Fluid unmixing/immiscibility as an ore-forming process in the giant REE–Nb–Fe deposit, Inner Mongolian, China: Evidence from fluid inclusions

The giant Bayan Obo REE–Nb–Fe deposit consists of replacement bodies hosted in dolomite marble made up of magnetite, REE fluorocarbonates, fluorite, aegirine, amphibole, calcite and barite. Two or three phase CO₂-rich, three phase hypersaline liquid–vapor–solid, and two phase liquid-rich inclusions have been recognized in mineralized fluorite and quartz samples. Microthermometry measurements indicate that the carbonic phase in CO₂-rich inclusions is nearly pure CO₂. Fluids involving in REE–Nb–Fe mineralization at Bayan Obo might be mainly of H₂O–CO₂–NaCl–(F–REE) system. Coexistences of brine inclusions and CO₂-rich inclusions with similar homogenization temperatures give evidence that immiscibility happened during REE mineralization. An unmixing of an original H₂O–CO₂–NaCl fluid probably derived from carbonatitic magma. The presence of REE-carbonates as an abundant solid in fluid inclusions shows that the original ore-forming fluids are very rich in REE, and therefore, have the potential to produce economic REE ores at Bayan Obo.     

中国还原性斑岩矿床研究进展及判别标志

世界上大多数斑岩矿床的成矿流体为氧化流体(CO_2 CH_4)。然而,Rowins(2000)提出一些斑岩Cu-Au矿床的成矿流体为富含CH_4的还原流体,矿床缺乏磁铁矿、赤铁矿和硬石膏等表征高氧逸度的矿物,而发育大量的磁黄铁矿,矿床规模小,矿床形成与含钛铁矿的还原性的Ⅰ型花岗岩类有关,并将其称之为还原性斑岩Cu-Au矿床。我国学者研究发现,中国不但发育还原性斑岩铜矿床,还发育还原性斑岩-矽卡岩铜矿床和还原性斑岩钼矿床,我们建议将这三种矿床统称为还原性斑岩矿床。本文基于课题组近十年来的研究工作,并结合前人的研究成果,综合分析了中国发育的大中型还原性斑岩矿床的典型实例,在此基础上,重点阐明中国大型还原性斑岩矿床的特点、流体中CH_4来源及其有关的成矿作用、容矿围岩特点、成矿岩浆氧化还原状态及其成因、矿床形成的构造背景等。与Rowins(2000)提出的还原性斑岩铜矿床规模小的特点不同,中国发育的一些还原性斑岩矿床规模大;我们研究还识别出该类矿床发育独特的热液矿物和矿石矿物,比如,还原性斑岩铜矿发育热液钛铁矿,矿石矿物以黄铜矿为主,罕见斑铜矿、辉铜矿等矿物;还原性斑岩钼矿床出现热液钛铁矿,矿石矿物以辉钼矿为主,罕见黑钨矿和锡石等矿物;还原性斑岩-矽卡岩铜矿床的矽卡岩期发育钙铝榴石、钙铁辉石等还原性矽卡岩矿物和大量的磁黄铁矿,热液期以发育黄铜矿而非斑铜矿和辉铜矿等矿石矿物为特征。因此,还原性斑岩矿床除了Rowins(2000)提出的发育富CH_4还原流体和磁黄铁矿等识别标志之外,还可辅以独特的脉石矿物(如钛铁矿、钙铝榴石、钙铁辉石等)和简单的矿石矿物(如黄铜矿、辉钼矿等)这两个标志进行识别。中国还原性斑岩矿床含矿岩体的围岩中普遍发育还原性岩石(如含碳质沉积岩或火山沉积岩、含亚铁的火山岩或火山沉积岩等);对于成矿流体中CH_4、C_2H_6等还原性气体的来源,多数学者认为CH_4、C_2H_6等还原性气体主要源于还原性围岩,部分源于岩浆。关于还原性斑岩矿床的成矿岩体是否为含钛铁矿的、还原性的花岗岩类,目前研究较少且存在争议,多数学者认为成矿原始岩浆为氧化性岩浆,但其氧逸度偏低,少数学者认为成矿岩浆始终为还原岩浆。还原性斑岩矿床与经典的斑岩矿床的成矿构造背景类似,二者没有明显区别。还原性斑岩矿床显示的还原性热液蚀变和成矿特点均与成矿流体富含CH_4还原气体密切相关,因此,富含CH_4还原流体是还原性斑岩矿床形成的关键。     

Genetic significance of fluid inclusions in the CSA Cu–Pb–Zn deposit, Cobar, Australia

CSA mine exploits a ‘Cobar-type’ Cu–Pb–Zn±Au±Ag deposit within a cleaved and metamorphosed portion of the Cobar Supergroup, central New South Wales. The deposit comprises systems of ‘lenses’ that encompass veins, disseminations and semi-massive to massive Cu–Pb–Zn ores. The systems and contained lenses truncate bedding, are approximately coplanar with regional cleavage and similarly oriented shear zones and plunge parallel to the elongation lineation. Systems have extreme vertical continuity (>1000 m), short strike length (400 m) and narrow width (100 m), exhibit vertical and lateral ore-type variation and have alteration haloes. Models of ore formation include classical hydrothermalism, structurally controlled remobilisation and polymodal concepts; syntectonic emplacement now holds sway.Fluid inclusions were examined from quartz±sulphide veins adjacent to now-extracted ore, from coexisting quartz–sulphide within ore, and from vughs in barren quartz veins. Lack of early primary inclusions precluded direct determination of fluids associated with D₂–D₃ ore and vein emplacement. Similarly, decrepitation (by near-isobaric heating) of the two oldest secondary populations precluded direct determination of fluid phases immediately following D₂–D₃ ore and vein emplacement. Post-decrepitation outflow (late D₃ to early post-D₃) is recorded by monophase CH₄ inclusions. Entrained outflow of deeply circulated meteoric fluid modified the CH₄ system; modification is recorded by H₂O+CH₄ and H₂O+(trace CH₄) secondary populations and by an H₂O+(trace CH₄) primary population. The contractional tectonics (D₂–D₃) of ore emplacement was superseded by relaxational tectonics (D_4P) that facilitated meteoric water penetration and return flow.Under D₂ prograde metamorphism, entrapment temperatures (Tt) and pressures (Pt) for pre-decrepitation secondary inclusions are estimated as Tt300–330 °C and Pt1.5–2 kbar≈Plith (the lithostatic pressure). Decrepitation accompanied peak metamorphism (T350–380 °C) in mid- to late-D₃, while in late-D₃ to early post-D₃, essentially monophase CH₄ secondary inclusions were entrapped at Tt350 °C and Pt=1.5–2 kbar≈Plith. Subsequently, abundant CH₄ and entrained meteoric water were entrapped as H₂O+CH₄ secondaries under slowly decreasing temperature (Tt330–350 °C) and constant pressure (Pt1.5–2 kbar). Finally, with increasingly dominant meteoric outflow, H₂O+(trace CH₄) populations record decreasing temperatures (Tt>300 to <350 down to 275–300 °C) at pressures of Phydrostatic<Pt (1 kbar) <Plith (1.5 kbar).The populations of inclusions provide insight into fluid types, flow regimes and P–T conditions during parts of the deposit's evolution. They indirectly support the role of basin-derived CH₄ fluids in ore formation, but provide no insight into a basement-sourced ore-forming fluid. They fully support post-ore involvement of meteoric water. The poorly constrained entrapment history is believed to span 10 Ma from 395 to 385 Ma.     

Geological features and origin of gold deposits occurring in the Baotou–Bayan Obo district, south-central Inner Mongolia, People's Republic of China

Located at western portion of northern margin of North China craton, the Baotou–Bayan Obo district is one of the most important Fe–REE–Nb and Au metallogenic provinces in China. Presently, about 52 gold deposits and prospects have been discovered, explored and mined, among which Shibaqinhao, Laoyanghao, Houshihua, Saiyinwusu, Wulashan and Donghuofang are the most important ones. All these gold occurrences can be subdivided into three groups (or types) according to its host rocks: (1) hosted by Archean high-grade metamorphic rocks; (2) hosted by Proterozoic sedimentary rocks; (3) hosted by or related to Hercynian alkaline intrusive rocks. The first group contains the Shibaqinhao, Laoyanghao and Houshihua gold deposits. Gold mineralization at these three deposits occurs within Archean amphibolite, gneiss and granulite as gold-bearing quartz veins and veinlet groups containing native gold, electrum, pyrite and chalcopyrite. The Saiyinwusu deposit belongs to the second group, and occurs within Proterozoic sandstone, quartzite and carbonaceous slate as quartz veins and replacement bodies along the fracture zones. Pyrite, marcasite, arsenopyrite, native gold and electrum are identified. The third group includes the Wulashan, Donghuofang and Luchang deposits. Gold mineralization at these three deposits occurs predominantly within the Hercynian alkaline syenite or melagabbro stocks and dyke swarms or along their contacts with Archean metamorphic wall rocks as K-feldspar–quartz veins, dissemination and veinlets. Pyrite, galena, chalcopyrite, native gold and calaverite are major metallic minerals.δ³⁴S value of sulfides (pyrite, galena and pyrrhotite) separates from groups 1 and 2 varies from −4.01‰ to −0.10‰ and −3.01‰ to 2.32‰, respectively. δ³⁴S values of Archean and Proterozoic metamorphic wall rocks for groups 1 and 2 deposits range from −20.2‰ to −17.0‰ and −15.8‰ to −16.2‰, respectively. The values are much lower than their hosted gold deposits. All these pyrite separates from Hercynian alkaline intrusions associated with the gold deposits show positive δ³⁴S values of 1.3‰ to 4.8‰, which is higher than those Precambrian metamorphic wall rocks and their hosted gold deposits. δ³⁴S values of the sulfides (pyrite and galena) from the Donghuofang and Wulashan deposits (group 3) increase systematically from veins (−14.8‰ to −2.4‰) to the Hercynian alkaline igneous wall rocks (2.8‰ to 4.8 ‰). All of these deposits in groups 1, 2 and 3 show relatively radiogenic lead isotopic compositions compared to mantle or lower crust curves. Most lead isotope data of sulfides from the gold ores plot between the Hercynian alkaline intrusions and Precambrian metamorphic wall rocks. Data are interpreted as indicative of a mixing of lead from mantle-derived alkaline magma with lead from Precambrian metamorphic wall rocks.Isotopic age data, geological and geochemical evidence suggest that the ore fluids for the groups 1 and 2 deposits were generated during the emplacement of the Hercynian alkaline syenite and mafic intrusions. The Hercynian alkaline magma may provide heat, volatiles and metals for these groups 1 and 2 deposits. Evolved metamorphic fluids produced by the devolatilization, which circulated the wall rocks, were also progressively involved in the alkaline magmatic hydrothermal system, and may have dominate the ore fluids during late stage of ore-forming processes. Most of these gold deposits hosted by Archean high-grade metamorphic rocks occur at or near the intersections of the NE- and E–W-trending fracture systems. The ore fluid of the group 3 deposits may have resulted from the mixing of Hercynian alkaline magmatic fluids and evolved meteoric waters. The deposits are believed to be products of Hercynian alkaline igneous processes along deep-seated fault zones within Archean terrain.     

Geological characteristics, tectonic setting and preliminary interpretations of the Jilau gold–quartz vein deposit, Tajikistan

The southern Tien Shan metallogenic province of Central Asia hosts a number of important gold resources including the Jilau gold–quartz vein system in western Tajikistan. These deposits were formed at the late stages of continent–continent collision in association with subduction-related magmatism, metamorphism and continental margin deformation attributed to the Central Asian Hercynian Orogeny. Jilau is hosted by a Hercynian syntectonic granitoid intrusive that was emplaced into bituminous dolomite country rocks. Economic mineralisation is associated with a dilational jog within a high-angle, oblique dextral-reverse slip shear zone that was undergoing brittle–ductile deformation. The orebody takes the form of shear-zone subparallel quartz veins and lenses that emanate from a steeply plunging ore shoot of veins and stringers within a silicified and sulphidised granodiorite core. It is thought to have formed by a dynamic process in which fluid flow was governed by a fault-valve mechanism. Numerous cycles of fluid pressure build-up, fault failure, jog dilation, fluid flow, phase separation of low salinity H₂O–CO₂–CH₄(–N₂) fluids, and sealing took place. Gold appears together with scheelite and bismuth minerals predominantly as inclusions in arsenopyrite in quartz veins and altered wall-rock, and is mainly associated with quartz containing fluid inclusions enriched in CH₄. The correlation between high gold grades and high CH₄ concentrations suggests that components of the mineralising fluids were derived from, or passed through, the reducing, carbonaceous rocks in the contact aureole of the intrusive. The occurrence of Au and W in an adjacent Hercynian skarn deposit and in the Jilau orebody, infers that the ore metals in both these systems were ultimately derived from a magmatic source. Received: 15 April 1999 / Accepted: 30 December 1999     

Origin and evolution of the calcic and magnesian skarns hosting the El Valle-Boinás copper–gold deposit, Asturias (Spain)

The El Valle-Boinás copper–gold deposit is located in the southern part of the Rio Narcea Gold Belt 65 km west of Oviedo (NW Spain), within the Cantabrian Zone (Iberian Hercynian Massif). The deposit is related to the Boinás stock, which ranges from quartz-monzonite to monzogranite and intruded (303 Ma) the carbonated Láncara Formation (early Cambrian) and the siliciclastic Oville Formation (middle-late Cambrian).A copper–gold skarn was developed along the contact between the igneous rock and the carbonated sedimentary rocks. The skarn distribution and mineralogy reflects both structural and lithologic controls. Two types of skarn exists: a calcic skarn mainly developed in the upper calcic member of the Láncara Formation, and a magnesian skarn developed in the lower dolomitic and organic-rich member. The former mainly consists of garnet, pyroxene and wollastonite. Retrograde alteration consists of K-feldspar, epidote, quartz, calcite, magnetite, ferroactinolite, titanite, apatite, chlorite and sulfides. Magnesian skarn mainly consists of diopside with interbedded forsterite zones. Pyroxene skarn is mainly altered to tremolite, with minor phlogopite and serpentine. Olivine skarn is pervasively altered to serpentine and magnetite, and is commonly accompanied by high sulfide and gold concentrations. This altered skarn results in a very dark rock, referred to as “black skarn”, which has great importance in gold reserves. Sulfide mineralization mainly consists of chalcopyrite, bornite, arsenopyrite, pyrrhotite and pyrite, while wittichenite, sphalerite, digenite, bismuthinite, native bismuth and electrum occur as accessory minerals.After extensive erosion, reactivation of the northeast-trending fracture zone provided conduits for the subsequent emplacement of porphyritic dikes (285±4 Ma) and diabasic dikes (255±5 Ma). Alteration, characterized by sericitization, silicification, carbonatization and hypogene oxidation took place, as did sulfide mineralization (pyrite, arsenopyrite, sphalerite, chalcopyrite, galena, bournonite, and Fe–Pb–Sb sulfosalts). Veins with quartz, carbonate, adularia and sulfide minerals crosscut all previous lithologies. Jasper and jasperoid breccias developed at the upper parts of the deposits.The fluid inclusion and stable isotope studies suggest a predominantly magmatic prograde-skarn fluid characterized by high-salinity (26–28 wt.% KCl and 32–36 wt.% NaCl) and high temperature, above 580°C. This fluid evolved into two immiscible fluids: a CO₂- and/or CH₄-rich, high-salinity aqueous fluid. Temperatures for the first retrograde-stage are between 350 and 425°C. A second stage is related to a more diluted aqueous fluid (3–6.2 wt.% NaCl eq.) and temperatures from 280 to 325°C. The fluid inclusion study performed on quartz from low-temperature mineralization indicates a very low salinity (0.2–6.2 wt.% NaCl eq.), low-temperature aqueous fluid (from 150 to 250°C), and trapping pressure conditions less than 0.2 kbar. In addition, the stable isotope study suggests that an influx of metamorphic waters derived from the country rocks produced these lower temperature fluids. The last control for the Au mineralization is the Alpine tectonism, which developed fault breccias (cataclasites to, locally, protomylonites) and gold remobilization from previous mineralization.     

Fault–valve action and vein development during strike–slip faulting: An example from the Ribeira Shear Zone, Southeastern Brazil

Fluid inclusion microthermometry and structural data are presented for quartz vein systems of a major dextral transcurrent shear zone of Neoproterozoic–Cambrian age in the Ribeira River Valley area, southeastern Brazil. Geometric and microstructural constraints indicate that foliation–parallel and extensional veins were formed during dextral strike–slip faulting. Both vein systems are formed essentially by quartz and lesser contents of sulfides and carbonates, and were crystallized in the presence of CO₂–CH₄ and H₂O–CO₂–CH₄–NaCl immiscible fluids following unmixing from a homogeneous parental fluid. Contrasting fluid entrapment conditions indicate that the two vein systems were formed in different structural levels. Foliation–parallel veins were precipitated beneath the seismogenic zone under pressure fluctuating from moderately sublithostatic to moderately subhydrostatic values (319–397 °C and 47–215 MPa), which is compatible with predicted fluid pressure cycle curves derived from fault–valve action. Growth of extensional veins occurred in shallower structural levels, under pressure fluctuating from near hydrostatic to moderately subhydrostatic values (207–218 °C and 18–74 MPa), which indicate that precipitation occurred within the near surface hydrostatically pressured seismogenic zone. Fluid immiscibility and precipitation of quartz in foliation–parallel veins resulted from fluid pressure drop immediately after earthquake rupture. Fluid immiscibility following a local pressure drop during extensional veining occurred in pre-seismic stages in response to the development of fracture porosity in the dilatant zone. Late stages of fluid circulation within the fault zone are represented dominantly by low to high salinity (0.2 to 44 wt.% equivalent NaCl) H₂O–NaCl–CaCl₂ fluid inclusions trapped in healed fractures mainly in foliation–parallel veins, which also exhibit subordinate H₂O–NaCl–CaCl₂, CO₂–(CH₄) and H₂O–CO₂–(CH₄)–NaCl fluid inclusions trapped under subsolvus conditions in single healed microcracks. Recurrent circulation of aqueous–carbonic fluids and aqueous fluids of highly contrasting salinities during veining and post-veining stages suggests that fluids of different reservoirs were pumped to the ruptured fault zone during faulting episodes. A fluid evolution trending toward CH₄ depletion for CO₂–CH₄–bearing fluids and salinity depletion and dilution (approximation of the system H₂O–NaCl) for aqueous–saline fluids occurred concomitantly with decrease in temperature and pressure related to fluid entrapment in progressively shallower structural levels reflecting the shear zone exhumation history.     

Origin of fluids in the Hetaoping Pb–Zn deposit,Baoshan–Narong–Dongzhi block metallogenic belt,Yunnan Province,SW China

The Hetaoping skarn type Pb–Zn deposit is located in the Baoshan–Narong–Dongzhi block metallogenic belt (BND belt), a belt between the Tengchong terrane and the Lanping basin. The deposit is hosted by marble of the upper Cambrian Hetaoping Formation and there are no outcrops of plutonic rocks present. This deposit is one of two large Pb–Zn deposits recently discovered in the BND belt. The Hetaoping deposit is a high Mn skarn. Four types of fluid inclusions were recognized in quartz from the deposit: vapor-rich inclusions (Type I), liquid-rich inclusions (Type II), pure vapor inclusions (Type III), and pure fluid inclusions (Type IV). The coexistence of Type I and Type III inclusions in Stage I (pre-ore stage) and Stage II (main ore stage) shows evidence of fluid boiling. Quartz-hosted fluid inclusions (Stage I and Stage II) display high homogenization temperatures and salinities (134–315 °C; 3.7–18.6 wt% NaCl equivalent) but calcite-hosted fluid inclusions in Stage III (post-ore stage) record lower homogenization temperatures and salinities (85–214 °C; 0.5–5.4 wt% NaCl equivalent). These data suggest a possible mixing between primary magmatic water and meteoric water. Based on chromatography data, the fluid inclusions in quartz contain abundant CO₂ and O₂ and subordinate CO, CH₄ and C₂H₂ + C₂H₄, suggesting an oxidizing environment. Based on their Na/K and Cl/SO₄ ratios, fluids contained in fluid inclusions are similar to volcanic spring waters. The low Na/K ratios (0.40–1.34) of the ore-forming fluids may have resulted from interaction with a deep alkaline intermediate-acid intrusion. Hydrogen and oxygen isotope determinations on quartz from different ore stages show low δ¹⁸O and δD values relative to VSMOW (−4.3‰ to 2.3‰; −109‰ to −91‰), indicating that the ore-forming fluids were diluted by external fluid sources as the skarn system cooled. Overall, geological and geochemical interpretations suggest that the Hetaoping deposit is a distal manganese skarn Pb–Zn deposit related to concealed intrusions.     

Gold ore-forming fluids of the Tanami region, Northern Australia

Fluid inclusion studies have been carried out on major gold deposits and prospects in the Tanami region to determine the compositions of the associated fluids and the processes responsible for gold mineralization. Pre-ore, milky quartz veins contain only two-phase aqueous inclusions with salinities ≤19 wt% NaCl eq. and homogenization temperatures that range from 110 to 410°C. In contrast, the ore-bearing veins typically contain low to moderate salinity (<14 wt% NaCl eq.), H₂O + CO₂ ± CH₄ ± N₂-bearing fluids. The CO₂-bearing inclusions coexist with two-phase aqueous inclusions that exhibit a wider range of salinities (≤21 wt% NaCl eq.). Post-ore quartz and carbonate veins contain mainly two-phase aqueous inclusions, with a last generation of aqueous inclusions being very CaCl₂-rich. Salinities range from 7 to 33 wt% NaCl eq. and homogenization temperatures vary from 62 to 312°C. Gold deposits in the Tanami region are hosted by carbonaceous or iron-rich sedimentary rocks and/or mafic rocks. They formed over a range of depths at temperatures from 200 to 430°C. The Groundrush deposit formed at the greatest temperatures and depths (260–430°C and ≤11 km), whereas deposits in the Tanami goldfield formed at the lowest temperatures (≥200°C) and at the shallowest depths (1.5–5.6 km). There is also evidence in the Tanami goldfield for late-stage isothermal mixing with higher salinity (≤21 wt% NaCl eq.) fluids at temperatures between 100 and 200°C. Other deposits (e.g., The Granites, Callie, and Coyote) formed at intermediate depths and at temperatures ranging from 240 to 360°C. All ore fluids contained CO₂ ± N₂ ± CH₄, with the more deeply formed deposits being enriched in CH₄ and higher level deposits being enriched in CO₂. Fluids from deposits hosted mainly by sedimentary rocks generally contained appreciable quantities of N₂. The one exception is the Tanami goldfield, where the quartz veins were dominated by aqueous inclusions with rare CO₂-bearing inclusions. Calculated δ ¹⁸O values for the ore fluids range from 3.8 to 8.5‰ and the corresponding δD values range from −89 to −37‰. Measured δ ¹³C values from CO₂ extracted from fluid inclusions ranged from −5.1 to −8.4‰. These data indicate a magmatic or mixed magmatic/metamorphic source for the ore fluids in the Tanami region. Interpretation of the fluid inclusion, alteration, and structural data suggests that mineralization may have occurred via a number of processes. Gold occurs in veins associated with brittle fracturing and other dilational structures, but in the larger deposits, there is also an association with iron-rich rocks or carbonaceous sediments, suggesting that both structural and chemical controls are important. The major mineralization process appears to be boiling/effervescence of a gas-rich fluid, which leads to partitioning of H₂S into the vapor phase resulting in gold precipitation. However, some deposits also show evidence of desulfidation by fluid–rock interaction and/or reduction of the ore-fluid by fluid mixing. These latter processes are generally more prevalent in the higher crustal-level deposits.     

内蒙古蓬勃山金矿床地质特征及矿床成因

蓬勃山金矿床为一产于石炭系浅变质地层中的石英脉型矿床; 矿脉产出主要受不同方向断裂构造控制,多分布于海西期闪长岩侵入体与围岩接触带附近。微量元素分析表明,海西期闪长岩含金性明显高于石炭系地层,表明其可能为金成矿作用提供了主要的物质来源。流体包裹体研究表明,矿区主要成矿阶段石英中发育含CO₂ 及气液两相包裹体,前者均一温度为211℃ ～ 289℃,盐度为4. 51 ～ 5. 23 wt%NaCl; 后者均一温度为150℃ ～ 320℃,盐度为2. 1 ～ 5. 1 wt% NaCl; 表明成矿流体为中温低盐度NaCl --CO₂ --H₂O 体系热液,分析其成矿流体主要来源于岩浆活动。因此,蓬勃山金矿床为产出于造山带中的中温岩浆热液脉型金矿床。通过对比,其成矿时代、地质特征及流体特征与穆龙套型金矿床具有一定相似性。     

Compositions of magmatic hydrothermal fluids determined by LA-ICP-MS of fluid inclusions from the porphyry copper–molybdenum deposit at Butte, MT

We analyzed 85 fluid inclusions from seven samples from the porphyry Cu–Mo deposit in Butte, MT, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The Butte deposit formed at unusually great depth relative to most porphyry deposits, and fluid inclusions in deep veins trapped a low-salinity, CO₂-bearing, magmatically derived, supercritical fluid as a single aqueous phase. This fluid is interpreted to be the parent fluid that cooled, decompressed, unmixed, and reacted with wall rock to form the gigantic porphyry Cu deposit at Butte. Few previous analyses of such fluids exist.Low-salinity, aqueous fluids from the earliest veins at Butte are trapped in deep veins with biotite-rich alteration envelopes (EDM veins). These veins, and the Butte quartz monzonite surrounding them, host much of the Butte porphyry Cu mineralization. Twenty fluid inclusions in one EDM quartz vein are dominated by Na, K, Fe (from 0.1 to 1 wt.%) and contain up to 1.3 wt.% Cu. These inclusions contain only small amounts (tens of ppm) of Pb, Zn, and Mn, and typically contain Li, B, Ca, As, Mo, Ag, Sn, Sb, Ba, and W in less than detectable quantities. The abundance of Cu in early fluids indicates that a low-salinity, Cu-rich, aqueous ore fluid can be directly produced by aqueous fluid separation from a granitic magma. Similar inclusions (eight) in an early deep quartz–molybdenite vein with a K-feldspar selvage have similar compositions but contain significantly less Cu than most inclusions in the biotite-altered vein. Analyzed inclusions in both veins contain less than detectable concentrations of Mo even though one is molybdenite-bearing.Low-salinity, CO₂-bearing aqueous fluids are also trapped in pyrite–quartz veins with sericitic selvages. These veins cut both of the above vein types and contain inclusions that were trapped at lower pressure and temperature. Thirty-nine inclusions in two such veins have compositions similar to early fluids, but are enriched by up to a factor of 10 in Mn, Pb, and Zn relative to early fluids, and are slightly depleted in Fe. Many of these inclusions contain as much or more Cu than early fluids, although little chalcopyrite is found in or around pyrite–quartz veins.Eighteen halite-bearing inclusions from three veins from both chalcopyrite-bearing and barren veins with both K-silicate and sericitic selvages were analyzed as well. Halite-saturated inclusions are dominated by Na, K, Fe, and in some inclusions Ca. Whereas these inclusions are significantly enriched in Ca, Mn, Fe, Zn, and Pb, fluids in all three veins contain significantly less Cu than early, high temperature, low-salinity inclusions.Analyses of all inclusion types show that whereas bulk-salinity of the hydrothermal fluid must be largely controlled by the magma, fluid–rock interactions have a significant role in controlling fluid compositions and metal ratios. Cu concentrations range over an order of magnitude, more than any other element, in all four samples containing low-salinity inclusions. We infer that variations are the result of fluid trapping after different amounts of fluid–rock reaction and chalcopyrite precipitation. Enrichment, relative to early fluids, of Mn, Pb, and Zn in fluids related to sericitic alteration is also likely the result of fluid–rock reaction, whereby these elements are released from biotite and feldspars as they alter to sericite. In halite-bearing inclusions, concentrations of Sr, Ca, Pb, and Ba are elevated in inclusions from the pyrite–quartz vein with sericitic alteration relative to halite-bearing inclusions from unaltered and potassically altered samples. Such enrichment is likely caused by the breakdown of plagioclase and K-feldspar in the alteration envelope, releasing Sr, Ca, Pb, and Ba.     

Fluorite deposits at Encantada–Buenavista, Mexico: products of Mississippi Valley type processes

Petroleum and aqueous fluid inclusions from the Encantada–Buenavista fluorite mineralized zone in northern Mexico were analyzed by microthermometry, UV fluorescence, Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR) and Confocal Scanning Laser Microscopy (CSLM) to evaluate the geochemical evolution of the mineralizing fluids. Two-phase (petroleum or brine+vapor) and three-phase (petroleum+brine+vapor) inclusions are described. Aqueous and petroleum-rich inclusions commonly occur in the same plane. Vapor-decrepitated and stretched fluid inclusions are present. A low-salinity methane-saturated fluid and a high salinity-fluid with highly variable methane contents are recognized. H₂S is not quantified but is always detected in close association with methane. Petroleum inclusions are of two types: a low methane petroleum fluid (20 mol%) with low T_h (60 °C) and a petroleum fluid with a methane of content near 30 mol% and a T_h of 90 °C.Pressure and temperature diagrams for the aqueous and petroleum inclusions show three main intersects that allow P–T–X reconstruction of fluid evolution at La Encantada–Buenavista. A CH₄- and H₂S-rich low-salinity brine was mixed with oil that migrated under hydrostatic conditions with a thermal gradient of 70 °C/km. The arrival and mixing of a high-salinity aqueous fluid produced overpressure to 300 bars. A return to hydrostatic conditions was accompanied by an increase in the thermal gradient.The brine related to the fluorite orebodies appears to have a genetic relationship with the brines reported from the Jurassic petroleum basins located west of the fluorite bodies and similarities with reported fluids from Mississippi Valley type deposits. It is interpreted that the fluorine-rich fluids migrated toward the platform margins during the mid-Tertiary (30 to 32 Ma) using extension zones related to Basin and Range tectonism. Mixing of two different brines was responsible for precipitation and mineralization. Heat from magmas, related to tectonic extension, caused decrepitation and changes in the shape of fluid inclusions near the contact zones.     

Geologic, Fluid Inclusion and Stable Isotope Constraints on Mechanisms of Ore Deposition at the Datuanshan Copper Deposit, Middle–Lower Yangtze Valley, Eastern China

The Datuanshan deposit is one of the largest and most representative stratabound copper deposits in the Tongling area,the largest ore district in the Middle-Lower Yangtze River metallogenic belt.The location of the orebodies is controlled by the interlayer-slipping faults between the Triassic and Permian strata,and all the orebodies are distributed in stratiform shape around the Mesozoic quartz monzodiorite dikes.Based on field evidence and petrographic observations,four mineralization stages in the Datuanshan deposit have been identified:the skarn,early quartz-sulfide,late quartzsulfide and carbonate stages.Chalcopytite is the main copper mineral and mainly formed at the late quartz-sulfide stage.Fluid inclusions at different stages were studied for petrography,microthermometry,laser Raman spectrometry and stable isotopes.Four types of fluid inclusions,including three-phase fluid inclusions(type 1),liquid-rich fluid inclusions(type 2),vapour-rich fluid inclusions(type 3) and pure vapour fluid inclusions(type 4),were observed.The minerals from the skarn,early and late quartz-sulfide stages contain all fluid inclusion types,but only type 2 fluid inclusions were observed at the carbonate stage.Petrographic observations suggest that most of the inclusions studied in this paper are likely primary.The coexistence of different types of fluid inclusions with contrasting homogenization characteristics(to the liquid and vapour phase,respectively) and similar homogenization temperatures(the modes are 440-480℃,380-400℃ and 280-320℃ for the skarn,early and late quartz-sulfide stages,respectively) in the first three stages,strongly suggests that three episodes of fluid boiling occurred during these stages,which is supported by the hydrogen isotope data.Laser Raman spectra identified CH_4 at the skarn and early quartz-sulfide stages.Combined with other geological features,the early ore-forming fluids were inferred to be under a relatively reduced environment.The CO_2 component has been identified at the late quartz-sulfide and carbonate stages,indicating that the late ore-forming fluids were under a relatively oxidized environment,probably as a result of inflow of and mixing with meteoric water.In addition,microthermometric results of fluid inclusions and H-O isotope data mdicate that the ore forming fluids were dominated by magmatic water in the early stages(skarn and early quartz-sulfide stages) and mixed with meteoric water in the late stages(late quartz-sulfide and carbonate stages).The evidence listed above suggests that the chalcopyrite deposition in the Datuanshan deposit probably resulted from the combination of multiepisode fluid boiling and mixing of magmatic and meteoric water.     

四川里伍黑牛洞铜矿床成矿流体特征及矿床成因研究

黑牛洞铜矿床经历了早期韧性变形-变质作用和成矿期的韧-脆性变形作用。早期韧性变形-变质作用过程中围岩可能分异出含CO2流体,并形成顺片理发育的磁黄铁矿、黄铜矿等矿化。成矿期为伴随江浪穹窿隆升的韧-脆性变形期,含矿石英脉中流体包裹体主要以富液相流体包裹体为主,次为纯气相流体包裹体。流体包裹体成分测试结果显示,富液相流体包裹体主要成分为水,含少量CO2和甲烷等烃类碳质流体;纯气相流体包裹体主要为甲烷,表明成矿流体为富水含炭质流体。流体包裹体氢、氧同位素测试结果表明,黑牛洞矿床含矿流体中的水主要来源于围岩中的变质水。燕山期花岗岩侵位,江浪穹窿隆升,韧-脆性变形形成系列滑脱断层。在此减压、降温过程中,成矿流体被活化并聚集、填充到滑脱断层内。     

滇西北雪鸡坪铜矿床流体包裹体特征研究及矿床成因讨论

雪鸡坪铜矿床产于印支晚期石英二长闪长玢岩-石英闪长玢岩-石英二长斑岩复式侵入体内,为一斑岩型铜矿床。矿床形成经历了多阶段热液成矿作用,主要有微细脉浸染状黄铁矿±黄铜矿-石英、细脉状辉钼矿±黄铁矿±黄铜矿-石英及微细脉状贫硫化物-石英-方解石等。流体包裹体岩相学、显微测温、激光拉曼及碳、氢、氧同位素综合研究表明,微细脉浸染状黄铁矿±黄铜矿-石英阶段石英中主要发育含Na Cl子矿物三相及气液两相包裹体,与含矿的石英二长斑岩石英中发育的流体包裹体特征相似,表明成矿流体主要为中高温、高盐度Na Cl-H2O体系热液,可能主要来源于印支期石英二长斑岩侵入体;辉钼矿±黄铁矿±黄铜矿-石英中主要发育含CO2三相及气液两相包裹体,成矿流体为中温、低盐度Na Cl-CO2-H2O体系热液,与前者来源明显不同;贫硫化物-石英-方解石石英中主要发育气液两相包裹体,成矿流体为中低温、低盐度Na Cl-H2O体系热液,推测其可能较多来自于大气降水。因此,雪鸡坪铜矿床为不同来源、不同地球化学性质热液叠加成矿作用的结果。     

Retrograde fluid evolution at the Rampura Agucha Pb-Zn-(Ag) deposit, Rajasthan, India

Fluid inclusions in mineralized graphite-sillimanite-mica schist from the Rampura-Agucha Pb-Zn-(Ag) deposit, Rajasthan, northwest India, have been investigated by microthermometry and Raman microspectrometry. Three different main types of fluid inclusions in quartz can be distinguished: (1) gaseous (CO₂, partially mixed with CH₄-N₂), (2) low salinity aqueous inclusions (0–8 eq. wt% NaCl) and (3) high salinity aqueous inclusions (NaCl ± MgCl₂-CaCl₂). Low density CO₂-rich and low salinity H₂O inclusions are contemporaneous and occur, together with CH₄-N₂ inclusions, in close association with sulfide mineral inclusions. This indicates immiscibility between the gaseous and aqueous phase and participation of these fluids during the deposition or remobilization of the ore, which occurred over a wide P (1220 to 200 bar) and T (450 to 250 °C). Raman spectra of graphite indicate upper greenschist-facies metamorphic conditions, although host rocks have been metamorphosed at upper amphibolite-facies metamorphic conditions. This indicates that graphite re-equilibrated with the CO₂-rich phase during retrograde metamorphism.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondônia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondônia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Bárbara deposit (Rondônia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sn (±W, ±Ta, ±Nb), and base-metal suite (Zn–Cu–Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0–19 wt.% NaCl eq.) CO₂-bearing aqueous fluids homogenizing at 245–450 °C, and (2) aqueous solutions with low CO₂, low to moderate salinity (0–14 wt.% NaCl eq.), which homogenize between 100 and 340 °C. In the Santa Bárbara deposit, the early inclusions are represented by (1) low-salinity (5–12 wt.% NaCl eq.) aqueous fluids with variable CO₂ contents, homogenizing at 340 to 390 °C, and (2) low-salinity (0–3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320–380 °C. Cassiterite, wolframite, columbite–tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0–6 wt.% NaCl eq.) CO₂-free aqueous solution, which homogenizes at (100–260 °C) and characterizes the sulfide–fluorite–sericite association in the Correas deposit. The late fluid in the Santa Bárbara deposit has lower salinity (0–3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240–450 °C, and 1.0–2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (δ¹⁸O_quartz from 9.9‰ to 10.9‰, δD_H2O from 4.13‰ to 6.95‰) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 °C. In the Santa Bárbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 °C, respectively), and that for the cassiterite-quartz-veins is 415 °C. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (δ¹⁸O_qtz-H2O=5.5–6.1‰) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (δ¹⁸O_mica-H2O=3.3–9.8‰) suggest mixing with meteoric water. Late muscovite veins (δ¹⁸O_qtz-H2O=−6.4‰) and late quartz (δ¹⁸O_mica-H2O=−3.8‰) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor columbite–tantalite precipitation. Change in the redox conditions related to mixing of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit.     

Isotope and fluid inclusion geochemistry of the Cangyuan Pb-Zn-Ag polymetallic deposit in Yunnan,SW China

The Cangyuan Pb-Zn-Ag polymetallic deposit is located in the Baoshan Block, southern Sanjiang Orogen. The orebodies are hosted in low-grade metamorphic rocks and skarn in contact with Cenozoic granitic rocks. Studies on fluid inclusions (FIs) of the deposit indicate that the ore-forming fluids are CO₂-bearing, NaCl-H₂O. The initial fluids evolved from high temperatures (462–498 °C) and high salinities (54.5–58.4 wt% NaCl equiv) during the skarn stage into mesothermal (260–397 °C) and low salinities (1.2–9.5 wt% NaCl equiv) during the sulfide stage. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O: 2.7–8.8‰; δD: −82 to −120‰) suggest that the ore-forming fluids are mixture of magmatic fluids and meteoric water. Sulfur isotopic compositions of the sulfides yield δ³⁴S values of −2.3 to 3.2‰; lead isotopic compositions of ore sulfides are similar to those of granitic rocks, indicating that the sulfur and ore-metals are derived from the granitic magma. We propose that the Cangyuan Pb-Zn-Ag deposit formed from magmatic hydrothermal fluids. These Cenozoic deposits situated in the west of Lanping-Changdu Basin share many similarities with the Cangyuan in isotopic compositions, including the Laochang, Lanuoma and Jinman deposits. This reveals that the Cenozoic granites could have contributed to Pb-Zn-Cu mineralization in the Sanjiang region despite the abundance of Cenozoic Pb-Zn deposits in the region, such as the Jingding Pb-Zn deposit, that is thought to be of basin brine origin.     

The Carlés copper–gold–molybdenum skarn (Asturias, Spain): geometry, mineral associations and metasomatic evolution

This paper presents the petrographical, mineralogical and geochemical characteristics of the Carlés Cu–Mo–Au ore deposit, located in the Rio Narcea Gold Belt (Cantabrian zone of the Iberian Massif). It is related to a small postkinematic calc-alkaline monzogranite, which intrudes as a cedar-tree laccolith into the upper siliciclastic Furada Formation (late Silurian age) and the Nieva carbonates (early Devonian age). The Carlés deposit consists mainly of a well-developed exoskarn. The exoskarn is mostly calcic skarn made up of early garnet and pyroxene, and later amphibole, magnetite and sulfides. The presence of magnesian skarn has been recorded on the north side of the intrusion (roof of granitoid). Magnesian skarn consists of olivine, which is partially replaced by diopside and phlogopite and spinel. Close to the igneous rock, skarns are overprinted by strong potassic alteration. The ore is related to the skarn retrogradation and post-skarn veining and faulting. The skarn-related ore consists of earlier, uneconomic magnetite and Fe–As sulfide assemblages and economic Cu–Au–Ag (Bi–Te) assemblages on the eastern and western sides of the contact aureole, and uneconomic Mo and subeconomic Fe–As–Cu–Au–Ag on the northern side of the contact. Later subeconomic Fe–As–Sb–(Zn–Sn–Cu–Au–Ag) assemblages crosscut the granitoid, skarn, marbles and mineral associations developed previously, and are related to younger episodes of fracturing and faulting. Fluid inclusions in the first hydrothermal stage consist of an aqueous solution with significant contents of CO₂, which reach unmixing conditions as a result of a decrease in P–T conditions. This led to two types of solutions, aqueous solutions of moderate to high salinity and hydrocarbon solutions of low salinity. This unmixing phenomenon controlled the first stage of gold precipitation. During the late hydrothermal activity, primary low-salinity-aqueous-carbonic inclusions with contrasting densities are found. They homogenize into vapor, critical or liquid phase. Homogenization temperatures are practically the same in all inclusions, indicating a boiling phenomenon that could control a new precipitation of gold.