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Cefadroxil is a widely used antibiotic with a low elimination efficiency in wastewater treatments plants, so it represents a contaminants of emerging concern that should be removed. The photosensitization process that involves natural pigments and visible sunlight can be offered as an environmentally friendly alternative to be considered for Cefadroxil degradation. In this investigation, we carried out a mechanistic and kinetic approach to Cefadroxil photodegradation sensitized by Riboflavin and Humic Acid, in individual and combined processes. Our experiments indicate that Cefadroxil is able to interact with the excited states of Riboflavin as well as with the photogenerated reactive oxygen species, with an important contribution of singlet oxygen. The antibiotic was less sensitive to the photodegradation in the presence of Humic Acids and in the mixture of Riboflavin and Humic Acids. Self-sensitization processes and internal filter effects are proposed as possible explanations for the observed phenomenon. The reaction between Cefadroxil and singlet oxygen showed a dependence with the pH of the medium, the photodegradation kinetic constants are greater at alkaline pH compared to neutral pH. The reaction is favored when the anionic species of the antibiotic is present. Microbiological tests on S. aureus indicated that the antibiotic reduce its antimicrobial activity as a consequence of the photooxidative process mediated by singlet oxygen. We believe that the results are relevant since, the sensitized photodegradation process could lead to the oxidation of Cefadroxil and to the progressive loss of its antimicrobial function, this fact could contribute to the decrease in the generation of bacterial multi-resistance to antibiotics in the environment.

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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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Silver nanoparticles (AgNPs) are among the most produced nanomaterials in the world and are incorporated into several products due to their biocide and physicochemical properties. Since freshwater bodies are AgNPs main final sink, several consequences for biota are expected to occur. With the hypothesis that AgNPs can interact with environmental factors, we analyzed their ecotoxicity in combination with humic acids and algae. In addition to the specific AgNPs behavior in the media, we analyzed the mortality, growth, and phototactic behavior of Chydorus eurynotus (Cladocera) as response variables. While algae promoted Ag+ release, humic acids reduced it by adsorption, and their combination resulted in an intermediated Ag+ release. AgNPs affected C. eurynotus survival and growth, but algae and humic acids reduced AgNPs lethality, especially when combined. The humic acids mitigated AgNP effects in C. eurynotus growth, and both factors improved its phototactic behavior. It is essential to deepen the study of the isolated and combined influences of environmental factors on the ecotoxicity of nanoparticles to achieve accurate predictions under realistic exposure scenarios.

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Droughts are becoming more intense and frequent in the Brazilian semiarid because of El Niño and global climate changes. The Jaguaribe River estuary is a semiarid ecosystem that experiences a reduction in freshwater discharges due to droughts and river damming. The decrease in freshwater fluxes has increased metal availability through the water residence time increase in the Jaguaribe River estuary. Then, this study aimed to evaluate the dissolved organic matter quality and its interaction with metals in the Jaguaribe River estuary after a severe drought period. It was performed through carbon analyses, fluorescence spectroscopy, ultrafiltration technique, and determinations of metals by ICP-MS. Optical analysis showed that the dissolved organic carbon (DOC) was preponderantly composed of terrestrial-derived humic compounds, while the low ratio between the particulate organic carbon (POC) and chlorophyll-a indicated that POC was predominantly phytoplankton-derived. DOC and POC presented non-conservative removal during the estuarine mixing. DOM and dissolved elements were mostly distributed within the LMW fraction and presented a low percentage in the colloidal fraction. Li, Rb, Sr, Mo, and U showed conservative behavior, while Cu, Fe, Cr, and V had non-conservative behavior with a significant positive correlation with DOM, suggesting DOM as a relevant driver of metal availability at the Jaguaribe River estuary even during the rainy season.

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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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Humified organic matter has been shown to decrease Pb toxicity in plants. However, there are still gaps in our understanding of the mechanism by which this phenomenon occurs. In this study, we aimed to assess the ability of humic substances (HSs), humic acids (HAs), and fulvic acids (FAs) to enhance defense mechanisms in rice plants under lead (Pb)-stressed conditions. HS fractions were isolated from vermicompost using the chemical fractionation methodology established by the International Humic Substances Society. These fractions were characterized by solid-state NMR and FTIR. Chemometric analysis was used to compare humic structures and correlate them with bioactivity. Three treatments were tested to evaluate the protective effect of humic fractions on rice plants. The first experiment involved the application of humic fractions along with Pb. The second comprised pretreatment with humic fractions followed by subsequent exposure to Pb stress. The third experiment involved Pb stress and subsequent treatment with humic fractions. The root morphology and components of the antioxidative defense system were evaluated and quantified. The results showed that HS + Pb, HA + Pb, and FA + Pb treatment preserved root growth and reduced the levels of O2- and malondialdehyde (MDA) in the roots by up to 5% and 2%, respectively. Pretreatment of the plants with humic fractions promoted the maintenance of root growth and reduced the contents of O2-, H2O2, and MDA by up to 48%, 22%, and 20%, respectively. Combined application of humic fractions and Pb reduced the Pb content in plant tissues by up to 60%, while pretreatment reduced it by up to 80%. The protective capacity of humic fractions is related to the presence of peptides, lignin, and carbohydrate fragments in their molecular structures. These results suggest that products could be developed that can mitigate the adverse effects of heavy metals on agricultural crops.

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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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BACKGROUND: Understanding the interaction mechanisms and the relevant binding constants between humic acids and emerging or regulated pollutants is of utmost importance in predicting their geochemical mobility, bioavailability, and degradation. Fluorescence spectroscopy, UV-vis spectroscopy, equilibrium dialysis, and solid-phase extraction combined with liquid chromatography-mass spectrometry have been employed to elucidate interactions of humic acids with organic micropollutants, especially pharmaceutical drugs. These methods demand large sample volumes, long equilibration times, and laborious extraction steps which may imply analytical errors. Monolithic high-performance affinity chromatography is an alternative and simpler method to investigate these interactions and determine the binding constants. RESULTS: Polymer monoliths based on aminated glycidyl methacrylate and ethylene glycol dimethacrylate served to immobilize Cu(II) and then humic acid to produce monolithic affinity chromatography columns with humic acid as the active interaction phase. About 86.5 mg of humic acid was immobilized per gram of polymer. The columns enabled a comparison of the binding strength of humic acid with herbicides and emerging pollutants at 25 °C and pH 6.0 ± 0.1. Paracetamol, acetylsalicylic acid, and salicylic acid did not retain. Among the compounds that interacted with humic acid, the order of increasing affinity, estimated by the global affinity constant (nKa) or partition coefficient (KD) was: caffeine < simazine < atrazine âˆ¼ propazine < benzophenone. The nKa (L mol-1) values ranged from (4.9 ± 0.3) × 102 for caffeine to (1.9 ± 0.3) × 103 for benzophenone, whereas KD (L kg-1) varied from 14 ± 1 to 56 ± 8 for the same compounds. SIGNIFICANCE AND NOVELTY: To our knowledge, this is the first paper demonstrating the use of a monolithic platform to immobilize supramolecular structures of humic acids exploiting immobilized metal affinity to comparatively evaluate their affinity towards emerging pollutants exploiting the concepts of high-performance affinity chromatography. The proposed approach needs only small amounts of humic acid, which is a relevant feature in preparing columns with humic substances isolated and purified from remote areas.

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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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It is known that copper can be used as catalyst in photo-Fenton-like process; however, there is a lack of information related with its use in the treatment of landfill leachate (LL) in solar photo-Fenton-like processes. Here, we studied the effect of the mass of a copper sheet, the pH of the solution, and the concentration of LL in the removal of the organic matter present in this water. Before the reaction with landfill leachate, the copper sheet used in the reaction was constituted by Cu+ and Cu2O, respectively. The results showed that in a volume of 0.5 L of a pretreated LL, the higher removal of organic matter resulted using a mass of 2.7 g of the copper sheet, a pH of solution of 5, and a concentration of LL of a 10%, obtaining a final value of C/C0 of chemical oxygen demand (COD) of 0.34, 0.54, 0.66, and 0.84 for concentrations of 25%, 50%, 75%, and 100%, respectively, and 0.0041, 0.0042, 0.0043, and 0.016 for concentration of 25%, 50%, 75%, and 100%, respectively, of C/C0 of humic acids. The photolysis on LL at its natural pH using solar UV removes very little humic acid and COD, going from 9.4 to 8.5 and 7.7 Abs254 for photolysis and UV + H2O2, obtaining 8.6 and 17.6% of removal, respectively, and 2.01 and 13.04% removal of COD, respectively. Copper sheet applied under Fenton-like conditions results in 65.9% removal and an increase of 0.2% for humic acid and COD, respectively. Removal using only H2O2 for Abs254 and COD was 11.95 and 4.3%, respectively. Raw LL produced a 29.1% inhibition of the biological activated sludge rate after the adjustment to pH 7 and the final process of inhibition was 0.23%.

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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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Vermicompost was used for humic acid (HA) preparation, and the adsorption of aflatoxin B1 (AFB1) was investigated. Two forms of HA were evaluated, natural HA and sodium-free HA (SFHA). As a reference, a non-commercial zeolitic material was employed. The adsorbents were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), energy-dispersive X-ray spectroscopy (EDS), zeta potential (ζ-potential), scanning electron microscopy (SEM), and point of zero charge (pHpzc). The adsorbent capacity of the materials when added to an AFB1-contaminated diet (100 µg AFB1/kg) was evaluated using an in vitro model that simulates the digestive tract of chickens. Characterization results revealed the primary functional groups in HA and SFHA were carboxyl and phenol. Furthermore, adsorbents have a highly negative ζ-potential at the three simulated pH values. Therefore, it appears the main influencing factors for AFB1 adsorption are electrostatic interactions and hydrogen bonding. Moreover, the bioavailability of AFB1 in the intestinal section was dramatically decreased when sorbents were added to the diet (0.2%, w/w). The highest AFB1 adsorption percentages using HA and SFHA were 97.6% and 99.7%, respectively. The zeolitic material had a considerable adsorption (81.5%). From these results, it can be concluded that HA and SFHA from vermicompost could be used as potential adsorbents to remove AFB1 from contaminated feeds.

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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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This work reports the development and application of a simple, rapid and low-cost voltammetric method for the determination of 3-methylmorphine at nanomolar levels in clinical and environmental samples. The proposed method involves the combined application of a glassy carbon electrode modified with reduced graphene oxide, chitosan and bismuth film (Bi-rGO-CTS/GCE) via square-wave voltammetry using 0.04 mol L-1 Britton-Robinson buffer solution (pH 4.0). The application of the technique yielded low limit of detection of 24 × 10-9 mol L-1 and linear concentration range of 2.5 × 10-7 to 8.2 × 10-6 mol L-1. The Bi-rGO-CTS/GCE sensor was successfully applied for the detection of 3-methylmorphine in the presence of other compounds, including paracetamol and caffeine. The results obtained also showed that the application of the sensor for 3-methylmorphine detection did not experience any significant interference in the presence of silicon dioxide, povidone, cellulose, magnesium stearate, urea, ascorbic acid, humic acid and croscarmellose. The applicability of the Bi-rGO-CTS/GCE sensor for the detection of 3-methylmorphine was evaluated using synthetic urine, serum, and river water samples through addition and recovery tests, and the results obtained were found to be similar to those obtained for the high-performance liquid chromatography method (HPLC)-used as a reference method. The findings of this study show that the proposed voltammetric method is a simple, fast and highly efficient alternative technique for the detection of 3-methylmorphine in both biological and environmental samples.

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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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Described is the enhancement of fluorescence intensity due to the interaction of a humic-like substance (HLS 1%) extracted from process water (PW) and Cd(II) ions in aqueous solution. Using Canonical Polyadic/Parallel Factor Analysis (CP/PARAFAC), two main components were seen that contributed to fluorescence, the first one increased it and the second one kept it constant in both static and dynamic fluorescence studies. Two-dimensional FTIR analysis indicated that the interaction of HLS 1% and Cd(II) ions occurred in the following order of affinity with the groups: C-O bonds in polysaccharides > C-O bonds in carboxylic acid. The results obtained suggest that the increase in fluorescence intensity and lifetime suggest a photoinduced charge transfer (PCT) between Cd(II) ions and carboxylic acid groups present in HLS 1%.

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The adsorption of ceftriaxone (CET) and doxycycline (DOX) from aqueous solution using ferrihydrite/plant-based composites (silica rice husk) to reduce their negative impact on the ecosystem was adequately studied. On the other hand, phosphate and humic acid are often found in water and soil; in view of this, their effects on the adsorption of CET and DOX were investigated. The results showed that the removal of ceftriaxone decreased with an increase in pH, while that of doxycycline did not. Ferrihydrite with 10% silica rice husk (Fh-10%SRH) has the highest maximum adsorption capacity of 139 and 178 mg g-1 for CET and DOX, respectively, at room temperature based on Liu's adsorption isotherm. This implies that the presence of silica rice husk increases CET and DOX uptake due to an increase in the pore volume of FH-10%SRH. The results showed that phosphate had a significant inhibition role on CET adsorption and minor on DOX, whereas humic acid salt affected neither case. Increase in temperature up to 333 K favored the adsorption of both contaminants. The proposed adsorption mechanisms of ceftriaxone are electrostatic interaction, n-π interaction, and hydrogen bond, while that of DOX entails n-π interaction and hydrogen bond.

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