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A method for evaluating the potential of reuse of biomasses for economic purposes is here presented starting from a case study. Juncus acutus plants and rhizospheres were harvested from abandoned Zn–Pb mine areas of southwest Sardinia (Italy). Thermogravimetry and Differential Thermal analyses were performed to evaluate the temperatures at which significant reactions occur. X-ray Diffraction (XRD) analysis was carried out on raw samples and on samples heated ex-situ (by a conventional diffractometer) or in-situ (by synchrotron-based diffraction). Raw samples mainly consist of quartz, phyllosilicates, and feldspars with minor amounts of sulfides, sulfates, and Fe, Pb, and Zn carbonates, concentrated in the rhizosphere. After heating, Zn and Fe oxides and willemite are observed in internal roots and stems, revealing the presence of these metals in the plant tissues. In-situ heating was less effective than ex-situ in revealing minor phases in organic samples, probably because the scarcity of oxygen within the sample holder did not allow the degradation of organic compounds and the oxidation of sulfides, resulting in a low quality XRD signal even if obtained with the high resolution ensured by a synchrotron light source. This method can be applied to plants from polluted sites for metal exploitation, and/or to biomasses from unpolluted sites for biochar production, since both applications take advantage of the knowledge of the minerals formed after heating.

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 favoring 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.

The consumption of water with fluoride concentration higher than 1.5 mg/L (WHO recommended limit) is recognized to cause serious diseases, and fluoride removal from natural contaminated waters is a health priority for more than 260 million people worldwide. The octacalcium phosphate (OCP), a mineralogical precursor of bio-apatite, is here tested as a fluoride remover. A new two-step method for the synthesis of OCP is proposed: 1) synthesis of brushite from calcium carbonate and phosphoric acid; 2) subsequent hydrolysis of brushite. Fluoride removal experiments are performed in batch-mode using different initial concentrations of fluoride (from 40 to 140 mg/L) and reaction times. Most of fluoride is removed within the first 2 h of all experiments, and the drinkable limit of 1.5 mg/L is reached within a minimum of 3 h for an initial fluoride concentration of 40 mg/L. The experimental fluoride removal capacity of OCP is 25.7 mg/g, and 4 g of OCP can effectively treat 1 L of water with fluoride concentration up to 50 times higher than the drinking limit of 1.5 mg/L. XRD and chemical characterization of the solid phases, before and after the removal experiments, indicate that OCP transforms into fluorapatite (FAP) uptaking fluoride from solution.