@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{Stuff2021,
  author    = {Stuff, Maria},
  title     = {Iron isotope fractionation in carbonatite melt systems},
  doi       = {10.25932/publishup-51992},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-519928},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xvi, 137},
  year      = {2021},
  abstract  = {Carbonatite magmatism is a highly efficient transport mechanism from Earth's mantle to the crust, thus providing insights into the chemistry and dynamics of the Earth's mantle. One evolving and promising tool for tracing magma interaction are stable iron isotopes, particularly because iron isotope fractionation is controlled by oxidation state and bonding environment. Meanwhile, a large data set on iron isotope fractionation in igneous rocks exists comprising bulk rock compositions and fractionation between mineral groups. Iron isotope data from natural carbonatite rocks are extremely light and of remarkably high variability. This resembles iron isotope data from mantle xenoliths, which are characterized by a variability in δ56Fe spanning three times the range found in basalts, and by the extremely light values of some whole rock samples, reaching δ56Fe as low as -0.69  per mille in a spinel lherzolite. Cause to this large range of variations may be metasomatic processes, involving metasomatic agents like volatile bearing high-alkaline silicate melts or carbonate melts. The expected effects of metasomatism on iron isotope fractionation vary with parameters like melt/rock-ratio, reaction time, and the nature of metasomatic agents and mineral reactions involved. An alternative or additional way to enrich light isotopes in the mantle could be multiple phases of melt extraction. To interpret the existing data sets more knowledge on iron isotope fractionation factors is needed. To investigate the behavior of iron isotopes in the carbonatite systems, kinetic and equilibration experiments in natro-carbonatite systems between immiscible silicate and carbonate melts were performed in an internally heated gas pressure vessel at intrinsic redox conditions at temperatures between 900 and 1200 °C and pressures of 0.5 and 0.7 GPa. The iron isotope compositions of coexisting silicate melt and carbonate melt were analyzed by solution MC-ICP-MS. The kinetic experiments employing a Fe-58 spiked starting material show that isotopic equilibrium is obtained after 48 hours. The experimental studies of equilibrium iron isotope fractionation between immiscible silicate and carbonate melts have shown that light isotopes are enriched in the carbonatite melt. The highest Δ56Fesil.m.-carb.melt (mean) of 0.13  per mille was determined in a system with a strongly peralkaline silicate melt composition (ASI ≥ 0.21, Na/Al ≤ 2.7). In three systems with extremely peralkaline silicate melt compositions (ASI between 0.11 and 0.14) iron isotope fractionation could analytically not be resolved. The lowest Δ56Fesil.m.-carb.melt (mean) of 0.02  per mille was determined in a system with an extremely peralkaline silicate melt composition (ASI ≤ 0.11 , Na/Al ≥ 6.1). The observed iron isotope fractionation is most likely governed by the redox conditions of the system. Yet, in the systems, where no fractionation occurred, structural changes induced by compositional changes possibly overrule the influence of redox conditions. This interpretation implicates, that the iron isotope system holds the potential to be useful not only for exploring redox conditions in magmatic systems, but also for discovering structural changes in a melt. In situ iron isotope analyses by femtosecond laser ablation coupled to MC-ICP-MS on magnetite and olivine grains were performed to reveal variations in iron isotope composition on the micro scale. The investigated sample is a melilitite bomb from the Salt Lake Crater group at Honolulu (Oahu, Hawaii), showing strong evidence for interaction with a carbonatite melt. While magnetite grains are rather homogeneous in their iron isotope compositions, olivine grains span a far larger range in iron isotope ratios. The variability of δ56Fe in magnetite is limited from - 0.17  per mille (± 0.11  per mille, 2SE) to +0.08  per mille (± 0.09  per mille, 2SE). δ56Fe in olivine range from -0.66 per mille (± 0.11  per mille, 2SE) to +0.10  per mille (± 0.13  per mille, 2SE). Olivine and magnetite grains hold different informations regarding kinetic and equilibrium fractionation due to their different Fe diffusion coefficients. The observations made in the experiments and in the in situ iron isotope analyses suggest that the extremely light iron isotope signatures found in carbonatites are generated by several steps of isotope fractionation during carbonatite genesis. These may involve equilibrium and kinetic fractionation. Since iron isotopic signatures in natural systems are generated by a combination of multiple factors (pressure, temperature, redox conditions, phase composition and structure, time scale), multi tracer approaches are needed to explain signatures found in natural rocks.},
  language  = {en}
}
@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}
}
@phdthesis{Pohlenz2019,
  author    = {Pohlenz, Julia},
  title     = {Structural insights into sodium-rich silicate - carbonate glasses and melts},
  doi       = {10.25932/publishup-42382},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-423826},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XXII, 117},
  year      = {2019},
  abstract  = {Carbonate-rich silicate and carbonate melts play a crucial role in deep Earth magmatic processes and their melt structure is a key parameter, as it controls physical and chemical properties. Carbonate-rich melts can be strongly enriched in geochemically important trace elements. The structural incorporation mechanisms of these elements are difficult to study because such melts generally cannot be quenched to glasses, which are usually employed for structural investigations. This thesis investigates the influence of CO2 on the local environments of trace elements contained in silicate glasses with variable CO2 concentrations as well as in silicate and carbonate melts. The compositions studied include sodium-rich peralkaline silicate melts and glasses and carbonate melts similar to those occurring naturally at Oldoinyo Lengai volcano, Tanzania. The local environments of the three elements yttrium (Y), lanthanum (La) and strontium (Sr) were investigated in synthesized glasses and melts using X-ray absorption fine structure (XAFS) spectroscopy. Especially extended X-ray absorption fine structure spectroscopy (EXAFS) provides element specific information on local structure, such as bond lengths, coordination numbers and the degree of disorder. To cope with the enhanced structural disorder present in glasses and melts, EXAFS analysis was based on fitting approaches using an asymmetric distribution function as well as a correlation model according to bond valence theory. Firstly, silicate glasses quenched from high pressure/temperature melts with up to 7.6 wt \% CO2 were investigated. In strongly and extremely peralkaline glasses the local structure of Y is unaffected by the CO2 content (with oxygen bond lengths of ~ 2.29 {\AA}). Contrary, the bond lengths for Sr-O and La-O increase with increasing CO2 content in the strongly peralkaline glasses from ~ 2.53 to ~ 2.57 {\AA} and from ~ 2.52 to ~ 2.54 {\AA}, respectively, while they remain constant in extremely peralkaline glasses (at ~ 2.55 {\AA} and 2.54 {\AA}, respectively). Furthermore, silicate and unquenchable carbonate melts were investigated in-situ at high pressure/temperature conditions (2.2 to 2.6 GPa, 1200 to 1500 °C) using a Paris-Edinburgh press. A novel design of the pressure medium assembly for this press was developed, which features increased mechanical stability as well as enhanced transmittance at relevant energies to allow for low content element EXAFS in transmission. Compared to glasses the bond lengths of Y-O, La-O and Sr-O are elongated by up to + 3 \% in the melt and exhibit higher asymmetric pair distributions. For all investigated silicate melt compositions Y-O bond lengths were found constant at ~ 2.37 {\AA}, while in the carbonate melt the Y-O length increases slightly to 2.41 {\AA}. The La-O bond lengths in turn, increase systematically over the whole silicate - carbonate melt joint from 2.55 to 2.60 {\AA}. Sr-O bond lengths in melts increase from ~ 2.60 to 2.64 {\AA} from pure silicate to silicate-bearing carbonate composition with constant elevated bond length within the carbonate region. For comparison and deeper insight, glass and melt structures of Y and Sr bearing sodium-rich silicate to carbonate compositions were simulated in an explorative ab initio molecular dynamics (MD) study. The simulations confirm observed patterns of CO2-dependent local changes around Y and Sr and additionally provide further insights into detailed incorporation mechanisms of the trace elements and CO2. Principle findings include that in sodium-rich silicate compositions carbon either is mainly incorporated as a free carbonate-group or shares one oxygen with a network former (Si or [4]Al) to form a non-bridging carbonate. Of minor importance are bridging carbonates between two network formers. Here, a clear preference for two [4]Al as adjacent network formers occurs, compared to what a statistical distribution would suggest. In C-bearing silicate melts minor amounts of molecular CO2 are present, which is almost totally dissolved as carbonate in the quenched glasses. The combination of experiment and simulation provides extraordinary insights into glass and melt structures. The new data is interpreted on the basis of bond valence theory and is used to deduce potential mechanisms for structural incorporation of investigated elements, which allow for prediction on their partitioning behavior in natural melts. Furthermore, it provides unique insights into the dissolution mechanisms of CO2 in silicate melts and into the carbonate melt structure. For the latter, a structural model is suggested, which is based on planar CO3-groups linking 7- to 9-fold cation polyhedra, in accordance to structural units as found in the Na-Ca carbonate nyerereite. Ultimately, the outcome of this study contributes to rationalize the unique physical properties and geological phenomena related to carbonated silicate-carbonate melts.},
  language  = {en}
}