Franck Bourdelle

Characterization of Ca-phosphate biological materials by scanning transmission X-ray microscopy (STXM) at the Ca L 2,3 -, P L 2,3 - and C K-edges

Several naturally occurring biological materials, including bones and teeth, pathological calcifications, microbial mineral deposits formed in marine phosphogenesis areas, as well as bio-inspired cements used for bone and tooth repair are composed of Ca-phosphates. These materials are usually identified and characterized using bulk-scale analytical tools such as X-ray diffraction, Fourier transform infrared spectroscopy or nuclear magnetic resonance. However, there is a need for imaging techniques that provide information on the spatial distribution and chemical composition of the Ca-phosphate phases at the micrometer- and nanometer scales. Such analyses provide insightful indications on how the materials may have formed, e.g. through transient precursor phases that eventually remain spatially separated from the mature phase. Here, we present scanning transmission X-ray microscopy (STXM) analyses of Ca-phosphate reference compounds, showing the feasibility of fingerprinting Ca-phosphate-based materials. We calibrate methods to determine important parameters of Ca-phosphate phases, such as their Ca/P ratio and carbonate content at the ∼25nm scale, using X-ray absorption near-edge spectra at the C K-, Ca L2,3- and P L2,3-edges. As an illustrative case study, we also perform STXM analyses on hydroxyapatite precipitates formed in a dense fibrillar collagen matrix. This study paves the way for future research on Ca-phosphate biomineralization processes down to the scale of a few tens of nanometers.

Deciphering temperature, pressure and oxygen-activity conditions of chlorite formation

Abstract The advantages and limits of empirical, semi-empirical and thermodynamic methods devoted to the estimation of chlorite-formation temperature are discussed briefly. The results of semi- empirical and thermodynamic approaches with different assumptions regarding the redox state of iron in chlorite are compared for a large set of natural data covering a range of pressure conditions from a few hundred bars to 18 kbar and temperature from 100 to 500°C. The T-XFe3+ evolution estimated using the thermodynamic approach of Vidal et al. (2005) shows a systematic increase in XFe3+ with decreasing temperature, which is compatible with the decrease in a02 buffered by magnetite- or hematite-chlorite equilibrium. This trend as well as the observed increase in vacancies in chlorite with decreasing temperature is interpreted as the incorporation of Fe3+-Sudoite. The standard-state properties of this end- member have been derived to reproduce the observed T-aO2-XFe3+ evolutions. It can be used to estimate T-aO2-XFe3 values with a Chl-Qtz-H2O multi-equilibrium approach. When combining our results with those of other studies published recently, it appears that thermodynamic approaches and mapping techniques developed for metamorphic rocks can be used to discuss the conditions of formation of very low-grade rocks where kinetics is much more sluggish than in metamorphic rocks. This requires use of appropriate analytical tools and techniques with a spatial resolution of a few hundred nanometres.

Retrieving past geodynamic events by unlocking rock archives with μ-XRF and μ-spectroscopy

Rocks are commonly polycrystalline systems presenting multi-scale chemical and structural heterogeneities inherited from crystallization processes or successive metamorphic events. This work illustrates how spatially resolved analytical techniques coupled with thermodynamic approaches allow rock compositional variations to be related to large-scale geodynamic processes. Emphasis is placed on the contribution of quantitative chemical imaging to the study of 2.2-2.0 Gy old metamorphic rocks from the West African Craton. A thorough analysis of elemental chemical maps acquired on rock thin sections enabled high pressure relic minerals to be located and re-analyzed later with precise point analyses. The pressure-temperature conditions of crystallization calculated from these analyses are typical of modern subduction zones. These results push back the onset of modern-style plate tectonics to 2.15 Gy, i.e. more than one billion years earlier than was consensually accepted. The second part of the paper describes the imaging capabilities offered by the new ultra-bright diffraction limited synchrotron sources. Experimental data acquired with the Maia detector at beamline P06 at Petra III as well as simulations of μ-XRF spectra that will be generated at the SRX beamline at NSLS-II are presented. These results demonstrate that cm2 large chemical maps can be acquired with submicron spatial resolution and a precision suitable for thermobarometric estimates, with dwell time smaller than 1 millisecond. The last part of the paper discusses the relevance of utilizing recent X-ray fluorescence nanoprobes for diagenetic to low grade metamorphism applications.

Contrasting degrees of recrystallization of carbonaceous material in the Nelson aureole, British Columbia and Ballachulish aureole, Scotland, with implications for thermometry based on Raman spectroscopy of carbonaceous material

Handling Editor: Doug Robinson Abstract The degree of recrystallization of carbonaceous material (CM), as monitored by Raman microspectroscopy, was examined as a function of metamorphic grade in two well‐studied contact aureoles containing carbonaceous pelites: the Nelson aureole, British Columbia and the Ballachulish aureole, Scotland. Here, we use (a) the R2 ratio extracted from the Raman spectrum of CM as a proxy for the degree of graphitization (0.0 in perfect graphite then increasing with structural defects) and (b) the second‐order S1 band (~2,700 cm) as a marker for the tridimensional ordering of CM. The Nelson aureole (garnet–staurolite–andalusite–sillimanite–K‐feldspar sequence, ~550–650°C, 3.5–4.0 kbar) was developed in rocks that were unmetamorphosed prior to contact metamorphism, whereas the Ballachulish aureole (cordierite–andalusite–K‐feldspar–sillimanite sequence, ~550– 700°C, ~3.0 kbar) was developed in rocks that had been metamorphosed to garnet grade conditions (~7 kbar, ~500°C) c. 45 Ma before contact metamorphism. Thirty‐one samples were examined from Nelson and 29 samples from Ballachulish. At Nelson, the R2 ratio steadily decreases from ~0.25 to 0.0 as the igneous contact is approached, whereas at Ballachulish, the R2 ratio remains largely unchanged from regional values (~0.20–0.25) until less than 100 m from the igneous contact. The second‐order S1 band reveals that carbonaceous material (CM) was transformed to highly “ordered” locally tridimensional graphitic carbon at Ballachulish by regional metamorphism prior to contact metamorphism, whereas CM was still a disordered turbostratic (bidimensional) material before contact metamorphism in the case of Nelson. Pretexturation of CM likely induced sluggish recrystallization of CM and delayed graphitization in the Ballachulish aureole. Temperatures of recrystallization of the CM in the two aureoles were estimated using different published calibrations of the thermometry based on Raman Spectroscopy of Carbonaceous Material (RSCM), with differences among the calibrations being minor. In the Nelson aureole, temperatures are in reasonable agreement with those indicated by the metapelitic phase equilibria (all within 50°C, most within 25°C). In the Ballachulish aureole, the retarded crystallization noted above results in increasing underestimates of temperatures compared to the metapelitic phase equilibria (up to ~75°C too low within 200 m of the igneous Received: 30 January 2018 | Accepted: 29 August 2018 DOI: 10.1111/jmg.12449