Cl-rich Fluids Research Articles

Y-Ho fractionation during basalt alteration in hydrothermal system: An implication for superchondritic Y/Ho signature recorded in Precambrian banded iron formations

The concentration of rare earth elements (REE) in Precambrian sedimentary rocks is widely used to estimate their depositional environment. Specifically, superchondritic Y/Ho value is a powerful indicator for determining whether a sedimentary rock was deposited in a marine environment. Currently, superchondritic Y/Ho value in seawater is believed to result from the preferential adsorption of Y onto Fe-Mn oxides. In modern oceans, Fe-Mn oxides are considered the sink for subchondritic Y/Ho value. On the contrary, Precambrian banded iron formations (BIFs) display superchondritic Y/Ho value, suggesting that Precambrian seawater also possessed a superchondritic Y/Ho value. However, Precambrian BIFs cannot account for the sink of subchondritic Y/Ho value. Thus, other processes must have been responsible for maintaining the superchondritic Y/Ho value of Precambrian seawater. A hydrothermal experiment involving mid-ocean ridge basalt (MORB) and a Cl-rich fluid was conducted at 300 °C and 500 bars to assess the role of basalt-hosted hydrothermal systems on the Y/Ho value of seawater. Over time, the fluid's Ca concentration increased while Na decreased, suggesting plagioclase albitization occurred. The REE pattern of the reacted fluids exhibited superchondritic Y/Ho values up to 63.2. Based on the presence of positive Eu anomaly and the degree of light REE depletion, the REE in the hydrothermal fluids was mainly sourced from plagioclase during albitization. The superchondritic Y/Ho values in the fluids can be explained by the preferential leaching of these elements due to differences in chloride complexing strength between REE. Subchondritic Y/Ho values observed in Precambrian hydrothermally altered basalts may be interpreted as remnants generating superchondritic Y/Ho values in coexisting Precambrian hydrothermal fluids. Therefore, we believe that the superchondritic Y/Ho value of Precambrian seawater was maintained by basalt-hosted hydrothermal system.

Formation of PGE- and sulfide-bearing chromitites and associated anorthositic rocks in layered intrusions by the infiltration of reactive, Cl-rich fluid

The chromatographic model for chromitite formation previously presented is updated to include sulfide as a possible participating phase. In the model, chromite is precipitated at an upward-moving reaction front as a Cr-bearing (gabbro)norite protolith reacts with a Cl-rich fluid that becomes progressively undersaturated in pyroxene as it rises into hotter parts of the crystal pile, leaving an anorthositic residue. The liberation of Fe during the dissolution of orthopyroxene can drive concurrent sulfide saturation. If the reaction front encounters an orthopyroxenite the model produces a first-order approximation for the Merensky Reef section of anorthosite–chromite–orthopyroxenite. In addition, MELTS modelling shows that the isothermal addition of Cr 2 O 3 alone to a nearly solid (gabbro)norite assemblage increases the amount of both chromite and liquid at the expense of other silicate minerals owing to the liberation of Ca, Na and Si, the latter two acting as fluxing agents. A generalized constitutional zone refining model is presented in which a variety of spinel–silicate layering types (e.g. Bushveld magnetite layers and Skaergaard trough layering) can develop over time.

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.

The important role of fluid chemistry in the hydrothermal alteration of ordinary chondrites: Insights from halite and sphalerite in the Sidi El Habib 001 (H5) meteorite

The important role that aqueous fluids played during the evolution of carbonaceous chondrites (CCs) and the carbonaceous asteroids that they derive from is well documented. In comparison, our understanding of how such fluids affected ordinary chondrites (OCs) and their S-type asteroid parent bodies is less mature in part due to the intense thermal metamorphism that overprinted the records of alteration. Further, that only a small suite of unequilibrated OCs shows evidence of hydration hinders our understanding of the role that fluids played in the evolution of OCs and S-type asteroids. Here we report a microstructural analysis on halite (NaCl) and sphalerite (ZnS) in Sidi El Habib 001 (SEH 001), a H5 OC that provides new insights into the role of fluids on the OC parent bodies. Our data reveal that halite contains alteration relicts of submicron silicates, and that widespread sphalerite spatially correlates with halite. This relationship suggests that sphalerite formed from the same hydrothermal fluid that precipitated halite, consistent with experimental and theoretical work showing that Cl-rich fluids induce complexation of Zn and significantly enhance its mobility. We hypothesize that Cl-rich hydrothermal fluids resulted from melting of locally concentrated HCl hydrate, which produced acidic fluids capable of dissolving chondritic mineral phases. The pH of the fluid presumably varied on a micrometer scale due to different rates of hydrolysis reactions as a function of grain size, as illustrated by the absence of halite in SEH 001 chondrules. Such a fluid-alteration model is attractive because it offers a reasonable explanation for the limited and heterogeneous alteration effects in OCs.

The geochemistry and geochronology of garnet from the Jinchanghe Fe-Cu-Pb-Zn deposit, Baoshan Block, western Yunnan

The Jinchanghe polymetallic Fe-Cu-Pb-Zn deposit is located in the northern region of the Baoshan Block in western Yunnan. Using electron probe micro-analysis and laser ablation inductively coupled plasma mass spectrometry, we analyzed the major, trace, and rare earth elemental contents of garnets from the Jinchanghe deposit. Moreover, U-Pb dating was performed using the laser ablation sector field inductively coupled plasma mass spectrometry (LA-SF-ICP-MS) method to determine the direct mineralization age of the Jinchanghe deposit. Petrographic analyses revealed three garnet generations: early (GrtI), middle (GrtII), and late (GrtIII). GrtI (And55.69-64.47Gro30.28-41.21Ura + Pyr + Spe + Alm2.35-5.49) was characterized by irregular shapes and weak optical properties, and primarily comprised Fe-rich grossular. GrtII (And53.69-96.17Gro2.78-45.07Ura + Pyr + Spe + Alm0.59-2.12) was characterized by andradite, in which GrtIIa was a homogeneous body, whereas GrtIIb shows exhibited oscillatory zoning with abnormal interference colors. Fine-veined andradite aggregates were predominant in GrtIII (And70.51-90.33Gro6.34-27.80Ura + Pyr + Spe + Alm1.03-3.32). The GrtI, GrtIIa, and the rims of GrtIIb were depleted in heavy rare earth elements and enriched in light rare earth elements, with positive Eu anomalies, indicating that these garnets crystallized from mildly acidic magmatic hydrothermal fluids. However, the cores of GrtIIb had negative Eu anomalies and may have crystallized from a relatively neutral Cl-rich fluid. GrtIII was severely depleted in light rare earth elements with positive Eu anomalies, indicating the presence of a weakly acidic environment. Accordingly, owing to a decrease in temperature and an increase in oxygen fugacity, the pH of the Jinchanghe deposit may have transitioned from an early weakly acidic to neutral, then to a late weakly acidic environment. Furthermore, the ages of GrtII and GrtIII ranged from 520 to 496 Ma, which places the formation of the Jinchanghe deposit during the Late Cambrian. The deposit is closely related to the arc magmatic rocks produced by the subduction of the Proto-Tethys Ocean.

Formation of Cu–Au porphyry deposits: hydraulic quartz veins, magmatic processes and constraints from chlorine

Copper–gold porphyry deposits are the world’s main source of copper and a significant source of gold. They consist of vein networks and their surrounding alteration zones. Commonly the deposits are centred on narrow intrusions (stocks), but calling these deposits ‘porphyries’ is unjustified because the name carries little descriptive or genetic value. Extensional veins were formed by hydraulic fracturing of the stocks, at depths where open spaces could not be maintained and where fluid pressure approaches lithostatic pressure. The post-crystallisation timing of the veins is important because it indicates that the host stocks could not have been the direct sources of either metals or ore-forming fluids. In the traditional magmatic model, precursor batholiths, lying at depth, are inferred to be the sources of the Cu and Au in the overlying host stocks. In this model, the batholiths are assumed to have crystallised and produced the mineralising aqueous fluids, Cu and Au. However, in many porphyry deposits, the concept of metal and fluid supply from deeper batholiths is problematic. Neither Cu nor Au is strongly enriched during the crystallisation of silicate magmas, and although hypersaline fluids are a characteristic of Cu–Au porphyry deposits globally, the source of the Cl remains unconstrained. There is little evidence that silicate magmas can release such Cl-rich fluids, and it remains unexplained how elevated levels of Cl may be achieved in a silicate magma. Therefore, the starting assumption that these deposits formed predominantly from magmatic sources and processes is questioned. This study has selectively focused on the roles of rheology, rock mechanics, vein control, metal-enrichment processes and the sources of Cl. Non-magmatic processes may be enough to facilitate strong partitioning of Cu and Au into high-temperature, oxidising, high-salinity, hydrothermal fluids to form Cu–Au porphyry deposits.

Ultraviolet-photoluminescence and trace element analyses in Ga-rich sphalerite from the Djebel Gustar Zn-Pb deposit, Algeria

The Djebel Gustar Zn-Pb deposit in northeastern Algeria is one of many carbonate-hosted base metal deposits in the Atlas metallogenic province of North Africa. The sphalerite in this deposit occurs in five distinct types that differ in texture, mineral assemblage, chemical composition, and UV photoluminescence signature. Detailed investigation of trace elements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that the sphalerite is significantly enriched in the critical metal Ga. The trace element concentrations of the different sphalerite types correlated well with their photoluminescence color; with Mn2+ (orange-yellow), Cu+ (green), and Ga3+ (red) being the dominant activators. We suggest that the Ga enrichment in the Djebel Gustar deposit is the result of formation conditions that include the mixing of a Cl-rich fluid carrying mainly Zn and Pb with a more reduced and Cl-poor fluid containing considerable organic matter and/or calcite with adsorbed Ga(OH)3. This Ga was subsequently incorporated into sphalerite, rather than forming a stoichiometric Ga phase. Furthermore, our study demonstrates that UV photoluminescence of low Fe sphalerite has the potential to become a simple and affordable tool for preliminary characterization of sphalerite ores in mining and exploration with respect to critical elements such as Ga.

Ferro-chloro-winchite in Northwest Africa (NWA) 998 apatite-hosted melt inclusion: New insights into the nakhlite parent melt

Melt inclusions are of major significance because they can constrain the volatile abundances in magmas. Here, we report the discovery of the first melt inclusion in a martian apatite containing the first chloro-amphibole reported in Northwest Africa (NWA) 998, a sample that crystallized early from the nakhlite-source. The amphibole is also the first sodic-calcic amphibole in a nakhlite, identified as ferro-chloro-winchite (4.75 wt% Cl) by FIB-TEM. The melt inclusion is present in a euhedral, cumulus apatite grain (Cl/F = 2.11) and is surrounded by a shell of voids. Evidence indicates that the melt inclusion remained as a closed system although syn- and post-entrapment processes may have modified the chemical composition of the original trapped melt. The inclusion also contains Fe-rich, Ca-poor pyroxene and a residual silicate melt consisting of pyroxene and interstitial K-rich glass. Additionally, Cl-enriched apatite is present within the boundaries of the melt inclusion. This apatite could result from cracking of host-apatite during contraction of the melt inclusion glass or represent daughter apatite crystallizing on the walls of the inclusion. Given that Cl-enrichments are found in the host apatite outside the melt inclusion, it is inferred that a later, fluid alteration event locally modified the composition of the apatite in and/or around the melt inclusion. The calculated bulk composition of the melt inclusion is generally consistent with previous work in other nakhlites. Prior to this study, Cl-rich amphiboles have only been found within olivine- and pyroxene-hosted melt inclusions in the later-formed nakhlites. The present study thus demonstrates that (i) the nakhlites record magmatic mixing with a Cl-rich exogenous component that is absent within olivine-hosted melt inclusions in the chassignites, (ii) Cl-rich amphiboles were able to crystallize from the earliest nakhlite parent melt, and (iii) the presence of a Cl-rich fluid was not required to stabilize chloro-amphiboles. We also conclude that magmatic martian amphiboles likely stabilized at lower pressures (and temperatures) than terrestrial amphiboles due to their higher Cl contents.

Porphyry copper mineralization triggered by sulfate reduction and alkali metasomatism: Constraints from an experimental investigation

The potassium silicate (K-silicate) alteration zone is the main ore contributor in porphyry copper deposits worldwide. Knowledge of element behaviors in the alteration and mineralization processes is essential for an improved understanding of porphyry copper mineralization, but they are still not well understood. In this study, we reacted synthetic Cl-rich fluids, containing K, Na, Cu, Mo, Zn, etc., with andesite in a complex experimental system to simulate the shallow porphyry copper mineralization process. We aimed to bridge the gap between simple experimental studies and complex natural systems and to evaluate the contribution of sulfate reduction to porphyry ore formation and its relationship with early alkali metasomatism. The results show that increasing temperature (from 300 to 500 °C) enhances the K-silicate alteration by promoting ion-exchange reactions, and the K-feldspar is mainly formed by the transformation of plagioclase via a dissolution-reprecipitation processes. The low-salinity vapor phase has a stronger capacity for K-silicate alteration than the liquid phase at similar temperatures. In addition, increasing temperature from 300 to 500 °C favors sulfate reduction to further enhance metal sulfide precipitation. The limited availability of reduced sulfur in the fluid causes preferential precipitation of Cu-(Mo) sulfides, while most of the Zn is soluble in the fluid, and Cu precipitation as sulfides in the vapor is much more efficient than in the coexisting liquid. The overlap between the K-silicate alteration zone and the mineralization triggered by sulfate reduction in porphyry copper deposits is controlled by several concomitant factors, e.g., relatively high temperature (e.g., at 400−500 °C), vapor formation, and decompression. Moreover, K-silicate alteration would further promote mineralization by changing fluid compositions, e.g., removing K from the fluid.

Multivariate statistical analysis of trace elements in apatite: Discrimination of apatite with different origins

Partial least squares-discriminant analysis (PLS-DA) was used to construct the link between trace element contents of magmatic or hydrothermal apatite and deposit and rock types. Apatite with different origins is discriminated by characteristic chemical composition. In average, ore magmatic apatite has higher light REE and Th, and lower Sr than barren rock apatite, independent of deposit types. Hydrothermal apatite has lower La, Ce, Pr, and Nd contents than magmatic apatite, probably because fluids prefer migrating light rare earth element out of apatite. Hydrothermal apatite from iron oxide copper gold (IOCG) and iron oxide apatite (IOA) deposits is discriminated by high Mn and Sr relative to magmatic apatite, probably because these elements are fluid mobile. Barren magmatic apatite from granitoid-related deposits is well separated from ore magmatic apatite by higher Sr, Eu, Gd, Tb, Dy, and lower Mn contents, which are likely related to the relatively low degree of differentiation and high aluminum saturation index of parental magma.Magmatic apatite from IOA deposits is discriminated by relatively high Nd, Sm, Gd, Tb, Dy, and low Mn and U contents, which are possibly related to the crystallization of Mn-compatible magnetite microlites and peraluminous magmas. Magmatic apatite from granitoid-related W deposits is relatively rich in Y, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The relative enrichment of Sr in magmatic apatite from granitoid-related Cu-Pb-Zn and Pb-Zn deposits is likely due to less fractionation of Sr-compatible plagioclase. Melt of sediment component accounts for high Mn and Th in magmatic apatite from granitoid-related Mo deposits. Magmatic apatite from porphyry deposits is discriminated by relatively high V, Sr, and Eu contents. Magmatic apatite from porphyry Mo deposits has relatively high Pr, Nd, and Sm and low Sr contents compared to other types of porphyry deposits due to the more evolved magma. Hydrothermal apatite from IOA deposits is discriminated by high V and Sr, whereas those from IOCG deposits have high Sm, Eu, Gd, Tb, and U contents, because the lower temperature of IOCG cause precipitation of REE in Cl-rich fluid. Relatively low Gd and Tb in hydrothermal apatite from skarn deposits are possibly due to the crystallization of amphibole.Apatite in carbonatite has high contents of trace elements possibly because high contents of Ca and P in melts cause high apatite-melt partition coefficients of trace elements. Apatite from sedimentary and metamorphic rocks is discriminated by relative enrichment of Sr and Eu. Compared to igneous rocks, apatite from sedimentary rocks has low REE contents, reflecting low REE budget in surface waters. Breakdown of some minerals to release and remobilize REE and U during metamorphism can interpret high heavy REE and U contents in apatite from high-grade metamorphic rocks relative to those from low- and medium-grade metamorphic rocks. The ability to discriminate apatite from different types of deposits and rocks indicates the application potential of apatite chemistry in mineral exploration. A flowchart was proposed to identify apatite with unknown origins.

Garnet U-Pb geochronology and geochemistry reveal deposit types and fluid evolution: An example from the Dongguashan Cu-Au deposit, eastern China

Dongguashan is one of the largest Cu-Au deposits in eastern China, with ubiquitous garnet in the stratiform and skarn orebodies. The stratiform ore-formation remains enigmatic. In this study, we describe the diverse textures and present new U-Pb age and chemical data for the Dongguashan garnet. Garnet in the skarn orebody can be divided into three generations (Grt-1, Grt-2, and Grt-3). Grt-1 and Grt-2 show three zones from core to inner rim to outer rim (a-b-c). Garnet in the stratiform orebody is homogeneous (Grt-s). All garnet types have low MnO, a wide range of Y/Ho ratios, and visible fluid inclusions, indicating that they formed from hydrothermal replacement. Grt-1a, Grt-1b, Grt-2a, Grt-2c, and Grt-3 are oscillatory-zoned, low-Sn, and HREE-rich grandite, which may have formed from reduced HREE-rich fluids. Meanwhile, Grt-1c and Grt-2b are high-Sn, LREE-rich andradite, and may have formed from oxidized LREE-rich fluids. Grt-s is pure, low-Sn, LREE-rich andradite, and that may have formed from oxidized LREE-rich fluids. The Eu behaviors are sensitive to the fluid physicochemical conditions and Cl content. Grt-1, Grt-2, and Grt-s have positive Eu anomalies, and may have formed from acidic and Cl-rich fluids. Grt-3 has negative Eu anomalies and was possibly formed from neutral and Cl-poor fluids. All garnet types at Dongguashan may have formed by infiltration metasomatism in an open system with multiple metasomatic pulses. Grt-1, Grt-2, and Grt-s yielded nearly the same in-situ U-Pb ages of 135.9 ± 2.1 Ma, 135.6 ± 2.2 Ma, and 134.6 ± 1.4 Ma, respectively. We propose that both ore types at Dongguashan deposit are closely related to the Early Cretaceous plutonism.

Trace elements in apatite from Gejiu Sn polymetallic district: Implications for petrogenesis, metallogenesis and exploration

The world-class Gejiu tin polymetallic district is located in southeastern Yunnan Province. Yet, the largest deposits are concentrated in the Masong and Laoka granites in the eastern area of Gejiu. To investigate the factors controlling Sn mineralization among intrusions in the Gejiu area, we collected apatite from eight different intrusions (including gabbro, monzonite, and granite) and determined the fertility indices of Sn deposits through the chemical composition of apatite. Analysis of the redox-sensitive elements in apatite showed that the ore-bearing granites have high Mn and low S content, high Y/∑REE and low La/Sm ratios, extreme negative Eu anomalies, and weak Ce positive anomalies compared to the barren intrusions, indicating that the formation environment of the ore-bearing granites was more reducing. The apatites in ore-bearing intrusions have lower Sr and higher Y contents, which suggests that these intrusions have a higher degree of fractionation than barren intrusions. The apatites in the Masong and Laoka granites have a high F content, which reflects the high F content of magma that contributed to the enrichment of Sn. The decreasing (Sm/Yb)N ratios with stable Sr content imply exsolution of Cl-rich fluids or crystallization of monazite and allanite. The exsolution of Cl-rich fluids can increase Sn solubility in the melt and promote the extraction of Cu from basalt. The apatites in the ore-bearing intrusions have high Li, Mn, Fe, and F contents and extremely low (Eu/Eu*)N ratios (<0.05). These results show that apatite can be used to distinguish Sn deposits from other deposit types and guide the Sn exploration.

Origin of metasomatic fluids in the Bayan Obo rare-earth-element deposit

The Bayan Obo REE–Fe–Nb deposit is the largest light rare earth element (REE) deposit in the world, and it has undergone serious hydrothermal reworking processes. However, the origin and nature of metasomatic fluids in this deposit remain controversial. To determine the origin of metasomatic fluids, we conducted a detailed mineralogical and geochemical investigation on the apatite from the ∼ 1.8-km drill core in the Bayan Obo deposit. The textural and geochemical variations of the apatite could trace the hydrothermal metasomatism during REE mineralization. Four types of apatites were identified according to their cathodoluminescence characteristics, including turbid euhedral apatite (Ap-0), rounded pinkish–violet apatite veinlets (Ap-1), yellowish–green apatite aggregates (Ap-2), and apatite with a pinkish–violet core and a yellowish–green rim (Ap-3). According to the in-situ Sr isotopic compositions, these apatites were classified into two groups. Ap-0, Ap-1, and Ap-2 display constant and low 87Sr/86Sr ratios (0.7030–0.7035), whereas Ap-3 displays various Sr isotopic compositions (0.7047–0.7105). The in-situ Th–Pb age of the bastnäsite associated with the Ap-0 ranges from 390 to 425 Ma. The Sr isotopic compositions and geochronological study indicate that metasomatic fluids in the Bayan Obo deposit were obtained from different sources, including the Silurian Bainaimiao arc plutons and sedimentary materials. The four apatite types display various REE distribution patterns, which could account for hydrothermal fluid properties. F-rich and Na-poor fluids metasomatized the precursor Ap-0, releasing REEs from apatites and resulting in low REE contents of Ap-0. Ap-1 and Ap-2 were derived from the same fluid but were characterized by different trace element compositions, which could be attributed to the evolution of hydrothermal fluids with changes in the Na content and F/Cl ratio. The primary Ap-3 was derived from a REE-rich source and was altered by Na-poor and Cl-rich fluids. Metasomatic fluids with different origins and variable chemical compositions result in complex mineral assemblages and geochemical features in the Bayan Obo deposit.

Arc magmatism and porphyry-type ore deposition are primarily controlled by chlorine from seawater

A better understanding of magmatism and ore metal deposition at convergent plate margins is essential to the safety and benefit of society. Despite their spatial and, to a certain extent, temporal association, a direct connection between these two geologic processes is enigmatic. A detailed evaluation of available data reveals that seawater is key to the connection between these processes as it is the source of the ubiquitous, hot aqueous fluid from the subducting slab that is central to the generation of primary arc magmas and transfer or recycling of crustal materials at convergent margins. Particularly regarding the transfer of fluid-mobile elements or the so-called subduction component from the slab to arc lavas, however, the slab-derived hydrothermal fluid is perceived as weak and, thus, other transfer agents are proposed. Most petrogenetic studies also do not connect the source and transfer of metals in the spatially associated ore deposits to the same fluid. Chlorine from seawater can provide the crucial link between the two processes. The presence of Cl makes the slab-derived fluid a potent solvent not only to transfer but also to solubilize both the subduction component and ore trace metals from the slab, mantle wedge and lower-middle arc crust to arc lavas and ore deposits, respectively. Moreover, the dissolution and mobility of many elements in the Cl-rich fluid are primarily dependent upon their respective ionic potential (i.p.) values. In general, elements with cations that have low (soft cations) and high (hard cations) i.p. are mobile whereas those with in-between (intermediate cations) values are immobile in the Cl-rich fluid. Subducted sediment provides the bulk of subduction component and ore metals. These results led to the creation of a unified conceptual model claiming that the mobility, or immobility, of almost all elements in hydrothermal fluids at or near the Earth's surface is primarily dependent upon the amount of Cl in the fluids.

Experimental study on Fe solubility in vapor-rich hydrothermal fluids at 400–500 °C, 215–510 bar: Implication for Fe mobility in seafloor vent systems

In seafloor hydrothermal systems, vent fluids usually contain elevated dissolved iron (Fe) that is significantly enriched relative to deep ocean seawater. It is commonly thought that Fe is preferentially transported in dense Cl-rich fluids due to the formation of aqueous Fe-Cl complexes. However, Fe enrichment in vapor-rich low-density fluids with low Cl concentrations (<550 mmol/kg) underscores the efficacy of the low-Cl vapor-rich phase to transport Fe in both subaerial and submarine hydrothermal systems. Currently, transport of Fe in low-density vapor-rich fluids is poorly understood due to the lack of high temperature–pressure (T-P) solubility experiments and requisite thermodynamic data. Here, we report new data of Fe solubility from experiments conducted at 400–500 °C, 215–510 bar, targeting fluids with low-density (∼0.1–0.35 g/cm3). The experiments were performed in the KCl-H2O system with hematite-magnetite and K-feldspar-muscovite-quartz as mineral buffering assemblages. Our results show that Fe solubility positively correlates with density and fluid chlorinity, which are affected by temperature and pressure. The equilibrium constants (log Khm) for Fe-buffering reaction Fe3O4(s) + 2HCl(aq) = Fe2O3(s) + FeCl2(aq) + H2O were determined. The new data and the data calculated using Helgeson-Kirkham-Flowers (HKF) equation of state were fit into a density model to extrapolate log Khm for hematite-magnetite Fe buffering reaction over a wide T-P range. The density models for magnetite dissolution reaction and pyrite-pyrrhotite equilibrium were also fit based on HKF to allow redox constraints. We show that calculated Fe solubility are in good agreement with measured values in vapor-rich fluids formed via phase separation in mineral buffered and basalt alteration experiments at elevated T-P. The density model was further applied to model Fe transport in fluids at the Brandon hydrothermal field at East Pacific Rise (EPR) 21°S, with T-P constrained by Si-Cl geothermobarometer. The calculations suggest that the reported Fe concentrations of vent fluids at Brandon reflect phase separation occurring at depth in the seafloor, with T-P up to 450 °C, 400 bar, and redox conditions buffered by pyrite-pyrrhotite-magnetite equilibrium.

Magma evolution leading to veinlet-disseminated tungsten mineralization at the Muguayuan deposit: In-situ analysis of igneous minerals

Whole rock geochemistry combined with spatially resolved geochemistry of zircon, apatite, biotite and plagioclase allows us to uncover the magmatic processes leading to ore formation at the Muguayuan deposit. The Sanxianba granite, associated with the Muguayuan veinlet-disseminated scheelite deposit, is located in the middle of the Jiangnan Orogen. Whole rock Sr and Nd isotopes, and zircon Lu-Hf isotopes suggest it might originate from the Neoproterozoic Banxi group strata. The Rb element modeling shows that, after ~35% of partial melting, the Banxi group metasandstone can generate the primary Sanxianba melt with 164 ppm Rb and 21 ppm W. The intra-/intercrystal texture and compositions of zircon and plagioclase indicate that W and other elements such as HREE, Th, U, Nb, Ta, and P increase in the melt during fractional crystallization. The water content in the early Sanxianba magma, calculated through the plagioclase-hydrometer, is ~4.4 wt%, and its enrichment in the melt is reflected by the increasing water content in biotite with fractionation. F content in the early apatite is relatively high and invariable but further elevated in the late apatite. Chlorine, LREE and Na contents in the early apatite also present an enrichment trend. When H2O and Cl start to be saturated with the magma fractionation in the deep magma chamber, Cl-, Na-, and LREE-rich but W-poor fluid exsolves from the melt, resulting in the albitization and chloritization of feldspar and biotite phenocrysts, respectively. The subsequent decrease of Cl, Na2O and La2O3 in the late apatite record this first fluid exsolution. Fluorine, P, H2O and W continue to enrich in the evolved melt with fractionation after the Cl-rich fluid exsolution. These fluxing components reach oversaturation during the shallow-ward emplacement of the magma, forming the F-, P- and W-rich fluids. The apex of the intrusion cools and forms a solid barrier, which prevents the escape of fluids. The exsolved fluids from the underlying magma continuously supply upward and react with the apex along fractures, resulting in greisenization and phyllic alteration. During alteration, Ca is released from calcium-rich plagioclase and combines with tungsten in the fluids to form scheelite mineralization. Magma evolution leading to the tungsten mineralization may be also the general scenarios in the other granite-related veinlet-disseminated scheelite deposits.

Magmatic volatiles and platinum-group element mineralization in the Stillwater layered intrusion, U.S.A.

Abstract The activity of volatile-rich fluids may be important in the evolution of basaltic magmatic systems and associated precious metal ore formation. There is evidence for Cl-rich fluids within the Stillwater Complex (Montana, U.S.A.), which have been linked to platinum and palladium mineralization in the economically important Johns-Manville (J-M) Reef ore body. We present the first data set for heavy halogens (Cl, Br, and I) and natural noble gas isotopes in bulk rock and mineral separates from the Peridotite Zone and the Olivine-Bearing Zone I of the Stillwater Complex, including samples from the J-M Reef and G Chromitite bodies. Our data reveal concentrations of 4 to 13 500 ppm for Cl, 26 ppb to 360 ppm for Br, and &amp;lt;1 ppb to 9 ppm I over the whole sample set. Cl, Br, and I correlate well with each other implying a shared process and/or distribution in mineral species. Br/Cl and I/Cl ratios span a range from 0.3 to 35 × 10−3 and 5 to 900 × 10−6 by weight, respectively, encompassing MORB-like to more enriched compositions, particularly for Br/Cl. High-Br/Cl ratios compared to MORB in some Stillwater samples suggest fractionation of halogens during the exsolution of a volatile-rich fluid to explain the most Br-enriched samples. More generally, the presence of minerals such as scapolite, hornblende, and apatite in the most halogen-enriched samples suggests that the halogen-bearing fluids were derived from the cooling of the intrusion rather than late-stage (low-temperature) metamorphism. The combined halogen abundance and noble gas isotope data set imply that crustal contamination may have played a limited role in the crystallization of pegmatoids and the G Chromitite but is not required to account for the halogen budget of the J-M Reef. High-halogen contents in the sulfide-bearing J-M Reef and associated lithologies are consistent with the influence of fluid-related activity during platinum-group element (PGE)-Reef formation, lending weight to the hydromagmatic model for mineralization in the Stillwater intrusion. Our new data also imply chalcophile tendencies of Br and I over Cl in sulfides in natural systems, hinting at the importance of sulfide liquid interaction with halogen-rich fluids in the formation of sulfide-hosted precious metal ore deposits.

Effect of salinity, pressure and temperature on the solubility of smithsonite (ZnCO3) and Zn complexation in crustal and upper mantle hydrothermal fluids

Modelling the reservoirs and fluxes of Zn in Earth's crust and mantle requires data on the solubility of its mineral hosts and ores in coexisting fluids, as well as on the complexation of Zn in these fluids as a function of fluid composition, pressure, and temperature. However, due to experimental challenges, the availability of such data is limited to pressures below 1 GPa, which are only representative of upper crust conditions.Here, we report the effects of salinity (0–4.5 m total Cl), pressure (0.5–6 GPa) and temperature (25–400 °C) on the solubility of smithsonite (ZnCO3) and speciation of Zn in aqueous fluids. Solubilities at mineral-fluid equilibria and Zn speciation in the coexisting aqueous fluids were determined in situ at high pressure-temperature (P-T) conditions by synchrotron X-ray fluorescence (XRF) and X-ray absorption spectroscopy (XAS) using resistively heated diamond anvil cells (RH-DAC). The solubility of smithsonite increases with salinity, pressure, and temperature. In agreement with previous studies, conducted at lower pressures (below 1 GPa), we observed a gradual transition from octahedral hydrated [Zn(H2O)6]2+ to tetrahedral hydrated and chlorinated [Zn(H2O)4-nCln]2-n (n = 1–4) complexes with increasing salinity and temperature. Our results suggest that these tetrahedral complexes remain stable under the conditions relevant to cold slab dehydration. This change of coordination further enhances the solubility of smithsonite in Cl-rich fluids and provides a likely mechanism for the efficient uptake of Zn by slab-derived fluids.

Compositional Variations of Apatite and REE-Bearing Minerals in Relation to Crystallization Trends in the Monchepluton Layered Complex (Kola Peninsula)

Abstract ––We have investigated the compositional variations of apatite (Ap) and rare-earth element (REE) minerals in the Monchepluton layered complex on the Kola Peninsula. On the basis of large sets of pertinent analytical data, we have estimated geochemical trends involving major, minor, and trace elements and studied their relation with the compositions of rock-forming silicate and oxide minerals. The variations observed in Ap differ considerably from trends reported for other layered intrusions. The composition fields of Ap are not consistent with the variations in the chemical composition of the bulk rocks and their constituent minerals, as determined along the representative cross sections of the entire complex. The compositional variations of Ap are fairly similar in all units of the complex. Chlorapatite (&amp;gt;6 wt.% Cl) is invariably abundant. There is no relationship between the Cl content of Ap and the degree of magnesium enrichment of the coexisting early magmatic silicates. In the F–Cl–OH diagram, broad fields of ternary solid solution are observed. There are no compositions along the Cl–F axis. The compositions of Ap are notably poor in Cl in the marginal series (the Nyud massif) and correspond to hydroxylapatite with a high content of fluorapatite component. Two composition fields of Ap are recognized in the Monchepluton complex: ≤3 wt.% and &amp;gt;6 wt.% Cl; there are, however, extensive overlaps. Two generations of apatite are thus implied. The first nucleated at the early stage of crystallization of H2O-bearing intercumulus melt as a result of substantial increase in the contents of P, F, Cl, and other incompatible components. The following stage of degassing of the crystallizing melt caused a decoupling of Cl and F. Fluorine remained mostly in the melt; in contrast, Cl was partitioned efficiently into an H2O-bearing fluid phase. At the early stage, the apatite incorporated combinations of hydroxylapatite and fluorapatite, with a low content of Cl. At the late stage, chlorapatite crystallized from a Cl-rich fluid, and ferrochloropargasite (4.1 wt.% Cl) formed in the Poaz massif as a result of autometasomatic alteration via reactions of this fluid with plagioclase and pyroxene. The apatite has high Sr contents (up to 4.1 wt.% SrO) in the highly magnesian cumulates of the Dunite block and the massifs of mounts Kumuzh’ya, Nittis, and Travyanaya. This enrichment illustrates the accumulation of Sr in the intercumulus melt, in which Ap was the only Sr-bearing phase in the absence or scarcity of intercumulus plagioclase. The REE contents also increased in the intercumulus melt and led to the formation of monazite-(Ce), REE-bearing Ap, and allanite-(Ce) in the remaining microvolumes of melt. Loveringite and Ap crystallized as coexisting phases in Mt. Sopcha. For the first time in a layered intrusion, an extensive range of compositions is documented in the Ce–La–Nd diagram for the REE-bearing phosphates (monazite and REE-rich apatite), which display a predominant La ↔ Nd substitution at the constant contents of Ce.

The prograde-to-retrograde evolution of the Huangshaping skarn deposit (Nanling Range, South China)

Huangshaping is a world-class skarn deposit hosting abundant W–Sn polymetallic mineralization in the Nanling Range, South China. Although the geochemistry of skarn-hosted mineral deposits has been extensively studied, the role of the prograde-to-retrograde stage transition in the enrichment and precipitation of metallic elements in high-temperature systems has received little study to date. Here, we analyzed garnet, scheelite, and cassiterite in high-temperature granite porphyry-related W–Sn polymetallic system of the Huangshaping deposit to investigate these processes. Three generations of garnet (Grt I, Grt II, and Grt III), two generations of scheelite (Sch I and Sch II), and two types of cassiterite (Cst I and Cst II) were distinguished with regard to their mineral associations, microscopic characteristics, and geochemical features. The results show that grossular–andradite garnet formed from Al-rich andradite (Grt I, Al2O3: 8.18 wt%) in the early prograde stage and pure Fe-andradite (Grt III, Al2O3: 0.15 wt%) in the late prograde stage. Mo-rich scheelite (Sch Ia, MoO3: 19.41 wt%) formed in the prograde stage and coexisted with Grt III, sharing the same REE patterns. A shift from HREE enrichment in Grt I to HREE depletion in Grt III reflects progressive uptake of REEs by secondary mineral phases. Grt III has the highest average contents of W (905 ppm), Mo (19 ppm), and Sn (5610 ppm), suggesting an enrichment of metallic elements at the end of the prograde stage. In contrast, Mo-poor scheelite (Sch II, MoO3: 0.63 wt%) co-crystallized with molybdenite and fluorite in the retrograde stage and shares similar REE patterns with the granite porphyry. Skarn mineralization at Huangshaping was a two-step process controlled by metamorphic stage. The prograde stage was characterized by high temperatures and fO2 and a Cl-rich fluid, and it resulted in enrichment of ore-forming elements with minor scheelite precipitation. The retrograde stage was characterized by lower temperatures and fO2 and a F-rich fluid, and it resulted in major precipitation of ore minerals (scheelite, molybdenite, and cassiterite). Dissolution–reprecipitation reactions played an important role in extraction of metallic elements from decomposing anhydrous skarn minerals and formation of ore minerals. A decrease in the high-field-strength element (HFSE) content of cassiterite from proximal skarn (Cst I) to distal skarn (Cst II) indicates declining temperature accompanied by precipitation of fluorite. This study examines the transition from the prograde stage to the retrograde stage in the Huangshaping deposit, and it provides insights into the genesis of other skarn W–Sn polymetallic deposits in the Nanling magmatic–tectonic–metallogenic belt.