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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.
Formation of epithermal Sn-Ag-(Zn) vein-type mineralization at the Pirquitas deposit, NW Argentina
(2018)
The Pirquitas Sn-Ag-(Zn) deposit in northwestern Argentina is thought to be an analogue to the Miocene polymetallic epithermal Sn-Ag deposits of the southern Bolivian Tin Belt, but little is known in detail about the origin and evolution of ore-forming fluids at Pirquitas. This paper reports on a microthermometric study of fluid inclusions in quartz, sphalerite, Ag-Sn sulfides, and Ag-rich sulfosalts using transmitted near infrared and visible light, combined with noble gas isotope analyses of fluids released from mineral separates. The study focused on the vein-hosted mineralization, which formed during two major mineralization events, whereby the first event I comprises two stages (I-1 and I-2). All studied minerals exclusively contain aqueous two-phase inclusions, indicating that the ore-forming fluids did not undergo two-phase phase separation (boiling). Salinity of fluid inclusions in I-1 quartz that precipitated along with pyrite and pyrrhotite ranges between 0 and 7.5 wt% NaCl equiv. and homogenization temperatures (Th) are between 233 and 370 degrees C. Stage I-2 is characterized by abundant Sn-Ag-Pb-Zn-sulfides and a variety of Ag-rich sulfosalts. Fluid inclusions in stage I-2 Ag-Sn sulfides have salinities up to 10.6 wt% NaCl equiv. and Th between 213 and 274 degrees C. The deposition of stage I-2 ore is likely related to a new pulse of saline magmatic fluids to the hydrothermal system. The mineralization event II deposited the richest Ag ores at Pirquitas. Colloform sphalerite and pyrargyrite deposited during event II contain two-phase aqueous fluid inclusions with homogenization temperatures between 190 and 252 degrees C and salinities between 0.9 and 4.3 wt% NaCl equiv. Noble gas concentrations and isotopic compositions of ore-hosted fluid inclusions were determined from crushing hand-picked ore minerals from both mineralization events. With one exception, all samples yielded He-3/He-4 ratios between 1.9 and 4.1 Ra, which is within the range of published data from the volcanic arc and somewhat higher than typical values of meteoric water-derived hot-springs in the region. This demonstrates a significant contribution of magmatic fluids to the Pirquitas mineralization although no intrusive rocks are exposed in the mine region. Taking the noble gas evidence for a magmatic fluid source, we interpret the trends of decreasing Th and salinity values in fluid inclusions from events I and II to represent waning of the magmatic-hydrothermal system and/or increased admixing of meteoric water to the magmatic fluids.