NaCl Equiv Research Articles

Geological and Geochemical Constraints on the Origin of the Sr Mineralization in Huayingshan Ore District, Chongqing, South China

There are many celestine deposits and mineralization points in the Huayingshan ore district which form the largest strontium resource base in China. Among these celestine deposits, the Yuxia and Xinglong are two of the larger deposits. Previous studies have displayed different views on the genesis of the celestine deposit in the Huayingshan ore district. In this study, we conducted field obversions, geochemistry, and fluid inclusion studies to investigate the sources of ore-forming matters and the metallogenic mechanism of the celestine deposit. Four types of fluid inclusion (FI), namely PL (pure liquid FI), PV (pure vapor FI), L-V (liquid-vapor two-phase FI), and L-V-S (liquid-vapor-solid three-phase FI) have been identified in celestine from different types of ore in the Xishan anticline. The ore-forming fluids belong to the NaCl-H2 O system with moderate to low temperature (190–220 °C) and moderate salinity (5–9 wt%, NaCl equiv.). Different types of ores were formed by the same period of hydrothermal activity, which is supported by the results of the microthermometer study. Geological, thermometric data, and published hydrogen and oxygen isotope results indicate that the hot brines associated with mineralization mainly originated from meteoric water and some of diagenetic fluid. The Sr (87Sr/86Sr = 0.7076–0.7078) and S (δ34S = 36.4–39.0) isotope values of celestine are consistent with those of the Jialingjiang Formation, indicating that ore metals in hot brines were predominantly derived from that formation. In situ analysis of celestine shows that there is a strong negative correlation between Sr and CaO (R2 = 0.95) and combined with mineralogical and isotope geochemical evidence, we concluded that the precipitation mechanism of celestine is the replacement of gypsum with Sr-rich hot brines. Based on the above research and the classification of celestine deposit type, we classified the celestine deposits in Huayingshan as being of hydrothermal type. The formation of celestine deposits can be divided into three periods: (1) evaporation period, forming the source bed; (2) hydrothermal activity period, forming celestine by replacement of gypsum with Sr-rich hot brines; (3) supergene period, where meteoric water dissolves orebodies and strontianization occurs.

Fluid evolution and metallogenic mechanism of the Xianghualing skarn-type Sn deposit, South China: Evidence from petrography, fluid inclusions and trace-element composition of cassiterite

The Xianghualing Sn-polymetallic deposit is a large skarn-type Sn deposit located in the Nanling polymetallic metallogenic belt, South China. The ore bodies are controlled by NE-trending faults and mainly hosted in the contact of Middle Devonian carbonate rock and granite. The Xianghualing deposit is divided into four mineralization stages, and two stages of Sn mineralization are identified. The mineralization stages from early to late include stage I (prograde stage), stage II (retrograde stage), stage III (cassiterite-magnetite-arsenopyrite-topaz-quartz stage), stage IV (sphalerite-galena-pyrite-chalcopyrite-quartz-calcite stage). Stage II is the initial stage of Sn mineralization where only minor cassiterite precipitates, and stage III is the main Sn mineralization stage where abundant cassiterite precipitates. On this basis, fluid inclusion microthermometry and Raman spectroscopy analyses were carried out for ore and/or gangue minerals at different stages. In addition, trace element composition analysis was also conducted on cassiterite. These data can contribute to reveal the fluid properties, evolution and formation mechanism of Xianghualing deposit. Three types of fluid inclusions were identified in different mineralization stages, including halite-bearing multi-phase inclusions (Type B), liquid-rich two-phase inclusions (Type L) and vapor-rich two-phase inclusions (Type V). Garnet (stage I) contains Type B inclusions and Type V inclusions, with homogenization temperatures and salinities of 511–549 °C, 37.6–48.9 wt% NaCl equiv. and 551–559 °C, 4.0–5.1 wt% NaCl equiv., respectively. Topaz (stage II) contains Type L inclusions with homogenization temperatures of 408–445 °C and salinities of 9.5–12.4 wt% NaCl equiv. Cassiterite (stage III) contains Type L inclusions with homogenization temperatures of 368–417 °C and salinities of 8.7–11.5 wt% NaCl equiv. Quartz (stage IV) contains Type L inclusions with homogenization temperatures of 162–227 °C and salinities of 2.6–5.0 wt% NaCl equiv. The temperature and salinity of the fluid from stage I to stage II decreased significantly, recording intense meteoric water mixing. The temperature of the fluid decreased from stage II to stage III, while the salinity changed little, indicating that, except for minor meteoric water mixing, cooling of fluid is predominant. The temperature and salinity of the fluid from stage III to stage IV continued to decrease, recording the further mixing of meteoric water. From stage II to stage III, the evolution temperature of the fluid is basically consistent with the temperature indicated by trace elements (Nb, Ta, Ti) of cassiterite in the two stages. Fluid mixing may be the predominant mechanism for the minor Sn mineralization occurred in stage II. Fluid cooling may be the predominant mechanism for the abundant cassiterite precipitation in stage III, which is accompanied by redox reactions of Sn (II)-Cl complexes with As (III) and/or CO2 as potential oxidants, and acid neutralization of carbonate rocks. Combined with the cassiterite composition, it is indicated that the ore forming fluid of the Xianghualing deposit mainly derived from the highly evolved granitic magma in the region, and the genesis of cassiterite is consistent with that of typical skarn-type Sn deposits.

Characteristics of the gold-bearing and barren quartz veins at the Zaylik-Sarilar epithermal deposit, Ahar-Arasbaran Zone, NW Iran: Evidence from mineralogy, alteration, texture and fluid inclusion

The Zaylik-Sarilar epithermal deposit is located 35 km southeast of Ahar in the Ahar-Arasbaran Zone in the Alborz-Azerbaijan Magmatic Belt, NW Iran. Exposed rocks in the Zaylik-Sarilar deposit are mainly composed of Eocene volcanic rocks and Miocene dacite-rhyodacite that are intruded by younger intrusions. The deposit occurs within a sequence of Eocene porphyritic andesite and andesitic lithic tuff. Mineralization occurs as open space filling, taking place as irregular veins, veinlets, and hydrothermal breccias. The mineralization zones can be categorized into two main groups according to sulfides and sulfosalts mineralogy, alteration assemblages, ore textures, and fluid inclusion data. The first group consists of gold-bearing quartz-sulfide ± breccia veins, silicified-phyllic ± argillic zones, and a few quartz-calcite veins. The second group is composed of barren milky (or white) quartz veins, silicified lithocaps, and argillic-kaolinite ± silicic zones. Pyrite, chalcopyrite, bornite, galena, sphalerite, and Au-Ag sulfosalts were identified in ore paragenesis of the gold-bearing veins. Pyrite is the main sulfide mineral in the barren quartz veins and silicified lithocaps. Gold and silver were enriched during oxidation and supergene alteration of the gold-bearing veins. Textural evidences from the gold-bearing veins, such as mosaic breccia monomicts, floating clast breccias, hydrothermal breccias, colloform-crustiform textures, ginguro bands, dendrite textures, and rarely lattice- and parallel-bladed calcite replacement textures, suggest that boiling occurred in the veins. Comb, cockade, reed molds, zonal, and feathery textures are common in the barren veins and silicified lithocaps. Fluid inclusion data show a decreasing trend in salinity and homogenization temperature (Th) from the gold-bearing quartz veins to the barren ones. The average salinity and homogenization temperature (Th) of fluid inclusions from the gold-bearing veins are 1.05 wt% NaCl equiv. and 297 °C, respectively; higher than the average salinity (0.68 wt% NaCl equiv.) and homogenization temperature (192 °C) of fluid inclusions from the barren quartz veins. Th versus salinity diagram suggests that boiling was the main mechanism of ore deposition in the gold-bearing quartz veins and silicified zones. These data propose that the barren quartz veins and silicified lithocaps were formed by cooling. A combination of the geologic, mineralogic, alteration, and fluid inclusion data from the Zaylik-Sarilar deposit represents an epithermal system of low-sulfidation type. Structurally, mineralization has been controlled through the NW-trending strike-slip principal displacement zone and it’s subsidiary Riedel fractures in response to a N-trending compression in the Arabia-Eurasia collision zone.

Fluid evolution and origin of the Tamazert fluorite deposits, Moroccan High Atlas

This study focuses on the origin of fluorite ore deposits that are associated with the Eocene alkaline igneous suite of the Tamazert complex in the Moroccan High Atlas. Based on field observations and mineralogy, two major ore styles were identified: 1) a disseminated purple fluorite in aegirine-rich nepheline syenites (stage 1) and 2) a banded purple-white fluorite ore in karstic cavities and veins hosted in the Jurassic carbonate (stage 2). Both fluorite mineralization stages are commonly accompanied by calcite. The distribution of fluorite deposits at the peripheries of syenite and the surrounding Jurassic carbonates suggests the development of long-lived hydrologic systems around the shallow intrusion. Based on fluid inclusion, Rare Earth Elements and Yttrium (REY), and C–O isotopic constraints, this study reveals that different fluid systems were responsible for the deposition of fluorite ores in and around the Tamazert alkaline igneous complex. The disseminated interstitial fluorite precipitated from a F-rich magmatic-hydrothermal fluid, which exsolved from the highly evolved alkaline-silicate melt and was subsequently altered by Na–Ca metasomatic brines. Vein-type fluorite deposits hosted in the Jurassic carbonates precipitated from low salinity (1.6–8.5 wt% NaCl equiv.) and heated (Th = 118–157 °C) meteoric fluids, which migrated in response to the heat flow around the shallow intrusion. Fluid cooling, fluid interaction with Jurassic carbonates, and pressure fluctuations were the most important fluorite deposition mechanisms. The evolved melt provided F and REY for the interstitial fluorites, whereas meteoric fluids leached F− from syenites and other F-bearing igneous rocks. Based on the fractionation pattern, the REY inventory of the vein fluorites was acquired by interaction of meteoric fluids with Jurassic carbonates.

Thermal history of Carlin-type gold deposits in Yukon (Canada) as revealed by organic matter geothermometry, clumped isotope data, fluid inclusion microthermometry, and apatite fission-track analyses

Sediment-hosted gold deposits in central Yukon have most of the diagnostic characteristics of Carlin-type gold deposits in Nevada. This study combines organic matter geothermometry with fluid inclusion microthermometry, clumped isotope data (Δ47) for late ore-stage hydrothermal calcite, and apatite fission-track analyses to constrain the thermal evolution of Carlin-type gold zones in central Yukon. The Tmax parameter derived from pyrolysis analyses indicates that organic matter is overmature and records regional temperatures of > 150 °C. Calcite and fluorite associated with the waning stage of mineralization at ca. 74 Ma have mean fluid inclusion homogenization temperatures of 123–173 °C, with an average salinity of 4.8 wt.% NaCl equiv. These temperatures overlap values of 91–162 °C determined from calcite clumped isotope measurements and are similar to data from Carlin-type deposits in Nevada. Fluid mixing is suggested by a variation of the isotopic composition of the fluid in equilibrium with calcite, with the higher temperature end-member having higher δ18OH2O values. In thermal models based on Tmax, fluid inclusion microthermometry, clumped isotope measurements, and apatite fission-track data, a higher temperature event at approximately 220 °C is consistent with pyrobitumen reflectance measurements. This event is either related to maximum tectonic burial prior to mineralization or to the flow of acidic hydrothermal fluids early in the main ore-stage. Each analytical technique used in this study is independent of the others and records part of the thermal and chemical evolution of the Yukon Carlin-type gold deposits and their host rocks.

Melt- and fluid-inclusions studies in the Wunugetushan porphyry Cu–Mo deposit, NE China: Constraints on the separation of Cu and Mo

The Wunugetushan large porphyry Cu–Mo deposit in NE China is hosted by Mesozoic quartz monzonite porphyry and has a Mo-rich core and Cu-rich rim in space. In this paper, melt inclusions in porphyry intrusions and fluid inclusions in different-stage quartz veins were studied to explore potential parameters leading to Cu–Mo decoupling. Melt inclusions in porphyry intrusions have rhyolitic compositions of 71.7–85.3 wt.% SiO2, 1.9–31.3 ppm Cu and 1.7–2.6 ppm Mo. Hydrothermal activity occurred over three stages: 1) Early Mo mineralization at high temperatures (543°C–560°C) and CO2-rich fluids of intermediate salinity (11.0–17.3 wt.% NaCl equivalent), accompanied by biotitization and minor K-feldspathization; 2) Late Mo mineralization involving high-salinity (up to 77.0 wt.% NaCl equiv.) oxidized fluids at intermediate temperatures (400°C–454°C), with K-feldspathization and minor sericitization; 3) A Cu-mineralization stage with high-salinity (up to 45.6 wt.% NaCl equiv.) and CO2-barren fluids characterized by temperature peaks at 250°C–300°C and 400°C–450°C, accompanied by sericitization and illitization. Given possible variations in melt Cu/Mo ratios during magmatic activity and redox conditions, pH, fluid composition, and temperature during the hydrothermal-fluid stage led to the separation of Cu and Mo, we found that integrated parameters including increased Cu/Mo ratios in residual melt, variations in the redox state and more acidic environment of hydrothermal fluids determine spatial separation of two metals.

Genesis of the Mianhuakeng granite-related uranium deposit, South China: Insights from cathodoluminescence imaging, fluid inclusions, and trace elements composition of hydrothermal quartz

The Mianhuakeng deposit is the largest granite-related U deposit in China, with multiple hydrothermal quartz veins. However, its genesis and ore-forming processes are still under discussion. In the present study, we have attempted to unveil the characteristics of ore-forming fluids and the metallogenesis of Mianhuakeng deposit with the help of cathodoluminescence (CL) imaging, fluid inclusions (FIs), trace elements, as well as hydrogen-oxygen (H-O) isotope compositions of hydrothermal quartz associated with U mineralization. Based on the crystallography and CL textures, four generations of hydrothermal quartz have been identified: early stage QtzⅠ quartz, main stage QtzⅡa and QtzⅡb quartzes, and late stage QtzIII quartz. QtzⅠ was formed by a continuous fluid flow in an open fluid system. The formation of QtzIIa was associated with a brief period of fluid flow in a compressive fluid system, whereas QtzIIb crystallized in an open system with a stable fluid flow. QtzIII was produced by fluid chemical fluctuation in an open system. These quartzes show high Al, variable Li, Na, K, and Ca, moderate Rb and Ba, and low Ti, Fe, Ge, and U contents. Al3+ and Ge4+ were incorporated into the quartz crystal lattice by substituting Si4+, helped by the change compensators composed of Li, Na, K, Rb, Ca, and Ba. The FIs microthermometry results suggested that ore-forming fluids were NaCl–H2O ± CO2 system with moderate to low temperatures and salinities. A gradually decreasing trend has been recorded for temperatures from 225 to 353 °C, through 153–302 °C, and toward 105–161 °C, respectively, with salinities changing from 6.0 to 10.1 wt% NaCl equiv, through 0.6–10.1 wt% NaCl equiv, to 0.5–5.7 wt% NaCl equiv from early to late stages. The H-O isotopic results indicated that the ore-forming fluids were originated from a mixture of deep magmatic and meteoric waters, with an increase in the amount of meteoric water from early to late stages. Fluid decompression and immiscibility were triggered by episodic fracturing of NS-trending fractures, which resulted in a fluid flow transition from extrusion to opening and the breakdown of uranyl complexes. The Fe2+ from altered granites reduced free U6+ to U4+, forming pitchblende (UO2) in hydrothermal quartz veins. Therefore, the Mianhuakeng deposit is thought to be of polygenic in origin and is controlled by several geological factors such as fracturing, fluid immiscibility, and redox reaction.

Genesis of the Shibaogou Mo–Pb–Zn deposit in the Luanchuan ore district, China: Constraints from geochronology, fluid inclusion, and H–O–S–Pb isotopes

The Shibaogou deposit is located in the Luanchuan ore district within the East Qinling orogenic belt (EQOB), central China, which is a newly discovered Mo–Pb–Zn skarn deposit. The skarn and Mo–Pb–Zn ore bodies are mostly hosted in the contact zones between the Shibaogou porphyritic granite and carbonaceous sedimentary rocks from the Luanchuan and Guandaokou sets. A study combined of geochronology, fluid inclusion (FI), and stable isotopes was performed to constrain the mineralization age, source of ore materials, and the origin and evolution of the ore-forming fluids and their relationship with the subduction of the Paleo-Pacific Plate. The mineralization process includes skarn and quartz–sulfide episodes, which has four stages: skarn (I), quartz–molybdenite (II), quartz–galena–sphalerite (III), and quartz–calcite (IV). Molybdenite Re-Os dating suggests that the deposit was formed in the Late Jurassic (147.4 ± 7.2 Ma). Reportedly, there are five primary types of fluid inclusions: L-type, V-type, H-type, S-type, and C-type. In the skarn stage, coexisting H-type (35.58 wt%–46.05 wt% NaCl equiv.) and low-salinity V-type (0.35 wt%–5.7 wt% NaCl equiv.) fluid inclusions show similar homogenization temperatures, which suggests that fluid boiling occurred at 513–550°C and 580–650 bar (2.19–2.45 km). In the quartz–molybdenite stage, the homogenization temperatures of L-type, V-type, minor H-type, and S-type fluid inclusions indicate continued fluid boiling at 324–387°C and 180–250 bar (0.49–0.94 km). In the quartz–galena–sphalerite stage, a fewer number of coexisting V-type and L-type fluid inclusions in quartz shows different salinities with similar homogenization temperatures, indicating that they are trapped at 303–347°C and <150 bar in the boiling process (<0.56 km hydrostatic depth). The minor primary L-type fluid inclusions that have lower salinities of 0.88 wt%–11.34 wt% NaCl equiv were observed in quartz and calcite in the quartz–calcite stage; in addition, their homogenization temperatures are 103–247°C (typical post-ore conditions). This study found that the ore-forming fluids at the Shibaogou deposit were dominantly magmatic water at the early stage, with input of atmospheric water during fluid evolution, with δ18Ofluid values from −1.168‰ to 8.997‰ and δ18Dfluid values from −106.5‰ to −79.9‰, based on the O and H isotope data from garnet, quartz, and calcite. Furthermore, the S isotopic compositions were measured ranging from 0.8‰ to 14.7‰, and it demonstrated that the ore-forming fluid was mainly derived from magmatic sources. The relatively homogeneous Pb isotopic compositions are similar to those of Shibaogou granite porphyry, which demonstrated that the ore-forming materials were mainly derived from magmatic sources. Molybdenite was precipitated as a result of fluid–rock interactions and fluid boiling, and the galena and sphalerite were precipitated as a result of the decreasing temperature. The subduction of the Paleo-Pacific plate has a critical impact on the complex evolution of ore formation in the Shibaogou skarn deposit in EQOB.

Nature and conditions of gold mineralization at the Tau deposit, Mupane mine, Tati Greenstone Belt, Botswana: Evidence from fluid inclusion and arsenopyrite geothermometer

AbstractThe gold mineralization at the Tau deposit in northeastern Botswana can be distinguished into two stages. The first stage of mineralization consists of invisible gold associated with early, sulfur‐rich arsenopyrite (Apy1). The second stage is characterized by native gold associated with late, sulfur‐poor arsenopyrite (Apy2). This study aims to constrain the nature of the ore‐forming fluid at the Tau deposit on the basis of fluid inclusion microthermometry and arsenopyrite geothermometry. Quartz crystals closely associated with gold‐bearing sulfides (Apy1) from the host rock host three types of fluid inclusions occurring in the same assemblages: Type I, two‐phase aqueous fluid inclusions, Type II three‐phase aqueous‐carbonic fluid inclusions and Type III one‐ or two‐phase CO2‐rich fluid inclusions. Microthermometric and Raman spectroscopic studies revealed the dominance of coexisting H2O+NaCl (Type I) and CO2N2CH4 (Type III) fluid inclusions. The coexisting Type I and Type III fluid inclusions could represent products of the immiscibility of a homogenous H2OCO2NaClN2CH4 primary ore fluid. The salinity of Type I (calculated from melting temperature of ice) and Type II (calculated from dissolution temperature of clathrate) fluid inclusions vary from 3.4 to 9.2 wt% NaCl equiv. and 5.8 to 9.8 wt% NaCl equiv., respectively. The overall fluid inclusion salinity range (<10 wt% NaCl equiv.) and gas compositions of fluids suggest that the primary ore‐forming fluid at the Tau deposit was of low salinity and H2OCO2N2CH4NaCl composition. Integration of fluid inclusion microthermometry and arsenopyrite geothermometer results suggest that the first stage and second stages of gold mineralization and the associated alteration at the Tau deposit occurred at pressure and temperature conditions of 75–145 MPa and 290–370°C and 85–160 MPa and 330–370°C, respectively. These results suggest that there was an increase in temperature from the first stage to the second stage of mineralization, resulting in the recrystallization of invisible gold‐bearing arsenopyrite in the first stage to form native gold‐bearing arsenopyrite in the second stage. Fluid composition and the estimated physico‐chemical conditions at the Tau deposit confirm that gold was transported as reduced bisulfide complexes and initial gold deposition was likely caused by a reduction in sulfur contents as a result of sulfidation reactions and pressure‐induced phase separation (fluid immiscibility).

МЕДНО-ПОРФИРОВАЯ МИНЕРАЛИЗАЦИЯ ТАЛЬНИКОВОГО РУДНОГО ПОЛЯ (ОХОТСКИЙ СЕГМЕНТ ОХОТСКО-ЧУКОТСКОГО ВУЛКАНОГЕННОГО ПОЯСА)

The Talnikovoye ore field where previous academic research and exploration work revealed porphyry copper mineralization is described. Our data show that mineralization is confined to the intrusions of Turonian granodiorite and quartz diorite (91 Ma, U-Pb metohod), as well as the accompanying hydrothermal-explosive breccias. Biotite-epidote-chlorite propylites are widespread within the ore field; in the southern part, phyllic alteration is superimposed on the halo of K-feldspar alteration. The ore occurs in zones of intense quartz, chlorite-epidote-quartz (with chalcopyrite and molybdenite), sulfide-potassium feldspar-quartz (with chalcopyrite and bornite), and sulfide-quartz-sericite (with chalcopyrite) stockwork veining with copper-molybdenum mineralization. They are characterized by moderate concentrations of Cu (0.1–0.3 %, reaching 1.1 %) and Mo (up to 0.1 %), low concentrations of Au (up to 0.1 g/t) and Ag (up to 2.6 g/t) and have a Cu-Mo-(Au, Ag, Pb, Zn, Sb, As) geochemical signature. Fluid inclusion data suggest the formation of mineralized veinlet quartz during the magmatic-hydrothermal transition (430–150 °С) with solutions at high (50 wt % NaCl equiv.), medium and low concentration (5–18.9 wt % NaCl equiv.) involved under the cooling-dilution scenario. Values of the main geochemical indicators, such as Cu/Mo (30–60) and Cu/Au (> 1 × 105) ratios allowed us to assign the Tal’nikovoye ore field to the porphyry copper-molybdenum type characteristic of continental-margin volcano-plutonic belts formed at the mafic island-arc basement. The geochemical parameters of porphyry granitoids indicate their formation in a setting of subduction-to-transform plate boundary transition.

A colorimetric investigation of copper(II) solutions

Complex ions containing transition metals, elements with incompletely filled d-orbitals, are usually colored, while similar ions from non-transition metals are not. Copper (Cu) is a transition metal with a flexible coordination sphere, meaning it can adopt many coordination geometries, and therefore have various colored complexes. Addition of Chloride (Cl-) to a CuCl2 solution causes color change away from blue toward a yellowish green. We hypothesized that adding acetone to an CuCl2-water solution would cause a similar shift in solution color. We made aqueous CuCl2 solutions with increasing acetone concentrations ranging from 0 to 100 percent and compared the resulting colors to aqueous CuCl2 solutions with increasing added amounts of NaCl to find the closest visual fit in color from the acetone solutions for each added NaCl equivalent. Our experiment showed that increasing the percent acetone in aqueous CuCl2 solutions gave rise to a color change parallel to that of adding Cl-, shifting solution color away from blue and toward yellow. We propose an explanation of this relationship by considering Cu2+ reduction in high acetone concentrations and discussing ligand field strength and the possible effects of tetrahedral versus octahedral geometries on splitting: weaker splitting may similarly affect color through equilibria leaning towards green/yellow products. This investigation could support our understanding of copper coordination and copper complex color behavior with future implications for other copper complex experiments or, in a broader perspective, detection and evaluation of Cu2+ levels in environmental and biological systems.

The Hydrothermal Evolution of the Alvo Açaí Cu (Au, Mo) Skarn Deposit, Carajás Province, Brazil

Abstract The Alvo Açaí Cu (Au, Mo) skarn deposit forms part of several poorly explored copper deposits in the western sector of the Carajás province in Brazil. Here, a 2.86 Ga metasyenogranitic basement and a 2.71 Ga quartzite of the Liberdade Group are crosscut by diabase and granitic pegmatite dikes in the deposit area. The sequence of hydrothermal alteration at Alvo Açaí is marked by (1) early pervasive calcic-sodic alteration (hastingsitealbite) and (2) potassic iron alteration (biotite-almandine-grunerite) overprinted by (3) silicification (quartz), (4) prograde (grossular-hedenbergite), and (5) retrograde (actinolite-biotite-epidote) skarn stages. Late pervasive chloritization along with epidote-calcite veinlets crosscut the previous alteration zones. The main stage of copper mineralization (I) is spatially and temporally related to the retrograde skarn alteration for which three chalcopyrite-bearing mineral assemblages are distinguished on the basis of textural relationships and mineral associations: (1) actinolite-chalcopyrite-pyrrhotite-pyrite-magnetite-molybdenite, (2) biotite-chalcopyrite-pyrite-magnetite, and (3) epidote-pyrite-chalcopyrite-sphalerite. Minor chalcopyrite occurs along rare latestage epidote-calcite veinlets (mineralization II). The evolution of a single hot H2O-NaCl-CaCl2–dominated magmatic fluid of moderate salinity (22.8–28.6 wt % NaCl + CaCl2 equiv) toward a cooler H2O-NaCl fluid, with likely variable amounts of FeCl2, MgCl2, and KCl of low to moderate salinity (0.1–33.2 wt % NaCl equiv). Fluid evolution as a result of progressive crystallization of the granitic pegmatite was likely the trigger for mineralization I as supported by calculated δ18OH2O values from retrograde quartz. The chalcopyrite and pyrite δ34S values (–1.5, –1.1, and –0.7‰) point to a magmatic origin for the sulfur, which was most probably leached from surrounding igneous host rocks. The evolution of the Alvo Açaí deposit encompasses the development of the first copper skarn mineralization recognized in the Carajás province.

Fluid Origin and Evolution of the Roc Blanc Silver Deposit (Jebilet Massif, Variscan Belt, Morocco): Constraints from Geology and Fluid Inclusions

The Roc Blanc Pb-Zn-Ag-Au vein deposit is located in the NW of Marrakech, in the Central Jebilet massif. It is spatially related to Bramram-Tabouchennt-Bamega (BTB) granodioritic pluton (ca. 330 Ma) metamorphism aureole. The main veins hosted in black shales are oriented N-S to NNW-SSE. Pb-Zn-Ag-Au ore is associated with quartz, chlorite, sericite, and carbonate gangue minerals. Two major stages of ore deposition were distinguished. The preore stage (stage I) comprises two quartz-mineralised vein generations with Fe, As, Zn, and Cu ores (vg1 and vg2). The main ore stage (stage II) consists mainly on Ag, Au, Pb, Zn, Cu, and Sb ores, which is hosted by carbonaceous vein (vg3) and by two late quartz generations veins (vg4 and vg5 with a geodic quartz). Three types of fluid inclusions have been recognized in silver mineralisation bearing quartz veins according to petrographic investigations, microthermometry, and Raman spectroscopy studies: (i) liquid-rich H2O-N2-CH4±CO2-(salt) fluid inclusions (type 1), (ii) vapour-rich H2O-CO2-CH4-N2-(salt) fluid inclusions (type 2), and (iii) aqueous H2O-(salt) fluid inclusions (type 3). The interpretation of fluid inclusion data shows a mixing of two fluids that are metamorphic and surface to subsurface origin, trapped at boiling state. The first mineralised stage was deposited at 350 ± 20 ° C (this temperature of ore deposition was supported also by chlorite geothermometry) with salinity of 13.7 wt% NaCl equiv., while the deposition of the argentiferous stage, which consists of the main economic mineralisation of the Roc Blanc deposit, occurs during decreasing temperature at 150°C with a salinity of 12.1 wt% NaCl equiv. The all-mineralised ore was deposited at relatively low pressure, below ~1-1.1 kbar. So, fluid dilution and cooling are probably the main factor for silver deposition in the Roc Blanc polymetallic vein deposit. In addition, fluid inclusion studies reveal that the mineralising fluid corresponds to a mixture of metamorphic fluid (H2O-CH4-N2-CO2) with surface to subsurface aqueous gas-free fluids (H2O-salt, meteoric, or brine).

The Tatatila–Las Minas IOCG skarn (Veracruz, Mexico): Mineralogical, fluid inclusion and stable isotope constraints

The Miocene skarn deposits at Tatatila–Las Minas are found in central-eastern Veracruz state, east Mexico, near the Palma Sola massif. These deposits are geologically associated with the early stages of the Trans-Mexican Volcanic Belt (TMVB) intruded Mesozoic carbonate rocks of the Sierra Madre Oriental. Skarn associations are distributed in the classic evolution from prograde to retrograde mineralization stage. Prograde associations consist mainly of grossular-andradite, clinopyroxene, quartz, wollastonite, clinopyroxene, potassium feldspar, quartz, epidote, chromian muscovite, and are rich in magnetite, whereas retrograde associations are richer in hematite than magnetite, chlorite, fuchsite, hornblende and additionally contain chalcopyrite, pyrite, bornite, and native gold. The systematic study of fluid inclusions shows a broad variety of petrographic and microthermometric features. Fluid inclusion associations in early prograde minerals show evidence for boiling and effervescence, which are hereby interpreted as deep boiling in the -magmatic environment (or “first boiling”) with no evidence for supercritic fluids. Such a process would account for the generation of two distinct brines at ≤650 °C (a) up to ∼20 wt% NaCl equiv. and (b) up to ∼70 wt% NaCl. Both brines have cooled down independently until the brittle-ductile transition (∼400 °C) bypassed it and were able to interact with other fluids, and perhaps between with each other. Later on, deep isothermal mixing would have occurred between both brines and deeply evolved meteoric water (thermally equilibrated with host rocks). REE geochemistry of garnet suggests that mineralizing fluids at prograde stage evolved from near neutral pH and oxidizing conditions to mildly acidic and reducing conditions, perhaps reflecting the entrainment of shallow fluids. Both brines or their mixed products have experienced further dilution leading to the precipitation of retrograde associations. The most noticeable features in the retrograde stages, however, are conductive cooling and shallow isothermal mixing, this time between the products of the two pathways that originated as two distinct types of magmatic brines. The occurrence of magmatic fluids is corroborated by C and O isotope geochemistry, in which such source presents different types of water/rock interaction with sedimentary C and O from local limestones (δ13CVPDB between 0.9 and 3.7‰ and δ18OVPDB between −7.5 and −3.7‰), thus drawing an isotopic zonation that parallels the marble front associated with skarns (endoskarn calcite, δ13CVPDB between −8.5 and −3.5‰, and δ18OVPDB between −22.4 and −15.0‰). δ34SVCDT values from pyrite, chalcopyrite and galena in retrograde associations (between −3 and 4.2‰) also indicate a dominant magmatic source for sulfur, with a minor sedimentary/metasedimentary contribution. Low H2S concentrations enhanced magnetite deposition in prograde stages, and the progressive increase in H2S concentrations, coupled with a decrease in temperature by conductive cooling, led to sulfide and gold precipitation during retrograde stages. These deposits are hereby classified as IOCG skarn that were developed in association with the regional adakitic stage of the TMVB.

Constraints of C[sbnd]H[sbnd]O[sbnd]S[sbnd]Pb isotopes and fluid inclusions on the origin of the giant Zhugongtang carbonate-hosted Pb–Zn deposit in South China

The Sichuan–Yunnan–Guizhou (SYG) metallogenic province on the western margin of the Yangtze Block has long been a research focus and is an important region of Pb–Zn mineralization in China, but its genesis is poorly constrained. This study examines the Zhugongtang carbonate-hosted Pb–Zn deposit (>3.0 Mt, 0.09–35.04 wt% Pb + Zn), the largest discovery made in the past decade in the southeastern part of the SYG metallogenic province. Fluid inclusions from sphalerite and calcite, CHO–isotopes from calcite, and S–Pb isotopes from sulfide minerals in the Zhugongtang Pb–Zn deposit were analyzed to understand the sources and genesis of the metals and hydrothermal fluids. Fluid inclusions in sphalerite and calcite from the largest ore body indicate that the fluids of the main mineralization stage had low temperatures (105 °C–210 °C) and moderate salinities (0.35–12.89 wt% NaCl equiv.). The sulfides are characterized by narrow ranges of sulfur isotope compositions (δ34Spyrite = +14.27 ‰ to +15.89 ‰, δ34Ssphalerite = +14.31 ‰ to +15.53 ‰, and δ34Sgalena = +10.64 ‰ to +12.97 ‰), indicating that reduced sulfur was derived from sedimentary sulfate in the Devonian to Permian carbonate host rocks by thermochemical sulfate reduction with the addition of organic matter. The δ13CPDB and δ18OSMOW values of calcite range from − 8.6 ‰ to +0.82 ‰ and +15.45 ‰ to +19.41 ‰, respectively, which are similar to values for mantle, marine carbonate rocks, and sedimentary organic matter. The negative correlation between δ13CPDB and δ18OSMOW values indicates that CO2 in the hydrothermal fluids was sourced from marine carbonate rocks and sedimentary organic matter. Calculated δ18OH2O and δDH2O values range from +3.5 ‰ to +7.5 ‰, and −93 ‰ to −52 ‰, respectively, indicating that the ore-forming fluids were dominantly metamorphic, but diluted by meteoric water that had reacted with organic matter. The galena samples yield 206Pb/204Pb values of 18.52 to 18.82, 207Pb/204Pb of 15.68 to 15.93, and 208Pb/204Pb values of 38.97 to 39.96. The μ and ω values of the sulfides range from 9.61 to 10.07 and 38.84 to 43.67, respectively. These data plot on the upper crust Pb evolution curve, generally in the field of Devonian to lower Permian sedimentary rocks, although the value for one sample falls in the field of Proterozoic metamorphic rocks, pointing to a complex origin for the ore-forming materials. Overall, the fluid inclusion and isotope data, together with geological evidence, suggest that the ore-forming fluids of the Pb–Zn deposit were sourced from deep metamorphic water with the features of low temperatures and moderate salinities, and the ore-forming metals were sourced from Devonian to lower Permian sedimentary rocks and partly from basement rocks. The genesis of the Zhugongtang ore is typical of SYG-type deposits.

Zangalou Manto‐type deposit in the Sabzevar zone, northeast Iran: Evidence of mineralogy, geochemistry, U–Pb dating, fluid inclusion, and stable isotopes

The Zangalou Cu deposit lies in the Sabzevar volcanic‐plutonic zone, northeastern Iran. The deposit is hosted by the middle Eocene volcanic‐sedimentary sequences and it has been affected by propylitic, carbonate, sericitic, and minor argillic alterations. The volcanics have features typical of calc‐alkaline and metaluminous magmas and are plotted in the continental volcanic arc region. Zircon U–Pb dating of the andesite porphyry yield ages of 41.2 and 38.4 Ma (Bartonian). Ore mineralization occurs as stratabound with open‐space filling, dissemination, veinlet, and replacement textures in mineralized conglomerate, andesite porphyry, and trachyandesite host rocks. Cu content in Zangalou deposit vary from 1,234 g/t to 6.24% which mostly occurred as chalcocite mineral. Fluid inclusion data of mineralization‐related calcites indicate medium salinities (12.8–16.6 wt.% NaCl equivalents) and a wide range of temperatures (154–295°C) and show evidence of fluid cooling trend during the ore formation. The δ13C (between 19.3 and −2.8‰) and δ18OSMOW (between 24.8 and 25.34‰) values of ore‐related calcites suggests a contribution of sedimentary organic matter and marine carbonates as the source of carbon in the ore‐forming fluid. High positive δ34S values (27.8–33.47‰) suggest that the source of sulphur is related to sedimentary country rocks. Mineralization is lithologically and structurally controlled and it is epigenetic. According to geological, petrological, alteration, mineralization textures and geometry of deposit, fluid inclusion, and isotopic studies, the Zangalou deposit is similar to manto‐type deposits.

The Baogutu gold deposit in west Junggar, NW China: An epizonal intrusion-related gold deposit

The Baogutu gold deposit (∼4 Mt ore @ 5.5 g/t Au) in West Junggar, is hosted by Early Carboniferous volcano-sedimentary rocks and Late Carboniferous dioritic dikes. Both the dikes and gold mineralization are controlled by NE-trending faults. Two diorite dikes in direct spatial association with gold-bearing quartz veins have LA–ICP–MS zircon U–Pb ages of 316 ± 5 Ma and 314 ± 3 Ma, respectively. The emplacement ages of the dikes are a little older than reported gold mineralization ages (312–311 Ma), which is consistent with their crosscutting relationships. Gold mineralization occurs in quartz veins and stockworks in altered tuff, tuffaceous siltstone, silty mudstone, and dikes. Three gold-bearing vein stages have been identified: (I) pyrite–quartz veins in the deep part of the system; (II) stibnite–quartz veins and (III) native arsenic–quartz veins at shallower-level. Fluid inclusion study shows that the pyrite–quartz veins of stage I formed at temperatures between 345 and 265 °C from fluids with salinities of 5.1–9.1 wt% NaCl equiv, whereas the native arsenic–quartz veins of stage III formed at ∼200 °C from fluids with salinities of 1.4–3.9 wt% NaCl equiv. The ore-forming pressure is estimated to be ∼50–62 MPa, corresponding to mineralization depth of ∼3.3–4.0 km. Oxygen and hydrogen isotope compositions of the fluids (δ18OH2O = 7.9 to 11.2 ‰, δD = -88 to −96 ‰) indicate that the initial hydrothermal fluids have a magmatic source, with involvement of meteoric water in the late stage. The in-situ lead isotopic compositions of pyrite in stage I pyrite–quartz veins are similar to those of bulk sulfide minerals in the Baogutu porphyry Cu deposit, and close to the porphyry stocks, whereas the stibnite and native arsenic in stage II and III quartz veins have more radiogenic lead isotopic signatures due to water–rock exchange with the wall rocks. The Baogutu gold deposit shows affinities to epizonal gold deposits in intrusion-related gold systems (IRGS). The IRGS model suggests that, sheeted, disseminated and vein-type Au–As–Bi mineralization might be found hosted in dioritic to granitic stocks and proximal strata, and vein-type Au–As–Sb mineralization in distal faults.

Fluid origin and evolution of the Pusangguo Cu–Pb–Zn skarn deposit in Tibet: Constraints from fluid inclusions and isotope compositions

he Pusangguo Cu–Pb–Zn skarn deposit is a representative Co-bearing deposit in the Gangdese metallogenic belt. The mineralization mainly has a close relationship with the biotite granodiorite. Here we identified four paragenetic stages during the ore formation: prograde skarn stage (stage 1) dominated by garnet and less diopside, retrograde stage (stage 2) which is characterized by epidote, chlorite and actinolite, quartz polymetallic sulfide stage (stage 3) featured by chalcopyrite, sphalerite, galena with minor cobaltite and aikinite, and quartz calcite stage (stage 4). In this study, fluid inclusion, H–O, He–Ar, S and Pb isotope compositions were determined to constrain the sources and evolution of the ore-forming fluids, metal deposition mechanisms and metallogenetic model for the Pusangguo deposit. The He–Ar isotopic compositions (3He/4He = 0.39–0.55 Ra, 40Ar/36Ar = 299–366) show that the ore-forming fluids predominantly derived from crust source with minor mantle input. The H–O isotopic analysis results (δ18OH2O = −13.3 to + 4.9 ‰, δD = −168 to −79.5 ‰) suggest that the ore-forming fluids were sourced from a magmatic origin that mixed with some meteoric water. The S–Pb isotopic results suggest that the ore-forming materials were mostly derived from the upper crust with a minor amount of mantle materials and the biotite granodiorite magma contributed most of the lead and possibly other metals. Fluid inclusion petrography and microthermometry results show that the fluid inclusion assemblages developed in the different mineralization stages of Pusangguo deposit changed from type II (vapor-rich two-phase fluid inclusions) + type III (daughter mineral-bearing three-phase fluid inclusions) to type I (liquid-rich two-phase fluid inclusions) + type II + type III + type IV and eventually evolved into type II. Correspondingly, the ore-forming fluids mainly belonged to H2O-NaCl solutions and changed from high temperature (413–532 °C), moderate–high salinity (15.5–53.1 wt% NaCl equiv.) fluid system in stage 1 to a lower-temperature (176–234 °C) and lower-salinity (0.7–4.2 wt% NaCl equiv.) meteoric water during stage 4. Fluid boiling and mixing were likely the vital factors controlling the metal precipitation.

Genesis of the Loma Galena Pb-Ag Deposit, Navidad District, Patagonia, Argentina: A Unique Epithermal System Capped by an Anoxic Lake

Abstract Loma Galena (978,852 t Pb, 206 Moz Ag) is one of eight epithermal deposits in the world-class Navidad Pb + Ag ± (Zn, Cu) district located in the Cañadón Asfalto continental foreland basin, northern Patagonia, Argentina. This basin formed during the Jurassic in an extensional tectonic regime during the breakup of Gondwana. Host rocks comprise major listric faulted and tilted blocks of K-rich andesite to dacite lava flows (173.9–170.8 Ma; U-Pb ages for zircon) unconformably overlain by mudstone interbedded with stromatolitic and pisolitic limestones, sandstone, coal, and an Sr-rich evaporite layer deposited in a lacustrine environment. The mineralization occurs as disseminations in the organic-rich sedimentary rocks, in veins and hydrothermal breccia dikes in the hanging walls and footwalls of NW- and NE-striking normal faults, in volcanic autobreccias, and in a phreatic breccia at the contact of volcanic and sedimentary rocks. The earliest hydrothermal minerals consist of veins of colloform, crustiform, and cockade calcite 1 (δ13Cfluid –4.7 to 0.8‰; δ18Ofluid 4.8–11.6‰) and siderite. The precipitating fluids were likely basement-exchanged basinal brines having salinities of 9.5 to 16.4 wt % NaCl equiv and temperatures of 154.7° to 212°C. The interaction of these fluids with the host volcanic rocks formed calcite, albite, adularia, and celadonite-glauconite-group minerals followed by chlorite and siderite as fO2 decreased. Fluids intermittently boiled, as evidenced by bladed (platy) texture in calcite 1. Subsequent mineralizing stages contributed to the metal endowment of Loma Galena. The abundance of organic-rich mudstone and δ34S from –15.4 to 12.9‰ for sulfides suggests that the bottom waters of the lake were anoxic and the loci of microbial sulfate reduction (evaporites have δ34S 35‰). Mixing of upflowing metal-rich basinal fluids carrying some S from depth with this H2S-rich connate water efficiently precipitated Ag-bearing framboidal pyrite, colloform pyrite-marcasite, chalcopyrite, bornite, tennantite-tetrahedrite, sphalerite, and galena as veins, breccias, and disseminations in host rocks. The highest grade and tonnage of the ores are found in autobreccias at the junction of the uppermost lava flow and in the overlying mudstone, where the addition of a strong microbial signature is recorded in sulfides. This event also led to partial dissolution of magmatic and hydrothermal feldspar and calcite 1 in the altered volcanic rocks. Mineralization was followed by hydrothermal brecciation and successive precipitation of chalcedony (δ18Ofluid 2.6–4.8‰), barite (δ34S 15.7–22‰; 160.9°–183.8°C; 7.7–9.7 wt % NaCl equiv), calcite 2 (δ18Ofluid –10.2 to –3.7‰, 58°–95°C; 1.9–7.0 wt % NaCl equiv), strontianite, and quartz in brecciated veins and breccias; kaolinite (δ18Ofluid 2–6.2‰), illite-smectite, smectite, and carbonates with minor chalcedony and barite in the volcanic rocks; and calcite, chalcedony, and barite in the sedimentary rocks. A trend of decreasing salinity with decreasing temperature and lowering δ18O of the fluids with time suggests dilution of the basinal fluids by mixing with Jurassic meteoric water (δ18O −9 to −5.2‰). Loma Galena is a unique example of a polymetallic epithermal system formed in a sublacustrine anoxic environment that promoted the efficient deposition and preservation of Ag-bearing sulfides, thereby contributing to the large size and relatively high grade of the deposit.

Unravelling the fluid flow evolution and precipitation mechanisms recorded in calcite veins in relation to Pangea rifting–Newark Basin, USA

Calcite veins hosted in the Triassic Stockton, Lockatong and Passaic formations of the Newark Basin are investigated to reconstruct the fluid evolution. To constrain the parameters of calcite precipitation, a microthermometry study was carried, which reveals precipitation of calcite from a low to moderate saline H2O-NaCl fluid (0.4 to 13.2 wt% NaCl equiv.) under low to moderate hydrothermal (137 °C to 232 °C) conditions. This fluid composition is interpreted to reflect mixing between a deep basement-derived heated diluted fluid and relatively low to moderate saline diagenetic formation waters hosted in the different Triassic formations. Carbon and strontium isotope analysis on the vein calcites suggests that these elements are derived from the pre-Triassic basement and the sedimentary cover through fluid-rock interactions. The aforementioned geochemical findings are supported by Rare Earth Elements and Yttrium (REY) systematics and oxygen isotope data.The Late Triassic extensional activity and gravity-driven fluid flow mechanism facilitated the infiltration of meteoric waters to deeper lithostratigraphic units (i.e., Precambrian-Paleozoic basement-Triassic Stockton Formation) where they became heated. In response to the extensional tectonics, the deep-seated hydrothermal basement-derived diluted fluids migrated upward along the tectonic-related fractures and the major faults to upper shallow crustal levels. Here, the heated, diluted meteoric waters were mixed with low, moderately saline, and relatively cooler formation waters, leading to calcite precipitation. The pH increase is suggested to be a contributing factor in the precipitation of calcite.