Late Hydrothermal Stage Research Articles

A Review on Uranium Mineralization Related to Na-Metasomatism: Indian and International Examples

Uranium mineralization related to Na-metasomatism is known as Na-metasomatite or albitite-type. They represent the fourth-largest uranium resource globally and constitute fifty thousand tons of U resources. The present work gives details about well-known Na-metasomatic uranium occurrences worldwide in terms of structures, metasomatic stages, geochemical characteristics, fluid inclusions, and compositions of stable isotopes. The host rocks are granite, granitoid, and metamorphosed volcano-sedimentary rocks, and these rocks experienced two/three deformational stages. U mineralization is mainly confined to faults and characterized by granitic intrusive, cataclasis, mylonitization, and albitization. The albitized rocks exhibit two to three metasomatic and late hydrothermal stages. The first stage is marked by the replacement of pre-existing host minerals during a ductile shear regime. The second stage is related to U mineralization contemporaneous with the brittle deformation. The albitized rocks exhibit depletion in Si, K, Ba, and heavy rare-earth elements relative to the host rocks and enrichments in Na, Ca, U, Zr, P, V, Sr, and light rare-earth elements. U-enrichment is positively correlated with Na, Mo, Cu, and high-field strength elements. The pressure–temperature (P-T) conditions of U mineralization are considered to be epithermal and mesothermal. Fluid inclusion studies indicate that the mineralizing fluids were rich in Na+, Mg2+, Cl−, CO2, H2O, F−, and PO43− and meteoric–magmatic derived. The geological processes responsible for the genesis of Na-metasomatic U deposits of the North Delhi Fold Belt (India) are comparable with some international examples, i.e., Australia, Ukraine, Cameroon, Brazil, Guyana, China, and the USA.

Hyper-enrichment of heavy rare earth elements in highly evolved granites through multiple hydrothermal mobilizations

Abstract Highly evolved granites can be important hosts of rare earth element (REE) resources, and more importantly, they commonly serve as the protolith for regolith-hosted REE deposits to form during weathering. Highly evolved granites in the Zudong pluton, South China, are extremely rich in the heavy (H)REE (up to 8000 ppm total HREE), and display significant REE fractionation. Moreover, the HREE enrichment is positively correlated with the degree of REE fractionation, indicating a unique process in preferentially enriching the HREE during the evolution of the granites. Multiple stages of hydrothermal re-mobilization of the REE can account for the HREE mineralization, and these are recorded in the texture and composition of the zircon. In these processes, fluctuations in the F activity of the fluid caused alternating dissolution-reprecipitation and continuous growth of the zircon. REE were repeatedly mobilized and enriched in the fluid to precipitate the major HREE mineral synchysite-(Y), and partially incorporated into the growth zone of zircon, while other elements were largely lost to the fluid during the extensive dissolution of the rock-forming minerals. LREE were also likely substantially mobilized in the late hydrothermal stage and lost through complexation with Cl, causing the significant LREE depletion and, thus REE fractionation. This process continuously enriched host granites in the HREE to a potentially economic grade, making them favorable protoliths for subsequent supergene regolith-hosted HREE deposits.

Geology and exploration indications of the lithocap in Qianpu area, Luzong Basin, Anhui

The lithocap is a large-scale alteration including silicification, advanced argillic and argillic that developed near the surface by hydrothermal activities. It is helpful for exploring high-sulfidation epithermal deposits and porphyry deposits in its root and deep parts, respectively, and is used as a new prospecting indicator. There are many minerals in the lithocap and it is difficult to identify them; alunite is the most representative mineral and one of the new minerals used to guide exploration; it plays an important role in assessing the metallogenic potential and guiding ore prospecting. The Luzong basin is dominated by iron oxide apatite deposits (IOAs). In recent years, many researchers have been searching for porphyry copper–gold deposits and epithermal deposits as studies on alunite and lithocaps in the basin have gradually been undertaken. In field explorations and investigations of the Luzong basin, the author found that in Qianpu area of the central basin, where kaolinite deposits were mainly explored in the past, Well-occurring alunite minerals and advanced argillic alterations have developed. A typical lithocap developed in Qianpu area after a series work of geology and mineralogy, such as alteration mineral species, alteration types, and alteration zoning, which were formed by the hydrothermal alteration of the volcanic rocks of the Zhuanqiao Formation. The minerals in this lithocap are mainly quartz, alunite (including aluminum-phosphate-sulfate, APS), pyrite, zunyite, dickite, pyrophyllite, kaolinite, and a small amount of illite, which are present sequentially from the center to the peripheral quartz-alunite-pyrite alteration, alunite-dickite alteration, dickite-pyrophyllite alteration, alunite-kaolinite-illite alteration, and alunite veins superimposed on quartz-alunite-pyrite alteration and alunite-dickite alteration. Three types of alunite were produced in large quantities and were formed in three kinds of environments. The I-type alunite, which was formed by hydrothermal metasomatism alteration in the early stage and is densely disseminated distribution, coexisting with quartz and pyrite, is a magmatic hydrothermal alunite. Relatively pure alunite veins (II-alunite) of varying thicknesses formed in the open space in the mid-hydrothermal period in a magmatic steam environment. The fine-grained III-alunite that coexists with kaolinite formed in the late hydrothermal period and in a steam-heated environment. The alunite produced by various origins represents multiphase hydrothermal activity in the Yanshanian period in the Qianpu area; the Na content decreased, the K and Pb content increased, and the K/Na molar ratios ranged from 2.82 to 6.58 (EPMA) and 1.59 to 3.93 (LA-ICP MS) from the early to middle and late hydrothermal stages, indicating that the formation temperatures were more than 200 °C and gradually decreased with hydrothermal evolution. There is a high-sulfidation epithermal system in Qianpu area. In combination with the specific environmental significance of zunyite indicating a high temperature and closeness to the fluid channel, as well as the characteristics and genesis of the Huangzhuyuan silver polymetallic deposit near Qianpu, it is inferred that the Qianpu-Huangzhuyuan area has prospecting potential for porphyry-epithermal deposits.

Magnetite chemistry of the Sarkuh Porphyry Cu deposit, Urumieh–Dokhtar Magmatic Arc (UDMA), Iran: A record of deviation from the path sulfide mineralization in the porphyry copper systems

The Miocene Sarkuh porphyry Cu deposit is located in the southwestern part of Urumieh-Dokhtar Magmatic Arc (UDMA) in Iran. Compared with the neighboring giant Sarcheshmeh porphyry Cu deposit, this is a low-grade sub-economic porphyry Cu system (110 million tons @ 0.26 % Cu) characterized by an unusual abundance of magnetite. The present work tried to answer the question of whether or not there are differences in the hydrothermal system of Sarkuh, resulting in the lack of considerable mineralization. In this way, the mineral associations and EMPA data of magnetite were considered to distinguish the different stages of magnetite crystallization reflecting the magmatic-hydrothermal evolution of the Sarkuh deposit. They include (1) magmatic stage magnetite, including magnetite inclusions within primary silicate minerals (i.e., plagioclase and biotite), (2) pre-ore stage magnetite associated with potassic alteration assemblages, (3) main ore stage magnetite tightly associated with sulfide mineralization, and (4) late stage magnetite forming overgrowths on the sulfides. The results of EPMA analysis confirm that magnetite of these four stages differ in Mn, Fe, Ti, Mg, Al, Cr, and V concentrations. Higher V concentrations are found in the magmatic and pre-ore stages, whereas Al and Si reach the highest in the ore and late stages. Our data show that increasing fluid-rock interaction and changes in the oxygen fugacity, especially during the main ore stage extending to the late stage, are key factors controlling the trace element partitioning of magnetite. Most of ore stage magnetite formed at temperatures >500 °C and high temperatures prevailed during it. Magnetite crystallization after the main stage of sulfide mineralization accompanied by (partial) martitization indicate the increase of oxygen fugacity towards the late hydrothermal stage. This could explain why the ore and late stage magnetites show chemical similarities to those from sulfur-poor iron oxide copper‑gold (IOCG) deposits rather than porphyry deposits.

Gold, antimony and mercury ore formation and metallogenic link in the Sandu-Danzhai area, Jiangnan Orogen, SW China

The turbidite-hosted Au-Sb-Hg deposits in the Sandu-Danzhai area are distributed along the southwestern marginal fault of the Jiangnan Orogen, yet any genetic link among the Au, Sb and Hg mineralization and their respective ore-forming process remain unclear. Here, we investigate the Paiting Au(-Hg) and Miaolong Au-Sb deposits and present a new metallogenic model based on detailed petrographic observations, and in-situ trace element (EPMA and LA-ICP-MS) and sulfur isotope (fs-LA-MC-ICPMS) analyses on sulfide minerals. Our results show that the ore formation in the Sandu-Danzhai metallogenic belt (SDMB) can be divided into Au (pyrite + arsenopyrite + dolomite), Au-Sb (pyrite + arsenopyrite + stibnite + quartz), Sb (stibnite + native antimony + barite + dolomite + quartz) and Hg (cinnabar + calcite) stages, based on mineral paragenetic and vein crosscutting relationships. Trace element compositions suggest that progressive As enrichment in pyrite is accompanied by increasing Au, Sb and Cu contents, implying that these elements may have been leached from the same source via fluid-rock reactions. Sulfur isotope compositions of the sulfates and sulfides in the Au-Sb-Hg ores reveal that the sulfur was originated from thermal-chemical sulfate reduction (TSR) of marine sulfates in the Cambrian ore-bearing strata. Thus, we propose that deep metamorphic fluids (as evidenced from the high fluid CO2 and CH4 contents) may have promoted ore-material (e.g., Au, Sb, As, Hg) mobilization in the metamorphic basement and/or Cambrian strata. As for the metal transport and precipitation mechanism, fluid-rock interaction may have decreased the ore-fluid As content and caused auriferous pyrite precipitation. Meanwhile, changes in temperature and oxygen-sulfur fugacity may have significantly decreased Sb solubility, leading to extensive stibnite precipitation. Cinnabar associated with calcite was likely deposited via carbonate dissolution in the Cambrian strata in late hydrothermal (waning) stage. Overall, we propose that the Au-Sb-Hg deposits in the SDMB are best classified as orogenic type, and the metallogeny was controlled by boundary faults of the Jiangnan Orogen.

Gold endowment and unloading along pathway for giant gold mineralization: Insights from spatiotemporal variations of in-situ pyrite geochemistry and gold fineness from the Jiaodong gold deposits, north China Craton

Over 5000 tonnes of gold were accumulated in the Jiaodong Peninsula at the early Cretaceous, the sources and critical ore-forming processes of which are still controversial. Here, we conducted comprehensive in-situ textural, elemental and isotopic analyses on pyrite and gold grains from the different mineralization styles, hydrothermal stages and depths for three representative gold deposits (Linglong, Xiadian and Jiangjiayao) from the northwestern Jiaodong Peninsula, with the aim to exactly constrain the sources and ore-forming processes. Three groups of δ34Spyrite were identified in the studied deposits, of which the Group 1 shows stable and low δ34S (4.8–7.6‰) throughout the hydrothermal evolution while the Group 2 has elevated δ34S (6.0–12.8‰) coupled with increasing As and Au concentrations. The Group 3 shows moderate δ34S (5.2–9.8‰) accompanied by high Al and Si concentrations. The Group 1 suggests a low-δ34S primary auriferous fluid derived from a mantle-related source, whereas the Group 2 indicates the primary auriferous fluid leaching additional S, As and Au from the Precambrian metasedimentary rocks along pathway. The Group 3 is petrographically coupled with numerous silicate inclusions, indicating enhanced fluid-rock interaction between the auriferous fluids and the granitic wallrcoks. Gold fineness decreases from the early to the late hydrothermal stages, combined with increasing deposition of polymetallic sulfides, suggesting an increase of pH resulting in efficient Au deposition. Gold fineness and Bi concentrations in pyrite decrease with shallowing, suggesting that cooling affected Au deposition as well. Bismuth-Te-S minerals were identified in the deep depths, combined with the well correlated Bi and Ag, implying that Bi-Te complexes might play a role in transporting Au and Ag at high-temperature conditions. The above results corroborate that multiple sources and ore-forming processes were responsible for the giant gold mineralization, of which the gold endowment from Precambrian wallrocks needs to be further concerned.

The Occurrence of Primary REE Minerals and Their Para genesis within S-Type Granite and Quartz Vein, South Bangka, Bangka Belitung Islands, Indonesia

Primary rare earth element (REE) minerals known as carbonate and phosphate were identified in some localities. The carbonate type consists mainly of parasite, allanite, and bastnaesite, while REE phosphate group comprises mainly monazite and xenotime. They are accompanied by thorite and zircon. REE-bearing quartz vein is associated with cassiterite, pyrite, chalcopyrite, sphalerite, and tourmaline. The hydrothermal fluid that plays a role in REE mineral precipitation is subdivided into three stages: early (> 316oC - 316oC), medium (< 316oC – 210oC), and late (<210oC190oC). The δ18O range which is 12, 7 ‰ – 13 ‰, and the δ34S range are 3, 9 ‰ – 5, 5 ‰ indicate that the origin of hydrothermal fluid comes from mixing fluids of both meteoric and magmatic sources, and also influenced by metamorphic waters. While the source of sulphur is granitic and sedimentary rocks. REE phosphate is thought to have formed in the early magmatic crystallization stage except for monazite formed in the medium magmatic-hydrothermal and late hydrothermal stages. Primary REE carbonate may have formed in a medium hydrothermal-magmatic stage except for parasite and allanite, they may have formed in late-stage hydrothermal. Chalcopyrite and sphalerite seem to be associated with REE minerals in the medium and late hydrothermal stages

Development of Tourmaline-Bearing Lithologies of the Peraluminous Tusaquillas Composite Granitic Batholith, NW Argentina: Evidence from Quartz and Tourmaline

ABSTRACT Textural and chemical characteristics of quartz and tourmaline found in tourmaline-rich orbicules, greisens, pegmatites, and tourmalinite segregations associated with the peraluminous leucogranitic Tusaquillas Batholith Complex of northwest Argentina exhibit both magmatic and hydrothermal features. Imaging of quartz by optical cathodoluminescence and scanning electron microscopy cathodoluminescence shows three stages of development. Stage-1 quartz, considered magmatic, develops as large grains in pegmatites that have optical cathodoluminescence homogeneity; as anhedral relict grains partially replaced by stage-2 hydrothermal quartz in tourmalinite segregations, orbicules, and greisens; and as idiomorphic grains with irregularly spaced oscillatory zoning seen in scanning electron microscopy cathodoluminescence in orbicules. Stage-2 quartz, interpreted as hydrothermal, partially replaces stage-1 quartz and generation-1 tourmaline in most lithologies. Stage-3 quartz, a late hydrothermal stage, occurs in all lithologies as weakly luminescing quartz in healed quartz fractures with abundant fluid inclusions, commonly associated with the crystallization of irregular late-stage tourmaline. Multiple generations of tourmaline span magmatic to hydrothermal phases of development. In all lithologies, generation-1 tourmaline is compositionally similar: highly aluminous (range of average values of Altotal = 6.31–6.95 apfu), markedly Fe- and X□-rich (XMg = 0.01–0.17, X□= 0.21–0.51), and having variable F and WO (F = 0.00–0.57 apfu, WO = 0.00–0.40). Generation-1 tourmaline is interpreted as magmatic with compositions reflecting the chemical environment of the host lithologies and with compositional zoning patterns characteristic of both closed- and open-system behavior, possibly related to the transition to subsolidus conditions. Similar to generation-1 tourmaline, later-stage generations-2 and -3 tourmaline compositions are highly aluminous (range of average values of Altotal = 6.38–6.79 apfu), markedly Fe- and X□-rich (XMg = 0.00–0.20, X□= 0.28–0.40), and variably F- and WO-enriched (F = 0.07–0.57 apfu, WO = 0.00–0.31), but notably poorer in Ca and Ti (<0.01 apfu). The later-stage tourmaline is considered to have developed during the subsolidus hydrothermal conditions. External chemical contributions to tourmaline compositions from the country rocks appear to be minor to nonexistent. The X-site and W-site occupancies of the late-generation tourmaline implies subsolidus invasive alkaline, saline aqueous fluids with high Na but minimal Ca contents derived from the crystallizing leucogranites and related rocks across the solidus-to-subsolidus transition.

The mineralization of Daxiao carbonate-hosted Pb-Zn deposit, northeast Yunnan province, SW China: Constraints from Rb-Sr isotopic dating and H[sbnd]O[sbnd]S-Pb isotopes

The Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province located in western Yangtze Block contains more than 400 carbonate-hosted Pb-Zn deposits. Uncertain mineralization age and ore-forming material source causing debates on the genesis of these carbonate-hosted Pb-Zn deposits. To address this issue, the Daxiao Pb-Zn deposit was chosen as a case study. The orebodies of Daxiao deposit are hosted in Mesoproterozoic Heishan formation argillaceous dolomite interbedded with slate. Three main mineralization stages have been identified, including syn-sedimentary stage, hydrothermal stage and supergene stage. The ore minerals consist of galena, sphalerite, chalcopyrite, argentite, smithsonite, anglesite and cerussite in the deposit. The early hydrothermal stage sphalerite yielded a Rb-Sr isochron age of 223.5 ± 2.9 Ma, consistent with the spike of Pb-Zn mineralization in SYG metallogenic province. Quartz in hydrothermal stage yields δDSMOW values of −69.6 to −65.8 ‰ and calculated δ18OFluid values of + 3.4 – +5.6 ‰, showing an affinity of metamorphic water. While the quartz in supergene stage yields δDSMOW values of −68.3 to −65.8 ‰ and calculated δ18OFluid values of −4.1 to −1.7 ‰, indicating abundant basinal brine or meteoric water had mixed into ore-forming fluid during its evolution from hydrothermal stage to supergene stage. Sulfur isotopic composition (δ34S = +6.3 – +19.1 ‰) of different stage sulfides reveal that the ore-forming sulfur originated from sulfates within the wall rocks, and mainly reduced by Thermal-chemical reduction (TSR). Moreover, the 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of early hydrothermal stage sphalerite are 18.282 – 18.312, 15.603 – 15.681and 38.287 – 38.311, respectively. Those of late hydrothermal stage galena are 18.315 – 18.491, 15.676 – 15.721 and 38.314 – 38.326, respectively. All of them plot in the overlapping area of Emeishan flood basalts, Kunyang and Huili groups and Sinian to Triassic strata, indicating that these wall rocks jointly contributed the ore-forming metals for these Pb-Zn deposits in SYG metallogenic province. Hence, a metallogenic model for Daxiao and other carbonate-hosted Pb-Zn deposit in SYG metallogenic province was proposed: In the thrustfold systems caused by the subduction of Paleo-Pacific and the closure of Jinshajiang-Ailaoshan Paleo-Tethys ocean in Late Triassic to Early Jurassic. The fluids originated from metamorphic water migrated along deep faults and extracted ore-forming materials from wall rocks (including Proterozoic basement rocks, Sinian to Triassic sedimentary wall rocks and Permian Emeishan flood basalts), and then precipitated ores in the secondary thrust faults or interlayered fractures within these thrustfold systems.

Ore-formation at the Halasheng Ag-Pb-Zn deposit, northeast Inner Mongolia as revealed by trace-element and sulfur isotope compositions of ore-related sulfides

The Early Cretaceous Halasheng Ag-Pb-Zn deposit in NE China, which is mainly hosted in Jurassic rhyolitic tuff, andesite, and volcanoclastic rocks, comprises both proximal skarns and more distal hydrothermal discordant ore veins and stockworks with associated Fe-Mn-carbonate, illite, and silica alteration in NNW-trending extensional faults. Suggestions of a magmatic-hydrothermal relationship are tested by LA-ICP-MS trace-element and sulfur isotope studies of ore minerals, particularly sphalerite which is a major ore mineral.Sphalerite has at least three types: SpS, anhedral, mainly dark red sphalerite in skarns; Sp1, euhedral, normally pale yellow coarse-grained, and rarely oscillatory zoned sphalerite formed in Stage 2 of hydrothermal vein mineralization; and Sp2, fine-grained, red, non-zoned sphalerite formed in Stage 3 of hydrothermal mineralization. Sphalerite with different textures has As, Ag, Cd, Sb, and Pb contents that increase from proximal skarn to distal hydrothermal mineralization consistent with the increase in sulfosalt minerals in the late hydrothermal stage. In situ time-resolved depth profiles, together with tangential profiles, and LA-ICP-MS element mapping of sphalerite indicate that trace elements are largely in solid solution in Halasheng sphalerite with substitution mechanisms including: Zn2+ ↔ Fe2+, Cd2+, Mn2+, and 3Zn2+↔ (As3+, Sb3+) + Ag++Pb2+. Enrichment of In and Sn, and depletion of Ga and Ge, together with In/Sn ratios indicate the high-temperature ore-forming fluids at Halasheng that are most likely closely related to intrusions. In situ mean δ34S values of SpS, Sp1, and Sp2 sphalerites are 5.3‰, 7.6‰, and 8.3‰, respectively, indicating that sulfur was derived both from magmatic-hydrothermal fluids and from wall rocks with higher (>10‰) values.These data help confirm that the Halasheng Ag-Pb-Zn deposit is an intrusion-related deposit with local proximal skarn mineralization at the contact of Tamulangou Formation andesite with Ergunahe Formation crystalline limestone, and more distal vein-type volcanic-hosted hydrothermal mineralization, with both ore and gangue mineral assemblages and available fluid inclusion data suggesting an intermediate-sulfidation epithermal association. As ore-forming hydrothermal fluids cooled and evolved they became enriched in silver, with silver-bearing sulfosalt minerals and silver-rich sphalerite precipitated in the latter stages of deposition.In terms of future exploration, there is potential for the concealed Lower Cretaceous Pb-Zn skarns and intermediate sulfidation Ag-Pb-Zn epithermal deposits at Halasheng to be part of a larger porphyry-related mineral system with porphyry Cu-Au-Mo deposits, similar to those of Middle Triassic to Early Jurassic age in the same metallogenic belt, at deeper crustal levels than the known deposits.

МИНЕРАЛЫ РЕДКИХ ЗЕМЕЛЬ В РЕДКОМЕТАЛЛЬНЫХ ГРЕЙЗЕНАХ МЕСТОРОЖДЕНИЯ ВЕРХНЕЕ (ХИНГАНО-ОЛОНОЙСКИЙ РАЙОН, ПРИАМУРЬЕ, РОССИЯ)

Rare minerals represented by oxides, fluorides, F-carbonates and REE arsenates associated with monazite-Ce, monazite-Th, xenothym-Y and REE zonal fluorite were identified in rare-metal ores of the Sn-W deposits of the Malyi Khingan in Priamurye. Rare lanthanide minerals are described, such as fluocerite, bastnesite, gasparite-Ce, first found in Russia in Sn-W greisens, and chernovite-Y, which is the second find in the greisens of the Russian Far East. The processes of sequential replacement of xenothyme-Y and monazite-Ce by arsenic fluids in the late hydrothermal stage with the formation of various REE minerals with different lanthanide ratios are shown, and the difference is revealed in their chemical composition from that of the previously described similar minerals in other deposits of the world. Due to the different valence of arsenic and the unlimited isomorphism of rare earths, arsenates can be used as indicators of redox conditions of their deposition.

Mineralogical characteristics and Sr–Nd–Pb isotopic compositions of banded REE ores in the Bayan Obo deposit, Inner Mongolia, China: Implications for their formation and origin

Rare earth elements (REEs) are a focus of current research due to their importance in a wide range of industries and technologies. Bayan Obo in China is the largest REE deposit in the world. Although some studies have investigated the banded REE ores in the Bayan Obo deposit, the origin and formation processes of the ores are unclear. In this study, we used X-ray powder diffraction, electron microprobe, laser ablation–inductively coupled plasma–mass spectrometry, and mass spectrometry methods to investigate the mineral assemblages and geochemical characteristics of minerals in banded ores in the Bayan Obo REE deposit. Based on petrographic observations, the early minerals that precipitated were alkali- and Fe-rich silicates, such as aegirine–augite and arfvedsonite, followed by bastnäsite, fluorite, barite, calcite, and monazite in the late stage. The REE minerals in the banded REE ores are mainly monazite, bastnäsite, and parisite (1–10 vol%) that overprinted gangue minerals, suggesting that REE mineralization occurred during the late hydrothermal stage. The sequence of mineral formation and their evolution caused progressive enrichment in REEs, F, Sr, and Ba. For example, fluorite in the banded REE ores has high concentrations of Sr (252–1910 ppm), Ba (1040–8230 ppm), and light REEs (1001–16,079 ppm), but is depleted in Nb and Ta. The bastnäsite is enriched in Sr (885–4046 ppm), Ba (1073–80,809 ppm), and ΣREEs (99,631–158,227 ppm). The fluorite, arfvedsonite, and bastnäsite in the banded REE ores have ɛNd(t) values of −3.68–1.78, −5.54, and 0.05, and initial (87Sr/86Sr)i (ISr) ratios of 0.70352–0.70478, 0.70620, and 0.70346, respectively. Based on these data, and the regional geological setting and Pb isotope data, it is proposed that fluorite and bastnäsite crystallized from ferrocarbonatite and fine-grained dolomite, and the REE source was a mixture of HIMU mantle and global marine sediments. We also suggest that the carbonatite- or dolomite-hosting ores in Bayan Obo formed by melting of the subcontinental lithospheric mantle, which might have been previously metasomatized by REE- and CO2-rich fluids derived from subducted marine sediments.

Iron and sulfur isotopic compositions of carbonatite-related REE deposits in the Mianning–Dechang REE belt, China: Implications for fluid evolution

Carbonatite-related rare earth element (REE) deposits are the most significant source of REEs worldwide. The processes of REE precipitation, enrichment, and mineralization remain controversial. The Cenozoic Mianning–Dechang (MD) REE belt, located in Sichuan Province, southwestern China, comprises one giant (Maoniuping), one large (Dalucao), and two small–medium (Muluozhai and Lizhuang) deposits. These deposits provide a continuous record of fluid evolution, and thus are ideal for investigating the processes of REE mineralization in carbonatite-related REE deposits. Given that sulfate (i.e., barite and celestite) and sulfide (i.e., pyrite and galena) minerals crystallized and precipitated in the pegmatitic to hydrothermal stages, respectively, the REE minerals formed later than the sulfate minerals. However, the formation sequence of the sulfide minerals and bastnäsite is unclear, although both pyrite and bastnäsite formed in the late hydrothermal stage. We used S isotope data for sulfate and sulfide minerals and Fe isotope data for pyrite to investigate the composition and evolution of ore-forming fluids during the magmatic–hydrothermal stages. The sulfate minerals have positive δ34SCDT values (+3.2‰ to +8.3‰), and the sulfide minerals have negative δ34SCDT values (−13.5‰ to − 5.6‰) in the four REE deposits. In the Maoniuping deposit, δ34SCDT values for barite from the pegmatitic stage (+4.7‰ to +5.7‰) are higher than for barite from the hydrothermal stage (+4.1‰ to +4.5‰), which indicate that hydrothermal activity led to relative enrichment in isotopically light S. The δ34SCDT values for barite (+3.2‰ to +5.5‰) are lower than for celestite (+6.2‰ to +7.2‰) from the pegmatitic stage in the Dalucao deposit. The δ34SCDT values for galena (−13.5‰) are also lower than for pyrite (−13.5‰ to −7.2‰) from the hydrothermal stage in the Guangtoushan section. In general, δ34SCDT values change from positive to negative values (+8.3‰ to −16.4‰) as the fluids evolved from the pegmatitic to hydrothermal stages, which can be attributed to a decrease in oxygen fugacity (fO2) and addition of sediment containing isotopically light S. Iron isotopic compositions of pyrite from the hydrothermal stage show significant variations (δ56FeIRMM-014 = −0.03‰ to +0.65‰ for the Maoniuping deposit; −0.14‰ to 0.00‰ for the Dalucao deposit; +0.05‰ to +0.35‰ for the Lizhuang deposit), and are higher than those for the carbonatites (δ56Fe IRMM-014 = −0.47‰ to −0.17‰). These data indicate there are two sources of Fe in the MD REE belt, which are the carbonatite–nordmarkite magma and 56Fe-rich sediment. Paleozoic–Mesozoic volcanic–sedimentary and Mesozoic clastic and carbonate rocks are exposed in the MD REE belt. In general, the S–Fe isotope data, along with geological and petrographic observations, indicate that the REE minerals formed later than the sulfate minerals, and the S–Fe were derived from both carbonatite magma and sediment containing isotopically light S and heavy Fe.

Gemology, Mineralogy, and Spectroscopy of an Attractive Tremolitized Diopside Anorthosite Gem Material from the Philippines: A New Type of Material with Similarities to Dushan Jade

In recent years, a new type of material called Philippines “Dushan jade” has appeared in the gemstone market in China. This new type of material, very similar in appearance and physical properties to Dushan jade, an important ancient jade with a long history in China, is causing confusion in the market and poses identification difficulties. Microscopy, electron probe microanalysis, Fourier transform infrared (FTIR) spectroscopy, Raman microprobe spectroscopy, and ultraviolet-visible (UV-Vis) spectroscopy were used to study the gemology, mineralogy, and spectroscopy of rock samples from the Philippines in order to differentiate them from Dushan jade. The studies showed that Philippines rock is composed mainly of anorthite and minor amounts of diopside, tremolite, uvarovite, titanite, chromite, zoisite, prehnite, thomsonite-Ca, and chlorite, among which uvarovite, diopside, and tremolite are the main color causing minerals. The origin of the color is related to the electronic transitions involving Cr3+, Fe2+, Fe3+, and charge transfer between the ions. The paragenetic mineral formation sequence of Philippines rock can be divided into three stages: (1) the magmatic stage: anorthite phenocryst, diopside, chromite, and titanite are formed first in the magma; (2) the metamorphic stage: anorthite phenocryst undergo fracture and recrystallization; the early fluid intrusion transforms diopside into tremolite forming uvarovite-grossular-andradite solid-solution around the anorthite and chromite; and (3) the late hydrothermal stage: the late hydrothermal solution fills in fractures with prehnite, thomsonite-Ca, and zoisite being formed. From the comparison studies, it was established that Philippines rock and Dushan jade are two completely different type of material. Philippines rock should be called “tremolitized diopside anorthosite”.

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.

Trace and Rare Earth Elements, and Sr Isotopic Compositions of Fluorite from the Shihuiyao Rare Metal Deposit, Inner Mongolia: Implication for Its Origin

Abundant fluorites occur in the Shihuiyao rare metal (Nb-Ta-Rb) deposit in Inner Mongolia of NE China, and they can be classified by their occurrence into three types. Type I occurs disseminated in greisen pockets of albitized granite. Type II occurs in the skarn zone between granite and carbonate host rocks, and it can be subdivided into different subtypes according to color, namely dark purple (II-D), magenta (II-M), green (II-G), light purple (II-P), and white (II-W). Type III are the fluorite-bearing veins in the silty mudstones. On the basis of petrography of the fluorites and their high contents of HFSEs (high field strength elements) and LILEs (large ion lithophile elements), strong negative Eu anomalies, and tetrad effects, we suggest that Type I fluorites crystallized in a late-magmatic stage with all the components derived from the granite. The high Y/Ho ratios suggest that the Type II fluorites crystallized in the early- or late-hydrothermal stage. The rare earth elements (REEs) characterized by various Eu anomalies of the Type II fluorites indicate a mixed origin for ore-forming metals from granite-related fluids and limestones, and the oxygen fugacity increased during fluid migration and cooling. Compared to the Type II fluorites, the similar trace element contents of the Type III suggest a similar origin, and remarkable positive Eu anomalies represent a more oxidizing environment. The Sr isotopic composition (87Sr/86Sr)i = 0.710861) of the Type I fluorites may represent that of the granite-derived fluids, whereas the (87Sr/86Sr)i ratios of the Type II (0.710168–0.710380) and Type III (0.709018) fluorites are lower than that of the Type I fluorites but higher than those of the Late Permian-Early Triassic seawater, suggesting a binary mixed Sr source, i.e., granite-derived fluids and marine limestones. Nevertheless, the proportion of limestone-derived Sr in the mixture forming the Type III fluorites is much higher than that of Type II. The rare metal Nb and Ta get into the granite-derived F-rich fluids by complexing with F and precipitate in the form of columbite-group minerals after the Type I fluorites crystallize. Most of Nb and Ta may have deposited as columbite-group minerals during the magmatic stage, resulting in no Nb-Ta mineralization in the hydrothermal stage when the Type II and III fluorites formed. Hence, the Type I fluorites in the Shihuiyao mining area can be used as an important exploration tool for the Nb-Ta mineralization.

Late Cretaceous granitic magmatism and Sn mineralization in the giant Yinyan porphyry tin deposit, South China: constraints from zircon and cassiterite U–Pb and molybdenite Re–Os geochronology

The Yinyan porphyry tin deposit in western Guangdong is spatially associated with quartz porphyry and granite porphyry. LA–ICP–MS zircon U–Pb dating defined an emplacement age of 78.5 ± 0.4 Ma for the quartz porphyry and 79.2 ± 0.9 Ma for the granite porphyry. LA–ICP–MS cassiterite U–Pb dating yielded Tera–Wasserburg lower intercept ages of 78.5 ± 0.6, 78.6 ± 1.2, and 78.2 ± 0.7 Ma, for cassiterite from a cassiterite–sulfide vein, cassiterite–sulfide ore, and a cassiterite–topaz–quartz stringer, respectively. Re–Os dating of molybdenite from seven different veins yielded an isochron age of 77.0 ± 0.5 Ma. All these new age data are indistinguishable within analytical uncertainty and, therefore, indicate a genetic relationship between the Sn mineralization and the porphyry magmatism in the Yinyan deposit. The REE tetrad effect and very low Nb/Ta and Zr/Hf ratios indicate that the quartz porphyry and the granite porphyry are highly evolved. The U–Pb dated cassiterite is enriched in Fe, W, and U and in high field strength elements (HFSEs) such as Zr, Hf, Nb, and Ta. The high Fe, Nb, and Ta contents may be responsible for the dark luminescence of cassiterite in CL images. The Zr/Hf ratio of cassiterite may potentially be used to distinguish the mineralization type. Cassiterite from pegmatites has lower Zr/Hf ratios (~ 5–6) in comparison with granite/greisen-related (~ 9–30) cassiterite. Cassiterite from the early hydrothermal stage typically contains higher amounts of Ti, Nb, Ta, Zr, and Hf than that from the late hydrothermal stage. In combination with published geochronological data of other Sn–W deposits in the western Guangdong Province, two Sn–W metallogenic events at ca. 85 and 77–80 Ma have been identified. These two metallogenic events are part of a larger-scale 75–100 Ma Sn–W mineralization event in South China, which we suggest was probably related to the subduction of the Neo-Tethyan oceanic plate.

Arsenotu\u010dekite, Ni18Sb3AsS16, a new mineral from the Tsangli chromitites, Othrys ophiolite, Greece

Arsenotučekite, Ni18Sb3AsS16, is a new mineral discovered in the abandoned chromium mine of Tsangli, located in the eastern portion of the Othrys ophiolite complex, central Greece. Tsangli is one of the largest chromite deposit at which chromite was mined since 1870. The Tsangli chromitite occurs as lenticular and irregular bodies. The studied chromitites are hosted in a strongly serpentinized mantle peridotite. Arsenotučekite forms anhedral to subhedral grains that vary in size between 5 μm up to 100 μm, and occurs as single phase grains or is associated with pentlandite, breithauptite, gersdorffite and chlorite. It is brittle and has a metallic luster. In plane-polarized light, it is creamy-yellow, the bireflectance is barely perceptible and the pleochroism is weak. In crossed polarized reflected light, the anisotropic rotation tints vary from pale blue to brown. Internal reflections were not observed. Reflectance values of arsenotučekite in air (Ro, Re′ in %) are: 41.8–46.4 at 470 nm, 47.2–50.6 at 546 nm, 49.4–52.3 at 589 nm, and 51.3–53.2 at 650 nm. The empirical formula of arsenotučekite, based on 38 atoms per formula unit, and according to the structural results, is (Ni16.19Co1.01Fe0.83)Σ18.03Sb3(As0.67Sb0.32)Σ0.99S15.98. The mass density is 6.477 g·cm−3. The simplified chemical formula is (Ni,Co,Fe)18Sb3(As,Sb)S16. The mineral is tetragonal and belongs to space group I4/mmm, with a = 9.7856(3) Å, c = 10.7582(6) Å, V = 1030.2(6) Å3 and Z = 2. The structure is layered (stacking along the c-axis) and is dominated by three different Ni-coordination polyhedral, one octahedral and two cubic. The arsenotučekite structure can be considered as a superstructure of tučekite resulting from the ordering of Sb and As. The name of the new mineral species indicates the As-dominant of tučekite. Arsenotučekite occurs as rims partly replacing pentlandite and irregularly developed grains. Furthermore, it is locally associated with chlorite. These observations suggest that it was likely precipitated at relatively low temperatures during: 1) the late hydrothermal stages of the ore-forming process by reaction of Sb- and As-bearing solutions with magmatic sulfides such as pentlandite, or 2) during the serpentinization of the host peridotite. The mineral and its name have been approved by the Commission of New Minerals, Nomenclature, and Classification of the International Mineralogical Association (number 2019–135).

Genesis and age of the Toudaoliuhe breccia-type gold deposit in the Jiapigou mining district of Jilin Province, China: Constraints from fluid inclusions, H–O–S–Pb isotopes, and sulfide Rb–Sr dating

The Jiapigou mining district (JMD) in the northeastern part of the North China Block mainly contains quartz vein- and altered rock-type gold deposits that have been prospected and mined for over 200 years. Recently, a breccia-type gold deposit, known as Toudaoliuhe, was discovered in the JMD, that has attracted attention for prospecting and exploration. In this paper, we report the ore geology, gold-bearing sulfide (i.e., pyrite, galena, and sphalerite) Rb–Sr age, fluid inclusions (FIs), and H–O–S–Pb–Sr isotope data of the Toudaoliuhe gold deposit to determine its genesis and ore-forming mechanisms. Gold orebodies mainly occur in the breccia cements, as well as in several quartz veins controlled by NW-trending brittle faults. There were three hydrothermal stages: the early (quartz–pyrite), main (quartz–polymetallic sulfide), and late (quartz–carbonate) stages. Gold mineralization occurred in the main hydrothermal stage. Three types of FIs were identified: CO2–H2O–NaCl (C-type), H2O–NaCl (W-type), and pure CO2 (PC-type). The FIs in quartz from the early hydrothermal stage are predominantly of the C- and W-types (with traces of PC-type), and have homogenization temperatures of 299.8–340.0 °C and salinities of 6.5–14.8 wt% NaCl equivalent (E). The FIs in the quartz and sphalerite forming the main hydrothermal stage are also predominantly of the C- and W-types (with trace PC type), and have homogenization temperatures of 169.1–298.7 °C and salinities of 5.7–16.5 wt% E. The FIs in the quartz and calcite from the late hydrothermal stage were solely of the W-type, and have homogenization temperatures of 126.0–210.2 °C and salinities of 2.1–11.4 wt% E. The ore-forming fluids are characterized by moderate temperature and low salinity, suggesting a CO2–H2O–NaCl system. The H–O–S–Pb–Sr isotopic results suggest that the ore-forming fluids were dominated by magmatic water, and that the ore-forming materials were mainly extracted from the Middle Jurassic magmatic reservoir (177–163 Ma), sourced mainly from the lower crust with trace mantle components. Fluid boiling was the dominant mechanism for gold and associated sulfide precipitation. The Rb–Sr isochron age of the gold-bearing sulfides at 177.7 ± 1.7 Ma indicates that gold mineralization occurred in the early Middle Jurassic. We therefore proposed that the Toudaoliuhe is a mesothermal gold deposit that formed in an extensional setting related to the subduction of the Paleo-Pacific Plate beneath the Eurasian continent.

Episodic hydrothermal alteration recorded by microscale oxygen isotope analysis of white mica in the Larderello-Travale Geothermal Field, Italy

Microscale oxygen isotope analysis (18O/16O) of minerals can identify distinct events of fluid-rock interaction. This method is, however, still limited to a few major and accessory minerals of which most are anhydrous minerals. We present the systematic study of oxygen isotope distribution in white mica by Secondary Ion Mass Spectrometry (SIMS). Texturally and chemically distinct white mica populations in granitic and contact metamorphic rocks from the Larderello-Travale geothermal field (LTGF), Italy, record stages of magmatic crystallization, metamorphic-hydrothermal replacement and fluid-rock interaction. The large range in intra- and inter-grain white mica δ18O values between 1 and 14‰ reflects varying protoliths and degrees of fluid-mineral interaction at variable temperatures (180–450°C present-day temperatures; p.d.T.). This variability reflects the large-scale circulation of both (1) magmatic, syn-intrusive to early contact metamorphic hydrothermal fluids with high-δ18O values, and (2) meteoric fluids with δ18O values of −7‰ during a post-intrusive, late hydrothermal stage.Metasedimentary rocks from the upper reservoir contain distinct white mica populations occurring in close proximity (μm-scale), including detrital grains (δ18O=12–14‰; high Na, low Mg), partially altered white mica (δ18O=8–9‰) and late hydrothermal white mica (1–6‰; low Na, mid Mg). The late hydrothermal white mica has similar δ18O values to other secondary minerals and is in equilibrium with meteoric-dominated fluids with a δ18O of −6 to 0.5‰, which circulated in the late hydrothermal stage. Downhole towards the lower reservoir, white mica from two contact metamorphic micaschist samples shows either (1) homogeneous δ18O values of ca. 9‰ likely due to recrystallization in the contact metamorphic hydrothermal stage (T ca. 600°C), or (2) a large spread in δ18O from 2 to 12‰ within and across grains of variable texture and chemistry in the host rock and a cross-cutting quartz-white mica vein (ca. 300°C, present day temperature; hereafter p.d.T.). This contrasting δ18O signature of white mica is also recorded in granite cored at up to 4.6km depth. The Carboli granite contains white mica with a homogeneous magmatic δ18O of 10±0.6‰, whereas older granite samples from Radicondoli have magmatic to hydrothermal white micas that vary in δ18O from 4 to 10‰. A pronounced intra-grain δ18O variability of up to 6‰ occurs in white mica domains with higher Fe-Mg-Ti halos around inclusions of chloritized biotite, as a result of interaction with dominantly meteoric fluids that infiltrated to depths of at least 4.6km. In the Porto Azzurro granite on Elba, Italy, altered white mica has δ18O values of 2.6‰ down from 10‰ in unaltered grains.The distribution of oxygen isotope ratios in white mica is thus firstly a result of pervasive versus selective fluid alteration (at depth, sample and grain scale). Secondly, the actual preservation of these μm-scale variabilities indicates that volume diffusion is not detectable at microscale at p.d.T at or below 350°C where most of the heterogeneous white mica is found. Selective, sample- and grain-scale fluid penetration occurs episodically and anisotropically, on micro- and megascale, along faults, fractures and cleavages, producing lower δ18O white mica at various times in zones of higher secondary permeability and active hydrothermal fluid circulation.