Abstract: The extensive P–T stability and the high chemical variability of tourmaline (Tur) together with its common occurrence in metasediments proves its high potential for petrological and (isotope) geochemical studies on fluid–rock interaction in subduction- and collision-related rocks. This paper reviews the occurrence, major element chemistry and boron isotopic composition of Tur in high- and ultrahigh-pressure metamorphic (UHPM) rocks. In addition, it presents a new discovery of coesite-bearing Tur (schorl) from the Erzgebirge (Germany), as well as Tur (dravite) related to the retrograde history of coesite- and diamond-bearing rocks from the Erzgebirge and the Kokchetav Massif (Kazakhstan). The scarce data on worldwide occurrences of (U)HPM Tur reveal a high occupation of the crystallographic X-site (dominated by Na) and the possible presence of excess B, with little further distinctiveness in its major element composition when compared with Tur from medium-grade rocks. High K 2 O contents in Tur are probably not related to UHP growth or equilibration. The B isotopic composition of (U)HPM Tur ranges in δ 11 B from −16 to +1‰, with many samples in or below the range of continental crust. In contrast, Tur formed during retrograde fluid influx typically shows high δ 11 B values (up to +28‰), suggesting heavy-B fluids infiltrating the exhuming (U)HPM units. Coesite inclusions in Tur, characterized by Raman spectroscopy, are regarded as the best indicator for its UHP stability. Supplementary material: Analytical methods, tourmaline compositions and boron isotope values are available at http://www.geolsoc.org.uk/SUP18354 .
High-grade metamorphic tourmaline and white mica from the Broken Hill area, NSW, Australia, were analyzed with laser-ablation ICP–MS and ion-probe techniques to investigate the partitioning of trace elements and fractionation of boron isotopes between these two coexisting phases. The results indicate that most trace elements show partition coefficients close to one; only elements such as Zn, Sr, the light rare-earth elements La and Ce, and Th, partition preferentially into tourmaline, whereas Rb, Ba, W, Sn, and Nb and Ta are preferentially partitioned into coexisting mica. The ion-probe measurements demonstrate that boron isotopes are strongly fractionated between mica and tourmaline, with the white mica being some 10‰ lower in δ 11 B than coexisting tourmaline, which is found to be in rather good agreement with previous measurements and predictions from theory.
Tourmaline grains extracted from rocks within three ultrahigh-pressure (UHP) metamorphic localities have been subjected to a structurally and chemically detailed analysis to test for any systematic behavior related to temperature and pressure. Dravite from Parigi, Dora Maira, Western Alps (peak P-T conditions ~3.7 GPa, 750 °C), has a structural formula of X(Na0.90Ca0.05K0.01⃞0.04) Y(Mg1.78Al0.99Fe2+0.12Ti4+0.03⃞0.08)Z(Al5.10Mg0.90)(BO3)3TSi6.00O18V(OH)3W[(OH)0.72F0.28]. Dravite from Lago di Cignana, Western Alps, Italy (~2.7-2.9 GPa, 600-630 °C), has a formula of X(Na0.84Ca0.09K0.01⃞0.06)Y(Mg1.64Al0.79Fe2+0.48Mn2+0.06Ti4+0.02Ni0.02Zn0.01)Z(Al5.00Mg1.00)(BO3)3T(Si5.98Al0.02)O18V(OH)3W[(OH)0.65F0.35]. "Oxy-schorl" from the Saxonian Erzgebirge, Germany (≥4.5 GPa, 1000 °C), most likely formed during exhumation at >2.9 GPa, 870 °C, has a formula of X(Na0.86Ca0.02K0.02⃞0.10)Y(Al1.63Fe2+1.23Ti4+0.11Mg0.03Zn0.01) Z(Al5.05Mg0.95)(BO3)3T(Si5.96Al0.04)O18V(OH)3W[O0.81F0.10(OH)0.09]. There is no structural evidence for significant substitution of [4]Si by [4]Al or [4]B in the UHP tourmaline ( distances ~1.620 Å), even in high-temperature tourmaline from the Erzgebirge. This is in contrast to high-T-low-P tourmaline, which typically has significant amounts of [4]Al. There is an excellent positive correlation (r2 = 1.00) between total [6]Al (i.e., YAl + ZAl) and the determined temperature conditions of tourmaline formation from the different localities. Additionally, there is a negative correlation (r2 = 0.97) between F content and the temperature conditions of UHP tourmaline formation and between F and YAl content (r2 = 1.00) that is best explained by the exchange vector YAlO(R2+F)-1. This is consistent with the W site (occupied either by F, O, or OH), being part of the YO6-polyhedron. Hence, the observed Al-Mg disorder between the Y and Z sites is possibly indirectly dependent on the crystallization temperature.
<p>Recent advances in analytical techniques and instrumentation allow for the analysis of increasingly smaller sample volumes and lower concentrations. This development significantly expands the possibilities of in-situ geochronology, <em>e.g.</em>, LA-MC-ICPMS. Minerals with low U (and Pb) contents such as garnet become the target of in-situ U-Pb geochronology since ages can potentially be obtained from single (sub-)mm-sized garnet grains in thin sections. In this contribution, we explore the current limits of in-situ U-Pb geochronology: what are the minimum concentrations from which an accurate and precise U-Pb age can be obtained?</p><p>For that purpose, we have analysed garnets from three different localities that were unsuccessfully analysed in the past using a single-collector sector-field Element XR instrument at FIERCE. These garnets have been re-analysed at FIERCE using a Neptune Plus MC-ICPMS coupled to a RESOLution-LR ArF Excimer laser. The analyses were performed in static mode measuring the masses <sup>206</sup>Pb and <sup>207</sup>Pb with Secondary Electron Multiplier (SEM) and <sup>202</sup>Hg, <sup>204</sup>Pb and <sup>238</sup>U with the Multiple Ion Counters (MIC). With a spot diameter of 193 &#956;m (round) and a fluence of 2 J/cm<sup>2 </sup>at 15 Hz, ca. 18 &#181;m pit depth was ablated in 18s analysis time, resulting in a total of 2 &#181;g of ablated material. This is more than 2,000 times less material compared to conventional isotope dilution analyses and 3,000 times less U than for a typical LA-ICPMS zircon analysis (20 &#181;m spot). Although the analysed garnets typically have U contents below 10 ng/g, about 15&#8211;30 spots are commonly sufficient to define a regression line in the Tera-Wasserburg diagram, yielding a precision of typically <3 % for the lower intercept age. Challenges and details of the method will be discussed using samples of metamorphic garnet from Kaapvaal craton granulites and Eastern and Western Variscan eclogites.</p>
Tourmaline-supergroup minerals are ubiquitous accessory minerals in rocks of the Earth’s crust. They can adjust their composition to suit a wide variety of environments, and therefore display a remarkable range in stability in terms of pressure, temperature, fluid composition, and host-rock composition. Because of this compositional sensitivity, tourmaline is an excellent indicator of the environmental conditions in its host. This is further enhanced by negligible diffusion up to high temperatures and a strongly refractory character during subsequent host-rock alteration and weathering, as well as mechanical transport of grains. Whereas most prior research on tourmaline has focused on chemical and crystallographic characterizations and systematics of the tourmaline-supergroup minerals, recent studies are shifting the focus to a quantitative reconstruction of environmental conditions in the host using a combination of structural, compositional and crystallographic characteristics of the tourmaline. This thematic issue, which follows a special session at the 2009 GAC–MAC–AGU meeting in Toronto, highlights these exciting advances; here we discuss some of the obstacles that will need to be overcome to insure the practical applicability of tourmaline. The papers presented in this thematic issue of The Canadian Mineralogist show that we are standing on the brink of a major breakthrough in the use of tourmaline as a quantitative indicator of the chemical and physical properties of its host environment these properties may well make tourmaline the prime mineral for this purpose.
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