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Antibiotics and pesticides, as well as various emerging contaminants that are present in surface waters, raise significant environmental concerns. Advanced oxidation processes, which are employed to eliminate these substances, have demonstrated remarkable effectiveness. However, during the degradation process, by-products that are not completely mineralized are generated, posing a substantial risk to aquatic ecosystem organisms; therefore, it is crucial to assess effluent ecotoxicity following treatment. This study aimed to assess the toxicity of effluents produced during the removal of amoxicillin and glyphosate with a Fenton-type process using a laminar structure catalyzed with iron (Fe) and copper (Cu). The evaluation included the use of Daphnia magna, Selenastrum capricornutum, and Lactuca sativa, and mutagenicity testing was performed using strains TA98 and TA100 of Salmonella typhimurium. Both treated and untreated effluents exhibited inhibitory effects on root growth in L. sativa, even at low concentrations ranging from 1% to 10% v/v. Similarly, negative impacts on the growth of algal cells of S. capricornutum were observed at concentrations as low as 0.025% v/v, particularly in cases involving amoxicillin-copper (Cu) and glyphosate with copper (Cu) and iron (Fe). Notably, in the case of D. magna, mortality was noticeable even at concentrations of 10% v/v. Additionally, the treatment of amoxicillin with double-layer hydroxides of Fe and Cu resulted in mutagenicity (IM ≥ 2.0), highlighting the necessity to treat the effluent further from the advanced oxidation process to reduce ecological risks.

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A grafting of N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMSPDETA) on natural clay was carried out to obtain an organic-inorganic hybrid clay material that was applied as an adsorbent to the uptake of Reactive Blue 19 (RB-19) and Reactive Green 19 (RG-19) dyes from aqueous wastewaters. This research demonstrates the effect of TMSPDETA contents on amino-functionalized clay materials' hydrophobic/hydrophilic behavior. The resultant material was utilized to uptake reactive dyes in aqueous solutions. The clay@TMSPDETA hybrid material was characterized by isotherm of adsorption and desorption of nitrogen, FTIR, elemental analysis, TGA, pHpzc, total acidity, total basicity groups, and hydrophilic balance. The hybrid samples were more hydrophilic than the pristine clay for ratios from 0.1 up to 0.5 due to adding amino groups to the pristine clay. FTIR spectra suggest that TMSPDETA was grafted onto the clay. The hybrid material presents a surface area 2.17-fold (42.7 m2/g) lower than pristine clay (92.7 m2/g). The total volume of pores of hybrid material was 0.0822 cm3/g, and the pristine clay material was 0.127 cm3/g, corresponding to a diminution of the total pore volume (Vtot) of 1.54 times. The kinetic data followed the pseudo-second-order (PSO) model for RB-19 and RG-19 reactive dyes. The equilibrium data were better fitted to the Liu isotherm model, displaying a Qmax as 178.8 and 361.1 mg g-1 for RB-19 and RG-19, respectively, at 20.0 °C. The main mechanism of interactions of the reactive dyes with the hybrid clay is electrostatic interaction. The clay@TMSPDETA has a very good effect on treating synthetic dye-textile wastewater. The removal percentage of simulated wastewater was up to 97.67% and 88.34% using distilled water and plastic industry wastewater as the solvents, respectively. The clay@TMSPDETA-0.1 could be recycled up to 5 cycles of adsorption and desorption of both dyes, attaining recoveries of 98.42% (RB-19) and 98.32% (RG-19) using 0.1 M HCl + 10% ethanol.

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The presence of ultrafine clay particles that are difficult to remove by conventional filtration creates many operational problems in mining processing systems. In this work, the removal of clay suspensions has been investigated using an electroflotation (EF) process with titanium electrodes. The results show that EF is a viable and novel alternative for removing ultrafine particles of kaolinite-type clay present in sedimentation tank overflows with low salt concentrations (<0.1 mol/L) in copper mining facilities based on the saline water splitting concept. Maximum suspended solid removal values of 91.4 and 83.2% in NaCl and KCl solutions, respectively, were obtained under the experimental conditions of the constant applied potential of 20 V/SHE, salinity concentration of 0.1 mol/L, and electroflotation time of 10 and 20 min in NaCl and KCl solutions, respectively. Furthermore, the visual evidence of particle aggregation by flocculation during the experiments indicates a synergy between EF and electrocoagulation (EC) that enhances the removal of ultrafine particles of kaolinite.

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This study focuses on the radiolysis (up to 36 kGy) of guanine and adenine (nitrogenous bases) adsorbed in hectorite and attapulgite to highlight the potential role of clays as protective agents against ionizing radiation in prebiotic processes. In this framework, the study investigated the nitrogenous bases' behavior in two types of systems: a) aqueous suspension of adenine-clay systems and b) guanine-clay systems in the solid state. This research utilized spectroscopic and chromatographic techniques for its analytical purposes. Regardless of the reaction medium conditions, the results reveal that nitrogenous bases are stable under ionizing irradiation when adsorbed on both clays.

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Supramolecular structures are of great interest due to their applicability in various scientific and industrial fields. The sensible definition of supramolecular molecules is being set by investigators who, because of the different sensitivities of their methods and observational timescales, may have different views on as to what constitutes these supramolecular structures. Furthermore, diverse polymers have been found to offer unique avenues for multifunctional systems with properties in industrial medicine applications. Aspects of this review provide different conceptual strategies to address the molecular design, properties, and potential applications of self-assembly materials and the use of metal coordination as a feasible and useful strategy for constructing complex supramolecular structures. This review also addresses systems that are based on hydrogel chemistry and the enormous opportunities to design specific structures for applications that demand enormous specificity. According to the current research status on supramolecular hydrogels, the central ideas in the present review are classic topics that, however, are and will be of great importance, especially the hydrogels that have substantial potential applications in drug delivery systems, ophthalmic products, adhesive hydrogels, and electrically conductive hydrogels. The potential interest shown in the technology involving supramolecular hydrogels is clear from what we can retrieve from the Web of Science.

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A clay-based adsorbent (CBA) was purified from a sustainable precursor (raw clay, RC), which was obtained from the Amazon region in Brazil. The CBA was characterized using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Brunauer-Emmet-Teller surface area (SBET, RC = 23.386 m2.g-1, CBA = 33.020 m2.g-1), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), thermogravimetric analysis (TGA), cation exchange capacity (CEC, CBA = 44.75 cmol/kg), and point of zero charge analyses (pHPZC, CBA = 2.20). Subsequently, CBA was used to adsorb basic yellow 2 (BY2) dye from aqueous solutions. A CBA dosage (1 g/L), initial concentration of dye (C0 = 15 mg/L), and pH (5.6) were ideal conditions for the BY2 dye removal of ~ 98%. The BY2 kinetics was better represented by the pseudo-first-order (PFO) model while the BY2 equilibrium was well represented by the Sips model, with a maximum adsorption capacity of qms = 18.04 mg/g at 28 °C. The negative values of ΔG° and ΔH° showed that the studied process is spontaneous and exothermic, while the values of isosteric heat (∆Hst, -16 to -20 kJ/mol) suggest a predominance of physical interactions. The molecular chemical reactivity of BY2 was investigated using quantum chemical descriptors calculated based on Density Functional Theory (DFT) optimization of the dye molecule, and the results revealed a large energy gap value (4.3900 eV) and considerable chemical hardness (η = 2.1950 eV). Therefore, the correlation between DFT and experimental results consistently sustains that BY2 dye tends to be adsorbed on the CBA surface by electrostatic interactions, thus, this is the possible adsorption mechanism of this process.

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The development of biomaterials has a substantial role in pharmaceutical and medical strategies for the enhancement of life quality. This review work focused on versatile biomaterials based on nanocomposites comprising organic polymers and a class of layered inorganic nanoparticles, aiming for drug delivery (oral, transdermal, and ocular delivery) and tissue engineering (skin and bone therapies). Layered double hydroxides (LDHs) are 2D nanomaterials that can intercalate anionic bioactive species between the layers. The layers can hold metal cations that confer intrinsic biological activity to LDHs as well as biocompatibility. The intercalation of bioactive species between the layers allows the formation of drug delivery systems with elevated loading capacity and modified release profiles promoted by ion exchange and/or solubilization. The capacity of tissue integration, antigenicity, and stimulation of collagen formation, among other beneficial characteristics of LDH, have been observed by in vivo assays. The association between the properties of biocompatible polymers and LDH-drug nanohybrids produces multifunctional nanocomposites compatible with living matter. Such nanocomposites are stimuli-responsive, show appropriate mechanical properties, and can be prepared by creative methods that allow a fine-tuning of drug release. They are processed in the end form of films, beads, gels, monoliths etc., to reach orientated therapeutic applications. Several studies attest to the higher performance of polymer/LDH-drug nanocomposite compared to the LDH-drug hybrid or the free drug.

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The use of layered double hydroxides (LDHs) as adsorbent for water treatment has been gaining relevance in recent years. In this context, this work aimed to map, through a bibliometric study, the extent of research that deals with the theme. The scientific database used was the Web of Science, and the chronology of the search consideredthe period from 1997 to 2022. The bibliometix R-package and VOSviewer software were used in this study. The searches retrieved a total of 663 documents, from 69 countries, distributed among all continents, which China (328), India (51) and Japan (40) were the most productive countries. Important journals in the environmental area and with high impact factor, such as Chemical Engineering Journal (44), Applied Clay Science (38), Journal of Hazardous Materials (35) and Chemosphere (27) most published in the area. The network of keywords used by the authors indicates that the publications retrieved deal mainly with aspects related to the efficiency of (LDHs) in the removal of different pollutants, the composition, the synthesis route and the association with other materials and/or techniques. The result of this study constitutes an important tool for directing future research on the subject.

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The bacterium Streptomyces sp. is a common genus of the actinomycetes class found in soils and rhizospheres. This bacterium can produce substances with bio-stimulant capacity through the fixation of nitrogen from the air. In this work, the Streptomyces sp. bacterium was immobilized on a ZnMgAl-hydrotalcite clay and embedded in calcium alginate beads to generate a novel bio-composite that functions as a bacterial reservoir and as a controlled release material for bacteria to be used as a bio-fertilizer.The results showed that the novel bacterium-hydrotalcite/alginate bio-composite was very efficient as a bio-fertilizer showing a plant length of 64 mm in only 14 days of growing, which corresponds to an increase of ca. 760% in the lettuce plant growth in comparison with the materials without bacteria. In short, the present results demonstrate that the hydrotalcite and alginate served as an excellent container to keep the bacteria alive, providing nutrients to them and controlling their delivery.

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RESUMO Os aterros sanitários são obras construídas para o confinamento seguro dos resíduos sólidos e, entre seus elementos de projeto, destaca-se a camada de impermeabilização da cobertura final, frequentemente construída com solo argiloso, que deve, entre outras funções, minimizar ao máximo a infiltração de águas pluviais para o interior do aterro e o fluxo de gases com o meio ambiente. As características físicas, químicas e mineralógicas dos materiais dessa camada devem ser analisadas para a avaliar seu potencial de utilização. O presente trabalho teve como objetivo avaliar o desempenho de argilas expansivas, sujeitas à variação de umidade, como material impermeabilizante de cobertura de aterros sanitários, sendo caracterizadas duas amostras por meio de ensaios geotécnicos. As características foram compatíveis com os requisitos exigidos nas normas consultadas. A parte superior de uma camada de argila compactada foi reproduzida com uma das amostras em um modelo experimental, sujeita à secagem, com observação da formação de trincas e medições do teor de umidade ao longo do tempo e profundidade. A formação de trincas na superfície se iniciou para teores de umidade acima do limite de plasticidade. A aplicação de uma carga hidráulica na superfície após a etapa de secagem resultou em um fechamento das trincas em razão da expansão da argila, indicando eficiência na restrição de entrada de águas pluviais. No entanto, o uso de material expansivo para esse fim deve ser investigado quanto ao seu desempenho em campo, tanto na fase de construção, durante a compactação, quanto de operação, quando estará sujeito às variações climáticas.

ABSTRACT Solid waste landfills are works built to contain solid urban waste, being the most used final disposal method in Brazil. One of the most important components of the project is the final cover, the low hydraulic conductivity layer, with clayey materials, which has the function of minimizing the infiltration of rainwater into the landfill and the entry and exit of gases. The physical, chemical and mineralogical characteristics of clayey materials must be analyzed for potential use as a cover layer. The present work aimed to evaluate the use of clays, with expansive characteristics, subject to water content variations, as cover material in landfills, being characterized two clay samples through geotechnical tests. The characterization indicated samples with characteristics compatible with the requirements demanded by the consulted standards. One of them was used in a laboratory model and reproduced the upper part of a layer of compacted clay, subject to drying on the surface, with observation of the formation of cracks, and with measurements of the water content over time and depth. Cracks on the clay surface occurred during the drying process, starting for water contents above the limit of plasticity of the clay. The application of a hydraulic head on the surface, after the drying step, resulted in cracks closure, due to the expansion of the clay, indicating efficiency in the restriction of rainwater entry. However, the use of expansive material for this purpose should be investigated regarding its performance in the field, both in the construction phase, during compaction, and in operation, subject to climatic variations.

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This research presents the results of a pilot system used for water treatment to be supplied to single-family or small housing nucleus at rural sector. The pilot system is constituted by an up-flow aerated filter with ceramic carrier, followed by a second down-flow filter of silica sand. The pilot plant was installed in a rural sector of the province of Loja, Ecuador, with the main purpose of monitoring the reduction in bacteria in the water for human consumption. Two natural clays from the area were tested. They were transformed into sphere-type ceramics, and then, they were placed in the pilot filters. These both natural clays are inorganic materials with high content of aluminosilicate clay minerals with favourable characteristics to achieve greater efficiency for the reduction in bacteria. The acclimatization time of 60 days allowed to achieve optimum treatment efficiency performance until 90 days of operation. The physicochemical parameters, namely temperature, pH, dissolved oxygen and total dissolved solids, were monitored throughout the experiments. Regarding microbiological parameters, up to 99% of total coliforms removal was reached for the clay called CF-CC and 79% for the other, called CF-CV. In addition, 100% of total coliforms and Escherichia Coli removal was reached for both clay systems. Social and economic viability of the proposed treatment is also analysed in the manuscript.

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Calcined clay has become the supplementary cementitious materials with the greatest potential to reduce the clinker/cement. In this research, the mechanical strengths and sulphate resistance of blended cements with a high content of calcined clay as a pozzolanic addition were evaluated to demonstrate that these cements could be designed as CEM (cement) type IV/A-SR and IV/B-SR cements by the current European standard UNE-EN 197-1: 2011. The blended cements were prepared by two Portland cements (P1 and PY6) with different mineralogical compositions and a calcined clay. The level of replacement was greater than 40% by weight. The results obtained confirm the decrease in the mechanical strengths and the increase in the sulfate resistance of the two Portland cements when they are replaced by calcined clay at a level of replacement greater than 40%. These results are a consequence of the chemical effect from the pozzolanic activity of the calcined clay. Therefore, there is an important decrease in portlandite levels of paste liquid phase that causes the increase in sulfate resistance and the decrease of the mechanical strengths.

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Due to their abundance in nature, clays have been frequently studied in the adsorption of different emergent contaminants, since they have good efficiency and low cost. Therefore, the present study aimed to evaluate the performance of commercial organoclays as an adsorbent in the environmental remediation of wastewater containing the herbicide Diuron. The clay was characterized by the techniques of N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and point of zero charge. In the batch adsorption experiments it was verified that the adsorption kinetics is ruled by the pseudo-second-order model (R2 > 0.97), and the adsorption equilibrium study at different temperatures (298, 302 and 308 K) showed that the non-linear models of Langmuir (R2 > 0.99) and Freundlich (R2 > 0.98) were those that present better adjustments to the experimental data. In addition, the adsorption capacity in monolayer (qmax) was 44.24 mg g-1, being higher or comparable to several works reported in the literature. As for the thermodynamic adsorption study, it was possible to infer that the process is spontaneous (ΔG°ads < 0) and endothermic (ΔH°ads = 71.58 kJ mol-1) in the temperature range studied. As far as the regeneration study was concerned, the maximum desorption capacity, 26.59 mg g-1, was obtained from the use of ethanol as eluent at 298 K.

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Mg-Fe layered double hydroxide intercalated with chloride (Mg-Fe-Cl LDH) was synthetized, characterized, and evaluated as adsorbent to remove nitrate from aqueous solution. The pH, initial nitrate concentration, adsorbent dosage, and particle size were investigated. Kinetic data was best represented by pseudo-second order model indicating that the rate limiting step was chemisorption. Intraparticle diffusion model indicates that adsorption kinetic is limited by external and intraparticle diffusion. Sips model was selected, based on R2, ARE, and AIC, to adequately represent the adsorption isotherms, which permits to affirm that the adsorption occurs in heterogeneous surface, obtaining the maximum adsorption capacity of 18.17 mg.g-1 at 30 oC. Thermodynamics parameters indicate that the adsorption was spontaneous, exothermic, and with structural modification. These findings come up with Mg-Fe-Cl LDH as a suitable adsorbent for nitrate and could contribute to its removal from the water and wastewater.

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Electrocoagulation consists of the in-situ generation of the coagulant by the electro dissolution of sacrificial electrodes (Mg and Al). This technique, besides being normally used for water treatment, can be used to synthesize Layered Double Hydroxides (LDH) or Hydrotalcites (HT) such as green rust, MgAlCl/LDH, and other oxides as Magnetite. The HT has a high tendency for water in the interlayer to be replaced by anions, these exchange characteristics generate a high interest in the fields of drug administration, photodegradation, catalyst supports, supercapacitors, and water oxidation. There are several routes of synthesis for these compounds such as co-precipitation, hydrolysis of urea, hydrothermal treatment and a novel route by electrocoagulation (EC). This work discloses the data of the energy consumption at laboratory-scale production in the synthesis of hydrotalcite (HT) or Layered Double Hydroxides (LDH) by electrocoagulation, the values obtained through these experiments are intended to provide support due to the lack of information on the energy consumption of this novel production method. Aluminum and AZ31 electrodes were used as a cations source during two- and four-hours operation, at 50 °C with 5 mA cm-2 of current density, and 5 minutes of polarity change for Aluminum and 8 minutes for AZ31 (Magnesium alloy).

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Two bentonites from Paraíba (Northeastern Brazil) were impregnated with heteropoly phosphomolybdic H3PMo12O40 (HPMo). The materials produced were characterized by various techniques such as N2 adsorption-desorption (specific surface area, SSA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermogravimetric analysis (TGA/DTG), Scanning Electron Microscopy (SEM) equipped with Dispersive Energy X-ray spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-vis), acid-base titration analysis. The catalytic activity of these materials was tested in the esterification of a waste from palm oil deodorization and the main results obtained (about 93.3% of conversion) indicated that these materials have potential to act as heterogeneous solid acid catalysts. The prepared materials exhibited satisfactory catalytic performance even after a very simple recycling process in three reuse cycles, without significant loss of their activities.

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In this study, natural and modified clays were evaluated as catalysts in an esterification reaction to obtain bio-based lubricants. The biolubricants are environmentally preferred to petroleum-based lubricants because they are biodegradable and non-toxic. Other advantages include very low volatility due to the high molecular weight and excellent viscosity properties with temperature variations. Modifications in natural clay were performed intending to obtain materials with different textural properties that could improve the reaction under study. The modified clays were obtained in two ways: by pillarization using Al13 Keggin polyoxocations or by acid treatments with H2SO4, HCl and HNO3. All samples were evaluated for the esterification reaction of fatty acids from castor oil (FACO) using 2-ethyl-hexanol. During the reaction step, a zeolite-based adsorbent was used for water removal to increase the reaction equilibrium conversion. Gas chromatography and nuclear magnetic resonance were performed to ensure the formation of the products. The highest conversion of fatty acids to esters was obtained using pillared clays. Adding adsorbent in the reaction medium (10 g of 3A zeolite to 100 g of FACO), the conversion improved from 74⁻88 wt % after 6 h at 50 °C.

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Iron nanoparticles can be incorporated on the structure of natural clays to obtain magnetic clays, an adsorbent that be easily removed from a wastewater by magnetic means. Magnetic clays have high adsorption capacities of different contaminants such as heavy metals, fungicides, aromatic compounds and colorants and show rapid adsorption kinetics, but crucial data for achieving its full or pilot scale application is still lacking. In this work, magnetic bentonites with different amounts of magnetite (iron fractions on the clay of 0.55, 0.6 and 0.6) were used to remove color from a real textile wastewater. On a first stage the optimal conditions for the adsorption of the dye, including pH, temperature and clay dosage were determined. Also design parameters for the separation process such as residence time, distance from magnet to magnetic clay and magnet strength were obtained. Finally a pilot scale magnetic drum separator was constructed and tested. A removal of 60% of the dye from a wastewater that contained more than 250 ppm of azo dye was achieved with only 10 min of residence time inside the separator.

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This study was conducted to evaluate color and anthocyanin stability of clarified acerola juice (CAJ) as affected by montmorillonite (Mnt) at different concentrations (0-6 wt%, dry basis). While non-complexed CAJ suffered noticeable color degradation with time and pH variations, the presence of Mnt (especially at 4-6 wt%) not only changed the initial color of CAJ but also made it more stable with time and pH changes. CAJ/Mnt mixtures were ultracentrifuged in order to separate them into supernatants and anthocyanin-complexed Mnt precipitates. The supernatants presented decreasing anthocyanin contents with increasing Mnt concentrations, indicating pigment retention by the precipitates. X-ray diffraction of precipitates showed that Mnt interlayer spacing was increased by increasing anthocyanin/Mnt ratios, corroborating anthocyanin intercalation. FTIR revealed a band at 1530 cm-1 ascribed to formation of anthocyanin-Mnt complexes. Moreover, chromatograms indicated the selective adsorption of two compounds by Mnt, which were identified by LC-MS as cyanidin-3-O-rhamnoside and pelargonidin-3-O-rhamnoside.

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Emerging contaminants in the environment have caused enormous concern in the last few decades, and among them, antibiotics have received special attention. On the other hand, adsorption has shown to be a useful, low-cost, and eco-friendly method for the removal of this type of contaminants from water. This work is focused on the study of ciprofloxacin (CPX) removal from water by adsorption on pillared clays (PILC) under basic pH conditions, where CPX is in its anionic form (CPX-). Four different materials were synthetized, characterized, and studied as adsorbents of CPX (Al-, Fe-, Si-, and Zr-PILC). The highest CPX adsorption capacities of 100.6 and 122.1 mg g-1 were obtained for the Si- and Fe-PILC (respectively), and can be related to the porous structure of the PILCs. The suggested adsorption mechanism involves inner-sphere complexes formation as well as van der Waals interactions between CPX- and the available adsorption sites on the PILC surfaces.