Michele Paternoster

Radiogenic helium degassing and rock fracturing: a case study of the southern Apennines active tectonic region

Gas from mud volcanoes, dry mofettes, springs, and wells were sampled in a region of active tectonics and high seismicity in the southern Apennines (Italy), where there is a long history of disastrous earthquakes, with the latest (Ms = 6.9) occurring in 1980. The fluids consist of a mixture of mantle-derived and crust-derived volatiles, with a low atmosphere-derived contribution, as identified by the He isotope signature and He/Ne ratio measurements. One year of monthly monitoring of the He concentrations and He isotopes revealed no seasonal modifications or variations induced by low seismicity. There are extraordinary high outputs of 4He produced in the crust in the area (up to 2.5 × 1028 atoms yr−1). These outputs cannot be solely due to the whole-rock production rate and a long-lasting diffusion degassing through the crust of the produced 4He. This study explored the relation between the volume of fractured rock and the related release of He. The results support that crustal degassing can be controlled by tectonic events resulting in earthquakes. The high seismicity in this sector of the Apennines provides the conditions necessary for a massive release of He that has accumulated in the rock over a long time period. We identified that the assessed high crustal 4He output can be attributed to an intense fracturing of a calculable volume of rock, which gives new constraints on the volume of rock involved in high-magnitude earthquakes in the region.

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.