Mineralogical Transformations in Granitoids during Heating at Fire-Related Temperatures

Fire is a major decay agent of rocks and can generate immediate catastrophic effects as well as directional and anisotropic damage that affect long-term weathering processes. Temperature increase is the most relevant factor, among other components in a fire, generating mineral transformations and bulk mechanical damage. Mineralogical changes at high temperatures are key to understanding the overall mechanical behaviour. However, most studies to date were carried out after rock specimens were heated to a target temperature and cooled down to room temperature. Therefore, these studies are missing the observation of the actual mineral processes during heating. This paper aims to compare mineralogical changes in crystalline rocks during heating by means of XPS and different XRD techniques. Samples of four different granitoids were heated to several temperatures up to 1000 °C to evaluate their chemical and structural changes. Results show how standardised thermal expansion coefficients are not a suitable indicator of the bulk effect of high temperatures on rocks. Results also show how thermal expansion estimations from XRD lattice measurements may be an alternative to bulk dilatometric tests, as they can be performed with limited sampling, which may be necessary in some studies. Nevertheless, XRD and XPS results need to be interpreted carefully in relation to the bulk effects of temperature increase in the rocks, as the structural behaviour may seemingly contradict the macroscopic effect.

Kinetically driven successive sodic and potassic alteration of feldspar

The dynamic evolutions of fluid-mineral systems driving large-scale geochemical transformations in the Earth’s crust remain poorly understood. We observed experimentally that successive sodic and potassic alterations of feldspar can occur via a single self-evolved, originally Na-only, hydrothermal fluid. At 600 °C, 2 kbar, sanidine ((K,Na)AlSi3O8) reacted rapidly with a NaCl fluid to form albite (NaAlSi3O8); over time, some of this albite was replaced by K-feldspar (KAlSi3O8), in contrast to predictions from equilibrium reaction modelling. Fluorine accelerated the process, resulting in near-complete back-replacement of albite within 1 day. These findings reveal that potassic alteration can be triggered by Na-rich fluids, indicating that pervasive sequential sodic and potassic alterations associated with mineralization in some of the world’s largest ore deposits may not necessarily reflect externally-driven changes in fluid alkali contents. Here, we show that these reactions are promoted at the micro-scale by a self-evolving, kinetically-driven process; such positive feedbacks between equilibrium and kinetic factors may be essential in driving pervasive mineral transformations.

Ultrafast olivine-ringwoodite transformation during shock compression

Meteorites from interplanetary space often include high-pressure polymorphs of their constituent minerals, which provide records of past hypervelocity collisions. These collisions were expected to occur between kilometre-sized asteroids, generating transient high-pressure states lasting for several seconds to facilitate mineral transformations across the relevant phase boundaries. However, their mechanisms in such a short timescale were never experimentally evaluated and remained speculative. Here, we show a nanosecond transformation mechanism yielding ringwoodite, which is the most typical high-pressure mineral in meteorites. An olivine crystal was shock-compressed by a focused high-power laser pulse, and the transformation was time-resolved by femtosecond diffractometry using an X-ray free electron laser. Our results show the formation of ringwoodite through a faster, diffusionless process, suggesting that ringwoodite can form from collisions between much smaller bodies, such as metre to submetre-sized asteroids, at common relative velocities. Even nominally unshocked meteorites could therefore contain signatures of high-pressure states from past collisions.

Where is the Hydrogen?

How is hydrogen distributed among minerals and how is it bonded in their crystal structures? These are important questions, because the amount of hydrogen and the bonding configuration of hydrogen in crystalline materials governs many of that material’s properties: its thermal and compressional behavior, P–T phase stability, rheology, and electrical conductivity. A reliable reconstruction of the Earth’s interior, or the prediction of mineral transformations in complex industrial processes, must account for these parameters. Neutron diffraction can locate hydrogen sites in mineral structures, reveal any static or dynamic hydrogen disorder, help define the libration regime of hydrogen, and elucidate hydrogen-bonding configurations. Thus, that most elusive element for X-ray probes is perfectly detectable using neutrons.