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Red mud (RM) is composed of a waste alkaline solution (pH = 13.3) obtained from the production of alumina. It contains high concentrations of hematite (Fe2O3), goethite (FeOOH), gibbsite [Al(OH)3], a boehmite (AlOOH), anatase (Tetragonal-TiO2), rutile (Ditetragonal dipyramidal-TiO2), hydrogarnets [Ca3Al2(SiO4)3-x(OH)4x], quartz (SiO2), and perovskite (CaTiO3). It was shown to be an excellent catalytic mixture for biodiesel production. To demonstrate the value of RM, an environmentally friendly process of transesterification in aqueous medium using waste cooking oil (WCO), MeOH, and waste alkaline solution (WAS) obtained from aluminum production was proposed. Triglycerides of WCO reacted with MeOH at 60 °C to yield mixtures of fatty acid methyl esters (FAMEs) in the presence of 0.019% (w/w) WAS/WCO using the WAS (0.204 mol L-1, predetermined by potentiometric titration) from aluminum production by the Bayer process. The use of the new catalyst (WAS) resulted in a high yield of the products (greater than 99% yield).

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In this work, hybrid hydrogels were synthesized with the inclusion of two types of clay materials that are considered industrial waste: red mud (RM) and ferrosilicomanganese fines (FeSiMn). These solid waste materials were characterized by studying their particle size and chemical composition, which are two key variables for their application in the synthesis of hybrid hydrogels. The morphology imaged by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), showed, in the case of RM, heterogeneous size and shape particles, with 73% of the particles having lengths of less than 5 µm. On the other hand, FeSiMn had particles with a circular morphology of nanometric sizes. Regarding the synthesis of the hybrid hydrogels, it was determined that the incorporation of small percentages (0.1%) of the inorganic phases improved the capacity of the materials to absorb water (swelling indices of 1678% and 1597% for the RM and FeSiMn hydrogels, respectively) compared to the conventional polyacrylamide hydrogel (1119%). An improvement in Vickers microhardness and storage modulus (G') was also observed: the hybrid with 10% RM presented a G', 50 times higher than conventional hydrogel. The results show the merit of RM and FeSiMn in improving the properties of hydrogels.

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Several floodplain lakes of the Orinoco River have been impacted by alkaline alumina-refining waste including red mud, a by-product from the Bayer process. Some of these impacted lakes have undergone algal overgrowth, which has been detected due to the unusual green color of water and the dissolved oxygen oversaturation. Thus, we conducted sampling campaigns in impacted and non-impacted lakes to measure the concentration of nitrogen (N) and phosphorous (P) in water to detect any change in the nutrient levels. Despite the content of N and P in red mud is low, our findings suggest that N is released from red mud accumulated in bed sediments to the water column in the impacted lakes, increasing the content of total N. However, the total P concentrations in impacted lakes were not affected from their background values probably due to the strong adsorptive behavior of P onto red mud minerals.

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This study investigated the water parameters and the levels of several heavy metals in leaves and roots of the aquatic macrophyte Paspalum repens and in bed sediments of one unpolluted lagoon and two polluted lagoons of the Orinoco River floodplain to know the impact of the alumina refining wastes on these ecosystems. The sampling was performed during four hydrological periods, covering one hydrological year. Chemical parameters in water (pH, conductivity, and total dissolved solids) and the levels of Al, Pb, Cr, and Cu in sediments were the highest in Macanillal (LMaca) lagoon, whereas sediments of Punta Cuchillo (LPC) lagoon also had elevated concentrations of Al and Fe in comparison with Las Aruhacas (LArh) lagoon (unpolluted lagoon). Chemical parameters in waters returned almost to natural values during high water stage because of the huge inundation of the Orinoco River during the high discharge periods. The solid/liquid discharges of industrial effluents over these systems also affected the grain size distribution of sediments in the lagoons. In all the studied lagoons, the distribution of elements in leaves of P. repens was in the order K ≥ Cr > Ca > Mg > Al > Fe > Mn > Cu > Pb, whereas Al was found to be the more abundant element in roots. The high abundance of Cr in P. repens was related with the high Cr accumulation potential shown by aquatic macrophytes. Despite this, the concentration of elements in P. repens did not show differences between the plants collected in the polluted lagoons versus the plants collected in the unpolluted lagoon. This suggests that P. repens is unsuitable for bio-monitoring studies of heavy metals in these aquatic environments impacted by alkaline residues.

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Composite materials from PET and red mud (RM) wastes were used as catalysts for environmental application such as the wastewater treatment. The PET-RM catalysts were obtained by a mechanical mixture of the residues followed by thermal treatment under an N2 atmosphere (300°C/1 h). An additional activation of the composites with CO2 was investigated (at 800-900°C) to reduce the red mud basicity. The CO2 activation affected the composites surface area and reduced their carbon content. XRD revealed that the haematite (α-Fe2O3) and maghemite/magnetite are the main iron oxides present in the composites. Mössbauer characterization indicated the formation of reduced iron species (Fe2+), highly reactive, after the composites heat treatment. The materials were very active catalysts for methylene blue (MB) and paracetamol (PRC) removal from aqueous solution. The catalytic activity revealed to be dependent on the surface area and mainly of the presence of reduced iron species in the catalysts. The MB removal reached 97% for both PET-RM 800/2 h and PET-RM 800/5 h, after 1 h of reaction. In the case of PRC, the highest removal was also obtained for PET-RM 800/2 h and PET-RM 800/5 h, of ≈25% and 40%, respectively. The contaminants removal mechanism likely occurred through combined adsorption and Fenton-like oxidation processes.

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Ozone and a Fe2+/TiO2-based catalyst were examined in the degradation of a synthetic solution of benzene toluene and xylene (BTX) in an advanced oxidation process (AOP). The catalyst beads were made from the slurry waste of aluminum production process, by inserting the TiO2 content and subsequent calcination. The reduction of the BTX concentration load was monitored by the reduction of chemical oxygen demand (COD) and BTX concentration. Different levels were used on factors: pH, time of treatment, initial concentration of BTX, and percentage of TiO2. The process was conducted in a bubble column reactor with the insertion of catalyst beads. A response surface methodology technique (CCD) was used to build a model based on COD reduction results. The model was optimized using the normal-boundary intersection (NBI) algorithm to maximize COD reduction and minimize the variance attributed to the process. Optimization led to COD reductions of 80% in 2 h of experiment. Correlation analysis of coefficient models from experimental data R2adj was 0.9966, showing a good fit of model data. In the optimized conditions, the possible increase of the biodegradability ratio of the BTX solution, through the biochemical oxygen demand (BOD) and COD, was also analyzed. Under pre-treatment conditions, the BOD/COD ratio was 0.13. After the treatment, it increased to 0.56. Graphical abstract ᅟ.

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In this work, iron oxide in the red mud (RM) waste was restructured to produce mesopores with surface [FeO x (OH) y ] sites for the efficient complexation/adsorption of ß-lactam antibiotics. Red mud composed mainly by hematite was restructured by an acid/base process followed by a thermal treatment at 150-450 °C (MRM150, MRM200, MRM300, and MRM450) and fully characterized by Mössbauer, XRD, FTIR, BET, SEM, CHN, and thermogravimetric analyses. The characterization data showed a highly dispersed Fe3+ oxyhydroxy phase, which was thermally dehydrated to a mesoporous α-Fe2O3 with surface areas in the range of 141-206 m2 g-1. These materials showed high efficiencies (21-29 mg g-1) for the adsorption of ß-lactam antibiotics, amoxicillin, cephalexin, and ceftriaxone, and the data was better fitted by the Langmuir model isotherm (R 2 = 0.9993) with monolayer adsorption capacity of ca. 39 mg g-1 for amoxicillin. Experiments such as competitive adsorption in the presence of phosphate and H2O2 decomposition suggested that the ß-lactamic antibiotics might be interacting with surface [FeO x (OH) y ] species by a complexation process. Moreover, the OH/Fe ratio, BET surface area and porosity indicated that this complexation is occurring especially on [FeO x (OH) y ]surf sites contained in the mesopore space.

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RESUMO Vários minerais e resíduos industriais têm sido estudados para uso como adsorvente, entre eles a lama vermelha e a anidrita. A lama vermelha é um resíduo insolúvel gerado em grande quantidade durante o processamento da bauxita. A anidrita é um sulfato de cálcio (CaSO4) cristalizado sob a forma rômbica e usada como matéria-prima na indústria. Nesta investigação, a capacidade de adsorção de Cd2+, Ni2+ e Zn2+ pela anidrita e pela lama vermelha foi avaliada usando isotermas de adsorção de Langmuir e Freundlich. Os materiais empregados apresentaram adsorção ≥75±1% para todos os metais em soluções aquosas com concentração de 0,5 mmol.25 mL-1. As isotermas baseadas no modelo de Langmuir foram as mais apropriadas para descrever o fenômeno de remoção de Cd2+, Ni2+ e Zn2+ para a anidrita e a lama vermelha, com valores de capacidade máxima de adsorção de 0,47 e 0,51 mmol.g-1 para o Cd2+, 1,18 e 1,56 mmol.g-1 para o Ni2+ e 0,84 e 1,47 mmol.g-1 para o Zn2+, respectivamente. Esses valores foram superiores a outros valores exibidos por materiais empregados como adsorventes descritos em estudos prévios.

ABSTRACT Various minerals and industrial waste have been studied for use as an adsorbent, in particular the anhydrite and the red mud. The red mud is an insoluble residue that is generated in large quantities during the processing of bauxite. The anhydrite is a calcium sulfate (CaSO4), crystallized as a rhombic way, and used as raw material in the industry. In this study, the Cd2+, Ni2+ and Zn2+adsorption capacity by anhydrite and by red mud was evaluated using adsorption isotherms obtained by the Langmuir and Freundlich models. The materials used showed adsorption ≥75±1% for all metals in aqueous solutions with a concentration of 0.5 mmol.25 mL-1. The Langmuir isotherm was more appropriate to describe the phenomenon of Cd2+, Ni2+ and Zn2+ removal, with highest adsorption capacity at 0.47 and 0.51 mmol.g-1 for Cd2+, 1.18 and 1.56 mmol.g-1 for Ni2+, and 0.84 and 1.47 mmol.g-1 for Zn2+, respectively. These values were higher than those ones obtained for other materials described in previous studies.

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This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS).

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In this study, we obtained a composite based on carbon/iron oxide from red mud and PET (poly(ethylene terephthalate)) wastes by mechanical mixture (10, 15 and 20wt.% of PET powder/red mud) followed by a controlled thermal treatment at 400°C under air. XRD analyses revealed that the α-Fe2O3 is the main phase formed from red mud. TPR analyses showed that the iron oxide present in the composites undergoes reduction at lower temperature to form Fe(2+) species present in Fe3O4, indicating that the iron oxide in the composite can exhibit greater reactivity in the catalytic processes compared to the original red mud. In fact, catalytic tests showed that the composites presented higher capacity to remove methylene blue dye (MB), presenting about 90% of removal after 24h of reaction. The MB removal was also monitored by mass spectrometer with ionization via electrospray (ESI-MS), which demonstrated the occurrence of the oxidation process, showing the formation of MB oxidation products. The stability of the composites was confirmed after four reuse cycles. The results seem to indicate that PET carbon deposited over the iron oxide from red mud promotes adsorption of the contaminant allowing its contact with the iron atoms and their consequent reaction.

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This study investigated two industrial by-products - red mud (RM) and its mixture with phosphogypsum (RMG), as amendments in an As((5+))-contaminated soil from a gold mining area in Brazil in order to grow three plant species: Brachiaria decumbens, Crotalaria spectabilis, and Stylosanthes cv. Campo Grande. These amendments were applied to reach a soil pH of 6.0. Using RM and RMG increased shoot dry matter (SDM) and root dry matter (RDM) of most plants, with RMG being more effective. Adding RMG increased the SDM of Brachiaria and Crotalaria by 18 and 25% and the RDM by 25 and 12%, respectively. Stylosanthes was sensitive to As toxicity and grew poorly in all treatments. Arsenic concentration in shoots of Brachiaria and Crotalaria decreased by 26% with the use of RMG while As in roots reduced by 11 and 30%, respectively. Also, the activities of the plant oxidative stress enzymes varied following treatments with the by-products. The plants grew in the As-contaminated soil from the gold mining area. Thus, they might be employed for phytoremediation purposes, especially with the use of RMG due to its potential advantage in terms of nutrient supply (Ca(2+) and SO4(2-) from phosphogypsum).

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