stabilization of the HS-TC complex. The molecular docking studies showed that the formation of the HS-TC complex is carried out spontaneously (ΔG = -7.1 kcal mol-1) and is stabilized by hydrogen bonds and electrostatic interactions, as observed in the experimental spectroscopic results. Finally, biological assays indicated that HS influenced the antimicrobial activity of TC. Thus, this study contributed to understanding the dynamics and distribution of TC in the environment and HS's potential in the remediation of antibiotics of this class in natural systems, as these can have adverse effects on ecosystems and human health.

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Introduction: The litterfall production, foliar nutrient dynamics and decomposition are essential to maintain nutrient cycling, soil fertility, and carbon regulation in terrestrial ecosystems. With several studies addressing the variation of these processes, their dynamics in tropical dry forests (TDFs) remain unclear, due to its complex interaction of biotic and abiotic factors. Objective: To evaluate litterfall, nutrient potential return and use efficiency, and decomposition variation in a TDF successional gradient in Tolima, Colombia. Methods: We quantified litterfall from November 2017 to October 2019 in 12 plots distributed in four successional stages: initial, early, intermediate, and late forests. We identified key tree species in foliar litter production and characterized the foliar decomposition of these species. At the community level, we quantified the C, N and P potential return, the N and P use efficiency, and the C:N and N:P ratio. Subsequently, we analyze relationships between vegetation characteristics and some soil chemical properties with these ecological processes. Results: We found that total litterfall in late forests (8.46 Mg ha-1 y-1) was double that found in initial forests (4.45 Mg ha-1 y-1). Decomposition was higher in initial (k = 1.28) compared to intermediate (k = 0.97) and late forests (k = 0.87). The nutrient potential return didn't change along succession, but it did show differences between study sites. The structural development and species richness favored litterfall, while soil chemical conditions influenced nutrient returns and decomposition. Conclusions: TDFs could recover key ecosystem function related to litterfall and nutrient dynamics after disturbances cessation; however, the soil quality is fundamental in return and release of nutrients.

Introducción: La producción de hojarasca, la dinámica de nutrientes foliares y la descomposición son esenciales para mantener el ciclo de nutrientes, la fertilidad del suelo y la regulación del carbono en ecosistemas terrestres. Con diversos estudios que abordan estos procesos, su variación en los bosques secos tropicales (BSTs) permanece incierta, por su compleja interacción de factores bióticos y abióticos. Objetivo: Evaluar la caída de hojarasca, el retorno potencial de nutrientes y eficiencia de uso, y la variación en descomposición en un gradiente sucesional de un BST en Tolima, Colombia. Métodos: Cuantificamos la caída de hojarasca entre noviembre 2017 y octubre 2019 en 12 parcelas distribuidas en cuatro estados sucesionales: bosque inicial, temprano, intermedio y tardío. Identificamos las especies arbóreas clave en la producción de hojarasca y caracterizamos la descomposición foliar de estas especies. A nivel comunitario, cuantificamos el retorno potencial de C, N y P, la eficiencia de uso de N y P y la relación C:N y N:P. Posteriormente, analizamos las relaciones entre las características de la vegetación y algunas propiedades químicas del suelo con estos procesos ecológicos. Resultados: Encontramos que la caída total de hojarasca en los bosques tardíos (8.46 Mg ha-1 año-1) fue el doble de la hallada en bosques iniciales (4.45 Mg ha-1 año-1). La descomposición fue mayor en bosques iniciales (k = 1.28) en comparación con bosques intermedios (k = 0.97) y tardíos (k = 0.87). El retorno potencial de nutrientes no cambió con el avance de la sucesión vegetal, pero exhibió diferencias entre los sitios de estudio. El desarrollo estructural y la riqueza de especies favorecieron la caída de hojarasca, mientras que las condiciones químicas del suelo influyeron en el retorno de nutrientes y descomposición. Conclusiones: Los BSTs tienen la capacidad de recuperar la función ecosistémica de aporte de hojarasca fina, retorno y liberación de nutrientes después del cese de alteraciones antrópicas; sin embargo, la calidad del suelo es fundamental en el retorno y liberación de nutrientes.

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In environmental systems, the soil is a principal route of contamination by various potentially toxic species. Roxarsone (RX) is an arsenic (V) organic compound used to treat parasitic diseases and as an additive for animal fattening. When the animal excretes RX, the residues may lead to environmental contamination. Due to their physicochemical properties, the soil's humic substances (HS) are important in species distribution in the environment and are involved in various specific interaction/adsorption processes. Since RX, an arsenic (V) compound, is considered an emerging contaminant, its interaction with HS was evaluated in simulated environmental conditions. The HS-RX interaction was analyzed by monitoring intrinsic HS fluorescence intensity variations caused by complexation with RX, forming non-fluorescent supramolecular complexes that yielded a binding constant Kb (on the order of 103). The HS-RX interaction occurred through static quenching due to complex formation in the ground state, which was confirmed by spectrophotometry. The process was spontaneous (ΔG < 0), and the predominant interaction forces were van der Waals and hydrogen bonding (ΔH < 0 and ΔS < 0), with an electrostatic component evidenced by the influence of ionic strength in the interaction process. Structural changes in the HS were verified by synchronized and 3D fluorescence, with higher variation in the region referring to the protein-like fraction. In addition, metal ions (except ions Cu(II)) favored HS-RX interaction. When interacting with HS, the RX epitope was suggested by 1H NMR, which indicated that the entire molecule interacts with the superstructure. An enzyme inhibition assay verified the ability to reduce the alkaline phosphatase activity of free and complexed RX (RX-HS). Finally, this work revealed the main parameters associated with HS and RX interaction in simulated environmental conditions, thus, providing data that may help our understanding of the dynamics of organic arsenic-influenced soils.

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Humic substances (HS) interact with trace metals such as As and Co, affecting their mobility and availability in aquatic systems. However, their combined effects on toxicity to aquatic organisms are not totally understood. The objective of this study was to evaluate the toxicity of Co(II) and As(III) to the water flea Ceriodaphnia dubia in the presence of HS, considering element speciation. Toxicity assays were performed in the presence and absence of HS at two different concentrations of As(III) (10 and 20 µg/L) and Co(II) (50 and 100 µg/L). The free As(III) and Co(II) (< 1 kDa, fraction most potentially bioavailable) in the test solutions were determined via ultrafiltration. While free Co(II) decreased by approximately 80% in the presence of HS, free As(III) decreased just by 1%. Despite the higher percentage of As(III) potentially bioavailable, the presence of HS reduced significantly the toxicity of As at 20 µg/L (no toxicity was observed at 10 µg/L). This was attributed to direct effects of HS such as hormesis, hormone-like effects of HS and/or formation of protective coating. These effects also stimulated the reproduction, including in the assays in the absence of As and Co. HS reduced the toxicity of Co(II) at both test concentrations. The results of this investigation support that HS should be considered when safe limits for As and Co are defined.

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Humic-like substances (HLS) are molecules extracted in an alkaline medium from different materials that have not been subjected to the natural process of humification that occurs in the soil. HLS have the potential to be used as organic fertilizers due to their ability to incorporate micronutrients such as Cu(II) and Co(II); in addition, they represent an alternative for the remediation of contaminated areas due to their high affinity for metals. HLS can be extracted from hydrochar (HC) but only with low yields of approximately 5%. Therefore, the present study aimed to increase the amount of HLS extracted from the HC produced from byproducts of the sugarcane industry through the oxidation of HC with HNO3. HLS extracted from oxidized and unoxidized HC were characterized by CHNS analysis and 13C CPMAS NMR. The interaction between HLS and Cu(II) was studied by molecular fluorescence quenching (EEM-PARAFAC) and applying the Ryan and Weber complexation model. The oxidation of HC with HNO3 allowed high yields of extracted HLS of above 80%. The oxidation carried out with 30% HNO3 for 2 h showed the best result, since the HLS30%(2h) were extracted with a very high yield (88.3%) in a short period of time. Oxidation promoted a decrease in HLS aromaticity and an increase in oxygen and nitrogen groups. HLS showed high affinity for Cu(II), as evidenced by the high logK values (between 5.5 and 5.9). HLS extracted from oxidized HCs showed higher complexation capacity due to the greater incorporation of the oxygenated groups promoted by oxidation, which are fundamental during the interaction with metallic cations. Therefore, the oxidation of HC substantially increased the production of HLS, representing a big advance for the production of carbonaceous materials with higher added value from byproducts of the sugarcane industry produced on a large scale in Brazil.

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Mining generates large quantities of mineral processing wastes that are typically stored in mine tailings (MT) ponds. Long-term exposure of the surrounding areas to the material from the tailings ponds has been reported to have adverse effects on both human health and the environment. The purpose of this study was to evaluate the ability of Atriplex atacamensis Phil. to phytostabilize metals (Cu, Fe, Mn, and Zn) and sulfur (S) when grown directly on mine tailings with and without compost (C) and humic substance (HS). The stress status of A. atacamensis Phil. was also evaluated through the 13C isotopic composition of bulk leaves. A 120-day greenhouse experiment was conducted and three treatments were evaluated: (i) MT without any amendments (control), (ii) MT + C (dose: 89 ton ha-1), and (iii) MT + HS (0.72 ton ha-1). Mine tailings material exhibited low salinity, alkaline pH, high extractable S-SO4 concentrations, and low fertility; total Fe, Mn, and Zn concentrations were within the reference range for mine tailings, but total Cu concentrations were high at 1860 ± 236 mg kg-1. The HS had higher pH, EC, CEC, and available concentrations of N, P, and K than compost, while S-SO4 concentrations were similar in both amendments. 13C NMR analysis showed that the HS contained more alkyl, aromatic, and phenolic groups, while the compost was dominated by O-alkyl and carboxyl groups. At the end of the experiment, the MT + C treatment achieved a significant decrease in Cu, Fe, and Mn concentrations in the roots and aboveground parts of A. atacamensis Phil. and an increase in Zn values in both tissues. Both amendments increased the sulfur content in the aboveground parts, while metal concentrations under the HS treatment proved similar to control. Furthermore, the δ13CV-PDB values obtained in this study indicate that the organic amendments did not cause additional physiological stress to the plants compared to the MT treatment. Overall, A. atacamensis Phil. was shown to have the ability to phytostabilize metals and sulfur, making it a potential candidate species for in situ evaluation of the phytostabilization process on mine tailings.

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The use of metal-based and, particularly, Al2O3 nanoparticles (Al2O3-NP) for diverse purposes is exponentially growing. However, the growth of such promissory market is not accompanied by a parallel extensive investigation related to the impact of this pollution on groundwater and biological systems. Pseudomonas species, ubiquitous, environmentally critical microbes, frequently respond to stress conditions with diverse strategies that generally include extracellular polymeric substances (EPS) formation. The aim of this study is to report that changes in the aqueous environment, particularly, the addition of Al2O3-NP without and with humic acids, induce different adaptive strategies of Pseudomonas aeruginosa early biofilms. To this purpose, early biofilms were incubated in diluted culture media without (control) and with Al2O3-NP, and with humic acids (HA-control, HA-Al2O3-NP) for 24 h. 3D colonies with EPS strings and isolated bacteria in their surroundings were detected in the control biofilms. Unlikely, an unusual adaptive behaviour was developed in the presence of Al2O3-NP. Bacteria opt to disassemble the 3D arrangements and to implement a 2D network promoting morphological and size changes of bacterial cells (small coccoid shapes). Remarkably, this strategy allows their temporarily non-EPS-depending survival without decreasing the number of cells. This behaviour was not observed with ZnO-NP, HA-Al2O3-NP, or HA-ZnO-NP. Physicochemical analysis revealed that HA were adsorbed on Al2O3-NP and promoted the Al(III) ions complexation. This supports the hypothesis that the reduction of toxicity of Al ions and the 3D colony formation in the presence of HA-Al2O3-NP is promoted by the complexation of the metal ions with HA components.

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The impact of pig slurry (PS) application on the structural dynamics of humic substances (HS) and on the mobility of Cu, Zn, Ni, and Pb in a dystrophic Red Nitosol planted with winter forage grasses was evaluated. After four PS applications, the humic acids (HA) and fulvic acids (FA) were characterized by spectroscopy techniques allied to chemometrics methods. The metals contents in soil, in HS and in the tissues of plant were quantified. PS application increases the total organic carbon, especially the nonhumic carbon, which contribute to increase FA content. The carbon in FA and HA increases with the highest PS dose applied, especially aliphatic structures in FA and aromatic structures in HA. The amount of Pb and Cu in FA and HA increases respectively, as well as Cu, Zn, Ni, and Pb bioavailable. PS applications increase the biomass production in grasses and the metals content accumulated in the tissues. Our study shows that the PS application modifies the structure of SOM, incorporating fragments, and modifying its dynamics, which regulates the dynamics and the accumulation of metals in soils and plants. The association of metals with soluble structures seems to inactivate their toxicity and does not affect plant growth.

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