High‐temperature gold‐copper extraction with chloride flux in lava tubes of Tolbachik volcano (Kamchatka)

Subvolcanic environments in supra‐subduction zones are renowned for hosting epithermal deposits that often contain electrum and native gold, including bonanza examples. This study examined mineral assemblages and processes occurring in shallow‐crust volcanic settings using recent eruption (2012–2013) of the basaltic Tolbachik volcano in the Kamchatka arc. The Tolbachik eruptive system is characterized by an extensive system of lava tubes. After cessation of magma input, the tubes maintained the flow of hot oxidized gases that episodically interacted with the lava surfaces and sulphate‐chloride precipitates from volcanic gases on these surfaces. The gas‐rock interaction had strong pyrometamorphic effects that resulted in the formation of molten salt, oxidized (tenorite, hematite, Cu‐rich magnesioferrite) and skarn‐like silicate mineral assemblages. By analogy with experimental studies, we propose that a combination of these processes was responsible for extraction of metals from the basaltic wall rocks and deposition of Cu‐, Fe‐ and Cu‐Fe‐oxides and native gold.     

Relationship between metamorphism and ore formation at the Sukhoi Log gold deposit hosted in black slates from the data of U-Th-Pb isotopic SHRIMP-dating of accessory minerals

The formation conditions and age of the Sukhoi Log gold deposit are considered on the basis of new isotopic-geochemical data. The U-Pb isotopic study of zircon and monazite from high-grade ore and host black slates at the Sukhoi Log deposit was carried out with SIMS technique using a SHRIMP II instrument. Two generations of monazite are distinguished on the basis of optical and scanning electron microscopy, cathodoluminescence, and micro X-ray spectroscopy. Monazite I is characterized by black opaque porphyroblasts with microinclusions of minerals pertaining to metamorphic slates and structural attributes of pre- and synkinematic formation. Monazite II occurs only within the ore zone as transparent crystals practically free of inclusions and as rims around monazite I. The REE contents are widely variable in both generations. Porphyroblastic monazite I differs in low U and Th (0.01–0.7 wt % ThO₂) contents, whereas transparent monazite II contains up to 4 wt % ThO2. The average weighted U-Pb isotopic age of monazite I is 650 ± 8.1 Ma (MSWD = 1.6; n = 9) and marks the time of metamorphism or catagenesis. The U-Pb age estimates of synore monazite II cover the interval of 486 ± 18 to 439 ± 17 Ma. Zircons of several populations from 0.5 to 2.6 Ga in age are contained in the ore. Most detrital zircon grains have porous outer rims composed of zircon and less frequent xenotime with numerous inclusions of minerals derived from slates. The peaks of ²⁰⁶Pb/²³⁸U ages in the most abundant zircon populations fall on 570 and 630 Ma and correspond to the age of newly formed metamorphic mineral phases. The discordant isotopic ages indicate that the U-ThPb isotopic system of ancient detrital zircons was disturbed 470–440 Ma ago in agreement with isotopic age of monazite II and the Rb-Sr whole -rock isochron age of black slates (447 ± 6 Ma). The new data confirm the superimposed character of the gold-quartz-sulfide mineralization at the deposit. Black shales of the Khomolkho Formation of the Bodaibo Synclinorium were affected by metamorphism over a long period; the peaks of metamorphism and catagenesis are dated at 570 and 650–630 Ma. The high-temperature ore formation was probably related to a hidden granitic pluton emplaced 450–440 Ma ago, that is, 200 Ma later than the events of greenschist metamorphism. Hercynian granitoid magmatism (320–270 Ma) did not exert a substantial effect on the U-Th-Pb isotopic system in accessory minerals from the ore and could not have been a major source of ore-forming fluids.     

Trace-element study and age dating of zircon from chromitites of the Bushveld Complex (South Africa)

The layered Bushveld Complex hosts a number of chromitite layers, which were found to contain significant amounts of zircon grains compared with adjacent silicate rocks. Cathodoluminescent-dark, partially metamict cores and transparent rims of composite zircon grains were analyzed for trace elements with SIMS and LA-ICPMS techniques. The cores are enriched in REE, Y, Th and U and are characterized by distinctly flatter REE patterns in contrast to those of the rims and transparent homogenous crystals. Zircon from the different stratigraphic units has specific Th/U ratios, the highest of which (1.5–4) occurs in a Merensky Reef zircon core. The Ti content of Bushveld zircon ranges from 12 to 52 ppm correlating to a crystallization temperature range of 760–930 °C. The geochemical characteristics of the first zircon generation are consistent with its high-temperature crystallization as the first major U, Th and REE acceptor from a highly-evolved residue of the high-Mg basalt magma, whereas the rims and coreless crystals have crystallized from percolating intercumulus liquid of new influx of the same magma. U-Pb SHRIMP dating of zircon cores and rims does not reveal a distinguishable difference between their ages indicating the absence of inherited zircon. Concordia ages of 2,051?±?9 Ma (2σ, MSWD?=?0.1) and 2,056?±?5 Ma (2σ, MSWD?=?0.05) for zircons from the Merensky Reef and the Upper Platreef located equally near the top of the Critical Zone are in agreement with published ages for the Merensky Reef. Zircon from the deeper-seated Lower Group, Middle Group and Lower Platreef chromitites yields younger concordia ages that may reflect prolonged late-stage volatile activity.     

Gaseous transport and deposition of gold in magmatic fluid: evidence from the active Kudryavy volcano, Kurile Islands

The distribution of gold in high-temperature fumarole gases of the Kudryavy volcano (Kurile Islands) was measured for gas, gas condensate, natural fumarolic sublimates, and precipitates in silica tubes from vents with outlet temperatures ranging from 380 to 870°C. Gold abundance in condensates ranges from 0.3 to 2.4 ppb, which is significantly lower than the abundances of transition metals. Gold contents in zoned precipitates from silica tubes increase gradually with a decrease in temperature to a maximum of 8 ppm in the oxychloride zone at a temperature of approximately 300°C. Total Au content in moderate-temperature sulfide and oxychloride zones is mainly a result of Au inclusions in the abundant Fe–Cu and Zn sulfide minerals as determined by instrumental neutron activation analysis. Most Au occurs as a Cu–Au–Ag triple alloy. Single grains of native gold and binary Au–Ag alloys were also identified among sublimates, but aggregates and crystals of Cu–Au–Ag alloy were found in all fumarolic fields, both in silica tube precipitates and in natural fumarolic crusts. Although the Au triple alloy is homogeneous on the scale of microns and has a composition close to (Cu,Ni,Zn)₃(Au,Ag)₂, transmission electron microscopy (TEM) shows that these alloy solid solutions consist of monocrystal domains of Au–Ag, Au–Cu, and possibly Cu₂O. Gold occurs in oxide assemblages due to the decomposition of its halogenide complexes under high-temperature conditions (650–870°C). In lower temperature zones (<650°C), Au behavior is related to sulfur compounds whose evolution is strongly controlled by redox state. Other minerals that formed from gas transport and precipitation at Kudryavy volcano include garnet, aegirine, diopside, magnetite, anhydrite, molybdenite, multivalent molybdenum oxides (molybdite, tugarinovite, and ilsemannite), powellite, scheelite, wolframite, Na–K chlorides, pyrrhotite, wurtzite, greenockite, pyrite, galena, cubanite, rare native metals (including Fe, Cr, Mo, Sn, Ag, and Al), Cu–Zn–Fe–In sulfides, In-bearing Pb–Bi sulfosalts, cannizzarite, rheniite, cadmoindite, and kudriavite. Although most of these minerals are fine-grained, they are strongly idiomorphic with textures such as gas channels and lamellar, banded, skeletal, and dendrite-like crystals, characteristic of precipitation from a gas phase. The identified textures and mineral assemblages at Kudryavy volcano can be used to interpret geochemical origins of both ancient and modern ore deposits, particularly gold-rich porphyry and related epithermal systems.     

Khatyrka,a new CV3 find from the Koryak Mountains,Eastern Russia

A new meteorite find, named Khatyrka, was recovered from eastern Siberia as a result of a search for naturally occurring quasicrystals. The meteorite occurs as clastic grains within postglacial clay‐rich layers along the banks of a small stream in the Koryak Mountains, Chukotka Autonomous Okrug of far eastern Russia. Some of the grains are clearly chondritic and contain Type IA porphyritic olivine chondrules enclosed in matrices that have the characteristic platy olivine texture, matrix olivine composition, and mineralogy (olivine, pentlandite, nickel‐rich iron‐nickel metal, nepheline, and calcic pyroxene [diopside‐hedenbergite solid solution]) of oxidized‐subgroup CV3 chondrites. A few grains are fine‐grained spinel‐rich calcium‐aluminum‐rich inclusions with mineral oxygen isotopic compositions again typical of such objects in CV3 chondrites. The chondritic and CAI grains contain small fragments of metallic copper‐aluminum‐iron alloys that include the quasicrystalline phase icosahedrite. One grain is an achondritic intergrowth of Cu‐Al metal alloys and forsteritic olivine ± diopsidic pyroxene, both of which have meteoritic (CV3‐like) oxygen isotopic compositions. Finally, some grains consist almost entirely of metallic alloys of aluminum + copper ± iron. The Cu‐Al‐Fe metal alloys and the alloy‐bearing achondrite clast are interpreted to be an accretionary component of what otherwise is a fairly normal CV3 (oxidized) chondrite. This association of CV3 chondritic grains with metallic copper‐aluminum alloys makes Khatyrka a unique meteorite, perhaps best described as a complex CV3 (ox) breccia.     

Lead isotopic composition from data of high-precession MC-ICP-MS and sources of matter in the large-scale Sukhoi Log noble metal deposit,Russia

The lead isotopic composition of 33 sulfide samples from orebodies of the Sukhoi Log deposit was studied by high-precession MC-ICP-MS with a precision of ±0.02% (±2SD from 120 analyses of the SRM 981 standard sample). The deposit is located in the Bodaibo gold mining district in the northern Baikal-Patom Highland. Gold mineralization is hosted in Neoproterosoic black slates. Variations of lead isotope ratios of the Sukhoi Log sulfides are generally typical of Phanerozoic deposits and ore fields. They are significant for ²⁰⁶Pb/²⁰⁴Pb (17.903–18.674), moderate for ²⁰⁸Pb/²⁰⁴Pb (37.822–38.457), and relatively narrow for ²⁰⁷Pb/²⁰⁴Pb (15.555–15.679). In the Pb-Pb isotope diagrams, the data points of pyrite and galena constitute a linear trend. The points corresponding to pyrite from metasomatic ore occupy the left lower part of the trend. Galena from late gold-quartz veins shows more radiogenic Pb, and corresponding data points are located in the upper part of the trend. According to the Stacey-Kramers model, the end points of the trend, which is regarded as a mixing line, have μ₂ = 9.6 and μ₂ = 13.2 and model Pb-Pb ages 455 and 130 Ma, respectively. The isotope characteristics of ore lead, their relationships in pyrite and galena, and the mixing trend of Pb isotopic compositions are clearly tied to two Paleozoic stages in the formation of the Sukhoi Log deposit (447 ± 6 and 321 ± 14Ma) and testify to the leading role of crustal sources, which are suggested as being the Neoproterozoic black-shale terrigenous-carbonate rocks.