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LA-ICPMS U-Pb dating reveals cassiterite inheritance in the Yazov granite, Eastern Siberia: Implications for tin mineralization

U-Pb dating of cassiterite and zircon from the Yazov granite (Transbaikalia region, Eastern Siberia, Russia) and cassiterite from spatially associated tin mineralization in the Tuyukan ore district in the Tonod uplift was conducted using in situ laser ablation inductively coupled plasma mass spectrometry. These analyses allow comparison of isotopic systematics for both minerals, especially related to transport in granitic magma. These data are also useful for understanding possible genetic links between the granite and the tin mineralization. Most of the U-Pb zircon analyses define a 206 Pb/ 238 U age of 719 ± 15 Ma for the granite; in addition, several zircon cores define an inheritance age of 1839 ± 21 Ma. U-Pb data for 10 nearly concordant analyses of disseminated cassiterite from the same samples yield a 206 Pb/ 238 U age of 1838 ± 34 Ma. This is the first documented evidence of cassiterite inheritance in granitic magma. These data indicate the robust character of U-Pb isotope systematics in cassiterite, comparable to that in zircon. The presence of numerous inclusions of cassiterite in zircon from the Yazov granite (revealed by nanotomography) supports the interpretation of inherited cassiterite included during Neoproterozoic zircon crystallization. The data indicate that high tin concentrations in the Yazov granite are due to the incorporation of older cassiterite crystals from country rock, not coeval cassiterite crystallization. Cassiterite samples from two ore occurrences spatially associated with the Yazov granite yield Pb-Pb isochron ages of 1.86–1.82 Ga, indicating that tin mineralization occurred in the Paleoproterozoic, nearly 1 Ga before emplacement of the Yazov granite. Tin mineralization of the ore region is probably related to ~ 1.85 Ga Chuya-Kodar tin-bearing granitic rocks that host tin deposits. These results have broad implications for understanding how critical elements, such as tin, may become enriched in rare-metal granites and how they are related to regional to global geodynamic processes.

Siberia↗

Geology, mineralogy, and cassiterite geochronology of the Ayawilca Zn-Pb-Ag-In-Sn-Cu deposit, Pasco, Peru

The Ayawilca deposit in Pasco, Peru, represents the most significant recent base-metal discovery in the central Andes and one of the largest undeveloped In resources globally. As of 2018, it hosts an 11.7 Mt indicated resource grading 6.9% Zn, 0.16% Pb, 15 g/t Ag, and 84 g/t In, an additional 45.0 Mt inferred resource grading 5.6% Zn, 0.23% Pb, 17 g/t Ag, and 67 g/t In, and a separate Sn-Cu-Ag inferred resource of 14.5 Mt grading 0.63% Sn, 0.21% Cu, and 18 g/t Ag. Newly obtained U–Pb dates for cassiterite by LA-ICP-MS (22.77 ± 0.41 and 23.05 ± 2.06 Ma) assign the Ayawilca deposit to the Miocene polymetallic belt of central Peru. The polymetallic mineralization occurs as up to 70-m-thick mantos hosted by carbonate rocks of the Late Triassic to Early Jurassic Pucará Group, and subordinately, as steeply dipping veins hosted by rocks of the Pucará Group and overlying Cretaceous sandstones-siltstones of the Goyllarisquizga Group. Relicts of a distal retrograde magnesian skarn and cassiterite (stage pre-A) were identified in the deepest mantos. The volumetrically most important mineralization at Ayawilca comprises a low-sulfidation assemblage (stage A) with quartz, pyrrhotite, arsenopyrite, chalcopyrite, Fe-rich sphalerite, and traces of stannite and herzenbergite. Stage A sphalerite records progressive Fe depletion, from 33 to 10 mol% FeS, which is compatible with the observed transition from low- to a subsequent intermediate-sulfidation stage (B) marked by the crystallization of abundant pyrite and marcasite. Finally, during a later intermediate-sulfidation stage (C) sphalerite (up to 11 mol% FeS), galena, native bismuth, Cu-Pb-Ag sulfosalts, siderite, Mn-Fe carbonates, kaolinite, dickite, and sericite were deposited. This paragenetic evolution shows striking similarities with that at the Cerro de Pasco Cordilleran-type polymetallic deposit, even if at Ayawilca stage C did not reach high-sulfidation conditions. The occurrence of an early retrograde skarn assemblage suggests that the manto bodies at Ayawilca formed at the transition between distal skarn and skarn-free (Cordilleran-type) carbonate-replacement mineralization. Mineral assemblages define a T- f S 2 evolutionary path close to the pyrrhotite-pyrite boundary. Buffering of hydrothermal fluids by underlying Devonian carbonaceous phyllites of the Excelsior Group imposed highly reduced conditions during stage A mineralization (log f O 2 < − 30 atm). The low f O 2 favored efficient Sn mobility during stages pre-A and A, in contrast to other known ore deposits in the polymetallic belt of central Peru, in which the occurrence of Sn minerals is minor. Subsequent cooling, progressive sealing of vein walls, and decreasing buffering potential of the host rocks promoted the shift from low- (stage A) to intermediate-sulfidation (stages B and C) states. LA-ICP-MS analyses reveal significant In contents in Fe-rich sphalerite (up to 1.7 wt%), stannite (up to 1908 ppm), and chalcopyrite (up to 1185 ppm). The highest In content was found in stage A sphalerite that precipitated along with chalcopyrite and stannite, thus pointing to the early, low-sulfidation assemblage as prospective for this high-tech metal in similar mineral systems. Indium was likely incorporated into the sphalerite crystal lattice via Cu + + In 3+ ↔ 2 Zn 2+ and (Sn, Ge) 4+ + (Ga, In) 3+ + (Cu + Ag) + ↔ 4 Zn 2+ coupled substitutions. Indium incorporation mechanisms into the stannite and chalcopyrite crystal lattices remain unclear.

Pasco↗

Vein-type gold formation during late extensional collapse of the Eastern Desert, Egypt: the Gidami deposit

Orogenic gold deposits, though construed to focused fluid flow during orogenesis, commonly post-date the main accretionary events. Several lines of evidence indicate that orogenic gold formation in the Arabian–Nubian Shield continued through the orogen collapse stage and associated rapid exhumation and thermal re-equilibration. The Gidami gold deposit in the Eastern Desert of Egypt is associated with post-foliation, brittle-ductile shear zones that deformed a weakly foliated tonalite-trondhjemite massif dated as ~ 704 Ma (U–Pb zircon age). Gold-sulfide quartz veins exhibit textural features indicative of repeated mylonitization, recrystallization, and muscovite crystallization. New 40 Ar/ 39 Ar ages of muscovite flakes from the auriferous quartz veins and from the altered wallrock overlap within analytical uncertainty at ~ 583 Ma, which corresponds to the climax of extension-related wrenching and rapid exhumation in the region (~ 596 to 582 Ma). Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data coupled with microtextural characteristics suggest that early formed pyrite generations experienced substantial fluid-mediated recrystallization, and that a set of metals was remobilized by later fluids. A late generation of fibrous pyrite, ubiquitous in microfractures, deposited while the veins re-opened and deformed. The occurrence of free gold particles along with a late-paragenetic assemblage of galena-sphalerite-chalcopyrite(± hessite ± cervelleite) was related to influx of low salinity, metalliferous H 2 O-NaCl-CO 2 -CH 4 fluids as indicated by the fluid inclusion laser Raman spectroscopy and microthermometry results. Au-mobilization and redeposition at T ≤ 350 °C and P ~ 1 to 1.7 kbar, triggered by intermittent fluid pluses and thermal re-equilibration, were most likely stimulated by extensional structures and within-plate magmatism. Coincident province- and deposit-scale pressure–temperature-time data highlight the pivotal role of the orogenic collapse tectonics in gold endowment in the Central Eastern Desert’s crust.

Gidami deposit↗

Zinc on the edge—Isotopic and geophysical evidence that cratonic edges control world-class shale-hosted zinc-lead deposits

The North Australian Zinc Belt is the largest zinc-lead province in the world, containing three of the ten largest known individual deposits (HYC, Hilton-George Fisher, and Mount Isa). The Northern Cordillera in North America is the second largest zinc-lead province, containing a further two of the world’s top ten deposits (Red Dog and Howards Pass). Despite this world-class endowment, exploration in both mineral provinces during the past 2 decades has not been particularly successful, yielding only two significant discoveries (Teena, Australia, and Boundary, Canada). One of the most important aspects of exploration is to choose mineral provinces and districts within geological belts that have the greatest potential for discovery. Here, we present results from these two zinc belts that highlight previously unused datasets for area selection and targeting. Lead isotope mapping using analyses of mineralized material has identified gradients in μ ( 238 U/ 204 Pb) that coincide closely with many major deposits. Locations of these deposits also coincide with a gradient in the depth of the lithosphere-asthenosphere boundary determined from calibrated surface wave tomography models converted to temperature. Furthermore, gradients in upward-continued gravity anomalies and a step in Moho depth correspond to a pre-existing major crustal boundary in both zinc belts. A spatial association of deposits with a linear mid- to lower-crustal resistivity anomaly from magnetotelluric data is also observed in the North Australian Zinc Belt. The change from thicker to thinner lithosphere is interpreted to localize prospective basins for zinc-lead mineralization and to control the gradient in lead isotope and geophysical data. These data, when combined with data indicative of paleoenvironment and changes in plate motion at the time of mineralization, provide new exploration criteria that can be used to identify prospective mineralized basins and define the most favorable parts of these basins.

Mineralium Deposita↗

Insights into the metamorphic history and origin of flake graphite mineralization at the Graphite Creek graphite deposit, Seward Peninsula, Alaska, USA

Graphite Creek is an unusual flake graphite deposit located on the Seward Peninsula, Alaska, USA. We present field observations, uranium-lead (U–Pb) monazite and titanite geochronology, carbon (C) and sulfur (S) stable isotope geochemistry, and graphite Raman spectroscopy data from this deposit that support a new model of flake graphite ore genesis in high-grade metamorphic environments. The Graphite Creek deposit is within the second sillimanite metamorphic zone of the Kigluaik Mountains gneiss dome. Flake graphite, hosted in sillimanite-gneiss and quartz-biotite paragneiss, occurs as disseminations and in sets of very high grade (up to 50 wt.% graphite), semi-massive to massive graphite lenses 0.2 to 1 m wide containing quartz, sillimanite, inclusions of garnet porphyroblasts, K-feldspar, and tourmaline. Restitic garnet, sillimanite, graphite, and biotite accumulations indicate a high degree of anatexis and melt loss. Strong yttrium depletion in monazite, high europium ratios (Eu/Eu*), and excursions of high strontium and thorium concentrations are consistent with biotite dehydration melting. Monazite and titanite U–Pb ages record peak metamorphism from ~ 97 to 92 million years ago (Ma) and a retrograde event at ~ 85 Ma. Raman spectroscopy confirms the presence of carbonaceous material and highly ordered, crystalline graphite. Graphite δ 13 C VPDB values of − 30 to − 12‰ and pyrrhotite δ 34 S VCDT values of − 14 to 10‰ are consistent with derivation from organic carbon and sulfur in sedimentary rocks, respectively. These data collectively suggest that formation of massive graphite lenses occurred approximately synchronously with high-temperature metamorphism and anatexis of a highly carbonaceous pelitic protolith. Melt extraction and fluid release associated with anatexis were likely crucial for concentrating graphite. High-temperature, graphitic migmatite sequences within high-strain shear zones may be favorable for the occurrence of high-grade flake graphite deposits.

Alaska↗

Hydrothermal monazite and xenotime chemistry as genetic discriminators for intrusion-related and orogenic gold deposits: Implications for an orogenic origin of the Pogo gold deposit, Alaska

Attempts to geochemically distinguish between metamorphic-hydrothermal systems that form orogenic gold deposits and both reduced and oxidized magmatic-hydrothermal systems using isotopes or metal associations have proven ambiguous, particularly for orogenic gold and reduced intrusion-related gold systems. The absence of conclusive geochemical discriminators and the overlap in geologic characteristics have led to gold deposit models being potentially incorrectly applied, which in turn negatively affect regional mineral exploration and mine planning. In this study, in situ electron microprobe geochemical analyses of hydrothermal monazite and xenotime crystals associated with different types of gold-bearing deposits are shown to be effective geochemical discriminators. There are notable differences in mineral chemistry such as rare earth element (REE) profiles, total light REE, Dy, Er, Pr, Y, Nd/Sm, and La/Sm that distinguish monazite precipitated from metamorphic-hydrothermal fluids that form orogenic gold deposits and those precipitated from magmatic-hydrothermal fluids that form both porphyry Cu-Mo-Au and reduced intrusion-related gold deposits. Notable differences in overall xenotime abundances and concentrations of heavy REEs, Ca, and Sc are distinctive between the different deposit classes for xenotime. The origin of the controversially classified Pogo gold deposit, Tintina gold province, Alaska, which has been characterized as both a reduced intrusion-related and an orogenic gold deposit, is tested based upon the noted chemical differences associated with these hydrothermal phosphates. The findings of this study have implications for exploration and mine development in the Tintina gold province and other areas that contain deposits that are controversially classified as either orogenic or as magmatic-hydrothermal gold deposits.

Alaska↗

Polyphase stratabound scheelite-ferberite mineralization at Mallnock, Eastern Alps, Austria

A peculiar type of stratabound tungsten mineralization in metacarbonate rocks was discovered and explored at Mallnock (Austria) during the late 1980s. It is the only tungsten occurrence in the Eastern Alps in which scheelite is associated with wolframite (96 mol% ferberite). The tungsten prospect is located in the Austroalpine Drauzug-Gurktal Nappe System recording polyphase low-grade regional metamorphism. Raman spectroscopy of carbonaceous material yield maximum metamorphic temperatures of 296 ± 27 °C and 258 ± 27 °C, which are assigned to Variscan and Eoalpine metamorphism, respectively. Scheelite and ferberite occur as polyphase stockwork-like mineralization in Fe-rich magnesite in the northern ore zone (Mallnock North), whereas in the western ore zone (Mallnock West), scheelite-quartz veinlets are exclusively hosted in dolomitic marbles. LA-ICP-MS analyses of scheelite and ferberite yield low contents of Mo, Nb, Ta, and rare earth elements, but high contents of Na and Sr. Uranium is particularly high in scheelite (up to 200 µg/g) and makes this mineral a suitable target for U–Pb dating. In situ U–Pb dating of scheelite yielded an early Permian age (294 ± 8 Ma) for Mallnock West and a Middle Triassic age (239 ± 3 Ma) for Mallnock North. A monzodioritic dike close to Mallnock yielded a U–Pb apatite date of 282 ± 9 Ma and supports the polyphase formation of this mineralization. The U–Pb scheelite ages indicate that a model for tungsten metallogeny in the Eastern Alps must also consider remobilization of tungsten by metamorphic fluids. In the Alps, the Permian to Triassic period (ca. 290–225 Ma) is characterized by an overall extensional geodynamic setting related to the breakup of Pangea. Lithospheric thinning caused higher heat flow, low-P metamorphism, and anatexis in the lower crust, which led to enhanced crustal fluid flow in the upper crust. These processes were not only responsible for the formation of metasomatic hydrothermal magnesite and siderite deposits in the Eastern Alps but also for this unique magnesite-ferberite-scheelite mineralization at Mallnock.

Mount Mallock↗

A time-space model of graphite mineral systems

Increasing demand for graphite in energy storage systems warrants review of graphite ore genesis in a mineral systems framework. Orogenic graphite encompasses the metamorphic and orogenic mineral systems that produce flake graphite and hydrothermal vein (lump and chip) graphite deposits, respectively. A common feature of orogenic graphite deposits is an association with upper amphibolite- to granulite-facies metasedimentary rocks in continent-continent or continent-island arc collisional orogens. Orogenic flake graphite deposits form primarily through graphitization of organic carbon during regional metamorphism, but strain localization and partial melting of pelitic protoliths are likely important processes for graphite grade and quality enrichment. Orogenic vein graphite deposits precipitate from hydrothermal fluids, possibly derived from metamorphism or anatexis at depth. Decarbonation reactions in mixed calcareous-carbonaceous metasedimentary sequences are the most likely carbon sources for the veins. In contrast, intrusion-related graphite includes magmatic-hydrothermal and metamorphic mineral systems that form primarily in continental arc settings via the interaction of magmas with carbonaceous sedimentary packages. Magmatic-hydrothermal flake graphite deposits are hosted in plutonic and volcanic rocks, and result from the exsolution of CO 2 -CH 4 -rich fluids from melts contaminated by such packages. Contact metamorphism of carbonaceous sedimentary rocks by plutons produces some microcrystalline (amorphous) graphite deposits, including many in China. Compilation of geologic data from known graphite deposits globally suggests that pulses of carbon deposition in the Paleoproterozoic, Mesoproterozoic, and Neoproterozoic provided source carbon material. Subsequent supercontinent orogenesis at ca. 2,100 to 1,700 Ma (Columbia), ca. 1,300 to 1,000 Ma (Rodinia), and ca. 650 to 500 Ma (Gondwana) resulted in the genesis of orogenic flake and vein graphite deposits, where favorable geologic components overlapped with organic ± carbonate carbon-rich strata. Cryogenian deposition of graphite protoliths and Cryogenian – Cambrian metamorphic mineralization account for nearly 75% of all known resources globally and coincide with profound carbon isotope excursions and climate variability, implying a link with the global carbon budget. Comparatively few graphite deposits are associated with Pangea-forming orogens, attributed to less exhumation and/or denudation. High-temperature metasedimentary belts containing organic carbon-rich protoliths are most favorable for hosting orogenic flake graphite deposits, whereas sequences that also contain carbonate protoliths are favorable for orogenic graphite veins. Continent-scale orogenic belts may host both deposit types along with vanadium deposits. Use of a time-space mineral systems framework for graphite deposits can improve exploration models needed to ensure future supply of this critical mineral and provide insights into Earth’s long-term carbon cycle.

Mineralium Deposita↗

Noble and base metal distribution and processes affecting ore tenors in the disrupted lower stratigraphy of the Stillwater Complex, USA

Exploration continues for contact-style Ni-Cu sulfide and chromitite-associated PGE mineralization in ultramafic rocks of the Stillwater Complex. At the Iron and Chrome Mountain areas, massive sulfides occur along the complex’s footwall contact and anomalous concentrations of PGE+Au are associated with the three lowermost chromitite seams. Southeast of Chrome Mountain, magmatic layering is highly disrupted by the presence of faults, magmatic breccias, serpentinized discordant dunites, pyroxenite pegmatoids, and disaggregated chromitite seams. The bulk rock chemistry, sulfide chemistry, and noble metal mineralogy of samples from this area were examined to determine the deportment of PGE and processes that led to enrichments in PGE, Au, Cu, Co and Ni. Results show that a sulfide liquid was the principal collector of PGE. If sulfide liquid was initially deposited with chromite, it was disaggregated or redistributed by subsequent melt or fluid infiltration, which may have resulted in the offset of peak PGE(+Cu, Ni) from peak Cr 2 O 3 concentrations, and upgraded PGE tenors. Upon cooling, PGE exsolved from sulfides to form discrete bismuth tellurides, arsenides, arsenic sulfides, antimonides, and alloys, commonly along the margins of sulfide globules. Calculated metal tenors are highest in the disseminated sulfides southwest of Chrome Mountain, whereas massive and net-textured sulfides near the Iron Mountain-Camp zone represent monosulfide solid solution cumulates. At progressively shallower levels, higher metal tenors combined with lower S/Se ratios are consistent with increasing R-factors from 100 to 100,000. Serpentinization and talc-tremolite alteration resulted in S loss through partial replacement of sulfides by secondary silicate+carbonate+magnetite+sulfide assemblages, further upgrading Ni-Cu-PGE tenors. The present work shows that processes responsible for the disruption of magmatic layering and post-magmatic fluid alteration along the intrusion’s lower contact led to noble and base metal enrichments.

Montana↗

Microtextural characteristics of adularia in banded quartz veins from the Midas low-sulfidation epithermal deposit, Nevada

High-grade ores at the Miocene Midas low-sulfidation epithermal deposit in northern Nevada are confined to crustiform quartz veins containing abundant adularia. Micro-X-ray fluorescence elemental mapping reveals that adularia is a common gangue mineral occurring in colloform bands, bands showing bladed textures, and bands with dendritic terminations. The adularia aggregates have delicate shapes and are comprised of stacked, submillimeter crystals hosted by fine-grained quartz. The textural evidence suggests that the adularia aggregates originally formed within a gel-like, noncrystalline silica matrix, which subsequently transformed into quartz. This indicates that the adularia did not precipitate in open space along the vein walls. Correlative microscopy, involving scanning electron microscopy-based automated mineralogy and optical petrography, demonstrates that bands containing abundant adularia are not the primary host to ore minerals. The ore minerals occur in different bands within the crustiform veins, implying that adularia and ore mineral precipitation did not always occur simultaneously. It is hypothesized here that fluid flow at Midas involved intermittent short-lived events of fluid flashing, causing rapid solute supersaturation in the liquid. During each flashing event, different amounts of vapor were produced along a given vein. Compositional differences between adjacent bands in the crustiform quartz veins may, therefore, be linked to variations in the amount of vapor formed during each flash event.

Nevada↗

Insights into Mountain Pass carbonatite formation from in-situ sulfur isotopes and geochemistry of sulfate and sulfide minerals

The Mountain Pass carbonatite stock hosts a world-class rare earth element deposit and may be classified as a carbonate-sulfate igneous rock, as it contains on average > 50 volume percent carbonate minerals and 20 to 30 volume percent sulfate minerals. The sulfates range in composition from barite to celestine and locally occur with sparse sulfide minerals. We investigate the origin of sulfur enrichment and the occurrence of sulfur-bearing minerals in the Mountain Pass carbonatite with in-situ sulfur isotope and mineral chemistry. Barite cores with δ 34 S of 1 to 3‰ do not coexist with sulfides, whereas celestine rims with δ 34 S of > 3‰ are associated with sulfides with δ 34 S < -10‰. We propose a model in which sulfur-bearing sediments were subducted during episodes of plate convergence in the Mojave Province that preceded Mountain Pass magmatism. Metasomatism of the overlying mantle by melts derived from the subducted sediments generated an unusually carbon- and sulfur-rich source to yield carbonatite magmas. Sulfur from primary carbonatite magmas and ~ 1 to 7% sulfur from subducted sediment melts yielded a slightly enriched δ 34 S composition (relative to depleted mantle δ 34 S of -1‰) for early crystallizing barite. Celestine rims on magmatic barite cores formed at low, hydrothermal temperatures (< 350 °C) based on S isotope thermometry for equilibrium celestine-galena and celestine-pyrite pairs. The sparse sulfides in the carbonatite stock are not in equilibrium with the primary barite cores and therefore do not permit S isotope thermometry estimates of magmatic temperatures. The S/Se ratios of sulfide minerals (> 3,400) typically exceed primitive mantle values (S/Se of 3,340), also consistent with their derivation from hydrothermal fluids. Trace occurrences of sulfide and sulfate minerals in alkaline silicate stocks related to the carbonatite stock have similar δ 34 S compositions and yield similarly low formation temperatures, suggesting regionally extensive and chemically similar sulfur-bearing hydrothermal fluids that imparted lithologically diverse rocks with a consistent sulfur isotope fingerprint.

California, Nevada↗

The use of fluorite geochemistry and machine learning to identify critical mineral systems

Fluorite (CaF 2 ) is a potential pathfinder to critical mineral and rare earth element (REE) deposits but its application has been limited to a narrow range of mineralization types. I show that fluorite is a robust recorder of mineralization fertility by applying statistical and machine-learning methods to a new global fluorite geochemical database. Distinct median rare earth and trace element patterns are observed among deposit types and genetic environments. Fluorite associated with carbonatites and REE deposits are relatively enriched in Sr and have minimal Eu anomalies. These characteristics define new bivariate discrimination diagrams that correctly identify 78% of carbonatite-related fluorite and 88% of fluorite from REE deposits. Random forest classifiers were developed for a wide range of mineralization types and genetic settings. Trained solely on rare earth element patterns, these models achieve accuracies of 77–79%. Higher classification accuracies (up to 88–96%) are obtained when including elements such as Sr, highlighting the significance of trace elements for optimal fluorite classification. The recognition of diagnostic fluorite compositional fingerprints, particularly in REE-fertile systems, underscores its potential as a pathfinder and indicator for critical mineral exploration in F-bearing environments.

Mineralium Deposita↗

Re-Os ages for Archean molybdenite and pyrite, Kuittila-Kivisuo, Finland and Proterozoic molybdenite, Kabeliai, Lithuania: Testing the chronometer in a metamorphic and metasomatic setting

Seven 18 7Re- 18 7Os ages were determined for molybdenite and pyrite samples from two well-dated Precambrian intrusions in Fennoscandia to examine the sustainability of the Re-Os chronometer in a metamorphic and metasomatic setting. Using a new 187Re decay constant (1.666 x 10 -1 1y -1 ) with a much improved uncertainty (±0.31%), we determined replicate Re-Os ages for molybdenite and pyrite from the Kuittila and Kivisuo prospects in easternmost Finland and for molybdenite from the Kabeliai prospect in southernmost Lithuania. These two localities contain some of the oldest and youngest plutonic activity in Fennoscandia and are associated with newly discovered economic Au mineralization (Ilomantsi, Finland) and a Cu-Mo prospect (Kabeliai, Lithuania). Two Re-Os ages for veinhosted Kabeliai molybdenite average 1486 ± 5 Ma, in excellent agreement with a 1505 ± 11 Ma U-Pb zircon age for the hosting Kabeliai granite pluton. The slightly younger age suggests the introduction of Cu-Mo mineralization by a later phase of the Kabeliai magmatic system. Mean Re-Os ages of 2778 ± 8 Ma and 2781 ± 8 Ma for Kuittila and Kivisuo molybdenites, respectively, are in reasonable agreement with a 2753 ± 5 Ma weighted mean U-Pb zircon age for hosting Kuittila tonalite. These Re-Os ages agree well with less precise ages of 2789 ± 290 Ma for a Rb-Sr whole-rock isochron and 2771 ± 75 Ma for the average of six Sm-Nd T(DM) model ages for Kuittila tonalite. Three Re-Os analyses of a single pyrite mineral separate, from the same sample of Kuittila pluton that yielded a molybdenite separate, provide individual model ages of 2710 ± 27, 2777 ± 28, and 2830 ± 28 Ma (Re = 17.4, 12.1, and 8.4 ppb, respectively), with a mean value of 2770 ± 120 Ma in agreement with the Kuittila molybdenite age. The Re and 187 Os abundances in these three pyrite splits are highly correlated (r = 0.9994), and provide a 187Re-187Os isochron age of 2607 ± 47 Ma with an intercept of 21 ppt 187Os (MSWD = 1.1). It appears that the Re-Os isotopic system in pyrite has been reset on the millimeter scale and that the 21 ppt 187Os intercept reflects the in situ decay of 187Re during the ~160 to 170 m.y. interval from ~2778 Ma (time of molybdenite ± pyrite deposition) to ~2607 Ma (time of pyrite resetting). When the Re-Os data for molybdenites from the nearby Kivisuo prospect are plotted together with the Kuittila molybdenite and pyrite data, a well-constrained five-point isochron with an age of 2780 ± 8 Ma and a 187Os intercept (-2.4 ± 3.8 ppt) of essentially zero results (MSWD = 1.5). We suggest that the pyrite isochron age records a regional metamorphic and/or hydrothermal event, possibly the time of Au mineralization. A proposed Re-Os age of ~2607 Ma for Au mineralization is in good agreement with radiometric ages by other methods that address the timing of Archean Au mineralization in deposits worldwide (so-called 'late Au model'). Molybdenite, in contrast, provides a robust Re-Os chronometer, retaining its original formation age of ~2780 Ma, despite subsequent metamorphic disturbances in Archean and Proterozoic time.

Mineralium Deposita↗

Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah

Uranium deposits containing molybdenum and fluorite occur in the Central Mining Area, near Marysvale, Utah, and formed in an epithermal vein system that is part of a volcanic/hypabyssal complex. They represent a known, but uncommon, type of deposit; relative to other commonly described volcanic-related uranium deposits, they are young, well-exposed and well-documented. Hydrothermal uranium-bearing quartz and fluorite veins are exposed over a 300 m vertical range in the mines. Molybdenum, as jordisite (amorphous MoS 2 ), together with fluorite and pyrite, increase with depth, and uranium decreases with depth. The veins cut 23-Ma quartz monzonite, 20-Ma granite, and 19-Ma rhyolite ash-flow tuff. The veins formed at 19-18 Ma in a 1 km 2 area, above a cupola of a composite, recurrent, magma chamber at least 24 × 5 km across that fed a sequence of 21- to 14-Ma hypabyssal granitic stocks, rhyolite lava flows, ash-flow tuffs, and volcanic domes. Formation of the Central Mining Area began when the intrusion of a rhyolite stock, and related molybdenite-bearing, uranium-rich, glassy rhyolite dikes, lifted the fractured roof above the stock. A breccia pipe formed and relieved magmatic pressures, and as blocks of the fractured roof began to settle back in place, flat-lying, concave-downward, “pull-apart” fractures were formed. Uranium-bearing, quartz and fluorite veins were deposited by a shallow hydrothermal system in the disarticulated carapace. The veins, which filled open spaces along the high-angle fault zones and flat-lying fractures, were deposited within 115 m of the ground surface above the concealed rhyolite stock. Hydrothermal fluids with temperatures near 200 °C, 18 O H2O ∼−1.5, D H2O ∼−130, log f O 2 about −47 to −50, and pH about 6 to 7, permeated the fractured rocks; these fluids were rich in fluorine, molybdenum, potassium, and hydrogen sulfide, and contained uranium as fluoride complexes. The hydrothermal fluids reacted with the wallrock resulting in precipitation of uranium minerals. At the deepest exposed levels, wallrocks were altered to sericite; and uraninite, coffinite, jordisite, fluorite, molybdenite, quartz, and pyrite were deposited in the veins. The fluids were progressively oxidized and cooled at higher levels in the system by boiling and degassing; iron-bearing minerals in wall rocks were oxidized to hematite, and quartz, fluorite, minor siderite, and uraninite were deposited in the veins. Near the ground surface, the fluids were acidified by condensation of volatiles and oxidation of hydrogen sulfide in near-surface, steam-heated, ground waters; wall rocks were altered to kaolinite, and quartz, fluorite, and uraninite were deposited in veins. Secondary uranium minerals, hematite, and gypsum formed during supergene alteration later in the Cenozoic when the upper part of the mineralized system was exposed by erosion.

Utah↗

Sulfur and lead isotope geochemistry of hypogene mineralization at the Barite Hill Gold Deposit, Carolina Slate Belt, southeastern United States: A window into and through regional metamorphism

The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110&thinsp;metric&thinsp;tons of gold over the past 10&thinsp;years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite&ndash;barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The &delta; 34 S values of massive barite cluster tightly between 25.0 and 28.0&permil;, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The &delta; 34 S values of massive sulfide range from 1.0 to 5.3&permil; and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, &delta; 34 S values for finer-grained, intergrown pyrite (5.1&ndash;6.8&permil;) and barite (21.0&ndash;23.9&permil;) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite&ndash;pyrite pairs (&Delta;=15.9&ndash;17.1&permil;) range from 332&ndash;355&thinsp;&deg;C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for 206 Pb/ 204 Pb from 18.005&ndash;18.294, for 207 Pb/ 204 Pb from 15.567&ndash;15.645, and for 208 Pb/ 204 Pb from 37.555&ndash;38.015. The data indicate derivation of the ore leads from the country rocks, which themselves show evidence for contributions from relatively unradiogenic, mantle-like lead, and more evolved or crustal lead. Geological relationships, and stable and radiogenic isotopic data, suggest that the Barite Hill gold deposit formed on the Late Proterozoic seafloor through exhalative hydrothermal processes similar to those that were responsible for the massive sulfide deposits of the Kuroko district, Japan. On the basis of similarities with other gold-rich massive sulfide deposits and modern seafloor hydrothermal systems, the gold at Barite Hill was probably introduced as an integral part of the formation of the massive sulfide deposit.

Georgia, North Carolina, South Carolina, Virginia↗

Major brazilian gold deposits - 1982 to 1999

Brazil has been a major but intermittent producer of gold since its discovery in 1500. Brazil led the world in gold production during the 18th and early 19th centuries. From the late 19th century to the late 20th century, total mining company and garimpeiro production was small and relatively constant at about 5 to 8 t/year. The discovery of alluvial deposits in the Amazon by garimpeiros in the 1970s and the opening of eight mines by mining companies from 1983 to 1990 fueled a major boom in Brazil's gold production, exceeding 100 t/year in 1988 and 1989. However, garimpeiro alluvial production decreased 'rapidly in the 1990s, to about 10 t/year by 1999. Company production increased about tenfold from about 4 t/year in 1982 to 40 t in 1992. Production from 1992 to the present remained relatively stable, even though several mines were closed or were in the process of closing and no new major mines were put into production during that period. Based on their production history from 1982-1999, 17 gold mines are ranked as major (> 20 t) and minor (3-8 t) mines. From 1982-1999, deposits hosted in Archean rocks produced 66% of the gold in Brazil, whereas deposits in Paleoproterozoic and Neoproterozoic rocks accounted for 19% and 15%, respectively. Deposits in metamorphosed sedimentary rocks, especially carbonate-rich rocks and carbonate iron-formation, yielded the great bulk of the gold. Deposits in igneous rocks were of much less importance. The Archean and Paleoproterozoic terranes of Brazil largely lack base-metal-rich volcanogenic massive sulfide deposits, porphyry deposits, and polymetallic veins and sedimentary exhalative deposits. An exception to this is in the Caraja??s Mineral Province.

Mineralium Deposita↗

Carbon dioxide in magmas and implications for hydrothermal systems

This review focuses on the solubility, origin, abundance, and degassing of carbon dioxide (CO2) in magma-hydrothermal systems, with applications for those workers interested in intrusion-related deposits of gold and other metals. The solubility of CO2 increases with pressure and magma alkalinity. Its solubility is low relative to that of H2O, so that fluids exsolved deep in the crust tend to have high CO2/H2O compared with fluids evolved closer to the surface. Similarly, CO2/H2O will typically decrease during progressive decompression- or crystallization-induced degassing. The temperature dependence of solubility is a function of the speciation of CO2, which dissolves in molecular form in rhyolites (retrograde temperature solubility), but exists as dissolved carbonate groups in basalts (prograde). Magnesite and dolomite are stable under a relatively wide range of mantle conditions, but melt just above the solidus, thereby contributing CO2 to mantle magmas. Graphite, diamond, and a free CO2-bearing fluid may be the primary carbon-bearing phases in other mantle source regions. Growing evidence suggests that most CO2 is contributed to arc magmas via recycling of subducted oceanic crust and its overlying sediment blanket. Additional carbon can be added to magmas during magma-wallrock interactions in the crust. Studies of fluid and melt inclusions from intrusive and extrusive igneous rocks yield ample evidence that many magmas are vapor saturated as deep as the mid crust (10-15 km) and that CO2 is an appreciable part of the exsolved vapor. Such is the case in both basaltic and some silicic magmas. Under most conditions, the presence of a CO2-bearing vapor does not hinder, and in fact may promote, the ascent and eruption of the host magma. Carbonic fluids are poorly miscible with aqueous fluids, particularly at high temperature and low pressure, so that the presence of CO2 can induce immiscibility both within the magmatic volatile phase and in hydrothermal systems. Because some metals, including gold, can be more volatile in vapor phases than coexisting liquids, the presence of CO2 may indirectly aid the process of metallogenesis by inducing phase separation.

Mineralium Deposita↗

Mississippi Valley-type lead-zinc deposits through geological time: Implications from recent age-dating research

Remarkable advances in age dating Mississippi Valley-type (MVT) lead-zinc deposits provide a new opportunity to understand how and where these deposits form in the Earth's crust. These dates are summarized and examined in a framework of global tectonics, paleogeography, fluid migration, and paleoclimate. Nineteen districts have been dated by paleomagnetic and/or radiometric methods. Of the districts that have both paleomagnetic and radiometric dates, only the Pine Point and East Tennessee districts have significant disagreements. This broad agreement between paleomagnetic and radiometric dates provides added confidence in the dating techniques used. The new dates confirm the direct connection between the genesis of MVT lead-zinc ores with global-scale tectonic events. The dates show that MVT deposits formed mainly during large contractional tectonic events at restricted times in the history of the Earth. Only the deposits in the Lennard Shelf of Australia and Nanisivik in Canada have dates that correspond to extensional tectonic events. The most important period for MVT genesis was the Devonian to Permian time, which corresponds to a series of intense tectonic events during the assimilation of Pangea. The second most important period for MVT genesis was Cretaceous to Tertiary time when microplate assimilation affected the western margin of North America and Africa-Eurasia. There is a notable paucity of MVT lead-zinc ore formation following the breakup of Rodinia and Pangea. Of the five MVT deposits hosted in Proterozoic rocks, only the Nanisivik deposit has been dated as Proterozoic. The contrast in abundance between SEDEX and MVT lead-zinc deposits in the Proterozoic questions the frequently suggested notion that the two types of ores share similar genetic paths. The ages of MVT deposits, when viewed with respect to the orogenic cycle in the adjacent orogen suggest that no single hydrologic model can be universally applied to the migration of the ore fluids. However, topographically driven models best explain most MVT districts. The migration of MVT ore fluids is not a natural consequence of basin evolution; rather, MVT districts formed mainly where platform carbonates had some hydrological connection to orogenic belts. There may be a connection between paleoclimate and the formation of some MVT deposits. This possible relationship is suggested by the dominance of evaporated seawater in fluid inclusions in MVT ores, by hydrological considerations that include the need for multiple-basin volumes of ore fluid to form most MVT districts, and the need for adequate precipitation to provide sufficient topographic head for topographically-driven fluid migration. Paleoclimatic conditions that lead to formation of evaporite conditions but yet have adequate precipitation to form large hydrological systems are most commonly present in low latitudes. For the MVT deposits and districts that have been dated, more than 75% of the combined metal produced are from deposits that have dates that correspond to assembly of Pangea in Devonian through Permian time. The exceptional endowment of Pangea and especially, North America with MVT lead-zinc deposits may be explained by the following: (1) Laurentia, which formed the core of North America, stayed in low latitudes during the Paleozoic, which allowed the development of vast carbonate platforms; (2) intense orogenic activity during the assembly of Pangea created ground preparation for many MVT districts through far-field deformation of the craton; (3) uplifted orogenic belts along Pangean suture zones established large-scale migration of basin fluids; and (4) the location of Pangea in low latitudes with paleoclimates with high evaporation rates led to the formation of brines by the evaporation of seawater and infiltration of these brines into deep basin aquifers during Pangean orogenic events.

Mineralium Deposita↗