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The Sulcis-Iglesiente district (SW Sardinia, Italy) has been, until recently, one of the most important Italian polymetallic mining areas for the extraction of lead. Epidemiological studies conducted over several decades have indicated this site at high risk of environmental crisis with possible adverse effects on the public health. In the present paper we discuss Pb isotope signatures in human scalp hair and road dust collected from the Sulcis-Iglesiente area in order to trace the exposure of populations to potential Pb sources. A total of 23 determinations (20 on hair samples and 3 on road dust samples) of lead isotope ratios (206Pb/207Pb and 208Pb/206Pb) were carried out. The obtained results were integrate with literature data regarding the total content of Pb in hair samples from the same study area. Hair from children living in Sant'Antioco exhibited lead isotope ratios in the ranges 1.152-1.165 for 206Pb/207Pb and 2.101-2.108 for 208Pb/206Pb, while hair samples from Iglesias resulted less radiogenic: 206Pb/207Pb~1.147-1.154 and 208Pb/206Pb~2.106-2.118. These values pointed to a multi-source mixing between the less radiogenic sources, corresponding to the Pb ore deposits, and the more radiogenic sources identified in local background.

Hemimorphite, Zn 4 Si 2 O 7 (OH) 2 ·H 2 O, one of the most common minerals in non-sulfide Zn deposits, together with smithsonite and hydrozincite, is one of the most abundant minerals in the “calamine” deposits in SW Sardinia. In spite of their importance for the development of ore genesis models, the stability properties of hemimorphite are poorly known. This paper presents solubility experiments on two different types of hemimorphite: a “geological” hemimorphite from a supergene non-sulfide Zn deposit, of supposed abiotic origin, and a hemimorphite precipitated by bacterial activity. Both specimens were characterized, before and after the experiment, by Synchrotron Radiation X-ray powder diffraction, Scanning Electron Microscopy, and X-ray Absorption Spectroscopy. The calculated solubility product constants (logK s ) are similar for both “geological” and biogenic hemimorphite (30.3 ± 0.4 and 30.5 ± 0.1, respectively). During the solubility experiment, biological hemimorphite undergoes an amorphous to crystalline phase transition, and the distinctive features (mineralized bacterial sheaths and organic filaments), that allowed us to demonstrate its biological origin, are no longer recognizable by Scanning Electron Microscopy. The results of this study may be useful for developing ore genesis models, including evolution in a supergene environment, and in general for performing geochemical speciation and equilibrium calculations. Moreover, our findings open the way for a new interpretation of hemimorphite-forming processes, and suggest the possibility that bacteria may have played a role in the formation of this mineral in ore deposits.

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and “green rust”), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants (Phragmites australis and Juncus acutus) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate). The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favouring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions.