The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

First results of U/Pb dating of detrital zircons from Early Paleozoic and Devonian sandstones of the Baltic-Ladoga region (south Ladoga Area)

The first results of U/Pb isotopic dating (LA ICP MS) of detrital zircons from sands from the Middle Cambrian Sablinka Formation, Upper Cambrian Ladoga Formation, Low Ordovician Tosna Formation, and calcareous sands from Syas’ Formation (Sargaevskii horizon of the Upper Frasnian) from Baltica-Ladoga Glint (BLG) of the Southern Ladoga area are presented. The obtained ages of detrital zircons span the intervals 492.7 ± 5.1-3196.4 ± 5.1 Ma (Sablino Formation); 577.9 ± 7–2972.6 ± 13.4 Ma (Ladoga Formation); 509.4 ± 8.5–3247.6 ± 10.1 Ma (Tosna Formation); 451.1 ± 14.7–2442.2 ± 6.9 Ma (Syas’ Formation). A comparison of the obtained isotopic ages of detrital zircons to ages of crystalline complexes composing the Kola-Karelian, Svecofennian, and Sveconorwegian domains of Baltic Shield and Pre-Uralian-Timanian structures of Subpolar and Polar Urals and basement of Pechora Basin was carried out. It is proposed that the Middle Paleozoic sedimentary basin accumulated Upper Frasnian rocks of Syas’ Formation. The basin ranged northward from the present-day BLG and occupied the eastern part of the Baltic Shield.     

Zr/Hf ratio as an indicator of fractionation of rare-metal granites by the example of the Kukulbei complex,eastern Transbaikalia

The concept of granitic melt fractionation as the main process in the concentration of rare elements in granites calls for the development of a reliable method to determine the evolutionary sequences of granite series. We propose to use for this purpose a zirconium-hafnium indicator, the Zr/Hf weight ratio in granitic rocks (Zaraisky et al., 1999, 2000). By the example of three classic regions of rare-metal deposits, eastern Transbaikalia, central Kazakhstan, and Erzgebirge (Czech Republic and Germany), it was empirically shown that the Zr/Hf ratio of granites decreases during the fractional crystallization of granite magmas in the sequence granodiorite → biotite granite → leucogranite → lithium-fluorine granite. The reason is the higher affinity of Hf compared with Zr to a granite melt. This implies that the crystallization and settling of accessory zircon will cause the progressive enrichment of Hf relative to Zr in the residual melt. As a result, the Zr/Hf ratio decreases regularly in the series of sequential phases of granite intrusion related to a single magma chamber from granodiorite to biotite granite, leucogranite, and Li-F granite (from 45-30 to 10-2). Our experimental investigations supported the preferential enrichment of haplogranite melt in Hf and zircon crystals in equilibrium with melt in Zr (T= 800°C and P = 1 kbar). The Zr/Hf indicator was tested by the example of the wellknown Kukulbei rare-metal granite complex of eastern Transbaikalia (J3), which is unique in the degree of fractionation of initial granite melt with the formation of three phases of granite emplacement and vein derivatives. An important feature of the complex is its “short” differentiation trend. It was supposed that the granite magma of the first phase is parental, and the later phases forming small intrusive bodies in large massifs of biotite granites of the first phase are sequential products of its crystallization differentiation in a magma chamber. The biotite granites of the first phase are barren. The leucocratic granites of the second phase are accompanied by tin-tungsten greisen deposits (e.g., Spokoininskoe), and the upper part of cupola-like stocks of Li-F amazonite granites of the third phase host apogranite-type tantalum deposits (Orlovka, Etyka, and Achikan). In addition to three granite phases, the Kukulbei complex includes dikes of ongonites, elvans, amazonite granites, and chamber miarolitic pegmatites. All of the granitic rocks of the complex have similar isotopic ages of 142± 0.6 Ma. The Zr/Hf ratio decreases systematically from phase 1 (40–25), to phase 2 (20–10), and phase 3 (10–2). The ongonites, elvans, and pegmatites have similar Zr/Hf ratios (15-5), falling between the ranges of leucocratic muscovite granites and Li-F granites. Compared with other granite series, the granitic rocks of the Kukulbei complex show specific petrographic and geochemical features: they are strongly enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From the early to late intrusion phases, the degree of enrichment and depletion in these element groups increases regularly. This is accompanied by a significant decrease (from 40 to 2) in Zr/Hf, which can be used as a reliable indicator of genetic relations, degree of fractionation, and rare-metal potential of granites. Granites with Zr/Hf values lower than 25 are promising for prospecting for Sn, W, Mo, and Be greisen deposits, whereas the formation of Ta deposits requires Zr/Hf values lower than 10.     

The first results of U/Pb dating and isotope geochemical studies of detrital zircons from the neoproterozoic sandstones of the Southern Timan (Djejim-Parma Hill)

This report presents the first results of U/Pb dating, isotope-geochemical, and geochemical studies of detrital zircons from the Neoproterozoic clastic rocks of the Southern Timan. Sixty-one zircon grains were treated, including 51 from red-colored sandstones and 10 grains from aleurosandstones of the Djejim Formation of the southern Chetlas-Djejim zone (Djejim-Parma Hill). It was found that the U/Pb-ages of zircons from the rocks of the Djejim Formation, varied from ∼2.97 to ∼1.20 Ga. The studies of microelement composition in 47 grains (of 61 U/Pb isotope ages obtained), on the basis of several empirical regularities found formerly, show that the detrital zircons had originated from “granites” (22 grains), “diorites” (12 grains), or their volcanic analogues, or more rarely, from “syenites” and “basites” (5 and 8 grains, respectively). The Lu/Hf isotope system of zircons allows one to estimate the model ages (T _DM^C) of the substrate magmatic rocks being parental to the zircons considered. In particular, Archean zircons are characterized by ∼2.84–3.36 Ga model ages of magmaforming rocks. For some of the grains, their model ages (∼2.84 Ga) are close to those of zircons as such (∼2.7–2.8 Ga), which points to the juvenile character of the substrate from which the parent magma of the zircons treated was fused. For Proterozoic (to Middle Riphean) zircons, the Lu/Hf isotope system allows one to estimate the model age of the substrate of their parental rocks within ∼2.00–3.36 Ga, which shows that these rocks were formed under the recycling of the Archean and Early-Proterozoic crust. The ages obtained for detrital zircons, as well as model ages of the substrate of the corresponding parental magmatic rocks, are quite comparable to the age of crystalline complexes of the ancient framework of the East European Platform (EEP), formed in the course of the Archean, Early-Proterozoic, and Early-Middle Riphean tectonomagmatic events. This permits us to conclude that the Neoproterozoic detrital complexes of the Timan were formed owing to the erosion of earlier Neoproterozoic and Early Precambrian complexes constituting the Neoproterozoic Baltica continent, presenting complexes of the passive margin of this continent. A variety of ages of detrital zircons from sandstones and aleurosandstones from the Djejim Formation of Djejim-Parma Hill, and of the estimates of magmatic rocks parental to these zircons, may be characterized as a Baltic Provenance signal.