Integration of iron in natural and synthetic Al-pyrophyllites: an infrared spectroscopic study

Numerous studies focus on the relationships between chemical composition and OHband positions in the infrared (IR) spectra of micaceous minerals. These studies are based on the coexistence, in dioctahedral micas or smectites, of several cationic pairs around the hydroxyl group which each produce a characteristic band in the IR spectrum. The aim of this work is to obtain the wavenumber values of the IR OH vibration bands of the (Al-Fe3+)-OH and (Fe3+-Fe3+)-OH local cationic environments of 'pyrophyllite type' in order to prove, disprove or modify a model of dioctahedral phyllosilicate OH-stretching band decomposition. Natural samples are characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopies and electron microprobe; the hydrothermal synthesis products are also analysed by powder XRD and FTIR after inductively coupled plasma measurements to obtain the chemical compositions of nascent gel phases. Natural samples contain some impurities which were eliminated after acid treatment; nevertheless, a small Fe content is found in the pyrophyllite structure. The amount of Fe which is incorporated within the pyrophyllite structure is much more important for the synthetic samples than for the natural ones. The IR OH bands were clearly observed in both natural and synthetic pyrophyllites and assigned to hydroxides bonded to (Al-Al), (Al-Fe) and (Fe-Fe) cationic pairs. During this study, three samples were analysed by DTG to check the cis- or trans-vacant character of the layers and to determine the influence of this structural character on the OH-stretching band position in IR spectroscopy

Permeability Evolution in Variably Glassy Basaltic Andesites Measured Under Magmatic Conditions

Heat from inflowing magma may act to seal permeable networks that assist passive outgassing at volcanic conduit margins and in overlying domes, reducing the efficiency of overpressure dissipation. Here we present a study of the evolution of permeability—measured under magmatic conditions—with increasing temperature in glassy and glass‐poor basaltic andesites from Merapi volcano (Indonesia). Whereas the permeability of glass‐poor rocks decreases little up to a temperature of 1,010°C, glassy specimens experience a pronounced decrease in permeability above the glass transition once the viscosity of the crystal suspension is low enough to relax under external stresses. Changes in temperature alone are thus not enough to significantly modify the permeability of the glass‐poor rocks that commonly form Merapi's dome. However, the presence of glass‐rich domains in a dome may lead to local sealing of the volcanic plumbing between eruptions, exacerbating localized overpressure development that could contribute to explosivity

Reactive transport experiments of coupled carbonation and serpentinization in a natural serpentinite. Implication for hydrogen production and carbon geological storage

Serpentinization and carbonation of ultramafic formations is a ubiquitous phenomenon, which deeply influences the biogeochemical cycles of water, hydrogen, carbon…while supporting the particular biosphere around the oceanic hydrothermal vents. Carbonation of peridotites and other mafic and ultramafic rocks is also a hot topic in the current energy landscape as the engineered sequestration of mineral CO2 in these formations could help reduce the atmospheric emissions and cope with climate change. In this study, we present two reactive percolation experiments performed on a natural serpentinite dredged from the ultraslow South-West Indian Oceanic Ridge. The serpentinite cores (length 3–4 cm and dia. 5.6 mm) were subjected for about 10 days to the continuous injection of a NaHCO3-saturated brine at respectively 160 °C and 280 °C. Petrographic and petrophysical results as well as outlet fluid compositions were compared to numerical batch simulations performed with the PHREEQC open software allowing to reconstruct the mineralogical evolution of both cores. The most striking observation is the fast and dramatic decrease of the permeability for both experiments principally due to the precipitation of carbonates. On the contrary, serpentine was found to be less impacting as it precipitates in low-flow zones, out of the main percolation paths. In total, about 5.6% of the total injected CO2 was retained in the core, at 280 °C. In the same time, hydrogen was consistently produced with a total recovered H2 corresponding to 0.8% of the maximum H2 possible. The global behavior of the cores is interpreted as the result from an interplay between interacting spatio-temporal lengthscales controlled by the Damköhler number

The impact of melt versus mechanical wear on the formation of pseudotachylyte veins in accretionary complexes

AbstractWhether seismic rupture propagates over large distances to generate mega-earthquakes or is rapidly aborted mainly depends on the slip processes within the fault core, including particularly frictional melting or intense grain-size reduction and amorphization. The record of seismic slip in exhumed fault zones consists in many instances in Black Faults Rocks, dark and glass-like-filled aphanitic veins that have been interpreted as resulting from the quenching of frictional melts, i.e. pseudotachylytes. Such interpretation has nevertheless been questioned as similar macro to nano-microstructures have been observed either on intensely comminuted natural fault rocks or on slow creep experiments conducted on crustal rocks, where melting is absent. Here, we report a new dataset of Raman Spectroscopy of Carbonaceous Material analyses, aimed at discriminating the slip weakening processes operating in the fault core during slip. Using high spatial resolution profiles on natural Black Fault Rocks from exhumed accretionary complexes and an experimentally calibrated modelling of Raman intensity ratio evolution with temperature, we assessed different scenarios of temperature evolution during fault slip. None of them is able to account for the distribution of Raman signal, so that in the three studied Black Fault Rocks interpreted so far as natural pseudotachylytes, Raman Spectroscopy of Carbonaceous Material rather reflects the effect of intense and localized strain during fault slip. Furthermore, the absence of thermal imprint on Raman signal puts upper bounds on the temperature reached within the fault zone. If one cannot rule out the occurrence of high and short-lived temperature increase due to friction, the latter was not high enough as to melt the large quartz fraction of the fault zone rocks.</jats:p

Experimental Constraints on the Crystallization of Silica Phases in Silicic Magmas

Abstract Low-pressure silica polymorphs, e.g. quartz (Qtz), tridymite (Trd), and cristobalite (Crs), are common in silicic magmas, but the conditions of their formation are still unclear. The stability fields of these polymorphs have been determined in the SiO2, SiO2–H2O, and haplogranite systems, but these simple systems are not directly applicable to silica polymorph crystallization in natural silicic magmas. The present study compiles an experimental database of new and previously-published data documenting the crystallization of silica phases in natural silicic magmas and simple synthetic systems. Silica polymorphs are identified using Raman spectroscopy and their pressure-temperature domains of occurrence and chemical compositions are determined at pressures between 0·1 and 200 MPa, temperatures between 685 to 1200° C, and under H2O-saturated and H2O-undersaturated conditions.  Qtz is the stable silica polymorph at pressures higher than 25–30 MPa, temperatures between ∼700 and 950° C, and occurs for a narrow range of melt SiO2 contents (∼79–81 wt %). Constraints on Qtz stability derived from simple systems are mutually compatible with, and thus applicable to natural compositions. This is consistent with Qtz compositions being close to ‘pure’ SiO2, both in experiments and nature. In volcanic systems, Qtz crystallization may occur in magmatic reservoirs and deep volcanic conduits.  Trd did not crystallize in the experiments conducted as part of this study despite several experiments having been performed in the Trd stability field. This is consistent with results from the literature which show that Trd crystallization is kinetically inhibited in particular relative to Crs. Natural Trd have compositions deviating substantially from ‘pure’ SiO2, so that stability limits determined in simple systems should not be applied directly to natural cases.  Crs was encountered at pressures below 20–30 MPa (or H2O contents &amp;lt; ∼1·5 wt %), from sub-solidus (∼800° C) to near-liquidus (up to 1040° C), and coexisting with melts having a large range of SiO2 contents (70–81 wt %). The Crs stability field is much larger in natural magmas compared to pure SiO2 systems. Crs is a metastable phase stabilized by components (Al, Na, K; about 3 wt %) present in the silicic melt. In volcanic systems, Crs crystallization may thus be restricted to subsurface manifestations such as lava domes.</jats:p