Computational and experimental assessment of efficient dye adsorption method from aqueous effluents by halloysite and palygorskite clay minerals.

The removal of dyes from effluents of textile industries represents a technological challenge, due to their significant environmental impact. The application of halloysite (Hal) and palygorskite (Pal) clay minerals as adsorbents for the removal of Congo red (CR) and methylene blue (MB) was evaluated in this work. The materials were applied both in natural and acid-treated forms, and characterized by XRD, XPS, SEM-EDS, FTIR, and N2 adsorption-desorption isotherm techniques to identify their properties and main active sites. The adsorbents showed potential to remove CR (> 98%) and MB (> 85%) within 180 min, using 0.3 g adsorbent and initial dye concentration of 250 mg L-1. Semi-empirical quantum mechanical calculations (SQM) confirmed the interaction mechanism between dyes and the adsorbents via chemisorption (- 69.0 kcal mol-1 < Eads < - 28.8 kcal mol-1), which was further observed experimentally due to the high fit of adsorption data to pseudo-second order kinetic model (R2 > 0.99) and Langmuir isotherm (R2 > 0.98). The use of Pal and Hal to remove dyes was proven to be economically and environmentally viable for industrial application.

Investigation into Brazilian Palygorskite for Its Potential Use as Pharmaceutical Excipient: Perspectives and Applications.

Palygorskite is an aluminum and magnesium silicate characterized by its fibrous morphology, providing it with great versatility in industrial applications, including pharmaceuticals. Although most of the reserves are in the United States, in recent years occurrences of commercially exploited deposits in Brazil have been recorded, mainly in the country's northeast region. This has motivated this study, which analyzes raw Brazilian palygorskite compared to a commercial sample (Pharmasorb® colloidal) to demonstrate its pharmaceutical potential. The chemical and mineral composition of the samples were evaluated for surface properties, granulometry, morphology, crystallography, thermal analysis, and spectroscopy. Raw palygorskite presented 67% purity, against 74% for Pharmasorb® colloidal. The percentage purity relates to the presence of contaminants, mainly carbonates and quartz (harmless under conventional conditions of pharmaceutical use). Furthermore, it was possible to confirm the chemical composition of these phyllosilicates, formed primarily of silicon, aluminum, and magnesium oxides. The crystallographic and spectroscopic profiles were consistent in both samples, showing characteristic peaks for palygorskite (2θ = 8.3°) and bands attributed to fibrous phyllosilicates below 1200 cm-1, respectively. The thermal analysis allowed the identification of the main events of palygorskite, with slight differences between the evaluated samples: loss of water adsorbed onto the surface (~85 °C), removal of water contained in the channels (~200 °C), coordinated water loss (~475 °C), and, finally, the dehydroxylation (>620 °C). The physicochemical characteristics of raw palygorskite align with pharmacopeial specifications, exhibiting a high specific surface area (122 m2/g), moderately negative charge (-13.1 mV), and compliance with the required limits for heavy metals and arsenic. These favorable technical attributes indicate promising prospects for its use as a pharmaceutical ingredient in the production of medicines and cosmetics.

Biocomposite for Prolonged Release of Water-Soluble Drugs.

This study aimed to develop a prolonged-release system based on palygorskite and chitosan, which are natural ingredients widely available, affordable, and accessible. The chosen model drug was ethambutol (ETB), a tuberculostatic drug with high aqueous solubility and hygroscopicity, which is incompatible with other drugs used in tuberculosis therapy. The composites loaded with ETB were obtained using different proportions of palygorskite and chitosan through the spray drying technique. The main physicochemical properties of the microparticles were determined using XRD, FTIR, thermal analysis, and SEM. Additionally, the release profile and biocompatibility of the microparticles were evaluated. As a result, the chitosan-palygorskite composites loaded with the model drug appeared as spherical microparticles. The drug underwent amorphization within the microparticles, with an encapsulation efficiency greater than 84%. Furthermore, the microparticles exhibited prolonged release, particularly after the addition of palygorskite. They demonstrated biocompatibility in an in vitro model, and their release profile was influenced by the proportion of inputs in the formulation. Therefore, incorporating ETB into this system offers improved stability for the administered product in the initial tuberculosis pharmacotherapy dose, minimizing its contact with other tuberculostatic agents in the treatment, as well as reducing its hygroscopicity.

Adsorption of Sodium Diclofenac in Functionalized Palygoskite Clays.

The effects of acid and organo-functionalizations on the surface of Brazilian palygorskite clay was investigated, evaluating its potential in the adsorptive capacity of the drug sodium diclofenac present in wastewaters. The modifications on the clay structure were investigated by X-ray diffraction, X-ray fluorescence, thermogravimetric, differential thermal analysis, Fourier transform infrared spectroscopy, surface area by N2 adsorption (77.5 K) and Zeta potential. The experimental design was carried out to find the best conditions for the adsorption tests, in which concentration, mass and pH were significant. In the kinetic study, the pseudo-second-order model better described the adsorption process for acid and organo-functionalized samples. Such results indicate that the adsorption behavior probably occurs due to the phenomenon of chemisorption. Regarding the adsorption isotherms, the Langmuir model was the one that best adjusted both the experimental data of acid and the organo-functionalized samples, whose maximum adsorption capacity were 179.88 and 253.34 mg/g, respectively. This model also indicates that the sodium diclofenac is adsorbed to monolayers homogeneously through chemisorption. In general, the studied clays proved to be suitable adsorbents for the removal of sodium diclofenac.

Adsorption Behavior of Crystal Violet and Congo Red Dyes on Heat-Treated Brazilian Palygorskite: Kinetic, Isothermal and Thermodynamic Studies.

The effect of heat treatment on the adsorptive capacity of a Brazilian palygorskite to remove the dyes crystal violet (CV) and congo red (CR) was investigated. The natural palygorskite was calcined at different temperatures (300, 500 and 700 °C) for 4 h. Changes in the palygorskite structure were evaluated using X-ray diffraction, X-ray fluorescence, thermogravimetric and differential thermal analysis, N2 adsorption/desorption and Fourier transform infrared spectroscopy. The adsorption efficiency of CV and CR was investigated through the effect of initial concentration, contact time, temperature, pH and dosage of adsorbent. The calcination increased the adsorption capacity of palygorskite, and the greatest adsorption capacity of CV and CR dyes occurred in the sample calcined at 700 °C (Pal-700T). The natural and calcined samples at 300 and 500 °C followed the Freundlich isothermal model, while the Pal-700T followed the Langmuir isothermal model. Adsorption kinetics results were well described by the Elovich model. Pal-700T showed better adsorption performance at basic pH, with removal greater than 98%, for both dyes. Pal-700T proved to be a great candidate for removing cationic and anionic dyes present in water.

Photocatalytic degradation of Novacron blue and Novacron yellow textile dyes by the TiO2/palygorskite nanocomposite.

The photocatalytic discoloration of industrial dyes, Novacron blue (NB) and Novacron yellow (NY), was investigated using composites based on TiO2 and natural palygorskite (Pal-Ti10 and Pal-Ti30). The method consisted of synthesizing the composites starting from a physical mixture of TiO2 and natural palygorskite in the presence of alcohol, for impregnation through calcination under conditions of temperature equal to 450 °C and atmospheric air. The characterization techniques used in this work were FTIR, XRD, XRF, SEM, particle size analysis and zeta potential. The photocatalysis for the NB dye was investigated through the application of a factorial 24 experimental design, aiming at the best experimental conditions and finally applying them in another NY industrial dye. The investigated concentrations of NB were 10 ppm and 30 ppm, the composites were synthesized using 10 and 30% (p/p) of titanium dioxide in palygorskite, the two pH values were 2.0 and 6.0 and the light intensities 9 and 18 W were used. Tests performed at pH 2.0, Pal-Ti30 composite, power 18 W and 10 ppm of dye showed 100% color removal of both dyes in 90 min. The bleaching process followed the pseudo-first order kinetic model, and the apparent constants (Kapp) were 0.0216 min-1 and 0.0193 min-1 for NB and NY dyes, respectively. The results of total organic carbon (TOC) showed mineralization of 61.70% and 58.06% for NB and NY, respectively, in 90 min of treatment, and the by-products were detected by GC-MS.

Phosphorus saturation and superficial fertilizer application as key parameters to assess the risk of diffuse phosphorus losses from agricultural soils in Brazil.

In Brazil, a steady increase in phosphorus (P) fertilizer application and agricultural intensification has been reported for recent decades. The concomitant P accumulation in soils potentially threatens surface water bodies with eutrophication through diffuse P losses. Here, we demonstrated the applicability of a soil type-independent approach for estimating the degree of P saturation (DPS; a risk parameter of P loss) by a standard method of water-soluble phosphorus (WSP) for two major soil types (Oxisols, Entisols) of the São Francisco catchment in Brazil. Subsequently, soil Mehlich-1P (M1P) levels recommended by Brazilian agricultural institutions were transformed into DPS values. Recommended M1P values for optimal agronomic production corresponded to DPS values below critical thresholds of high risks of P losses (DPS=80%) for major crops of the catchment. Higher risks of reaching critical DPS values due to P accumulation were found for Entisols due to their total sorption capacities being only half those of Oxisols. For complementary information on soil mineralogy and its influence on P sorption and P binding forms, Fourier transformation infrared (FTIR) spectroscopic analyses were executed. FTIR analyses suggested the occurrence of the clay minerals palygorskite and sepiolite in some of the analyzed Entisols and the formation of crandallite as the soil specific P binding form in the investigated Oxisols. Palygorskite and sepiolite can enhance P solubility and hence the risk of P losses. In contrast, the reshaping of superphosphate grains into crandallite may explain the chemical processes leading to previously observed low dissolved P concentrations in surface runoff from Oxisols. To prevent high risk of P losses, we recommend avoiding superficial fertilizer application and establishing environmental thresholds for soil M1P based on DPS. These measures could help to prevent eutrophication of naturally oligotrophic surface waters, and subsequent adverse effects on biodiversity and ecosystem function.

The effect of natural and organophilic palygorskite on skin wound healing in rats

In view of growing interest in natural treatments, clays would appear to be a good alternative for speeding up the healing process during the treatment of wounds. Of the various clays, palygorskite, a clay from the Brazilian State of Piauí, composed of silicon and aluminum, has shown itself to be pharmaceutically useful as a healing agent. The aim of this article is to evaluate the effect on the healing of wounds of Piauí palygorskite, both in its natural state and when organophilic, by way of comparative analysis of macroscopic and histological tests on skin wounds in adult male and female two-month-old Wistar rats. To this end, a circular trichotomy of the dorsal cornus of the rats was carried out to confirm the effects of treatments involving 0.9% saline solution, collagenase, natural palygorskite, organophilic palygorskite with cetyltrimethylammonium chloride, and organophilic palygorskite with alkyldimethylbenzylammonium chloride. The testing of all the clays involved microbiological evaluation using the depth of plaque and surface striation methods, along with post-treatment macroscopic analysis of skin wounds by way of organoleptics, pachymetry and histological analysis. Microbiological evaluation revealed the need for sterilization of the clay prior to incorporation in the pharmaceutical form. Macroscopic analysis suggests that healing of the wounded area occurred, and histological analysis showed the beneficial effect of the topical use of clay material. Our data suggest that palygorskite may be more powerful than other healing agents, although, on completing treatment, all the animals studied showed the same degree of tissue repair.

Devido ao crescente interesse da população pelos tratamentos naturais, as argilas representam uma boa alternativa para a aceleração da cicatrização durante o tratamento de feridas. Dentre as argilas, a paligorsquita, uma argila piauiense, devido à sua composição com silício e alumínio, demonstra certa aplicabilidade farmacêutica como agente cicatrizante. O objetivo deste artigo é avaliar a ação cicatrizante da paligorsquita piauiense em sua forma natural e organofilizadas por meio da análise comparativa da macroscopia e dos exames histológicos em feridas cutâneas de ratos machos e fêmeas Wistar adultos com 2 meses de idade. Para tanto, foram realizadas tricotomia circular no corno dorsal dos ratos para verificar os efeitos dos tratamentos realizados com solução salina 0,9%, colagenase, paligorsquita natural, paligorsquita organofilizada por cloreto de cetiltrimetilamônio e paligorsquita organofilizada por cloreto de alquildimetilbenzilamônio. Para todas as argilas testadas foi feita a avaliação microbiológica pelo método de plaqueamento em profundidade e do método de estrias em superfície, bem como foi realizada após tratamento, a análise macroscópica das feridas cutâneas por meio organoléptico, medição em paquímetro e análise histológica. Por meio da avaliação microbiológica foi detectada a necessidade de esterilização da argila para posterior incorporação na forma farmacêutica. A análise macroscópica sugere que houve cicatrização da área lesionada, bem como a análise histológica demonstrou efeito benéfico após o uso tópico do material argiloso. Nossos dados sugerem que a paligorsquita pode exercer um maior efeito cicatrizante em relação aos demais tratamentos, embora após o término deste tratamento, todos os animais analisados apresentaram a mesma reparação tecidual.