@article{KutzschbachWunderKrstulovicetal.2016, author = {Kutzschbach, Martin and Wunder, Bernd and Krstulovic, Marija and Ertl, Andreas and Trumbull, Robert B. and Rocholl, Alexander and Giester, Gerald}, title = {First high-pressure synthesis of rossmanitic tourmaline and evidence for the incorporation of Li at the X site}, series = {Physics and chemistry of minerals / in cooperation with the International Mineralogical Association (IMA)}, volume = {44}, journal = {Physics and chemistry of minerals / in cooperation with the International Mineralogical Association (IMA)}, publisher = {Springer}, address = {New York}, issn = {0342-1791}, doi = {10.1007/s00269-016-0863-0}, pages = {353 -- 363}, year = {2016}, abstract = {Lithium is an important component of some tourmalines, especially in chemically evolved granites and pegmatites. All attempts at synthesizing Li-rich tourmaline have so far been unsuccessful. Here we describe the first synthesis of rossmanitic tourmaline at 4 GPa and 700 degrees C in the system Li2OAl2O3SiO2B2O3H2O (LASBH) from seed-free solid starting materials consisting of a homogenous mixture of Li2O, gamma-Al2O3, quartz and H3BO3. The solid run products after 12-day run duration comprise rossmanitic tourmaline (68 wt\%), dumortierite (28 wt\%) and traces of spodumene (3 wt\%) and coesite (1 wt\%). Tourmaline forms idiomorphic, large prismatic crystals (30 X 100 mu m), which are inclusion free and chemically unzoned. The refined cell dimensions of the tourmaline are: a = 15.7396(9) angstrom, c = 7.0575(5) angstrom, V = 1514.1(2) angstrom 3. Conventionally, the Li+ ion is assumed to exclusively occupy the octahedral Y site in the tourmaline structure to a maximum of 2 Li per formula unit (pfu). However, the chemical composition of our synthetic tourmaline determined by electron microprobe and secondary ion mass spectroscopy results in the formula: (X)(square Li-0.67(11)(0.33(11)))(Y)(Al2.53(10)Li0.47(10))(Z)(Al-6)T(Si5.42(15)B0.58(15))O-18(B)(BO3)(3)(V+W)[(OH)(2.40(3))O-1.60(3)], wherein a significant amount of Li occupies the X site for charge balance requirements. Reliable assignment of the OH-stretching vibrations in a polarized single-crystal Raman spectrum such as a single-crystal XRD structure refinement, confirms the incorporation of Li at the X site [0.24(9) and 0.15(5) Li-X pfu, respectively]. The SREF data show that the LiO1 distances are shortened significantly in order to compensate for the smaller ionic radius of Li+ compared to Na+, K+ or Ca2+ at the X site, i.e., Li is closer to the Si6O18 ring and to a sevenfold coordination with oxygen.}, language = {en} } @phdthesis{Codeco2019, author = {Codeco, Marta Sofia Ferreira}, title = {Constraining the hydrology at Minas da Panasqueira W-Sn-Cu deposit, Portugal}, doi = {10.25932/publishup-42975}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-429752}, school = {Universit{\"a}t Potsdam}, pages = {xxviii, 232}, year = {2019}, abstract = {This dissertation combines field and geochemical observations and analyses with numerical modeling to understand the formation of vein-hosted Sn-W ore in the Panasqueira deposit of Portugal, which is among the ten largest worldwide. The deposit is located above a granite body that is altered by magmatic-hydrothermal fluids in its upper part (greisen). These fluids are thought to be the source of metals, but that was still under debate. The goal of this study is to determine the composition and temperature of hydrothermal fluids at Panasqueira, and with that information to construct a numerical model of the hydrothermal system. The focus is on analysis of the minerals tourmaline and white mica, which formed during mineralization and are widespread throughout the deposit. Tourmaline occurs mainly in alteration zones around mineralized veins and is less abundant in the vein margins. White mica is more widespread. It is abundant in vein margins as well as alteration zones, and also occurs in the granite greisen. The laboratory work involved in-situ microanalysis of major- and trace elements in tourmaline and white mica, and boron-isotope analysis in both minerals by secondary ion mass spectrometry (SIMS). The boron-isotope composition of tourmaline and white mica suggests a magmatic source. Comparison of hydrothermally-altered and unaltered rocks from drill cores shows that the ore metals (W, Sn, Cu, and Zn) and As, F, Li, Rb, and Cs were introduced during the alteration. Most of these elements are also enriched in tourmaline and mica, which confirms their potential value as exploration guides to Sn-W ores elsewhere. The thermal evolution of the hydrothermal system was estimated by B-isotope exchange thermometry and the Ti-in-quartz method. Both methods yielded similar temperatures for the early hydrothermal phase: 430° to 460°C for B-isotopes and 503° ± 24°C for Ti-in-quartz. Mineral pairs from a late fault zone yield significantly lower median temperatures of 250°C. The combined results of thermometry with variations in chemical and B-isotope composition of tourmaline and mica suggest that a similar magmatic-hydrothermal fluid was active at all stages of mineralization. Mineralization in the late stage shows the same B-isotope composition as in the main stage despite a ca. 250°C cooling, which supports a multiple injection model of magmatic-hydrothermal fluids. Two-dimensional numerical simulations of convection in a multiphase NaCl hydrothermal system were conducted: (a) in order to test a new approach (lower dimensional elements) for flow through fractures and faults and (b) in order to identify conditions for horizontal fluid flow as observed in the flat-lying veins at Panasqueira. The results show that fluid flow over an intrusion (heat and fluid source) develops a horizontal component if there is sufficient fracture connectivity. Late, steep fault zones have been identified in the deposit area, which locally contain low-temperature Zn-Pb mineralization. The model results confirm that the presence of subvertical faults with enhanced permeability play a crucial role in the ascent of magmatic fluids to the surface and the recharge of meteoric waters. Finally, our model results suggest that recharge of meteoric fluids and mixing processes may be important at later stages, while flow of magmatic fluids dominate the early stages of the hydrothermal fluid circulation.}, language = {en} } @article{RibackiTrumbullLopezDeLuchietal.2022, author = {Ribacki, Enrico and Trumbull, Robert B. and Lopez De Luchi, Monica Graciela and Altenberger, Uwe}, title = {The chemical and B-Isotope composition of Tourmaline from intra-granitic Pegmatites in the Las Chacras-Potrerillos Batholith, Argentina}, series = {The Canadian mineralogist : journal of the Mineralogical Association of Canada}, volume = {60}, journal = {The Canadian mineralogist : journal of the Mineralogical Association of Canada}, number = {1}, publisher = {Association of Canada}, address = {Ottawa}, issn = {0008-4476}, doi = {10.3749/canmin.2100036}, pages = {49 -- 66}, year = {2022}, abstract = {The Devonian Las Chacras-Potrerillos batholith comprises six nested monzonitic to granitic intrusions with metaluminous to weakly peraluminous composition and a Sr-Nd isotopic signature indicating a dominantly juvenile mantle-derived source. The chemically most evolved units in the southern batholith contain a large number of intra-granitic, pod-shaped tourmaline-bearing pegmatites. This study uses in situ chemical and boron isotopic analyses of tourmaline from nine of these pegmatites to discuss their relationship to the respective host intrusions and the implications of their B-isotope composition for the source and evolution of the magmas. The tourmalines reveal a diversity in element composition (e.g., FeO, MgO, TiO2, CaO, MnO, F) which distinguishes individual pegmatites from one another. However, all have a narrow 5 11 B range of -13.7 to -10.5\%0 (n = 100) which indicates a relatively uniform magmatic system and similar temperature conditions during tourmaline crystallization. The average delta(11) B value of -11.7\%0 is typical for S-type granites and is within the range reported for peraluminous granites. pegmatites, and metamorphic units of the Ordovician basement into which the Las Chacras-Potrerillos batholith intruded. The B-isotope evidence argues for a crustal boron source like that of the Ordovician basement, in contrast to the metaluminous to weakly peraluminous composition and juvenile initial Sr and Nd isotope ratios of the Las Chacras-Potrerillos batholith magmas. We propose that the boron was not derived from the magma source region but was incorporated from dehydration melting of elastic metasedimentary rocks higher up in the crustal column.}, language = {en} }