Mn-rich layers and interbedded shales from a well exposed natural section of the Northern-Calabrian Unit (Late Jurassic-Early Oligocene) in the surroundings of the Terranova del Pollino village, southern Italy, have been mineralogically and chemically analyzed, in order to reveal the factors controlling their formation. Mn-rich layers are composed of micas/clay minerals, rhodochrosite, siderite, chlorite and quartz whereas shales are formed by micas, clay minerals, chlorite, quartz, and feldspars. The MnO abundances in the Mn-rich layers, which are depleted relatively to the UCC in SiO2, TiO2, Al2O3, Na2O, K2O, and P2O5, are in the range of 11.01 ÷ 18.41 (wt. %). R-mode Factor analysis indicate that SiO2, Al2O3, TiO2, Na2O and K2O have high positive weights in the first factor (59.8% of the total variance) whereas high negative weights are observed for Fe2O3, MnO, and CaO. This factor accounts for the competition between the terrigeneous component, the authigenic carbonate phases accumulating Mn and Fe which likely formed during paucity of detrital supply. The negative weight of CaO and MnO in this factor, the higher Ca contents in the Mn-rich layers compared to shales, and the lack of calcite, suggest the presence of a mixed Mn-Ca carbonate rather than pure rhodochrosite. It is generally retained that Ca-rhodochrosite precipitates within the pore waters of reducing sediments since neither rhodochrosite nor siderite can form in equilibrium with bottom seawater. Thus the resulting sediment should be a mixing between the detrital component and the authigenic one. Assuming Al2O3 as an index of the detrital component, it is clearly envisaged that in the Al2O3/MnO vs. Al2O3 diagram the carbonate-rich samples fall on the mixing curve having as end members the average shale and the richest MnO sediment. This supports the idea that carbonate-rich samples formed through precipitation of carbonate minerals in the pore waters of the terrigenous detritus accumulating at the sea bottom. Further the REE distribution of unaltered marine carbonates is expected to be representative of ambient seawater where carbonates precipitated. Carbonates normalized to fine-grained siliciclastic sediments, have typical HREE enrichment, negative Ce-anomaly, and lower total REE. In our case, the carbonate-rich samples normalized to the average composition of the interbedded free-carbonate shale, show HREE enrichment, lower total REE contents, and the lack of negative Ce-anomaly, due to the anoxic environment of formation for Mn- and Fe-carbonate. Finally was observed that the mineralization is enhanced if the site of accumulation is protected from dilution by clastic sediment input. The alternation between Mn- and Fe-carbonate silts and carbonate-free shales along the studied sedimentary succession, were likely controlled by eustatic sea-level oscillations which are well documented in the western Tethys during Middle and Late Triassic.
This study is focused on fluids characterization and circulations through the crust of the Irpinia region, an active seismic zone in Southern Italy, that has experienced several high-magnitude earthquakes, including a catastrophic one in 1980 (M = 6.9 Ms). Using isotopic geochemistry and the carbon‑helium system in free and dissolved volatiles in water, this study aims to explore the processes at depth that can alter pristine chemistry of these natural fluids. Gas-rock-water interactions and their impact on CO2 emissions and isotopic composition are evaluated using a multidisciplinary model that integrates geochemistry and regional geological data. By analyzing the He isotopic signature in the natural fluids, the release of mantle-derived He on a regional scale in Southern Italy is verified, along with significant emissions of deep-sourced CO2. The proposed model, supported by geological and geophysical constraints, is based on the interactions between gas, rock, and water within the crust and the degassing of deep-sourced CO2. Furthermore, this study reveals that the Total Dissolved Inorganic Carbon (TDIC) in cold waters results from mixing between a shallow and a deeper carbon endmember that is equilibrated with carbonate lithology. In addition, the geochemical signature of TDIC in thermal carbon-rich water is explained by supplementary secondary processes, including equilibrium fractionation between solid, gas, and aqueous phases, as well as sinks such as mineral precipitation and CO2 degassing. These findings have important implications for developing effective monitoring strategies for crustal fluids in different geological contexts and highlight the critical need to understand gas-water-rock interaction processes that control fluid chemistry at depths that can affect the assessment of the CO2 flux in atmosphere. Finally, this study highlights that the emissions of natural CO2 from the seismically active Irpinia area are up to 4.08·10+9 mol·y-1, which amounts is in the range of worldwide volcanic systems.
Geochemical investigations carried out at the Campano–Lucano Apennine (Southern Italy) revealed the presence of fluids composed of a mixing between components of shallow and deep origin, where mantle‐derived helium is also detectable. For the gas phase, the deep component is represented by both CH 4 and CO 2 ‐rich gases, while the shallow one is N 2 ‐dominated. Coinciding with the 3 April 1996 M L =4.9 earthquake, the CH 4 ‐rich component mixed with the shallow, N 2 ‐dominated one at the Tramutola well (Val d’Agri), displaying wide variations in mixing proportions. In contrast, no significant modifications occurred in relation to the 1998 M L =5.5 event. According to the collected data, an earthquake‐related transient modification of local crustal permeability is suggested for the 1996 event. The different crustal response to the two events may be related to different stress distributions around the epicentres or may suggest a different tectonic connection between the Val d’Agri and the two earthquake locations.
Abstract 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 ( M s = 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 4 He produced in the crust in the area (up to 2.5 × 10 28 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 4 He. 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 4 He 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.
Two distinct eruptive events characterize the volcanic activity at Mount Etna during the 2002 to 2005 period. We identified signals of magma ascent preceding these eruptions by geochemical monitoring of both chemical composition and He‐isotope ratio of gas emissions from five locations in the peripheral area of the volcano. The geochemical signals are interpreted using the models proposed by Caracausi et al. (2003a, 2003b) and allow identification of episodes of magma ascent and estimation of the pressures of degassing magma. As observed for the 2001 eruption (Caracausi et al., 2003b), magma ascent probably triggered the onset of the 2002–2003 eruption, and minor events of magma ascent were observed between May and December 2003. In contrast to the previous two eruptions, the 2004–2005 eruption was not preceded by significant geochemical signals of volcanic unrest, suggesting that this eruption was mainly triggered by the failure of the upper portion of the volcanic edifice under the magmatic hydrostatic pressure in the conduits. High 3 He/ 4 He ratio revealed new volatile‐rich magma accumulation. The 2002–2003 eruption was preceded by a much shorter period of new magma accumulation from deep levels of the feeding system. Few minor signals of magma migration were detected at some of the sites during the months preceding the 2004–2005 eruption, suggesting that the degassed 3 He‐depleted magma resident in the volcanic conduits was not replaced by new volatile‐rich magma. This is in agreement with the lack of explosive activity during the 2004–2005 eruption and with petrologic observations that the parent magma probably erupted in 2000 and 2001. New geochemical signals of magma ascent from the deep reservoir have been identified since June 2005, indicating that the volcanic activity of Mount Etna is evolving toward new pre‐eruptive conditions.
