Geochemistry and geochronology of alkaline dykes from the Finero Phlogopite Peridotite (Ivrea-Verbano Zone): insights into the Triassic-Jurassic tectono-magmatic events of the Southern Alps

<p>The Ivrea-Verbano Zone (IVZ, westernmost sector of the Southern Alps) represents a unique opportunity to investigate the Paleozoic to Mesozoic geodynamic evolution of the Gondwana and Laurasia boundary from the perspective of the lower continental crust. Only recently, the petrochemical record of Triassic-Jurassic magmatism has been recognized. It mainly affected the northernmost tip, the Finero Complex, where the continental crust was tectonically thinned before opening of Alpine Tethys. However, the Mesozoic magmatism in the Finero Complex is still poorly-constrained. Firstly, its extent is largely unknown, because the mantle and crustal intrusives were already enriched by Paleozoic processes. Secondly, Mesozoic melts migration started when the Finero Complex was still placed at P-T conditions typical of a continental crust-mantle transition (1 GPa): this has promoted the reopening of the geochronological clocks in both Paleozoic and Mesozoic rocks, which usually provides wide time intervals. Lastly, the finding of Mesozoic magmatism as composite veins/pods and metasomatised layers has not allowed an exhaustive reconstruction of the primitive melts geochemistry. To place further constraints on such issue, a new dyke swarm cropping out in the Finero Phlogopite Peridotite mantle unit has been investigated. Dykes usually cut at high angle the mantle foliation and are up to 60 cm thick. They are composed by coarse-grained hornblendite to anorthosite, both phlogopite/biotite-bearing. Many dykes are composite, showing variable proportions of hornblendite and anorthosite. In places, the dyke swam was affected by volatiles overpressure as late magmatic stage, which produced plastic flow and development of a porphyroclastic structure by deformation of the early cumulates, with widespread segregation of a fine-grained mica matrix.</p><p>Dykes mainly consist of pargasite, phlogopite/biotite, albite (An 8-10), in association with apatite, monazite, ilmenite, zircon, Nb-rich oxides, carbonates. Enrichments in Fe (amphibole and biotite) and Na (plagioclase) suggest segregation from evolved melts, strongly enriched in H<sub>2</sub>O, P, C. The large LILE and LREE contents in amphiboles, sometimes associated to high Nb, Ta, Zr and Hf concentrations, as well as the mineral assemblage, support an alkaline affinity of the melts. The strongly positive εHf<sub>t </sub>(+10) of zircons and the isotopic Sr composition of amphiboles (0.7042) point to a derivation of the melts from mildly enriched sources, possibly located at the crust-mantle interface.</p><p>Zircons from anorthosite layers are mostly anhedral fragments. They show homogenous internal structure or sector zoning. Concordant <sup>206</sup>Pb/<sup>238</sup>U zircon ages vary from 221 ± 9 Ma to 192 ± 8 Ma. The results of this study confirm that mantle input to the Southern Alps magmatism was of alkaline affinity from Norian to Sinemurian. A widespread fluids circulation induced by such magmatism at high P-T conditions was likely the main cause of the diffuse geochronological reset towards Mesozoic ages of the northern IVZ.</p>

Distribution of Trace Elements Controlled by Sector and Growth Zonings in Zircon from Feldspathic Pegmatites (Ilmen Mountains, the Southern Urals)

The present study contains the detailed ion microprobe data on trace and rare earth elements distribution in the large zircon crystal about 10 × 6 mm in size with distinct growth and sector zonings from Ilmen Mountains feldspathic pegmatite. The zircon crystal morphology is a combination of a prism {110} and a dipyramid {111}. It is found out that the growth sector of the prism {110} generally contains higher concentrations of Th, U, REE, Y, and Nb and exhibits a more gently sloping HREE distribution pattern and a steeper LREE distribution pattern, in contrast to zircon from the growth sector of the dipyramid {111} development. Such a sector zoning pattern was formed at a late stage in crystal growth, when the prism {110} began to prevail over the dipyramid {111}. The zircon studied displays the growth zoning formed of alternating bands in back-scattered electron (BSE) image: wide dark and thin light bands. The last ones contain elevated Th, U, REE, Y, Nb, and Ti concentrations, Th/U ratio and Ce/Ce*. This growth zoning is most probably due to simultaneous crystallization of other minerals that concentrate trace elements, e.g., apatite and monazite, and the lack of equilibrium between zircon and fluid (melt).

Periodic Mixing of Magmas Recorded by Oscillatory Zoning of the Clinopyroxene Macrocrysts from an Ultrapotassic Lamprophyre Dyke

Ultrapotassic rocks are volumetrically minor, but widely distributed in different geological settings. Extensive studies have concerned mantle melting processes that generated these rocks. However, crustal processes that they may have involved are poorly known. In this paper, we describe complex oscillatory zoning patterns of clinopyroxene (Cpx) macrocrysts from an ultrapotassic lamprophyre dyke in the Kyrgyz North Tianshan orogen. These macrocrysts commonly have a corroded or patchy-zoned core surrounded by a mantle with distinct oscillatory zoning, which is, in turn, surrounded by a euhedral rim. The oscillatory zoning of the mantle is composed of alternating coarse and fine layers with a clear resorption surface, or closely packed layers with a straight or wavy boundary in back-scattered electron images. High-amplitude oscillation of Mg#, Ti, Al, Cr and Sr across the layers of the mantle is attributed to magma mixing. Low-amplitude, high-frequency oscillation of Mg# across the closely packed layers was probably developed as a result of kinetic effects or crystal movement under thermal and chemical gradients. In addition, cryptic sector zoning of some macrocrysts clearly shows a Si- and Mg-rich hourglass sector and an Al- and Ti-rich prism sector. The sector zoning indicates crystallization of these macrocrysts under low degrees of undercooling, and the presence of concentric Cr-rich and Cr-poor layers within the same grain indicates that the growth process was disrupted by multiple magma recharging events. The cores of the macrocrysts have Mg# with three distinctive ranges: <84–90 (Core I), 74–84 (Core II) and 60–70 (Core III). The mantles have Mg# ranging from 64 to 90 without a distinct gap. The rims have a narrow range of Mg# from 76 to 80. The cores and mantles with high Mg# (≥85) have variable La/Yb from 1·8 to 5·0 and Dy/Yb from 2·3 to 4·6. The macrocrysts overall have variable 87Sr/86Sr from 0·7072 to 0·7084. Highly variable trace elements and 87Sr/86Sr within a single grain indicate that both primary and evolved magmas with different compositions were periodically recharged into the crustal magma reservoirs. Modelling results reveal that the melts in equilibrium with the Cpx macrocrysts may have been derived from the magma reservoirs at three different depths equivalent to crystallization pressures of ∼5·4, ∼3·3 and ∼1·6 kbar, respectively, making up a transcrustal magmatic system. The Cpx-laden melts in deep magma reservoirs may have been frequently transported to shallower reservoirs. Magma mixing in the shallower reservoirs led to heterogeneous magmas with different cooling rates and chemical compositions. Early crystallized Cpx crystals were overprinted with diverse zoning patterns during overgrowth and accumulation. Thus, the complex zoning patterns and compositions of the Cpx macrocrysts have important implications for a transcrustal magmatic system in the formation of ultrapotassic rocks.

Episodic Fluid Action in Chinese Southwestern Tianshan HP/UHP Metamorphic Belt: Evidence from U–Pb Dating of Zircon in Vein and Host Eclogite

Fluid plays a key role in metamorphism and magmatism in subduction zones. Veins in high-pressure (HP) to ultrahigh-pressure (UHP) rocks are the products of fluid–rock interactions and can thus provide important constraints on fluid processes in subduction zones. In this study, we present an integrated study of zircon in situ U–Pb dating, trace element and mineral inclusion analysis for a complex vein and its host eclogite in the southwestern Tianshan UHP terrane, aiming to decipher the episodic fluid action during slab subduction and exhumation. Both zircon in eclogite and vein have euhedral, prismatic morphology similar to those crystallized from metamorphic fluid. Zircon in eclogite shows core–rim structures with distinct bounds and mineral inclusions. Zircon in the vein shows sector zoning or weak zoning, with bright rims around most zircon grains, which suggests recrystallization of the zircon crystals after their formation and multiple evolution of the vein. Eclogite zircon rims yield a weighted mean of 311 ± 3 Ma and cores yield a range from 413 ± 4 to 2326 ± 18 Ma, respectively. Vein zircon yields four groups of age (~355 Ma, ~337 Ma, ~315 Ma, and ~283 Ma), which date four episodes of fluid flow involving zircon growth. The first two groups of age may represent prograde epidote–amphibolite facies and amphibolite/blueschist facies metamorphism stage, respectively. The third group is similar to that of eclogite zircon rims, which is thought to date the eclogitic facie metamorphism (320–305 Ma), and the fourth group dates a later retrograde metamorphism after greenschist facies. The vein-forming fluid system was supposed to be an open system indicated by trace element of vein zircon and mineral assemblage of the vein. The coexistence of rutile, zircon, and garnet in prograde vein and the heavy rare earth elements (HREE) enrichment characteristic of vein zircon suggest that the vein-forming fluid are enriched in high field strength elements (HFSE) and HREE, and such fluid could be formed under low P–T conditions.

Clinopyroxene–Liquid Equilibria and Geothermobarometry in Natural and Experimental Tholeiites: the 2014–2015 Holuhraun Eruption, Iceland

Clinopyroxene–liquid geothermobarometry is a widely used tool for estimating the conditions under which mafic magmas are stored before they erupt. However, redox variability, sector zoning and disequilibrium crystallization present major challenges to the robust estimation of magma storage conditions. Moreover, most recent studies seeking to address these challenges have focused on clinopyroxenes from alkalic systems and are thus of limited use for understanding clinopyroxenes from the tholeiitic systems that dominate global magma budgets. Here we combine observations on natural clinopyroxenes from the 2014–2015 Holuhraun lava in Iceland with observations on experimental clinopyroxenes synthesized during high-pressure, high-temperature experiments on the same lava in order to investigate clinopyroxene–liquid equilibria in tholeiitic systems and optimize of geothermobarometric strategies. Natural clinopyroxenes from the 2014–2015 Holuhraun lava are sector zoned, with {1-11} hourglass sectors being enriched in the enstatite–ferrosillite component at the expense of all other components with respect to {hk0} prism sectors. In contrast with observations on clinopyroxenes from alkalic systems, sector zoning in clinopyroxenes from the 2014–2015 Holuhraun lava is characterized by differences in Ca and Na contents as well as in Ti and Al contents. The products of crystallization experiments performed at 100–600 MPa and 1140–1220 °C on a powdered starting glass at two sets of melt H2O content–oxygen fugacity conditions (∼0·1 wt % H2O and close to the graphite-oxygen redox buffer, and 0·5–1·0 wt % H2O and approximately one and half log units above the quartz–fayalite–magnetite redox buffer) demonstrate that clinopyroxene crystals from nominally equilibrium experiments can preserve strongly disequilibrium compositions. The compositional systematics of experimental clinopyroxenes are consistent with the presence of sector zoning. Furthermore, the magnitude of compositional variability increases with decreasing melt H2O content and increasing deviations of experimental temperatures below clinopyroxene liquidus temperatures (i.e. degrees of undercooling sensu lato), indicating that kinetic processes play a key role in controlling clinopyroxene compositions, even under notionally equilibrium conditions. Few published analyses of experimental clinopyroxene crystals may thus represent truly equilibrium compositions. Stoichiometric calculations on natural and experimental clinopyroxenes show that Fe3+ is a major constituent of clinopyroxenes from tholeiitic magmas under naturally relevant oxygen fugacity conditions. They also show that Fe3+ is most likely incorporated as Ca- and Al- bearing Ca–Fe-Tschermak’s component rather than Na-bearing aegirine component at oxygen fugacities up to one and a half log units above the quartz–fayalite–magnetite buffer. Elevated oxygen fugacities are thus less likely to compromise clinopyroxene–liquid geothermobarometry than previously thought. Guided by our experimental results, we combined published descriptions of clinopyroxene–liquid equilibria with geothermobarometric equations to develop an internally consistent and widely applicable method for performing geothermobarometry on tholeiitic magmas that does not require equilibrium zones to be selected a priori. Applying this method to natural clinopyroxene crystals from the 2014–2015 Holuhraun lava that formed under low but variable degrees of undercooling (perhaps 25 °C or less) returns values in excellent agreement with those from independent methods (232 ± 86 MPa, 1161 ± 11 °C). Robust estimates of magma storage conditions can thus be obtained by performing clinopyroxene–liquid geothermobarometry on tholeiitic magmas when disequilibrium is suitably accounted for.

Columbite U-Pb Geochronology of Kalu’an Lithium Pegmatites in Northern Xinjiang, China: Implications for Genesis and Emplacement History of Rare-Element Pegmatites

The Kalu’an-Azubai pegmatite field, one of the most important rare-metal metallogenic regions in China, contains a large number of pegmatite dikes belonging to spodumene and lepidolite subtypes. Columbite-group minerals (CGMs) collected from three spodumene subtype pegmatites (No. 802, No. 803, and No. 805 pegmatites) were analyzed for major element contents using EPMA (electron probe micro-analyzer) and dated using LA-ICP-MS (laser ablation-inductively coupled plasma mass spectrometer). The crystallization ages of the CGMs from No. 802, No. 803, and No. 805 pegmatites are 209.5 ± 1.4 Ma (2σ), 198.3 ± 2.0 Ma (2σ), and 224.3 ± 2.9 Ma (2σ), respectively. Oscillatory zoning and/or sector zoning along with the associated mineral assemblages suggest that the dated columbite is of magmatic origin. The crystallization ages of the columbite grains thus represent the emplacement ages of the Li pegmatites. Therefore, our dating results indicate that there were three emplacement events of the Li-rich pegmatite-forming melts in a timeframe of ~30 Ma. In combination with previous studies, we conclude that the Li pegmatites were formed before the Be-Ta-Nb pegmatites (~194–192 Ma), which precludes the genesis of rare-metal pegmatites via fractional crystallization of a granitic magma in the Kalu’an-Azubai region.

Chemical Evolution of Nb-Ta Oxides and Cassiterite in Phosphorus-Rich Albite-Spodumene Pegmatites in the Kangxiwa–Dahongliutan Pegmatite Field, Western Kunlun Orogen, China

The Kangxiwa–Dahongliutan pegmatite field in the Western Kunlun Orogen, China contains numerous granitic pegmatites around a large granitic pluton (the Dahongliutan Granite with an age of ca. 220 to 217 Ma), mainly including barren garnet-, tourmaline-bearing pegmatites, Be-rich beryl-muscovite pegmatites, and Li-, P-rich albite-spodumene pegmatites. The textures, major element contents, and trace element concentrations of columbite-group minerals (CGM) and cassiterite from three albite-spodumene pegmatites in the region were investigated using a combination of optical microscopy, SEM, EPMA and LA-ICP-MS. The CGM can be broadly classified into four types: (1) inclusions in cassiterite; (2) euhedral to subhedral crystals (commonly exhibiting oscillatory and/or sector zoning and coexisting with magmatic cassiterite); (3) anhedral aggregates; (4) tantalite-(Fe)-ferrowodginite (FeSnTa2O8) intergrowths. The compositional variations of CGM and cassiterite are investigated on the mineral scale, in individual pegmatites and within the pegmatite group. The evolution of the pegmatites is also discussed. The variation of Nb/Ta and Zr/Hf ratios of the cassiterite mimics the Nb-Ta and Zr-Hf fractionation trends in many LCT pegmatites, indicating that these two ratios of cassiterite may bear meanings regarding the pegmatite evolution.

Rutile from Panasqueira (Central Portugal): An Excellent Pathfinder for Wolframite Deposition

Abundant W-rich rutile in the tourmalinized wall-rocks from the Panasqueira W-deposit appears to be a marker of the onset of the main wolframite depositing event. Rutile displays spectacular zoning, both sector (SZ) and oscillatory (OZ). An extensive set of compositional data obtained on crystals, beforehand studied using back-scattered electron images and X-ray maps, was used to address (i) the effects of SZ on differential trapping of minor elements, and (ii) the significance of the OZ in deciphering fluid sources and fluid circulation dynamics. Particular attention was paid to Sn, W (Nb, Ta) concentrations in rutile as pathfinders of the W deposition. Concerning the sector zoning, W is more incorporated than (Nb, Ta) onto more efficient faces, whereas Sn contents are nearly not impacted. The net effect of the sector zoning is thus a progressive increase of the relative weight of Sn from pyramid to prism faces, in combination with a less significant increase in the relative weight of Nb + Ta. The oscillatory zoning concerns most minor elements: W, Nb (Ta), Fe, V, Cr and Sn. In the frequent doublets, the clear bands are in general enriched in W relatively to the dark ones, whereas the inverse is true for Nb and Ta. The doublets may be viewed as the result of the successive influx of (i) a W-rich, Nb + Ta poor fluid, abruptly replaced by (or mixed to) (ii) a Nb + Ta-rich and W-poor fluid. The Nb + Ta-rich fluid could be in turn related to a rare-metal granite layer observed atop of the Panasqueira granite.

Apatite with lamellae of sulfide and other phases in ultrahigh-pressure eclogites from Nové Dvory, Moldanubian Zone, Czech Republic

Exsolution lamellae of baryte, Fe sulfides, Cu sulfides and Fe oxides were observed in apatite enclosed in garnet and omphacite and their intergranular spaces in ultrahigh-pressure eclogite in the Moldanubian Zone, Czech Republic. Micro-textural relations and compositional mapping of the apatite indicates a close relationship between the density of the exsolution lamellae and compositional domains that are rich in sulfur and iron. No relation between compositional domains and fluorine or chlorine content or any evidence of apatite metasomatisation was observed. On the basis of cathodoluminescence images, the compositional domains reflect sector zoning in apatite crystals by preferential uptake of elements due to differences in surface charge and morphology on the growth plane. It is concluded that the lamellae are products of exsolution in a closed system resulting from temperature decrease during metamorphism.