Fluid Inclusions In Quartz Research Articles

Formation of miarolitic-class, segregation-type pegmatites in the Taishanmiao batholith, China: The role of pressure fluctuations and volatile exsolution during pegmatite formation in a closed, isochoric system

Abstract The Taishanmiao granitic batholith, located in the Eastern Qinling Orogen in Henan Province, China, contains numerous small (mostly tens of centimeters in maximum dimension) bodies exhibiting textures and mineralogy characteristics of simple quartz and alkali feldspar pegmatites. Analysis of melt inclusions (MI) and fluid inclusions (FI) in pegmatitic quartz, combined with Rhyolite-MELTS modeling of the crystallization of the granite, have been applied to develop a conceptual model of the physical and geochemical processes associated with the formation of the pegmatites. These results allow us to consider the formation of the Taishanmiao pegmatites within the context of varios models that have been proposed for pegmatite formation. Field observations and geochemical data indicate that the pegmatites represent the latest stage in the crystallization of the Taishanmiao granite and occupy ≤4 vol% of the syenogranite phase of the batholith. Results of Rhyolite-MELTS modeling suggest that the pegmatite-forming melts can be produced through continuous fractional crystallization of the Taishanmiao granitic magma, consistent with the designation of the pegmatites as a miarolitic class, segregation-type pegmatites rather than the more common intrusive-type of pegmatite. The mineral assemblage predicted by Rhyolite-MELTS after ~96% of the original granite-forming melt had crystallized consists of ~51 vol% alkali feldspar, 34 vol% quartz, 14 vol% plagioclase, 0.1 vol% biotite, and 1 vol% magnetite, similar to the alkali feldspar + quartz dominated mineralogy of the pegmatites. Moreover, the modeled residual melt composition following crystallization of ~96% of the original melt is similar to the composition of homogenized MI in quartz within the pegmatite. Rhyolite-MELTS predicts that the granite-forming melt remained volatile-undersaturated during crystallization of the batholith and contained ~6.3 wt% H2O and ~500 ppm CO2 after ~96% crystallization when the pegmatites began to develop. The Rhyolite-MELTS prediction that the melt was volatile-undersaturated at the time the pegmatites began to form, but became volatile-saturated during the early stages of pegmatite formation, is consistent with the presence of some inclusion assemblages consisting of only MI, while others contain co-existing MI and FI. The relationship between halogen (F and Cl) and Na abundances in MI is also consistent with the interpretation that the very earliest stages of pegmatite formation occurred in the presence of a volatile-undersaturated melt and that the melt became volatile saturated as crystallization progressed. We propose a closed system, isochoric model for the formation of the pegmatites. Accordingly, the Taishanmiao granite crystallized isobarically at ~3.3 kbar, and the pegmatites began to form at ~734 °C and ~ 3.3 kbar, after ~96% of the original granitic melt had crystallized. During the final stages of crystallization of the granite, small pockets of the remaining residual melt became isolated within the enclosing granite and evolved as constant mass (closed), constant volume (isochoric) systems, similar to the manner in which volatile-rich melt inclusions in igneous phenocrysts evolve during post-entrapment crystallization under isochoric conditions. As a result of the negative volume change associated with crystallization, pressure in the pegmatite initially decreases as crystals form, and this leads to volatile exsolution from the melt phase. The changing PTX conditions produce a pressure-induced “liquidus deficit” that is analogous to liquidus undercooling and results in crystal growth as required to return the system to equilibrium PTX conditions. Owing to the complex closed system, isochoric PVTX evolution of the melt-crystal-volatile system, the pressure does not decrease rapidly or monotonically during pegmatite formation but, rather, gradually fluctuates such that at some stages in the evolution of the pegmatite the pressure is decreasing while at other times the pressure increases as the system cools to maintain mass and volume balance. This behavior, in turn, leads to alternating episodes of precipitation and dissolution that serve to coarsen (ripen) the crystals to produce the pegmatitic texture. The evolution of the pegmatitic melt described here is analogous to that which has been well-documented to occur in volatile-rich MI that undergo closed system, isochoric, post-entrapment crystallization.

Petrogenesis and U[sbnd]Pb geochronology of charnockites flanking the Pranhita Godavari rift in peninsular India-link between the Bastar and Eastern Dharwar Cratons

Charnockites constitute an integral component of granulite belts exposed on the northern and southern flanks of the Godavari rift, which marks the contact between the Bastar and Eastern Dharwar cratons in peninsular India. In this study, we attempt to constrain the petrogenesis of granulites from Gondpipri, Bhopalpatnam on the northern flank and Karimnagar on the southern flank of the Pranhita-Godavari valley using petrography, mineral and whole-rock geochemistry, fluid inclusion studies, and UPb zircon geochronology. The presence of relict magmatic textures and orthopyroxene chemistry is suggestive of an igneous protolith while CO2-rich fluid inclusions in quartz correspond to subsequent granulite-facies overprint. Geochemically, charnockites from both granulite belts are metaluminous, magnesian, and calc-alkaline, having similar Sr and Y concentrations, Rb/Sr, Sr/Y, LaN/SmN, GdN/YbN, and Eu/Eu* ratios, and positive BaPb and negative Nb-Ta-Ti anomalies. Zircons in charnockites from both granulite belts furnish magmatic crystallization ages of ~2.5 Ga (UPb isotope) and also record a metamorphic overprint at ca. 2473 Ma. The similarity in protolith composition and UPb ages of zircons in charnockites on the northern and southern flanks of the Godavari rift suggest that they constitute a cogenetic and coeval suite emplaced at ~2.5 Ga in an undivided and continuous Palaeo-Mesoarchean landmass that included the Bastar and Eastern Dharwar cratons, possibly as a part of the Ur-supercontinent. This undivided landmass subsequently got split along the Pranhita-Godavari rift zone into the Bastar and Dharwar cratons. The rift valley eventually developed into a sedimentary basin hosting the Proterozoic and Gondwana Group of sediments sequentially, apparently separating the two cratons on the map.

Fluid inclusions, H-O-S isotopic characteristics and genesis of the Chambishi copper deposit, Zambia

In this paper, fluid inclusions and H-O-S isotope geochemistry of the Chambishi copper deposit in Zambia are studied. According to the fluid inclusion in quartz and H-O-S isotope characteristics, it is concluded that ore-forming hydrothermal fluid is derived from mantle source and crust source magma mingling, the cause of copper precipitation, sedimentary type sulfur layered mineralization are mainly from diagenetic sulfides and seawater sulfate. Sulfate is mainly reduced by thermochemical method. The hydrothermal vein mineralization of Chambishi copper deposit is closely related to the magmatic activity in the middle Neoproterozoic, and the sedimentary stratified mineralization is mainly related to the large-scale orogeny and regional metamorphism in the late Neoproterozoic.

Fluid characheristics of the Baoxingchang Cu-Mo Deposit, Yunnan Province, SW China

The Baoxingchang Cu-Mo deposit is an important deposit in the Jinshajiang-Red River alkali-rich porphyry area, Western Yunnan. Fluid inclusion petrography and inclusion microscopic thermometric analysis of quartz phenocrysts in non-mineralized porphyritic granite, lamprophyre quartz veins, molybdenite quartz veins, copper-pyrite-molybdenite quartz veins, and pyrite quartz veins show that the development in primary inclusion of quartz phenocrysts and quartz veins can include vapour-rich inclusions and liquid-rich inclusions. Fluid inclusions are characterised by their medium-high temperature and moderate salinity. However, the temperature and salinity of non-mineralised quartz fluid inclusions are higher than those of quartz fluid inclusions in the mineralisation stage. Captured pressure and mineralisation depth during mineralisation reveal that the copper-molybdenum deposit is formed in hypabyssal environment, which is consistent with porphyry metalloginic systems.

Early Paleozoic Orogenic Gold Deposit in the Cathaysia Block, China: A first example from the Shuangqishan Deposit

The Shuangqishan gold deposit (>20t gold) is located in a hitherto poorly-documented gold province in the southeastern Cathaysia Block, South China. It is hosted by Neoproterozoic amphibolite-facies metamorphic rocks and consists of quartz-sulfide veins with distinct alteration haloes. Three stages of hydrothermal activity have been identified, and gold is mainly associated with veins of Stage II (quartz-pyrite±chalcopyrite). Gold occurs both as refractory gold hosted by pyrite and free gold enclosed in, or filling, microfractures of pyrite and quartz. U-Pb isotope dating of hydrothermal apatite from the Substage IIa veins yielded an age of 436.8 ± 7.6 Ma. The ore fluid was of carbonic-aqueous composition and low oxygen fugacity. Total homogenization temperatures in Substage IIa and IIb range from 270° to 310°C and 250° to 295°C, respectively. Variable CO2/H2O ratios indicate fluid unmixing under fluctuating pressures. Stage I quartz veins show evidence of ductile deformation and have δ18Ofluid and δD values of 10.3 to 11.2‰ and −67to −66‰, respectively, consistent with a metamorphic fluid. Stage II veins have slightly higher δ18O values of 10.9 to 13.7‰, with calculated δ18Ofluid values of 4.8 to 8.0‰. The 3He/4He ratios of pyrite are elevated (0.06–0.23 Ra) relative to crustal He reservoirs (<0.01 Ra). Fluid inclusions in quartz yielded δ13CCO2values of −23.0to −11.4‰ (V-PDB), reflecting variable contributions of organic carbon. The sulfide δ34SV-CDT values range from −4.7to −1.0‰, consistent with a deep-seated sulfur source. The Pb isotope compositions of pyrite (206Pb/204Pb=17.141–17.871, 207Pb/204Pb=15.484–15.570) are more radiogenic than those of unaltered host rocks. All available data demonstrate that the Shuangqishan deposit is the first report orogenic gold deposit formed during the late Wuyi-Yunkai intracontinental orogeny in the Cathaysia Block.

Genesis of the Nailenggele Mo-Cu-Pb-Zn polymetallic orefield in the Boluokenu Metallogenic Belt, Western Tianshan, China: Constraints from geochronology, fluid inclusions and isotope geochemistry

The Nailenggele orefield, located in the northwestern Chinese Tianshan Orogenic Belt, is composed of the Lailisigao’er Mo deposit, No. 3571 Cu prospect and Qixing Pb-Zn deposit. Lailisigao’er is a typical porphyry deposit with characteristic veinlet-disseminated ores and potassic, phyllic and propylitic alterations. No. 3571, situated in the peripheral of Lailisigao’er, is characterized by large amounts of oxidized ores at surface with limited intrusions outcropped. Qixing, about 3 km from Lailisigao’er, is characterized by quartz-sulfide veins controlled by fractures. This study aims to examine the genetic relationships between these deposits and/or occurrences, and discuss the significance for further exploration in the orefield and elsewhere in the region. LA-ICP-MS U-Pb dating on zircons from the ore-bearing porphyry in the Lailisigao’er deposit yielded an age of 367.5 ± 4.8 Ma. The molybdenite Re-Os and sphalerite Rb-Sr isochron ages recalculated from previously published data are 365.9 ± 2.1 Ma for Lailisigao’er and 362.0 ± 5.7 Ma for Qixing, respectively, suggesting that they are coeval and both related to the granodiorite porphyries. Three types of fluid inclusions occur in the Mo-bearing quartz from Lailisigao’er, including two-phase aqueous inclusions (Type I), solid mineral-bearing aqueous inclusions (Type II) and CO2-H2O inclusions (Type III). The total homogenization (Th) temperatures cluster from 260 to 320 °C (to liquid) for type I inclusions, 310 to 332 °C (to liquid) for type II inclusions, and 268 to 324 °C (to CO2 phase) for type III inclusions. The salinities are mainly in the ranges of 2.0–8.0, 32.9–42.0, and 1.4–5.5 wt% NaCleq for types I, II and III inclusions, respectively. By contrast, only type I inclusions were identified in the Pb-Zn-bearing quartz from Qixing, with Th values of 149–261 °C and salinities of 1.7–5.3 wt% NaCleq. The δ34SCDT values of hydrothermal sulfides from Lailisigao’er, No. 3571 and Qixing range from 2.8‰ to 4.0‰, 4.0‰ to 4.6‰ and 0.7‰ to 4.9‰, respectively. Sulfides from these three locations have uniform Pb isotopic compositions. The (87Sr/86Sr)0 ratios of fluid inclusions (average 0.70971) in Mo-bearing quartz at Lailisigao’er and sphalerite (average 0.71020) at Qixing are similar to those of Mo-mineralized porphyries (average of 0.70886) from Lailisigao’er. The δ18OH2O and δDH2O values of Pb-Zn-bearing quartz from Qixing are similar to those of Mo-bearing quartz from Lailisigao’er, both plotting close to the field of magmatic water but shifted toward the meteoric line. These geochronological, fluid inclusions and isotopic data suggest that the mineralization at different localities in the Nailenggele orefield constitutes part of an integrated magmatic-hydrothermal system centered on the Lailisigao’er porphyry Mo deposit, with the Qixing Pb-Zn polymetallic deposit representing a distal end-member. Both metals and sulfur were dominantly derived from porphyritic intrusions, whereas the ore-forming fluids were initially derived from the magmatic intrusions, with increasing involvement of meteoric water in time and distance from magmatic-hydrothermal center. Fluid immiscibility in the early stage and fluid mixing in the later stage, together with cooling, were responsible for ore precipitation. Based on this mineralization model, it is inferred that concealed porphyry Cu-Mo mineralization may be developed underneath the No. 3571 and Qixing.

Gold Mineralization at the Maletoyvayam Deposit (Koryak Highland, Russia) and Physicochemical Conditions of Its Formation

Microthermometry study of fluid inclusions in quartz veins of the Maletoyvayam deposit (Koryak Highland, Russia) was carried out. This epithermal gold deposit contains unique Au compounds including maletoyvayamite, which has not been reported anywhere else. Two paragenetic mineral associations (pyrite-quartz and maletoyvayamite-quartz) with quartz of different generations corresponding to different pulses were also described. Only early generations of quartz (Q1) include ore minerals: pyrite for the first mineral assemblage, and in Au-bearing minerals, sulfosalts, bismuthinite, and others—for the second assemblage. A study on fluid inclusions in quartz showed a salinity (mainly NaCl + KCl) range from 0.2 to 4.3 wt.% NaCl eq., increasing from the first mineral association to the second due to boiling fluids. The obtained temperature variations for quartz crystallization were 295–135 °C, the fluid pressure ranged from 79 to 4 bar. On the other hand, the range of conditions obtained for the gold productive ore association is more narrow: salinity of the fluid inclusions is 4.3 wt.% NaCl eq., the temperatures vary from 255 °C to 245 °C, and the pressure from 39 to 32 bar. These physicochemical characteristics of the Maletoyvayam ore deposit greatly coincide with other HS-type epithermal deposits; however, within the Central Kamchatka Volcanic Belt it is so far the only deposit of this type reported.

Multistage evolution of the Neoproterozoic “El Tarumán” gold vein-type mineralization, Dom Feliciano orogenic belt, Uruguay

Vein-type gold occurrences are found along the western margin of the Neoproterozoic Dom Feliciano Belt (Uruguay) and its Archean to Proterozoic basement. The “El Tarumán” gold prospect is related to quartz veins hosted in dolomitic marble, which is part of the Cebollati Complex, metamorphosed in amphibolite facies. The quartz veins formed in fold hinges and sheared marble bands in a transpressive regime. Their orientation coincides with the Brasiliano structural grain, striking mostly NNE-SSW. Pyrite is the most important ore mineral, besides minor galena, chalcopyrite, and sphalerite, and accessory enargite, chalcocite and tennantite. The oxidation of sulfides produced free gold besides malachite.In our study, we combined fluid inclusion data with microstructures, which represent successive alteration stages after hydrothermal quartz mineralization and are made visible by cathodoluminescence (CL)-microscopy. In this way, the fluid evolution during the main mineralization and subsequent cooling could be constrained. The vein mineralization was associated with post-collisional magmatism and hydrothermal fluid circulation at ca. 500–550 °C/3 kbar, postdating the peak of metamorphism. The mineralizing fluid with an estimated composition of H2O(55) CO2(40) NaCl(5) was trapped as primary fluid inclusions in non-deformed quartz (T0) showing blue CL. Alteration structures (T1-T4) are marked by quartz showing brown and reddish CL hosting different types of fluid inclusions, and are characterized by (T1) a diffusive intragranular mosaic structure (subgrains), most likely related to minor ductile shearing, (T2) grain boundaries which formed as a result of dynamic recrystallization (secondary grain growth), (T3) shear bands of fine-grained quartz, and (T4) healed microfractures. The fluid inclusions trapped in these structures represent retrograde fluids characterized by a systematic loss of CO2 because of carbonation, slightly increasing salinity and the introduction of CaCl2. The latter solutes were mainly trapped around the quartz brittle-ductile transition zone between 350 and 300 °C/2.5–3 kbar (T1), and 300-260 °C/2–2.5 kbar (T2), together with the precipitation of pyrite. This shows that the sulfides formed by the interaction of cooling hydrothermal fluids and the host rock. The CaCl2/NaCl ratio for the inclusions in the T2-structures is ca. 0.65 at maximum. Late shear bands of fine-grained quartz (T3) are free of fluid inclusions. The latest fluids preserved in the quartz veins were trapped in healed microfractures below ca. 280 °C and represent the influx of low salinity (6–7 wt %) NaCl-bearing solutions (T4).The structural data and high fluid trapping temperatures indicate that the veins host an orogenic gold mineralization associated with magmatic hydrothermal fluids. The finding of an Ediacaran K–Ar cooling age of 592.8 ± 8.7 Ma for muscovite in the veins is consistent with regional sinistral shearing and strong basement reworking during the Neoproterozoic Brasiliano Orogeny.

Metallogenesis of the orosirian epithermal coringa gold-silver (Cu-Pb-Zn) deposit, southeastern Tapajós mineral Province, Amazonian craton, Brazil

The Coringa gold-silver (Cu-Pb-Zn) deposit, in southeastern of Tapajós Mineral Province, is hosted in felsic volcanic rocks the Vila Riozinho Formation (1996 ± 21 Ma) and in the Serra Alkali Feldspar Granite (1999 ± 25 Ma), and has been interpreted to have formed in a post-collisional volcano-plutonic setting. The mineralized shear-vein system follows the NNW-SSE trend of the main regional structures and is coincident with a magnetic trend that can represent a crustal discontinuity at the boundary zone between a magnetic pyroclastic facies of the Vila Riozinho Formation and the pluton of the Serra Alkali Feldspar Granite. The hydrothermal alteration stages comprise: (a) proximal chlorite-hematite alteration, (b) intermediate-proximal sericite-pyrite alteration, with an estimated temperature of 400 °C (white mica chemistry), and (c) late, distal Mn-carbonate-chlorite-epidote alteration, with an average temperature of 234 °C (chlorite chemistry). There are discontinuous massive barren quartz veins (veins type 1), and two types of quartz-sulfide veins (veins types 2 and 3). The veins type 2 are sulfide-poor, gold-bearing, open-space filling veins with pyrite, galena, and hematite, with an average temperature formation of 243 °C (fluid inclusions in quartz). The veins type 3 are sulfide-rich, and gold-bearing quartz veins with sulfide phases represented by pyrite, galena, sphalerite, and chalcopyrite and presented a minimum temperature of 340 °C (fluid inclusions in quartz). Chemical analyses of the sulfides detected significant Mo, Bi, Ni, and Co, with decreasing contents according to the crystallization sequence of the sulfide phases (pyrite-chalcopyrite-sphalerite-galena-gold). The mineralizing fluids are H2O-rich and CO2-poor, low salinity, and the stable isotope compositions of the alteration minerals are mostly consistent with a magmatic source that mixed with a diluted and colder meteoric fluid. The geological setting, the timing of mineralization being nearly contemporaneous with the host rocks (given by previous works), the genetic characteristics, and the local presence of adularia and Mn-carbonate led us to classify Coringa as formed by an intermediate-sulfidation epithermal system.

Fluid inclusions in buried quartz of the Yanchang sandstone in the Jiyuan area, Ordos Basin, China: Implications for basin evolution and petroleum accumulation

A fluid inclusion petrographic and microthermometric study was performed on the sandstones gathered from the Yanchang Formation, Jiyuan area of the Ordos Basin. Four types of fluid inclusions in quartz can be recognized based on the location they entrapped. The petrographic characteristics indicate that fluid inclusions in quartz overgrowth and quartz fissuring-I were trapped earlier than that in quartz fissuring-IIa and fissuring-IIb. The homogenization temperature values of the earlier fluid inclusions aggregate around 80 to 90°C; exclusively, it is slightly higher in Chang 6 member, which approaches 95°C. The later fluid inclusions demonstrate high homogenization temperatures, which range from 100 to 115°C, and the temperatures are slightly higher in Chang 9 member. The calculated salinities show differences between each member, including their regression characteristics with burial depth. Combining with the vitrinite reflection data, the sequence and parameters of fluid inclusions indicate that the thermal history of the Yanchang formation mostly relied on burial. Salinity changes were associated with fluid-rock interaction or fluid interruption. Hydrocarbon contained fluid inclusions imply that hydrocarbon generation and migration occurred in the Early Cretaceous. The occurrence of late fluid inclusions implied that quartz cement is a reservoir porosity-loose factor.

Fluid evolution and metallogenesis of the Meiling Cu‐polymetallic deposit in the East Tianshan, NW China: Constraints from ore geology, fluid inclusions, stable isotope, and U–Pb geochronology

The Meiling Cu‐polymetallic deposit is located in the Kalatag Cu metallogenic belt of the East Tianshan, Xinjiang, NW China. Multiple‐stage hydrothermal activities have resulted in the silicification, chlorite alteration and sericite alteration in this deposit. At least three mineralization stages are recorded: (a) a phase comprising quartz–pyrite veining, (b) a quartz–chalcopyrite–pyrite–sphalerite phase and (c) a quartz–calcite phase, respectively. LA–ICP–MS zircon U–Pb dating yielded 302 ± 2.1 Ma for an ore‐bearing quartz porphyry and 296 ± 3.2 Ma for a post‐mineralization diorite porphyry dyke, respectively, indicating that the copper mineralization took place during the Late Carboniferous period (302–296 Ma). Fluid evolution during the three stages of mineralization was determined by a detailed fluid inclusion study: (a) Stage I fluids were trapped under two‐phase conditions, as evidenced by the coexistence of vapour‐rich (type II) inclusions (Th = 183–242°C, average salinity = 4.8 wt% NaCl equiv.), liquid‐rich (type I) inclusions (Th = 171–259°C, average salinity = 5.3 wt% NaCl equiv.), and daughter‐bearing (type III) inclusions (Th = 192–208°C, average salinity = 8.6 wt% NaCl equiv.). (b) Stage II fluid inclusions in quartz were also trapped under two‐phase conditions (boiling), as identified by the coexistence of V‐ and L‐type fluid inclusions; L‐type inclusions Th between 136 and 218°C (average = 189°C), with salinities of 2.2–7.6 wt% NaCl equiv. (average = 3.8 wt% NaCl equiv.). V‐type inclusions homogenized temperatures between 153 and 226°C (average = 192°C), with salinities of 2.4–6.7 wt% NaCl equiv. (average = 3.5 wt% NaCl equiv.). (c) Stage III fluids are represented by inclusions in barren quartz–carbonate veinlets, characterized by homogenization temperatures ranging from 98 to 177°C (average = 135°C) and salinities between 0.5 and 3.2 wt% NaCl equiv. (average = 1.9 wt% NaCl equiv.). The initial hydrothermal fluids are characterized by low–intermediate temperature, low‐salinity and near‐neutral pH condition, belonging to a H2O–NaCl bearing hydrothermal system. The mineralization of the Meiling deposit occurred at a shallow crustal level (~0.5 km), and the decrease of temperature was likely an important factor responsible for metal accumulation and deposition in the subvolcanic hydrothermal system.

Trace element and fluid inclusion geochemistry constraint for genesis of gold-polymetallic mineralization in the Songhung deposit, DPR Korea

The Songhung deposit is located in the southwestern part of the Yangdok metamorphic core complex (YMCC) in the northern portion of the Pyongnam Basin, the eastern part of the Sino-Korean Craton. In this paper, we present a detailed study on the magma sources of the granitoids (Yangdok and Hoechang graintic intrusions), genesis of pyrite and fluid inclusion characteristics for sufficient and additional understanding of tectonic events, petrogenesis of the granitoids and mineralization in the study deposit. The Yangdok granite has lower Al2O3/TiO2 ratios (mean value of 60.58) than the Hoechang granite (mean value of 994.46), indicating the higher temperature magma source of the former. On the Rb/Ba vs. Rb/Sr and CaO/(TFeO + MgO + TiO2) vs. (CaO + TFeO + MgO + TiO2) discriminant diagrams, the magma source of the Yangdok granite belongs in the plagioclase-rich and clay-poor source rocks, while those of the Hoechang granite plots either in the plagioclase-rich and clay-poor source rocks (for granite and fine-grained granite) or in the plagioclase-poor and clay-rich source rocks (for granite porphyry and felsite). On the Nb vs. Y, Ta vs. Yb, Rb vs. Y + Nb and Rb vs. Yb + Ta tectonomagmatic discrimination diagrams, these two granites are connected with the volcanic arc-related setting and plot in post-collision setting. Moreover, some data of the Hoechang granite fall in WPG field, suggesting that the volcanic arc setting may be changed to an intraplate setting from Middle Cretaceous.The pyrite trace element geochemistry, showing the high Co/Ni ratio than one with an average of 8.2 and high Co content and low Ni content, suggests that its formation was closely linked with I-type granitic magma-derived hydrothermal fluid mixed with meteoric water. It could also be assumed by the Co and As contents in pyrite, indicating a certain degree of meteoric water in the ore forming fluid. It is consonant to the Pb, S, C and O isotope geochemistry in the previous study, suggesting that ore-forming fluids and metals could be derived from both the Yangdok granite and the Proterozoic and Paleozoic meta-sedimentary rocks exposed in the study area. All of the pyrite grains have not compositional zoning and the similar distribution patterns of Co and Ni are appeared in single pyrite grain (from core to rim), suggesting the stable crystallization environment of pyrites and same ore forming fluid source. In pyrite grains, the positive correlation between gold and arsenic is appeared. The Au exists either as a micro- and nano-size inclusion in pyrite and other minerals or as a solid solution in pyrite lattice. Based on the petrological and microthermometric characteristics of the fluid inclusions in ore-bearing quartz, we suggest that the ore-forming fluid is represented as NaCl + H2O or NaCl + KCl + H2O systems with low salinity. The absence of CO2-enriched phase and vapor-only or liquid-only primary inclusions in quartz indicates the homogenous magma-derived ore forming fluids and a lack of boiling during ore-forming process. The formation temperature and pressure of this deposit approximately vary from 317 to 326 °C and from 105.46 to 111.69 × 105 Pa, respectively, exhibiting the hydrothermal deposit origin. In conclusion, the Songhung deposit is originated from I-type granitic magma source-derived hydrothermal fluid which was mixed with meteoric water.

Bismuth minerals from the intragranitic La Elsa NYF pegmatite, Potrerillos granite, Argentina: Monitors of fluid evolution from magmatic to hydrothermal stage

ABSTRACTThe NYF La Elsa pegmatite forms a subcircular, ∼30 m long, ∼20 m wide body enclosed in the parental Potrerillos granite, Las Chacras-Potrerillos batholith, Argentina. The pegmatite has a typical zonal internal structure with a volumetrically significant quartz core and pods of magmatic fluorite. Along with biotite, mostly in the outer units, tourmaline (schorl, fluor-schorl) is common to abundant in most pegmatite units. Accessory minerals include common strongly hematitized ilmenite and rare euhedral crystals of bismuthinite, up to 2 cm long, occurring at the transition between the blocky zone and the quartz core. The bismuthinite was significantly replaced by bismutite I according to the reaction Bi2S3(s) + CO2(aq) + 6O2(aq) + 3H2O(l) = Bi2CO3O2(s) + 3H2SO4(aq). Subsequently, bismutite I was replaced by bismutite II and kettnerite. The former requires an influx of Ca and F and its formation can be characterized by the reaction Bi2CO3O2(s) + 2Ca2+(aq) + 2F–(aq) + CO32–(aq) = 2CaBiCO3OF(s). At the late hydrothermal stages bismutite was replaced by clinobisvanite/pucherite during influx of V according to the reaction Bi2CO3O2s + 2H3VO4(aq) = 2BiVO4(s)+ CO2(aq) + 3H2O(l). All Bi minerals are close to the ideal formulae with only minor Pb and ±Cu in bismuthinite and its secondary products. The crystallization sequence of Bi minerals is magmatic bismuthinite (S2–) → early hydrothermal bismutite I (CO32–) → medium stage bismutite II + kettnerite (CO32–, F–) → late stage clinobisvanite, pucherite (VO43–). Pegmatite-derived early subsolidus fluids were enriched in CO2, which was confirmed by confocal Raman microspectroscopy of fluid inclusions in quartz and caused breakdown of bismuthinite to bismutite. Calcium and F, necessary for kettnerite formation, were released during alteration of magmatic fluorite at acidic conditions. Vanadium was supplied by meteoritic H2O enriched in elements from altered magmatic minerals (biotite, ilmenite), either from the pegmatite or from the host granite.

Diamond resorption and immiscibility of C-O-H fluid in kimberlites: Evidence from experiments in H2O – CO2 – SiO2 – MgO – CaO system at 1–3 GPa

Kimberlites are the deepest sourced magmas emplaced at the Earth's surface. They provide a “window” into the processes at the base of the subcratonic mantle. A better understanding of the origin, composition, and emplacement mechanisms of kimberlites is hampered by uncertainties in the contents of the two main volatiles, H2O and CO2. Diamond dissolution in H2O and in CO2 fluids produces distinct resorption features offering an opportunity to determine the composition of the magmatic fluid in kimberlites. Here we examined the relationship between H2O:CO2 ratio of the fluid and the style of diamond resorption by conducting experiments in C-O-H fluid saturated with silicates with variable H2O:CO2 ratios at the conditions of kimberlite ascent of 1–3 GPa and 1150–1350 °C. Our results showed that the geometry of etch pits on diamond and the resorption style evolve consistently as bulk CO2 content of the fluid changes from 0 to 50 to 50–90 and 90–100 mol%. The fluid composition at the run conditions was monitored by entrapment of synthetic fluid inclusions in olivine and quartz. The inclusions demonstrated the existence of a fluid miscibility gap at 1–3 GPa and 1250 °C with two fluid endmembers, an aqueous and a carbonic phase, which H2O:CO2 ratio at 1 GPa determined with confocal Raman microscopy is (H2O)0.62(CO2)0.38 and (H2O)0.12(CO2)0.88 respectively. Hence, diamond resorption morphology depends on the proportions of the end-member aqueous and carbonic fluids, which vary with the bulk composition of the fluid. The different density and ability of aqueous and carbonic fluids to dissolve silicates (olivine) would promote their separation in the rising magma column. Concentration of the lower density aqueous fluid towards the tip of the propagating dyke would facilitate more efficient fracturing of the country rocks and faster ascent of the kimberlite magma causing explosive eruption. We propose that preferential attachment of aqueous fluid bubbles would help to increase the buoyancy of olivine xenocrysts and possibly diamond in the kimberlite magma offering a mechanism for transporting the heavy mantle cargo.

Mineral composition and formation conditions of the Inkur tungsten deposit ores (Dzhidinsky ore field, South-Western Transbaikalia)

The aim of the study is to clarify the mineral composition and determine the conditions of the formation of the quartz-hubnerite veins of the Inkur stockwork tungsten deposit (the Dzhidinsky ore field, South-Western Transbaikalia). The research methods include a mineralogical and petrographic description of the ore quartz-hubnerite veins; an electron microprobe analysis of the mineral associations; thermometry, cryometry, and Raman spectroscopy of the individual fluid inclusions in quartz, fluorite, hubnerite, and muscovite. The mineralogical and petrographic studies has made it possible to clarify the mineral composition of the Inkur deposit ores and determine the mineral paragenesis formation sequence. The fluid inclusion studies have established that the ore deposition was occurring in the relatively low-salinity (~5.7–14.6 wt. % eq. NaCl) homogeneous solutions due to a decrease of the temperature. The study of the salt composition of the solutions has identified Ca chloride as a prevailing component, with NaCl, KCl, and MgCl as admixtures. CO2 and N2 have been identified in the gas phase of inclusions. Two stages of mineral formation have been defined: high-temperature (≥300 °С) and low-temperature (≥2.00–300 °С). The conducted studies allow qualitative estimation of the chemical composition of the ore-forming solutions. It has been established that one of the main factors of the hubnerite deposition is a temperature factor.

Vosnesensky Cu-porphyry deposit (Southern Urals): formation conditions, trace elements, sulfur isotopes and fluid sources

The paper shows new fluid inclusion and isotopic-geochemical data for minerals from sulphide-carbonate-quartz veins of Vosnesensky Cu-porphyry deposit. Fluid inclusions were analyzed by means Linkam TMS-600 cryostage equipped with Olympus BX 51 optical microscope; trace element amounts were performed used Agilent 7700x and ELAN 9000 mass-spectrometers; sulphur isotopic composition was analyzed on DeltaPLUS Advantagе mass-spectrometer. We determined that fluid inclusions in quartz were homogenized between 215 and 315 ºС, and in latest calcite, they are 230–280 ºС. Fluids are К-Na water chloride with salinity of 3–12 wt % NaCl-eq. Quartz contain high amounts of Al (184–5180 ppm), K (20.1–1040 ppm), Na (30.2–1570 ppm) and Ti (38.4–193 ppm). The REE distribution spectra of pyrite are characterized by light lanthanides accumulation (LaN/YbN = 3.6–6.44), and negative of Ce anomalies (0.7–0.92) and Eu (0.78–0.99). The Y/ Ho ratio in pyrite varies from 27.6 up to 36.8. The δ34S values in pyrite were –1.01…0.8 ‰, in chalcopyrite – 0.9 ‰. The data testify the Cu-porphyry mineralization of Vosnesensky deposit was formed due to magmatic acid high-aluminous К-Na chloride fluid enriched with light REE in mesothermal environment. We identified the geochemical markers of interaction between fluid and host rocks.

Fluid inclusion, H–O–S isotope and rare earth element constraints on the mineralization of the Dong’an Sb deposit, South China

Systematic geochemical study on the Cambrian strata-hosted Dong’an Sb deposit in the Central Hunan Sb belt would provide key information on the origin of the low-temperature mineralization in South China. In this study, microthermometric, H–O isotopic and fluid composition analyses on ore-bearing quartz, S isotopic analyses on sulfides, and rare earth element (REE) analyses on wall-rocks and monominerals (stibnite, pyrite and quartz) in ores were conducted to constrain the genesis of the Dong’an Sb deposit. Two major stages of mineralization were identified in the Dong’an deposit: (1) an early pyrite-stibnite-quartz stage mineralization with intense wall-rock alteration occurring at depth of the deposit, and (2) a late quartz-stibnite stage mineralization occurring at shallow depths. Microthermometric analyses reveal a low temperature (150 to 230 °C), low salinity (4.5–7.0 wt% NaCl equiv.), low density (0.88–0.96 g/cm3), low pressure (4.5 MPa) and weakly acid (pH = 5.74) fluid for the Sb mineralization. Compositional analyses for fluid inclusions show that the main ion compositions are Na+, K+, Mg2+, Ca2+, F−, Cl− and SO42−, while the gas compositions are dominated by H2O and CO2. This suggests that the ore-forming fluids were enriched in alkali metals, sulfur and halogen. The H–O isotopic compositions (δ18OH2O = 2.52‰ to 7.13‰, δ2HH2O = −88.6‰ to −58.3‰) of fluid inclusions in quartz suggest a mixture of magmatic water, metamorphic rocks-derived brine and meteoric water. The δ34S values of stibnite (−1.32‰ to +2.86‰) and pyrite (+17.4‰ to +23.6‰) are very different, suggesting multi-sulfur sources involving buried magmatic rocks, ore-bearing meta-sedimentary rocks and deep basement rocks. The decreasing of REE contents from early to late mineralization stages reflects a decrease of temperature, reduction of fluid-rock interaction and input of meteoric water along with the stibnite precipitation. We propose that Precambrian strata that underwent regional metamorphism during Early Paleozoic acted as a Sb source bed, whereas strong tectono-magmatism in the early Mesozoic provided thermal driving force for the Sb mineralization occurring under a tensile stress in secondary faults at the shallow crust. This study highlights the use of multi-geochemical methods to constrain the genesis of large-scale Sb mineralization in South China.

Archean to Paleoproterozoic seawater halogen ratios recorded by fluid inclusions in chert and hydrothermal quartz

AbstractPast changes in the halogen composition of seawater are anticipated based on the differing behavior of chlorine and bromine that are strongly partitioned into seawater, relative to iodine, which is extremely depleted in modern seawater and enriched in marine sediments due to biological uptake. Here we assess the use of chert, a chemical sediment that precipitated throughout the Precambrian, as a proxy for halide ratios in ancient seawater. We determine a set of criteria that can be used to assess the primary nature of halogens and show that ancient seawater Br/Cl and I/Cl ratios can be resolved in chert samples from the 2.5 Ga Dales Gorge Member of the Brockman Banded Iron Formation, Hamersley Group, Western Australia. The values determined of Br/Cl ~2 × 10-3 M and I/Cl ~30 × 10-6 M are comparable to fluid inclusions in hydrothermal quartz from the 3.5 Ga North Pole area, Pilbara Craton, Western Australia, that were the subject of previous reconstructions of ancient ocean salinity and atmospheric isotopic composition. While the similar Br/Cl and I/Cl values indicate no substantial change in the ocean halide system over the interval 2.5–3.5Ga, compared to modern seawater, the ancient ocean was enriched in Br and I relative to Cl. The I/Cl value is intermediate between bulk Earth (assumed chondritic) and the modern seawater ratio, which can be explained by a smaller organic reservoir because this is the major control on marine iodine at the present day. Br/Cl ratios are about 30% higher than both modern seawater and contemporary seafloor hydrothermal systems, perhaps indicating a stronger mantle buffering of seawater halogens during the Archean.

Laser-Raman spectral analysis of the Baoxingchang Cu-Mo deposit, Yunnan Province, SW China

Baoxingchang Cu-Mo deposit is one of several Cu-Mo-(Au) polymetallic deposits have been found in the Tethys metallogenic province. Laser-Raman spectral analysis shows that the vapour-phase components of fluid inclusions in quartz are mainly composed of water vapour and a little CO2, while the fluid-phase components contain Na+ and Cl− metallogenic fluid, which generally belongs to a NaCl-H2O system. In conclusion, the characteristics of fluid inclusions in porphyry-type Cu-Mo polymetallic deposits in Baoxingchang are closely related to multi-stage intrusions along the Jinshajiang-Red River shear zone.

Reaction between Cu-bearing minerals and hydrothermal fluids at 800 °C and 200 MPa: Constraints from synthetic fluid inclusions

Abstract Transport and deposition of copper in the Earth's crust are mainly controlled by the solubility of Cu-bearing phases and the speciation of Cu in magmatic-hydrothermal fluids. To improve our understanding of copper mobilization by hydrothermal fluids, we conducted an experimental study on the interaction between Cu-bearing phases (metallic copper, Cu2O, CuCl) and aqueous chloride solutions (H2O ± NaCl ± HCl; with Cl concentrations of 0 to 4.3 mol kg-1). The experiments were run in rapid heat/rapid quench cold-seal pressure vessels at 800 °C, 200 MPa, and logfO2 ~ NNO+2.3. Either Cu or Au capsules were used as containers. The reaction products were sampled in situ by the entrapment of synthetic fluid inclusions in quartz. Fluid composition was subsequently determined by analyzing individual fluid inclusions using a freezing cell and laser ablation inductively coupled plasma-mass spectrometry. Our results show that large isolated and isometric inclusions, free of late-stage modifications, can be preserved after the experiment even when using a high cooling rate of 25 K s-1. The obtained results demonstrate that: (1) reaction between native Cu, NaCl solution, and quartz (± silica gel) leads to the coexistence of fluid inclusions and Na-bearing silicate melt inclusions. Micrometer-to submicrometer-sized cuprite (Cu2O) crystals have been observed in both types of the inclusions, and they are formed most probably due to the dissociation of CuOH. (2) When Cu0 reacts with HCl and CuCl solutions, or Cu+ reacts with NaCl solution, nantokite (CuCl) formed due to oversaturation has been found in fluid inclusion. Copper concentration in the fluid shows a strong positive dependence on the initial chlorine content, with Cu/Cl molal ratios varying from 1:9 to 1:1 in case 1 and case 2, respectively. When Cl is fixed to 1.5 m, initial fluid acidity has a major control on the Cu content, i.e., 0.17 ± 0.09 and 1.29 ± 0.57 m Cu were measured in fluids of case 1 and case 2, respectively. Cu solubility in pure water and in 1.5 m NaCl solutions are 0.004 ± 0.002 and 0.16 ± 0.07 m, respectively. The main responsible Cu-bearing complexes are CuOH(H2O)x in water, NaCuCl2 in NaCl solutions and HCuCl2 in alkali-free solutions. These results provide quantitative constraints on the mobility of Cu in hydrothermal solutions and confirm that Cl is a very important ligand responsible for Cu transport. The first observation that silicate melt can be generated in the fluid-dominated and native-copper-bearing system implies that transitional thermosilicate liquids can coexist with metal-rich fluids and may enhance Cu mobility in magmatic-hydrothermal systems. This may have important implications for the formation of Cu deposits in the systems with low S activities.