Quantifying biomineralization of zinc in the Rio Naracauli (Sardinia, Italy), using a tracer injection and synoptic sampling

Streams draining mined areas throughout the world commonly have high concentrations of Zn. Because Zn is not easily removed from stream water and because it can be toxic to aquatic organisms, its presence is a persistent problem. The discovery of biomineralization of Zn-bearing solids in the mine drainage of Rio Naracauli, in Sardinia, Italy, provides insights into strategies for removing Zn and improving water quality in streams affected by mine drainage. Until now, the transport and attenuation of Zn has not been quantified in this stream setting. A continuous tracer injection experiment was conducted to quantify the biomineralization process and to identify the loading of constituents that causes a change from precipitation of hydrozincite [Zn5(CO3)2(OH)6] in the upstream reach to precipitation of a Zn-silicate phase downstream. Based on the mass-load calculations derived from the tracer experiment, about 1.2 kg/day of Zn is sequestered in hydrozincite. This biomineralization represents nearly 90% removal of Zn. Other elements such as Pb and Cd also are sequestered, either in the hydrozincite, or in a separate phase that forms simultaneously. In the lower 600 m of the stream, where the Zn-silicate forms, as much as 0.7 kg/day Zn are sequestered in this solid, but additions of Zn to the stream from groundwater discharge lead to an overall increase in load in that portion of the Rio Naracauli.