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Quartz solubility in the H2O-NaCl system: A framework for understanding vein formation in porphyry copper deposits

Porphyry copper deposits consist of low-grade stockwork and disseminated sulfide zones that contain characteristic vein generations formed during the evolution of the magmatic-hydrothermal systems. The present contribution proposes an interpretive framework for the formation of porphyry veins that is based on quartz solubility calculations in the H 2 O-NaCl system at temperatures of 100° to 1,000°C and pressures of 1 to 2,000 bar. The model predicts that high-temperature (≳500°C) quartz in A veins of deep (≳4 km) porphyry deposits forms as a result of the cooling of ascending intermediate-density fluids at lithostatic conditions. In deposits of intermediate depths (~1.5–4 km), A vein quartz is mostly formed through cooling of ascending hydrothermal fluids under closed-system conditions or quasi-isobaric cooling under open-system conditions within the two-phase field of the H 2 O-NaCl system. In shallow (≲1.5 km) porphyry deposits, rapid decompression can also result in quartz precipitation, forming so-called banded veins. The high-temperature quartz in A veins is associated with potassic alteration. During continued cooling of the magmatic-hydrothermal system, quartz is formed at intermediate temperatures (≳375°–500°C). This quartz overprints earlier A veins and forms B veins. The fluid inclusion inventory of this quartz generation suggests formation at fluctuating pressure conditions, marking the lithostatic to hydrostatic transition, and the change of wall-rock behavior from ductile to brittle conditions. The quartz is precipitated because of cooling and decompression of the magmatic-hydrothermal fluids under K-feldspar-stable conditions. Textural evidence from many porphyry veins suggests that hypogene sulfide minerals present in A and B veins postdate the quartz, as contacts between quartz and sulfide minerals commonly show dissolution textures. Hypogene sulfide minerals in C veins form at conditions of retrograde quartz solubility, explaining why these veins contain little to no quartz. The quartz solubility calculations suggest that C vein formation occurs at temperatures of ~375° to 450°C from low-salinity, single-phase fluids escaping from the lithostatic to the hydrostatic environment. At the upper end of this temperature range, C veins are biotite stable. However, these veins are associated with chlorite, chlorite-K-feldspar, or chlorite-sericite alteration in most deposits. Late quartz is formed during continued cooling of the hydrothermal fluids at ≲375°C within the single-phase field of the H 2 O-NaCl system as quartz solubility under these conditions decreases with temperature. This process is responsible for the formation of quartz in D veins and later base metal-bearing E veins, which are associated with phyllic, advanced argillic, or argillic alteration.

Economic Geology↗

Magmatic origin for sediment-hosted Au deposits, Guizhou Province, China: In situ chemistry and sulfur isotope composition of pyrites, Shuiyindong and Jinfeng deposits

The southwest Guizhou Province, China, contains numerous sediment-hosted Au deposits with Au reserves greater than 700 tonnes. To date, the source of ore fluids that formed the Guizhou sediment-hosted Au deposits is controversial, hampering the formulation of genetic models. In this study, we selected the Shuiyindong and Jinfeng Au deposits, the largest strata-bound and fault-controlled deposits in Guizhou, respectively, for detailed research on pyrite chemistry and S isotope composition using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS), respectively. Petrography and pyrite chemistry studies distinguished five generations of pyrite. Among these, pre-ore pyrite 2 and ore pyrite are the most abundant types in the deposits. Pre-ore pyrite 2 is anhedral to euhedral and with ~2,639 ppm As and wider ranges of Cu, Sb, and Pb (<~22–4,837 ppm, <~6 to 532 ppm, and <~4 to 1,344 ppm, respectively). Gold in pre-ore pyrite 2 is below the detection limit of LA-ICP-MS (~2 ppm). Pre-ore pyrite 2 is interpreted to have a sedimentary (syngenetic or diagenetic) origin. Ore pyrite commonly rims the four identified pre-ore pyrites or occurs as individual, anhedral to euhedral crystals. Ore pyrite is enriched in Au (~641 ppm), As (~9,147 ppm), Cu (~1,043 ppm), Sb (~188 ppm), Hg (~43 ppm), and Tl (~22 ppm) in both deposits. Ore pyrite formed mainly by sulfidation of Fe in Fe-bearing host rocks, mainly Fe dolomite, and As, Cu, Sb, Hg, and Tl, also in ore fluids, were incorporated into ore pyrite. In situ δ 34 S isotope ratios for pre-ore pyrite 2 and ore pyrite were measured by LA-MC-ICP-MS. Pre-ore pyrite 2 from Shuiyindong and Jinfeng deposits resulted in δ 34 S values ranging from −0.8 to +3.4‰ and from 5.1 to 10.5‰, respectively. Analyses of ore pyrite from the Shuiyindong have δ 34 S values that vary from −3.3 to +2.5‰, with a median of 0.7‰; analyses of ore pyrite from the Jinfeng range from 8.9 to 11.2‰, with a median at 10.3‰. Available bulk and in situ δ 34 S data in the literature for pre-ore pyrites 1 and 2 and ore-related sulfide minerals including ore pyrite, arsenopyrite, and late ore-stage stibnite, realgar, orpiment, and cinnabar from several Guizhou sediment-hosted Au deposits were compiled for comparison. Pre-ore-stage pyrites from Guizhou sediment-hosted Au deposits have a broad range of δ 34 S values, from −33.8 to + 17.9‰ (including in situ and available bulk δ 34 S data). Ore-related sulfide minerals in all Guizhou sediment-hosted Au deposits, except Jinfeng, have very similar δ 34 S values, and most data plot between ~−5 and +5‰. In the Jinfeng deposit, the ore-related sulfide minerals exhibit δ 34 S values ranging from 1.9 to 18.1‰, with most data plotting between 6 and 12‰. The broad range of S isotope compositions for the sedimentary pyrites (pre-ore pyrites 1 and 2) indicate that S in these pre-ore pyrites was most likely generated by bacterial reduction from marine sulfate. The narrow range of δ 34 S values (~−5–+5‰) for ore-related sulfide minerals in all Guizhou sediment-hosted Au deposits, excepting the Jinfeng deposit, suggests that the deposits may have formed in response to a single widespread metallogenic event. As the S isotope fractionation between hydrothermal fluids and sulfide minerals in a sulfide-dominated system is small (<2‰) at ~250°C, the initial ore fluids that formed the Guizhou sediment-hosted Au deposits would have had δ 34 S values similar to the ore-related sulfide minerals, between ~−5 and +5‰. At Jinfeng, initial ore fluids may have mixed with local fluids with heavier δ 34 S, possibly basin brine ( δ 34 S basin brine >18‰), resulting in elevated δ 34 S values of ore-related sulfide minerals and especially late ore-stage sulfide minerals. Although few igneous rocks are exposed in the mining area around these deposits, there is evidence of magmatic activity ~20 km away. Furthermore, gravity and magnetic geophysical investigations indicate the presence of a pluton ~5 km below the surface of the Shuiyindong district. Based on in situ S isotope results and recent data indicating proximal intrusions, we interpret a deep magmatic S source for the ore fluids that formed the Guizhou sediment-hosted Au deposits. However, as the age for Au mineralization of Guizhou sediment-hosted Au deposits is still debated, the mineralization-magma connection remains hypothetical. Identifying an ore fluid source and time frame for Guizhou Au mineralization continues to be a critically important research goal for this district.

Yunnan-Guizhou-Guangxi region↗

Magmatic-hydrothermal gold mineralization at the Lone Tree Mine, Battle Mountain district, Nevada

The Lone Tree deposit is located in the northern Battle Mountain mining district, Nevada. Prior to mine closure in 2006, Santa Fe Pacific Gold and Newmont produced 4.2 Moz of gold at an average grade of 2.06 g/t at Lone Tree, primarily from the N-S– to NNW-SSE–striking Wayne zone. The ore is located between the Roberts Mountain and Golconda thrusts in siliciclastic rocks of the Ordovician Valmy Formation and in the Pennsylvanian-Permian Battle Mountain and Edna Mountain Formations, and above the Golconda thrust in siliciclastic and carbonate rocks of the Mississippian to Permian Havallah sequence. Ore is also hosted by rhyolitic dikes that were emplaced at 40.95 ± 0.06 Ma based on zircon U-Pb chemical abrasion-thermal ionization mass spectrometry. The gold is associated with sericitic and argillic alteration of the siliciclastic rocks and dikes and with decarbonatization and Fe carbonate alteration of the carbonate-bearing units, as well as in Fe-As sulfide and finegrained quartz alteration of all rock types. Oxidation affects 30 to 45% of the deposit, penetrating into the stratigraphy along numerous steeply dipping north-south, east-west, and north-northeast–south-southwest structures. Gold is positively correlated with Ag, As, Hg, and Sb. The highest Au grades occur in quartz-sulfide ore hosted in siliciclastic and carbonate sedimentary rocks and rhyolitic intrusions. In this ore style, fine-grained quartz and sericite are intergrown with disseminated sulfide minerals (quartz-sericite-pyrite alteration), constituting cores of weakly mineralized pyrite or marcasite, which are surrounded by fuzzy arsenopyrite rims that contain up to ~2,000 ppm Au. Low gold grades occur in late-stage banded pyrite breccias consisting of a finely zoned Au-poor pyrite matrix surrounding jigsaw-fit clasts of quartz-, illite-, barite-, and adularia-altered siliciclastic rock. The timing of main-stage mineralization is bracketed between the emplacement of the dikes and an adularia 40 Ar/ 39 Ar age of 40.14 ± 0.74 Ma. Sericite intergrown with arsenopyrite-rimmed pyrite in phenocrysts of the rhyolite dikes gave δ 18 O values of 1.6 to 9.5‰ and δ D values of –105 to –145‰. For temperatures of 300 ± 100°C, the calculated fluid isotopic compositions are consistent with felsic magmatic water and minor modifications by mixing with meteoric water and exchange with wall rocks. In the silica-sulfide ore, in situ isotopic laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) analyses of pyrite cores yielded δ 34 S values ranging from 3.4 to 7.7‰, with average values of 5.6‰ in the felsic dikes, 4.5‰ in the siliciclastic rocks, and 5.3‰ in the carbonate rocks. These values match conventional pyrite δ 34 S data reported for Eocene porphyry systems elsewhere in the district. Nanoscale secondary ion mass spectrometry analyses show that gold and associated trace elements occur in submicron-scale zones within arsenopyrite rims on pyrite. The average δ 34 S values of the arsenopyrite rims are 5.3 to 6.5‰ heavier than the pyrite cores, indicating cooling and an increasing H 2 S/SO 2 ratio. The highest grades resulted from episodic pulses of a gold-rich fluid that was partly derived from, or exchanged with, the sedimentary host rocks. In situ LA-MC-ICP-MS δ 34 S values for the late-stage banded pyrite breccia become progressively lighter from veinlet margin to center, reaching a low of –32‰. These veinlets indicate a shift from main-stage quartz-sericite-pyrite and intermediate argillic alteration to more neutral pH and oxidizing conditions during late-stage mineralization, indicating either increasing interaction between the fluid and sedimentary sulfur sources in the host-rock package or bacterial sulfate reduction and supergene sulfide precipitation.

Nevada↗

The Zn–Pb mineralization of Florida Canyon, an evaporite-related Mississippi Valley-type deposit in Bongará district, northern Peru

The Florida Canyon evaporite-related Zn–Pb sulfide deposit, in northern Peru, is one of the largest Mississippi Valley-type (MVT) deposits in South America. Triassic carbonate and former evaporite-bearing rocks of the Pucará Group host the ore bodies that comprise two different styles: (i) predominantly stratabound ore associated with hydrocarbon-rich porous dolostones and evaporite dissolution breccias; and (ii) high-grade ore associated with evaporite breccias representing diapiric injections along faults. A dome structure that controls the location of the ore deposit was defined by drillhole spatial data; the dome likely resulted from halokinetic processes during Andean deformation. NNE-trending steeply dipping secondary faults linked to major NW structures appear to control the distribution of ore grades in the deposit. Mineralization post-dated hydrocarbon migration and accumulation. Strontium, carbon, and oxygen data isotopic signatures allow distinction between pre-and syn-mineralization carbonate stages. The sulfur isotopic composition of sulfides in the deposit suggests they precipitated as the result of mixing of a metal-rich fluid with resident hydrogen sulfide in the dome. Local thermochemical sulfate reduction (TSR) may have contributed to the reduced sulfur budget during mineralization.

Economic Geology↗

Reconstruction of an early Permian, sublacustrine magmatic-hydrothermal system: Mount Carlton epithermal Au-Ag-Cu deposit, northeastern Australia

The Mt. Carlton Au-Ag-Cu deposit, northern Bowen basin, northeastern Australia, is an uncommon example of a sublacustrine hydrothermal system containing economic high-sulfidation epithermal mineralization. The deposit formed in the early Permian and comprises vein- and hydrothermal breccia-hosted Au-Cu mineralization within a massive rhyodacite porphyry (V2 open pit) and stratabound Ag-barite mineralization within volcano-lacustrine sedimentary rocks (A39 open pit). These orebodies are all associated with extensive advanced argillic alteration of the volcanic host rocks. Stable isotope data for disseminated alunite ( δ 34 S = 6.3–29.2‰; δ 18 OSO 4 = –0.1 to 9.8‰; δ 18 O OH = –15.3 to –3.4‰; δ D = –102 to –79‰) and pyrite ( δ 34 S = –8.8 to –2.7‰), and void-filling anhydrite ( δ 34 S = 17.2–19.2‰; δ 18 O SO4 = 1.8–5.7‰), suggest that early advanced argillic alteration formed within a magmatic-hydrothermal system. The ascending magmatic vapor ( δ 34 S ΣS ≈ –1.3‰) was absorbed by meteoric water (~50–60% meteoric component), producing an acidic (pH ≈ 1) condensate that formed a silicic → quartz-alunite → quartz-dickite-kaolinite zoned alteration halo with increasing distance from feeder structures. The oxygen and hydrogen isotope compositions of alunite-forming fluids at Mt. Carlton are lighter than those documented at similar deposits elsewhere, probably due to the high paleolatitude (~S60°) of northeastern Australia in the early Permian. Veins of coarse-grained, banded plumose alunite ( δ 34 S = 0.4– 7.0‰; δ 18 O SO4 = 2.3–6.0‰; δ 18 O OH = –10.3 to –2.9‰; δ D = –106 to –93‰) formed within feeder structures during the final stages of advanced argillic alteration. Epithermal mineralization was deposited subsequently, initially as fracture- and fissure-filling, Au-Cu–rich assemblages within feeder structures at depth. As the mineralizing fluids discharged into lakes, they produced syngenetic Ag-barite ore. Isotope data for ore-related sulfides and sulfosalts ( δ 34 S = –15.0 to –3.0‰) and barite ( δ 34 S = 22.3–23.8‰; δ 18 O SO4 = –0.2 to 1.3‰), and microthermometric data for primary fluid inclusions in barite (Th = 116°– 233°C; 0.0–1.7 wt % NaCl), are consistent with metal deposition at temperatures of ~200 ± 40°C (for Au-Cu mineralization in V2 pit) and ~150 ± 30°C (Ag mineralization in A39 pit) from a low-salinity, sulfur- and metal-rich magmatic-hydrothermal liquid that mixed with vapor-heated meteoric water. The mineralizing fluids initially had a high-sulfidation state, producing enargite-dominated ore with associated silicification of the early-altered wall rock. With time, the fluids evolved to an intermediate-sulfidation state, depositing sphalerite- and tennantite-dominated ore mineral assemblages. Void-filling massive dickite ( δ 18 O = –1.1 to 2.1‰; δ D = –121 to –103‰) with pyrite was deposited from an increasingly diluted magmatic-hydrothermal liquid (≥70% meteoric component) exsolved from a progressively degassed magma. Gypsum ( δ 34 S = 11.4–19.2‰; δ 18 O SO4 = 0.5–3.4‰) occurs in veins within postmineralization faults and fracture networks, likely derived from early anhydrite that was dissolved by circulating meteoric water during extensional deformation. This process may explain the apparent scarcity of hypogene anhydrite in lithocaps elsewhere. While the Mt. Carlton system is similar to those that form subaerial high-sulfidation epithermal deposits, it also shares several key characteristics with magmatic-hydrothermal systems that form base and precious metal mineralization in shallow-submarine volcanic arc and back-arc settings. The lacustrine paleosurface features documented at Mt. Carlton may be useful as exploration indicators for concealed epithermal mineralization in similar extensional terranes elsewhere.

Economic Geology↗

Noble gases fingerprint the source and evolution of ore-forming fluids of Carlin-type gold deposits in the Golden Triangle, south China

Precise constraints on the source and evolution of ore-forming fluids of Carlin-type gold deposits in the Golden Triangle (south China) are of critical importance for a better understanding of the ore genesis and a refined genetic model for gold mineralization. However, constraints on the source of ore fluid components have long been a challenge due to the very fine grained nature of the ore and gangue minerals in the deposits. Here we present He, Ne, and Ar isotope data of fluid inclusion extracts from a variety of ore and gangue minerals (arsenian pyrite, realgar, quartz, calcite, and fluorite) representing the main and late ore stages of three well-characterized major gold deposits (Shuiyindong, Nibao, and Yata) to provide significant new insights into the source and evolution of ore-forming fluids of this important gold province. Measured He isotopes have R/R A ratios ranging from 0.01 to 0.4 that suggest a maximum of 5% mantle helium with an R/R A of 8. The Ne and Ar isotope compositions are broadly comparable to air-saturated water, with a few analyses indicating the presence of an external fluid containing nucleogenic 38 Ar and radiogenic 40 Ar. Plotted on the 20 Ne/ 4 He vs. helium R/R A and 3 He/ 20 Ne vs. 4 He/ 20 Ne diagrams, the results define two distinct arrays that emanate from a common sedimentary pore fluid or deeply sourced metamorphic fluid end-member containing crustal He. The main ore-stage fluids are interpreted as a mixture of magmatic fluid containing mantle He and sedimentary pore fluid or deeply sourced metamorphic fluid with predominantly crustal He, whereas the late ore-stage fluids are a mixture of sedimentary pore fluid or deeply sourced metamorphic fluid bearing crustal He and shallow meteoric groundwater containing atmospheric He. Results presented here, when combined with independent evidence, support a magmatic origin for the ore-forming fluids. The ascending magmatic fluid mixed with sedimentary pore fluid or deeply sourced metamorphic fluid in the ore stage and subsequently mixed with the meteoric groundwater in the late ore stage, eventually producing the Carlin-type gold deposits in the Golden Triangle.

Golden Triangle, south China↗

The nature and composition of the J-M Reef, Stillwater Complex, Montana, USA

In this contribution, we analyze 30 years of mine development data and quantitatively identify the processes that control the grade and tenor of the mineralized rock. An assay database of more than 60,000 samples was used to examine variations in ore grade and tenor of the sulfide mineralization in the J-M reef horizon of the Stillwater Complex along the strike and down the dip of the deposit in the area of the Stillwater mine. We compare these results with data from the East Boulder mine and whole-rock lithogeochemistry of samples collected along the entire strike length of the complex. We find significant variation in the composition of the reef sulfides in different spatial domains of the Stillwater mine area and between the Stillwater and East Boulder mines. Most of the variation in the grade and tenor can be explained by a variation in the mass of silicate magma with which the sulfide liquid equilibrated (i.e., R factor); however, geochemical and textural evidence suggests that parts of the reef may have experienced significant S loss following initial sulfide melt segregation. Some variability in the reef tenor and grade can be attributed to variable amounts of sulfur loss due to low-temperature hydrothermal fluids and the overestimation or underestimation of metal concentrations in reef assays due to the nugget effect. Furthermore, we address the Pd/Pt ratio of the reef samples and suggest that the lower solubility of Pt in the parental silicate melt may have caused the crystallization and removal of Pt alloys at some point before the melt reached sulfide saturation and Pt could partition into the sulfide liquid. This disparity between the prior evolution of Pt and Pd in the silicate melt resulted in the observed Pd/Pt ratio of ~3.65 across all areas of the reef—a value significantly larger than anticipated for primitive mantle-derived magmas.

Montana↗

Paragenesis of an orogenic gold deposit: New insights on mineralizing processes at the Grass Valley District, California

The Grass Valley orogenic gold district in the Sierra Nevada foothills province, central California, is the largest historical gold producer of the North American Cordillera. Gold mineralization is associated with shallowly dipping north-south veins hosted by the 160 Ma Grass Valley granodiorite to the southwest of the Grass Valley fault and steeply dipping east-west veins in accreted oceanic rocks to the northeast of this major fault. Quartz veins from both vein types show well-preserved primary textural relationships. Using a combination of petrographic and microanalytical techniques, the paragenetic sequence of minerals within the veins and the compositions of ore minerals were determined to constrain the mechanisms of quartz vein formation and gold deposition. The veins are composed of early quartz that formed through cooling of hydrothermal fluids derived from a geopressured reservoir at depth. The early quartz shows growth zoning in optical cathodoluminescence and contains abundant growth bands of primary inclusions. The primary inclusion assemblages and myriads of crosscutting secondary fluid inclusions have been affected by postentrapment modification, suggesting that early quartz formation was postdated by pronounced pressure fluctuations. These pressure fluctuations, presumably involving changes from lithostatic to hydrostatic conditions, may be related to fault failure of the host structure as predicted by the fault-valve model. Fluid flow associated with pressure cycling took place along microfractures and grain boundaries resulting in extensive recrystallization of the early quartz. Deposition of pyrite, arsenopyrite, and first-generation gold from these hydrothermal fluids causing recrystallization of the early quartz occurred as a result of wall-rock sulfidation. The gold forms invisible gold in the compositionally zoned pyrite or micron-sized inclusions within pyrite growth zones. The latest growth zones in euhedral quartz crystals that formed in association with this stage of the paragenesis contain very rare primary fluid inclusions that have not been affected by postentrapment modification. The hydrothermal system transitioned entirely to hydrostatic conditions immediately after formation of the latest quartz, explaining the preservation of the primary fluid inclusions. The formation of minor quartz in open spaces was followed by the deposition of second-generation native gold and telluride minerals that are commonly associated with base metal sulfides. Ore formation at this stage of the paragenesis is attributed to the rapid decompression of hydrothermal fluids escaping from the geopressured part of the crust into the overlying hydrostatic realm. There is no fluid inclusion evidence that this pressure drop resulted in fluid immiscibility of the hydrothermal fluids. Fluid inclusion evidence suggests that the north-south veins formed at a paleodepth of ~8 km, whereas the east-west veins appear to have formed at ~10 to 11 km below surface, confirming previous inferences that the NE-dipping Grass Valley reverse fault accommodated a large displacement. The findings of the study at Grass Valley have significant implications for the model for orogenic gold deposits, as the reconstruction of the paragenetic relationships provides evidence for the occurrence of two discrete events of gold introduction that occurred at different conditions during the evolution of the hydrothermal system.

California↗

Calcite U-Pb dating unravels the age and hydrothermal history of the giant Shuiyindong Carlin-type gold deposit in the Golden Triangle, south China

The ages of Carlin-type gold deposits in the Golden Triangle of South China have long been questioned due to the general lack of minerals unequivocally linked to gold deposition that can be precisely dated using conventional radiogenic isotope techniques. Recent advances in U-Pb methods show that calcite can be used to constrain the ages of hydrothermal processes, but few studies have been applied to ore deposits. Herein, we show that this approach can be used to constrain the timing of hydrothermal activity that generated and overprinted the giant Shuiyindong Carlin-type gold deposit in the Golden Triangle. Three stages of calcite (Cal-1, Cal-2, and Cal-3) have been recognized in this deposit based on crosscutting relationships, cathodoluminescence colors, and chemical (U, Pb, and rare earth element [REE]) and isotope (C, O, Sr) compositions. Cal-1 is texturally associated with ore-stage jasperoid and disseminated Au-bearing arsenian pyrite in hydrothermally altered carbonate rocks, which suggests it is synmineralization. Cal-2 fills open spaces and has a distinct orange cathodoluminescence, suggesting that it precipitated during a second fluid pulse. Cal-1 and Cal-2 have similar carbonate rock-buffered chemical and isotopic compositions. Cal-3 occurs in veins that often contain realgar and/or orpiment and are chemically (low U, Pb, and REE) and isotopically (higher δ 13 C, lower δ 18 O and Sr i values) distinct from Cal-1 and Cal-2, suggesting that it formed from a third fluid. U-Pb isotope analyses, by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) for U-rich Cal-1 and Cal-2 and by LA-multicollector (MC)-ICP-MS for U-poor Cal-3, yield well-defined age constraints of 204.3 to 202.6, 191.9, and 139.3 to 137.1 Ma for Cal-1, Cal-2, and Cal-3, respectively. These new ages suggest that the Shuiyindong gold deposit formed in the late Triassic and was overprinted by hydrothermal events in the early Jurassic and early Cretaceous. Given the association of Cal-3 with orpiment and realgar, and previous geochronologic studies of several other major gold deposits in the Golden Triangle, we infer that the latest stage of calcite may be associated with an early Cretaceous regional gold metallogenic event. Combined with existing isotopic ages in the region, these new ages lead us to propose that Carlin-type gold deposits in the Golden Triangle formed during two metallogenic episodes in extensional settings, associated with the late Triassic Indochina orogeny and early Cretaceous paleo-Pacific plate subduction. This study shows that the calcite U-Pb method can be used to constrain the timing of Carlin-type gold deposits and successive hydrothermal events.

Golden Triangle, south China↗

Antimony in mine wastes: Geochemistry, mineralogy, microbiology

Antimony (Sb) is a valuable mined commodity, used mostly in fire retardants, and considered a critical element. It is also a potential environment hazard classed as a carcinogen. Antimony is concentrated in tailings and waste rock from Sb mines as well as other locations, such as precious metal deposits, where Sb is present in the ore but not recovered. This review covers the aqueous geochemistry, isotope chemistry, mineralogy, and microbiology of Sb in the context of mine waste. The primary minerals stibnite and sulfosalts may release Sb in surface and groundwaters and result in contamination of soils, plants, and river sediments. In some cases, Sb mobility is limited by its adsorption and incorporation into Fe (oxyhydr)oxides. At higher Sb concentrations, precipitation of Sb secondary hosts such as tripuhyite (FeSbO 4 , relatively insoluble) and brandholzite (Mg[Sb(OH) 6 ] 2 · 6H 2 O, highly soluble) influence Sb concentrations in water associated with mine waste. Although Sb is nonessential to organisms, microorganisms are involved in oxidation, reduction, and methylation processes that can drive biogeochemical transformations. Limited toxicological information about Sb makes it challenging to establish regulations or guidelines limiting the concentration of Sb. Antimony is frequently associated with arsenic in mine waste, and remediation design is often based on the assumption that both metalloids behave in a similar way. However, new research suggests that in some environments, this is not the case, and Sb should be considered based on its unique biogeochemical behavior.

Economic Geology↗

Trace elements in quartz: Insights into source and fluid evolution in magmatic-hydrothermal systems

Quartz trace elements record information about fluid evolution as well as metal migration and precipitation. Here, we summarize most of the reported (including this study) quartz trace element data ( N = ~4,600) generated by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) on various textural types and paragenetic stages of quartz in I-type porphyry-epithermal (Cu-Mo-Au-Ag-Te) and S- and A-type granitegreisen (Sn-W and rare metal) systems in the world. The results show that Li versus Al diagrams, combined with Ti-Ge-As-Sb contents, can be used to decipher the source and evolution of fluids in magmatic-hydrothermal systems. In I-type porphyry-epithermal systems, magmatic quartz has low Li/Al ratios from 0.001 to 0.173 ( N = 483) with a mean of 0.039 ± 0.032. Hydrothermal quartz has progressively higher Li and Al concentrations that are dominated by cooling along fluid pathways. Quartz evolves from Ti rich to Ge rich from early to late stages in porphyry hydrothermal veins and is As and Sb rich in epithermal veins. In S- and A-type granite-greisen systems, magmatic quartz has high Li/Al ratios from 0.007 to 0.502 ( N = 604) with a mean of 0.130 ± 0.063 and from 0.009 to 0.327 ( N = 325) with a mean of 0.126 ± 0.065, respectively. Hydrothermal quartz has progressively lower Li and Al concentrations that are dominated by fluid-rock reactions and cooling along fluid pathways. Quartz evolves with decreasing Ti concentrations from magmatic to hydrothermal stages. Ge is abundant in pegmatite quartz in S-type systems. Variations in pH or precipitation rate along fluid pathways have a small influence on Li/Al ratios. The variation of quartz trace elements with elevation in individual systems suggests that they can be used as a vector to guide exploration in magmatic-hydrothermal systems.

Economic Geology↗

Fluids and melts at the magmatic-hydrothermal transition, recorded by unidirectional solidification textures at Saginaw Hill, Arizona, USA

Fluid exsolution and melt evolution at the magmatic-hydrothermal transition are critical processes driving the metal enrichment of porphyry systems. Coeval fluid and melt inclusion assemblages in unidirectional solidification textures (USTs) at Saginaw Hill—a small, porphyry Cu system in southwestern Arizona—record a dynamic and repetitious process of fluid accumulation and release. The cores of quartz crystals throughout the UST bands host coeval silicate melt and brine inclusions but lack vapor-rich inclusions. This could indicate preferential expulsion of vapor and trapping of high-density brine during episodes of fracturing or the direct exsolution of single-phase high-salinity brine from the silicate melt. In contrast, the rims of UST quartz host abundant coeval brine and vapor inclusions, consistent with liquid-vapor immiscibility at lower pressures compared to the corresponding quartz cores. This transition from dominantly coeval silicate melt inclusions and brine in phenocryst cores to coeval brine and vapor in the rims suggests that the Saginaw Hill system underwent cyclic processes of fluid exsolution, accumulation, overpressure, and decompression at relatively stable temperatures (consistently ~650°C) during UST formation. Melt inclusion data indicate that the melt at this stage was highly fractionated and tended toward muscovite saturation. Metal concentrations in the brine were comparable to or higher than those in fluids reported in world-class porphyry Cu systems and were likely the result of both igneous fractionation and the high chloride content of the exsolved fluids. While limited in scale, Saginaw Hill provides evidence for processes that are predicted to occur at the magmatic-hydrothermal transition during the formation of large, well-mineralized porphyry systems.

Arizona↗

U-Pb scheelite ages of tungsten and antimony mineralization in the Stibnite-Yellow Pine district, central Idaho

The Stibnite-Yellow Pine district contains the largest antimony resource in the United States, as well as significant gold, and is a historic producer of tungsten. Application of in situ laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) direct dating of scheelite from two Au-Sb-W ore deposits, Yellow Pine and Hangar Flats, yielded an older group of U-Pb ages in the range of 60.0 ± 2.8 to 57.0 ± 1.1 Ma and a younger U-Pb age for scheelite intergrown with stibnite of 47.4 ± 1.1 Ma. These in situ analyses were calibrated by isotope dilution-thermal ionization mass spectrometry (ID-TIMS) U-Pb lower intercept ages of two coarsely crystalline scheelite samples that yielded ages of 57.52 ± 0.22 and 56.62 ± 0.16 Ma. Scheelite of the latter age is of sufficient quality to serve as a primary reference material for LA-ICP-MS scheelite U-Pb geochronology. The group of older U-Pb scheelite ages agrees with 40 Ar/ 39 Ar ages of 56.9 ± 1.2 to 56.38 ± 0.54 Ma on adularia from Yellow Pine and Hangar Flats, whereas the younger U-Pb scheelite age is similar to an 40 Ar/ 39 Ar age of 46.00 ± 0.40 Ma on adularia from an epithermal gold-silver deposit in the adjacent Thunder Mountain caldera. Our results indicate that the main stage of tungsten mineralization occurred at ca. 57 Ma, whereas the main stage of antimony mineralization occurred at ca. 47 Ma—thereby providing first-time age constraints for antimony and tungsten mineralization in the Stibnite-Yellow Pine district.

Idaho↗

Timing of rhyolite intrusion and Carlin-type gold mineralization at the Cortez Hills Carlin-type deposit, Nevada, USA

Carlin-type gold deposits (CTDs) of Nevada are the largest producers of gold in the United States, a leader in world gold production. Although much has been resolved about the characteristics and origin of CTDs in Nevada, major questions remain, especially about (1) the role of magmatism, whether only a source of heat or also metals, (2) whether CTDs only formed in the Eocene, and (3) whether pre-Eocene metal concentrations contributed to Eocene deposits. These issues are exemplified by the CTDs of the Cortez region, the second largest concentration of these deposits after the Carlin trend. Carlin-type deposits are notoriously difficult to date because they rarely generate dateable minerals. An age can be inferred from crosscutting relationships with dated dikes and other intrusions, which we have done for the giant Cortez Hills CTD. What we term “Cortez rhyolites” consist of two petrographic-geochemical groups of siliceous dikes: (1) quartz-sanidine-plagioclase-biotite-phyric, high-SiO 2 rhyolites emplaced at 35.7 Ma based on numerous 40 Ar/ 39 Ar dates and (2) plagioclase-biotite-quartz ± hornblende-phyric, low-SiO 2 rhyolites, which probably were emplaced at the same time but possibly as early as ~36.2 Ma. The dikes form a NNW-trending belt that is ~6 to 10 km wide × 40 km long and centered on the Cortez Hills deposit, and they require an underlying felsic pluton that fed the dikes. Whether these dikes pre- or postdated mineralization has been long debated. We show that dike emplacement spanned the time of mineralization. Many of both high- and low-SiO 2 dikes are altered and mineralized, although none constitute ore. In altered-mineralized dikes, plagioclase has been replaced by kaolinite and calcite, and biotite by smectite, calcite, and marcasite. Sanidine is unaltered except in a few samples that are completely altered to quartz and kaolinite. Sulfides present in mineralized dikes are marcasite, pyrite, arsenopyrite, and As-Sb–bearing pyrite. Mineralized dikes are moderately enriched in characteristic Carlin-type elements (Au, Hg, Sb, Tl, As, and S), as well as elements found in some CTDs (Ag, Bi, Cu, Mo), and variably depleted in MgO, CaO, Na 2 O, K 2 O, MnO, Rb, Sr, and Ba. In contrast, some high-SiO 2 rhyolites are unaltered and cut high-grade ore, which shows that they are post-ore. Both mineralized and post-ore dikes have indistinguishable sanidine 40 Ar/ 39 Ar dates. These characteristics, along with published interpretations that other giant CTDs formed in a few tens of thousands of years, indicate the Cortez Hills CTD formed at 35.7 Ma. All Cortez-area CTDs are in or adjacent to the Cortez rhyolite dike swarm, which suggests that the felsic pluton that fed the dikes was the hydrothermal heat source. Minor differences in alteration and geochemistry between dikes and typical Paleozoic sedimentary rock-hosted ore probably reflect low permeability and low reactivity of the predominantly quartzofeldspathic dikes. Despite widespread pre-35.7 Ma mineralization in the Cortez region, including deposits near several CTDs, we find no evidence that older deposits or Paleozoic basinal rocks contributed metals to Cortez-area CTDs. Combining our new information about the age of Cortez Hills with published and our dates on other CTDs demonstrates that CTD formation coincided with the southwestern migration of magmatism across Nevada, supporting a genetic relationship to Eocene magmatism. CTDs are best developed where deep-seated (~6–8 km), probably granitic plutons, expressed in deposits only as dikes, established large, convective hydrothermal systems.

Nevada↗

The Sukari gold deposit, Egypt: Geochemical and geochronological constraints on the ore genesis and implications for regional exploration

The Sukari gold deposit (>15 Moz Au) in the Eastern Desert of Egypt is hosted by a deformed granitoid stock (Sukari tonalite-trondhjemite intrusion) and mainly occurs as a network of crosscutting sulfide-bearing quartz (± carbonate) veins and intensely sulfidized-silicified-sericitized wall rock. Emplacement of the Sukari intrusion into a tectonized Neoproterozoic accretionary complex was controlled by a system of NE- to NNE-trending oblique faults that are related to a deep-seated positive flower structure. A robust genetic model has been hampered by the poorly understood relationships between gold mineralization and host rocks. In this study, zircon U-Pb ages of three samples from the Sukari intrusion define a crystallization age of ~695 ± 2 Ma. In contrast, hydrothermal sericite from the ore zone yields an 40 Ar/ 39 Ar age of ~625 ± 3 Ma, which coincides with the onset of major sinistral transpression in the region. Features including sigmoidal morphology of gold quartz veins and abundant subhorizontal tension gashes alongside widespread brecciation and recrystallization suggest that quartz veining occurred during renewed shortening and exhumation through the brittle-ductile transition. Petrographic and micro-X-ray fluorescence (µXRF) studies indicate that disseminated gold and sulfides, commonly associated with sericite and carbonate alteration, are mostly confined to stylolitic bands in the quartz veins. Oscillatory and sector zoning patterns, irregular As-rich bands, and truncations between early- and late-genetic pyrites reflect variations in temperature and mechanism of ore deposition, demonstrated by variable As/S and Co/Ni ratios in the different pyrite generations. Laser ablation-inductively coupled plasma-mass spectrometry analysis pinpoints the covariance of gold and arsenic contents in pyrite, but free milling gold inclusions in microfractures consistently have a mercury-bearing electrum composition, depicting different ore formation stages. Ore fluids with δ 34 S H 2 s "> S H 2 s values of –1.9 to –3.0‰, modeled from gold-associated pyrite and arsenopyrite assemblages with nearly identical δ 34 S values, suggest a likely single source of sulfur. Alternatively, multisourced sulfur could have extensively mixed and equilibrated by fluid reaction with carbonaceous wall rock. Gold deposition was triggered by abrupt changes in fluid pH and ƒ f O 2 "> O 2 ⁠ . As an implication for future exploration, sites of maximized strain gradients adjacent to granitoid bodies along extensive transpression zones in the district could be highly prospective targets, particularly where imprinted by sericite-carbonate ± graphite alteration.

Sukari gold deposit↗

Geochronology and mapping constraints on the time-space evolution of the igneous and hydrothermal systems in the Taurus Cu-Mo district, eastern Alaska

The Taurus porphyry Cu-Mo district contains four mineralized porphyry centers in the eastern interior of Alaska. All four centers were emplaced during a magmatic episode that spanned from ca. 72 to 67 Ma, with seven distinct igneous suites. Each igneous suite resulted in hydrothermal alteration and mineralization, with younger pulses overprinting older pulses. Each magmatic-hydrothermal system is not present at all four mineralized centers. Apart from the Dennison occurrence, each mineralized center records pulses of repeated intermediate-silicic magmatism and associated alteration and mineralization. Laser ablation-inductively coupled plasma-mass spectrometry U-Pb zircon crystallization ages indicate that an early quartz porphyry dike swarm ranges in age from ca. 71 to 70 Ma and is associated with potassic, sericitic, and propylitic alteration. Quartz latite intrusions were emplaced at ca. 69 Ma and exhibit early sodiccalcic alteration overprinted by potassic, sericitic, and propylitic alteration. The Taurus monzonite suite is cut by quartz latite but yielded an ca. 70 Ma emplacement age and exhibits the largest footprint of potassic and sericitic alteration. Feldspar porphyry dikes were emplaced ca. 69 Ma and have significant tourmaline-bearing potassic and sericitic alteration. This suite was followed by development of an igneous breccia with a monzonitic igneous matrix. Sodic-calcic alteration was associated with the igneous brecciation. A small stock of monzonite was emplaced at ca. 68 Ma causing locally pervasive sericite-tourmaline-pyrite alteration. The youngest suite of magmatism dated in the district is a series of granodiorite porphyry dikes with weak sodic-calcic and propylitic alteration that truncates earlier alteration assemblages. Mineralization in the district consists of chalcopyrite and molybdenite associated with sugary quartz veins with potassium feldspar and biotite alteration envelopes (A veins). Less common banded quartz-molybdenite veins (B veins) occur with potassium feldspar envelopes. Gold occurs throughout the district and is strongly correlated with copper grade. Sericitic alteration contains lower copper contents and is predominantly associated with quartz-pyrite veins with sericite envelopes (D veins). Pyrrhotite and local arsenopyrite are present in sericitic assemblages. Pyrrhotite also occurs as inclusions in pyrite within D veins. Magmas across the district exhibit oxidized characteristics, evidenced by the presence of abundant magnetite, rare titanite, and elevated Eu/Eu* and Ce/Ce* in zircon. Zircon Th/U and Yb/Gd compositions suggest a fractionation path controlled by apatite, titanite, and hornblende. Zircon rare earth element ratios and trace element data indicate two distinct batches of magma evolved from mafic parental compositions to monzonite and granodioritic compositions via fractional crystallization. In the early pulse of magma (ca. 72–69 Ma), fractional crystallization was key to ore formation. Earlier, better mineralized suites evolve to less negative Eu anomalies (Eu/Eu* > 0.7), indicating more oxidized and higher-water-pressure conditions evidenced by the suppression of plagioclase crystallization, compared to later, more poorly mineralized suites. The temporal and spatial evolution of the district was determined from mapping and U-Pb and Re-Os geochronology. Mapping of igneous and hydrothermal assemblages indicates that the locus of the intrusive suites and hydrothermal systems shifted spatially over time, based on the presence of high-temperature (K-silicate–dominant) alteration, which is coincident with the highest Cu and Au grades. The earliest hydrothermal system was centered at Bluff and East Taurus and transitioned to West Taurus during emplacement of the second magmatic suite. Emplacement of the third magmatic suite was centered back at East Taurus, and the fourth and fifth suites were centered at West Taurus. The latest suites were widespread without a core of high-temperature alteration marking a central locus. East Taurus contains the overlap of six of the seven magmatic and hydrothermal suites and has the highest intersected grades and tonnages in the district. The Bluff and Dennison occurrences exhibit fewer igneous suites and hydrothermal assemblages with weak mineralization. Sodic-calcic alteration, common on the deep and distal flanks of porphyry systems, is only present at West Taurus and is indicative of a localized source of high-salinity nonmagmatic fluids.

Alaska, Yukon Territory↗

Genesis of the Questa Mo porphyry deposit and nearby polymetallic mineralization, New Mexico, USA

The Oligocene Latir magmatic center in northern New Mexico is an exceptionally well-exposed volcanoplutonic complex that hosts a variety of magmatic-hydrothermal deposits, ranging from relatively deep, F-rich porphyry Mo mineralization to shallower epithermal deposits. We present new whole-rock chemical and isotopic data for plutonic rocks from the Latir magmatic center, including extensive sampling of drill core samples of intrusive rocks from the Questa porphyry Mo deposit. These data document temporal chemical trends of porphyry-related mineralization that occurred after caldera-forming magmatism and during postcaldera batholith assembly. Silicic magmas were generated multiple times throughout the history of the Latir magmatic center, but few are associated with the formation of a mineral deposit. Whole-rock trace element ratios and Sr, Nd, and Pb isotope compositions vary throughout the protracted history of silicic magmatism. The caldera-forming ignimbrite and early phase of postcaldera intrusions are unmineralized, more enriched in high field strength elements, and generally contain less radiogenic Sr and Pb and more radiogenic Nd than later intrusions. The Questa porphyry Mo deposit formed immediately after the most isotopically primitive phase of the batholith was assembled, ruling out simple reworking of juvenile mantle-derived crust as the source for mineralizing magmas. Rhyolite dikes associated with polymetallic sulfide deposits intruded ~800 k.y. after Mo mineralization, and Nd isotope data indicate that these dikes are associated with different batches of magma and are unrelated to the Mo-mineralizing intrusions at the Questa mine. Together, these data indicate that the source of magmas changed significantly throughout the 10-m.y. history of the magmatic center. We assess multiple genetic models for porphyry-related magmatism against this data set, favoring models with discrete periods of magma genesis from a deep hybridized zone in the lower crust giving rise to the punctuated periods of mineralization. These observations suggest that the formation of mineral deposits within a central magmatic locus is likely the result of the piecemeal assembly of individual hydrothermal-magmatic systems, and that distal and younger polymetallic mineralization commonly observed near known porphyry deposits represents decoupled processes.

New Mexico↗

Timing of hydrothermal alteration and Au-Sb-W mineralization, Stibnite-Yellow Pine district, Idaho

The Stibnite-Yellow Pine district of central Idaho was mined from the early 1900s until the 1990s, extracting gold, antimony, tungsten, and mercury from veins and disseminated and replacement ores in mountainous terrain along the headwaters of the Salmon River. Mining during the two World Wars supplied critical antimony and tungsten to the war efforts. Recent exploration has delineated mineral resources of over 187 metric tons Au, 274 metric tons Ag, and 93,000 metric tons Sb. Mineralization is hosted in Cretaceous Idaho batholith granitic rocks and a sequence of Neoproterozoic to Paleozoic metasedimentary strata of carbonate and siliciclastic compositions. Historical studies outlined some of the complex paragenesis but debated the absolute age of mineralization. New petrographic and geochronologic work documents a sequence of five hydrothermal events in the Stibnite-Yellow Pine district. Event 1 is related to Cretaceous magmatic and hydrothermal activity and includes events ranging in age from 86 to 75 Ma, including sparse quartz-molybdenite veins dated at 86 Ma. Disseminated gold mineralization of event 2 is associated with sericitic alteration and sulfidation of igneous biotite and replacement of plagioclase by potassium feldspar, largely in granodiorite. Gold is present in zoned arsenian pyrite in both disseminated ores and in crosscutting carbonate-quartz veins containing pyrite and arsenopyrite. The large Yellow Pine deposit, localized at a dilatant bend in the Meadow Creek fault, hosts such disseminated and vein gold. Event 2 is interpreted as the major gold-forming event; 40 Ar/ 39 Ar ages of sericite and potassium feldspar alteration range, respectively, from 70 to 59 and 66 to 56 Ma. The long span is interpreted to reflect the age of gold mineralization and local overprinting by event 3. A narrower range from 66 to 61 Ma is interpreted to date the peak of gold mineralization and alteration. Event 3, tungsten mineralization with scheelite, is texturally later than event 2 gold and localized along the Meadow Creek structure. Event 3 scheelite has been dated by isotope dilution-thermal ionization mass spectrometry (ID-TIMS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb methods at 57 Ma. Event 4, best developed in the West End area, includes gold-silver–bearing quartz-carbonate-pyrite veins and breccias with epithermal textures and potassium feldspar alteration envelopes. Adularia from event 4 yields 40 Ar/ 39 Ar plateau ages of 52 to 51 Ma. Event 5 antimony and mercury mineralization consists of stibnite veins and breccia cements at the Yellow Pine and Hangar Flat deposits as well as cinnabar veins and replacements at the peripheral Fern and Hermes deposits; it is constrained by an LA-ICP-MS U-Pb date on scheelite (ca. 47 Ma) intergrown with stibnite. Minor propylitic and argillic alteration is evident in 47 Ma igneous dikes, which do not contain economic mineralization. The Au-Sb-W ores in the Stibnite-Yellow Pine mining district formed over an extended time period from about 70 to 45 Ma in multiple pulses that were localized along the Meadow Creek fault zone. Each event corresponds to episodes of magmatism and/or hydrothermal activity in the region. Insignificant event 1 skarn and molybdenum mineralization is similar in age to the Thompson Creek porphyry molybdenum deposit in central Idaho. Event 2 gold mineralization occurred during a magmatic gap in central Idaho but was synchronous with magmatism in the Bitterroot lobe further north; event 2 is similar in age to orogenic gold-arsenic mineralization at the Beartrack mine in eastern Idaho. Event 3 scheelite mineralization coincides with tungsten mineralization at the Quartz Creek deposit, late magmatism in the Bitterroot lobe, and rapid exhumation of the Atlanta lobe of the Idaho batholith. Event 4 gold mineralization is coincident with the onset of regional Challis magmatism and extension. Event 5 antimony and mercury mineralization is time-equivalent to epithermal gold mineralization in the nearby Thunder Mountain volcanic field and the peak of Challis magmatism.

Idaho↗