@phdthesis{Libon2023,
  author    = {Libon, L{\´e}lia},
  title     = {Stability of magnesite in the Earth lower mantle: insight from high-pressure and high-temperature experiments},
  doi       = {10.25932/publishup-60461},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-604616},
  school      = {Universit{\"a}t Potsdam},
  pages     = {ix, 114, xvi},
  year      = {2023},
  abstract  = {Carbonates carried in subducting slabs may play a major role in sourcing and storing carbon in the deep Earth's interior. Current estimates indicate that between 40 to 66 million tons of carbon per year enter subduction zones, but it is uncertain how much of it reaches the lower mantle. It appears that most of this carbon might be extracted from subducting slabs at the mantle wedge and only a limited amount continues deeper and eventually reaches the deep mantle. However, estimations on deeply subducted carbon broadly range from 0.0001 to 52 million tons of carbon per year. This disparity is primarily due to the limited understanding of the survival of carbonate minerals during their transport to deep mantle conditions. Indeed, carbon has very low solubility in mantle silicates, therefore it is expected to be stored primarily in accessory phases such as carbonates. Among those carbonates, magnesite (MgCO3), as a single phase, is the most stable under all mantle conditions. However, experimental investigation on the stability of magnesite in contact with SiO2 at lower mantle conditions suggests that magnesite is stable only along a cold subducted slab geotherm. Furthermore, our understanding of magnesite's stability when interacting with more complex mantle silicate phases remains incomplete. In the first part of this dissertation, laser-heated diamond anvil cells and multi-anvil apparatus experiments were performed to investigate the stability of magnesite in contact with iron-bearing mantle silicates. Sub-solidus reactions, melting, decarbonation and diamond formation were examined from shallow to mid-lower mantle conditions (25 to 68 GPa; 1300 to 2000 K). Multi-anvil experiments at 25 GPa show the formation of carbonate-rich melt, bridgmanite, and stishovite with melting occurring at a temperature corresponding to all geotherms except the coldest one. In situ X-ray diffraction, in laser-heating diamond anvil cells experiments, shows crystallization of bridgmanite and stishovite but no melt phase was detected in situ at high temperatures. To detect decarbonation phases such as diamond, Raman spectroscopy was used. Crystallization of diamonds is observed as a sub-solidus process even at temperatures relevant and lower than the coldest slab geotherm (1350 K at 33 GPa). Data obtained from this work suggest that magnesite is unstable in contact with the surrounding peridotite mantle in the upper-most lower mantle. The presence of magnesite instead induces melting under oxidized conditions and/or foster diamond formation under more reduced conditions, at depths ∼700 km. Consequently, carbonates will be removed from the carbonate-rich slabs at shallow lower mantle conditions, where subducted slabs can stagnate. Therefore, the transport of carbonate to deeper depths will be restricted, supporting the presence of a barrier for carbon subduction at the top of the lower mantle. Moreover, the reduction of magnesite, forming diamonds provides additional evidence that super-deep diamond crystallization is related to the reduction of carbonates or carbonated-rich melt. The second part of this dissertation presents the development of a portable laser-heating system optimized for X-ray emission spectroscopy (XES) or nuclear inelastic scattering (NIS) spectroscopy with signal collection at near 90◦. The laser-heated diamond anvil cell is the only static pressure device that can replicate the pressure and temperatures of the Earth's lower mantle and core. The high temperatures are reached by using high-powered lasers focused on the sample contained between the diamond anvils. Moreover, diamonds' transparency to X-rays enables in situ X-ray spectroscopy measurements that can probe the sample under high-temperature and high-pressure conditions. Therefore, the development of portable laser-heating systems has linked high-pressure and temperature research with high-resolution X-ray spectroscopy techniques to synchrotron beamlines that do not have a dedicated, permanent, laser-heating system. A general description of the system is provided, as well as details on the use of a parabolic mirror as a reflective imaging objective for on-axis laser heating and radiospectrometric temperature measurements with zero attenuation of incoming X-rays. The parabolic mirror improves the accuracy of temperature measurements free from chromatic aberrations in a wide spectral range and its perforation permits in situ X-rays measurement at synchrotron facilities. The parabolic mirror is a well-suited alternative to refractive objectives in laser heating systems, which will facilitate future applications in the use of CO2 lasers.},
  language  = {en}
}
@article{KaaSternemannAppeletal.2022,
  author    = {Kaa, Johannes M. and Sternemann, Christian and Appel, Karen and Cerantola, Valerio and Preston, Thomas R. and Albers, Christian and Elbers, Mirko and Libon, Lelia and Makita, Mikako and Pelka, Alexander and Petitgirard, Sylvain and Pl{\"u}ckthun, Christian and Roddatis, Vladimir and Sahle, Christoph J. and Spiekermann, Georg and Schmidt, Christian and Schreiber, Anja and Sakrowski, Robin and Tolan, Metin and Wilke, Max and Zastrau, Ulf and Konopkova, Zuzana},
  title     = {Structural and electron spin state changes in an x-ray heated iron carbonate system at the Earth's lower mantle pressures},
  series = {Physical review research},
  volume    = {4},
  journal   = {Physical review research},
  number    = {3},
  publisher = {American Physical Society},
  address   = {College Park},
  issn      = {2643-1564},
  doi       = {10.1103/PhysRevResearch.4.033042},
  pages     = {9},
  year      = {2022},
  abstract  = {The determination of the spin state of iron-bearing compounds at high pressure and temperature is crucial for our understanding of chemical and physical properties of the deep Earth. Studies on the relationship between the coordination of iron and its electronic spin structure in iron-bearing oxides, silicates, carbonates, iron alloys, and other minerals found in the Earth's mantle and core are scarce because of the technical challenges to simultaneously probe the sample at high pressures and temperatures. We used the unique properties of a pulsed and highly brilliant x-ray free electron laser (XFEL) beam at the High Energy Density (HED) instrument of the European XFEL to x-ray heat and probe samples contained in a diamond anvil cell. We heated and probed with the same x-ray pulse train and simultaneously measured x-ray emission and x-ray diffraction of an FeCO3 sample at a pressure of 51 GPa with up to melting temperatures. We collected spin state sensitive Fe K beta(1,3) fluorescence spectra and detected the sample's structural changes via diffraction, observing the inverse volume collapse across the spin transition. During x-ray heating, the carbonate transforms into orthorhombic Fe4C3O12 and iron oxides. Incipient melting was also observed. This approach to collect information about the electronic state and structural changes from samples contained in a diamond anvil cell at melting temperatures and above will considerably improve our understanding of the structure and dynamics of planetary and exoplanetary interiors.},
  language  = {en}
}
@article{KrstulovićRosaFerreiraSanchezetal.2022,
  author    = {Krstulović, Marija and Rosa, Angelika D. and Ferreira Sanchez, Dario and Libon, L{\´e}lia and Albers, Christian and Merkulova, Margarita and Grolimund, Daniel and Irifune, Tetsuo and Wilke, Max},
  title     = {Effect of temperature on the densification of silicate melts to lower earth's mantle conditions},
  series = {Physics of the earth and planetary interiors},
  volume    = {323},
  journal   = {Physics of the earth and planetary interiors},
  publisher = {Elsevier},
  address   = {Amsterdam},
  issn      = {0031-9201},
  doi       = {10.1016/j.pepi.2021.106823},
  pages     = {13},
  year      = {2022},
  abstract  = {Physical properties of silicate melts play a key role for global planetary dynamics, controlling for example volcanic eruption styles, mantle convection and elemental cycling in the deep Earth. They are significantly modified by structural changes at the atomic scale due to external parameters such as pressure and temperature or due to chemistry. Structural rearrangements such as 4- to 6-fold coordination change of Si with increasing depth may profoundly influence melt properties, but have so far mostly been studied at ambient temperature due to experimental difficulties. In order to investigate the structural properties of silicate melts and their densification mechanisms at conditions relevant to the deep Earth's interior, we studied haplo basaltic glasses and melts (albite-diopside composition) at high pressure and temperature conditions in resistively and laser-heated diamond anvil cells using X-ray absorption near edge structure spectroscopy. Samples were doped with 10 wt\% of Ge, which is accessible with this experimental technique and which commonly serves as a structural analogue for the network forming cation Si. We acquired spectra on the Ge K edge up to 48 GPa and 5000 K and derived the average Ge-O coordination number NGe-O, and bond distance RGe-O as functions of pressure. Our results demonstrate a continuous transformation from tetrahedral to octahedral coordination between ca. 5 and 30 GPa at ambient temperature. Above 1600 K the data reveal a reduction of the pressure needed to complete conversion to octahedral coordination by ca. 30 \%. The results allow us to determine the influence of temperature on the Si coordination number changes in natural melts in the Earth's interior. We propose that the complete transition to octahedral coordination in basaltic melts is reached at about 40 GPa, corresponding to a depth of ca. 1200 km in the uppermost lower mantle. At the core-mantle boundary (2900 km, 130 GPa, 3000 K) the existence of non-buoyant melts has been proposed to explain observed low seismic wave velocity features. Our results highlight that the melt composition can affect the melt density at such extreme conditions and may strongly influence the structural response.},
  language  = {en}
}