@phdthesis{Schifferle2024,
  author    = {Schifferle, Lukas},
  title     = {Optical properties of (Mg,Fe)O at high pressure},
  doi       = {10.25932/publishup-62216},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-622166},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XIV, 90},
  year      = {2024},
  abstract  = {Large parts of the Earth's interior are inaccessible to direct observation, yet global geodynamic processes are governed by the physical material properties under extreme pressure and temperature conditions. It is therefore essential to investigate the deep Earth's physical properties through in-situ laboratory experiments. With this goal in mind, the optical properties of mantle minerals at high pressure offer a unique way to determine a variety of physical properties, in a straight-forward, reproducible, and time-effective manner, thus providing valuable insights into the physical processes of the deep Earth. This thesis focusses on the system Mg-Fe-O, specifically on the optical properties of periclase (MgO) and its iron-bearing variant ferropericlase ((Mg,Fe)O), forming a major planetary building block. The primary objective is to establish links between physical material properties and optical properties. In particular the spin transition in ferropericlase, the second-most abundant phase of the lower mantle, is known to change the physical material properties. Although the spin transition region likely extends down to the core-mantle boundary, the ef-fects of the mixed-spin state, where both high- and low-spin state are present, remains poorly constrained. In the studies presented herein, we show how optical properties are linked to physical properties such as electrical conductivity, radiative thermal conductivity and viscosity. We also show how the optical properties reveal changes in the chemical bonding. Furthermore, we unveil how the chemical bonding, the optical and other physical properties are affected by the iron spin transition. We find opposing trends in the pres-sure dependence of the refractive index of MgO and (Mg,Fe)O. From 1 atm to ~140 GPa, the refractive index of MgO decreases by ~2.4\% from 1.737 to 1.696 (±0.017). In contrast, the refractive index of (Mg0.87Fe0.13)O (Fp13) and (Mg0.76Fe0.24)O (Fp24) ferropericlase increases with pressure, likely because Fe Fe interactions between adjacent iron sites hinder a strong decrease of polarizability, as it is observed with increasing density in the case of pure MgO. An analysis of the index dispersion in MgO (decreasing by ~23\% from 1 atm to ~103 GPa) reflects a widening of the band gap from ~7.4 eV at 1 atm to ~8.5 (±0.6) eV at ~103 GPa. The index dispersion (between 550 and 870 nm) of Fp13 reveals a decrease by a factor of ~3 over the spin transition range (~44-100 GPa). We show that the electrical band gap of ferropericlase significantly widens up to ~4.7 eV in the mixed spin region, equivalent to an increase by a factor of ~1.7. We propose that this is due to a lower electron mobility between adjacent Fe2+ sites of opposite spin, explaining the previously observed low electrical conductivity in the mixed spin region. From the study of absorbance spectra in Fp13, we show an increasing covalency of the Fe-O bond with pressure for high-spin ferropericlase, whereas in the low-spin state a trend to a more ionic nature of the Fe-O bond is observed, indicating a bond weakening effect of the spin transition. We found that the spin transition is ultimately caused by both an increase of the ligand field-splitting energy and a decreasing spin-pairing energy of high-spin Fe2+.},
  language  = {en}
}
@phdthesis{Biedermann2020,
  author    = {Biedermann, Nicole},
  title     = {Carbonate-silicate reactions at conditions of the Earth's mantle and the role of carbonates as possible trace-element carriers},
  doi       = {10.25932/publishup-48277},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-482772},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xvii, 127},
  year      = {2020},
  abstract  = {Carbonates play a key role in the chemistry and dynamics of our planet. They are directly connected to the CO2 budget of our atmosphere and have a great impact on the deep carbon cycle. Moreover, recent studies have shown that carbonates are stable along the geothermal gradient down to Earth's lower mantle conditions, changing their crystal structure and related properties. Subducted carbonates may also react with silicates to form new phases. These reactions will redistribute elements, such as calcium (Ca), magnesium (Mg), iron (Fe) and carbon in the form of carbon dioxide (CO2), but also trace elements, that are carried by the carbonates. The trace elements of most interest are strontium (Sr) and rare earth elements (REE) which have been found to be important constituents in the composition of the primitive lower mantle and in mineral inclusions found in super-deep diamonds. However, the stability of carbonates in presence of mantle silicates at relevant temperatures is far from being well understood. Related to this, very little is known about distribution processes of trace elements between carbonates and mantle silicates. To shed light on these processes, we studied reactions between Sr- and REE-containing CaCO3 and Mg/Fe-bearing silicates of the system (Mg,Fe)2SiO4 - (Mg,Fe)SiO3 at high pressure and high temperature using synchrotron radiation based μ-X-ray diffraction (μ-XRD) and μ-X-ray fluorescence (μ-XRF) with μm-resolution in a laser-heated diamond anvil cell. X-ray diffraction is used to derive the structural changes of the phase reactions whereas X-ray fluorescence gives information on the chemical changes in the sample. In-situ experiments at high pressure and high temperature were performed at beamline P02.2 at PETRA III (Hamburg, Germany) and at beamline ID27 at ESRF (Grenoble, France). In addition to μ-XRD and μ-XRF, ex-situ measurements were made on the recovered sample material using transmission electron microscopy (TEM) and provided further insights into the reaction kinetics of carbonate-silicate reactions. Our investigations show that CaCO3 is unstable in presence of mantle silicates above 1700 K and a reaction takes place in which magnesite plus CaSiO3-perovskite are formed. In addition, we observed that a high content of iron in the carbonate-silicate system favours dolomite formation during the reaction. The subduction of natural carbonates with significant amounts of Sr leads to a comprehensive investigation of the stability not only of CaCO3 phases in contact with mantle silicates but also of SrCO3 (and of Sr-bearing CaCO3). We found that SrCO3 reacts with (Mg,Fe)SiO3-perovskite to form magnesite and gained evidence for the formation of SrSiO3-perovskite. To complement our study on the stability of SrCO3 at conditions of the Earth's lower mantle, we performed powder X-ray diffraction and single crystal X-ray diffraction experiments at ambient temperature and up to 49 GPa. We observed a transformation from SrCO3-I into a new high-pressure phase SrCO3-II at around 26 GPa with Pmmn crystal structure and a bulk modulus of 103(10) GPa. This information is essential to fully understand the phase behaviour and stability of carbonates in the Earth's lower mantle and to elucidate the possibility of introducing Sr into mantle silicates by carbonate-silicate reactions. Simultaneous recording of μ-XRD and μ-XRF in the μm-range over the heated areas provides spatial information not only about phase reactions but also on the elemental redistribution during the reactions. A comparison of the spatial intensity distribution of the XRF signal before and after heating indicates a change in the elemental distribution of Sr and an increase in Sr-concentration was found around the newly formed SrSiO3-perovskite. With the help of additional TEM analyses on the quenched sample material the elemental redistribution was studied at a sub-micrometer scale. Contrary to expectations from combined μ-XRD and μ-XRF measurements, we found that La and Eu were not incorporated into the silicate phases, instead they tend to form either isolated oxide phases (e.g. Eu2O3, La2O3) or hydroxyl-bastn{\"a}site (La(CO3)(OH)). In addition, we observed the transformation from (Mg,Fe)SiO3-perovskite to low-pressure clinoenstatite during pressure release. The monoclinic structure (P21/c) of this phase allows the incorporation of Ca as shown by additional EDX analyses and, to a minor extent, Sr too. Based on our experiments, we can conclude that a detection of the trace elements in-situ at high pressure and high temperature remains challenging. However, our first findings imply that silicates may incorporate the trace elements provided by the carbonates and indicate that carbonates may have a major effect on the trace element contents of mantle phases.},
  language  = {en}
}
@phdthesis{Mulyukova2015,
  author    = {Mulyukova, Elvira},
  title     = {Stability of the large low shear velocity provinces},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-82228},
  school      = {Universit{\"a}t Potsdam},
  pages     = {139},
  year      = {2015},
  abstract  = {We study segregation of the subducted oceanic crust (OC) at the core mantle boundary and its ability to accumulate and form large thermochemical piles (such as the seismically observed Large Low Shear Velocity Provinces - LLSVPs). Our high-resolution numerical simulations suggest that the longevity of LLSVPs for up to three billion years, and possibly longer, can be ensured by a balance in the rate of segregation of high-density OC-material to the CMB, and the rate of its entrainment away from the CMB by mantle upwellings. For a range of parameters tested in this study, a large-scale compositional anomaly forms at the CMB, similar in shape and size to the LLSVPs. Neutrally buoyant thermochemical piles formed by mechanical stirring - where thermally induced negative density anomaly is balanced by the presence of a fraction of dense anomalous material - best resemble the geometry of LLSVPs. Such neutrally buoyant piles tend to emerge and survive for at least 3Gyr in simulations with quite different parameters. We conclude that for a plausible range of values of density anomaly of OC material in the lower mantle - it is likely that it segregates to the CMB, gets mechanically mixed with the ambient material, and forms neutrally buoyant large scale compositional anomalies similar in shape to the LLSVPs. We have developed an efficient FEM code with dynamically adaptive time and space resolution, and marker-in-cell methodology. This enabled us to model thermochemical mantle convection at realistically high convective vigor, strong thermally induced viscosity variations, and long term evolution of compositional fields.},
  language  = {en}
}
@phdthesis{Budweg2002,
  author    = {Budweg, Martin},
  title     = {Der obere Mantel in der Eifel-Region untersucht mit der Receiver Function Methode},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0000704},
  school      = {Universit{\"a}t Potsdam},
  year      = {2002},
  abstract  = {Die Eifel ist eines der j{\"u}ngsten vulkanischen Gebiete Mitteleuropas. Die letzte Eruption ereignete sich vor ungef{\"a}hr 11000 Jahren. Bisher ist relativ wenig bekannt {\"u}ber die tieferen Mechanismen, die f{\"u}r den Vulkanismus in der Eifel verantwortlich sind. Erdbebenaktivit{\"a}t deutet ebenso darauf hin, dass die Eifel eines der geodynamisch aktivsten Gebiete Mitteleuropas ist. In dieser Arbeit wird die Receiver Function Methode verwendet, um die Strukturen des oberen Mantels zu untersuchen. 96 teleseismische Beben (mb > 5.2) wurden ausgewertet, welche von permanenten und mobilen breitbandigen und kurzperiodischen Stationen aufgezeichnet wurden. Das tempor{\"a}re Netzwerk registrierte von November 1997 bis Juni 1998 und {\"u}berdeckte eine Fl{\"a}che von ungef{\"a}hr 400x250 km². Das Zentrum des Netzwerkes befand sich in der Vulkaneifel. Die Auswertung der Receiver Function Analyse ergab klare Konversionen von der Moho und den beiden Manteldiskontinuit{\"a}ten in 410 km und 660 km Tiefe, sowie Hinweise auf einen Mantel-Plume in der Region der Eifel. Die Moho wurde bei ungef{\"a}hr 30 km Tiefe beobachtet und zeigt nur geringe Variationen im Bereich des Netzwerkes. Die beobachteten Variationen der konvertierten Phasen der Moho k{\"o}nnen mit lateralen Schwankungen in der Kruste zu tun haben, die mit den Receiver Functions nicht aufgel{\"o}st werden k{\"o}nnen. Die Ergebnisse der Receiver Function Methode deuten auf eine Niedriggeschwindigkeitszone zwischen 60 km bis 90 km in der westlichen Eifel hin. In etwa 200 km Tiefe werden im Bereich der Eifel amplitudenstarke positive Phasen von Konversionen beobachtet. Als Ursache hierf{\"u}r wird eine Hochgeschwindigkeitszone vorgeschlagen, welche durch m{\"o}gliches aufsteigendes, dehydrierendes Mantel-Material verursacht wird. Die P zu S Konversionen an der 410 km Diskontinuit{\"a}t zeigen einen sp{\"a}teren Einsatz als nach dem IASP91-Modell erwartet wird. Die migrierten Daten weisen eine Absenkung der 410 km Diskontinuit{\"a}t um bis zu 20 km Tiefe auf, was einer Erh{\"o}hung der Temperatur von bis zu etwa 140° Celsius entspricht. Die 660 km Diskontinuit{\"a}t weist keine Aufw{\"o}lbung auf. Dies deutet darauf hin, dass kein Mantelmaterial direkt von unterhalb der 660 km Diskontinuit{\"a}t in der Eifel-Region aufsteigt oder, dass der Ursprung des Eifel-Plumes innerhalb der {\"U}bergangszone liegt.},
  language  = {de}
}