The Effects of High-Grade Metamorphism on Cr-Spinel from the Archean Sittampundi Complex, South India

We investigated the crystal and structural behavior of Cr-bearing spinels from the Archean chromitites of Sittampundi (India), which had been subjected to very high-grade metamorphism. The structural data show that their oxygen positional parameters are among the highest ever recorded for Cr-bearing spinels with similar Cr# and Mg# and very similar to those found for other Archean occurrences. The general agreement between electron microprobe and Mössbauer data indicates that the analyzed spinels are stoichiometric. It is therefore most likely that the PH2O and Ptotal values as well as both the oxygen fugacity and the temperature reached during high-grade metamorphism inhibited the possibility of the non-stoichiometry of chromites, contrary to what can happen in ophiolites, where non-stoichiometry has recently been documented.

Apatite and Zircon Geochemistry in Yao’an Alkali-Rich Porphyry Gold Deposit, Southwest China: Implications for Petrogenesis and Mineralization

The Yao’an gold deposit is located in the middle of the Jinshajiang-Ailaoshan alkali-rich metallogenic belt, and this belt hosts many porphyry-type Cu-Au-Mo deposits formed at 46–33 Ma. Yao’an porphyry gold-mineralization is intimately associated with biotite syenite porphyry, whereas the contemporaneous quartz syenite porphyry is barren. In this study, we compared the major and trace elements of apatite and zircon and isotopic compositions of zircon from the biotite syenite porphyry and quartz syenite porphyry, to explore their geochemical differences that may affect their mineralization potential. The results show that both porphyries were derived from the partial melting of the thickened lower crust, which has been modified by slab-derived fluids, but has different mineral crystallization sequences, magma fluid activities, and magma oxidation states, respectively. REE contents in apatite and zircon can be used to reveal the crystallization sequence of minerals. A rapid decrease of (La/Yb)N ratio in apatite from both porphyries may be caused by the crystallization of allanite. Large variation of Cl contents and negative correlation between F/Cl and (La/Yb)N in apatite from fertile porphyry indicate that it has experienced the exsolution of Cl-bearing hydrothermal fluid. Higher Y/Ho and lower Zr/Hf in zircon from fertile porphyry indicate a stronger fluid activity than barren porphyry. The high S, V, As contents, δEu, low δCe in apatite, as well as high Ce4+/Ce3+ and log(fO2) estimated from zircon geochemistry from fertile porphyry, indicate high a oxidation state of fertile porphyry, similar to other fertile porphyries in this metallogenic belt. High fluid activity and fluid exsolution are conducive to the migration and enrichment of metal elements, which are very important for mineralization. High oxygen fugacity inhibits the precipitation of metal in the form of sulfide, thereby enhancing the mineralization potential of rock. Therefore, the exsolution of Cl-bearing hydrothermal fluid and high oxygen fugacity are the key factors promoting mineralization in Yao’an area.

Whole-rock and zircon evidence for evolution of the Late Jurassic high Sr/Y Zhoujiapuzi granite, Liaodong Peninsula, North China Craton

Middle-Late Jurassic high Sr/Y granitic intrusions are extensively exposed in the Liaodong Peninsula, in the eastern part of the North China Craton (NCC). However, the genesis of the high Sr/Y signature in these intrusions has not been studied in detail. In this study, we report results of zircon U-Pb dating, Hf isotopic analysis and zircon and whole-rock geochemical data for the Late Jurassic Zhoujiapuzi granite in the middle part of the Liaodong Peninsula. The Zhoujiapuzi granite is high-K (calc-alkaline) and peraluminous in nature, with high SiO2 (68.1–73.0 wt %) and Al2O3 (14.5–16.8 wt %), low in TFe2O3 (1.10–2.49 wt %) and MgO (0.10–0.44 wt %), and with high Sr/Y (19.9–102.0) and LaN/YbN (14.59–80.40). Morphological and chemical studies on zircon grains show that there are two stages of zircon growth, interpreted as magmatic evolution in two distinct stages. The early stage of zircons (ESZ) reflects a crystallization environment of low oxygen fugacity and high TZr-Ti (Ti-in-zircon thermometer values: 669–792 °C); the late stage of zircons (LSZ) formed with high oxygen fugacity and lower TZr-Ti (498–720 °C). LA-ICP-MS U-Pb zircon dating yielded the formation ages of the ESZ and LSZ of ~162 ± 1 Ma and ~158 ± 1 Ma, respectively, with similar εHf(t) values in the range of &minus26.3– −22.8. Interpretation of the elemental and isotopic data suggests that the Zhoujiapuzi granite was a I-type granite derived from partial melting of basement in the region: ~2.17 Ga Liaoji granites. The high Sr/Y signature is most likely inherited from these source rocks. Based on the geochemical features and regional geological data, we propose that the Liaodong Peninsula in the Late Jurassic was part of a mature continental arc, with extensive melting of thick crust above the Paleo-Pacific subduction zone.

Atypical Mineralization Involving Pd-Pt, Au-Ag, REE, Y, Zr, Th, U, and Cl-F in the Oktyabrsky Deposit, Norilsk Complex, Russia

Highly atypical mineralization involving Pd-Pt, Au-Ag, REE, Y, Zr, U, Th, and Cl-F-enriched minerals is found in zones with base metal sulfides (BMS; ~5 vol.% to 20 vol.%) in the eastern portion of the Oktyabrsky deposit in the Norilsk complex (Russia). The overall variations in Mg# index, 100 Mg/(Mg + Fe2+ + Mn), in host-rock minerals are 79.8 → 74.1 in olivine, 77.7 → 65.3 in orthopyroxene, 79.9 → 9.2 in clinopyroxene, and An79.0 → An3.7. The span of clinopyroxene and plagioclase compositions reflects their protracted crystallization from early magmatic to late interstitial associations. The magnesian chromite (Mg# 43.9) trends towards Cr-bearing magnetite with progressive buildups in oxygen fugacity; ilmenite varies from early Mg-rich to late Mn-rich variants. The main BMS are chalcopyrite, pyrrhotite, troilite, and Co-bearing pentlandite, with less abundant cubanite (or isocubanite), rare bornite, Co-bearing pyrite, Cd-bearing sphalerite (or wurtzite), altaite, members of the galena-clausthalite series and nickeline. A full series of Au-Ag alloy compositions is found with minor hessite, acanthite and argentopentlandite. The uncommon assemblage includes monazite-(Ce), thorite-coffinite, thorianite, uraninite, zirconolite, baddeleyite, zircon, bastnäsite-(La), and an unnamed metamict Y-dominant zirconolite-related mineral. About 20 species of PGM (platinum group minerals) were analyzed, including Pd-Pt tellurides, bismuthotellurides, bismuthides and stannides, Pd antimonides and plumbides, a Pd-Ag telluride, a Pt arsenide, a Pd-Ni arsenide, and unnamed Pd stannide-arsenide, Pd germanide-arsenide and Pt-Cu arseno-oxysulfide. The atypical assemblages are associated with Cl-rich annite with up to 7.54 wt.% Cl, Cl-rich hastingsite with up 4.06 wt.% Cl, ferro-hornblende (2.53 wt.% Cl), chlorapatite (>6 wt.% Cl) and extensive solid solutions of chlorapatite, fluorapatite and hydroxylapatite, Cl-bearing members of the chlorite group (chamosite; up to 0.96 wt.% Cl), and a Cl-bearing serpentine (up to 0.79 wt.% Cl). A decoupling of Cl and F in the geochemically evolved system is evident. The complex assemblages formed late from Cl-enriched fluids under subsolidus conditions of crystallization following extensive magmatic differentiation in the ore-bearing sequences.

Melt Percolation, Melt-Rock Reaction and Oxygen Fugacity in Supra-Subduction Zone Mantle and Lower Crust from the Leka Ophiolite Complex, Norway

Samples of peridotites and pyroxenites from the mantle and lower crustal sections of the Leka Ophiolite Complex (LOC; Norway) are examined to investigate the effects of melt-rock reaction and oxygen fugacity variations in the sub-arc oceanic lithosphere. The LOC is considered to represent supra-subduction zone (SSZ) oceanic lithosphere, but also preserves evidence of pre-SSZ magmatic processes. Here we combine field and microstructural observations with mineral chemical and structural analyses of different minerals from the major lithologies of the LOC. Wehrlite and websterite bodies in both the mantle and lower crust contain clinopyroxene likely formed at a pre-SSZ stage, characterised by high Al, high Cr, low Mg crystal cores. These clinopyroxenes also exhibit low Al, low Cr, high Mg outer rims and intracrystalline dissolution surfaces, indicative of reactive melt percolation during intrusion and disruption of these lithologies by later, SSZ-related, dunite-forming magmas. Chromian-spinel compositional variations correlate with lithology; dunite-chromitite Cr-spinels are characterised by relatively uniform and high TiO2 and Al2O3, indicating formation by melt-rock reaction associated with SSZ processes. Harzburgite Cr-spinel compositions are more variable but preserve a relatively high Al2O3, low TiO2 endmember that may reflect crystallisation in a pre-SSZ oceanic spreading centre setting. An important finding of this study is that the LOC potentially preserves the petrological signature of a transition between oceanic spreading centre processes and subsequent supra-subduction zone magmatism. Single crystal Cr-spinel Fe3+/ΣFe ratios calculated on the basis of stoichiometry (from electron microprobe [EPMA] and crystal structural [X-ray diffraction; XRD] measurements) correlate variably with those calculated by point-source (single crystal) Mössbauer spectroscopy. Average sample EPMA Fe3+/ΣFe ratios overestimate or underestimate the Mössbauer-derived values for harzburgites, and always overestimate the Mössbauer Fe3+/ΣFe ratios for dunites and chromitites. The highest Fe3+/ΣFe ratios, irrespective of method of measurement, are therefore generally associated with dunites and chromitites, and yield calculated log(fO2)FMQ values of up to ~+1.8. While this lends support to the formation of the dunites and chromitites during SSZ-related melt percolation in the lower part of the LOC, it also suggests that these melts were not highly oxidised, compared to typical arc basalts (fO2FMQ of >+2). This may in turn reflect the early (forearc) stage of subduction zone activity preserved by the LOC and implies that some of the arc tholeiitic and boninitic lava compositions preserved in the upper portion of the ophiolite are not genetically related to the mantle and lower crustal rocks, against which they exhibit tectonic contacts. Our new data also have implications for the use of ophiolite chromitites as recorders of mantle oxidation state through time; a global comparison suggests that the Fe3+/ΣFe signatures of ophiolite chromitites are likely to have more to do with local environmental petrogenetic conditions in sub-arc systems than large length-scale mantle chemical evolution.