@article{DietrichBehrensWilke2018, author = {Dietrich, Marcel and Behrens, Harald and Wilke, Max}, title = {A new optical cell for in situ Raman spectroscopy, and its application to study sulfur-bearing fluids at elevated pressures and temperatures}, series = {American mineralogist : an international journal of earth and planetary materials}, volume = {103}, journal = {American mineralogist : an international journal of earth and planetary materials}, number = {3}, publisher = {Mineralogical Society of America}, address = {Chantilly}, issn = {0003-004X}, doi = {10.2138/am-2018-6244}, pages = {418 -- 429}, year = {2018}, abstract = {Sulfur is an important component in volcanic gases at the Earth surface but also present in the deep Earth in hydrothermal or magmatic fluids. Little is known about the evolution of such fluids during ascent in the crust. A new optical cell was developed for in situ Raman spectroscopic investigations on fluids allowing abrupt or continuous changes of pressure up to 200 MPa at temperatures up to 750 degrees C. The concept is based on a flexible gold bellow, which separates the sample fluid from the pressure medium water. To avoid reactions between aggressive fluids and the pressure cell, steel components in contact with the fluid are shielded by gold foil. The cell was tested to study redox reactions in fluids using aqueous ammonium sulfate solutions as a model system. During heating at constant pressure of 130 MPa, sulfate ions transform first to HSO4- ions and then to molecular units such as H2SO4. Variation of pressure shows that the stability of sulfate species relies on fluid density, i.e., highly charged species are stable only in high-density fluids. Partial decomposition of ammonium was evident above 550 degrees C by the occurrence of a nitrogen peak in the Raman spectra. Reduced sulfur species were observed above 700 degrees C by Raman signals near 2590 cm(-1) assigned to HS- and H2S. No clear evidence for the formation of sulfur dioxide was found in contrary to previous studies on aqueous H2SO4, suggesting very reducing conditions in our experiments. Fluid-mineral interaction was studied by inserting into the cell a small, semi-open capsule filled with a mixture of pyrite and pyrrhotite. Oxidation of the sample assembly was evident by transformation of pyrite to pyrrhotite. As a consequence, sulfide species were observed in the fluid already at temperatures of similar to 600 degrees C.}, language = {en} } @article{NunezValdezEfthimiopoulosTaranetal.2018, author = {Nunez Valdez, Maribel and Efthimiopoulos, Ilias and Taran, Michail and Mueller, Jan and Bykova, Elena and McCammon, Catherine and Koch-M{\"u}ller, Monika and Wilke, Max}, title = {Evidence for a pressure-induced spin transition in olivine-type LiFePO4 triphylite}, series = {Physical review : B, Condensed matter and materials physics}, volume = {97}, journal = {Physical review : B, Condensed matter and materials physics}, number = {18}, publisher = {American Physical Society}, address = {College Park}, issn = {2469-9950}, doi = {10.1103/PhysRevB.97.184405}, pages = {9}, year = {2018}, abstract = {We present a combination of first-principles and experimental results regarding the structural and magnetic properties of olivine-type LiFePO4 under pressure. Our investigations indicate that the starting Pbnm phase of LiFePO4 persists up to 70 GPa. Further compression leads to an isostructural transition in the pressure range of 70-75 GPa, inconsistent with a former theoretical study. Considering our first-principles prediction for a high-spin to low-spin transition of Fe2+ close to 72 GPa, we attribute the experimentally observed isostructural transition to a change in the spin state of Fe2+ in LiFePO4. Compared to relevant Fe-bearing minerals, LiFePO4 exhibits the largest onset pressure for a pressure-induced spin state transition.}, language = {en} } @article{PohlenzRosaMathonetal.2018, author = {Pohlenz, Julia and Rosa, A. D. and Mathon, O. and Pascarelli, S. and Belin, S. and Landrot, G. and Murzin, V. and Veligzhanin, A. and Shiryaev, A. and Irifune, T. and Wilke, Max}, title = {Structural controls of CO2 on Y, La and Sr incorporation in sodium-rich silicate - carbonate melts by in-situ high P-T EXAFS}, series = {Chemical geology : official journal of the European Association for Geochemistry}, volume = {486}, journal = {Chemical geology : official journal of the European Association for Geochemistry}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0009-2541}, doi = {10.1016/j.chemgeo.2017.12.023}, pages = {1 -- 15}, year = {2018}, 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 transport properties. Carbon-rich melts can be strongly enriched in trace elements, but the structural incorporation mechanisms of these elements are difficult to study because such melts generally cannot be quenched to glasses. In this contribution we investigate the influence of CO2 on the local environments of trace elements contained in silicate glasses with variable CO2 concentrations and in silicate and carbonate melts. The melts were studied in-situ at high pressure and temperature conditions using the Paris-Edinburgh press (2.2 to 2.6 GPa and 1200 to 1500 degrees C). The compositions studied include sodium-rich peralkaline silicate melts and glasses and carbonate melts similar to those occurring naturally at Oldoinyo Lengai volcano. The local environments of yttrium (Y), lanthanum (La) and strontium (Sr) were investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. Main findings of the study suggest: (1) In peralkaline silicate glasses the local structure of Y is unaffected by the CO2 content. Contrary, a slight increase of oxygen bond lengths of Sr and La is inferred with increasing CO2 content in peralkaline glasses, while they remain constant in glasses of even higher peralkalinity independent of the CO2 content. (2) In silicate melts of different CO2 contents Y-O bond lengths are constant, while a slight increase within carbonate melt compositions is deduced. On the other hand, a steady bond lengths increase over the whole compositional range is inferred for La-O and Sr-O. This may well be explained by distinct preferences of these elements for specific local environments. Based on these new data, we suggest potential mechanisms for the structural incorporation of these elements, a key step towards understanding their partitioning behavior in natural magmatic systems.}, language = {en} } @misc{CaupinHoltenQiuetal.2018, author = {Caupin, Frederic and Holten, Vincent and Qiu, Chen and Guillerm, Emmanuel and Wilke, Max and Frenz, Martin and Teixeira, Jose and Soper, Alan K.}, title = {Comment on "Maxima in the thermodynamic response and correlation functions of deeply supercooled water"}, series = {Science}, volume = {360}, journal = {Science}, number = {6390}, publisher = {American Assoc. for the Advancement of Science}, address = {Washington}, issn = {0036-8075}, doi = {10.1126/science.aat1634}, pages = {2}, year = {2018}, abstract = {Kim et al. recently measured the structure factor of deeply supercooled water droplets (Reports, 22 December 2017, p. 1589). We raise several concerns about their data analysis and interpretation. In our opinion, the reported data do not lead to clear conclusions about the origins of water's anomalies.}, language = {en} } @article{BenardKlimmWoodlandetal.2018, author = {Benard, Antoine and Klimm, Kevin and Woodland, Alan B. and Arculus, Richard J. and Wilke, Max and Botcharnikov, Roman E. and Shimizu, Nobumichi and Nebel, Oliver and Rivard, Camille and Ionov, Dmitri A.}, title = {Oxidising agents in sub-arc mantle melts link slab devolatilisation and arc magmas}, series = {Nature Communications}, volume = {9}, journal = {Nature Communications}, publisher = {Nature Publ. Group}, address = {London}, issn = {2041-1723}, doi = {10.1038/s41467-018-05804-2}, pages = {10}, year = {2018}, abstract = {Subduction zone magmas are more oxidised on eruption than those at mid-ocean ridges. This is attributed either to oxidising components, derived from subducted lithosphere (slab) and added to the mantle wedge, or to oxidation processes occurring during magma ascent via differentiation. Here we provide direct evidence for contributions of oxidising slab agents to melts trapped in the sub-arc mantle. Measurements of sulfur (S) valence state in sub-arc mantle peridotites identify sulfate, both as crystalline anhydrite (CaSO4) and dissolved SO42- in spinel-hosted glass (formerly melt) inclusions. Copper-rich sulfide precipitates in the inclusions and increased Fe3+/Sigma Fe in spinel record a S6+-Fe2+ redox coupling during melt percolation through the sub-arc mantle. Sulfate-rich glass inclusions exhibit high U/Th, Pb/Ce, Sr/Nd and delta S-34 (+ 7 to + 11\%), indicating the involvement of dehydration products of serpentinised slab rocks in their parental melt sources. These observations provide a link between liberated slab components and oxidised arc magmas.}, language = {en} } @article{PetitgirardSahleWeisetal.2019, author = {Petitgirard, Sylvian and Sahle, C. J. and Weis, C. and Gilmore, K. and Spiekermann, Georg and Tse, J. S. and Wilke, Max and Cavallari, C. and Cerantola, V and Sternemann, Christian}, title = {Magma properties at deep Earth's conditions from electronic structure of silica}, series = {Geochemical perspectives letters}, volume = {9}, journal = {Geochemical perspectives letters}, publisher = {Association of Geochemistry}, address = {Paris}, issn = {2410-339X}, doi = {10.7185/geochemlet.1902}, pages = {32 -- 37}, year = {2019}, abstract = {SiO(2 )is the main component of silicate melts and thus controls their network structure and physical properties. The compressibility and viscosities of melts at depth are governed by their short range atomic and electronic structure. We measured the O K-edge and the Si L-2,L-3-edge in silica up to 110 GPa using X-ray Raman scattering spectroscopy, and found a striking match to calculated spectra based on structures from molecular dynamic simulations. Between 20 and 27 GPa, Si-[4] species are converted into a mixture of Si-[5] and Si-[6] species and between 60 and 70 GPa, Si-[6] becomes dominant at the expense of Si-[5] with no further increase up to at least 110 GPa. Coordination higher than 6 is only reached beyond 140 GPa, corroborating results from Brillouin scattering. Network modifying elements in silicate melts may shift this change in coordination to lower pressures and thus magmas could be denser than residual solids at the depth of the core-mantle boundary.}, language = {en} } @article{WeisSpiekermannSternemannetal.2018, author = {Weis, Christopher and Spiekermann, Georg and Sternemann, Christian and Harder, Manuel and Vanko, Gyorgy and Cerantola, Valerio and Sahle, Christoph J. and Forov, Yury and Sakrowski, Robin and Kupenko, Ilya and Petitgirard, Sylvain and Yavas, Hasan and Bressler, Christian and Gawelda, Wojciech and Tolan, Metin and Wilke, Max}, title = {Combining X-ray K beta(1,3), valence-to-core, and X-ray Raman spectroscopy for studying Earth materials at high pressure and temperature}, series = {Journal of analytical atomic spectrometry}, volume = {34}, journal = {Journal of analytical atomic spectrometry}, number = {2}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0267-9477}, doi = {10.1039/c8ja00247a}, pages = {384 -- 393}, year = {2018}, abstract = {X-ray emission and X-ray Raman scattering spectroscopy are powerful tools to investigate the local electronic and atomic structure of high and low Z elements in situ. Notably, these methods can be applied for in situ spectroscopy at high pressure and high temperature using resistively or laser-heated diamond anvil cells in order to achieve thermodynamic conditions which appear in the Earth's interior. We present a setup for combined X-ray emission and X-ray Raman scattering studies at beamline P01 of PETRA III using a portable wavelength-dispersive von Hamos spectrometer together with the permanently installed multiple-analyzer Johann-type spectrometer. The capabilities of this setup are exemplified by investigating the iron spin crossover of siderite FeCO3 up to 49.3 GPa by measuring the Fe M2,3-edge and the Fe Kβ1,3 emission line simultaneously. With this setup, the Fe valence-to-core emission can be detected together with the Kβ1,3 emission line providing complementary information on the sample's electronic structure. By implementing a laser-heating device, we demonstrate the strength of using a von Hamos type spectrometer for spin state mapping at extreme conditions. Finally, we give different examples of low Z elements' absorption edges relevant for application in geoscience that are accessible with the Johann-type XRS spectrometer. With this setup new insights into the spin transition and compression mechanisms of Earth's mantle materials can be obtained of importance for comprehension of the macroscopic physical and chemical properties of the Earth's interior.}, language = {en} } @article{TaranNunezValdezEfthimiopoulosetal.2019, author = {Taran, Michail N. and Nunez Valdez, Maribel and Efthimiopoulos, Ilias and M{\"u}ller, J. and Reichmann, Hans-Josef and Wilke, Max and Koch-M{\"u}ller, Monika}, title = {Spectroscopic and ab initio studies of the pressure-induced Fe2+ high-spin-to-low-spin electronic transition in natural triphylite-lithiophilite}, series = {Physics and Chemistry of Minerals}, volume = {46}, journal = {Physics and Chemistry of Minerals}, number = {3}, publisher = {Springer}, address = {New York}, issn = {0342-1791}, doi = {10.1007/s00269-018-1001-y}, pages = {245 -- 258}, year = {2019}, abstract = {Using optical absorption and Raman spectroscopic measurements, in conjunction with the first-principles calculations, a pressure-induced high-spin (HS)-to-low-spin (LS) state electronic transition of Fe2+ (M2-octahedral site) was resolved around 76-80GPa in a natural triphylite-lithiophilite sample with chemical composition (LiFe0.7082+Mn0.292PO4)-Li-M1-Fe-M2 (theoretical composition (LiFe0.52+Mn0.5PO4)-Li-M1-Fe-M2). The optical absorption spectra at ambient conditions consist of a broad doublet band with two constituents (1) (similar to 9330cm(-1)) and (2) (similar to 7110cm(-1)), resulting from the electronic spin-allowed transition (T2gEg)-T-5-E-5 of octahedral (HSFe2+)-Fe-M2. Both (1) and (2) bands shift non-linearly with pressure to higher energies up to similar to 55GPa. In the optical absorption spectrum measured at similar to 81GPa, the aforementioned HS-related bands disappear, whereas a new broadband with an intensity maximum close to 16,360cm(-1) appears, superimposed on the tail of the high-energy ligand-to-metal O2-Fe2+ charge-transfer absorption edge. We assign this new band to the electronic spin-allowed dd-transition (1)A(1g)(1)T(1g) of LS Fe2+ in octahedral coordination. The high-pressure Raman spectra evidence the Fe2+ HS-to-LS transition mainly from the abrupt shift of the P-O symmetric stretching modes to lower frequencies at similar to 76GPa, the highest pressure achieved in the Raman spectroscopic experiments. Calculations indicated that the presence of Mn-M2(2+) simply shifts the isostructural HS-to-LS transition to higher pressures compared to the triphylite Fe-M2(2+) end-member, in qualitative agreement with our experimental observations.}, language = {en} } @article{CerantolaWilkeKantoretal.2019, author = {Cerantola, Valerio and Wilke, Max and Kantor, Innokenty and Ismailova, Leyla and Kupenko, Ilya and McCammon, Catherine and Pascarelli, Sakura and Dubrovinsky, Leonid S.}, title = {Experimental investigation of FeCO3 (siderite) stability in Earth's lower mantle using XANES spectroscopy}, series = {American mineralogist : an international journal of earth and planetary materials}, volume = {104}, journal = {American mineralogist : an international journal of earth and planetary materials}, number = {8}, publisher = {Mineralogical Society of America}, address = {Chantilly}, issn = {0003-004X}, doi = {10.2138/am-2019-6428}, pages = {1083 -- 1091}, year = {2019}, abstract = {We studied FeCO3 using Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy at pressures up to 54 GPa and temperatures above 2000 K. First-principles calculations of Fe at the K-edge in FeCO3 were performed to support the interpretation of the XANES spectra. The variation of iron absorption edge features with pressure and temperature in FeCO3 matches well with recently reported observations on FeCO3 at extreme conditions, and provides new insight into the stability of Fe-carbonates in Earth's mantle. Here we show that at conditions of the mid-lower mantle, ~50 GPa and ~2200 K, FeCO3 melts and partially decomposes to high-pressure Fe3O4. Carbon (diamond) and oxygen are also inferred products of the reaction. We constrained the thermodynamic phase boundary between crystalline FeCO3 and melt to be at 51(1) GPa and ~1850 K. We observe that at 54(1) GPa, temperature-induced spin crossover of Fe2+ takes place from low to high spin such that at 1735(100) K, all iron in FeCO3 is in the high-spin state. A comparison between experiment and theory provides a more detailed understanding of FeCO3 decomposition observed in X-ray absorption spectra and helps to explain spectral changes due to pressure-induced spin crossover in FeCO3 at ambient temperature.}, language = {en} } @article{HoltenQiuGuillermetal.2017, author = {Holten, Vincent and Qiu, Chen and Guillerm, Emmanuel and Wilke, Max and Ricka, Jaroslav and Frenz, Martin and Caupin, Frederic}, title = {Compressibility Anomalies in Stretched Water and Their Interplay with Density Anomalies}, series = {The journal of physical chemistry letters}, volume = {8}, journal = {The journal of physical chemistry letters}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.7b02563}, pages = {5519 -- 5522}, year = {2017}, abstract = {Water keeps puzzling scientists because of its numerous properties which behave oppositely to those of usual liquids: for instance, water expands upon cooling, and liquid water is denser than ice. To explain this anomalous behavior, several theories have been proposed, with different predictions for the properties of supercooled water (liquid at conditions where ice is stable). However, discriminating between those theories with experiments has remained elusive because of spontaneous ice nucleation. Here we measure the sound velocity in liquid water stretched to negative pressure and derive an experimental equation of state, which reveals compressibility anomalies. We show by rigorous thermodynamic relations how these anomalies are intricately linked with the density anomaly. Some features we observe are necessary conditions for the validity of two theories of water.}, language = {en} }