Geochemical and mineralogical datasets on waters and stream precipitates from an abandoned mining site: Montevecchio-Ingurtosu district, Rio Irvi (SW Sardinia)

Geochemical modelling data and Powder X-Ray Diffraction data on samples collected along Rio Irvi (Montevecchio-Ingurtosu mining district, SW Sardinia, Italy) are reported in this paper. The data show the results of data processing to calculate water chemical speciation of ions and saturation indices of relevant mineral phases. These data are related with the research article: De Giudici G. et al (2018), Application of hydrologic-tracer techniques to the Casargiu adit and Rio Irvi (SW-Sardinia, Italy): Using enhanced natural attenuation to reduce extreme metal loads, Applied Geochemistry, vol.96, 42–54. The comparison of the calculated saturation indices of relevant Fe-bearing phases with the PXRD data of samples collected along the stream confirm the quality of the SI dataset and the good correlation between the calculations and the observed data. The comparison of this dataset with others can help to deeper understand and quantify the impact of past and current mining activity on water bodies, contributing to implement the scientific background for the application of remediation actions

Fossichnus solus and Oichnus simplex, two peculiar ichnospecies in modern benthic foraminifera from a polluted area in SW coast of Sardinia, Italy

The modern benthic foraminiferal tests collected from a coastal area of south-western Sardinia (Portoscuso-Portovesme) that is heavily polluted by industrial activity reveal intense and widespread bioerosional structures induced by diversifi ed microborers. A large number of the foraminifera reveals microscopic round holes (1-60 μm in diameter) and roundish concavities (25x40 μm in external diameter) on their surface that belong, respectively, to the ichnospecies Oichnus simplex Bromley, 1981, and Fossichnus solus Nielsen et al., 2003. These traces just occur in the tests of the foraminifera which are heavily infested by microendolithic cyanobacteria, algae and fungi suggests comparable ethological behaviour between the ichnospecies Fossichnus and Oichnus and the microbial euendoliths that are ascribed to individual biological taxa. The greater occurrence of F. solus and O. simplex in the high-Mg foraminiferal porcelanaceous tests than in the low-Mg foraminiferal hyaline tests reveals that the bioerosional processes seem to be related to the Mg/Ca ratio, as well as to morphological structures of the taxa

MINERALOGICAL STUDIES OF THE W-Sn VEIN SKARNS OF MONTE TAMARA (NUXIS, SULCIS DISTRICT): INSIGHTS FOR STRATEGIC MINERALS EXPLORATION IN SW SARDINIA (ITALY).

Skarn deposits are a relevant source of critical raw materials such as W, Sn, and In. Recent studies conducted in South Sardinia pointed out the relationships between various Sn-W-Mo deposits and the early Permian (289-286 Ma) F-bearing, ilmenite-series ferroan granites (e.g., Sulcis pluton). This new evidence triggered a broad re-examination of granite-related deposits including skarn deposits hosted by Cambrian limestones of the low-grade Variscan basement of the Sulcis district (SW Sardinia). With this purpose, field investigations and OM, SEM-EDS, EMPA, and LA-ICP-MS observations, and analyses have been conducted on the skarn ores of Monte Tamara (Nuxis, northern Sulcis) where scheelite has been reported in the old San Pietro and Sinibidraxiu mines. The San Pietro mine exploited a 1-5 m thick and 70 m deep, steeply dipping skarn orebody located at the tectonized contact between early Cambrian sandstones and limestones. The orebody includes layers of Grt-Cpx-Wo, magnetite, and Zn-Pb-Cu-Fe sulfide bands. Prograde and retrograde stages with oxides and sulfides can be recognized. Clinopyroxene is the foremost mineral of the prograde stage; garnets (andradite-grossular) are usually dark green with typical anomalous birefringence and distinctly zoned (Fe-rich cores and Al-rich rims). Hematite turned to mushketovite, and Mo-rich scheelite, followed by In-bearing cassiterite, occasionally occur in the prograde assemblages. Amphiboles and epidotes mark the retrograde stage, together with abundant Zn-Cu-Fe-Pb sulfides and accessory molybdenite, stannite, bismuthinite, and Bi-Ag-Pb sulfosalts. At San Pietro, dominant sphalerite displays highly variable Fe, Mn, and Cd contents. Relictlooking blebs of Fe-Mn-poor Sp are scattered in high-Fe-Mn Sp where Sn EMPA peaks may correlate with cassiterite-stannite micro-inclusions. Galena composition suggests localized intergrowths with micro-inclusions of bismuthinite, Bi-Se, and Bi-Te sulfosalts. The stannite-sphalerite geothermometer provided a temperature range of 325-200°C for the sulfide stage. The Sinibidraxiu old mine exploited a 1,5 m thick and 60 m deep columnar body, hosted in early Cambrian marbles. It consists of a sphalerite-wollastonite assemblage with late sulfides, quartz, and calcite, hosting cm-sized arsenopyrite and scheelite. Scheelite is Mo-poor; Sn-, other Mo-phases and Bi-phases are absent. High-Fe Sp, rimmed by low-Fe Sp and blebby galena, is finely intergrown with wollastonite cockades. The results from this study suggest that a wide range of skarn-related mineralizing phenomena occurred in the Monte Tamara area. Both orebodies resulted from a structurally controlled migration of metasomatic fluids inside the hosting carbonate formation. Mineral zonation and composition of the San Pietro skarn point towards skarn development under varying fO2 conditions, oxidizing then rapidly turning to moderately reducing within the prograde W-Sn skarn stage and into the sulfide stage. The features of the Sinibidraxiu orebody (e.g., Mo-poor, As-devoid scheelite) suggest a formation from reducing metasomatic fluids but S-poor compared to San Pietro, probably at more distal environments (e.g. low Sn-Bi contents). From this point of view, the Monte Tamara area still maintains an economic potential, linked to the possible presence of proximal skarn ores at depth; thereby representing a key area for further exploration for granite-related strategic and critical metals in SW Sardinia

Ex situ phytoremediation trial of Sardinian mine waste using a pioneer plant species

The mitigation of metals contamination is currently a crucial issue for the reclamation of mine sites. Indeed, mine wastes are often disposed in open dumps and consequently pollutants are subjected to dispersion in the surrounding areas. In this study, the potential use of Helichrysum microphyllum subsp. tyrrhenicum for phytostabilization was evaluated in ex situ conditions. Ninety specimens were randomly selected and were planted in three substrates (reference substrate, mine waste materials, and mine wastes with compost). Mineralogical compositions of substrates, rhizosphere, and roots were assessed through X-ray diffraction (XRD). Zn, Pb, and Cd concentrations of substrates, rhizosphere, soil pore waters, and plant tissues were determined. The phytostabilization potential was determined through the application of biological accumulation coefficient (BAC), biological concentration factor (BCF), and translocation factor (TF). Moreover, survival and biometric parameters were assessed on plant specimens. The polluted substrates and related rhizosphere materials were mainly composed of dolomite, quartz, pyrite, and phyllosilicate. Zn was the most abundant metal in substrates, rhizosphere, and soil pore waters. XRD analysis on roots showed the presence of amorphous cellulose and quartz and Zn was the most abundant metal in plant tissues. H. microphyllum subsp. tyrrhenicum restricts the accumulation of the metals into roots limiting their translocation in aereal parts, indicating its potential use as phytostabilizer (BCF, BAC, TF < 1). Survival and growth data showed a great adaptability to different substrates, with an evident positive effect of the implementation of compost which increased the plant survival and decreased the metals uptake into roots

Fossichnus solus and Oichnus simplex, two peculiar ichnospecies in modern benthic foraminifera from a polluted area in SW coast of Sardina, Italy

The modern benthic foraminiferal tests collected from a coastal area of south-western Sardinia (Portoscuso-Portovesme) that is heavily polluted by industrial activity reveal intense and widespread bioerosional structures induced by diversified microborers. A large number of the foraminifera reveals microscopic round holes (1-60 μm in diameter) and roundish concavities (25x40 μm in external diameter) on their surface that belong, respectively, to the ichnospecies Oichnus simplex Bromley, 1981, and Fossichnus solus Nielsen et al., 2003. These traces just occur in the tests of the foraminifera which are heavily infested by microendolithic cyanobacteria, algae and fungi suggests comparable ethological behaviour between the ichnospecies Fossichnus and Oichnus and the microbial euendoliths that are ascribed to individual biological taxa. The greater occurrence of F. solus and O. simplex in the high-Mg foraminiferal porcelanaceous tests than in the low-Mg foraminiferal hyaline tests reveals that the bioerosional processes seem to be related to the Mg/Ca ratio, as well as to morphological structures of the tax

Mineralogy of the scheelite-bearing ores of Monte Tamara, SW Sardinia: insights for the evolution of a Late Variscan W–Sn skarn system

Southwestern Sardinia, Italy, hosts several skarn, W–Sn–Mo greisen and hydrothermal deposits related to a 289±1 Ma Late Variscan granite suite. Among them, the most representative scheelite-bearing skarns belong to the San Pietro and Sinibidraxiu localities, in the Monte Tamara area, Sulcis region. The San Pietro deposit is a typical calc-silicate skarn whereas Sinibidraxiu is a sharply bounded orebody hosted in a marble unit. Optical petrographic observations and compositional data of major and trace elements were obtained for samples from both localities. San Pietro data suggests evolution from an oxidising prograde skarn stage (andradite–diopside, hematite and scheelite), to progressively more reducing conditions from the early retrograde (magnetite–cassiterite) to the late sulfide stage (arsenopyrite, stannite, molybdenite, Bi sulfosalts and Zn–Cu–Pb–Fe sulfides); Sinibidraxiu has diffuse carbonate–quartz intergrowths pseudomorphic over an early mineral assemblage with fibrous habit, followed by abundant ore mineral precipitation under reducing conditions (scheelite, arsenopyrite and Pb–Zn–Cu–Fe sulfides). Geothermometers indicate a comprehensive temperature range of 460–270°C for the sulfide stages of both deposits. The differences between the two deposits might be controlled by the distance from the source intrusion coupled with the different reactivity of the host rocks. The San Pietro mineralogy represents a more proximal skarn, contrasting with more distal mineralogical and chemical features characterising the Sinibidraxiu orebody (lack of Mo–Sn–Bi phases; LREE–MREE–HREE signature of scheelite). This investigation contributes for the first time to the identification of a W–Sn skarn system in SW Sardinia, thereby suggesting the Monte Tamara area and its surroundings as favourable for further exploration

Efficient artificial mineralization route to decontaminate Arsenic(III) polluted water -the Tooeleite Way

Increasing exposure to arsenic (As) contaminated ground water is a great threat to humanity. Suitable technology for As immobilization and removal from water, especially for As(III) than As(V), is not available yet. However, it is known that As(III) is more toxic than As(V) and most groundwater aquifers, particularly the Gangetic basin in India, is alarmingly contaminated with it. In search of a viable solution here, we took a cue from the natural mineralization of Tooeleite, a mineral containing Fe(III) and As(III)ions, grown under acidic condition, in presence of SO42- ions. Complying to this natural process, we could grow and separate Tooeleite-like templates from Fe(III) and As(III) containing water at overall circumneutral pH and in absence of SO42- ions by using highly polar Zn-only ends of wurtzite ZnS nanorods as insoluble nano-acidic-surfaces. The central idea here is to exploit these insoluble nano-acidic-surfaces (called as INAS in the manuscript) as nucleation centres for Tooeleite growth while keeping the overall pH of the aqueous media neutral. Therefore, we propose a novel method of artificial mineralization of As(III) by mimicking a natural process at nanoscale

PRELIMINARY STUDIES ON BIOPRECIPITATION PROCESSES MEDIATED BY SULFATE REDUCING BACTERIA (SRB) AND METAL IMMOBILIZATION IN MINE IMPACTED ENVIRONMENTS.

Mining activity often leaves a critical legacy represented by huge volumes of mine wastes and residues, usually made up of highly reactive materials, which lead to the mobilization and dispersion of harmful elements in soils and waters. Although these extreme environments are adverse to the development of living organisms, it has been observed that some microorganisms are able to adapt, playing a role in metal mobility, and becoming part of the resilience of the system itself. The Iglesiente and Arburese (SW Sardinia, Italy) mine districts, now abandoned, have been exploited for centuries by mining activities aimed at Pb-Zn extraction from sulfides and non-sulfides (calamine) deposits. Here, biogeochemical barriers naturally occur as an adaptation of the ecosystem to environmental stresses. Studies, from macroscale to microscale, showed that sulfate-reducing bacteria (SRB) may influence metal mobility by mediating the precipitation of secondary authigenic metal sulfides under reducing conditions. Specifically, framboids of Zn sulfides and Fe sulfides have been observed in the sections of stream sediments core characterized by the presence of abundant organic matter, especially residues of vegetal tissues (e.g. roots and stems of Juncus acutus and Phragmites australis). Laboratory-scale experiments were performed to better understand the bioprecipitation processes. For this purpose, anaerobic batch tests were carried out using high polluted mining waters (Zn and sulfate concentrations up to 102 and 103 mg/l, respectively) inoculated with native selected sulfate-reducing bacteria from stream sediments collected in the investigated areas. Dramatic decrease (up to 100%) in Zn and sulfate was observed in solutions. Moreover, scanning electron microscopy - energy dispersive spectroscopy (SEM-EDS) analysis, performed on solids recovered at the end of the experiments, showed the presence of precipitates characterized by a tubular morphology and made up by S and Zn. SRB inocula were studied by next-generation sequencing (NGS) approach, with the aim to compare the microbial diversity of the different SRB communities and to search for indigenous novel metal-tolerant sulfidogenic microorganisms. These findings represent a valuable step forward to plan effective bioremediation strategies for reducing metal mobility and dispersion. Also, bioprecipitation mediated by SRB can have great potentialities for metal recovery and our results can help to develop biomining techniques. The authors acknowledge CESA (E58C16000080003) from RAS and RAS/FBS (F72F16003080002) grants, and the CeSAR (Centro Servizi d'Ateneo per la Ricerca) of the University of Cagliari, Italy, for SEM analysis

Natural attenuation can lead to environmental resilience in mine environment

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