The Genesis of the Giant Shuangjianzishan Epithermal Ag-Pb-Zn Deposit, Inner Mongolia, Northeastern China

The newly discovered Shuangjianzishan Ag-Pb-Zn deposit, with 145 Mt of ore grading 128.5 g/t Ag (locally up to 32,000 g/t) and 2.2 wt % Pb + Zn, is located in the Great Hinggan Range metallogenic belt, northeastern China, and is currently the largest Ag deposit in Asia. The Ag-Pb-Zn orebodies occur as veins and are hosted primarily by a Permian slate. Recent drilling and core logging have identified a partially Mo mineralized granite porphyry intrusion adjacent to the Ag-Pb-Zn mineralized veins. This well-preserved magmatic-hydrothermal system therefore offers an excellent opportunity to evaluate the possible temporal and genetic relationship between Mo-mineralized porphyry intrusions and Ag-Pb-Zn veins. Three primary paragenetic stages of veining have been recognized: (I) early pyrite + quartz ± K-feldspar, (II) main ore sulfide + sulfosalt + quartz + calcite + sericite + chlorite ± epidote, and (III) post-ore quartz. The silver mineralization occurs mainly in the late paragenetic part of Stage II, in which canfieldite (Ag8SnS6), argentite (Ag2S) and freibergite [(Ag, Cu)12Sb4S13] are the dominant Ag-bearing ore minerals. A combination of ore mineral chemical and sulfur isotope geothermometers and physicochemical calculations suggest that the Ag-Pb-Zn mineralization took place at a temperature of 250° to 200°C, a pH of 6.7 to 5.6, and a Δlogfo2 (HM) of –2.4 to –8.7. A conspicuous enrichment of Sn and Se in the ore, which is represented by minerals containing the metal suite Ag-Pb-Zn-(Cu-Sn-Se-Sb), likely reflects a close genetic association between the base metal mineralization and a magma. In situ analyses show that the δ34S values of the sulfides and Ag-bearing sulfosalts from the Ag-Pb-Zn mineralized veins vary from –4.67 to +2.44‰; the mean value is –2.11 ± 1.49‰ (n = 77). The calculated mean δ34SH2S value of the ore-forming fluid is –1.65 ± 0.83‰, which is indicative of a magmatic sulfur source. In situ Pb isotope analyses of the ore minerals yielded a narrow range of values (206Pb/204Pb of 18.243–18.310, 207Pb/204Pb of 15.503–15.563 and 208Pb/204Pb of 38.053–38.203, n = 59). Comparisons to corresponding isotopic data for the various rock units in the area and sulfides from nearby ore deposits indicate that there were substantial contributions of Pb and other metals (e.g., Ag and Zn) to the Shuangjianzishan deposit from a Mesozoic granitic source. Diorite-granodiorite dikes and dacite are crosscut by the Ag-Pb-Zn veins, and therefore, predate ore formation. These rock units have zircon U-Pb ages of 250.2 ± 2.0 and 133.9 ± 1.4 Ma, respectively. A concealed, weakly Mo mineralized granite porphyry intrusion proximal to the Ag-Pb-Zn mineralized vein system yielded zircon U-Pb ages of 134.4 ± 1.0 (MSWD = 0.1) and 134.4 ± 1.0 Ma (MSWD = 0.2), for coarse- and fine-grained facies, respectively. These ages are indistinguishable within the uncertainty from the zircon ages for the dacite and a granite intrusion ~2 km north of the mineralized veins, which has a weighted mean zircon U-Pb age of 135.2 ± 1.4 Ma (MSWD = 0.78). Molybdenite from three quartz vein/veinlet samples hosted by slate immediately above the porphyry intrusion yielded Re-Os model ages from 136.3 ± 0.9 to 133.7 ± 1.2 Ma and a weighted mean Re-Os age of 134.9 ± 3.4 Ma. Finally, three pyrite samples separated from the Ag-Pb-Zn mineralized veins have a weighted mean Re-Os model age of 135.0 ± 0.6 Ma. The very similar zircon U-Pb ages for the Mo-mineralized granite porphyry and dacite, and Re-Os ages for molybdenite and pyrite in the Shuangjianzishan ore district indicate that the Mesozoic magmatic-hydrothermal activity was restricted to a relatively short time interval (~136–133 Ma). They also suggest that the weakly Mo mineralized granite porphyry was likely the source of the fluids and metals that produced the Ag-Pb-Zn mineralization. Based on our geological observations and an extensive analytical database, a model is proposed for the genesis of the giant Shuangjianzishan Ag-Pb-Zn deposit in which the ore-forming fluid and its metals (i.e., Ag, Pb, and Zn) were exsolved during crystallization of the final phase of a composite granite porphyry intrusion. This fluid transported metals to the distal parts of the system, where they were deposited in preexisting faults or fractures created by the withdrawal of magma during the waning stages of the magmatic-hydrothermal event. The present study of the Shuangjianzishan Ag-Pb-Zn deposit and those of other magmatic-hydrothermal ore deposits in the region provide compelling evidence that the widespread Mesozoic felsic magmatism and Ag-Pb-Zn mineralization in the southern Great Hinggan Range took place in an intracontinental extensional tectonic setting, which was synchronous with, and spatially associated to, Paleo-Pacific slab rollback and lithospheric delamination and thinning.

Geology and age of the Morrison porphyry Cu–Au–Mo deposit, Babine Lake area, British Columbia

The Morrison porphyry Cu–Au–Mo deposit is genetically and spatially related to Eocene plagioclase–hornblende–biotite porphyry intrusions. One porphyry intrusion yielded a U–Pb age of 52.54 ± 1.05 Ma. Mineralization occurs in three stages: (1) vein-type and disseminated chalcopyrite and minor bornite (associated with potassic alteration and gold mineralization); (2) vein-type molybdenite (associated with weak phyllic alteration); and (3) polymetallic sulfide–carbonate veins (dolomite ± quartz–sphalerite–galena–arsenopyrite–chalcopyrite, associated with weak sericite–carbonate alteration). Re–Os dating of molybdenite yielded ages of 52.54 ± 0.22 and 53.06 ± 0.22 Ma, similar to the age of the host porphyry intrusion. Stage 1 vein fluids were predominantly of magmatic origin: Th = 400–526 °C; salinity = 39.8–47.8 wt.% NaCl equiv.; δ18Ofluid = 3.7‰–6.3‰; disseminated chalcopyrite–pyrite δ34SCDT = 0.2‰ and −0.8‰ (CDT, Canyon Diablo Troilite). Stage 2 fluids were a mixture of magmatic and meteoric water: Th = 320–421 °C; salinity = 37.0–43.1 wt.% NaCl equiv.; δ18Ofluid values range from 0.3‰ to 3.4‰; molybdenite and pyrite δ34SCDT = −2.1‰ and −1.2‰. Stage 3 fluids were predominantly of meteoric water origin: Th = 163–218 °C; salinity = 3.1–3.9 wt.% NaCl equiv.; δ18Ofluid = −2.3‰ to 3.9‰ for early vein quartz, and 1.1‰ to 6.1‰ for late vein dolomite; sphalerite and pyrite δ34SCDT = −7.1‰ to −5.6‰. Morrison is interpreted to be a typical porphyry Cu–Au–Mo deposit related to a calc-alkaline to a high-K calc-alkaline diorite to granodiorite intrusive suite, generated in a continental arc in response to early Eocene subduction of the Kula–Farallon plate beneath North America.

Kerimasite, {Ca3}[Zr2](SiFe3+2)O12 garnet from the Vysoká-Zlatno skarn, Štiavnica stratovolcano, Slovakia

Kerimasite {Ca3}[Zr2](SiFe23+)O12, a rare member of the garnet supergroup, has been identified in association with andradite–grossular and their hydrated analogues, monticellite, perovskite, clintonite, anhydrite, hydroxylellestadite–fluorellestadite, spinel, magnetite, brucite, valeriite and other minerals from a Ca-Mg skarn in the exocontact of a granodiorite porphyry intrusion in Vysoká-Zlatno Cu-Au skarn-porphyry deposit, the Štiavnica stratovolcano, Central Slovakia. Kerimasite forms euhedral-to-anhedral crystals, 2 to 100 μm across with 0.73–1.62 atoms per formula unit (a.p.f.u.) Zr (16.2–33.6 wt.% ZrO2), 0.34–0.66 a.p.f.u. Ti (4.6–9.3 wt.% TiO2), 0.01 to 0.05 a.p.f.u. Hf (0.4–1.7 wt.% HfO2: the largest Hf content reported in kerimasite), and small amounts of Sn, Sc and Nb (≤0.02 a.p.f.u.). Tetrahedral Si (0.99–1.67 a.p.f.u.; 9.8–18.1 wt.% SiO2) is balanced by 0.85–1.26 a.p.f.u. Fe3+ and by 0.46–0.76 a.p.f.u. Al. The crystals commonly show regular, oscillatory concentric zoning or irregular patchy internal textures due to Zr, Ti, Fe, Al and Si variations during growth or partial alteration and dissolution-reprecipitation. The main substitutions in kerimasite are Y(Fe,Sc)3+ + ZSi4+ = Y(Zr,Ti,Hf,Sn)4+ + Z(Fe,Al)3+ and Ti4+ = Zr4+. Associated andradite locally contains irregular Ti- and Zr-rich zones with ≤11 wt.% TiO2 and ≤4.4 wt.% ZrO2. In comparison with common Ca-rich garnets, the micro-Raman spectrum of kerimasite shows that many bands shift towards much lower wavenumbers, either due to Fe3+ substitution on the Z site or to the strong influence of neighbouring octahedrally-coordinated Zr4+ on internal vibrations of tetrahedra that share oxygens. The formation of kerimasite, monticellite, perovskite and other phases indicate a relatively Ca-rich and Si, Al-poor environment, analogous to other known occurrences of Ca-Zr garnets (Ca-rich skarns and xenoliths, carbonatites). Kerimasite and associated skarn minerals originated during contact-thermal metamorphism of Upper Triassic marl slates with limestone, dolomite, anhydrite and gypsum by Miocene granodiorite porphyry at T ≈ 700°C and P ≈ 50–70 MPa.