Rosa Sinisi

Fe concentration in palaeosols and in clayey marine sediments : two case studies in the Variscan basement of Sardinia (Italy)

Abstract Within the Variscan basement of Sardinia (Italy), two main Fe concentrations occur in the low-grade metamorphic tectonic units: (1) an uppermost-Ordovician oolitic ironstone of shallow anoxic water environment; and (2) a concentration of Fe oxyhydroxides lying on a palaeosurface. Two sets of samples were picked from the marine ironstone and from the continental Fe concentration following stratigraphic criteria. Chemical analysis, X-ray diffraction, scanning electron microscopy-energy dispersive X-ray analysis and thin-section studies were performed on 34 samples. Marine ironstones formed under a highly reducing, anoxic, non-sulphidic methanic environment, and their Fe phases are chamosite, siderite and magnetite. Detrital chlorite and illite, produced during physical weathering, were chamosite precursors. Using the V/Cr proxy, an emergence stage that caused a transition to an oxic environment is documented. In contrast, continental ironstones formed under oxic conditions and the dominant Fe phase is goethite, which can adsorb Zn2+ and U6+. Unexpected negative Ce anomalies occur in this set of samples, suggesting that the oxyhydroxides originated from Ce-depleted solutions. Although the ironstones of Sardinia formed in different environments (marine vs. continental) and under contrasting climatic conditions (sub-glacial vs. tropical) they share similar geochemical features. These dramatic palaeoenvironmental differences did not result in large differences between the geochemistry of the chemical sediments.

Messinian palaeoclimate and palaeo-environment in the western Mediterranean realm: insights from the geochemistry of continental deposits of NW Sardinia (Italy)

To evaluate the palaeo-environmental parameters of a portion of the Sardinia–Corsica microplate during the Messinian drop in sea level, we examined the chemistry and mineralogy of upper Tortonian–lower Messinian (late Miocene) clayey continental deposits from NW Sardinia. Differences exist between the uppermost part of the succession, which is devoid of carbonate phases, and the lower part, reflecting changes in provenance and climate. The carbonate-free samples were probably derived from quartzite of the metamorphic basement and were deposited under a climate characterized by alternating dry and relatively wet periods. The other samples were derived from basement phyllite and were deposited under a warm, dry climate that promoted the capillary rise of Ca2+ and bicarbonate from a shallow water table, and therefore, the precipitation of carbonate. This part of the succession contains both calcite and dolomite. The presence of barite indicates an important concentration of SO4 2− in the solution from which the CaMg(CO3)2 precipitated. The formation of dolomite under hypersaline conditions may be explained by bacterial degradation of organic matter, which produced CO2 and ammonia, thereby increasing the solution alkalinity. The succession formed in an oxic environment, except for a calcite-rich level that formed under relatively reducing conditions. For this level, the large amount of calcite and the lack of dolomite indicate an alkaline environment and a very low Mg2+/Ca2+ ratio in the soil solution. These observations, coupled with the reducing conditions, indicate the availability of large amounts of degraded organic matter, probably related to a period typified by a wetter climate.

Trace element geochemistry of the Mt Vulture carbonatites, southern Italy

The Mt Vulture carbonatites are the only carbonatite occurrence in the southern Apennines. We present new trace element data for these rocks in order to evaluate the factors influencing rare earth element (REE) and other trace element fractionations and their REE grade. This study focuses on massive hyalo-alvikites from two lava flows and one dike, which have different relative abundances of silicate and carbonate (i.e. Si/Ca). These differences are also evident from CaO/(CaO + MgO + FeO(T) + MnO) and Sr/Ba ratios. The REE grade of the Mt Vulture carbonatites is very similar to that of the global average for calcio-carbonatites. R-mode factor analysis shows that most of the trace element variance reflects the relative roles of carbonate and silicate minerals in influencing trace element distributions. Silicates largely control heavy rare earth element (HREE), transition metal, Zr, and Th abundances, whereas carbonate minerals control light rare earth element (LREE), Ba, and Pb abundances. In addition, apatite influences LREE concentrations. Increasing silica contents are accompanied by decreases in (La/Yb)N and (La/Sm)N ratios and less marked LREE enrichment. In contrast, higher carbonate contents are associated with increases in (La/Yb)N and (La/Sm)N. The Si/Ca ratio has little influence on Eu anomalies and middle rare earth element (MREE) to HREE fractionations. Apatite has a negligible effect on inter-REE fractionations amongst the carbonatites.

Trace elements and REE fractionation in subsoils developed on sedimentary and volcanic rocks: case study of the Mt. Vulture area, southern Italy

There is an increasing interest in the distribution of rare earth elements (REEs) within soils, primarily as these elements can be used to identify pedogenetic processes and because soils may be future sources for REE extraction, despite much attention should be paid to the protection and preservation of present soils. Here, we evaluate the processes that control the distribution of REEs in subsoil horizons developed over differing lithologies in an area of low anthropogenic contamination, allowing estimates of the importance of source rocks and weathering. Specifically, this study presents new data on the distribution of REEs and other trace elements, including transition and high-field-strength elements, in subsoils developed on both Quaternary silica-undersaturated volcanic rocks and Pliocene siliciclastic sedimentary rocks within the Mt. Vulture area of the southern Apennines in Italy. The subsoils in the Mt. Vulture area formed during moderate weathering (as classified using the chemical index of alteration) and contain an assemblage of secondary minerals that is dominated by trioctahedral illite with minor vermiculite. The REEs, high-field-strength elements, and transition metals have higher abundances in subsoils that developed from volcanic rocks, and pedogenesis caused the Mt. Vulture subsoils to have REE concentrations that are an order of magnitude higher than typical values for the upper continental crust. This result indicates that the distribution of REEs in soils is a valuable tool for mineral exploration. A statistical analysis of inter-elemental relationships indicates that REEs are concentrated in clay-rich fractions that also contain significant amounts of low-solubility elements such as Zr and Th, regardless of the parent rock. This suggests that low-solubility refractory minerals, such as zircon, play a significant role in controlling the distribution of REEs in soils. The values of (La/Yb)N and (Gd/Yb)N fractionation indices are dependent on the intensity of pedogenesis; soils in the study area have values that are higher than typical upper continental crust ratios, suggesting that soils, especially those that formed during interaction with near neutral to acidic organic-rich surface waters, may represent an important source of both light REEs and medium REEs (MREEs). In comparison, MREE/heavy REE fractionation in soils that form during moderate weathering may be affected by variations in parent rock lithologies, primarily as MREE-hosting minerals, such as pyroxenes, may control (La/Sm)N index values. Eu anomalies are thought to be the most effective provenance index for sediments, although the anomalies within the soils studied here are not related to the alteration of primary minerals, including feldspars, to clay phases. In some cases, Eu/Eu* values may have a weak correlation with elements hosted by heavy minerals, such as Zr; this indicates that the influence of mechanical sorting of clastic particles during sedimentary transport on the Eu/Eu* values of siliciclastic sediments needs to be considered carefully.

Genesis of carbonate-rich veins in the serpentinites at the Calabria-Lucania boundary (southern Apennines)

In the northern sector of the Pollino massif (southern Apennines, Italy) well-exposed lens-shaped bodies of serpentinites and sediments of the Frido Unit belonging to the Liguride Complex crop-out. Most serpentinite rocks are cross-cut by carbonate and quartz-carbonate veins with different thickness. This study focuses on petrographic, mineralogical, geochemical, and isotopic analysis of the carbonate veins embedded in serpentinite rocks, collected at the Fosso Arcangelo site and at the Pietrapica quarry (Calabria-Lucanian boundary). The paragenesis of the carbonate veins from the Fosso Arcangelo site is dominantly made by calcite and aragonite with minor amount of rhodochrosite. In quartz-carbonate veins from Pietrapica quarry, dolomite, Mg-calcite, quartz, with minor ankerite were observed.The δ13CV-PDB isotope ratios of carbonates in the carbonate veins are in the range from +2.16‰ to -3.66‰ and corresponding δ18OV-SMOW values are between +15.02‰ and +21.53‰. The δ13CV-PDB values of carbonates in quartz-carbonate veins are in the range from -3.60‰ to -1.78‰ and the corresponding δ18OV-SMOW average value is around +21.3‰. The results suggest that the carbonate at both site occurredunder the same environmental conditions from crustal-derived andlow-moderate temperatures hydrothermal fluids having different chemical composition.