Alessandro C. Martins

The antioxidant activity of teas measured by the FRAP method adapted to the FIA system: optimising the conditions using the response surface methodology.

This study proposes a FRAP assay adapted to FIA system with a merging zones configuration. The FIA system conditions were optimised with the response surface methodology using the central composite rotatable design. The optimisation parameters studied were: the carrier flow rate, the lengths of the sample and reagent loops, and reactor length. The conditions selected in accordance with the results were: carrier flow rate of 1.00 ml/min, length of the loops 18.2 cm and length of the reaction coil 210.1 cm. The detection and quantification limits were, respectively, 28.6 and 86.8 μmol/l Fe(2+), and the precision was 1.27%. The proposed method had an analytical frequency of 30 samples/h and about 95% less volume of FRAP reagent was consumed. The FRAP assay adapted to the FIA system under the optimised conditions was utilised to determine the antioxidant activity of tea samples.

From ionic liquid-modified cellulose nanowhiskers to highly active metal-free nanostructured carbon catalysts for the hydrazine oxidation reaction

Ionic liquid (or [C4mim][CH3SO3])-modified cellulose nanowhiskers (CNWs) are synthesized and successfully used as precursors to make heteroatom (N and S)-doped nanostructured carbon catalysts. The catalysts can efficiently electrocatalyze the hydrazine oxidation reaction (HOR) with an onset potential close to the reactions thermodynamic value, or with a value better than those obtained for other related materials. The synthesis of these metal-free carbon electrocatalysts generally involves only a few, relatively less demanding synthetic steps. Based on relevant control experiments, the outstanding catalytic activity of the materials is attributed to the heteroatom dopants and defect sites in the materials, which form during carbonization due to the [C4mim][CH3SO3] placed around the CNWs. However, it is not necessarily the density of heteroatom dopant species introduced into the nanostructured carbon materials by the ILs that directly affect the electrocatalytic activity of these materials; it is rather the specific type of dopant-associated chemical moiety and vacancy site created in the materials, which are the main factors positively affecting the electrocatalytic activity of the materials toward the reaction. The surface areas of the materials play a relatively lesser role in affecting the electrocatalytic properties of the materials toward the HOR as well.

Phytotoxicity and distribution of copper in tropical soil amended with sewage sludge and copper sulfate

Abstract A greenhouse experiment was conducted to evaluate phytotoxicity and distribution of Cu in a tropical soil amended with sewage sludge (Sw) and copper sulfate (CuSO4.5H2O). Samples of a clay soil from the State of Paraná, Brazil were collected at depth of 0–20; 20–40 and 40–60 cm, and brought to the laboratory to be properly accommodated in experimental units (PVC tubes). The Cu treatments were performed by the application of Sw (10 t ha-1) amended with Cu (SB-T), and by CuSO4. H2O (WB-T). Lettuce plants were cultivated in the amended soil in order to predict the toxicity of the Cu. The experiment was conducted for 70 days, and then the lettuce plants and soil samples were collected for analysis. A sequential method was used to separate soil Cu into following fractions: exchangeable, amorphous iron oxide bound, crystalline iron oxide bound, organic matter bound and residual bound. The experimental results showed that Fe, Zn, K, P, Cu and organic matter amounts of the soil increased with the treatment SB-T. The toxic phyto-available Cu content in the soil for the lettuce plants was 80.00 mg kg-1. A percolation study showed that the Cu contents were larger for the first 20 cm of depth, indicating that the metal was not transported down the soil profile. The Cu content of different fractions declined in an order residual > amorphous iron oxide > crystalline iron oxide > organic matter > exchangeable, regardless of treatment performed. Additionally, the Cu contents added from treatments were determined mainly in amorphous iron oxide fraction.

Optimization and Validation of an Extraction Method for Evaluating the Availability of Cu, Zn, Mn, Ni, Cr and Cd in Soil with the Use of the Mehlich-1 Extractor

The Mehlich-1 extractor is routinely used to evaluate the bioavailability of metals in soil since it has a high closeness between the amount of these elements absorbed by the plants and those available in soil, as well as being simple and practical to use. Thus, the aim of this work was to improve (optimize) a Mehlich-1 extraction method for evaluating the availability of Cu, Zn, Mn, Ni, Cr and Cd in soil using Box-Behnken type response surface method (RSM). After optimizing the soil amount, Mehlich-1 extractor volume and stirring time, the validation of the newly developed method was performed by evaluating the following parameters: matrix adjustment, linearity, linear range, limits of detection (LOD) and of quantification (LOQ), precision and accuracy. The analytical method proposed by this study can be routinely employed for the evaluation of soil toxicity since it presented advantages such as simplicity, speed and efficacy, as well as being precise and accurate.