Fluid Exsolution Research Articles

Sulfide resorption contributes to porphyry deposit formation in collisional settings

Production of Cu-rich melts via melting of sulfide-bearing lower crustal cumulates is thought to contribute to porphyry Cu formation in the post-collisional Gangdese belt (Tibet). We present new whole rock, including platinum group elements (PGE) data, for ore-causative granites (OCG), ore-related granites (ORG) and barren granites (BG) from the Gangdese belt. The OCG, ORG and BG show indistinguishable Cu, PGE and Cu/Ag behavior during differentiation down to ∼2 wt% MgO. These systematics, together with the occurrence of sulfides, demonstrate that the propensity for some Gangdese magmas to be ore-associated is unrelated to melting of sulfide-bearing cumulates or the relative timing of sulfide fractionation. The behavior of chalcophile and siderophile elements during differentiation of the OCG, ORG and BG diverges when melts evolve past 2–3 wt% MgO and exsolve H2O, S and Cl: the BG show a decrease in Cu, whereas the OCG and ORG show highly variable Cu, Au, and PGE trends. Because S degassing causes melts to become sulfur undersaturated and because Cu is highly soluble in Cl-rich fluids, any sulfides in contact with the melt or magmatic fluids following volatile exsolution would dissolve. Continual injection, cooling and ascent of magmas through the Gangdese crust is expected to have resulted in the development of regions of crystal-rich partially molten crust beneath the intrusive granites. We suggest that prior to porphyry mineralization, extension and erosion caused exhumation of these long-lived sulfide-bearing mush zones. This exhumation may have caused a change in magmatism style from volatile exsolution after the melts transited sulfide-bearing mushes (i.e., the BG), to volatile exsolution during magma transit through sulfide-bearing mushes (i.e., the OCG). We suggest that only the magmas and that exsolved fluids during their ascent through sulfide-bearing mushes were able to assimilate sufficient Cu-rich sulfides to fuel the formation of porphyry Cu deposits in the region.

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.

Contribution discrepancy of two distinct wall rocks to wolframite mineralization from Dongshanwan quartz-vein tungsten deposit, Southern Great Xing’an Range, China

The Southern Great Xing’an Range is a significant polymetallic metallogenic belt in Northeast China. The ages of granite related to tungsten mineralization have been well quantified, however, the timing and mechanism of quartz vein-type wolframite deposition remain unclear. Therefore, our study focused on the Dongshanwan tungsten deposit, representing a typical wolframite-bearing quartz vein-type deposit in the Southern Great Xing’an Range. Quartz vein-type tungsten mineralization was mainly contained in the Early Cretaceous granite porphyry, with few exceptions in the Permian tuff. Representative wolframite samples were collected from intragranitic (Wol-I) and intra-tuff (Wol-II) quartz veins for wolframite U–Pb dating, electron probe microanalysis (EPMA), and trace elemental analysis. Wolframite U–Pb dating recognized an Early Cretaceous mineralization event at 139–141 Ma, consistent with the previous Dongshanwan granite’s ages (∼142 Ma) but much younger than tuff (∼260 Ma). All the wolframite samples belonged to the ferberite series (FeO/MnO = 4.0–6.9), which indicates a link to the highly fractionated granite. Wol-I showed high contents of Nb, Ta, Sc, and HREEs and a strongly negative Eu anomaly (0.02–0.29), while these elements in Wol-II were approximately one order of magnitude lower than in Wol-I and the Eu anomaly was highly variable (0.17–1.02). The redox characteristics reflected by the Eu anomaly of wolframite may correspond to the variations in oxygen fugacity. Based on petrology, geochemistry, and element mass migration, this study suggests that the granite porphyry and tuff in the Dongshanwan deposit contributed differently to the wolframite precipitation even if the ore-forming fluids were of a common magmatic-hydrothermal origin. The exsolved fluid reserved in the closed system interacts with granite to achieve continuous enrichment in Nb, Ta, Sn, and REEs and accepts external Fe supply from granite alteration to precipitate Wol-I. In contrast, the fluids in relatively open and non-granitic systems have lower Nb, Ta, Sn, and REEs than the former, and Fe supply depends on the alteration of tuff. The abundance of fluorite and the non-CHARAC (CHArge-and-RAdius-Controlled) behavior of Y/Ho and Zr/Hf in the wolframite suggested that fluorine plays an important role in the migration and enrichment of tungsten and other elements during tungsten mineralization.

Extreme Sn isotope fractionation in highly evolved granites

Stable Sn isotopes have been widely used to trace the planetary differentiation processes, the provenance and trade paths of ancient bronze artifacts, the mineralization history of tin ore deposits, and the terrestrial magmatic processes. However, systematic Sn isotope studies of felsic igneous rocks especially the Sn mineralization-related highly evolved granites are still lacking. In this study, we present the first high-precision Sn isotope data of two Sn-rich highly evolved S-type granites (Laochang and Kafang) from the world-class Gejiu Sn ore district. These granite samples show remarkably variable δ122/118Sn values (relative to the Sn standard solution NIST 3161a) ranging from 0.11 ± 0.02‰ to 0.93 ± 0.02‰ (2σ), which is the largest variation range reported in granites so far. The absence of correlations between Sn isotopes and LOI (loss-on-ignition) and εNd(t) values, along with the low magmatic oxygen fugacity (△FMQ < 0) for these granites, rule out hydrothermal alteration, wall-rock assimilation, source composition heterogeneity, and anatexis processes as causes of the Sn isotope fractionation. The Laochang granites show negative correlations between δ122/118Sn values and magmatic differentiation indicators (e.g., CaO, Fe2O3, Ti, Eu/Eu*, F/Cl), suggesting fractional crystallization increased the δ122/118Sn isotopes in the residual melts. The fractional crystallized minerals are mainly composed of biotite, plagioclase, and minor ilmenite. Compared with the Laochang granites, the Kafang granites show higher SiO2 contents, F/Cl ratios, and δ122/118Sn values, suggesting the magma at this stage was fluid-saturated and fluid exsolution coupled with fractional crystallization would further enrich the heavy Sn isotopes in the residual melts. We further quantified the contributions of crystal fractionation and fluid exsolution on Sn isotopic variability using a Rayleigh fractionation model. The modeling indicates that △122/118Sncrystal-melt = −0.6 to −0.5‰ and △122/118Snfluid-melt = −1.9 to −0.7‰ with an initial H2O content of 2 wt.% can explain the observed δ122/118Sn values of Gejiu granites. This study implies that both crystal fractionation and fluid exsolution processes cause increase of Sn isotopic values in the highly evolved granites and Sn isotopes are useful for tracing the evolution of highly differentiated igneous 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.

Magmatic–hydrothermal evolution of the Koktokay No. 3 pegmatite, Altai, northwestern China: Constraints from in situ boron isotope and chemical compositions of tourmaline

Lithium–Cs–Ta-enriched (LCT-type) pegmatites are characterized by zoning texture and extreme enrichment of rare-metals. The role of fluids in zonation development and rare-metal mineralization remains a topic of debate. The Koktokay No. 3 pegmatite in northwestern China represents a typical LCT-type pegmatite characterized by economically significant Li–Be–Nb–Ta–Cs mineralization. This pegmatite exhibits a complete evolutionary sequence from outer to inner zones, with diverse rare-metal mineralization. Tourmaline is ubiquitously present in all textural zones of LCT-type pegmatites. In the Koktokay No. 3 pegmatite, the tourmalines exhibit a range of compositions from dravite and schorl to elbaite and rossmanite. The tourmalines in this pegmatite are characterized by significantly enriched light B isotope compositions (δ11B = −14.8‰ to −8.1‰), similar to those typically observed in most pegmatites derived from continental crust sources. The tourmalines in the outer zones have less variable δ11B values (−13.8‰ to −11.5‰) and are interpreted to have crystallized in a viscous magma. The tourmalines in the inner zones exhibit larger variations in δ11B values (−14.8‰ to −8.1‰) than those from the outer zones. The decreasing δ11B values of tourmalines from the outer to inner zones are attributed to the separation of an immiscible fluid phase that preferentially incorporated heavy B isotopes. The occurrence of hydrothermal tourmaline as veinlets indicates the exsolution of fluids in inner zones, with high δ11B values ranging from −10.2‰ to −9.3‰. Therefore, the hydrothermal fluid can be saturated when the magma has been strongly evolved. In addition to fractional crystallization, exsolved fluids play a significant role in the formation of internal zones and rare-metal mineralization in LCT-type pegmatites. The rare-metals are gradually enriched through fractional crystallization of magma, and the fluid contains mobile elements such as Cs that facilitate precipitation of rare-metal minerals.

Significant mobilization of REE from calc-alkaline melt into fluid during fluid exsolution: Insights from magmatic amphibole composition from Tieshan skarn Fe-Cu deposit (Hubei Province, China)

Hydrothermal fluids associated with carbonatites and peralkaline silicate rocks typically exhibit high REE content, but this is generally not the case for calc-alkaline rocks. However, the Tieshan skarn Fe-Cu deposit in the Edong district of Hubei Province in China demonstrates economic REE mineralization potential linked to calc-alkaline rocks. To investigate the presence of REE enrichment in the fluid, we present textural and compositional data of rock-forming mineral amphibole from the quartz diorite in the Tieshan deposit. Three distinct types of amphibole are identified in the Tieshan quartz diorite, namely Early amphibole, Main-stage amphibole, and Late amphibole, following the crystallization sequence. Early amphibole (813–864 °C, 115–152 MPa) crystallized when the magma was emplaced at a depth of approximately 4.8 km. Main-stage amphibole (741–806 °C, 58–103 MPa) crystallized at a depth of roughly 3 km. Between the early and main-stage amphibole crystallization, the magma experienced fractional crystallization of pyroxene, amphibole, and plagioclase, resulting in a REE enrichment in the residual melt. Late amphibole crystallized subsequent to the transition from lithostatic to hydrostatic stress states (656–729 °C, 27–52 MPa). Significantly, the transport of REE from the magma system initiated towards the end of Main-stage amphibole crystallization. A comparison with the Tonglvshan granitic rocks in the same district indicates an elevated F content and extended fractional crystallization history in the Tieshan magma, contributing to REE enrichment in its melt. Furthermore, the high F content lowered the solidus temperature of the Tieshan magma, thereby facilitating the more efficient removal of REE into the fluid. The assimilation of evaporate into the magma possibly led to heightened sulfur and chlorine levels in the fluid, enabling the transport of a significant amount of REE.

Boron isotopes in tourmaline from drill core of the Jiajika granitic pegmatite type lithium deposit: Insights for granitic magma evolution and lithium enrichment

The Jiajika pegmatite-type Li deposit located in the southeastern Songpan-Ganze terrane of the eastern Tibetan Plateau is one of the largest hard-rock Li deposit in China, and its ore-genetic mechanism is still controversial. To understand the Li concentration of potentially economic levels in the Jiajika pegmatite-type Li deposit, the association between Li enrichment and granitic magma evolution is investigated using B isotope in tourmaline grains along the entire 3211-m-depth of the JSD-1 drill core in this work. Tourmalines hosted in granite, pegmatite, barrovian-type metamorphic rock and calc-magnesium-silicate metamorphic rock are being plotted in the fields of Li-poor granitoids and associated pegmatites and aplites on the Al-Fe-Mg and Ca-Fe-Mg ternary diagrams. These characteristics, along with their high Fe/Mg ratios and high Al cation numbers in Y position, are indicative of a magmatic origin. The B isotope (δ11B) of tourmalines in granite and pegmatite in Jiajika granitic pegmatite type Li deposits vary from −9.49 to −7.06‰, in line with the range observed in 90 % of worldwide granites and pegmatites. In comparison of the measured data of δ11B vs. Li to the modeled curves indicates that the differentiation process of granitic magma follows an equilibrium crystallization model better than a fractional crystallization model. The compiled evidence proves that magma differentiation accompanied by fluid exsolution facilitates the enrichment of Li during granitic magmatic evolution. The formation of the domal structure of granitic sheets due to the decompressing effect of magma ascent favors massive fluid exsolution at the late-stage granitic magma, which contributes to the deposition of spodumene dominated ore body at the shallower depth of 5–150 m.

The Mechanism of Fluid Exsolution and Sn–W Precipitation: Example from the Hongling Pb–Zn Polymetallic Deposit and the Surrounding Area in Northern China

Metal migration and precipitation in hydrothermal fluids are important topics in economic geology. The Hongling polymetallic deposit comprises one of the most important parts of the Huanggangliang–Ganzhuermiao polymetallic metallogenic belt, which is in eastern Inner Mongolia. Except for lead–zinc skarn, minor cassiterite in the skarn and disseminated W–Sn mineralization in granitic rocks have also been found. The dominant Sn–W mineralization is in the northern part of the deposit, occurring as disseminated wolframite and cassiterite in aplite hosted in Mesozoic granite porphyry. The aplite together with pegmatite K-feldspar–quartz comprises vein dikes hosted in the granite porphyry, providing evidence for the transition from melt to fluid. The veins, dikes, and Sn–W mineralization in the aplite provide an opportunity to investigate fluid exsolution and the mechanics of metal precipitation. Based on field observations, the micrographic and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) results of the vein dikes, chronology, and the whole-rock geochemistry of the host rock, together with the fluid inclusion results, this paper discusses the characteristics of the causative magma, the mechanics of fluid exsolution and W–Sn precipitation. Our results show that the causative magma is of highly fractionated A-type granite affinity and has an intrusive age of late Mesozoic (133.3 ± 0.86 Ma). The magmatic evolution during shallow emplacement led to immiscibility between highly volatile, high-silica, and W- and Sn-enriched melts from the parent magma, followed by fluid exsolution from the water-rich melt. The alkaline-rich fluid exsolution led to a change in the redox state of the magma and the chilling of the melt. Fluid boiling occurred soon after the fluid exsolution and was accompanied by the degassing of CO2. The boiling and escape of CO2 from the fluid led to changes in fluid redox and W and Sn precipitation; thus, the W and Sn mineralization are mostly hosted in causative intrusions or peripheral wall rocks, which can be used as indicators for Sn–W exploration in the area.

Oxidation of magmas during gain and loss of H2O recorded by trace elements in zircon

Hydroxylation-oxidation reactions of the type H2O + Fe→2+Fe3+ + OH− + 1/2 H2 oxidise Fe2+ in olivine and pyroxenes in oceanic lithosphere prior to subduction and in the supra-subduction-zone mantle wedge and oxidise Fe2+ in silicate melts as dissolved H2O accumulates during magmatic differentiation. Collectively, the coupled hydroxylation-oxidation of melts and of minerals in melt sources tends to produce positive correlations of hydration state and oxidation state of silicate melts, about which there has been much dispute and discussion in literature. We introduce a melt “hygro-barometer” which provides evidence from trace elements in zircon that melt oxidation state rose as dissolved H2O accumulated in fluid-undersaturated residual melts during mafic-to-felsic differentiation at Moho-vicinity depths. Zircon-based measures are consistent with experimental evidence of melt oxidation during gain of dissolved H2O. Examples from many arc igneous complexes demonstrate further oxidation of residual melts as hydrothermal fluid exsolved and segregated during trans-crustal ascent of the magmas. Zircons in those suites show that much of the contrast between redox states of dry mid-ocean-ridge and hydrous arc magmas (especially porphyry copper magmas) develops as H2O is lost during trans-crustal ascent of arc magmas because decompression-induced exsolution and open-system fractional segregation of hydrothermal fluid selectively extracts reduced members of the principal redox couples (H2–H2O, S4+–S6+, Fe2+–Fe3+), thereby raising the oxidation state of residual melt.

Magmatic-hydrothermal evolution of the aquamarine-bearing Yamrang Pegmatite, Eastern Nepal: Insights from beryl, garnet, and tourmaline mineral chemistry

The Ikhabu Pegmatite Field (IPF) in the Nepal Himalaya is a newly discovered rare-element (REL) pegmatite field that hosts the Yamrang pegmatite, the primary source of the famous Nepalese aquamarines. In this contribution, we provide a comprehensive description of the geology of both the IPF and the Yamrang pegmatite, offering insights into the evolutionary stages of the Yamrang pegmatite based on its internal texture and the mineral chemistry of beryl, garnet, and tourmaline. The Yamrang pegmatite is classified as a beryl-columbite subtype of REL pegmatite, exhibiting axial symmetric zonation and is differentiated into five mineralogical-textural zones during magmatic and hydrothermal stages. The magmatic stage involves undercooling, disequilibrium crystallization, and fractional crystallization whereas the hydrothermal stage comprises alkali-enriched fluid exsolution, the formation of miarolitic cavities, and the crystallization of aquamarine. Yamrang aquamarines are enriched in FeO, up to 1.1 wt%, with Fe2+ as the primary chromophore, resulting in their blue color. Two types of beryl have been identified: magmatic beryl in zones 3 and 4 and hydrothermal beryl in miarolitic cavities (zone 5). Magmatic beryls are characterized by their alkali-poor to sodic composition, prismatic to columnar habit, homogeneous texture, and the presence of Fe-Al octahedral substitution. In contrast, hydrothermal beryls belong to the sodic to Li-Cs beryl group, with tabular to acicular habit, weak compositional zoning, and channel-tetrahedral substitution. Yamrang garnet belongs to the almandine-spessartine series, while the tourmalines are Mg-Ca rich dravite-schorl to Fe-Mn rich schorl variety. Alkali-poor to Li-Cs beryl with low REE contents, spessartine garnet (spessartine component, Xsps ∼ 52) with high HREE, and schorl with high Ti but low Li, Pb, and REE contents suggests that the Yamrang Pegmatite is an intermediate-fractionated REL pegmatite. Potential pegmatite evolution indicators for IPF include high alkali, Fe, Mn, and Rb contents in beryl, high Xsps in garnet, and an increase in Li, Fe, Mn, Zn, Ga, and Nb, alongside depletion of Mg, Ca, Ti, and Ta in schorl. The identification of a rare metal pegmatite field in the Nepalese Himalaya reinforces the general rare metal mineralization potential of the entire Himalaya region.

Barium isotope fractionation during granitic magmatism and potential of δ138/134Ba for distinguishing magmatic-hydrothermal transition in granitic magma systems

The geochemistry of Ba is commonly used to study igneous processes and fluid-melt interaction in subduction zone and granitic environments. Recent advances in analytical techniques have also indicated that Ba isotope geochemistry has the potential to significantly augment these studies. Understanding the Ba isotope fractionation mechanisms is thus critical if this potential is to be fully realized. Hence, we have used the first-principles calculations based on the density functional theory (DFT) and long-time ab initio molecular dynamics (AIMD) simulation to calculate Ba isotope fractionation during felsic magma evolution. In fluids, the reduced partition function ratio (β factor) of aqueous Ba2+ is highly variable, depending on the coordination number (n) of H2O in the first hydration shell. At ambient surface conditions on the Earth, n = 8 best represents the aqueous Ba2+ species in natural fluid, and the temperature-dependent equilibrium Ba isotope fractionation between barite/witherite and fluids can be described by the relationships: 103lnαwitherite-fluid = −0.00009×(106/T2)2 + 0.0603×(106/T2) + 0.0003 and 103lnαbarite-fluid = −0.0001×(106/T2)2 + 0.0648×(106/T2) + 0.0004, which is consistent with previous theoretical and experimental studies. In hydrothermal fluids, the hydration number of Ba2+ varies from 4 to 6 at high P-T, and the cumulative average of 103lnβ is derived to be 0.0798 ± 0.005‰ in 923.15 K and 0.2 GPa. In silicate minerals, the enrichment of heavy Ba isotopes decreases in the sequence of muscovite > microcline ≈ celsian ≈ sanbornite > barylite > phlogopite. Variations in Ba concentrations and the degree of Al-Si disordering only induce limited Ba isotope fractionation, which would be hard to distinguish analytically. At high temperatures (> 600 °C), the melt phase is enriched in heavy Ba isotopes relative to any coexisting aqueous fluid and crystallizing minerals. During the early stages of felsic magma differentiation involving plagioclase crystallization as the main mineral, the δ138/134Ba and concentration in the residual melt remain close to their initial values, but any fluid exsolved from the melt will have light δ138/134Ba values. The high Ba distribution coefficient of K-feldspar means that the resultant K-feldspar granite inherits > 90% of the Ba contained in the initial magma reservoir. Hence, the δ138/134Ba of K-feldspar is close to that of the initial melt. During the final stage of felsic magma evolution, mixing of exsolved fluids from deeper reservoirs may significantly reduce the δ138/134Ba of the now Ba-depleted melt, and can account for the low δ138/134Ba values measured in highly differentiated leucogranites and pegmatites.

Petrogenesis of Late Cretaceous Muscovite-Bearing Peraluminous Granites in the Youjiang Basin, South China Block: Implications for Tin Mineralization

Most primary Sn deposits worldwide are associated with muscovite-bearing peraluminous granites, commonly believed to originate from the partial melting of metasedimentary rocks. We studied the whole-rock geochemistry and Sm–Nd isotopes of Late Cretaceous (~90 Ma) Laojunshan muscovite-bearing peraluminous granites in the Youjiang Basin, South China Block. The globally significant Dulong tin mineralization was co-genetic with the Laojunshan muscovite-bearing monzogranites. The Laojunshan granites exhibit slightly higher εNd(t) values than the Precambrian basement, indicating a hybrid crustal source comprising both Precambrian rock and juvenile components. Characterized by weakly peraluminous compositions, these granites display highly evolved geochemical features: notably low levels of Ca, P, Mg, Fe, and Ti contents, elevated Si content, a high FeOT/MgO ratio, and a low Zr/Hf ratio. These distinctive geochemical features can be attributed to the differentiation of plagioclase, biotite, and zircons, with the remarkably low Nb/Ta and K/Rb ratios further suggesting a fluid exsolution process. The geochemical data propose that tin-enriched Laojunshan granites originate from mineral differentiation and fluid exsolution of crust-derived melts during magmatic evolution. By integrating these novel findings with existing data on coeval muscovite-bearing granites co-genetic with tin mineralization in the Youjiang Basin, it is deduced that these granites share a unified origin. Their genesis can be attributed to mineral differentiation and fluid exsolution of crust-derived melts rather than a direct melting of metasedimentary rocks.

Petrology of an apatite-calcite segregationary kimberlite from the Andriesfontein pipe, Kaapvaal craton

Here, we present a case study of an apatite-calcite segregationary kimberlite from the Andriesfontein pipe (Kaapvaal craton) using EPMA and LA-ICP-MS data of olivine macrocrysts and groundmass phases to constrain magma evolution. The primary objectives are to first constrain magma evolution in the SCLM using olivine followed by late-stage evolution and the timing of fluid exsolution using groundmass phases and importantly, apatite. Olivine cores display a range in Mg# (87.2–93.6) with no distinguishable gap in compositions. Aluminium, however, clearly divides the cores into two populations: 1) high-Al cores (>100 ppm Al; >400 ppm Ca; Mg# 87.2–92.7; 52% of cores) interpreted to predominantly reflect the disaggregation of megacrysts, and 2) low-Al cores (<100 ppm Al; <200 ppm Ca; Mg# >92; 48% of cores) interpreted to reflect sampling of garnet peridotite at depths of 84.5–138 km estimated using the Al-in-olivine thermometer. Groundmass phlogopite and spinel are well-zoned recording evolution of the kimberlite melt with increasing oxidation state indicated by the presence of MUM spinel and tetraferriphlogopite rims. Perovskite trace elements concentrations are typical of kimberlite perovskite worldwide. Apatites are observed in late-stage segregations as both equant grains and radiating clusters of acicular laths, however, their compositions are identical (SrO ∼2.2 wt%, SiO2 < 1 wt%, and low REE e.g., La2O3 + Ce2O3 - <0.01 wt%). The relatively high SrO and low SiO2 suggests formation from a fluid phase rather than directly from the melt, consistent with the presence of apatite in segregations and predominantly acicular habit. Chondrite normalised REE profiles for apatite display sinusoidal patterns, which can be modelled by melt evolution through small degrees of predominantly perovskite fractionation. Ultimately, we present a five-stage model for melt evolution from melt-SCLM interactions to magma evolution through groundmass crystallisation and late-stage fluid exsolution, highlighting the complexity of kimberlite magma evolution from source to surface.

Mineralization and Skarn Formation Associated with Alkaline Magma Chambers Emplaced in a Limestone Basement: A Review

The emplacement of shallow magma chambers within a carbonate basement is a typical feature of many volcanic systems around the world. The accompanying formation of exoskarns, endoskarns, cumulates, exsolved fluids and differentiated melts at the interface between the magma chamber and carbonate host-rock is well documented through mineralogical and geochemical studies of ejected skarns and cumulates and through fluid and melt inclusion studies. This review presents the current knowledge on the interaction of alkaline magma chambers with carbonate-bearing host-rocks, with a focus on the geochemical evolution and mineralization at the outer margins of the magma chamber and the accessory mineral phases at Somma-Vesuvius, Colli Albani and Merapi volcanic systems. Furthermore, we discuss how this interaction and its products, especially the CO2 released during the thermometamorphic decarbonation of the carbonate host-rock, impacts the eruptive behavior in all three systems.

Large Si isotope fractionation reveals formation mechanism of quartz in silicon-poor carbonatite

Abstract Carbonatites, the most silica-poor igneous rocks, have a close relationship with rare earth element (REE) ore deposits, where low SiO2 activity is considered to contribute to economic REE mineralization. However, a paradox is raised by quartz, commonly regarded as a Si-saturation proxy, which occurs in some giant carbonatites or carbonatite-related REE deposits such as those at Bayan Obo, China, and Mountain Pass, California, USA. A unique perception for the origin of quartz in carbonatites is provided here using Si isotope analysis. Quartz grains from the Bayan Obo carbonatite and REE ores commonly occur as inclusions in fluorite, or they coexist with fluorite, thus implicating the importance of fluorine in their hydrothermal origin. The quartz grains have remarkably large variations in δ30Si values, ranging from −4.55‰ to 1.71‰ in secondary ion mass spectrometry analyses, which have not been documented elsewhere in high- to medium-temperature magmatic-hydrothermal processes. Theoretical calculations demonstrate that such large Si isotopic fractionation can be generated during the formation and breakdown of Si-O and Si-F bonds due to their difference in bond strength. These results imply the presence of silicon fluoride species in the fluid and highlight the role of fluorine in quartz formation in silicon-poor carbonatite. The exsolved fluids from carbonatite magmas containing silicon fluoride species may decrease silica activity, which has the potential to impede incorporation of REEs into magmatic apatite, and thus facilitate late-stage hydrothermal REE enrichment and formation of REE orebodies.

Quenching of basaltic melts by volatile exsolution

Normally, volatiles in silicate melts are ephemeral components that escape as gases when the melt reaches fluid saturation. When fluid saturation occurs at elevated pressure, magmatic fluids may have large amounts of oxide solute dissolved, are less volatile, and may resemble viscous gels. In Cyprus we have the rare case that solutes of a magmatic fluid coexist with H2O saturated basaltic to boninitic glasses. Quenching of the melts and fluid solutes was induced by fluid segregation. When the fluids exsolved, the liquidus temperature was raised and the melts were left supercooled, while the system temperature remained ± constant. Quenching rates deduced from the morphologies and compositions of quench crystals were high. We analyzed coexisting glasses and fluid solutes for major and trace elements. The fluid mobile trace elements (Rb, K, Pb, Sr) are enriched in both the glasses and fluid solutes. Both endmembers (melt and fluid) have a common parentage and originated within a hydrous mantle source. The glasses have 2.5 ± 0.25 wt.% H2O and record residual H2O contents left after fluid exsolution was completed. Water contents in glasses correspond to an H2O partial pressure (pH2O) of 65 ± 10 MPa and an emplacement depth on the seafloor of 6500 ± 1000 m, provided equilibrium was reached between the pH2O imposed by the melts and the seawater column. Following fluid exsolution, the degree of supercooling ∆T of the melts relative to the dry MgO-in-melt liquidus temperature was – 65 ± 10 °C. The cooling rate ∆T/t at the time of crystallization of dendritic clinopyroxene crystals can be semi-quantified from the distribution of Al2O3 between metastable clinopyroxene dendrites and melt, to at least – 50 °C h−1. Toward the end of the article we speculate if other cases exist where quenching was triggered by fluid exsolution. A possible example are spinifex textures deep inside komatiite flows where quenching rates by conductive cooling did not exceed 0.3 to 1 °C h−1. Our proposition assumes that many spinifex-textured komatiites were hydrous, that they contained H2O in quantities sufficient to reach fluid saturation at emplacement pressure, and that spinifex textures formed as a result of supersaturation by fluid loss.

Controls on metal fertility of dioritic intrusions in the Laiwu district, North China Craton: Insights from whole-rock geochemistry and mineral compositions

Several large high-grade iron skarn deposits in the Laiwu district of Shandong Province (North China Craton) are developed along the contact zone between the Early Cretaceous Kuangshan diorite pluton and Middle Ordovician dolomitic limestone. In sharp contrast, no iron skarn mineralization has been recognized in association with other contemporaneous dioritic intrusions (Jiaoyu, Jinniushan, Tietonggou) in this district. The reason for this contrast remains elusive. Here we present a comparative study of the ore-related Kuangshan pluton and its barren equivalents using whole-rock and mineral (zircon, apatite) geochemistry combined with existing Sr-Nd isotope data to provide new insights into the critical controls on iron skarn mineralization and shed light on future mineral exploration. Geochemical and Sr-Nd isotope data suggest that both the ore-related and barren intrusions were derived from a common enriched lithospheric mantle source following variable degrees of fractional crystallization and crustal assimilation. Modeling based on whole-rock Sr-Nd isotopes implies that the magmas responsible for the Kuangshan and Jinniushan diorite plutons assimilated significant quantities of the Ordovician evaporite-bearing carbonates. Both the fertile and barren diorites show high whole-rock Sr/Y ratios, high zircon Eu/Eu* and Eu/Eu*/Y ratios, and low zircon Dy/Yb ratios. These data, combined with high magmatic water contents (4.4−8.0 wt%) calculated from amphibole compositions, indicate that those four plutons crystallized from hydrous magmas. High whole-rock Fe2O3/FeO, and high ΔFMQ values (mostly &amp;gt;1; fayalite-magnetite-quartz oxygen buffers) estimated from zircon, apatite, and amphibole suggest that the magmas from which the diorite intrusions crystallized were all oxidized. Using available partitioning coefficients for Cl between apatite and magma, the parental melts of the Kuangshan and Jinniushan diorite are estimated to have had higher Cl contents (0.15−0.77 wt%) than the Jiaoyu and Tietonggou diorites (0.06−0.34 wt%). Two types of apatite from the intrusions studied are recognized based on their paragenetic relations: Type 1 apatite (Ap1) is an early-formed phase enclosed in euhedral amphibole, plagioclase, and biotite, whereas type 2 (Ap2) is a late-formed variety hosted in, or intergrown with, anhedral K-feldspar (± anhedral amphibole ± subhedral to anhedral quartz). In the fertile Kuangshan diorite, Cl and OH contents of apatite decrease, but Sr contents increase from Ap1 to Ap2. However, those parameters show reverse trends or remain constant from Ap1 to Ap2 in barren diorites. Such distinctive apatite geochemical signatures are best interpreted as reflecting more efficient fluid exsolution from the parental magma of the Kuangshan diorite than from the barren intrusions. This view is supported by the presence of abundant fluid inclusions in apatite and quartz exclusively from the mineralized intrusion, indicating its crystallization from volatile oversaturated melts. The results presented here indicate that elevated magma Cl contents and efficient separation of magmatic hydrothermal fluid from cooling magmas have been the critical factors controlling iron skarn mineralization in the Laiwu district. Mass balance constraints on Cl budget indicate that a minimum of 44−60 km3 of magma was required to form the Fe deposits associated with the Kuangshan pluton. Our preliminary results suggest that decreasing OH and Cl contents from early to late apatite in intermediate rocks can be used as an indicator for efficient fluid exsolution and consequently metal fertility of those rocks.

Iron Isotope Systematics of the Skaergaard Intrusion and Implications for its Liquid Line of Descent

Abstract The Skaergaard intrusion is one of the most thoroughly studied layered mafic intrusions on Earth and an exceptional example of (near) closed-system magmatic differentiation. We report new Fe isotope data for whole rocks, and magnetite and ilmenite separates through the layered series (LS) and upper border series (UBS) of the intrusion. δ56Fe values for gabbroic rocks range from 0.033‰ to 0.151‰ with an abrupt step increase at the base of Lower Zone c (LZc) within LS with the appearance of cumulus magnetite and subsequent decline accompanying FeTi oxide fractionation. The lowest δ56Fe values are found near the Upper Zone b (UZb) to c (UZc) boundary followed by a sharp rise across UZc approaching the Sandwich Horizon. Magnetite–ilmenite separates straddle bulk rock compositions with fractionation factors (Δ56Femt-ilm) of 0.081‰ to 0.239‰, consistent with subsolidus equilibration. Granophyric rocks occurring as pods, sheets and wispy layers from the upper zone and UBS equivalents and having unradiogenic Sr similar to gabbroic rocks of Skaergaard, are isotopically heavier than their host ferrodiorites (Δ56Fegranophyre-ferrodiorite ≥ 0.1‰) reaching a maximum δ56Fe of 0.217‰ in UBS. A fused xenolith from UBS has δ56Fe = 0.372‰. This range in δ56Fe spans much of that reported for terrestrial igneous rocks, and like the global dataset, shows a pronounced increase in δ56Fe with inferred silica content of modeled Skaergaard liquids. Forward modeling of closed system fractional solidification was undertaken to account for Fe isotope systematics, first by testing published liquid lines of descent (LLD), and then by exploring improvements and considering the impacts of liquid immiscibility, crustal contamination, fluid exsolution and diffusional processes. Our modeling relies on published Fe+2 and Fe+3 force constants for magmatic minerals and silicate glasses, and the most reliable estimates of the average bulk composition and mass proportions of the well-defined subzones of the intrusion. We show that the increase in δ56Fe across the LZb–LZc boundary is readily explained by the increased incorporation of Fe+3 into the crystallizing solid including magnetite. We further demonstrate that the classic Fenner LLD, involving strong Fe enrichment at nearly constant silica, does not lead to a rise in δ56Fe toward the end stages of evolution, while a Bowen-like LLD, with little Fe enrichment and strong Si enrichment, also underestimates enrichment in heavy Fe isotopes in the ferrodiorites of UZc. A LLD following an intermediate path involving modest Fe and Si enrichment, followed by Fe depletion best explains the observations. We predict ~3.5% (by mass) residual liquid after crystallization of UZc having a composition similar to felsic segregations in pegmatitic bodies found in the intrusion. While liquid immiscibility may have been encountered within fractionating mush at the margins of the intrusion, the Fe isotope systematics do not support liquid phase separation of the bulk magma. Crustal contamination, fluid exsolution, hydrothermal alteration and thermal diffusion are also shown to have no resolvable effect on the Fe isotope composition of the gabbroic and granophyric rocks. We conclude that the Fe isotope systematics documented in the Skaergaard intrusion reflect the dominant role of fractionating Fe-rich minerals from gabbroic through ferrodioritic to rhyolitic liquids. The success of our model to account for the observed Fe isotope systematics for Skaergaard demonstrates the utility of Fe+2 and Fe+3 force constants determined at ambient conditions to model magmatic conditions and gives critical insights into plutonic processes fractionating Fe isotopes complementary to the volcanic record.

Mica geochemistry as an indicator of magmatic-hydrothermal processes in the Ta-Nb-Sn-W mineralization of the Limu deposit, South China

Limu deposit is one of the representative deposits with coexisting Ta-Nb and Sn-W mineralization in the Nanling Range, South China. It consists of three stages of granites, with the Ta-Nb and Sn-W mineralization mainly restricting in the third-stage granite. However, the details of the polymetallic mineralization process in this deposit are still obscure. This study utilizes mica geochemistry to trace the ore-related magmatic and hydrothermal processes. The primary micas evolved from Li-phengite in the first- and second-stage granites to zinnwaldite-lepidolite in the third-stage granite. The micas are increasingly enriched in Li, F, Rb and Cs elements with decreasing K/Rb and K/Cs ratios, suggesting a dominant fractional crystallization of feldspars, particularly plagioclase, with minor mica fractionation during magma evolution. The Li-phengites from the first- to the second-stage granites increase in Ta (average value: 38 to 61 ppm) and Nb concentrations (average value: 160 to 180 ppm) but decrease in Nb/Ta ratios (average value: 4.4 to 3.5), consistent with the bulk-rock Ta-Nb enrichment trends. However, the zinnwaldite in the third-stage granite has significantly lower Nb (110 ppm in average) but higher Ta concentration (170 ppm in average), and evolves to lepidolite toward decreasing Nb and Ta concentration (51 and 63 ppm in average, respectively) and increasing Nb/Ta ratios (average value: 0.7 to 1.0). These chemical features of the micas are controlled by co-crystallization of columbite group minerals (CGM) during the evolution of third-stage granitic magma, which was likely Nb-rich at the early stage and evolved toward Ta enrichment. Thus, magmatic processes played a critical role in the Ta-Nb mineralization. Secondary hydrothermal micas in the third-stage granite distinctly depleted in Li, F, Rb and Cs recrystallized from the primary zinnwaldite-lepidolite via replacing reaction, which are closely associated with cassiterite, wolframite and pyrite in the granite. The consistent δ34S values of the disseminated pyrite (0.71‰) and vein-type pyrite (1.12‰) in the granite indicate that the hydrothermal system was dominated by magmatic fluids without notable involvement of external fluids. The lower Ta and Nb concentrations (31 and 35 ppm in average, respectively) of the hydrothermal micas compared to primary ones suggest that at least small amounts of Ta and Nb were transferred by the fluids. Indicated by the mica concentrations, Sn and W were enriched with magma evolution and likely concentrated in the volatile and flux components of the third-stage magma. Furthermore, cassiterite and wolframite in the granite precipitated by fluid-rock interaction, and a portion of W and Sn migrated away with exsolved fluids to form the quartz vein W-Sn mineralization. This study demonstrates that mica geochemistry can effectively indicate magmatic-hydrothermal processes in granite-related Ta-Nb and Sn-W mineralization.