@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{BorchertWilkeSchmidtetal.2010, author = {Borchert, Manuela and Wilke, Max and Schmidt, Christian and Cauzid, Jean and Tucoulou, R{\´e}mi}, title = {Partitioning of Ba, La, Yb and Y between haplogranitic melts and aqueous solutions : an experimental study}, issn = {0009-2541}, doi = {10.1016/j.chemgeo.2010.06.009}, year = {2010}, abstract = {Barium, lanthanum, ytterbium, and yttrium partitioning experiments between fluid-saturated haplogranitic melts and aqueous solutions were conducted at 750 to 950 degrees C and 0.2 to 1 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. Partition coefficients were determined using different experimental methods. On one hand quenched experiments were performed, and on the other hand, trace element contents in the aqueous fluid were determined directly using a hydrothermal diamond-anvil cell and synchrotron radiation X-ray fluorescence microanalysis of K-lines. The latter required a high excitation energy of 50 key due to the high energies necessary to excite the K-lines of the studied elements. The data from these two techniques showed good agreement for chloridic solutions, whereas quenching had a significant effect on results of the experiments with only water in the case of Ba. In Cl-free experiments, lanthanum and yttrium, trace element contents were even below detection limit in the quenched fluids, whereas small concentrations were detected in comparable in-situ experiments. This distinct difference is likely due to back reactions between fluid and melt upon cooling. The partitioning data of all elements show no dependence on the temperature and only small dependence on pressure. In contrast, the partitioning is strongly influenced by the composition of the starting fluid and melt. For chloridic fluids, there was a sharp increase in the Ba, La, Y and Yb partition coefficients with the alumina saturation index (ASI). The Ba partition coefficient increased from 0.002 at an ASI of 0.8 to 0.55 at an ASI of 1.07. At higher ASI, it decreased slightly to 0.2 at an ASI of similar to 1.3. Likewise, it was one to two orders of magnitude higher in chloridic fluids compared to those found in H2O experiments. Fluid-melt partition coefficients of La and Y increased from 0.002 at an ASI of similar to 0.8 to similar to 0.1 at an ASI of 1.2. In the same ASI range, the Yb partition coefficient increased to a maximum value of 0.02. Even at high salinities all elements fractionate into the melt. The compositional dependence of the partitioning data imply that both melt composition and fluid composition have a strong influence on trace element behavior and that complexation of Ba. REE and Y tin the fluid is not only controlled by the presence of Cl- in the fluid. Instead, interaction of these elements with major melt components dissolved in the fluid is very likely.}, language = {en} } @article{BorchertWilkeSchmidtetal.2009, author = {Borchert, Manuela and Wilke, Max and Schmidt, Christian and Rickers, Karen}, title = {Partitioning and equilibration of Rb and Sr between silicate melts and aqueous fluids}, issn = {0009-2541}, doi = {10.1016/j.chemgeo.2008.10.019}, year = {2009}, abstract = {Trace element concentrations in aqueous fluids in equilibrium with haplogranitic melt were determined in situ at elevated P-T conditions using hydrothermal diamond-anvil cells and synchrotron-radiation XRF microanalyses. Time- resolved analyses showed that the Rb and Sr concentrations in the fluids became constant in less than 2000 s at all temperatures (500 to 780 degrees C). Although fluid-melt equilibration was very rapid, the change in the concentration of both elements in the fluid with temperature was fairly small (a slight increase for Rb and a slight decrease for Sr). This permitted partitioning data for Rb and Sr between haplogranitic melt and H2O or NaCl+KCl+HCl aqueous solutions at 750 degrees C and 200 to 700 MPa to be obtained from EMP analyses of the quenched melt and the in situ SR-XRF analyses of the equilibrated fluid. The resulting D-Rb(f/m) and D-Sr(f/m) were 0.01 +/- 0.002 and 0.006 +/- 0.001 for water as starting fluid, and increased to 0.47 +/- 0.08 and 0.23 +/- 0.03 for 3.56 m (NaCl+KCl)+0.04 in HCl at pressures of 224 to 360 MPa. In the experiments with H2O as starting fluid, the partition coefficients increased with pressure, i.e. D- Rb(f/m) from 0.01 +/- 0.002 to 0.22 +/- 0.02 and D-Sr(f/m) from 0.006 0.001 to 0.02 +/- 0.005 with a change in pressure from 360 to 700 MPa. At pressures to 360 MPa, the Rb/Sr ratio in the fluid was found to be independent of the initial salt concentration (Rb/Sr = 1.45 +/- 0.6). This ratio increased to 7.89 +/- 1.95 at 700 MPa in experiments with chloride free fluids, which indicates different changes in the Rb and Sr speciation with pressure.}, language = {en} } @article{BorchertWilkeSchmidtetal.2010, author = {Borchert, Manuela and Wilke, Max and Schmidt, Christian and Rickers, Karen}, title = {Rb and Sr partitioning between haplogranitic melts and aqueous solutions}, issn = {0016-7037}, doi = {10.1016/j.gca.2009.10.033}, year = {2010}, abstract = {Rubidium and strontium partitioning experiments between haplogranitic melts and aqueous fluids (water or 1.16- 3.56 m (NaCl + KCl) +/- HCl) were conducted at 750-950 degrees C and 0.2-1.4 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. In addition, we studied if the applied technique (rapid and slow quench, and in-situ determination of trace element concentration in the fluid) has a bearing on the obtained data. There is good agreement of the data from different techniques for chloridic solutions, whereas back reactions between fluid and Melt upon cooling have a significant effect on results from the experiments with water. The Rb fluid-melt partition coefficient shows no recognizable dependence on melt composition and temperature. For chloridic Solutions, it is similar to 0.4, independent of pressure. In experiments with water, it is one to two orders of magnitude lower and increases with pressure. The strontium fluid-melt partition coefficient does not depend on temperature. It increases slightly with pressure in Cl free experiments. In chloridic fluids, there is a sharp increase in the Sr partition coefficient with the alumina saturation index (ASI) from 0.003 at an ASI of 0.8 to a maximum of 0.3 at an ASI of 1.05. At higher ASI, it decreases slightly to 0.2 at an ASI of 1.6. It is one to two orders of magnitude higher in chloridic fluids compared to those found in H2O experiments. The Rb/Sr ratio in non-chloridic solutions in equilibrium with metaluminous melts increases with pressure, whereas the Rb/Sr ratio in chloridic fluids is independent of pressure and decreases with fluid salinity. The obtained fluid-melt partition coefficients are in good agreement with data from natural cogenetic fluid and melt inclusions. Numerical modeling shows that although the Rb/Sr ratio in the residual melt is particularly sensitive to the degree of fractional crystallization, exsolution of a fluid phase, and associated fluid-melt partitioning is not a significant factor controlling Rb and Sr concentrations in the residual melt during crystallization of most granitoids.}, language = {en} } @article{BotcharnikovKoepkeHoltzetal.2005, author = {Botcharnikov, Roman E. and Koepke, J. and Holtz, Francois and McCammon, C. and Wilke, Max}, title = {The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt}, issn = {0016-7037}, year = {2005}, abstract = {Experimental investigations have been performed at T = 1200 degrees C, P = 200 MPa and fH(2) corresponding to H2O-MnO-Mn3O4 and H2O-QFM redox buffers to study the effect of H2O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mossbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe3+/Sigma Fe ratio of the glass is directly related to aH(2)O in a H-2-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H2O <-> H-2 + 1/2 O-2). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO(2) and Fe3+/Fe2+ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of similar to 0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + 1/4 O-2 = FeO1.5). The mean centre shifts for Fe2+ and Fe3+ absorption doublets in Mossbauer spectra show little change with increasing Fe3+/Sigma Fe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses. Copyright (c) 2005 Elsevier Ltd}, language = {en} } @article{BotcharnikovKoepkeHoltzetal.2004, author = {Botcharnikov, Roman E. and Koepke, J. and Holtz, Francois and McCammon, C. and Wilke, Max}, title = {The oxidation and structural state of Fe in hydrous ferrobasaltic melt}, year = {2004}, language = {en} } @misc{BenardKlimmWoodlandetal.2018, author = {B{\´e}nard, 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 = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, number = {717}, issn = {1866-8372}, doi = {10.25932/publishup-42618}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-426184}, 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+/∑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 δ34S (+ 7 to + 11 per mille), 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} } @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{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{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} }