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The tanning industry generates effluents with high chromium content, which require treatment prior to discharge into the sewage system. This article explores the use of magnetic magnetite nanoparticles (MNPs) to remove Cr(VI) from aqueous solutions, such as tanning effluents. The MNPs were synthesized by coprecipitation reaction using the Olea europaea extract as a reducing agent. Subsequently, they were characterized by dynamic light scattering spectroscopy (DLS), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). MNPs with irregular morphology and diameters ranging from 73.28 to 162.90 nm were obtained. Cr(VI) removal was performed using jar test methodology, and its efficiency was evaluated in the laboratory for different initial Cr(VI) (mg/L) concentration and nanoparticle (g/L) concentration. A kinetic study was developed and indicated that the equilibrium adsorption mechanism corresponds to a pseudo-second-order model. Furthermore, the isotherm analysis revealed that chromium adsorption best fits the Langmuir isotherm. Finally, Cr(VI) removal rates from 85% to 100% were achieved in tanning and retanning effluents.

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One of the main environmental issues caused by the tanning industry is given by the high concentration of chromium contained on its effluents. The removal of this pollutant has become a technological challenge. To solve this issue, this work proposes a continuous process based on mixers-settlers for the removal of the chromium present in effluents from the tanning industry. The process involves the use of liquid-liquid extraction systems. The study includes the development of isotherms for the removal and stripping, which are further represented through a mathematical model to determine the number of theoretical extraction stages and other operational variables. The results show that a better extraction is achieved in a system with two theoretical stages using Cyanex 272 as extractant, reaching more than 94% of removal of chromium with an extractant concentration of 0.32 mol/L. For stripping, sulfuric acid is used, obtaining a maximum recovery of 94%.

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Brewer's spent grain (BSG) is a residue from brewery production, that can be reused as adsorbent of heavy metals like Chromium (Cr). In this study, BSG was used as a biochar for Cr adsorption in batch adsorption experiments. The biochar pyrolysis temperature (500, 600 and 700ºC), pyrolysis time (30, 105 and 180 minutes) and zinc chloride concentration (5, 12.5 and 20%) were evaluated and optimized from a fractional factorial design. An equilibrium adsorption capacity of 78.13 mg.g-1 and a yield of 26.42% were achieved using 700ºC, 30 min, 12.5%. This biochar was applied to the adsorption of Cr in aqueous solution, under different stirring speeds (100, 150 and 200 rpm). The higher agitation speed reduced the adsorption capacity of the coal from 90 to 72 mg.L-1. In addition, the Cr adsorption equilibrium was reached before 100 min. The pseudo-first order model best described the Cr adsorption kinetics. The Redlich-Peterson isothermal model best fitted the experimental data, with the parameter g (close to 1) suggesting Langmuir's assumptions as the most appropriate to describe the adsorption of Cr on the optimized activated carbon.

O bagaço de malte (BM) é um resíduo da produção cervejeira, que pode ser reaproveitado como adsorvente de metais pesados como o Cromo (Cr). Neste estudo, BM foi usado como um biochar para adsorção de Cr em experimentos de adsorção em batelada. O biochar foi avaliado e otimizado a partir de um planejamento fatorial fracionário com as variáveis: temperatura de pirólise (500, 600 e 700ºC), tempo de pirólise (30, 105 e 180 minutos) e concentração de cloreto de zinco (5, 12,5 e 20%). Uma capacidade de adsorção em equilíbrio de 78,13 mg.g-1 e um rendimento de 26,42% foram obtidos usando 700ºC, 30 min, 12,5%. Este biochar foi aplicado na adsorção de Cr em solução aquosa, sob diferentes velocidades de agitação (100, 150 e 200 rpm). Maior velocidade de agitação reduziu a capacidade de adsorção do biochar de 90 para 72 mg.L-1. Além disso, o equilíbrio de adsorção de Cr foi alcançado antes de 100 min. O modelo de pseudo-primeira ordem melhor descreveu a cinética de adsorção de Cr. O modelo isotérmico de Redlich-Peterson foi o que melhor se ajustou aos dados experimentais, com o parâmetro g (próximo de 1) sugerindo as hipóteses de Langmuir como as mais apropriadas para descrever a adsorção de Cr no carvão ativado otimizado.

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In this work, a continuous flow extraction system assisted by ultrasound (US) was developed for the extraction of Cr(III) from residual tanned leather shavings. US energy was delivered into the system by a tubular applicator (clamp-on tube US applicator). The effect of the US energy was investigated at 20 kHz of frequency and electrical input power of 75, 150, 300 and 600 W. Residence time and temperature profile were also evaluated. It was observed that the internal temperature profile was affected by the presence of US and inverted in comparison with the conditions without US. In this way, the temperature profile generated by the US was reproduced by using electrical resistances in order to compare the obtained results. The US intensity was measured using a hydrophone connected to a sound pressure meter. The use of the US did not alter the dynamic behavior of the system but increased the extraction efficiency when compared to the silent condition. US power above 75 W did not lead to increased extraction efficiency, when the residence time was 30 min. However, when 60 min of residence time were employed, the optimized US power was 150 W, resulting in an extraction efficiency of 71.7 ± 0.7 %, about 28 % higher when compared to the silent condition in the same temperature and other conditions. The US energy allowed a reduction in processing time and operational temperature when compared to the silent condition with the same temperature profile. The overall energy consumption with US was similar or lower than that observed without US, showing the feasibility of the proposed extraction system.

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The green synthesis of metal oxide nanoparticles is presented as an excellent sustainable alternative for achieving nanostructures, with potential applications. This research provides important information regarding the influence of the type of solvent used in extracting organic reducing agents from E. globulus on the FeO NPs green synthesis protocol. A broad approach to characterization is presented, where UV-vis spectrophotometry suggests the presence of this type of nanoparticulate material. Likewise, the reduction mechanism was evaluated by FT-IR and the magnetic properties were evaluated by PPSM. In addition, characterizations were linked via elemental analysis (EDX), crystallographic characterization (XRD), electron microscopy (SEM/STEM), and Z potential to evaluate colloidal stability. The results show the influence of the type of solvent used for the extraction of organic reducing agents from E. globulus, and the effect on the synthesis of FeO NPs. In addition, the nanostructure material obtained showed excellent efficiency in the remediation of agricultural soil, eliminating metals such as Cr-VI, Cd, and, to a lesser extent, Pb.

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Two chromium removal experiments were performed in bioreactors with and without a magnetic field under the same conditions. The release of the chromium present in the biomass was tested in two experiments one with the initial pH of the medium and one with pH 4.0. The objective was to remove Cr(VI) and total Cr from the effluent, this was carried out by placing biological treatments of synthetic effluent contaminated with 100 mg/L of Cr(VI) in a bioreactor with neodymium magnets that applied a magnetic field (intensity 85.4 mT) to the mixed culture. The removal of Cr(VI) was approximately 100.0% for the bioreactor with a magnetic field and 93.3% for the bioreactor without a magnetic field for 9 hr of recirculation of the synthetic effluent by the bioreactor. The removal of total Cr was 61.6% and 48.4%, with and without a magnetic field, respectively, for 24 hr. The desorption of Cr(VI) in the synthetic effluent was 0.05 mg/L, which is below the limit established by Brazilian legislation (0.1 mg/L) for the discharge of effluent containing Cr(VI) into bodies of water. The results obtained for the removal of chromium in synthetic effluent suggested that there was no significant influence on the viable cell count of the mixed culture. The desorption of Cr(VI) in synthetic effluent after bioadsorption of chromium by the mixed culture in the process of removal of chromium in bioreactors with and without a magnetic field was not significant in either of the experiments with different initial pHs.

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The highly toxic species of Chromium in its hexavalent state is an important hazard to the flora and fauna, causing a rupture in balance especially in aquatic environments. The removal of Cr(VI) ions from aqueous solutions using fungal biomass of Rhizopus sp. was investigated under batch experiments. The biomass was produced and treated with NaCl to compare pre-treated and untreated biosorbents capacity. Adsorption of Cr(VI) was investigated with a 23 experimental design to determine the best operational parameters including pH [2.0-4.0], temperature [20-40 °C] and agitation [50-150 rpm]. Maximum Cr(VI) uptake (99%) indicated that pH 2.0 is the optimal for Cr(VI) removal. Linear and non-linear kinetic models were evaluated. The best fitting for linear kinetics was the pseudo-second order linear equation and the Elovich model in its non-linear form, suggesting chemisorption as the controlling step of adsorption. Results followed Langmuir isotherm equation, the qm was 9.95 (mg·g-1) for Rhizopus sp. + NaCl. Thermodynamic parameters were calculated using the adsorption equilibrium constant obtained from Langmuir isotherm and indicated that the adsorption process was spontaneous and endothermic. The surface characteristics of the biomass were analyzed by Fourier transform infrared (FTIR) spectra; the analysis showed the involvement of amino groups in the bonding with Cr(VI). SEM and EDX analysis confirmed the presence of Cr in the biomass after adsorption. The results of these experiments may be utilized for modeling, simulation, and scale-up processes in the future.

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In this study, the steel manufacturing waste Basic Oxygen Furnace Sludge (BOFS) was tested as permeable reactive material for the remediation of soil contaminated with chromium. The material presents a high content of elemental iron and iron oxides typical of the steel manufacturing process. Here we propose a scheme of the chemical reactions responsible for remediation process including BOFS dissolution, Cr(VI) reduction and Cr(III) precipitation. Batch reactors showed that Cr(VI) removal increases as the pH decreases. Column tests demonstrated that the simulated PRB with BOFS as the reactive media was quite effective for removing Cr(VI) from groundwater, with a sorption capability of 0.213 mg Cr per gram of BOFS at an initial Cr(VI) concentration of 50 mg L-1 at pH 5.5. A long-term test lasting 71 days confirmed the proposed mechanisms and the suitability of using BOFS in a permeable reactive barrier.

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The purpose of this study was to investigate the influence of increasing sulfate concentrations on chromium removal, to evaluate the effect of the presence of Cr(VI) on sulfate removal by Streptomyces sp. MC1 and to analyze the differential protein expression profile in the presence of this metal for the identification of proteins repressed or overexpressed. In the presence of Cr(VI) but in the absence of sulfate ions, bacterial growth was negligible, showing the Cr(VI) toxicity for this bacterium. However, the sulfate presence stimulated bacterium growth and Cr(VI) removal, regardless of its concentrations. Streptomyces sp. MC1 showed ability to remove chromium and sulfate simultaneously. Also, the sulfate presence favored the decrease of total chromium concentration from supernatants reaching a decrease of 50% at 48 h. In presence of chromium, seven proteins were down-expressed and showed homology to proteins involved in protein biosynthesis, energy production and free radicals detoxification while two proteins involved in oxidation-reduction processes identified as dihydrolipoamide dehydrogenase and S-adenosyl-l-methionine synthase were overexpressed.

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Chitosan particles (CH) were obtained from seafood processing wastes (shrimp shells) and physicochemically characterized; deacetylation degree of CH was measured by Infrared Spectroscopy (FTIR) and potentiometric titration; polymer molecular weight was determined by intrinsic viscosity measurements. Reticulated micro/nanoparticles of chitosan (MCH) with an average diameter close to 100nm were synthesized by ionic gelation of chitosan using tripolyphosphate (TPP), and characterized by SEM, size distribution and Zeta-potential. Detoxification capacities of CH and MCH were tested analyzing the removal of hexavalent chromium Cr(VI) from contaminated water, at different initial chromium concentrations. The effect of pH on adsorption capacity of CH and MCH was experimentally determined and analyzed considering the Cr(VI) stable complexes (anions) formed, the presence of protonated groups in chitosan particles and the addition of the reticulating agent (TPP). Chitosan crosslinking was necessary to adsorb Cr(VI) at pH<2 due to the instability of CH particles in acid media. Langmuir isotherm described better than Freundlich and Temkin equations the equilibrium adsorption data. Pseudo-second order rate provided the best fitting to the kinetic data in comparison to pseudo-first order and Elovich equations. Chemical analysis to determine the oxidation state of the adsorbed Cr, showed that Cr(VI) was adsorbed on CH particles without further reduction; in contrast Cr(VI) removed from the solution was reduced and bound to the MCH as Cr(III). The reduction of toxic Cr(VI) to the less or nontoxic Cr(III) by the reticulated chitosan micro/nanoparticles can be considered a very efficient detoxification technique for the treatment of Cr(VI) contaminated water.

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The effect of pre-treated peat moss on the ability of a sulfate-reducing microbial consortium to remove chromium and lead in solution was evaluated. The most active bacterial community (235.7 mmol H2S/g VSS) was selected from among eight consortia. The peat moss was pre-treated with different HCl concentrations and contact times. The best combination of treatments was 20% HCl for 10 min. The constant substrate affinity Ks was 740 mg COD/L and the ratio COD/SO4(2-) was 0.71. At pH 5, higher production of biogenic sulfide was observed. The up-flowpacked bed bioreactor operated at a flow of 8.3 mL/min for 180 h to obtain removal efficiency (by sulfate-reducing activity) of 90% lead and 65% chromium. It is important to consider that peat moss is a natural adsorbent that further influences the removal efficiency of metal ions.

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