Development of adsorbent rigid structure based on Spirulina sp./chitosan bioblends coatings for dye adsorption in fixed bed column.

The glass particles were coated with Spirulina sp. LEB-18 and bioblends of Spirulina sp. LEB-18/chitosan by casting technique and, afterward, it was verified its potential as adsorbents for basic and acid dyes. Nine Spirulina sp. suspensions with different components were used to coat the glass particles, and in the best condition of coating were prepared the bioblends with chitosan. The coated glass particles with Spirulina sp. and its bioblends with chitosan were applied in adsorption of the allura red (acid) and methylene blue (basic) dyes in a batch operation evaluate the pH effect, and a fixed bed column operation, being evaluated to the removal percentage and adsorption capacity of the column. The glass particles coated with Spirulina sp. applied in batch adsorption showed the highest removal percentages for allura red dye (35 to 45%) at pH 4.0, and for methylene blue dye (35 to 80%) at pH 6.0 and 8.0. In fixed bed column using glass particles coated with bioblends were reached the amount dye of 54.2 mg of adsorbed allura red dye and 60.2 mg of the of adsorbed methylene blue dye, respectively. Moreover, it was found good dye adsorption capacities, around 89 mg g-1, for both dyes, in acidic and basic pH values. Based on these results, these bioblends coated glass particles can be applied as an adsorbent for different types of dyes in adsorption column.

Leaching of rare earth elements from phosphogypsum.

High amounts of phosphogypsum (PG) are generated in the production of phosphoric acid. Previous literature demonstrates that obtaining rare earth elements (REE) from PG is a promising alternative to managing this waste. However, the reported leaching efficiencies are low in most cases, or drastic leaching conditions are required. Therefore, this work aimed to study the leaching conditions of REE from PG to obtain high leaching efficiency values. Initially, a 24 factorial experimental design investigated the factors that affect the conventional acid leaching of REE from PG (leaching acid (citric and sulfuric acid), solid/liquid ratio, acid concentration, and temperature). Better leaching efficiency values of the sum of all REE (62.0% and 89.7% for citric and sulfuric acid, respectively) were obtained using an acid concentration of 3 mol L-1, solid/liquid ratio of 1/20 g mL-1, and temperature of 80 °C. Subsequently, the experiments optimization, performed through a central composite rotational design, indicated that the maximum leaching efficiency was achieved using a sulfuric acid concentration of 2.9 mol L-1, solid/liquid ratio of 1.7/20 g mL-1, and 55 °C. Under these conditions, the leaching efficiency of the sum of all REE was 90.0%. Leaching kinetics results showed that the equilibrium was reached in about 20 min for most REE. The mechanism investigation suggested that surface chemical reaction and diffusion through the boundary layer controlled the leaching.

Green synthesis of carbon nanotubes impregnated with metallic nanoparticles: Characterization and application in glyphosate adsorption.

In the present work, multi-walled carbon nanotubes (MWCNTs) were used as support material for the impregnation of metallic nanoparticles (MNPs) produced by green synthesis. The influences of the plant extracts (pomegranate (Punica Granatum), Eucalyptus, and pecan (Carya illinoinensis, leaves), metal species (copper and iron), metallic concentrations, and type of functionalization (OH and COOH) on the characteristics of the obtained materials were studied. The precursor and impregnated MWCNTs were characterized through X-ray diffraction, Fourier transformed infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, point of charge, N2 adsorption/desorption isotherms and, X-ray photoelectron spectroscopy. All the synthesized materials were tested as adsorbents to remove glyphosate (GLY) in an aqueous medium. The MWCNTs were resistant to withstand the synthesis process, preserving its structure and morphological characteristics. The copper and iron on the surface of MWCNTS confirm the successful synthesis and impregnation of the MNPs. The MWCNTs impregnated with high metallic concentrations showed favorable adsorption of GLY. The adsorption capacity and percentage of removal were 21.17 mg g-1 and 84.08%, respectively, for the MWCNTs impregnated with iron MNPs using the pecan leaves as a reducing agent. The results indicated that an advanced adsorbent for GLY could be obtained by green synthesis, using MWCNTs as precursors and pecan leaves as a reducing agent.

Anthocyanins concentration by adsorption onto chitosan and alginate beads: Isotherms, kinetics and thermodynamics parameters.

The anthocyanins health benefits are diverse, but numerous factors affect the anthocyanins stability, thus, this work aimed to extract anthocyanins from Pinot Noir grape skins and, afterward, to concentrate them onto edible and safety adsorbents, chitosan and alginate beads, by adsorption operation. Chitosan was obtained from shrimp waste, and alginate was purchased. Batch adsorption experiments were carried out as pH function, and the highest adsorption capacities and removal percentages were, respectively, 216 mg g-1 and 65% for chitosan beads at pH 8, and 126.4 mg g-1 and 38% for alginate beads at pH 4. All equilibrium isotherms models were suitable for chitosan beads, while for alginate beads only Langmuir and Freundlich models showed fitting. The thermodynamic parameters demonstrated physical adsorption and endothermic behavior for the chitosan and alginate beads. The pseudo-first order model best described the kinetic behavior for both beads. It was demonstrated that is possible to concentrate the different molecular structures of anthocyanins onto chitosan and alginate beads with high yields.

Nanominerals assemblages and hazardous elements assessment in phosphogypsum from an abandoned phosphate fertilizer industry.

The present work investigates hazardous elements and nanomineralogical assemblages of phosphogypsum waste from an abandoned phosphate fertilizer industry located in Santa Catarina state (Brazil). Correlations between the chemical composition, nanominerals, and ultrafine particles are discussed. Multifaceted physical-geochemical study provided a careful understanding of the nanomineralogical assemblage of the phosphogypsum waste. The electron beam investigation revealed the presence of many hazardous elements in the ultrafine particles. Cr, Pb, Mn, Se, Sr, and Zr, among others, were found in individual ultrafine particles and nanominerals in all studied samples. Besides that, rare earth elements were found in different concentration ranges, being Ce, La, and Nd, the rare earth elements, found in the higher concentrations, above 900 mg kg-1. The data supplied by this article are important to characterize the phosphogypsum waste, assessing the potential hazard to the environment and human health, and also, provides information to enable the designing of alternatives to manage this waste.

Development of chitosan/Spirulina sp. blend films as biosorbents for Cr6+ and Pb2+ removal.

Chitosan film, Spirulina sp. film and its blend were developed as biosorbents to remove Cr6+ and Pb2+ ions from aqueous solutions. The kinetic study and the pH effect on biosorption efficiency were evaluated to comprehend the interactions between the ions and biosorbents. The characterization analyses pointed out that occurred interaction between both biomaterials, which resulted in structural alterations through the blend. The Spirulina sp. film exhibited the highest biosorption capacities for Cr6+ (43.2 mg g-1) and Pb2+ (35.6 mg g-1) ions, however, its physical integrity was not kept in acid medium. The blend film showed results slightly lower (35.8 mg g-1 for Cr6+ and 31.6 mg g-1 for Pb2+), but its physical integrity remained intact in all assays. Chitosan film presented the lower biosorption capacities (15.4 mg g-1 for Cr6+ and 20.9 mg g-1 for Pb2+). Elovich and pseudo-second order models were the most suitable to express the kinetic behaviors for Cr6+ and Pb2+, respectively. Therefore, chitosan/Spirulina sp. blend could be a green alternative for Cr6+ and Pb2+ removal, because this biosorbent showed high biosorption capacity obtained from Spirulina sp. and great physical integrity obtained of chitosan.

Removal of fluoride from fertilizer industry effluent using carbon nanotubes stabilized in chitosan sponge.

Adsorption of fluoride from fertilizer industry effluent using carbon nanotubes stabilized in chitosan sponge as adsorbent was evaluated. The effluent was produced in the washing of acid gases during the reaction in fertilizer production and all assays were performed using this hazardous material. Adsorbent characterization and ions interactions were elucidated from differential scanning calorimetry, thermal gravimetric analyses, X-ray diffraction, scanning electron microscopy dispersive energy X-ray spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The effluent presented pH 3 and its value not changed in the adsorption assays, maintaining the conditions of the process. The kinetics assays of fluoride from industry effluent were performed in different stirring rates from 100 to 300 rpm. It was observed that adsorption was initially fast reaching the equilibrium at 300 rpm in 20 min. The adsorption capacity was around 975.4 mg g-1, showing the potential of the hybrid material to remove fluoride from a real matrix. The high adsorption capacity was attributed to the chitosan functional groups and the high interaction area promoted by sponge form and the carbon nanotube. Reuse and regeneration of the CNT-CS were investigated and 5 cycles were obtained. The adsorption capacity kept similar values in all cycles.

Simultaneous determination of the quaternary ammonium pesticides paraquat, diquat, chlormequat, and mepiquat in barley and wheat using a modified quick polar pesticides method, diluted standard addition calibration and hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry.

In this study, a modified Quick Polar Pesticides (QuPPe) method, optimized by a central composite design, was developed to determine quaternary ammonium pesticides (QUATs) residues in barley and wheat by ultra-high-performance liquid chromatographic tandem mass spectrometry (UHPLC-MS/MS) using a hydrophilic interaction chromatography (HILIC) column. Considering the high polarity of these compounds, special conditions of sample preparation and analysis are required. Different mobile phases, extraction procedure and clean-up were evaluated. An isocratic elution with aqueous solution of ammonium formate 60 mmol L-1 (pH 3.7) and acetonitrile, 40:60 (v/v), was selected. Water and acidified methanol as extraction solvent, without heating, and a clean-up with dichloromethane, chitosan and acetonitrile presented good results. The validated method presented satisfactory selectivity, linearity, matrix effect, trueness and precision, providing recoveries from 93 to 110% with RSD < 13% for barley, and 70 to 115% with RSD < 18% for wheat. The complexity of these matrices requires the calibration in matrix and the diluted standard addition calibration (DSAC) procedure has been shown to be an excellent option to compensate for the matrix effect and the losses of the analytes in the extraction. Real samples of barley and wheat were analyzed and 60% presented concentrations of paraquat above the maximum limits allowed by the European Union. The modified QuPPe method combined with DSAC and HILIC-UHPLC-MS/MS demonstrated to be an effective approach to determine QUATs in barley and wheat, and is a good alternative for routine analysis. The use of the biosorbent chitosan is effective, low cost and more ecological when compared to others conventional sorbents.

Cu(II) adsorption from copper mine water by chitosan films and the matrix effects.

Adsorption of copper ions onto chitosan films was studied, and the matrix effect was evaluated using a synthetic solution and a real effluent from closed copper mine. Chitosan films were prepared by casting technique and characterized. The adsorption study was carried out by equilibrium isotherms, thermodynamics, and kinetics. The thermodynamic parameters indicated that the copper adsorption onto chitosan film was favorable, spontaneous, and exothermic, suggesting an increased randomness at the solid/solution interface. The matrix effect was evaluated in kinetic assays, where a synthetic solution and a real system were carried out at different stirring rates. The highest values of adsorption capacity reached in all stirring rates were about 20% lower in the real effluent, and this reduction in the competitiveness was due to the presence of other ions in the matrix of the real effluent. The maximum adsorption capacity of copper ions onto chitosan films for the synthetic solution was of 450 mg g-1, and the removal percentage was in the range from 78 to 96%, and these values for the real effluent were of 360 mg g-1 and removal ranging from 62 to 76%. The mapping done of ions present in the water adsorbed of the mine in the films showed that the same was homogeneously distributed in the films' surfaces.