Tracking Metamorphic Dehydration Reactions in Real Time with Transmission Small- and Wide-Angle Synchrotron X-ray Scattering: the Case of Gypsum Dehydration

We present a review of a unique non-destructive method for the real-time monitoring of phase transformations and nano-pore evolution in dehydrating rocks: transmission small- and wide-angle synchrotron X-ray scattering (SAXS/WAXS). It is shown how SAXS/WAXS can be applied to investigating rock samples dehydrated in a purpose-built loading cell that allows the coeval application of high temperature, axial confinement, and fluid pressure or flow to the specimen. Because synchrotron sources deliver extremely bright monochromatic X-rays across a wide energy spectrum, they enable the in situ examination of confined rock samples with thicknesses of ≤ 1 mm at a time resolution of order seconds. Hence, fast kinetics with reaction completion times of about hundreds of seconds can be tracked. With beam sizes of order tens to hundreds of micrometres, it is possible to monitor multiple interrogation points in a sample with a lateral extent of a few centimetres, thus resolving potential lateral spatial effects during dehydration and enlarging sample statistics significantly. Therefore, the SAXS/WAXS method offers the opportunity to acquire data on a striking range of length scales: for rock samples with thicknesses of ≤ 10-3 m and widths of 10-2 m, a lateral interrogation-point spacing of ≥ 10-5 m can be achieved. Within each irradiated interrogation-point volume, information concerning pores with sizes between 10-9 and 10-7 m and the crystal lattice on the scale of 10-10 m is acquired in real time. This article presents a summary of the physical principles underpinning transmission X-ray scattering with the aim of providing a guide for the design and interpretation of time-resolved SAXS/WAXS experiments. It is elucidated (1) when and how SAXS data can be used to analyse total porosity, internal surface area, and pore-size distributions in rocks on length scales from ∼1 to 300 nm; (2) how WAXS can be employed to track lattice transformations in situ; and (3) which limitations and complicating factors should be considered during experimental design, data analysis, and interpretation. To illustrate the key capabilities of the SAXS/WAXS method, we present a series of dehydration experiments on a well-studied natural gypsum rock: Volterra alabaster. Our results demonstrate that SAXS/WAXS is excellently suited for the in situ tracking of dehydration kinetics and the associated evolution of nano-pores. The phase transformation from gypsum to bassanite is correlated directly with nano-void growth on length scales between 1 and 11 nm for the first time. A comparison of the SAXS/WAXS kinetic results with literature data emphasises the need for future dehydration experiments on rock specimens because of the impact of rock fabric and the generally heterogeneous and transient nature of dehydration reactions in nature. It is anticipated that the SAXS/WAXS method combined with in situ loading cells will constitute an invaluable tool in the ongoing quest for understanding dehydration and other mineral replacement reactions in rocks quantitatively.