Dissolution of Metals in Different Bromide-Based Systems: Electrochemical Measurements and Spectroscopic Investigations.

The dissolution of the main metals (Cu, Zn, Sn, Pb and Fe) found in waste printed circuit boards (WPCBs) was investigated by electrochemical corrosion measurements (potentiodynamic polarization and electrochemical impedance spectroscopy (EIS)) in different bromide-based systems that could be used as lixiviants in hydrometallurgical route of metals recovery. The analysis of the corrosion products was carried out by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. All measurements showed that the addition of bromine in the electrolyte favors to great extents the dissolution process of all studied metals as compared to bromine-free electrolytes. In the investigated experimental conditions, the highest dissolution rates of the metals were obtained in acidic KBr solution containing 0.01 mol/L bromine and they decreased in the following order: Zn >> Sn > Pb > Fe > Cu. The XRD and XPS chemical assessment allowed the identification of the dissolution products formed on the metallic surfaces after exposure to the electrolytes. They consisted mainly of oxides in the case of Cu, Zn, Sn and Fe, while the presence of PbBr2 was also noticed on the lead surface. Based on the results of EIS and surface investigations, several models explaining the corrosion behavior of the metals were proposed and discussed. The obtained results demonstrate that all studied metals could be successfully leached using brominated solutions, providing a viable alternative for the selective and efficient recovery of the base metals from WPCBs through a multi-step hydrometallurgical processing route.

EPR detection of sulfanyl radical during sulfhemoglobin formation - Influence of catalase.

Hemoglobin in its ferryl form oxidizes hydrogen sulfide and is transformed to sulfhemoglobin, where the sulfur is inserted covalently at the heme edge. Shown here is evidence that-as previously proposed by others-this process involves oxidation of hydrogen sulfide to a sulfanyl radical detectable by spin-trapping in electron paramagnetic resonance (EPR) spectroscopy. The yields and rates of formation of sulfhemoglobin as well as of the sulfanyl radical are affected by the same factors that affect the reactivity of hemoglobin ferryl, in bovine hemoglobin and in phytoglobins as well. A freely-diffusing sulfanyl radical is thus proposed to be involved in sulfhemoglobin formation. Catalase is shown to accelerate this process due to a previously described hydrogen sulfide oxidase activity, within which EPR evidence for sulfanyl generation is shown here for the first time. The reaction of preformed ferryl with hydrogen sulfide-in absence of hydrogen peroxide-is studied by stopped-flow at several pH values and explained in light of reactivity and redox potential control.