Four sites in the western sector of Lipari Island with still active hydrothermal activity are here considered. The petrography (mesoscopic observations and XRPD) and geochemistry (major, minor and trace elements chemistry) of ten representative and extremely altered volcanic rocks were characterized. Two types of parageneses of altered rocks are discriminable, one rich in silicate phases (opal/cristobalite, montmorillonite, kaolinite, alunite and hematite) and one in sulphates (gypsum, plus minor amounts of anhydrite or bassanite). The altered silicate-rich rocks are rich in SiO2, Al2O3, Fe2O3 and H2O, and depleted in CaO, MgO, K2O and Na2O, while the sulphate-rich ones are extremely enriched in CaO and SO4 in comparison with local unaltered volcanic rocks. The content of many incompatible elements is similar in altered silicate-rich rocks and lower in sulphate-rich ones with respect to the pristine volcanic rocks; conversely, almost all REEs are markedly enriched in silicate-rich rocks and heavy REEs are enriched in sulphate-rich altered rocks compared to unaltered volcanic rocks. Reaction path modelling of basaltic andesite dissolution in local steam condensate predicts the production of amorphous-silica, anhydrite, goethite, and kaolinite (or smectites and saponites) as stable secondary minerals and alunite, jarosite, and jurbanite as ephemeral minerals. Considering possible post-depositional reactions and admitting that the presence of two distinct parageneses is apparent, since gypsum is prone to form large crystals, it can be concluded that there is an excellent agreement between the alteration minerals occurring in nature and those predicted by geochemical modelling. Consequently, the modelled process is the main responsible for the production of the advanced argillic alteration assemblage of "Cave di Caolino" on Lipari Island. Since rock alteration is sustained by the H2SO4 solution produced by hydrothermal steam condensation, there is no need to invoke the involvement of SO2-HCl-HF-bearing magmatic fluids, in line with the absence of fluoride minerals.
Eleven compositions along the join Na(NaMg)Mg5Si8O22(OH)2-Na(NaCa)Mg5Si8O22(OH)2 ("magnesiorichterite"-richterite) have been synthesized at T = 800-850 °C and PH₂O = 0.35-0.5 GPa. The run products have been characterized by electron probe microanalysis (EPMA), synchrotron and conventional X-ray powder diffraction (XRPD), Fourier transformed infrared (FTIR) spectroscopy, and selected area electron diffraction (SAED-TEM). Nominally, the chemical variation along the join can be expressed as BMgxBCa1-x with 0 ≤ x ≤ 1. A combination of EPMA and FTIR data in the OH-stretching region show that a complete solid solution is obtained under the conditions used. Nevertheless, a slight deviation from the nominal compositions involving a limited loss of Na at A and B sites, balanced by an increase of Ca at the B site, is present. Several indications of a displacive and coelastic P21/m → C2/m transformation induced by the Ca-Mg chemical substitution are observed. The phase transition occurs at B-site composition (Xc) close to B(Na1Mg0.7Ca0.3). C2/m samples with a Ca content of 0.34, 0.45, and 0.54 apfu show a significant strain tail related to local compositional inhomogeneities. This residual strain disappears as the amount of BCa significantly increases with respect to that of BMg. The transformation behavior observed here mirrors that of pyroxenes along the join diopside (CaMgSi2O6)-enstatite (Mg2Si2O6). The cell parameters of amphiboles with CMg5, TSi8, and W(OH)2 and variable A- and B-site populations follow almost linear and continuous trends, indicative of small amounts of spontaneous strain accompanying these monoclinic phase transitions and the absence of significant miscibility gaps among different amphibole groups when quenched from higher temperatures of crystallization.
Amphiboles were hydrothermally synthesized at 500 °C and 4 kbar in the system Li2O-Na2OFeO- Fe2O3-SiO2-H2O, with nominal compositions along the riebeckite [□Na2Fe32+Fe23+Si8O22(OH)2]-ferri-clinoferroholmquistite [□Li2Fe32+Fe23+Si8O22(OH)2] join, where the exchange vector is NaLi-1 at the B-site. Experimental products were characterized by powder XRD and SEM-EDAX, confirming very high amphibole yield along the join (>95%, plus minor quartz). The XRD patterns can be indexed in C2/m, and the refined cell parameters show linear variation as a function of composition. For the BLi end-member, the IR spectrum shows a single sharp main band centered at 3614 cm-1, which is assigned to the FeFeFe-OH-A□ configuration. With increasing BNa in the mineral, this band broadens and shifts 4 cm-1 to higher frequencies. This effect can be attributed to the change in M4 site occupancy. Minor ANa (partial solid-solution toward arfvedsonite) is also observed with increasing sodium in the system. Mössbauer spectroscopy confirms the cation distribution provided by IR data, and shows that a small, but significant amount of Fe2+ occurs at M4 along the join. Infrared spectroscopy shows that the Li end-member has a very ordered structure, whereas intermediate compositions show local heterogeneities associated with the presence of two different B sites occupied by Na or Li.
Abstract The crystal-chemical variations of spinels grown as a function of cooling rate (ΔT/Δt) were analyzed via X-ray electron-microprobe (EPMA) maps. Maps were collected serially by using a fixed distance. Spinels solidified from a tholeiitic MOR basaltic liquid (B100) cooled at cooling rates (ΔT/Δt) of 1, 7, 60, and 180 °C/h, between 1300 and 800 °C and at ambient P and fO2. As ΔT/Δt increases, the amount of spinel is invariably <5 area% and its size decreases. Compared to the previous data set collected by common single and selected EPMA analytical points (112 analyses), the kinetic effects induced by ΔT/Δt are here quantitatively captured by a large number of analyses (2052). The TiO2, Al2O3, MgO, and FeOtot show large compositional variations at low cooling rates (from 1 to 60 °C/h), and only the average TiO2 concentration shows a well-defined trend as a function of ΔT/Δt. However, calculated average cation amounts (apfu) unveil quantitative kinetic effects. When ΔT/Δt increases (from 1 to 180 °C/h), only Ti4+ shows a linear decreasing trend, whereas the other major Al3+, Fe3+, Fe2+, and Mg2+ cations alone are scattered. Conversely, the sums of trivalent (Al3++Fe3+) and divalent (Mg2++Fe2+) cations quantitatively capture the effect of the ΔT/Δt. These new outcomes could be the base of novel geospeedometers with significant implications in volcanology, geophysics, and material sciences in regard to silicate melt rheology on Earth. They should be extended to high-pressure, hydrated, and low oxygen fugacity conditions. Furthermore, the analytical approach used here to capture kinetic effects on spinel growth and compositions can be also applied to other crystalline phases grown from silicate liquids.
