Magmatic-hydrothermal Processes Research Articles

Origin and evolution of a porphyry-skarn-stratabound system: constraints from geology, magmatic-hydrothermal zircon U–Pb and molybdenite Re–Os geochronology, and in situ S isotopes of the Dongguashan Cu(–Au) deposit, eastern China

Intrusion-related stratabound deposits within Late Carboniferous carbonate units are an abundant and highly economically significant ore type in eastern China. In such deposits, stratabound mineralization commonly coexists with porphyry and/or skarn mineralization, and the vast majority of reserves (>90 %) are derived from extensive stratabound orebodies, which are easy to exploit and of great interest to geologists. However, it is unclear whether these deposits were formed via the Late Carboniferous seafloor sedimentary exhalation formation or the Early Cretaceous magmatic-hydrothermal processes. Moreover, the fluid and sulfur isotope variations within porphyry-skarn-stratabound systems have not been adequately constrained. We investigated the Dongguashan deposit, one of the largest and most representative stratabound Cu(–Au) deposits in eastern China. Three mineralization types were recognized based on field and petrologic studies: porphyry, skarn, and stratabound. In the stratabound mineralization zone, magmatic and hydrothermal zircons from laminated ores yielded concordant U–Pb ages of 137.3 ± 1.1 and 135.7 ± 1.4 Ma, respectively, while molybdenite samples from vein-like ores yielded Re–Os model ages of 137.8–133.1 Ma (isochron age, 135.9 ± 1.4 Ma). These ages were consistent with the zircon U–Pb age of quartz monzodiorite (137.8 ± 1.7 Ma). A total of 146 in situ S isotope analyses yielded δ34S values (1.9–7.4 ‰) indicating that the sulfur was derived from a magmatic source. Therefore, the Dongguashan deposit resulted from Early Cretaceous magmatism rather than submarine exhalative sedimentary processes. The fluctuations in S isotopes of sulfides across the three mineralization types are attributable to different factors (pH, temperature, and oxygen fugacity) during the evolution of hydrothermal ore-forming fluids. This study demonstrates the importance of geochronology of mineralization and in situ sulfur isotope analysis under robust geological and petrographic frameworks, which can yield information about the ore-forming processes and ore genesis.

Cadmium isotope fractionation in a S-type granite related large magmatic–hydrothermal system

Granite-associated deposits are one of the important ore types in the Earth’s crust and can dominantly be subdivided into S-, I- and A-type granite-related deposits with different mineralization elements and isotopic signatures (e.g., sulphur and boron). The object of this study is to investigate whether Cd isotopic difference exists between I- and S-type granite-related deposits, and to provide new insights on geochemical behavior of Cd in such systems that have not been well constrained. The Dulong deposit in southwest China is a world-class skarn-type polymetallic Zn–Sn–In deposit that is thought to be genetically related to the emplacement of the highly fractionated S-type Laojunshan granite. The extremely negative δ114/110Cd values of sulfides (−0.82 ‰ to −0.42 ‰) within the Dulong deposit are all lower than those of sulfides from other Zn–Pb ore deposits globally. In comparison, representative sphalerites from I-type granite-related deposits yield heavier Cd isotopic compositions relative to the samples from the Dulong deposit. The Laojunshan granite samples are enriched in light Cd isotopes and have δ114/110Cd values that range from −0.73 ‰ to −0.40 ‰, overlapping with the δ114/110Cd values of sphalerite within the Dulong deposit and suggesting that the Cd in the deposit was derived from the Laojunshan granite. Similarly, I-type granite-related deposits elsewhere have Cd isotopic compositions that are similar to mafic–intermediate igneous rocks, suggesting little or no Cd isotopic fractionation took place during the magmatic–hydrothermal processes that formed these deposits. These results suggest that geochemical signatures of metal sources are the most likely control on Zn/Cd ratios and δ114/110Cd values of sulfides in these deposits, with different mineral deposit types having different Zn/Cd ratios and δ114/110Cd values. In summary, Cd isotopes provide a potentially effective tool for discriminating between different types of hydrothermal system and may also be useful in the investigation of granite petrogenesis.

Sulfur isotope and trace element geochemistry of sulfides from the unique Yaojialing Zn-Au-Cu deposit, Lower Yangtze River Metallogenic Belt, China: Implications for ore-forming process and exploration

The Yaojialing Zn-Au‑Cu deposit is a porphyry-skarn-epithermal vein-type compound deposit that consists of epithermal vein-type lead‑zinc‑silver orebodies, skarn Zn-Cu-Au orebodies, and porphyry CuAu orebodies from shallow level to depth. We decipher the source and metallogenic mechanism by studying the trace element and S isotopic compositions of sulfides (pyrite, sphalerite, chalcopyrite, and galena) from three types of orebodies. The collected pyrite can be divided into two types. PyI coexists with chalcopyrite, and PyII coexists with sphalerite or galena. In addition, PyI was further divided into PyIa (collected from porphyry copper bodies) and PyIb (collected from skarn copper bodies). PyII can be further divided into PyIIa (collected from skarn-type lead‑zinc ore body) and PyIIb (collected from vein lead‑zinc ore body in strata). Sphalerite and galena from skarn-type PbZn ore bodies and shallow vein-type PbZn ore bodies are named SpI and GnI, and SpII and GnII, respectively.Pyrite and sphalerite trace element thermometers revealed that the temperature of the ore-forming fluids decreased from 500 to 600 °C in the porphyry ore body to 300– 360 °C in the skarn ore body and then to 240– 280 °C in the shallow vein ore body. The decrease in the Co and Ni contents of pyrite collected from deep to shallow depths may indicate that meteoric water precipitated in the late ore-forming hydrothermal system. Rapid crystallization and variations in the physicochemical states (such as temperature, pH, fO2, and geochemical composition) of the fluids resulted in an obvious oscillating zone of euhedral PyI pyrite particles. It also affects the solubility of trace metal elements and leads to the selective entry of these elements into pyrite. PyII also shows obvious zonation characteristics rather than oscillating zonation, indicating that the growth rate of pyrite is relatively slow. Moreover, the relationships between the Au and As contents in the two types of pyrite are different. PyI is coupled, while PyII shows decoupling. We believe that this phenomenon is due to the high content of As in ore-forming fluid systems, which may inhibit the absorption of Au on the surface of pyrite rather than the decoupling of Au and As caused by rapid crystallization, based on the rapid increase in As content and non-oscillating zonation in PyII. According to the analysis of the sulfur isotopes of various sulfides, the solid evidences suggest that the ore-forming materials of each type of orebody in the Yaojialing deposit were mainly derived from magmatic-hydrothermal processes and that the fractionation of sulfur isotopes was the result of variations in physicochemical conditions caused by magma-hydrothermal evolution rather than the addition of foreign sulfur sources.

New precise age constraints of the Hatu gold belt, west Junggar, NW China: Implications for a 300 Ma magmatic hydrothermal event in post-collisional setting

A 300 Ma magmatic hydrothermal ore-forming process is identified in the Hatu gold belt in west Junggar, northwest China, based on precise age constraint by secondary ion mass spectroscopy U-Pb dating of hydrothermal zircon and Ar-Ar dating of muscovite. The gold deposits in the Hatu belt (Hatu, Qi-V, Huilvshan, etc.) are similar in geology, with NE- and NW-trending orebodies composed of gold-bearing quartz veins and auriferous altered tuffaceous wall-rocks. Hydrothermal zircon grains separated from gold-bearing quartz veins in the Qi-V gold deposit provide a concordia age of 299.6 Ma and a nearly identical weighted mean 206Pb/238U age of 300 ± 2 Ma. Muscovite samples also from the gold-bearing quartz veins yield 40Ar/39Ar plateau ages of 299.6 ± 1.7 Ma, 299.9 ± 1.8 Ma, and 300.6 ± 1.9 Ma. By comprehensive compilation of geological and geochemical characteristics, tectonic evolution, and geochronology of the gold deposits in the Hatu gold belt, our new precise age data confirm that the gold deposits in the Hatu belt formed simultaneously at ca. 300 Ma, and likely formed during a post-collisional extensional setting by magmatic hydrothermal fluid from cooling magmatic sources.

Apatite as a Record of Magmatic–Hydrothermal Evolution and Metallogenic Processes: The Case of the Hongshan Porphyry–Skarn Cu–Mo Deposit, SW China

Apatite, as a common accessory mineral found in magmatic–hydrothermal deposits, effectively yields geochemical insights that facilitate our understanding of the mineralization process. In this research, multiple generations of magmatic and hydrothermal apatite were observed in the Hongshan porphyry–skarn Cu–Mo deposit in the Yidun Terrane in SW China. The geochemical compositions of the apatite were studied using in situ laser ablation–inductively coupled plasma mass spectrometry and an electron probe microanalysis to understand the magmatic–hydrothermal processes leading to ore formation. The apatite (Ap1a) occurs as subhedral to euhedral inclusions hosted in the phenocrysts of the granite porphyry. The Ap1b occurs later than Ap1a in a fine-grained matrix that intersects the earlier phenocrysts. Increases in F/Cl, F/OH, and F/S and decreases in ΣREE and (La/Yb)N from Ap1a to Ap1b suggest the exsolution of a volatile-rich phase from the magma. The skarn hosts three types of hydrothermal apatite (Ap2a, Ap2b, and Ap3), marking the prograde, retrograde, and quartz–sulfide stages of mineralization, respectively. The elemental behaviors of hydrothermal apatite, including the changes in Cl, Eu, As, and REE, were utilized to reflect evolutions in salinity, pH, oxygen fugacity, and fluid compositions. The composition of Ap2a, which occurs as inclusions within garnet, indicates the presence of an early acidic magmatic fluid with high salinity and oxygen fugacity at the prograde skarn stage. The composition of Ap2b, formed by the coupled dissolution-reprecipitation of Ap2a, indicates the presence of a retrograde fluid that is characterized by lower salinity, higher pH, and a significant decrease in oxygen fugacity compared to the prograde fluid. The Ap3 coexists with quartz and sulfide minerals. Based on studies of Ap3, the fluids in the quartz–sulfide stage exhibit relatively reducing conditions, thereby accelerating the precipitation of copper and iron sulfides. This research highlights the potential of apatite geochemistry for tracing magmatic–hydrothermal evolution processes and identifying mineral exploration targets.

Zircon in tin granite as tracer for fluid metasomatism and Sn mineralization

Most tin deposits in the world are genetically related to tin granite and form during complex magmatic-hydrothermal processes. Zircon is a common accessory mineral in granite and related ore systems and can host a number of ore metals, such as Sn, W, Nb, Ta, U and Th, in its crystal lattice. However, whether metal enrichment/depletion can trace ore-forming processes is still unclear. Here, we report that the metal concentrations in various types of zircons from the Mopanshan tin granites in the southern Great Xing'an Range (Northern China) can be used as good indicators of fluid metasomatism and Sn mineralization. Two lithological zones are developed in the Mopanshan pluton, including porphyritic syenogranite (PG) in the center and fine-grained syenogranite (FG) at the margin. Zircons in the PG (PGZ-1, PGZ-2, and PGZ-3) are all magmatic in origin, while zircons in the FG can be categorized into magmatic zircons (FGZ-1 and FGZ-2) and metasomatic zircons (FGZ-3). The PGZ-1 and FGZ-1 grains are transparent prismatic crystals with bright oscillatory zonation, whereas the PGZ-2 grains are murky crystals with dark oscillatory zonation. PGZ-3 and FGZ-2 grains occur as overgrowths of previously formed zircon (PGZ-1, PGZ-2, and FGZ-1) or as brown individual crystals, showing dark and homogeneous cathodoluminescence (CL) textures. The metasomatic FGZ-3 grains are translucent-opaque porous crystals with vermicular CL zonation and commonly replace FGZ-2. The trace element compositions of magmatic zircons are completely melt controlled, providing a record of magmatic evolution as a constant decrease in Zr/Hf ratios and a gradual increase in Th, U, Nb, and Ta contents. Moreover, the structure of magmatic zircons transforms from a crystalline state to an amorphous state as a consequence of radioactive decay of U and Th. A coupled dissolution-reprecipitation process is proposed for the formation of metasomatic FGZ-3. The reactive fluid is the magmatic fluid that exsolved from the melt in the late magmatic stage. The magmatic fluid replaced biotite and rare earth phosphates (mainly monazite and apatite) enclosed within biotite, resulting in significant amounts of Nb, Ta, Sn, P, Al, Ca, Fe, and REEs, which subsequently reacted with the FGZ-2 zircons to leach Th, U, Y, and HREEs. Eventually, REEs, Y, Th, and U in the fluid combined with P to form monazite and xenotime, while the other elements partially precipitated with the crystallization of the FGZ-3 zircons. Although the alteration of biotite only released approximately 190 ppm of Sn into the fluid, this is still a significant Sn source for the Sn deposits surrounding the Mopanshan pluton, taking the granite size (~50 km2) and the volume proportion of biotite (~5%) into account. Furthermore, based on previous studies on tourmaline from the Mopanshan granite and regional geochemistry, it may be inferred that the addition of wall rock components may also play an important role in Sn mineralization.

Enrichment mechanisms of Nb, Zr, and REY in the Late Permian coal-bearing strata in western Guizhou, SW China

Niobium, Zr, REE, and Y are widely enriched in the Upper Permian coal-bearing strata in southwestern China and are regarded as a substantial resource. To better understand the occurrence modes and enrichment mechanisms of these rare metals, comprehensive heavy-mineral separation, Micro-Raman spectroscopy, EPMA, and LA-ICP-MS analyses of primary and secondary metal minerals were conducted in the polymetallic beds in western Guizhou. In addition, the XRD, XRF, and ICP-MS analyses of bulk rocks were carried out. Our results suggest that Nb is primarily hosted in secondary TiO2 polymorphs which converted from primary Nb-rich rutile, and occurs as minor ilmenorutile and columbite-(Fe). The Zr is sequestered in both detrital zircon and secondary microcrystalline zircon. REE and Y (REY) are mainly incorporated into secondary florencite-(Ce), rhabdophane-(Ce), churchite-(Y), and zircon, also partially adsorbed by clay minerals. The assemblage of detrital zircon, Nb-rich rutile, and discrete Nb minerals reveals that rare metals are preconcentrated during the waning-stage Emeishan alkaline magmatisms. Complex zonings in rutile crystals may result from the diffusion of Nb5+ and Fe2+, and these grains are further overprinted by magmatic-hydrothermal and enveloped by ilmenorutile and columbite-(Fe). Furthermore, magmatic rutile is commonly converted into anatase, brookite, and leucoxene under supergene conditions, and then persisted as stable phases. Authigenic REY-rich (Al)-phosphates and zircon are sourced from the leaching, even decomposition of primary REY-phosphates and zircons. Their colloidal aggregates are precipitated from the acidic and oxidizing low-temperature fluids, which are superposed onto clay matrix. The mineralogical and geochemical features suggest that the polymetallic beds are enriched by both alkaline magmatic-hydrothermal processes in source rocks and supergene fluid alterations in sediments. This study gives new insights into the enrichment processes and conditions, and further extraction of critical metals in the coeval coal-bearing strata in southwestern China.

Pyrochlore composition and Sm[sbnd]Nd isotope signature as indicators of magmatic-hydrothermal processes: The case of Ririwai complex, north-Central Nigeria

This study presents a geochemical and SmNd isotopic study on pyrochlore from the Ririwai alkaline complex in north-central Nigeria, aiming to reconstruct the magmatic-hydrothermal history and provide insights into the formation of niobium deposit hosted in alkaline igneous rocks. Three texturally and compositionally distinct types of pyrochlore (Pcl I, II, and III) are identified. Primary Pcl I grains are enriched in Nb2O5 (mean of 60.5 wt%) and other high field strength elements (HFSE), rare earth elements (mean of 17.2 wt% REE2O3), Ca, Na, and F, suggesting that they crystallized in a Nb-rich peralkaline magma. The occurrence of patchy zoning as well as the development of microfractures and pores within these pyrochlore grains indicate two stages of hydrothermal alteration responsible for the formation of Pcl II and Pcl III. The first stage of alteration from Pcl I to Pcl II was induced by high-temperature, alkali-rich, and F-moderate fluids, leading to the removal of Na, Ca, and F while filling the vacant A- and Y-sites with K, Rb, Y, and Zn. The Nb and REE contents in Pcl III (mean of 41.3 wt% and 9.4 wt%, respectively) are lower than those in Pcl I and Pcl II (mean of 58.1 wt% and 17.3 wt%, respectively). Thereby, the second stage of alteration from Pcl II to Pcl III was related to low-temperature, Si- and Al-rich alkaline fluids, which resulted in the leaching of Nb, Ti, Th, U, and REE (mainly LREE) from the A- and B-sites, compensated by the incorporation of Si, Pb, K, Al, Fe, and Mn. The leached elements either precipitated into Nb-bearing minerals such as rutile, thorite, and zircon in alteration assemblages as an in-situ replacement of Pcl II or remobilized locally to form hydrothermal veins of Si, Al, Nb, and CO2-bearing oxides. The comparable εNd(t) values between hydrothermal Pcl II and III (−1.9 to −2.8 and − 1.5 to −3.2, respectively) and magmatic Pcl I (−2.0 to −2.6) indicate that there was only a minimal external contribution to Nd (and by analogy Nb as well) from fluids. Two-stage hydrothermal fluids in the Ririwai alkaline complex have limited effects on Nb mobilization, without significantly enhancing or reducing the Nb grade.

Indium partitioning between silicate melts and magmatic fluids: implications for indium ore genesis and the tracing of magma degassing

Most of the global indium resources are from deposits associated with felsic rocks. Considering that the indium concentration in the average upper crust is extremely low, magmatic-hydrothermal processes play a critical role in the enrichment and mineralization of indium. However, the extraction efficiency of indium by magmatic fluids remains unclear. We performed experiments at 800 °C, 150 MPa and oxygen fugacity of Ni-NiO buffer to determine the partition coefficient of indium between aqueous fluids and granitic melts (DInf/m). To counteract the rapid loss of indium into the noble metal container wall, the DInf/m were obtained by the method of local equilibrium between microscopic-sized fluid bubbles and surrounding silicate melt. The results show that indium has the highest fluid-melt partition coefficients of all metals investigated so far. At a constant aluminum saturation index (ASI = 1.07–1.12), DInf/m correlates linearly with the total Cl concentration in the coexisting fluid (mCltotal), increasing from 61 ± 11 (1σ) at mCltotal = 1.0 mol/kg H2O to 895 ± 105 (1σ) at mCltotal = 16 mol/kg H2O. When the HCl concentration in the solution increases from 0.13 to 0.49 mol/kg H2O at a fixed mCltotal = 2 mol/kg H2O, DInf/m increases parabolically from 129 ± 21 to 320 ± 24. The observed partitioning data suggest that indium was dominantly present as In(OH)2Cl in the low-HCl and In(OH)Cl2 in high-HCl aqueous fluid at the experimental conditions. Numerical modeling indicates that the extraction efficiency of indium from S-type felsic magmas is very high (>85 %) and magmatic fluids may be the major source of indium for most indium deposits. Due to the high DInf/m values, fluid saturation and exsolution result in a sharp drop of indium concentration in both the residual melt and crystallized minerals, which makes the indium concentration in whole rock and minerals an indicator of fluid exsolution.

Influence of magmatic and magmatic-hydrothermal processes on the lithium endowment of micas in the Cornubian Batholith (SW England)

AbstractThe Cornubian Batholith (SW England) is an archetypal Variscan rare metal granite with potential for Li-mica mineralization. We present a petrographic, trace element and multivariate statistical study of micas from the Cornubian Batholith granite series and related hydrothermally altered units to assess the role of magmatic vs subsolidus processes and of fluxing elements (F and B) on the Li cycle during the evolution of the system. The mica types are as follows: (1) magmatic, which include Fe-biotite, protolithionite I and phengite-muscovite from the most primitive granites, and zinnwaldite I from more fractionated lithologies; (2) subsolidus, which encompass high-temperature autometasomatic Li-micas and low-temperature hydrothermal muscovite-phengite. Autometasomatic species include protolithionite II, zinnwaldite II and lepidolite, which were observed in the most fractionated and hydrothermally altered units, and occur as replacements of magmatic micas. Low-temperature hydrothermal Li-poor micas formed via alteration of magmatic and autometasomatic micas or as replacement of feldspars, and albeit occur in all studied lithologies they are best represented by the granite facies enriched in metasomatic tourmaline. The evolution of micas follows two major trends underlining a coupling and decoupling between the Li(F) and B fluxes. These include as follows: (1) a Li(F)-progressive trend explaining the formation of protolithionite I and zinnwaldite I, which fractionate Li along with Cs, Nb and Sn during the late-magmatic stages of crystallization, and of zinnwaldite II and lepidolite forming from the re-equilibration of primary micas with high-temperature Li-B-W-Tl-Cs-Mn-W-rich autometasomatic fluids; (2) a Li(F)-retrogressive trend explaining the low-temperature hydrothermal muscovitization, which represents the main Li depletion process. Trace element geochemistry and paragenesis of late muscovite-phengite support that muscovitization is a district-scale process that affected the upper parts of the granite cupolas through acidic and B(Fe-Sn)-saturated hydrothermal fluids associated with metasomatic tourmalinization, which were mixed with a low Eh meteoric component.

Lithium isotope fractionation in highly evolved granites and associated magmatic-hydrothermal process: the case of the Xintianling granites in the Nanling Range, South China

ABSTRACT The highly evolved granites are closely associated with rare-metal mineralization. It is still debated whether the enrichment of rare metals is mainly controlled by magmatic or hydrothermal processes. Lithium is a fluid-mobile element that preferentially partitions to the fluid phase when the melt reaches H2O saturation, making the Li isotope system a powerful geochemical tool to record the potential melt-fluid interaction during magma evolution. This study addresses the issue of Li isotope fractionation in highly evolved fine syenogranites (FSGs) from the Xintianling pluton in the Nanling Range, South China. The Xintianling pluton consists of the coarse biotite monzogranites (CBMGs) and evolved FSGs. The identical Nd isotope data of the CBMGs (εNd(t) = -8.2–-8.8) and FSGs (εNd(t) = -7.9–-8.9) suggest that they were derived from the same crustal magma. The FSGs were derived from the highly evolved melts extracted from CBMGs through the fractionation of major rock-forming minerals. This is supported by the compositional shifts and validated by Rb, Sr, and Ba trace element modelling. Li isotopic analysis shows that highly evolved FSGs have heavier Li isotope compositions (δ7Li = 2.6–7.9 ‰) than the CBMGs (δ7Li = 0.1–1.9 ‰). Isotopic modelling, coupled with variations in Li concentrations in FSGs, suggests that diffusive kinetic fractionation by disequilibrium fluid exsolution during the late stage of the granitic magma evolution controls the Li isotope fractionation of the Xintianling granites. Rapid fluid exsolution not only modified the Li isotope composition of the FSGs but also transported the rare metals (e.g. W) and fluxing components (Li, F, and Cl), which resulted in the formation of the large Xintianling W deposits.

Iron isotope systematics of the Jiajika granite-pegmatite lithium deposit, Sichuan, China

The Jiajika deposit in western Sichuan is the largest pegmatite-type lithium deposit in China, but the mechanism of rare metal element enrichment in this giant deposit remains a topic of debate. This study presents a comprehensive Fe isotope study of granites, aplites, pegmatites, metamorphic rocks, and associated mineral separates from the 3211 m long deep Jiajika scientific drilling core (JSD-1) to constrain the magmatic-hydrothermal processes in the Jiajika deposit. Aplites and pegmatites have variable δ56Fe values that range from –0.12 ± 0.02 ‰ to 0.38 ± 0.02 ‰, by contrast, two-mica granite samples show limited variation in δ56Fe compositions (0.11 ± 0.04 ‰ to 0.21 ± 0.04 ‰). The Fe isotope data of the coexisting Fe-bearing minerals can impose critical constraints on crystal fractionation. Garnet shows the lightest δ56Fe compositions (–0.19 ± 0.06 ‰ to –0.06 ± 0.02 ‰) and tourmaline has the highest δ56Fe values (0.15 ± 0.01 ‰ to 0.22 ± 0.02 ‰) among all the investigated minerals, whereas the δ56Fe values of biotite range from 0.06 ± 0.02 ‰ to 0.18 ± 0.02 ‰. According to the compositional homogeneity of minerals and the relatively consistent offsets in δ56Fe between the three Fe-bearing mineral pairs, the co-existing Fe-bearing minerals in the Jiajika granitic pegmatites are interpreted to be in Fe isotope equilibrium. Additionally, based on the differences in mineral composition and geochemistry of bulk-rock samples at different observation depths, as well as the modeling results, the significant Fe isotope variation in Jiajika deposit reflect the combined results of biotite fractionation, hydrothermal alteration (tourmalinization), and garnet accumulation during multistage magmatic-hydrothermal processes. Spodumene-bearing pegmatites located in the upper portion of the drill core exhibit enrichment in heavy Fe isotopes (0.18 ± 0.04 ‰ and 0.30 ± 0.03 ‰) which can be attributed to their higher degree of magma evolution and the most abundant magmatic fluids related to enrichment and migration of rare metals. Furthermore, we conducted a comprehensive statistical analysis on the available Fe isotope data of granitic pegmatites, providing new insights into granite-pegmatite systems and related rare-metal mineralization processes from a Fe isotope perspective.

U–Pb Dating, Gemology, and Chemical Composition of Apatite from Dara-e-Pech, Afghanistan

Minerals of the apatite group commonly occur in granite pegmatites, and their ability to incorporate a wide range of trace elements makes them a good indicator of magma composition and magmatic–hydrothermal processes. Gem-quality purple apatite crystals from the Dara-e-Pech pegmatite field in Afghanistan have rarely been reported. Here, we investigated apatite crystals originated from this locality, using gemological testing, chemical analysis, and in situ U–Pb dating, with the purpose of identifying their origin, the constraints on the magma source in which the apatite crystals were formed, and the timing of the magmatic–hydrothermal activity. Our findings demonstrate that the purple apatite crystals were impure fluorapatite, characterized by heavy rare-earth element (HREE) enrichment, intermediate Eu anomalies, and non-CHARAC Y/Ho ratios. The results showed that these apatite crystals yielded a lower intercept age of 135.8 ± 6.9 Ma. We proposed that the pegmatitic apatite samples formed in a transitional magmatic–hydrothermal pegmatitic system with moderate fO2 in the Early Cretaceous (~135 Ma). Our study helps to constrain the magmatic–hydrothermal activities of the little-known Dara-e-Pech pegmatite field.

Mineralogical constraints on pegmatite genesis and rare metal mineralization in the Mufushan batholith, South China

Pegmatites are commonly associated with or strongly influenced by the crystallization of magmatic volatile phases (MVP) as ascending magmas undergo differentiation. The mechanism of fractional crystallization, liquid immiscibility, and water–rock interactions that influence the rare metals concentration in pegmatites are still unclear. We analyzed the mineralogy (incl. monazite, garnet, zircon, and muscovite) from pegmatites to unravel the timing and magmatic-hydrothermal processes for the giant Renli-Chuanziyuan pegmatite Li-Nb-Ta mineralization in the Mufushan region (South China). Five types of pegmatites have been identified at Mufushan, i.e., those containing mainly orthoclase (O-pegmatite), microcline (M-pegmatite), albite-orthoclase (AO-pegmatite), microcline-albite (MA-pegmatite), and spodumene-albite (S-pegmatite).Monazites from the Renli high-Th Li-mica pegmatite exhibit magmatic affinity. The ∼140 Ma age of monazite U-Pb suggests a temporal relationship between the Li-rich pegmatite and its muscovite granite host. Garnet from these pegmatites is magmatic and belongs to the almandine-spessartite series, and contains feldspar and apatite inclusions. Continuous fractional crystallization likely controlled the pegmatite development, as the garnet spessartite content increases with distance from the Mufushan batholith. Garnet in the spodumene-albite pegmatites has very low REE content, and it represents a late stage of crystallization related to magmatic-hydrothermal fluids. Compositional variation in muscovite from all of the pegmatites is negligible. The K/Rb ratio (a proxy for the degree of fractionation) increases gradually from the O- to S-pegmatite, whilst the muscovite F content correlates positively with the degree of magma fractionation. The transformation of muscovite to lepidolite in pegmatites can occur through magmatic-hydrothermal crystallization or metasomatism. Zircon in pegmatites generally occurs as metasomatic remnants, with uneven zoning shown in cathodoluminescence (CL) images. Hydrothermal zircon U-Pb ages are concentrated in the 140–134 Ma range, consistent with the garnet leucogranite ages. This suggests that pegamtites and the garnet leucogranite were formed in the same magmatic-hydrothermal activity. The accumulated MVP and incompatible elements may have migrated from deeper, more crystal-rich zones under medium degree of fractionation. The MVP may contain abundant dissolved melt components as single-phase hydrous silicate liquids, forming typical quartz-/feldspar-dominated pegmatite and the diversity of rare-metal deposits.

Corrigendum to “Compositional variation and Sn isotope fractionation of cassiterite during magmatic-hydrothermal processes” [Earth Planet. Sci. Lett. 613 (2023) 118,186]

Corrigendum to “Compositional variation and Sn isotope fractionation of cassiterite during magmatic-hydrothermal processes” [Earth Planet. Sci. Lett. 613 (2023) 118,186]

Tracing tungsten-tin mineralization processes with tourmaline geochemistry in the Wangxianling-Hehuaping district, Nanling Range (South China)

The mechanisms controlling the enrichment and separate precipitation of tungsten and tin ores are obscure. To unravel the physicochemical changes in the mineralization system during the magmatic-hydrothermal transition, we investigate the petrography, geochemistry, and boron isotopes of tourmaline in the Wangxianling-Hehuaping district (Nanling Range, South China). Four types of tourmalines were identified: Magmatic (Tur-WG) and hydrothermal (Tur-WV) tourmaline in the Triassic W-mineralized tourmaline-two-mica granite (ca. 220 Ma); Magmatic (Tur-SnG) and hydrothermal (Tur-SnV) tourmaline in the Jurassic Sn-mineralized biotite granite (ca. 155 Ma). Tur-WV and Tur-SnV have lower Fe3+/(Fe2+ + Fe3+) ratios than those of Tur-WG and Tur-SnG, suggesting that W-Sn mineralization occurred in a relatively reducing environment. In addition, the δ11B values of all four types of tourmalines are similar, suggesting that the ore-forming fluids were primarily exsolved from the granitic magma. Significant chemical variations (e.g., Mg, Fe, Sc, V, Ni, and REEs) between Tur-SnG and Tur-SnV may have been resulted from fractionation and intense ore fluid-wall rock reactions. In contrast, Tur-WG has similar chemical compositions to Tur-WV, suggesting that the Triassic W mineralization may have undergone a magmatic-hydrothermal process with little ore fluid-wall reaction. Tur-SnV has exceptionally high F content, which could enhance the Sn solubility and enrichment. This explains the low Sn content of granitic magmas with large-scale Jurassic tin mineralization. Considering that W has a large melt-fluid partition coefficient, we conclude that in the Triassic, W is enriched in the exsolved fluid from the granitic magma and precipitated with temperature drop. This may have caused the decrease in W content in the protolith and limited the Jurassic W mineralization. Subsequently, the mantle-derived F addition along the Chenzhou-Linwu fault in the Jurassic had led to Sn enrichment in the fluids, and mineralization is triggered by temperature drop and fluid-rock reactions. Eventually, the extensive Triassic W mineralization and Jurassic Sn mineralization exhibit the separation of tungsten-tin mineralization. The separated tungsten-tin mineralization model based on different volatile components could also be applicable to other tungsten-tin metallogenic belts.

Petrogenesis and rare-metal mineralization of the Ririwai alkaline granitoids, north-central Nigeria: mineralogical and geochemical constraints

ABSTRACT The Ririwai anorogenic alkaline complex harbours extensive rare metal (Nb-Zr-Sn-Zn) mineralization. However, uncertainty still surrounds their origin and magmatic-hydrothermal processes responsible for their rare metal mineralization. The complex is composed of peralkaline arfvedsonite ± albite-bearing granites, mildly peralkaline fayalite-bearing granite porphyries, and weakly peraluminous biotite-bearing granites, all of which show diagnostic A1-type characteristics. Zircon U-Pb dating reveals emplacement ages between 181.4 ± 0.81 and 188.6 ± 7 Ma for the three rock units. Sm-Nd and Pb isotopes (εNd (t) = –0.6 to −5.4, 206Pb/204Pb = 17.68–17.93) constrained the Ririwai A-type granites to represent highly fractionated products of enriched mantle-derived magmas. Mass-balance modelling suggests that magma evolution was fuelled by extensive fractional crystallization of 50 ~ 60 vol.% K-feldspar, 30 ~ 35 vol% fayalite, 5 ~ 10 vol.% amphibole, and ~ 5 vol.% apatite under reduced and water-undersaturated (ΔFMQ = –1.55; logfo2 = –18.63; H2O =  <2.0 wt.%) conditions and assimilation of ~ 50 vol.% crust. Whole rock and amphibole compositions revealed an increasing degree of fractionation from the fayalite-bearing granite porphyries through biotite-bearing granites to the arfvedsonite ± albite-bearing granites. This extended fractionation at the late stage of magma differentiation, facilitated by fluorine dissolution and concentration of excess HFSE and REE as alkali-fluorocomplexes in the fluorine-rich silicate melt, allowed the accumulation of economic rare metal pyrochlore and columbite mineralizations in the highly fractionated arfvedsonite± albite- and biotite-bearing granites, respectively. Nonetheless, the metasomatic reaction rim textures around the magmatic pyrochlore, coupled with the M-type lanthanide tetrad effect (TE1,3 >1.10) indicate the subsequent effect of hydrothermal processes. Tectonically, reactivated shear fractures and transcurrent faults following lithospheric stresses in a transtensional regime allowed magma uprising and emplacement of A-type granites in the Ririwai complex.

Nature of magma and ore-forming conditions at the Randu Kuning porphyry Cu-Au deposit, Indonesia: a comparative study with other Cu-Au deposits in the region

ABSTRACT The subduction-related Sunda-Banda arc hosts several giant and major Cu–Au–Mo porphyry and epithermal Au systems, making it one of the most important magmatic-related metallogenic belts in Indonesia. They are accompanied by a number of smaller systems, one of which is the recently discovered Randu-Kuning porphyry Cu-Au deposit on Java Island. The present study investigates the geochemical characteristics of this deposit through whole-rock and mineral geochemistry and mineral geothermobarometry, focusing on three sequential dioritic intrusions that make up the host igneous complex, two barren and the third mineralized. Moreover, a comparative analysis is performed between other porphyry deposits in the Sunda-Banda arc and with Grasberg in Papua. This study shows that the older porphyry deposits have mostly similar geochemical characteristics to the younger deposits, suggesting the same magma source, which is mantle-derived oxidized I-type magma. Amphibole geothermobarometry shows that the formation of syn-ore intrusion in the older porphyry was higher in temperature and pressure than those at the younger porphyry. The halogen and oxygen fugacities inferred from biotite and amphibole chemistry indicate an oxidized, water- and halogen-rich melt. Our study shows that combining amphibole and biotite chemistry and whole-rock geochemical data is useful to fingerprint the magmatic-hydrothermal processes, especially where multiple magmatic phases occur. This research also provides valuable insights into the magmatic-hydrothermal physiochemical conditions during the formation of the mineralized system.

Magma and fluid sources in an intracontinental porphyry system: A case study of the Relin Mo–W(–Cu) deposit, southern Yidun terrane, SW China

The Relin Mo–W (–Cu) deposit in the northern Sanjiang area is bound to a Late Cretaceous intracontinental porphyry showing variable alteration. Here we present whole-rock chemistry and Sr, Nd, Pb, Li, and B isotope data to constrain the sources of ore-magmas and to understand how magmatic-hydrothermal processes mobilize the ore elements and alter the magmatic rocks. Chemical variations indicate the ore-bearing porphyries reflect two processes: fractional crystallization and late-magmatic alteration. Fresh and weakly altered porphyries are metaluminous to weakly peraluminous, showing I-type affinity. Chemical variation among these rocks can be explained by fractional crystallization. Most of these rocks show narrow ranges of isotopic compositions with –8.6 to –6.6 for εNd80, 0.70660 to 0.71028 for 87Sr/86Sr80, and high 207Pb/204Pb80 (15.57–15.66) and 208Pb/204Pb80 (39.21–39.51) values at 206Pb/204Pb80 values of 17.37 to 18.96. The chemical and isotopic compositions of these rocks indicate that the porphyries represent mantle melts that mixed with partial melts from the Paleoproterozoic crust. Fresh and weakly altered porphyries have uniform δ7Li (–2.3 to 1.5 ‰) and δ11B (–8.0 to –12.0 ‰). The strong sericite alteration of the porphyries resulted in the loss of Na2O and Sr (breakdown of feldspar) and the strong enrichment of the ore elements Cu, Mo, W, and Sn. Porphyries with varying degrees of alteration show large ranges of δ7Li (–6.0 ‰ to 11.4 ‰) and δ11B (–8.0 to –29.2 ‰). The anomalously high δ7Li and low δ11B values of the altered rocks indicate that the intrusions drove the flow of external fluids that altered the magmatic rocks and leached the ore elements W, Mo, Cu, and Sn from the porphyries and possibly the local wall rocks.

Zircon as a Monitoring Tool for the Magmatic–Hydrothermal Process in the Granitic Bedrock of Shitouping Ion-Adsorption Heavy Rare Earth Element Deposit, South China

The Shitouping pluton in Jiangxi Province, southern China, hosts an ion-adsorption heavy rare earth element (HREE) deposit identified by a recent geological survey. This study reveals the HREE pre-enrichment mechanism during the magmatic–hydrothermal process of granitic bedrock based on the comprehensive study of zircon structure and composition. Zircon from the Shitouping pluton, composed of syenogranite and monzogranite, can be categorized into three types based on structure and compositions. The Type-1 zircons, the predominate type in monzogranite, are early magmatic zircons with prismatic crystals and bright oscillatory zoning in CL images. In contrast, the late magmatic-hydrothermal zircons (Type-2 and Type-3) mainly occur in the syenogranite. The Type-2 zircons occur as dark CL images and euhedral crystals crystallized during the late magmatic stage. The Type-3 zircons with irregular zoning and abundant mineral inclusions in BSE images are possibly formed via intense hydrothermal alteration during the hydrothermal stage. The increase in Y/Ho ratios from Type-1 to Type-3 zircon indicates that the Shitouping syenogranites underwent magmatic to hydrothermal evolution. Compared with Type-1 and Type-2 zircons, Type-3 zircons exhibit the highest concentrations of F and HREEs. The significant increase in HREE concentrations both in zircons and bulk-rock composition of syenogranite can be attributed to the introduction of HREE-rich fluids during magma evolution. Therefore, we propose that the increase in HREE contents in zircon reflect the exsolution of HREE-rich fluids during a late stage in the magma evolution, which is an important factor controlling HREE enrichment in Shitouping syenogranites and furthermore in the generation of ion-adsorption HREE deposits.