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Institute
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 Å). 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 Å and from ~ 2.52 to ~ 2.54 Å, respectively, while they remain constant in extremely peralkaline glasses (at ~ 2.55 Å and 2.54 Å, 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 Å, while in the carbonate melt the Y-O length increases slightly to 2.41 Å. The La-O bond lengths in turn, increase systematically over the whole silicate – carbonate melt joint from 2.55 to 2.60 Å. Sr-O bond lengths in melts increase from ~ 2.60 to 2.64 Å 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.
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 ‰ 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 ‰ 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 ‰ 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 ‰ (± 0.11 ‰, 2SE) to +0.08 ‰ (± 0.09 ‰, 2SE). δ56Fe in olivine range from -0.66‰ (± 0.11 ‰, 2SE) to +0.10 ‰ (± 0.13 ‰, 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.