Seasonal studies of aquatic humic substances from Amazon rivers: characterization and interaction with Cu (II), Fe (II), and Al (III) using EEM-PARAFAC and 2D FTIR correlation analyses.

Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

Photoelectrocatalytic removal of bromate using Ti/TiO2 coated as a photocathode.

These studies represent the rare use of a TiO2 material as a photocathode and the first application of photoelectrocatalysis for BrO3- removal. Photoelectrocatalytic reduction of BrO3- to Br- can reach 70% at neutral pH under an applied potential of -0.20 V versus SCE (saturated calomel electrode) after 75 min on the irradiated nanoporous thin-film TiO2-coated working electrode, which presented a flat band potential of -0.0274 V versus SCE. Regardless of the potential applied in these experiments, no BrO3- removal was observed in the counter electrode compartment or during electrolysis or photocatalysis, confirming that reduction of BrO3- to Br requires the combination of a negative potential (ideally near -0.20 V) and ultraviolet irradiation of the Ti/TiO2 electrode. The process was selective for BrO3- removal in that this process did not significantly reduce levels of Ca2+ and Mg2+ in drinking waters.

Simultaneous removal of chromium and leather dye from simulated tannery effluent by photoelectrochemistry.

The feasibility of the photobleaching of a leather acid dye, acid red 151, simultaneously to degradation of anionic surfactant, Tamol, and reduction of Cr(VI) to the less toxic Cr(III) was investigated by photoelectrocatalytic oxidation. The best experimental conditions were found to be pH 2.0 and 0.1 mol L(-1) sodium sulfate when the nanoporous Ti/TiO2 photo anode was biased at +1.0 V and submitted to UV-irradiation. The photoelectrocatalytic oxidation promotes 100% discoloration, reducing around 98-100% of Cr(VI) and achieving an abatement of 95% of the original total organic carbon. The effect of pH, the applied potential, the Cr(VI) concentration and the complexation reaction between Cr(VI) and acid red dye were evaluated as to their effect on the kinetics of the reaction.