Karel Breiter

Evolution of rare-metal granitic magmas documented by quartz chemistry

The study documents changes in the chemical composition of igneous quartz during evolution of two contrasting late-Variscan granite suites in the Erzgebirge/Krusne Hory Mts., Czech Republic. Quartz is the chemically most resistant rock-forming mineral in granitoids, so trace-element signatures in quartz preserve its magmatic character during all common post-magmatic alterations. Six quartz populations were optically distinguished in each of the studied granite suites: a highly peraluminous phosphorus-rich (S-type) from Podlesi, and slightly peraluminous P-poor (A-type) from Hora Svate Kateřiny. Contents of Li, Be, B, Al, Ge, P, K, Na, Ca, Ti, Mn, and Fe were determined in situ in all quartz types using laser ablation inductively coupled plasma mass spectrometry, LA-ICP-MS. Of all the determined elements, only Ti decreases with increasing fractionation. Al reached the highest contents in all samples (100–1200 μg g −1 ), followed by Ti, Li, and K (in the range of 10–100 μg g −1 ). The Ti vs . Al diagram is the most fitting indicator of the evolution of the melt from which the quartz crystallised. Al enters the quartz lattice according to coupled substitution Si 4+ ↔ Al 3+ + (Li, K, H) + . No first-hand correlation between Al in quartz and the peraluminosity of the melt was found. Contents of Al increase from the early to the late quartz populations, by factors of 3 in Podlesi and 10 in Katerina, despite the aluminium saturation index of both granite systems increasing only slightly or becoming stable: 1.20–1.35 in Podlesi and 1.05 in Katerina. The contents of B, Be, Ge, Fe, Mn, and P in quartz are usually lower than 10 μg g −1 and their abundances are generally positively correlated with whole-rock chemical compositions. Erratic, high contents of Fe and Mn in quartz from marginal pegmatite may be attributed to infiltration of fluid from the exocontact during quartz crystallisation.

Oxy-schorl, Na(Fe2+2Al)Al6Si6O18(BO3)3(OH)3O, a new mineral from Zlatá Idka, Slovak Republic and Přibyslavice, Czech Republic

Abstract Oxy-schorl (IMA 2011-011), ideally Na(Fe22+Al)Al6Si6O18(BO3)3(OH)3O, a new mineral species of the tourmaline supergroup, is described. In Zlatá Idka, Slovak Republic (type locality), fan-shaped aggregates of greenish black acicular crystals ranging up to 2 cm in size, forming aggregates up to 3.5 cm thick were found in extensively metasomatically altered metarhyolite pyroclastics with Qtz+Ab+Ms. In Přibyslavice, Czech Republic (co-type locality), abundant brownish black subhedral, columnar crystals of oxy-schorl, up to 1 cm in size, arranged in thin layers, or irregular clusters up to 5 cm in diameter, occur in a foliated muscovite-tourmaline orthogneiss associated with Kfs+Ab+Qtz+Ms+Bt+Grt. Oxy-schorl from both localities has a Mohs hardness of 7 with no observable cleavage and parting. The measured and calculated densities are 3.17(2) and 3.208 g/cm3 (Zlatá Idka) and 3.19(1) and 3.198 g/cm3 (Přibyslavice), respectively. In plane-polarized light, oxy-schorl is pleochroic; O = green to bluish-green, E = pale yellowish to nearly colorless (Zlatá Idka) and O = dark grayish-green, E = pale brown (Přibyslavice), uniaxial negative, ω = 1.663(2), ε = 1.641(2) (Zlatá Idka) and ω = 1.662(2), ε = 1.637(2) (Přibyslavice). Oxy-schorl is trigonal, space group R3m, Z = 3, a = 15.916(3) Å, c = 7.107(1) Å, V = 1559.1(4) Å3 (Zlatá Idka) and a = 15.985(1) Å, c = 7.154(1) Å, V = 1583.1(2) Å3 (Přibyslavice). The composition (average of 5 electron microprobe analyses from Zlatá Idka and 5 from Přibyslavice) is (in wt%): SiO2 33.85 (34.57), TiO2 <0.05 (0.72), Al2O3 39.08 (33.55), Fe2O3 not determined (0.61), FeO 11.59 (13.07), MnO <0.06 (0.10), MgO 0.04 (0.74), CaO 0.30 (0.09), Na2O 1.67 (1.76), K2O <0.02 (0.03), F 0.26 (0.56), Cl 0.01 (<0.01), B2O3 (calc.) 10.39 (10.11), H2O (from the crystal-structure refinement) 2.92 (2.72), sum 99.29 (98.41) for Zlatá Idka and Přibyslavice (in parentheses). A combination of EMPA, Mössbauer spectroscopy, and crystal-structure refinement yields empirical formulas (Na0.591Ca0.103□0.306)Σ1.000(Al1.885Fe2+ 1.108Mn0.005Ti0.002)Σ3.000(Al5.428Mg0.572)Σ6.000(Si5.506Al0.494)Σ6.000O18 (BO3)3(OH)3(O0.625OH0.236F0.136Cl0.003)Σ1.000 for Zlatá Idka, and (Na0.586Ca0.017K0.006□0.391)Σ1.000(Fe2+1.879Mn0.015 Al1.013Ti0.093)Σ3.00(Al5.732Mg0.190Fe3+0.078)Σ6.000(Si5.944Al0.056)Σ6.000O18(BO3)3(OH)3(O0.579F0.307OH0.115)Σ1000 for Přibyslavice. Oxy-schorl is derived from schorl end-member by the AlOFe-1(OH)-1 substitution. The studied crystals of oxy-schorl represent two distinct ordering mechanisms: disorder of R2+ and R3+ cations in octahedral sites and all O ordered in the W site (Zlatá Idka), and R2+ and R3+ cations ordered in the Y and Z sites and O disordered in the V and W sites (Přibyslavice).

Granitoids in the Rozvadov Pluton, Western Bohemia and Oberpfalz

The Rozvadov Pluton is a complex of mainly Variscan granitoid rocks situated near the Bohemian-Bavarian border between Bärnau, Tachov, Rozvadov and Waidhaus, 25 km ESE of the KTB site. Five mappable units can be distinguished, which intruded as folows: (1) slightly deformed leucocratic meta-aplite/metapegmatite dykes with garnet and tourmaline; (2) a complex of cordierite-bearing granitoids, which have been divided into three facies (a) biotite granite with cordierite (at the margin of the complex), (b) biotite-cordierite granite and (c) cordierite tonalite (in the centre of the complex; (3) fine-grained biotite granite of the Rozvadov type with associated pegmatite bodies; (4) two-mica Bärnau granite; and (5) geochemically specialized albite-zinnwaldite-topaz granite (Krížový kámen/Kreuzstein granite) with indications of Sn-Nb-Ta mineralization and associated phosphorus-rich pegmatite cupolas. Rare earth element data suggest that meta-aplite/pegmatite dykes are the result of a batch partial melting process, whereas the compositional variation of the other rock types was mainly controlled by fractional crystallization. The genesis of the cordierite granitoid suite is best explained in terms of a batch melting of metapelitic source followed by crystallization of a cordierite-rich cumulate and K-feldspar enriched melt. The leucocratic pluton constituents — the meta-aplites and the Bärnau and Křížový kámen granites are rich in phosphorus (0.5–0.8%). The main carriers of phosphorus are alkali feldspars, especially K-feldspar (up to 0.8% P2O5). The presence of P-rich leucocratic granites is one of the features distinguishing the Variscan granitoids within the Moldanubian zone from the nearly contemporaneous granitoids in the Saxothuringian zone.

Vertical zonality of fractionated granite plutons reflected in zircon chemistry: the Cínovec A-type versus the Beauvoir S-type suite

Abstract We studied vertical changes in the chemical composition of zircon from two contrasting Variscan granite systems. The Beauvoir system (Massif Central, France) composed of three successive intrusions (B1, B2, B3) represents typical peraluminous S-type granite extremely enriched in P, F, Li, Rb, Cs, Be, Sn, Nb, Ta, and poor in Zr, Th, REE and Y. The Cínovec system (Krušné hory Mts/Erzgebirge, Czech Republic/Germany) composed of two successive intrusions (protolithionite granite, zinnwaldite granite) is only slightly peraluminous, P-poor, F, Li, Rb, Cs, U, Th, REE, Y, Sc, Sn, W, Nb, Ta-rich granite, which may be classified as A-type. In both localities, the most fractionated intrusions are located on the top of the system. Samples from borehole GPF-1 (Beauvoir) represent an 800 m long vertical section through the entire granite stock, while CS-1 borehole (Cínovec) reached a depth of 1600 m. Chemical compositions of zircons from both granite systems show distinct vertical zonality, but their shape and elemental speciation is highly contrasting. At Beauvoir, zircon shows a remarkable increase in Hf-content from 2-4 wt. % HfO2 (~0.03 apfu Hf) in the deepest B3-unit to 15-19 wt. % HfO2 (up to 0.18 apfu Hf) in the uppermost B1-unit. The highest contents of F, P, and U were detected in the intermediate unit B2 at a depth of 400-600 m. At Cínovec, Hf shows only moderate enrichment from ca. 2 wt. % HfO2 in the deeper protolithionite granite to 5-10 wt. % HfO2 in the uppermost part of the zinnwaldite granite. High contents of Th (3-8 wt. % ThO2) are entirely bound in the uppermost section of the granite copula to a depth of 200 m, but below this level the contents only sporadically exceed 1 wt. % ThO2. Concentrations of U, Y, HREE, Sc and Bi also reach their highest values in the uppermost parts of the zinnwaldite granite, but their decrease downward is much gentler. Extreme enrichment of outer zones of zircon crystals from some granites with Hf or high contents of Th, U, REE, Y, Nb and of some other elements in zircons from other localities is not considered to be a specific phenomenon characterizing melts of A- or S-type granite, but reflects a high degree of fractionation of systems rich in Na and F.

Water content of granitic melts from Cornwall and Erzgebirge: A Raman spectroscopy study of melt inclusions

Melt inclusions (MIs) occurring in quartz of late-Variscan Sn-specialized granites from the Lands End pluton in SW England and from the eastern Erzgebirge volcano-plutonic complex in Germany were analyzed by Raman spectroscopy, secondary ion mass spectrometry and electron microprobe. Crystallized MIs were homogenized using cold-sealed autoclaves operating at 850°C and 2 kbar for 24 hours. The H2O concentration of homogenized MIs from the Lands End granites determined by confocal Ramanspectroscopyrangebetween1.5and5.4wt.%.SeveralMIsfromtheLandsEndgranitescontainahypersalinefluidwith18.2 to38.6wt.%H2O.Such mixedfluidandsilicate-MIsare typical for magmasthat were oversaturatedinvolatiles. The ratioofsilicate glass/saline phase decreases with increasing degree of differentiation of the granite host. The H2O content of MIs from the Niederbobritzsch granite, Schonfeld rhyodacite, Teplice rhyolite, Altenberg-Frauenstein microgranite and Schellerhau granite inthe eastern Erzgebirge varies between 0.7 and 11.9 wt.%. The MIs from the volcanic rocks have more variable concentrations than the MIs from the granites. The high chemical discrepancies between MIs and whole rock suggest that the quartz phenocrysts in the Schonfeld rhyodacite were injected into a stratified magma chamber during the course of multiple recharge events at the chambers base. MIs from granites from the eastern Erzgebirge do not contain hypersaline fluids, however they have F concentrations of up to 11.2 wt.%. The Li, Be and B contents of representative homogenized MIs were determined by SIMS. The light lithophile element ratios of MIs are constant for eachmagmatic province despite different fractionation degrees of the host rocks. MIs from rocks of the eastern Erzgebirge volcano-plutonic complexare relatively enriched in Li and Be, whereas MIs in granites of the Lands End pluton have higher B contents. The distinctive ratio of light lithophile elements of the silicate melt is also reflected in the light lithophile element ratio of the magmatic host quartz.

Petrogenesis of contrasting granitoid plutons in western Bohemia (Czech Republic)

SummaryLate-Variscan granitoid plutons in western Bohemia (Bor, Waidhaus-Rozvadov) have distinct petrographic, geochemical and isotopic features that suggest different magmatic evolutions. The Bor pluton comprises a suite of metaluminous tonalites and quartz diorites (Bor I), weakly peraluminous (monzo-)granites and granodiorites (Bor II) and medium-aluminous, late vein-forming leucomonzogranites (Bor III). The Waidhaus-Rozvadov pluton is strongly peraluminous, comprising a cordierite-biotite granitoid (CBG), the Rozvadov granite (ROG), the Bärnau granite (BÄG) and the subordinate, highly evolved Kreuzstein (Křížový kámen) granite (KG). Geochemical parameters and initial87Sr/86Sr ratios straddle the boundary between I- and S-type granites in the Bor pluton and are characteristic of purely S-type granites in the Waidhaus-Rozvadov pluton.The Bor II granitoids have been dated by the Rb-Sr whole-rock method at 341±17 Ma (ISr = 0.70724±0.00060). K-Ar biotite and muscovite ages of all units of the Bor pluton are mainly in the range 321-315 Ma. The K-Ar mineral ages are in good agreement with recently published U-Pb zircon data of these rocks. The different units of the Waidhaus-Rozvadov pluton have yielded less well-constrained Rb-Sr whole-rock ages, ranging from 313 to 300 Ma. However, the intrusion sequence is constrained by K-Ar muscovite ages (312-302 Ma), which define a systematic decrease towards the chemically more evolved granite types. Taken as a whole, it seems likely that the new radiometric ages characterize two temporally distinct periods of late-Variscan granitoid intrusion. The regional significance of these periods is emphasized by contemporaneous ages previously found in the adjacent northeastern Bavarian granitoids.The initial Sr and Nd isotope systematics indicate that the Bor and the WaidhausRozvadov plutons were derived from different source rocks. The Bor granitoids reflect the influence of less evolved crustal material which may have been similar to paragneisses of the Teplá-Barrandian region, including the Zone of ErbendorfVohenstrauß (ZEV). The Waidhaus-Rozvadov granitoids probably resulted from anatexis of rocks resembling surrounding Moldanubian paragneisses or metapelites. In addition, the two plutons exhibit poorly defined, opposite trends of εNd(T) variation which are ascribed to assimilation processes.ZusammenfassungSpätvariscische Granitplutone in Westböhmen (Bor, Waidhaus-Rozvadov) weisen petrographische, geochemische und isotopische Kontraste auf, die unterschiedliche magmatische Entwicklungen nahelegen. Der Bor Pluton umfaßt metalumine Tonalite und Quarzdiorite (Bor I), schwach peralumine (Monzo-)granite und Granodiorite (Bor II) und mäßig alumine, gangbildende Leukomonzogranite (Bor III). Der WaidhausRozvadov Pluton besitzt stark peralumine Zusammensetzung und läßt sich in einen Cordierit-Biotit Granitoid (CBG), den Rozvadov Granit (ROG), den Bärnau Granit (BÄG) und den stofflich hochentwickelten Kreuzstein (Křížový kámen) Granit (KG) untergliedern. Geochemische Parameter und initiale87Sr/86Sr-Verhältnisse liegen im Falle des Bor Plutons im Übergangsbereich zwischen I- und S-Typ Graniten und im Falle des Waidhaus-Rozvadov Plutons im Bereich reiner S-Typ Granite.Die Bor II Granitoide wurden nach der Rb-Sr Gesamtgesteinsmethode auf 341±17 Ma (ISr = 0.70724±0.00060) datiert. K-Ar Biotit- und Muskovitalter der Bor Granitoide liegen zwischen 321 and 315 Ma. Die K-Ar Mineralalter stehen im Einklang mit den kürzlich publizierten U-Pb Zirkondaten dieser Gesteine. Die verschiedenen Teilintrusionen des Waidhaus-Rozvadov Plutons liefern weniger gut definierte Rb-Sr Gesamtgesteinsalter zwischen 313 and 300 Ma. Die Intrusionsabfolge läßt sich dennoch durch K-Ar Muskovitalter festlegen (312-302 Ma), die eine systematische Abnahme von den weniger zu den starker entwickelten Granittypen aufweisen. Als Ganzes betrachtet dokumentieren die neuen radiometrischen Daten zwei zeitlich voneinander getrennte spdtvariscische Intrusionsereignisse. Die regionale Signifikanz dieser Ereignisse wird durch eine analoge Altersverteilung in den benachbarten nordostbayerischen Granitoiden untermauert.Anhand der initialen Sr und Nd Isotopensystematik können für die Bor und Waidhaus-Rozvadov Plutone unterschiedliche Quellen abgeleitet werden. Die Bor Granitoide spiegeln den Einfluß von gering entwickelten krustalen Material wider, das ähnliche stoffliche Eigenschaften besaß, wie Paragneise des Teplá-Barrandiums und der Zone von Erbendorf-Vohenstrauss (ZEV). Die Waidhaus-Rozvadov Granitoide lassen sich als Derivate moldanubischer Paragneise and Metapelite oder vergleichbarer Gesteine auffassen. Die zwei Plutone weisen schwach ausgeprägte gegensätzliche εNd(T)-Variationen auf, was auf unterschiedliche Assimilationsprozesse zurückgeführt wird.

Gallium and germanium geochemistry during magmatic fractionation and post-magmatic alteration in different types of granitoids: a case study from the Bohemian Massif (Czech Republic)

Abstract Contents of Ga and Ge in granites, rhyolites, orthogneisses and greisens of different geochemical types from the Bohemian Massif were studied using inductively coupled plasma mass spectrometry analysis of typical whole-rock samples. The contents of both elements generally increase during fractionation of granitic melts: Ga from 16 to 77 ppm and Ge from 1 to 5 ppm. The differences in Ge and Ga contents between strongly peraluminous (S-type) and slightly peraluminous (A-type) granites were negligible. The elemental ratios of Si/1000Ge and Al/1000Ga significantly decreased during magmatic fraction: from ca. 320 to 62 and from 4.6 to 1.2, respectively. During greisenization, Ge is enriched and hosted in newly formed hydrothermal topaz, while Ga is dispersed into fluid. The graph Al/Ga vs. Y/Ho seems to be useful tool for geochemical interpretation of highly evolved granitoids.

Intensive low-temperature tectono-hydrothermal overprint of peraluminous rare-metal granite: a case study from the Dlhá dolina valley (Gemericum, Slovakia)

Abstract A unique case of low-temperature metamorphic (hydrothermal) overprint of peraluminous, highly evolved rare-metal S-type granite is described. The hidden Dlhá dolina granite pluton of Permian age (Western Carpathians, eastern Slovakia) is composed of barren biotite granite, mineralized Li-mica granite and albitite. Based on whole-rock chemical data and evaluation of compositional variations of rock-forming and accessory minerals (Rb-P-enriched K-feldspar and albite; biotite, zinnwaldite and di-octahedral micas; Hf-(Sc)-rich zircon, fluorapatite, topaz, schorlitic tourmaline), the following evolutionary scenario is proposed: (1) Intrusion of evolved peraluminous melt enriched in Li, B, P, F, Sn, Nb, Ta, and W took place followed by intrusion of a large body of biotite granites into Paleozoic metapelites and metarhyolite tuffs; (2) The highly evolved melt differentiated in situ forming tourmaline-bearing Li-biotite granite at the bottom, topaz-zinnwaldite granite in the middle, and quartz albitite to albitite at the top of the cupola. The main part of the Sn, Nb, and Ta crystallized from the melt as disseminated cassiterite and Nb-Ta oxide minerals within the albitite, while disseminated wolframite appears mainly within the topaz-zinnwaldite granite. The fluid separated from the last portion of crystallized magma caused small scale greisenization of the albitite; (3) Alpine (Cretaceous) thrusting strongly tectonized and mylonitized the upper part of the pluton. Hydrothermal low-temperature fluids enriched in Ca, Mg, and CO2 unfiltered mechanically damaged granite. This fluid-driven overprint caused formation of carbonate veinlets, alteration and release of phosphorus from crystal lattice of feldspars and Li from micas, precipitating secondary Sr-enriched apatite and Mg-rich micas. Consequently, all bulk-rock and mineral markers were reset and now represent the P-T conditions of the Alpine overprint.

Trace element composition of quartz from different types of pegmatites: A case study from the Moldanubian Zone of the Bohemian Massif (Czech Republic)

Abstract The evolution of the trace-element patterns of quartz during crystallization of pegmatite melt was investigated using laser ablation inductively coupled plasma mass spectrometry. The contents of Al, B, Ba, Be, Cr, Fe, Ge, Li, Mn, P, Rb, Sn, Sr and Ti were analysed in quartz from the border, intermediate and core zones of four granitic pegmatites differing in degree of fractionation and origin. The material investigated originates from the pegmatite district of the Strážek Unit, Moldanubian Zone, Bohemian Massif, Czech Republic and includes: lepidolite LCT (Li-Cs-Ta) pegmatite from Rožná; berylcolumbite LCT pegmatite from Věžná; anatectic pegmatite from Znětínek; and intragranitic NYF (Nb- Y-F) pegmatite Vladislav from the Třebíč Pluton. The abundances of the elements analysed varied over wide intervals: <1 to 32 ppm Li, 0.5 to 6 ppm B, <1 to 10 ppm Ge, 1 to 10 ppm P, 10 to 450 ppm Al, 1 to 45 ppm Ti and <1 to 40 ppm Fe (average sample contents). Concentrations of Be, Rb, Sr, Sn, Ba, Cr and Mn are usually <1 ppm. Quartz from LCT pegmatites exhibits a distinct evolutionary trend with a decrease in Ti and an increase in Al, Li and Ge from the pegmatite border to the core. In comparison with the most fractionated rare-metal granites, pegmatitic quartz is relatively depleted in Al and Li, but strongly enriched in Ge. Quartz from simple anatectic and NYF pegmatites is poor in all trace elements with their evolution marked by a decrease in Ti and a small increase in Ge. There is little Al or Li and neither shows any systematic change with pegmatite evolution. Using the Ti-in-quartz thermobarometer, the outer zones of the Znětínek and Vladislav pegmatites crystallized at ~670°C, whereas the border zone in the Rožná pegmatite yields a temperature near 610°C.

Topaz as an important host for Ge in granites and greisens

Abstract The composition of topaz from different granites and greisen in the Krušné Hory/Erzgebirge area was investigated using electron microprobe analysis (EMPA) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). All topaz grains are rich in F (17.9−19.8 wt.%, 1.73−1.90 a.p.f.u.) and the most important minor/trace elements are P, Ge and Ga. Contents of P up to 1 wt.% P2O5 (0.025 a.p.f.u.) were found in topaz from the strongly peraluminous P-rich magmatic systems at Podlesí. Regardless of genetic type, topaz from granites typically contains 50−100 ppm Ge. The greatest amounts (up to 204 ppm Ge) were found in topaz from quartz-topaz-apatite greisen in Krásno. In fractionated granites and greisens, topaz is calculated to contain 23−87% of the bulk Ge content in the rock. In contrast, topaz does not concentrate Ga. The Ga content of topaz (typically 5−35 ppm in S-type granites, <10 ppm Ga in A-type granites) is usually smaller than the bulk Ga content of the rock. In addition, up to 16 ppm Sc, 23 ppm Sn and >400 ppm Fe may be present.