Fluid inclusion evidence for the magmatic-hydrothermal evolution of closely linked porphyry Au, porphyry Mo, and barren systems, East Qinling, China

The Xiong’ershan district in central China hosts broadly coeval porphyry Au (Qiyugou deposit), porphyry Mo (Leimengou deposit), and barren (Huashan pluton) systems. The key controls on the ore potential and different mineralization styles in these systems are not well understood, with first-order differences in fluid chemistry and melt sources being the main alternatives. The fluid inclusion characteristics of all three porphyry systems have been studied using an integrated approach that combines field geology, petrography, microthermometry, and laser ablation−inductively coupled plasma−mass spectrometry analysis of single fluid inclusions. The results permit a reconstruction of the magmatic-hydrothermal evolution of the ore-forming fluids, and to elucidate whether specialized hydrothermal fluids strongly enriched in ore metals (i.e., Mo, Au, Cu) were essential to form the economically significant deposits. The fluid compositions across the three hydrothermal stages from the Qiyugou Au deposit remain approximately the same over time, suggesting that progressive magma fractionation, fluid-rock reaction along fluid path, and mineral precipitation had a limited effect on fluid composition. The syn-ore stage fluids of the Leimengou Mo deposit are characterized by higher Cs/Na, Sr/Na, and B/Na, but lower K/Na and Cl/Na ratios, and also have salinities and homogenization temperatures distinct from the earlier fluids. This demonstrates that Mo mineralization was caused by a second pulse of fluid input from a highly fractionated felsic magma subsequent to the pre-ore stage. At the Huashan barren pluton, fluids from phase II have higher Cs/Na, B/Na, Li/Na, and Rb/Na ratios with lower homogenization temperatures than fluids occurring in porphyritic rocks of phase III, reflecting a higher degree of magma fractionation of this plutonic complex. The Huashan pluton does not host economic mineralization which is likely caused by the low ore metal tenor, inefficient fluid extraction from the melt, or the flat-roof geometry preventing accumulation of a large volume of fluid in the apical part. The Au tenor of the Qiyugou deposit was most likely contributed by mantle-derived material of higher Mg/Na, Fe/Na, Pb/Na, and Zn/Na ratios. Taken together, the metal charged magmatic-hydrothermal fluids, steeply dipping geometry, and small volume of the porphyry stocks all suggest that a much larger magma chamber feeding the porphyry systems should be present at deeper levels with good potential for Mo mineralization below the current level of exposure at Qiyugou deposit.

Aillikites and Alkali Ultramafic Lamprophyres of the Beloziminsky Alkaline Ultrabasic-Carbonatite Massif: Possible Origin and Relations with Ore Deposits

The 650–621 Ma plume which impinged beneath the Siberian craton during the breakup of Rodinia caused the formation of several alkaline carbonatite massifs in craton margins of the Angara rift system. The Beloziminsky alkaline ultramafic carbonatite massif (BZM) in the Urik-Iya graben includes alnöites, phlogopite carbonatites and aillikites. The Yuzhnaya pipe (YuP) ~ 645 Ma and the 640–621 Ma aillikites in BZM, dated by 40Ar/39Ar, contain xenoliths of carbonated sulfide-bearing dunites, xenocrysts of olivines, Cr-diopsides, Cr-phlogopites, Cr-spinels (P ~ 4–2 GPa and T ~ 800–1250 °C) and xenocrysts of augites with elevated HFSE, U, Th. Al-augites and kaersutites fractionated from T ~ 1100–700 °C along the 90 mW/m2 geotherm. Higher T trend for Al-Ti augite, pargasites, Ti-biotites series (0.4–1.5 GPa) relate to intermediate magma chambers near the Moho and in the crust. Silicate xenocrysts show Zr-Hf, Ta-Nb peaks and correspond to carbonate-rich magma fractionation that possibly supplied the massif. Aillikites contain olivines, rare Cr-diopsides and oxides. The serpentinites are barren, fragments of ore-bearing Phl carbonatites contain perovskites, Ta-niobates, zircons, thorites, polymetallic sulphides and Ta-Mn-Nb-rich magnetites, ilmenites and Ta-Nb oxides. The aillikites are divided by bulk rock and trace elements into seven groups with varying HFSE and LILE due to different incorporation of carbonatites and related rocks. Apatites and perovskites reveal remarkably high LREE levels. Aillikites were generated by 1%–0.5% melting of the highly metasomatized mantle with ilmenite, perovskite apatite, sulfides and mica, enriched by subduction-related melts and fluids rich in LILE and HFSE. Additional silicate crystal fractionation increased the trace element concentrations. The carbonate-silicate P-bearing magmas may have produced the concentration of the ore components and HFSE in the essentially carbonatitic melts after liquid immiscibility in the final stage. The mechanical enrichment of aillikites in ore and trace element-bearing minerals was due to mixture with captured solid carbonatites after intrusion in the massif.

Carbon–Strontium Isotope Decoupling in Carbonatites from Caotan (Qinling, China): Implications for the Origin of Calcite Carbonatite in Orogenic Settings

Mantle-derived carbonatites emplaced in orogenic belts and some extensional settings are hypothesized to contain recycled crustal material. However, these carbonatites are typically composed of calcite showing a typical mantle range of C–O isotopic values devoid of recognizable sedimentary fingerprints. Here, we report the first known instance of C–Sr isotope decoupling between intimately associated dolomite carbonatites and magnetite–forsterite–calcite carbonatites from the northern Qinling orogen, central China. The calcite-dominant variety is developed at the contact between the dolomite carbonatite and metasomatized wall-rock gneiss. The two types of carbonatites have similar δ18OVSMOW (6·98‰ to 9·96‰), εNd(i) (-3·01 to -6·47) and Pb (206Pb/204Pb(i) = 17·369–17·584, 207Pb/204Pb(i) = 15·443–15·466) isotopic compositions, but significantly different C and Sr isotopic signatures (δ13CVPDB = -3·09 to -3·58‰ and -6·11 to -7·19‰; 87Sr/86Sr(i) = 0·70373 to 0·70565 vs 0·70565 to 0·70624 for the dolomite and calcite rocks, respectively). The relative enrichment of the early-crystallizing dolomite carbonatite in 13C and its depletion in 87Sr are primary isotopic characteristics inherited from its mantle source. The observed field relations, petrographic and geochemical characteristics of the Caotan dolomite and calcite carbonatites imply that the strong C–Sr isotopic decoupling between them could not result from mixing of different mantle reservoirs (e.g. HIMU and EM1), or from magma fractionation processes. We propose that the calcite carbonatites were a by-product of metasomatic reactions between primary dolomitic melts and felsic wall-rock. These reactions involved the loss of Mg and CO2 from the magma, leading to depletion of the evolved calcite-saturated liquid in 13C and its enrichment in radiogenic Sr. We conclude that calcite carbonatites in plate-collision zones may not represent primary melts even if their isotopic signature is recognizably ‘mantle-like’.

Composition of zircons from the Cornubian Batholith of SW England and comparison with zircons from other European Variscan rare-metal granites

Zircon from 14 representative granite samples of the late-Variscan Cornubian Batholith in SW England was analysed for W, P, As, Nb, Ta, Si, Ti, Zr, Hf, Th, U, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Al, Sc, Bi, Mn, Fe, Ca, Pb, Cu, S and F using electron probe microanalyses. Zircons from the biotite and tourmaline granites are poor in minor and trace elements, usually containing 1.0–1.5 wt.% HfO2, <0.5 wt.% UO2 and P2O5, <0.25 wt.% Y2O3, <0.2 wt.% Sc2O3 and Bi2O3 and <0.1 wt.% ThO2. Zircon from topaz granites from the St. Austell Pluton, Meldon Aplite and Megiliggar Rocks are slightly enriched in Hf (up to 4 wt.% HfO2), U (1– 3.5 wt.% UO2) and Sc (0.5–1 wt.% Sc2O3). Scarce metamictized zircon grains are somewhat enriched in Al, Ca, Fe and Mn. The decrease of the zircon Zr/Hf ratio, a reliable magma fractionation index, from 110–60 in the biotite granites to 30–10 in the most evolved topaz granites (Meldon Aplite and Megiliggar Rocks), supports a comagmatic origin of the biotite and topaz granites via long-lasting fractionation of common peraluminous crustal magma. In comparison with other European rare-metal provinces, the overall contents of trace elements in Cornubian zircons are low and the Zr/Hf and U/Th ratios show lower degrees of fractionation of the parental melt.

Petrogenetic significance of LA-ICP-MS trace-element data on quartz from the Borborema Pegmatite Province, northeast Brazil

Quartz from different zones within five granitic pegmatites of the rare-element class from the Borborema Pegmatite Province in northeast Brazil were analysed for fourteen trace elements using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The concentrations of Li (6—150 ppm), B (1—9 ppm) and Ge (1—23 ppm) in quartz show a positive correlation with Al (30—770 ppm). The concentrations of these elements increase from the border zone to the quartz core of pegmatites of the spodumene or lepidolite subtypes. The Ge concentrations in the quartz core are the highest so far reported in igneous quartz. In the less evolved pegmatites of the beryl-columbite subtype, the Al, Li, B, and Ge concentrations in quartz from all zones remain at the same level as the border and wall zones. The Ti concentrations in quartz from the core of the more evolved pegmatites are below 3 ppm (with Al >250 ppm), contrasting with 7—25 ppm (with Al <280 ppm) in samples from the border and wall zones of the less evolved and more evolved pegmatites. The concentrations of Al. Li, B, Ge, and Ti in quartz are therefore confirmed as good indicators of the degree of magma fractionation and analyses of pegmatite quartz cores can be used for exploration purposes to distinguish pegmatites with high metallogenic potential. Atoms of Li and Al are incorporated into quartz such that Li/Al ranges between 0.75 and 1.0. This suggests a coupled substitution of the form Si4+ ↔ (Li+ + Al3+). The other elements analysed either showed an erratic distribution (e.g. Be and P) or were below the respective limits of detection (Na, K, Rb, Ca, Sr, Mn, Fe) in most samples.