Ferrihydrite flocs, native copper nanocrystals and spontaneous remediation in the Fosso dei Noni stream, Tuscany, Italy

The Fosso dei Noni stream drains the abandoned mixed-sulfide mining area of Fenice Capanne in Italy. Water pollution mostly derives from two tributaries, one of which adds Cu and the other Zn. Downstream, water pollution is progressively remediated through the spontaneous precipitation of abundant, deeply-colored flocs. Within 1 km, flocs change from yellow-red to whitish and green, as the pH increases from 4.59 to 7.70 and the Eh decreases from +311 to +165 mV. Flocs are initially amorphous; with a near-neutral pH, their X-ray diffraction properties suggest the presence of two-line ferrihydrite. Transmission electron microscopy reveals major nanotextural modifications in flocs along the entire stream. Upstream, flocs consist of globular particles with a radius of 25-50 nm. Downstream, they change to globular particles with elongated features. Lastly, further downstream, flocs consist of elongated features interconnected by continuous films. Nanochemical data are consistent with Al and Fe hydroxides (largely contaminated by S, Si, Ca, Cu and Zn); the Cu content increases progressively downstream to a maximum of 18 at. %. The increasing Cu content is paralleled by the appearance of isolated Cu nanocrystals adsorbed on floc surfaces. Spontaneous processes in the Fosso dei Noni stream (water neutralization, formation of ferrihydrite-like flocs and crystallization of native Cu) allow the temporary storage of Cu, providing hints on how to optimize remediation processes and Cu recovery.