Magmatic-hydrothermal Transition Research Articles

Zirconium isotope tracing of the magmatic-hydrothermal transition

Zirconium (Zr) isotopes have significant potential for tracing magmatic processes, particularly late-stage fractionation involving fluids. However, the fractionation of Zr isotopes between magma and fluid is still unclear. In-situ Zr isotope analyses of zircons from three granite-pegmatite suites in the Tibetan plateau show a wide range of δ94/90Zr values (IPGP-Zr) between −0.23 ‰ and 1.38 ‰, with the highest values in hydrothermally altered zircons from pegmatites. A coupled dissolution-reprecipitation process of zircons in a fluid-rich magma is the most plausible mechanism to explain the strong enrichment of heavy Zr isotopes in hydrothermally altered zircons. During the formation of granitic pegmatite, exsolution of F-Na-Si-bearing fluids can enhance zircon solubility and is capable of significant removal of Zr from the melt. Faster diffusion of 90Zr into the fluid channel will result in preferential accumulation of light Zr isotope in the fluid, and drive heavy Zr isotope enrichment in the residual melt under disequilibrium conditions. Later reprecipitated zircons will inherit the heavy Zr isotope composition of the melt. Rayleigh fractionation models suggest fluid-melt fractionation factors for Zr isotope of about 0.99911–0.99930. The results show the major controls of fluid on Zr isotope fractionation during crystal-magma-fluid differentiation. Zr isotope can be a powerful tracer for the magmatic-hydrothermal transition.

Trace element (Be, Zn, Ga, Rb, Nb, Cs, Ta, W) partitioning between mica and Li-rich granitic melt: Experimental approach and implications for W mineralization

Mica is the most important carrier of rare alkalis (Li, Rb and Cs) and volatiles, and also a major host of rare metals such as Sn, W, Nb and Ta. Thus, the knowledge of trace element partitioning between mica and silicate melt is crucial to understand enrichment mechanisms of ore metals in evolved silicic systems. However, experimental data are scarce, mainly because the synthesis of large mica grains which can be analyzed with laser ablation techniques is challenging. To address this issue, we conducted two-step experiments, using a high-temperature step at 800 °C, and a low-temperature step at 600 °C with a temperature cycling interval of 30 °C, and variable run durations from 21 to 60 days. The experimental products, at 600 °C, 200 MPa, are mainly composed of mica and alkali feldspars. Ferroholmquistite (Fhlm; a Li-bearing amphibole) was also observed in the Li-bearing systems.Beryllium, Zn and Cs are highly incompatible in all run products with mineral/melt partitioning of mineral/meltDBe between 0.01 and 0.08, mineral/meltDZn between < 0.01 and 0.24 and mineral/meltDCs between <0.01 and 0.19. Gallium is mildly incompatible in mica and feldspars with mica/meltDGa, K-feld/meltDGa and Na-feld/meltDGa of 0.24–0.35, 0.60–0.67 and 0.69–0.72, respectively, whereas Fhlm/meltDGa is nearly 1. Rubidium is characterized by a slight enrichment in mica and K-rich feldspar with respect to melt. Niobium and Ta are highly incompatible in feldspars, while they are compatible in ferroholmquistite. Li-mica crystallization would cause Nb/Ta fractionation with mica/meltDNb and mica/meltDTa of 4.46 and 0.88, respectively. Tungsten is preferentially incorporated in Li-rich mica with mica/meltDW > 22. The strong partitioning of W into Li-rich mica implies that minor Li-rich mica fractionation (>5 %) will strongly deplete W in the residual melt, thus inhibiting transfer to the magmatic fluid at the magmatic-hydrothermal transition. Based on the observed mineral/meltD value, a multi-stage quantitative fractionation model for the behavior of metals during the crystallization of Li-bearing granitic magmas was developed. The results suggest that crystal fractionation is an effective mechanism that could further enrich Be, Ga, Rb, Cs, Nb and Ta in residual melts. Li-rich mica and muscovite are more effective in causing Nb/Ta fractionation as compared with biotite. The very low Nb/Ta ratios found in natural granite may have resulted via extreme, i.e., >99 wt% of fractional crystallization, even if without the precipitation of columbite-group minerals or increasing hydrothermal activity. Due to the very high Li-mica/meltDW value, water saturation in the melt and subsequent magmatic fluid exsolution should occur before Li-mica starts to crystallize to avoid W sequestration in the magma. At 175 MPa, the efficiency of extracting W from Li-poor granitic system is at least 15 % higher than that from Li-rich granitic system. Li-poor granitic systems are thus expected to have a greater W-mineralization potential than Li-rich system, which is consistent with the fact that most parental magmas of large/giant W deposits are Li-poor in composition.

Magmatic–Hydrothermal Evolution at the Barren Wushan Pluton, Southeast China: Insight into Controls on Mineralization Potential

Abstract A-type granites typically exhibit enrichment and mineralization of critical metals such as molybdenum and tin, essential for emerging technologies. However, the key factors influencing their mineralization potential remain elusive. The scarcity of studies on barren systems impedes the understanding of this question. Here, a detailed melt and fluid inclusion study was conducted on the barren Wushan pluton to reconstruct its magmatic evolution and magmatic–hydrothermal transition and explore the factors controlling the metallogenic potential of Mo and Sn in A-type granites. The Wushan pluton displays apparent lithological zoning consisting of two major phases, i.e., medium-grained seriate to porphyritic alkali feldspar granite and fine-grained porphyritic granite. Miarolitic cavities are widely developed in each lithofacies. The silicate melt inclusions from two granitic phases are rhyolitic, with moderate F contents (0.06–0.53 wt %) and depleted H2O contents (2.0–3.5 wt %). Melt inclusions show a wide range of incompatible element contents, such as Cs (9–1977 μg/g) and Rb (268–2601 μg/g), suggesting that Wushan has undergone a high degree of magma evolution. Mo behaves incompatibly in the magmatic evolution, and its content is enriched with the increasing degree of fractional crystallization, but remains constant after the Cs content exceeds 50 μg/g. Rayleigh fractionation model suggests that a large amount of Mo is extracted from fluid exsolution, which restrains Mo from further enrichment. In contrast, Sn behaves as a mildly incompatible element during the entire magmatic evolution history. The contents of Sn increase slowly compared to the trend of Mo, and the maximum contents reach ~30 μg/g in the highly evolved melts. The separation and crystallization of Sn-bearing minerals such as biotite, magnetite, and titanite inhibit the enrichment of Sn. Intermediate-density (ID-type) fluid inclusions hosted in the miarolitic quartz, representing the initial fluid exsolving from magma, display high Mo but low Sn concentrations. Constrained from two assemblages of coexisting ID-type fluid and melt inclusions, the fluid/melt partition coefficients of metals are obtained, with DMo, fluid/melt at 16–19, while DSn, fluid/melt is only about 1. The comparison between Mo-mineralized and barren intrusions worldwide shows that the metal contents in melts and fluids are not fundamentally different. The mineralized intrusions are characterized by the lower melt viscosity and the development of apophyses, both of which facilitate the extraction of metals and fluids from large magma chambers, followed by their concentration into a small rock volume. Consequently, it appears that physical and structural conditions rather than chemical compositions play a crucial role in the Mo mineralization process. Enrichment of Sn in melts is necessary but not decisive for Sn mineralization, whereas Sn enrichment in the initial exsolving fluid determines the Sn mineralization potential of a given granitic system. Compared to Sn enrichment in source melting and fractional crystallization which commonly enhance final Sn fertility in the highly evolved melts, the efficiency of Sn partitioning between melt and fluid plays a fundamental role in converting melt fertility into Sn-enriched fluids and thereby high mineralization potential of the magmatic–hydrothermal system. Our findings suggest a prospect for Mo exploration in the coastal A-type granite belt in South China, while the potential for Sn mineralization is expected to be limited.

Geochronology and geochemistry of zircon and columbite–tantalite group minerals from the Weilasituo Sn–polymetallic deposit, northeastern China: Implications for the relationship between mineralization and the magmatic–hydrothermal transition

The Weilasituo Sn–polymetallic deposit, located in the southern portion of the Great Xing'an Range of Inner Mongolia, China, is a super-large Sn deposit associated with abundant Li, Rb, Nb, Ta, Zn, and Cu resources. Despite that previous studies have characterized the age, hydrothermal evolution, and genetic relationship between the alkali feldspar granite porphyry and associated Sn–polymetallic mineralization, the magmatic–hydrothermal evolution and ore–forming processes remain ambiguous. To address these ambiguities and bridge this knowledge gap, this contribution characterizes the texture, geochemistry, and U–Pb isotope composition of zircon and columbite–tantalite group minerals (CGMs) from amazonitized alkali feldspar granite (AMG) and albitized alkali feldspar granite (ABG) in the Weilasituo deposit. Type-I zircon (Zr1) is inclusion-poor, translucent, and is characterized by low light rare earth element (LREE) contents, high (Sm/La)N ratios (mean = 655.7), and low Th/U (mean = 0.21 < 0.3), Zr/Hf (mean = 5.46), and Y/Ho ratios (mean = 4.42), indicating that it formed during the magmatic–hydrothermal transition. Type-II zircon (Zr2) is inclusion-rich, porous, has a low CL response, and is characterized by low Th/U ratios (0.08–0.32, mean = 0.17), high LREE contents, weakly positive Ce anomalies, and low (Sm/La)N ratios (mean = 20.7), indicating that it formed via hydrothermal alteration of Zr1 (i.e., magmatic–hydrothermal zircon). Type-I CGM (CGM1) generally lacks oscillatory zoning, and has similar and positively correlated Ta/(Nb + Ta) and Mn/(Mn + Fe) values (AMG: R2 = 0.93; ABG: R2 = 0.75), indicative of a magmatic origin. Type-II CGMs (CGM2) occur as rims on CGM1 and are characterized by higher Ta/(Nb + Ta) and lower Nb/Ta ratios than CGM1, indicative of precipitation from a hydrosilicate liquid during the magmatic–hydrothermal transition. Based on the characteristics of CGMs, two stages are evident in the evolution of the Weilasituo granite porphyry: an earlier magmatic differentiation stage and a later magmatic–hydrothermal transition stage. Furthermore, the magmatic–hydrothermal transition stage can be subdivided into the AMG and ABG substages within the porphyry system based on petrological and mineralogical characteristics. The U–Pb ages for zircons and CGMs from the alkali feldspar granite porphyry range from 137.2 ± 2.0 Ma to 129.8 ± 1.4 Ma, without a notable age gap. The similarity in U–Pb ages between CGM1–CGM2 and Zr1–Zr2 indicates that the magmatic stage and the magmatic–hydrothermal transition at Weilasituo were continuous processes that occurred during the Early Cretaceous.

Magmatic–hydrothermal stage recorded by mica zonation and Nb–Ta–W–Sn mineralization: New insight into the genesis of highly evolved Songshugang Nb–Ta deposit (Jiangxi, SE China)

The role of magmatic and hydrothermal processes in niobium-tantalum mineralization is still controversial and has been limited by a lack of mineralogical records in the evolving magmatic–hydrothermal system. Micas as essential rock-forming minerals and comprise the amount of elements (especially rare-metal elements), become one of the ideal indicator. The Songshugang rare-metal granite (RMG) located in the southern part of Jiangxi Province, China, is renowned as the largest tantalum reservoir in South China. The albite–topaz–K-feldspar granite is the major granite, with layers of pegmatite, topaz-K-feldspar granite, and greisen overlay on it. It is the typical highly evolved peraluminous with low phosphorous RMGs (PLP-type) according to geochemistry. The Songshugang pluton preserves analogical characters in topaz-albite-K feldspar granites and topaz-K feldspar granite, and partly reserves in greisen. Detailed petrographic, mineralogy, and chemical composition study of zoned mica and accessory Nb–Ta minerals suggest that zinnwaldite and Nb-Ta oxides have experienced magmatic fractionation with gradually decrease of K/Rb and Nb/Ta ratio in prismatic zinnwaldite and columbite-(Fe). The leap of Rb (Rb2O up to 4.08 wt%) and Ta (Ta# up to 0.29) at the rim of zinnwaldite and columbite is likely attributed to supersaturation. Afterwards the overgrowth of Rb-deficit zinnwaldite (0.56–0.72 wt% Rb2O) is coeval with the Ta-highest wodginite, taking place during the magmatic-hydrothermal transition associated with a fluid-melt interaction in hydrosaline melt. The ascent of fluxing elements contributes to the formation of hydrothermal zinnwaldite and cassiterite through greisenization. The systemic coupling mineralization of zinnwaldite and Nb–Ta oxides altogether record the both the melt-driven and fluid-driven processes in highly evolved Songshugang deposit that is critical for rare-metal mineralization. The Songshugang displays a great similarity to the typical PLP RMGs Cínovec cupola in geochemistry, which are metaluminous to peraluminous, containing low phosphorous, intermediate REE, Zr, Hf, and Th content. But Songshugang has experienced strong supersaturation; the latter is more akin to highly evolved melts alike Yichun or Beauvoir. The strong supersaturation and crystallization demonstrate its discrepant mineralization mechanism in Songshugang RMGs.

Mn–Fe-rich genthelvite from pegmatites associated with the Madeira Sn–Nb–Ta deposit, Pitinga, Brazil: new constraints on the magmatic-hydrothermal transition in the albite-enriched granite system

AbstractGenthelvite from pegmatite veins hosted by the albite-enriched granite (ca.1.8 Ga) corresponding to the Sn–Nb–Ta (F, REE, Li, Zr, U, Th) Madeira deposit, Amazonas, Brazil was studied. Genthelvite, the exclusive Be-bearing mineral within the deposit, occurs as massive crystals of up to 4.7 cm in size. Compositions are homogeneous within individual crystals, although there is moderate variation in the overall composition reflecting relatively limited substitutions within the helvine–genthelvite–danalite solid-solution series, with relatively high Zn contents (36.96 to 49.45 wt.% ZnO), lower Mn contents (0.61 to 3.03 wt.% MnO), and variable Fe contents (2.10 to 10.94 wt.% FeO), completing an existing compositional gap in this system. Genthelvite formed in an alkaline and subaluminous environment, under stable conditions within the late-evolved fluids, at relatively high temperature (&gt;400°C), in a reducing environment. The extremely high concentration of fluorine in the magma and the crystallisation of magmatic galena resulted in an effective reduction of H2S fugacity. This resulted in the stabilisation of genthelvite during the transition from the late magmatic to early hydrothermal stages of the albite-enriched granite evolution. The variability in Fe content within genthelvite is associated primarily with localised variations in the mineral assemblage (e.g. the presence of riebeckite and polylithionite). Genthelvite was altered by low-temperature aqueous fluids rich in F which resulted in the incorporation of Fe, Mn, Mg, Pb, Ba, Na, K, U and REE into the Zn2+ structural site and the allocation of excess Si, Al, Ti and P in the IVSi and IVBe structural sites. The substantial content of U and REE substituting for Zn, together with Si substituting for Be, is charge balanced by the presence of vacancies at the A site.

Tourmaline chemical and boron isotopic constraints on the magmatic-hydrothermal transition and rare-metal mineralization in alkali granitic systems

Tourmaline chemical and boron isotopic constraints on the magmatic-hydrothermal transition and rare-metal mineralization in alkali granitic systems

Tourmaline geochemical and boron isotopic compositions of the Bailongshan rare-metal pegmatite deposit: Implications for magmatic-hydrothermal evolution of the West Kunlun Orogen (NW China)

The Bailongshan in the West Kunlun Orogen (northern Tibet) is a newly-discovered super-large rare-metal (Li-Rb(-Be-Ta-Nb)) pegmatite deposit. Tourmaline occurs widely in muscovite granites and pegmatites at Bailongshan, but comprehensive study is yet to be done on the geochemical evolution of tourmaline from the magmatic to the hydrothermal stages. Here, we present a systematic study of in-situ major, trace elemental and boron isotopic variations of tourmaline from Bailongshan deposit, and discuss the tourmaline genesis and how boron isotopes change during the magmatic to hydrothermal stage. Three types of tourmaline have been identified at Bailongshan deposit, including disseminated tourmaline in the muscovite granite, medium-coarse-grained euhedral tourmaline in the barren pegmatite, and multicolored medium-coarse-grained tourmaline in the ore-bearing pegmatite. EPMA and LA-ICP-MS geochemical analyses reveal that the tourmaline samples belong mainly to alkali group, with the tourmalines from the muscovite granite and the barren pegmatite falling into the schorl solid-solution series and the ore-bearing pegmatite falling into elbaite. There is a major chemical change from Fe-rich compositions with moderate Al in the Y-sites (muscovite granite and barren pegmatite) to Li-rich compositions with high YAl and relatively high F (ore-bearing pegmatite). Most trace element contents vary over several orders of magnitude with median concentrations of 0.1–10 μg/g. High concentrations are found for Ga, Zn, Be, Sc, Sn and Li (several tens to thousands of μg/g), whereas low concentrations (<0.1 μg/g) are found for V, Rb, U, Th, W, and Hf. The tourmalines from muscovite granite and barren pegmatite yielded δ11B = -8.9 to −7.5 ‰ and −8.7 to −6.0 ‰, respectively, whilst the tourmaline in the ore-bearing pegmatite show a wider δ11B range (-8.8 to −5.2 ‰). The B isotopic values indicate a source of the continental crust in a post-collisional setting. The estimated δ11B value of parental granitic magma is −10.0 ‰. The overlap in δ11B values between muscovite granite and barren pegmatite indicates a little isotopic fractionation between tourmaline and melt. Rayleigh fractionation results in the observed δ11B decrease from zone I (-6.9 ‰) to zone V (-8.0 ‰). After the barren-pegmatite-hosted tourmaline formation, the δ11B value of boron-rich magma would have been about −11.5 ‰. The intragrain δ11B variation of tourmaline in the ore-bearing pegmatite is 2.7 ‰, much larger than that from the other zones, indicating the rim of the tourmaline crystallized from fluid exsolved. We calculated the boron-isotope fractionation (between fluid and melt) to be 4.2–5.7 ‰ at 600–450 °C. Chemical variations in tourmaline are continuous in the muscovite granite and barren pegmatite, consistent with fractional crystallization, whereas the tourmaline from the ore-bearing pegmatite may have formed during the magmatic-hydrothermal transition. The boron isotopic variations could be attributed to fractionation between melt-tourmaline, melt-fluid and tourmaline-fluid and Rayleigh fractionation.

Whole-Rock Geochemistry and Mica Compositions in Lijiagou Pegmatite Spodumene Deposit, Western Sichuan, China

The Lijiagou pegmatite spodumene deposit, located in the middle of the Songpan–Garze Fold Belt and southeast of the Ke’eryin ore field, is a newly discovered super-large deposit. In order to reveal the metallogenic tectonic environment and evolution process of pegmatite, based on the study of the geological characteristics of pegmatite, we carried out a whole-rock geochemical analysis of Ke’eryin two-mica granite and Lijiagou pegmatite and carried out a detailed electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analysis of mica minerals in each zonal pegmatite. The results show that the Ke’eryin two-mica granite is mainly formed in the transition period from syn-collision to post-collision. After the end of the continental collision, the crust is squeezed and thickened in the post-collision extensional transition tectonic environment. Mica from the microcline pegmatite zone (MP) to the albite spodumene pegmatite zone (ASP) in pegmatite show different compositions and structural characteristics, with the evolution trend in the direction from muscovite to Li-bearing mica. The type of mica from MP to AP is mainly muscovite, and Li-bearing mica appears in ASP, which is secondary and metasomatic at the edge of primary muscovite. From MP to ASP, there was a negative correlation between Nb/Ta, K/Rb and the Li, Rb, and Cs contents of mica, while the contents of Li, Rb, Cs, and F in the Li-bearing mica of ASP increased sharply. This evidence illustrates that the favorable tectonic environment contributed to the formation of the Lijiagou pegmatitic spodumene deposit. Lijiagou pegmatite experienced the magmatic–hydrothermal evolution process and has a high degree of differentiation and evolution from MP to ASP, which gradually increased. Combined with the change in mica type, it is considered that ASP formed from the stage of magmatic transition to hydrothermal and was a hydrothermal environment, and Li, Rb, and Cs mainly began to enrich at the stage of magmatic–hydrothermal transition.

Petrogenesis and tectonic-magmatic context of emplacement of lepidolite and petalite pegmatites from the Fregeneda-Almendra field (Variscan Central Iberian Zone): clues from Nb-Ta-Sn oxide U-Pb geochronology and mineral geochemistry

The Fregeneda-Almendra pegmatite field of the Iberian Massif represents a typical expression of peraluminous rare-metal magmatism that occurred over western Europe at the end of the Variscan orogeny. It is the host for two main types of Li-mineralized intrusions, identified at the scale of the Variscan belt, including petalite- or spodumene-rich pegmatites, as well as Li-mica-rich pegmatites, for which the origin of mineralogical-chemical differences is not yet understood. Here, we provide cassiterite and columbite-group mineral (CGM) U-Pb ages along with oxide, mica and phosphate mineral compositions for Li-pegmatites from the Fregeneda-Almendra field in order to assess their petrogenesis and tectonic-magmatic context of emplacement. U-Pb geochronology indicates that petalite-rich and Li-mica-rich pegmatites were mostly emplaced sub-synchronously from 315 ± 6 to 308 ± 6 Ma, during strike-slip deformation and granitic magmatism within an anatectic dome bounding the pegmatite field. U-Pb data and pegmatite geographic zonation suggest that Li-pegmatites were sourced from buried equivalents of leucogranites and migmatites from the dome. Li-pegmatites experienced a complex crystallization including K-feldspar, petalite, topaz, Nb-Ta-Fe-Mn-rich cassiterite, amblygonite-group minerals (AGM) and CGM as early magmatic phases, followed by lepidolite for Li-mica-rich pegmatites. At the magmatic-hydrothermal transition, notably leading to the formation of Nb-Ta-Mn-Fe-poor cassiterite hosting CGM inclusions, earlier minerals were resorbed by muscovite and albite. A later F-rich hydrothermalism is locally reflected by zinnwaldite overgrowths on muscovite. Cassiterite, CGM and micas from petalite-rich pegmatites show lower Mn/Fe ratios and higher Ti contents, along with lower Zr-Ga contents for cassiterite, than that from Li-mica-rich pegmatites. Such behavior is consistent with a magmatic differentiation process whereby Ti content decreased and the degree of Mn-Fe geochemical fractionation and solubilities of Ga and Zr increased in the melts, possibly in relation with high fluorine activity. In Li-mica-rich pegmatites, AGM equilibrated with a melt with up to 2 wt% F, similar to that in equilibrium with lepidolite (1–3 wt%). In petalite-rich pegmatites, the relatively high F concentration of the melts equilibrated with AGM (≤ 1.5 wt% F) contrasts with the liquid equilibrated with muscovite (&lt; 0.5 wt% F). This can be accounted for by muscovite crystallization after the exsolution of a F-rich aqueous phase at the magmatic-hydrothermal transition. Relatively similar F contents in the initial melts of petalite- and Li-mica-rich pegmatites support the hypothesis that the stability of lepidolite does not only involve high F but also a low H2O/F activity ratio. For the Fregeneda-Almendra Li-mica-rich pegmatites, this could be explained by a decrease of melt H2O solubility due to a relatively low pressure of emplacement.

Silver Behavior During Magmatic and Magmatic-Hydrothermal Evolution of a Highly Evolved Reduced Granitic System Related to the Giant Shuangjianzishan Ag-Pb-Zn-(Sn) Epithermal Deposit, Northeast China

Abstract Magmatic-related epithermal silver-rich polymetallic deposits are among the most important sources of Ag in the world, and they are found associated with magmatic systems with striking differences. Most of the time, they are associated either with I-type oxidized (magnetite-series granite) intermediate to evolved intrusions or with S-type/A-type reduced (ilmenite-series granite) highly evolved intrusions. To better understand these associations, the Ag evolution has been tracked during the magmatic differentiation and the magmatic-hydrothermal transition stage of A-type highly evolved porphyritic granites associated with the giant Shuangjianzishan Ag-Pb-Zn-(Sn) epithermal deposit, the largest known Ag deposit of Asia (145 million tonnes at 128.5 g/t Ag and 2.2 wt % Pb + Zn) located in the largest known metallogenic province for Ag in China (the southern Great Xing’an Range). At the Shuangjianzishan deposit, the porphyritic granite complex consists of three temporally distinct intrusions—a coarse-grained monzogranite porphyry, a fine-grained syenogranite porphyry, and a fine-grained syenogranite—having crystallized at ~2 kbar and ~750°C and recording a continuous magmatic differentiation trend. The silicate melt that generated the last highly differentiated intrusion (fine-grained syenogranite) is interpreted as the source of the mineralizing fluids forming the Shuangjianzishan Ag-Pb-Zn-(Sn) epithermal deposit, as it is the only intrusive unit that reached fluid saturation, as indicated by cotrapped fluid and melt inclusions in quartz phenocrysts and by the occurrences of unidirectional solidification textures (USTs). Silver evolution in the different porphyritic granite facies was reconstructed with laser ablation-inductively coupled plasma-mass spectrometry analyses of quartz-hosted silicate melt inclusions, amphibole-hosted magmatic sulfide inclusions, and chemical modeling. The silicate melt forming the porphyritic granite complex was sulfide saturated during the first crystallization stage, as shown by the occurrence of Ag-rich monosulfide solid solution (MSS) inclusions hosted in amphibole phenocrysts from the coarse-grained monzogranite porphyry and from mafic microgranular enclaves hosted in the coarse-grained monzogranite porphyry. However, these Ag-rich MSSs had only a minimal impact on the Ag budget of the magmatic system, as shown by the increase of the Ag concentration (~100–1,000 ppb) in quartz-hosted silicate melt inclusions during the further evolution of the system until fluid exsolution was reached. These results combined with mass balance modeling suggest that Ag and Sn are efficiently transferred to the evolving residual melt during crystallization and crystal-melt segregation. The results of this study indicate that highly Ag endowed epithermal polymetallic deposits can be formed from the exsolution of Ag-rich mineralizing fluids from relatively low volume, highly evolved, reduced melts, similar to those responsible for the formation of Sn-rich greisen deposits.

Mineral Chemistry of Pyrochlore Supergroup Minerals as Records of Nb Mineralization Processes in NYF-Type Pegmatites: A Case Study of the Emeishan Large Igneous Province, SW China

Alkaline igneous rocks have become a potentially important source of Nb, except for the carbonatites. The metallogenetic mechanism of Nb during the magmatic-hydrothermal evolution of alkaline rocks remains ambiguous. From the perspective of Nb minerals, the mineral chemistry of pyrochlore supergroup minerals provides the mineralogical evidence for indicating the respective contributions of magma and hydrothermal fluids to Nb mineralization. In the Miyi County of the Panzhihua-Xichang (Pan-Xi) area, the central zone of the Permian Emeishan large igneous province (ELIP) in SW China, hundreds of Nb-Y-F mineralized pegmatites (NYF-type) are exposed. This study conducted in situ mineral chemistry analyses on four types of pyrochlores to elucidate the Nb mineralization process. Both Pcl-I and Pcl-II exhibit well-developed oscillatory zoning (OZ), representing magmatic pyrochlore formed through disequilibrium crystallization in an oscillatory environment. Pcl-III, with a homogeneous and less variable composition, is also considered of magmatic origin due to its coherent chemical evolution with Pcl-II. Pcl-IV is considered of hydrothermal origin based on its irregular zoning texture, extremely high Na2O contents, and compositional gap compared with magmatic types. The decrease in TiO2 contents, coupled with the increase in Na2O, F, and Nb2O5 contents from Pcl-I to Pcl-III and from the core to the rim of zoned Pcl-II, indicates that fractional crystallization facilitates the crystallization of albite and the enrichment of volatiles, as well as the precipitation of Nb from the early to late stages. During the magmatic-hydrothermal transition stage, the reductive, Na- and F-enriched fluid transports Nb more effectively, leading to further Nb enrichment in pyrochlore. Consequently, there are two-stage Nb mineralization processes associated with the magmatic-hydrothermal evolution in the Miyi pegmatite, with the primary magmatic ore assemblages being the dominant Nb mineralization, which may be a general model for the mineralization of NYF-type pegmatites.

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.

Lithium enrichment of the magmatic-hydrothermal fluid in albite-spodumene pegmatite from Lijiagou, Eastern Tibetan Plateau: Evidence from fluid inclusions

Albite-spodumene pegmatites, which are remarkable resources of Li worldwide, may experience both magmatic-hydrothermal transition and sub-solidus hydrothermal alteration during their formation and evolution. However, fluids involved in the different stages of the evolution of a spodumene-bearing pegmatitic systems are not well defined, especially at the magmatic-hydrothermal transition stage. In the Lijiagou deposit, western Sichuan Province, fluid inclusions of a typical albite-spodumene pegmatite were studied to determine the degree of magmatic-hydrothermal fluid Li enrichment and the potential for lithium mineral crystallization at the magmatic-hydrothermal transition stage.Micro-petrographic analyses identified different types of fluid inclusions of either primary, pseudo-secondary or secondary origin and inclusions containing devitrified silicate glass. The presence of these inclusions suggests that the pegmatite underwent both the magmatic-hydrothermal transition stage and a post-crystallization hydrothermal process over its evolution. The results of fluid inclusion LA-ICP-MS analyses show that the aqueous ± carbonic fluids represented by the pseudo-secondary type 1a and 1b inclusions carry significant amount of Li, with Na and Li predominating the cation budget of these pegmatitic fluids. The aqueous ± carbonic fluids exhibit typical magmatic-hydrothermal fluid compositional characteristics and exhibit high abundance of Li in this pegmatitic system at the magmatic-hydrothermal transition stage. The relative abundance of Li to Na and K lies within the uppermost range of those reported from lithium-cesium-tantalum pegmatite systems. This is consistent with the elevated incorporation of Li in pegmatitic quartz from the albite-spodumene pegmatite. The compositional characteristics of the fluids at the magmatic-hydrothermal transition stage may be used to imply the Li mineralization potential of the pegmatitic system.

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.

The Mineral Chemistry of Magnetite and Its Constraints on Ore-Forming Mechanism in the Sandaozhuang Skarn-Type W-Mo Deposit in East Qinling, China

The Sandaozhuang super-large W-Mo deposit is located in the southern margin of the North China Craton, within the well-known East Qinling Mo mineralization belt, and is one of the typical skarn-type W-Mo deposits in China. Based on EMPA and LA-ICP-MS analyses, major and trace elements were presented, and the mineral chemistry of magnetite at various mineralization stages was discussed. Combining field observations, petrography, and geochemical characteristics, the magnetite at the Sandaozhuang deposit can be classified into three types, namely early-magmatic-stage high-temperature magnetite (Mag1), potassic-alteration-stage magnetite (Mag2), and retrograde-alteration-stage magnetite (Mag3). The Mag1 and Mag2 magnetites primarily occurred in granites in association with potassium (K) feldspar and biotite, whereas Mag3 is associated with metallic sulfide minerals that occurred mainly in vein-like structures in skarn. The three magnetites Mag1, Mag2, and Mag3 can be distinguished as having magmatic, magmatic–hydrothermal transition, and hydrothermal origins, respectively. All three types of magnetite exhibit a depletion of high-field-strength elements (HFSEs) such as Zr, Hf, Nb, Ta, and Ti, and large-ion lithophile elements (LILEs) including Rb, K, Ba, and Sr, compared to the mean continental crust composition. Conversely, they are enriched in elements such as Sn, Mo, V, Cr, Zn, and Ga. Mag3 showed no significant depletion of Co, Ni, Cu, and Bi, indicating that the influence of coexisting sulfides on the composition of magnetite at the Sandaozhuang deposit is limited. There are systematic variations in major and trace elements from Mag1 to Mag3, which exhibited similar patterns in trace element spider and rare earth element diagrams, and Y/Ho ratio, indicating a consistent source for the three types of magnetite. The changes in V and Cr contents and (Ti + V) vs. (Al + Mn) diagram of magnetite at the Sandaozhuang deposit reflected the evolution of ore-forming fluids with an initial increase in oxygen fugacity and a subsequent decrease, as well as a gradual decrease in temperature during skarn mineralization. The early high-temperature and high-oxygen-fugacity magmatic fluids became W and Mo enriched by hydrothermal fluid interaction. The rapid change in fluid properties during the retrograde alteration stage led to the precipitation of scheelite and molybdenite.

Effects of Metasomatism on Granite-Related Mineral Systems: A Boron-Rich Open Greisen System in the Highiş Granitoids (Apuseni Mountains, Romania)

Greisenization is typically linked with highly fractionated granites and is often associated with hydrothermal vein systems. Late to postmagmatic metasomatic processes involve the enrichment of volatile components such as boron and halogens as well as several metallic elements. The purpose of this study is to reveal the main metasomatic effects and paragenetic sequences of the related mineralizations in Highiş granitoids, Romania. In a natural outcrop, more than 30 samples were collected from granitoids, felsic veins, and country rocks. We carried out a detailed mineralogical and petrological characterization of carefully selected samples using X-ray powder diffractometry, electron microprobe analysis, and microscopic methods together with K–Ar ages of whole rocks and K-bearing minerals. Several characteristic features of albitization, sericitization, tourmalinization, epidotization, and hematitization were recognized in the studied samples. Crystallization of quartz, K-feldspar, and magnetite represents the first stage during the magmatic-hydrothermal transition. The mineral assemblage of albite, sericite, schorl, and quartz originates from the early and main stages of greisenization. While the subsequent mineral assemblages, which predominantly include dravite, specular hematite, and epidote, are closely related to the late vein-depositing stage. We propose that the study area could belong to a boron-rich open greisen system in the apical portion of Guadalupian A-type granite. Based on a new hypothesis, the previously published Permian crystallization ages (between ~272 Ma and ~259 Ma) could be homogenized and/or partially rejuvenated during the hydrothermal mineralization processes due to uraniferous vein minerals. Additionally, the Highiș granite-related system suffered a Cretaceous thermal overprint (between ~100 Ma and ~96 Ma). The results may help to understand the evolution of highly evolved granite intrusions worldwide and improve our knowledge of the effect of hydrothermal mineralization processes on the emplacement ages.

Cadomian Iron ore bodies in the Bafq-Saghand metallogenic province, Iran: genetic constraints from field observations and laser ablation ICP-MS mineral studies

ABSTRACT The volcano-sedimentary unit in the Bafq-Saghand metallogenic province (BSMP) of Central Iran hosts various types of iron ore bodies including Fe-oxides with jaspilite beds, Mn-dominated iron lenses, magnetite-apatite lenses, and massive magnetite-apatite deposits. The Fe-oxides with jaspilite beds and Mn-dominated iron lenses have limited outcrops and show volcano-sedimentary features in the field. The main features are the presence of syngenetic submarine rhyolite-hosted magnetite, lamination and bedding of iron ore body, jaspilite and dropstone. Volcano-sedimentary origin is testified by magnetite composition showing affinity to BIF and positive Eu and negative Ce anomaly. Magnetite-apatite lenses and massive magnetite-apatite deposits that having spatio-temporal correlation form the main economically important deposits. They have magmatic to high-temperature hydrothermal field characteristics (lava flow-like ore bodies, the presence of degassing tubes in ore bodies, occurrence of brecciated texture and developed Na-Ca metasomatism). Mineral composition (enrichment of LREE, magnetite and apatite negative Eu anomaly and Co/Ni < 1 in pyrites) is in agreement with magmatic and high temperature hydrothermal origin. We propose a hydrous and oxidizing mantle derived iron-rich basic magma that formed in an extensional post-collisional setting for origin of Kiruna-type IOA ore bodies of the BSMP. Fe-oxides with jaspilite beds and Mn-dominated iron lenses resulted from degassing or eruption of iron-rich magma during Ediacaran in a submarine environment. However, magnetite-apatite lenses and massive magnetite-apatite deposits formed from an Early Cambrian magmatic-hydrothermal transition system from a magnetite-crystal mush zone.

The magmatic-hydrothermal transition in P-rich pegmatitic melts: Crystal-melt-fluid interactions recorded by phosphate minerals

Rare-element pegmatites are the crystallization product of melts strongly enriched in incompatible elements. Some of these elements, e.g., Li, B, P, F, and H2O, function as melt structure modifiers, allowing such melts to reach unusually low crystallization temperatures and regulating the saturation of aqueous-carbonic fluids from the melt. However, the timing of fluid saturation is highly debated, and the processes that mark the magmatic-hydrothermal transition in rare-element pegmatites are still elusive. The crystallization sequence of phosphate minerals can be used to assess the timing and nature of fluid-related processes in pegmatitic systems. In the Buranga pegmatite, western Rwanda, magmatic phosphates are replaced by (hydrous) alkali-rich phosphates and later by strongly hydrated phosphates as the dike cools. This reaction series indicates a disequilibrium in the crystal-melt-fluid system and records complex fluid-rock interactions during dike consolidation. This contribution compares these interactions with the fluid record preserved in fluid inclusions in the main phosphates of the crystallization sequence. Three major fluid inclusion types are observed, aqueous-carbonic (mostly-two-phase, L-V), carbonic-aqueous (two-phase, V-L, or three-phase, L-L-V), and crystal-rich inclusions (multiphase, L-V-Solids). Crystal-rich fluid inclusions in trolleite [Al4(PO4)3(OH)3], the last primary phosphate to precipitate from the melt, show a paragenesis of solid phases similar to the secondary phosphates observed in the dike. LA-ICPMS analyses of individual fluid inclusions show high concentrations of Na and K, with some content of Li, Rb, Cs, B, Fe, and Mn in the fluid. A similar composition is present in all inclusion types within the same mineral. Crystal-rich fluid inclusions demonstrate that during the magmatic-hydrothermal transition, primary phosphates react with the fluid in the presence of melt to generate secondary phosphates. No evidence of external fluid sources has been observed during the magmatic-hydrothermal transition. The fluid inclusion record shows that the fluid salinity is kept constant due to fluid-mineral interactions and corroborates the hypothesis that fluid-soluble elements are internally remobilized in the melt-crystal-fluid system during the magmatic-hydrothermal stage. These interpretations have implications for the general evolution of P-rich pegmatitic melts and the mineralization of Nb and Ta in these systems.

Constraints on the timing of magmatism and rare-metal mineralization in the Fangzheng Rb deposit, Altai, NW China: Implications for the spatiotemporal controls on rare-metal mineralization

Amazonite granites are potential Rb resources given the abundance of Rb-bearing minerals they contain. The Altai Orogen, located in the southwestern portion of the Central Asian Orogenic Belt, is the world's most famous rare-metal metallogenic belt, containing numerous Li–Be–Nb–Ta–Cs deposits (e.g., the Koktokay No. 3 pegmatite deposit). The Fangzheng deposit, however, is the only known independent Rb deposit in this belt, with a proven Rb2O reserve of ∼12,940 tons at an average grade of 0.07%. The deposit is hosted by the Jiangjunshan pluton, which is composed largely of two-mica alkali feldspar granite and lesser amazonite granite on the peripheries, with amazonite pegmatite veins cutting the pluton and its wall-rocks. Although the pluton has been dated using various geochronological techniques, the magmatic and the rare-metal mineralization ages remain ambiguous given the complexity in zircon genesis and evolution, and their high Th and U contents. In this contribution, U–Pb geochronology of zircon, monazite, cassiterite, and columbite-group minerals, as well as their trace-element characteristics, are utilized to constrain the timing and evolution of magmatism and mineralization in the Fangzheng Rb deposit. Based on morphological and geochemical features, and cathodoluminescence images, zircon grains from different lithofacies are classified into three types — magmatic zircon, hydrothermally overprinted magmatic zircon, and hydrothermal zircon. The first two types of zircon grains are characterized by low Th/U ratios (0.22–4.00, with an average of 0.84) and ΣLREE contents (8.66–466, with an average of 90.6), indicative of a magmatic origin, whereas the third type is characterized by high Th/U ratios (0.22–7.26, with an average of 2.26) and ΣLREE contents (1154–4944 ppm, with an average of 2905 ppm), indicative of a hydrothermal origin. The magmatic and hydrothermally overprinted magmatic zircon grains from the two-mica alkali feldspar granite and amazonite granite yield U–Pb ages of 272.7±1.4 Ma and 272.5±1.7 Ma, respectively. Therefore, the earliest age of magmatism of the Jiangjunshan pluton is approximately 272 Ma (early–middle Permian). Based on the internal structure and geochemical characteristics of accessory minerals (monazite, cassiterite, and columbite-group minerals) selected from the ore bodies (amazonite granite and amazonite pegmatite), it is suggested that they crystallized during the magmatic–hydrothermal transition. The U–Pb ages of hydrothermal zircons (253.2±17.0 Ma), monazite (254.4±0.9 Ma), and columbite-group minerals (254.9±1.4 Ma) from the amazonite granite, as well as the U–Pb ages of monazite (253.3±0.7 Ma), cassiterite (250.4±1.4 Ma), and columbite-group minerals (254.5±0.8 Ma) from the amazonite pegmatite indicate that the age of rare-metal mineralization in the Fangzheng deposit is approximately 255–250 Ma (i.e., close to Permian/Triassic boundary). Combined with previous geochronological results and interpretations of tectonic evolution, it is evident that i) the middle Permian to Late Triassic is an important period of granitic magmatism and related rare-metal mineralization in the Chinese Altai, and ii) the rare-metal deposits formed in an intracontinental extensional setting after the tectonic transition from subduction to extension.