Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

First-principles calculation of H/D isotopic fractionation between hydrous minerals and water

Hydrogen fractionation laws between selected hydrous minerals (brucite, kaolinite, lizardite, and gibbsite) and perfect water gas have been computed from first-principles quantum-mechanical calculations. The β-factor of each phase was calculated using the harmonic phonon dispersion curves obtained within density functional theory. All the fractionation laws show the same shape, with a minimum between 200 °C (brucite) and 500 °C (gibbsite). At low temperatures, the mineral/liquid water fractionation laws have been obtained using the experimental gas/liquid water fractionation laws. The resulting fractionation laws systematically overestimate measurements by 15‰ at low temperatures to 8‰ at ≈400 °C. Based on this general agreement, all calculated laws were empirically corrected with reference to brucite/water data. These considerations suggest that the experimental or natural calibrations by Xu and Zheng (1999) and Horita et al. (2002) (brucite/water), Gilg and Sheppard (1996) (kaolinite/water), Wenner and Taylor (1973) (lizardite/water), and in some extents Vitali et al. (2001) (gibbsite/water) are representative of equilibrium fractionations. Besides, internal isotopic fractionation of hydrogen between inner-surface and inner hydroxyl groups has been computed for kaolinite and lizardite. The obtained fractionation is large, of opposite sign for the two systems (respectively, −23‰ and +63‰ at 25 °C) and is linear in T^-2. Internal fractionation of hydrogen in TO phyllosilicates might thus be used in geothermometry.     

Hydrogeochemistry of Roccamonfina volcano (Southern Italy)

This is the first hydro-geochemical investigation carried out on the Roccamonfina Volcanic Complex groundwaters. The chemistry of Roccamonfina waters is defined by water–rock and water–rock–gas interactions. In fact, interactions between rocks of the first eruptive high-K formations and circulating groundwaters are recognized by high K concentrations. On the other hand, inverse concentration of calcium versus alkali metals is related to two different rock interactions occurring in different areas of the volcano: (a) within the caldera where groundwaters flow within latite and pyroclastic formations releasing calcium, and (b) similarly at the base of the volcano where groundwaters flowing from surrounding carbonates got strongly enriched in Ca. These geochemical processes are also associated with K (SE of caldera) and Mg/Ca (in sites located at the NE base of the volcano) decrease. Completely different dynamics occurs at Riardo groundwaters (SE). Here waters are the result of a mix between the Roccamonfina deep aquifer and the carbonate aquifer of the Riardo plain. Rich-CO₂ emissions make these waters strongly mineralized. Minor elements show a similar geochemical behavior of major ions and are crucial defining interactions processes. The evolution of Roccamonfina groundwaters is also evident along the simultaneous enrichment of Ba, Sr, and Ca. Ba increase is the result of deep local carbonate alteration enhanced by CO₂ emissions and, the lower Sr/Ca ratio, from 10 to 2 (ppb/ppm), is also due to the same process. In the light of our results the Roccamonfina aquifer can be schematically divided into two main reservoirs: (a) a superficial aquifer which basically follows the volcanic structure morphology and tectonics and (b) a deeper reservoir, originating within the oldest Roccamonfina volcano ultra potassic lavas and then flowing into the carbonate aquifers of the neighboring plain. Eventually, the chemistry of the Roccamonfina aquifer does not show any specific and visible pollution, contrary to what happens in the volcano surrounding plains. In fact, only 14% of the samples we collected (206) show a NO₃ content >30 mg/l. These sites are all located at the base of the volcano, near the plain.     

Linear relationship between thermo-dehydroxylation and induced-strain by mechanical processing in vacuum: The case of industrial kaolinite, talc and montmorillonite

The thermal behaviour and the structural properties of three important industrial phyllosilicates, such as kaolinite, talc and Ca-rich montmorillonite, have been examined after mechanical treatment in a specifically built planetary ball mill working in vacuum (P = 0.13 Pa) at room temperature (25 °C). It is found that, on increasing the grinding time, the temperature of the dehydroxylation reaction decreases linearly as a result of a decrease of the crystallite size and structural order. To be noted that the mechanical treatment in our milling conditions did not induce significant amorphization. The temperature at which there is the maximum of dehydroxylation and the weight losses of the intralayer OH are linearly related to the increase of the FWHM of the 001 basal plane. These results are useful for predicting the thermal behaviour of layer silicates to be subjected to mechanical processing in industrial application.     

Cooling and exhumation history of deep‐seated and shallow level,late Hercynian granitoids from Calabria

The thermal and exhumation history of late Hercynian granitoids from Calabria (Sila and Serre massifs) has been studied using thermobarometry and radiometric age determinations. The uplift and erosion which followed contractional tectonics of Tertiary age exposed in Calabria a nearly complete section of the Hercynian crust. Field data, constrained by igneous thermobarometrical data, have enabled us to draw simplified crustal profiles. In both the Sila and Serre massifs, granitoids make up the intermediate portions of the crustal sections and are stacked as tabular intrusions for up to 13 km cumulative thickness. Shallow granitoids are characterized by a weak fabric, mostly developed in the magmatic stage, whereas deep‐seated granitoids display a strong fabric developed in the magmatic state and, with decreasing temperatures, in the subsolidus state. The intrusive bodies were emplaced at 300–290 Ma, at a time when the Calabrian crust was undergoing extensional tectonics and crustal thinning. The subsequent post‐Hercynian evolution is recorded by Rb‐Sr dates of micas and fission track ages of zircon and apatite obtained from granitoids emplaced at different depths. A decrease in Rb‐Sr and fission track ages is observed as depth of emplacement increases. Data on the post‐Hercynian geological evolution of Calabria were used to model in three stages the cooling and exhumation history of deep‐seated and shallow granitoids. The first stage, in Permian to Triassic times, was characterized by slow erosion. It was followed by a second stage of extensional tectonics in Jurassic times. The third stage was exhumation during the Apenninic Orogeny. The model has generated two P–T–t arrays, one for deep‐seated and the other for shallow granitoids of the Serre massif. The T–t paths suggest that the dates of micas, zircon and apatite are cooling ages. They also show that deep‐seated granitoids remained at temperatures above the brittle–plastic transition for a long time, whereas shallow granitoids cooled rapidly. Distinct P–T–t paths explain why deep‐seated and shallow granitoids display different fabric and microstructural features. Copyright © 2000 John Wiley & Sons, Ltd.     

Petrology of basic and intermediate orogenic granitoids from the Sila Massif (Calabria,southern Italy)

Hercynian gabbroic, dioritic and tonalitic rocks crop out in the neighbourhood of Rovale (Sila Grande, Calabria). They make up a crude rectangular outcrop with the western part consisting of gabbroic rocks and the eastern of dioritic and tonalitic rocks. They come into contact with medium to high grade metapelites on the western side and with heterogeneous granodiorites on the other sides. In the gabbroic body both opx ± ol bearing cumulates and amphibole differentiates occur and are characterized by the widespread presence of brown pargasite. Sporadic magmatic to subsolidus corona textures between olivine and plagioclase or orthopyroxene and plagioclase can be observed and their preservation clearly suggests a post-tectonic emplacement for the gabbroic magma. Diorites and tonalites display hypidiomorphic textures free of olivine and orthopyroxene and bearing green Mg-hornblende. The granitoids, on the basis of chemical data, display orogenic features of the continent-continent collision type. The gabbroic rocks have high Al tholeiitic composition and fractionation of orthopyroxene and plagioclase played an important part in their evolution. The Rb/Sr isochron method did not give a precise emplacement age for the granitoids as a whole. Initial ⁸⁷Sr/⁸⁶Sr ratios (at 290 Ma) are higher in the gabbroic body (0.7091–0.7095) than in diorites and tonalites (0.7083–0.7092). Thus gabbroic rocks appear more displaced than diorites and tonalites towards crustal isotopic composition. The eNd data seem to confirm this feature, thus suggesting that the gabbroic rocks and diorites derived from distinct mantle magma batches. Interestingly, small isotropic gabbroic masses occur within the diorites and show general features that allow them to be considered as possibly parental with respect to the host diorites. The evolution to the dioritic composition might have occurred through fractionation and minor mixing with a more acidic component such as the northern granodiorites. Geochemical, Sr and Nd isotopic data indicate a scenario of a composite plutonic body formed by distinct magma batches of mixed crust and mantle origin.