The widespread use of the trace metal chromium in industrial processes and the known toxicity of CrVI species have stimulated interest in chromium speciation analysis. However, some analytical detection systems are not suitable for the quantification of CrIII and CrVI species. In the present study, an aqueous biphasic system (ABS) was employed as an environmentally safe, simple, and economical alternative. The ABS allows the implementation of an efficient separation step before quantifying of the species of interest by flame atomic absorption spectrometry. A robust speciation and preconcentration method was developed, which can be applied to samples with a wide concentration range, without the use of any extractants and interconversion of the species during the procedure. The proposed method was successfully used to determine the chromium species present in tap, treatment plant, river, and electroplating wastewater samples. Recovery percentages of 87.9-107% were achieved, suggesting minor water matrix interference. The proposed method had acceptable limits of detection and quantification of 5.38 and 16.3 µg kg-1, respectively.

Azure A (AZA) and azure B (AZB) phenothiazine dyes are used for clinical and medical purposes, and their functions can be altered via interactions with proteins. However, no kinetics information on the interactions between phenothiazine dyes and bovine serum albumin (BSA) is available. Surface plasmon resonance was used to determine the energetic and dynamic of the BSA-AZA and BSA-AZB complexes formation at pH 7.4. At temperature ≤ 16 °C, the formation of activated (DH‡a,12°C,AZA= -310.57 kJ mol-1 and DH‡a,12 °C,AZB= -256.37 kJ mol-1) and thermodynamically stable (DH°12°C,AZA= -314.56 kJ mol-1 and DH°12°C,AZB= -265.73 kJ mol-1) complexes was driven by enthalpy, while at temperature ≥ 20 °C, by entropy, (TDS‡a,28°C,AZA= 207.49 and TDS‡a,28°C,AZB= 190.69; TDS°28°C,AZA= 277.50 and TDS°28°C,AZB= 257.26 kJ mol-1). Hydrophobic interactions were fundamental to the complex stability and the increase in number of -CH3 groups in the dyes do not affect kinetic and thermodynamic parameters. Our results could help optimize the medical and pharmaceutical applications of phenothiazine dyes.

Aqueous two-phase systems (ATPSs) have proven to be efficient and environmentally safe methods for extracting chemical species. However, the driving forces behind the partition of solutes in these systems are still little understood. A complete thermodynamic partitioning of phenothiazine dyes was investigated in poly(ethylene oxide) (PEO) + salt + water ATPSs. Standard transfer parameters (Gibbs free energy change (ΔtrGº), enthalpy change (ΔtrHº) and entropy change (TΔtrSº)) were evaluated, and their dependence on the dye structure, electrolyte nature and tie line length (TLL). All phenothiazine dyes are concentrated predominantly in the polymer enriched phase, with ΔtrGº values ranging from -4.1 up to -13.4 kJ mol-1. Due to the dye-PEO attractive interactions that occur mainly via benzene condensed ring present in the structures of phenothiazine dyes, the partitioning of these dyes was enthalpically driven, with -11.4 ≥ ΔtrHº ≥ -52 kJ mol-1 and -4.93 ≥ TΔtrSº ≥ -38 kJ mol-1.

Bismuth is a critical metal broadly used in cosmetic, medicine and metallurgy. However, its scarcity in Earth’s crust may impair further applications. An alternative is to recover bismuth from secondary sources. In this work, a methodology to extract bismuth from safety valves of discharged gas cylinders is proposed. Extraction and purification of bismuth were carried out using aqueous two-phase systems (ATPS) prepared with poly(ethylene oxide) polymer or poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymer (L35) and electrolytes (NaNO3, NH4NO3, sodium citrate or Na2SO4). The influence of iodide extractant concentration, tie-line length, electrolyte nature and polymer hydrophobicity on the bismuth extraction behavior were evaluated. Bismuth was significantly recovered in the absence of extractant, and its extraction depends on the ATPS composition, macromolecule and electrolyte nature. After three consecutive extractions bismuth was obtained with high purity (94.7%), resulting on a recovery of 38.5 g of bismuth per 1.00 kg of fusible plug, using L35 + NH4NO3 + H2O ATPS, without any extractant.

The effects of low contents of acetonitrile (AN) or N,N-dimethylformamide (DMF) on the aggregation of sodium alkyl sulfate surfactants, in the absence and presence of poly(ethylene oxide) (PEO), were investigated using conductivity and isothermal titration calorimetry. The cosolvents slightly changed the critical micellar concentrations and did not alter the critical aggregation concentrations of the surfactants sodium decyl sulfate (DSS) and sodium dodecyl sulfate (SDS) with PEO. However, AN and DMF turned the micellization of the surfactants and their binding to the polymer enthalpically more favorable. For instance, for SDS, the micellization enthalpy, ΔHomic, decreased from close to 0 kJ mol-1 in water to -14.3 kJ mol-1 in the presence of 2.50 mol% AN, and the integral enthalpy change for aggregate formation with the polymer, ΔHagg(int), decreased from -1.1 kJ mol-1 in water to -15.5 kJ mol-1 in the same AN concentration. This was attributed to the modification of the solvation shells of both SDS and PEO by the cosolvent molecules, which reduced the entropic contribution to formation of the aggregates. Consequently, when SDS was replaced with DSS, the AN affected ΔHomic to a lesser extent, with a decrease of 9.1 kJ mol-1, while the ΔHagg(int) values were not altered, highlighting the influence of hydrophobic interactions in the surfactant aggregation process.

O objetivo do presente trabalho foi avaliar o efeito de diferentes enriquecimentos minerais na compostagem de resíduos provenientes da produção de biodiesel sobre características químicas do produto final. Foram utilizados os seguintes resíduos: bagaço de cana, cinza de bagaço de cana, esterco de galinha poedeira, torta de filtro e farelo de mamona. Estes materiais foram misturados e enriquecidos com fertilizante mineral NPK, pós de rochas de serpentinito + micaxisto e pó de gnaisse, obtendo-se oito compostos orgânicos distintos. Aos 0, 30, 90 e 120 dias de compostagem, essas misturas foram amostrados e realizadas análises de pH, condutividade elétrica, C, N, cinzas e na última amostragem foram determinados CTC e nutrientes totais. Apenas o composto enriquecido com NPK, sendo o N na forma de sulfato de amônio, atendeu a legislação pertinente a compostos orgânicos, enquanto os compostos contendo torta de filtro e mamona com e sem enriquecimento apresentaram pH abaixo do limite e os demais apresentaram teores de N ou C abaixo do mínimo estabelecido na legislação brasileira. A adição de pós de rochas de serpentinito + micaxisto contribuiu para elevação da CTC dos compostos.

The aim of this work was to evaluate the effect of different mineral enrichments during composting of biodiesel production residues on chemical characteristics of the end product. The following materials were used: sugar cane bagasse, ashes of sugar cane bagasse, poultry manure, filter cake and castor oil cake. These materials were mixed and enriched with mineral nutrients NPK, serpentinite and micaxist powdered rocks and gneiss powdered rocks, to obtain eight different composts. At 0, 30, 90 and 120 days after starting composting, these materials were sampled to measure pH, electrical conductivity, C, N, ashes, and, at the last sampling, CEC and total nutrients. Only the compost enriched with NPK (with N as ammonium sulphate) comply with the legislation pertinent to compost, while the composts that received filter cake and castor oil cake, with and without, mineral addition presented pH below the accepted limit and had C and N concentrations below the minimum established in the Brazilian legislation. The addition of serpentinite and micaxist powdered rocks contributed to raise the CEC of composts.