Magmatic-hydrothermal Systems Research Articles

Unravelling the effects of magmatic fractionation, fluid phase separation and dilution on the composition of magmatic-hydrothermal fluids of the Cornubian Batholith (SW England)

The compositional evolution of magmatic-hydrothermal fluids from the SnW mineralized Cornubian batholith was investigated via in situ fluid inclusion LA-ICP-MS microanalysis and reveals a large degree of variation between intrusive stages and at the sample scale, with complexities due to superposition of several mechanisms affecting fluids chemistry during the protracted evolution of the batholith. Despite large ranges of salinities (from <1 wt% to 48 wt% NaCleq.), the effects of individual processes such as magmatic differentiation, fluid saturation and boiling, fluid mixing and dilution can all be discerned on the basis of fluid inclusion trace element geochemistry combined with detailed petrography and microthermometry.In all samples, different fluid types (aqueous liquid-rich, vapor-rich and brine inclusions) were identified in variable proportions and microthermometry revealed complex temporal trends. Granite-related samples from the G5 intrusive stage are characterized by intermediate density fluids undergoing magmatic fractionation under pressure conditions above 1.5 kbar, indicated by successively decreasing fluid salinities with concomitant increases in Li, B, Rb and Cs concentrations. The latter two elements later strongly partitioned in the brine phase upon boiling, together with most of the other Cl-complexing elements (e.g., Fe, Mn, Pb, Zn). Those brines subsequently underwent progressive dilution with meteoric waters that caused a decrease in the concentration of all elements (besides B) and homogenization temperatures. In G3 granite from Dartmoor, on the other hand, brine inclusions represent the earliest fluid type while intermediate density fluids are absent, and a large salinity range in the fluid inclusion record associated with a decrease in homogenization temperatures represents their progressive dilution with meteoric fluid. The lack of intermediate density fluids at Dartmoor indicates fluid exsolution at relatively low pressures resulting in immediate phase separation into brine and vapor.All studied samples associated with ore mineralization display only the trend of dilution of high-salinity magmatic fluids. Their transition metal contents (e.g. Fe, Mn, Pb and Zn) show the expected positive correlation with salinity of the fluids. Conversely, the compositional trends observed for Sn and particularly W are more enigmatic, as they do not appear to significantly fractionate during most of the physicochemical processes outlined above and appear to be unrelated to fluid salinity, opposite of what would be expected for Sn as it is dominantly transported in Cl-complexes.This study highlights the key advantages of high-resolution geochemical fluid inclusion studies in discerning a variety of magmatic and post-magmatic processes in fluids in comparison to bulk fluid inclusion techniques or more simplistic fluid inclusions studies which might overlook important aspects of the typically complex history of fluids evolution in magmatic-hydrothermal systems.

The role of iron-rich hydrosaline liquids in the formation of Kiruna-type iron oxide-apatite deposits.

Kiruna-type iron oxide-apatite (IOA) deposits, an important source of iron, show close associations with andesitic subvolcanic intrusions. However, the processes of ore formation and the mechanism controlling iron concentration remain uncertain. Here, we report the widespread presence of high-temperature (>800°C) water-poor multisolid hydrosaline liquid inclusions in pre- and syn-ore minerals from IOA deposits of eastern China. These inclusions consistently homogenize to a liquid phase by vapor disappearance and mostly contain 3 to 10 wt % Fe, signifying a substantial capacity for iron transportation by such hydrosaline liquids. We propose that the hydrosaline liquids were likely immiscible from the dioritic magmas with high Cl/H2O in subvolcanic settings. Subsequent reaction with host rocks and/or decompression and cooling of the hydrosaline liquids is deemed responsible for the simultaneous formation of high-temperature alteration and magnetite ores, thereby providing important insights into the distinctive characteristics of IOA deposits in shallow magmatic-hydrothermal systems.

Mineralogical evidence for the role of deep magmatic fluids in beryllium enrichment in magmatic-hydrothermal systems

Vein-type and greisen-type beryllium (Be) mineralization is closely associated with the magmatic-hydrothermal evolution in highly fractionated granites. However, the source of ore-forming fluids and their role in the migration and enrichment of Be is poorly understood. Although whole rock Ba-Rb isotope researches highlight that even deep magmatic fluids beneath the shallow magmatic-hydrothermal systems could provide rare metals and promote mineralization, it is still challenging to determine the influences of such fluids via using conventional geochemical indicators. Here we present zircon-monazite-xenotime-wolframite U-Pb ages, whole-rock geochemistry, monazite Nd isotopes, as well as muscovite and beryl geochemistry for the Zhujiayingzi quartz vein-type Be mineralization in the southern Great Xing’an Range (SGXR), Northeast (NE) China, and introduce the neighboring Nasigatu gresien-type Be mineralization for comparison. Geochronological results reveal that the Zhujiayingzi beryl-wolframite-bearing quartz veins formed in the Early Cretaceous (149–147 Ma), much younger than the host Permian (270–267 Ma) crystal tuffs, but coeval with the Nasigatu highly fractionated alkali-feldspar granite (144–139 Ma). Similar muscovite-beryl compositions and monazite Nd isotopes, combining with their close temporal-spatial relationships indicate that the Zhujiayingzi and Nasigatu Be mineralization have consistent hydrothermal assemblages and enrichment processes. Higher silica, K, and lower Al contents of muscovites from Be-rich veins (M2) and greisens (M4) than those recorded in barren crystal tuffs (M1) and alkali-feldspar granite samples (M3) at both Zhujiayingzi and Nasigatu are consistent with the evolution of the Early Cretaceous granitic magma, proving the involvement of shallow magmatic fluids exsolved from the Nasigatu-like highly evolved granitic melts. However, ore-related M2 and M4 samples have higher Mg (>1 wt%) and Ti contents than those of M1 and M3 samples, which violates the conventional hydrothermal evolution trend. Trace element compositions as well as K/Rb, K/Cs, and Rb/Sr ratios of four-type muscovites, together with the core-rim geochemical variations of muscovites at Zhujiayingzi and beryls at Nasigatu, indicate the existence of deep magmatic fluids rather than fluid-rock interaction to account for the anomalous mineralogical evidence. Such deep magmatic fluids were exsolved from large silicic magmatic reservoirs beneath the shallow magmatic-hydrothermal system, and thus likely display low evolution degrees and high Mg-Ti contents. They can not only provide heat and promote fluid-mineral interactions, but also can efficiently extract and transport Be enriched in deep crystal mushes at different depths. Thus we invoke that the Early Cretaceous Be mineralization in the SGXR was achieved under the combined action of both shallow and deep magmatic fluids derived from the crystal mush-dominated transcrustal magmatic system.

Magmatic evolution of the Kolumbo submarine volcano and its implication to seafloor massive sulfide formation

AbstractSeafloor massive sulfides form in various marine hydrothermal settings, particularly within volcanic arcs, where magmatic fluids may contribute to the metal budget of the hydrothermal system. In this study, we focus on the Kolumbo volcano, a submarine volcanic edifice in the central Hellenic Volcanic Arc hosting an active hydrothermal system. Diffuse sulfate-sulfide chimneys form a Zn-Pb massive sulfide mineralization with elevated As, Ag, Au, Hg, Sb, and Tl contents. These elements have similar behavior during magmatic degassing and are common in arc-related hydrothermal systems. Trace-element data of igneous magnetite, combined with whole rock geochemistry and numerical modelling, highlights the behavior of chalcophile and siderophile elements during magmatic differentiation. We report that, despite early magmatic sulfide saturation, chalcophile element contents in the magma do not decrease until water saturation and degassing has occurred. The conservation of chalcophile elements in the magma during magmatic differentiation suggests that most of the magmatic sulfides do not fractionate. By contrast, upon degassing, As, Ag, Au, Cu, Hg, Sb, Sn, Pb, and Zn become depleted in the magma, likely partitioning into the volatile phase, either from the melt or during sulfide oxidation by volatiles. After degassing, the residual chalcophile elements in the melt are incorporated into magnetite. Trace-element data of magnetite enables identifying sulfide saturation during magmatic differentiation and discrimination between pre- and post-degassing magnetite. Our study highlights how magmatic degassing contributes to the metal budget in magmatic-hydrothermal systems that form seafloor massive sulfides and shows that igneous magnetite geochemistry is a powerful tool for tracking metal-mobilizing processes during magmatic differentiation.

Origin of fluids in the Lancangjiang tin belt, southwestern Yunnan Province, China: Evidence from trace element and boron isotopic compositions of tourmaline

The Lancangjiang tin belt is located on the eastern margin of the Tibetan Plateau, which is in the northern part of the Southeast Asian tin belt that contains Sn, W, and base metal ore deposits. Tourmaline alteration and high B contents are typical features of the magmatic–hydrothermal systems in the Lancangjiang tin belt. Our new data for tourmaline intergrown with cassiterite reveal complex geochemical features that provide important insights into the origins of ore-forming fluids in this B-rich tin belt. Most of the tourmaline in the Sn deposits and metamorphic rocks belongs to the alkali-group dravite series, except for some that is part of the X-vacant group. The tourmaline compositions differ among the ore districts, but all exhibit Fe-poor (0.61–1.08 apfu) and Mg-rich (1.43–2.06 apfu) compositions, with Fe/(Fe + Mg) = 0.18–0.46. Most trace elements in the tourmaline occur at low contents (<50 ppm), including the large-ion lithophile elements (e.g., Cs and Ba) and high-field-strength elements (e.g., Nb, Ta, Hf, and Th). However, some trace elements (e.g., Zn, Sr, and V) and Sn have high contents (up to several hundreds or thousands of ppm). The δ11B values of tourmaline from the Sn deposits range from −14.7 ‰ to −11.3 ‰, except for those in the Man Makhsan Sn deposit, which range from −12.0 ‰ to −8.1 ‰. The δ11B values (−14.7 ‰ to −8.1 ‰) and the positive correlation between Sn contents and Nb/Ta, Al/Ga, and K/Cs ratios in the ore-related tourmaline indicate that the exsolved ore-forming fluids were derived from highly fractionated S − type granitic magmas. The fluids were mainly B-, Sn-, and Al-enriched. The low Fe/(Mg + Fe) ratios, high oxygen fugacity, and Al saturation were favorable for cassiterite precipitation, and are proxies for the ore-forming potential of large-scale Sn deposits.

Geochemistry of hydrothermal illitizations in Eocene Kösedağ magmatic rocks, Zara-Suşehri area, NE Sivas, East-Central Anatolia: Origin and age of alteration

The study area located at the periphery of the collision zone between the Eurasian plate (i.e. Pontides) and Tauride-Anatolide platform, NE of Sivas in the east-central Turkey, which is part of the Tethyan Metallogenic Belt. Mixed-layer illite-smectite (IS) and illite minerals are derived within the hydrothermal alteration zones with a few km2 surface areas (up to 30 km2) in Eocene volcanic and plutonic rocks. The representative IS and illite samples taken from plutonic- and volcanic-hosted alteration zones are investigated by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), major and trace elements and OH isotope geochemistry and KAr dating methods. Different types of hydrothermal alterations, such as propylitic and phyllic alteration in the plutonic rocks and argillic alteration in the volcanic rocks were developed as a result of intrusion of Kösedağ Pluton (syenite) into Karataş Volcanics (basaltic trachy-andesite and trachyte) with relations of hot-hot contact. The main phyllosilicate/clay minerals are characterized by kaolinite and IS in volcanic-hosted argillic alteration zones, whereas IS and illite in plutonic-hosted phyllic zones. The ordering types (Reichweite) of IS and illites are represented by R1 IS (I = 65–80 % in IS) + R3 IS (I = 90 % in IS) in the volcanic-hosted rocks, and R3 IS (I = 90 % in IS) and illite (S = 3–5 %). Dioctahedral (d060 ≤ 1.500 Å) R3 IS and illites have 1 Md + 1 M and 1 Md + 1 M + 2 M1 polytypes, respectively. The major and trace elements such as TiO2, Fe2O3, MgO, Na2O, P2O5, Sc, V, Cu, Ge, Sr, Hf, Zr and Y increase in the volcanic-hosted IS, whereas SiO2, Al2O3, K2O, Pb, W, Mo, As, Sb, Rb and U in the plutonic-hosted IS and illites. The chondrite-normalized distributions of IS and illites present a great similarity to those of host rocks. The chondrite-normalized rare earth element (REE) concentrations are more enriched in the volcanic-hosted IS in comparison with the plutonic-hosted IS and illites having distinctive Eu negative anomaly, which indicate deriving from volcanic matrix and K-feldspar, respectively. Oxygen and hydrogen isotope data of illitic clays indicate that the hydrothermal fluids are originated from magmatic water. According to stable isotopes and fluid inclusion data, IS and illites were formed at the temperature conditions ~150 °C in volcanic-hosted argillic zone, whereas ~250 °C in plutonic-hosted phyllic zones. KAr dating of alunite, IS and illite minerals indicate that the hydrothermal alteration was started at 40.45 ± 1.28 Ma, almost 2 Ma after the Q-syenite intrusion, within the plutonic body as phyllic alteration stage, and continued up to 35.27 ± 2.81 Ma, with a duration of ~5 Ma, and finalized before the exhumation of the Kösedağ Pluton (28–30 Ma). The geochemical characteristics of IS and illites were controlled by host-rock, condition, origin, and ages of alterations and they can be used as an important tool for magmatic-hydrothermal systems.

Physico-chemical constraints associated with hypogene hydrothermal alteration and supergene oxidation at the Farallón Negro intermediate-sulfidation epithermal Au-Ag deposit, NW Argentina

The Farallón Negro deposit is located in the Farallón Negro Volcanic Complex (FNVC; ∼9.40 to 4.88 Ma) in NW Argentina and includes intermediate-sulfidation, epithermal Au-Ag mineralization in the Alto de la Blenda deposit. Detailed mineralogical and geochemical investigations of the Esperanza-Esperanza Sureste, Cecilia veins, both hosted in the Alto de la Blenda monzonite, and the Laboreo vein, hosted in the volcaniclastic Morada Central andesitic breccia, reveal four hypogene vein stages. Each of these four stages are comprised of a texturally early quartz, followed by a sulfide-sulfosalt and a late Mn-carbonate sub-stage. Stage 1 is characterized by a quartz, base metal and Mn-carbonate sub-stage showing high δ18OVSMOW (δ18OQuartz = 13.7 ± 0.4‰ and δ18OMn-Calcite = 11.6 ± 0.2‰) and low δ13CVPDB values (δ13CMn-Calcite = –4.7 ± 0.2‰). Stage 2 includes most gold and silver minerals in a tennantite-tetrahedrite-sphalerite-pyrite-galena±electrum sub-stage. Fluid inclusions trapped in vein-anhydrite, only associated with stage 2, record the highest temperatures (TEntrapment = 327–335°C) and highest salinity (3.8NaCleq.wt.%) when compared to all other stages. Stage 2 quartz (δ18OQuartz = 9.9 to 11.9‰) and carbonate display lower δ18OVSMOW (δ18OMn-Calcite = 7.9 to 10.3‰), as well as lower δ13CVPDB values (δ13CMn-Calcite = -5.2 to 4.7‰) than all other stages. Stages 3 and 4 consist of barren quartz and carbonate sub-stages that show lower temperatures (TEntrapment = 187–262°C) and higher δ18OVSMOW (δ18OQuartz = 13.4 to 13.9‰ and δ18OMn-Calcite = 10.7 to 11.8‰) and δ13CVPDB values (δ13CMn-Calcite = –3.5 to −3.9‰) when compared to earlier stages.Petrographic, sulfide mineral chemistry, microthermometric, and stable isotope data combined with distinct alteration mineral assemblages allow the reconstruction of a model for the Alto de la Blenda deposit. During the hypogene hydrothermal fluid flow stage, around 7.16 Ma, at ∼2.2 km depth (PHYDROSTATIC = 220 bars), the high temperature alteration mineralogy, low fluid salinities and 18O and 13C isotope compositions indicate cooling of ascending magmatic-hydrothermal fluids. These fluids were derived from a contracted magmatic vapor phase that exchanged with unexposed sedimentary rocks of the Sierras Pampeanas. Hypogene quartz-R3 illite/smectite-chlorite-calcite-pyrite alteration in the andesitic-breccia and quartz-illite-R3 illite/smectite-chlorite-calcite-pyrite alteration in the monzonite are temporally and spatially to the hydrothermal vein minerals deposited between 187 and 335°C. During the post-hydrothermal supergene weathering event, around 2.70 Ma, sulfuric acids generated by meteoric fluids and supergene oxidation of hypogene sulfides, particularly pyrite, descended along normal fault zones and related vein and fracture networks to at least 450 m depth below the surface level, forming the supergene alteration assemblage of dioctahedral smectite-kaolinite-Mn-/Fe-oxides/-hydroxides-gypsum±interstratified chlorite/smectite±interstratified R1 illite/smectite in both wall rock types at temperatures <50°C.The dominant hypogene alteration assemblage, present in the monzonite and volcaniclastic andesitic breccia, may be indicative of deeper-seated, transitional magmatic-hydrothermal systems (>1 km depth), generally controlled by fluid cooling, as is the case at Farallón Negro. Pervasive supergene alteration can conceal these systems but the identified supergene alteration assemblage of dioctahedral smectite-kaolinite-interstratified chlorite/smectite-interstratified R1 illite/smectite that replaces the hypogene alteration assemblage along the permeable fault, vein and fracture zone network may present a useful vectoring tool towards concealed, deeper-seated, epithermal Au-Ag mineralization in arid climates.

Tectonic and Crustal Processes Drive Multi-Million Year Arc Magma Evolution Leading up to Porphyry Copper Deposit Formation in Central Chile

Abstract Subduction zone magmatism is a major control of volcanism, the generation of modern continental crust and the formation of economically important porphyry Cu–(Mo–Au) deposits. Reading the magmatic record of individual arc segments and constraining the rates of magmatic changes are critical in order to fully understand and quantify the processes that drive magma evolution in subduction settings during arc growth. This study focuses on the San Francisco Batholith and the Rio Blanco-Los Bronces porphyry deposit cluster in central Chile, which provides an igneous rock record over ~13.5 Myr of arc evolution. We use whole-rock geochemistry, zircon geochronology and Hf isotope geochemistry to track changes in the crustal magmatic system of this arc segment during crustal thickening and porphyry Cu deposit formation. By combining the analytical dataset with Monte Carlo fractional crystallisation and assimilation fractional crystallisation modelling, we test a model for significant crustal involvement during magma evolution. Systematic and continuous increases in Dy/Yb, La/Yb, V/Sc and Sr/Y in the magmas over time indicate a transition in the main fractionation assemblage from plagioclase-dominated to amphibole-dominated that reflects deeper crystallisation and/or a higher meltwater content. Concomitant decreases in εHf and Th/La as well as increasing Ba/Th are best explained by assimilation of progressively deeper crustal lithologies from low (Chilenia) to high Ba/Th (Cuyania) basement terranes. Our study highlights that an increasingly hydrous magma and a deepening locus of crustal magma differentiation and assimilation, driven by crustal thickening contemporaneous with increased tectonic convergence and ingression of the aseismic Juan Fernandez ridge, can account for all investigated aspects of the multi-Myr magmatic evolution leading up to the formation of the Rio Blanco-Los Bronces porphyry Cu deposits. Our findings corroborate the importance of high-pressure differentiation of hydrous magma for the formation of Andean-style porphyry deposits. Once magmas favourable for porphyry Cu mineralisation were generated in the lower crust, multiple episodes of efficient magma migration into the upper crust fed several, discrete, shallow magmatic-hydrothermal systems over ~3.5 Myr to form the world’s largest known Cu resource at Rio Blanco-Los Bronces.

Copper skarn mineralization related to reduced monzodioritic magma at the Huanren deposit, northeastern China

Most known copper (Cu) skarns are associated with oxidized intrusions. In this contribution, we report a Cu skarn associated with a reduced monzodioritic intrusion at Huanren, northeastern China, which contains 0.41 Mt of Cu accompanied by economic concentrations of Zn, Pb, Fe, Mo, and Ag. Copper-polymetallic mineralization in the Huanren deposit is concentrated in skarns located between the contacts of the monzodiorite (SiO2 = 52−55 wt%) and the Cambrian carbonate rocks, with minor molybdenite-bearing veinlets/veins and dissimilated chalcopyrite mineralization hosted within the monzodiorite. Laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS) U-Pb zircon geochronology indicates the monzodiorite crystallized at 125.4 ± 0.6 Ma (2σ). Isotope dilution (ID)-ICP-MS Re-Os molybdenite geochronology indicates mineralization at Huanren occurred at 125.3 ± 0.8 Ma (2σ). Whole-rock major- and trace-element and zircon Hf isotopic compositions suggest enriched (subduction metasomatized) lithospheric mantle−derived sources for the parental magma of the monzodiorite without significant crustal assimilation. Zircon trace-element and magmatic apatite major-element compositions indicate the reduced nature of the monzodiorite, as evidenced by low magmatic oxygen fugacity (fayalite-magnetite-quartz [FMQ] buffer = −1.09 ± 0.19) and negligible apatite SO3 contents (&amp;lt;0.05 wt%). A reduced magmatic-hydrothermal system at Huanren is also supported by the predominance of magmatic ilmenite over magnetite in the monzodiorite and by the presence of pyrrhotite and the absence of anhydrite and hematite in the ore. Chalcopyrite from the Huanren deposit has an average δ34S value of 4.34‰ ± 0.88‰ (1σ), which is clearly higher than values from most porphyry-skarn Cu ± Mo ± Au deposits. Accordingly, we suggest that interaction between (1) external oxidized fluids equilibrated with evaporites and (2) reduced Cl-bearing magmas and related exsolved fluids may have played a critical role in the formation of the Huanren Cu skarn by increasing the ability of fluids to scavenge Cu from the reduced magma and subsequently precipitate Cu in the carbonate rocks. This study defines a new type of Cu skarn and thereby opens new potential for Cu skarn exploration proximal to intrusive units previously deemed too reduced to be Cu fertile, especially in non-arc settings. Moreover, we conclude that the availability of Cl and S in magmatic-hydrothermal systems may be as critical as fO2 in facilitating the actual ore-forming event in Cu skarn systems.

Hyperspectral mapping of magmatic-hydrothermal sericite, Battle Mountain mining district, Nevada

We demonstrate the utility of multi-scale imaging spectroscopy data (hyperspectral data) to differentiate magmatic-hydrothermal sericite from other white micas based on grain size, in a case study of the Battle Mountain mining district in Humboldt and Lander Counties, Nevada. The Battle Mountain mining district contains porphyry, skarn, and distal disseminated deposits that formed in magmatic-hydrothermal systems, as well as sedimentary-rock hosted gold deposits of less certain origin. We generated spectral-based mineral maps of the Battle Mountain mining district to examine the spatial distribution of spectrally dominant minerals such as kaolinite, montmorillonite, and white micas (muscovite, sericite, and illite). We then used spectral-based mineral mapping to characterize the grain size and composition of white micas, enabling us to differentiate igneous muscovite from magmatic-hydrothermal sericite. By integrating our spectral-based maps with geologic mapping, airborne aeromagnetic data, and prior studies on mines and deposits in Battle Mountain, we determined that finer grained, higher Al sericite spatially correlated with the footprints of known magmatic-hydrothermal systems and is interpreted as forming from magmatic-hydrothermal alteration. Larger grained, lower Al muscovites are distal from known magmatic-hydrothermal systems and are interpreted as being igneous derived siliciclastic sediments that became constituents of the host sedimentary rocks. Techniques described in this contribution can be applied to any appropriate hyperspectral data, regardless of sensor type used to collect the data.

Fluorine enrichment and mineralization in magmatic-hydrothermal systems

Fluorine enrichment and mineralization in magmatic-hydrothermal systems

Hydrothermal monazite and xenotime chemistry as genetic discriminators for intrusion-related and orogenic gold deposits: implications for an orogenic origin of the Pogo gold deposit, Alaska

Attempts to geochemically distinguish between metamorphic-hydrothermal systems that form orogenic gold deposits and both reduced and oxidized magmatic-hydrothermal systems using isotopes or metal associations have proven ambiguous, particularly for orogenic gold and reduced intrusion-related gold systems. The absence of conclusive geochemical discriminators and the overlap in geologic characteristics have led to gold deposit models being potentially incorrectly applied, which in turn negatively affect regional mineral exploration and mine planning. In this study, in situ electron microprobe geochemical analyses of hydrothermal monazite and xenotime crystals associated with different types of gold-bearing deposits are shown to be effective geochemical discriminators. There are notable differences in mineral chemistry such as rare earth element (REE) profiles, total light REE, Dy, Er, Pr, Y, Nd/Sm, and La/Sm that distinguish monazite precipitated from metamorphic-hydrothermal fluids that form orogenic gold deposits and those precipitated from magmatic-hydrothermal fluids that form both porphyry Cu-Mo-Au and reduced intrusion-related gold deposits. Notable differences in overall xenotime abundances and concentrations of heavy REEs, Ca, and Sc are distinctive between the different deposit classes for xenotime. The origin of the controversially classified Pogo gold deposit, Tintina gold province, Alaska, which has been characterized as both a reduced intrusion-related and an orogenic gold deposit, is tested based upon the noted chemical differences associated with these hydrothermal phosphates. The findings of this study have implications for exploration and mine development in the Tintina gold province and other areas that contain deposits that are controversially classified as either orogenic or as magmatic-hydrothermal gold deposits.

Enrichment of Se-Te-Au in the Jilongshan Au-Cu Skarn Deposit, Hubei Province: Insight from Pyrite Texture and Composition

Selenium and Te are two important critical metals, which are often produced as by-products in Au-Cu deposits related to magmatic–hydrothermal systems, such as porphyry and skarn deposits. The Jilongshan Au-Cu deposit is a typical skarn deposit located in the middle and lower parts of the Yangtze River metallogenic belt. Previous studies show that it has valuable Se and Te resources, but their occurrence, particularly the relationship between the texture and composition of pyrite, and the enrichment mechanism of Se, Te, and Au remain unclear. Here, the textures and the major and trace elements of the Jilongshan pyrites were studied by using an optical microscope, EMPA, and LA-ICP-MS to reveal the occurrence of Se, Te, and Au in pyrite, as well as their genetic links with the pyrite mineralogical signature. The results show that there are three types of ores in the Jilongshan deposit, including granite porphyry-hosted, skarn-hosted, and carbonate-hosted ores. All of these ores contain major amounts of pyrite, which can be divided into four different generations. The first generation of pyrite (Py1) belongs to sedimentary genesis with a typical framboid texture and its Co/ Ni ratios are less than 1, whereas Py2, Py3, and Py4 belong to hydrothermal genesis and their Co/ Ni ratios are between 1.0 and 30.2. Selenium concentrations in Py2 and Py3 are relatively high (median, 138 ppm and 344 ppm, respectively), which are mainly present as isomorphism and a small amount as selenite in pyrite. Compared with granite porphyry-hosted and skarn-hosted ores, pyrite from carbonate-hosted ores has the highest Se concentrations. The latest generation of pyrite (Py4) contains the highest concentrations of Te (average, 140 ppm) and Au (average, 12 ppm) among the hydrothermal pyrites. Therefore, the precipitation of Se mainly occurs in pyrite during the early high-temperature stage, whereas higher concentrations of Te and Au are mainly enriched in pyrite during the late stage with low temperatures.

Modeling the behavior of sulfur in magmatic systems from source to surface: Application to Whakaari/White Island, Aotearoa New Zealand, and Etna, Italy

Our understanding of the role of volcanoes in the global sulfur cycle and how volcanic gas emissions can be used to monitor volcanoes is limited by the complex interactions between hydrothermal systems and volcanic sulfur emissions. Hydrothermal systems influence the amount and speciation of volcanogenic sulfur, which is ultimately released to the surface and atmosphere via a range of physicochemical processes. To understand the effect of the hydrothermal system on surface emissions, we model the magmatic-hydrothermal systems at Whakaari/White Island, Aotearoa New Zealand, and Etna, Italy. We quantify the magmatic sulfur inputs using mass balance and MELTS modeling (thermodynamic model of crystallization); model the effects of degassing using Sulfur_X (an empirical model of melt-gas equilibria); and model the influence of the hydrothermal system using CHIM-XPT and EQ3/6 (thermodynamic and kinetic models of gas+water±rock reactions), which we compare to measured plume and fumarole compositions. We find that the sulfur inputs can broadly equal sulfur outputs over long timescales. However, the hydrothermal system can modulate the total mass of sulfur released and its H2S/SO2 ratio on shorter timescales, especially as the system evolves from water- to gas-dominated through the development of dry, gas-dominated pathways.

Carbon flux from hydrothermal skarn ore deposits and its potential impact to the environment

Magmatic-hydrothermal systems transport metal, sulfur, and carbon from deep to shallow crust, providing materials to the society and potentially affecting Earth’s long-term environment. The fluxes of elements and, accordingly the environmental effects, are ultimately functions of the time-integrated amounts and durations of magmatic-hydrothermal system. In this study, we calculate the duration of prograde metamorphism induced by fluid infiltration and amount of carbon released by skarn ore deposits. This study finds that skarn ore deposits can decarbonize CO2 at an efficiency up to 1014 g/(y.km3), which is much higher than volcanism on different tectonic settings. The CO2 flux of skarn deposits increased from late Jurassic to early Cretaceous and reached a maximum value to 7.8 Mt/y at J/K boundary.Our finding provided an previously unquantified but important outgassing source in the subduction zone. This result consistent with global warming pattern based on global sedimentary records. The maximum outgassing at J/K boundary may have important impact on global warming and perhaps mass extinction.

Zircon fertility indicators compromised by mineral inclusion contamination: A case study from the Taoxikeng W deposit, South China

Zircon trace element compositions have been widely used as a tool to assess the ore-forming potential of magmatic-hydrothermal systems. However, many zircons contain accessory mineral inclusions which, if accidentally analyzed, could compromise reported zircon trace element signatures, especially when the mineral inclusions are sub-micrometer and thus hard to monitor using conventional microscopes. However, how mineral inclusion contamination influences the robustness of zircon fertility indicators (e.g., Ce and Eu anomalies) is still not well illustrated. In this study, we report U-Pb ages and trace element compositions of zircons from ore-forming muscovite granite plutons of the Taoxikeng W deposit, South China. The studied zircons are characterized by abundant small apatite inclusions. Although these had little influence on zircon Eu/Eu* (and thus probably the interpreted level of magmatic fractionation and melt water concentration), they could have resulted in a misestimation of the magmatic oxidation state either via the zircon Ce/Ce* or Loucks et al. (2020) methods. This is especially important for granite-related W-Sn systems since their magmatic zircons generally contain abundant mineral inclusions, which may be accidentally sampled during zircon trace element analysis. In practice, we can use La as a monitor of REE-enriched mineral (i.e., apatite, titanite) inclusions, although the criterion for identifying pure zircon trace element data is still controversial and awaits further work.

Molybdenum isotope heterogeneity of metal sulfides from magmatic hydrothermal systems

The sensitivity of molybdenum (Mo) stable isotopes to redox changes enables innovative geochemical means of tracing the evolution of medium- to high-temperature magmatic hydrothermal processes. However, the Mo isotope geochemical behaviors and fractionation mechanisms in magmatic-hydrothermal systems are still unclear. This study performed high-precision Mo isotope research on well-characterized hydrothermal metal sulfides (pyrite, chalcopyrite, molybdenite and pyrrhotite) from different metallogenic stages and the ore-forming porphyries and surrounding rocks from the giant Pulang porphyry copper deposit in Yunnan, Southwest China, to better understand Mo isotope behaviors in magmatic hydrothermal systems. The results show that compared to the high-temperature magmatic system with homogeneous Mo concentrations (1.44 ppm to 11.3 ppm) and δ98Mo values (−0.41‰ ± 0.05 to −0.08‰ ± 0.03), medium- to high-temperature hydrothermal stage molybdenite displays slightly lighter δ98Mo values (−0.90‰ ± 0.04 to 0.08‰ ± 0.04), and pyrite, chalcopyrite and pyrrhotite, which have low Mo concentrations (0.13 ppm to 28.5 ppm), feature significant δ98Mo variations from −0.34 ± 0.04‰ to 3.01 ± 0.03‰. The absence of fractionated but low δ98Mo values in the magmatic system, combined with the lack of any correlation between the δ98Mo and geochemical index values (e.g., Co/Ni value) of the metal sulfides, implies that the Mo isotope signatures of sulfides in the hydrothermal stage were not inherited from component signatures of the magmatic phase or contamination of surrounding rocks. Our study proposes that heterogeneous partitioning and transportation of heavy/light Mo isotopes into progressively precipitated metal sulfides as a result of changes in the redox-driven metallogenic setting and differential geochemical behaviors of Mo species contribute to the observed δ98Mo variations and that the heavier and strongly variable Mo isotopic signatures correspond to the dominant metallogenic stage of the deposit. Such fractionation may be explained by the Rayleigh fractionation model, whereby 95Mo is preferentially partitioned into isotopically light molybdenite, and the subsequent precipitation of pyrite, chalcopyrite and pyrrhotite from the residual 98Mo-rich ore-forming fluids manifests heavier isotopic compositions. We therefore highlight that the Mo isotopes of metal sulfides provide valuable insights into the precipitation of metal-rich fluids, the identification of favorable mineralization zones, and the ability to trace the evolution of sophisticated magmatic-hydrothermal systems.

Formation of magnetite-(apatite) systems by crystallizing ultrabasic iron-rich melts and slag separation

Magnetite-(apatite) ore deposits are interpreted as being formed by the crystallization of iron-rich ultrabasic melts, dominantly generated by the interaction of silicate melts with oxidized P-F-SO4-bearing sedimentary rocks. This hypothesis is supported by geologic evidence, experimental studies, numerical modeling, stable and radiogenic isotope geochemistry, mineralogy, and melt- and mineral-inclusion data. Assimilation of crustal rocks during ascent promotes separation from a silicate magma of Fe-rich, Si-Al-poor melts with low solidus temperatures and viscosities, allowing coalescence, migration, and emplacement at deep to subaerial crustal environments. When the iron-rich melt attains neutral buoyancy, fractional crystallization leads to melt immiscibility similar to that observed in industrial blast furnaces, which promotes separation of massive magnetite ore overlain by different types of “slag” containing actinolite or diopside ± phosphates ± magnetite ± feldspar ± anhydrite ± scapolite, commonly enriched in high field strength elements. The mineralogy and morphology of this iron-depleted cap strongly depend on the depth of emplacement and composition of the iron-rich magma. Most of these systems exhibit high oxygen fugacity, which inhibits the precipitation of significant sulfide mineralization. The initially high fO2 of these systems also promotes the formation of low-Ti (< 1 wt%) magnetite: Ti acts as an incompatible component and is enriched in the iron-poor caps and in the hydrothermal aureole. High fluid-phase pressures produced during massive crystallization of magnetite from the melt further facilitate the exsolution of magmatic-hydrothermal fluids responsible for the formation of aureoles of alkali-calcic-iron alteration with hydrothermal replacement-style iron mineralization. On the whole, these systems are dramatically different from the magmatic-hydrothermal systems related to intermediate to felsic igneous rocks; they are more akin to carbonatite and other ultramafic rocks.

H2 generation versus H2 consumption in volcanic gas systems: A case study in the Afar hot spot in Djibouti

The Djibouti area is located in the Afar depression which corresponds to the core of a major hot spot at the junction of three rifts: The Red Sea oceanic rift, the Gulf of Aden oceanic rift and the East African continental rift. In the extension of the Gulf of Aden, the opening of the Gulf of Tadjourah in the last 30 million years was followed by the establishment of parallel NW-SE oriented depressions (Gobaad, Hanle, Gaggade, Assal-Ghoubbet). This region is characterised by high heat flow, complex volcanic and tectonic activity, and a dense network of faults favorable to the development of hydrothermal activities. A field survey was conducted to study the gas composition and origin in thermal springs and fumaroles along a transect running from the Lake Abbhé to Djibouti. Hydrogen traces were detected at fumaroles and hot springs associated with hydrothermal systems at the edges of the Gobaad, Hanlé, Gaggade, Assal-Ghoubbet and Arta area. The processes governing to the origin of H2 and its consumption at different levels of the magmatic-hydrothermal systems are discussed. H2 is interpreted as related to several processes including, chemical equilibrium in magmatic gases, alteration of FeII-rich rocks, and oxidation of volcanic H2S. Methane associated with the hydrogen has mostly an abiotic origin and could result from the reaction of hydrogen with carbon oxides. Also, helium emanations have been observed notably on the sides of the Lake Abbhé in boiling hot springs. Gas samples have shown R/RA isotopic ratios of helium up to 10, which is are characteristic values for helium of mantle origin characterized an 3He enrichment with respect to air values.

Mineralogy and chemistry of columbite-tantalite from Bugarura-Kuluti area, Karagwe-Ankole Belt, Rwanda: Indicators of pegmatite and granite evolution

Our study characterizes in detail the mineralogical, textural, and compositional features of Ta-Nb oxides from the Bugarura – Kuluti deposit located in the eastern Rwanda. The research presents the chemical evolution of oxides at all scales, from a single crystal, through a single host body, to the regional granite – pegmatite scale. Finally, we propose an evolutionary model of a B-rich magmatic – hydrothermal system hosting Ta-Nb-Sn mineralisation. Ta-Nb oxides are hosted by LCT (lithium-caesium-tantalum) pegmatites, rarely in greisens and two-mica peraluminous granites. They display a wide range of composition including all types of columbite group minerals, wodginite, tapiolite and microlite. The internal texture of columbite-tantalite exhibits a multiple zoning pattern indicating primary composition modified by the extreme fractionated, volatile and water saturated residual melt. Hydrothermal origin of columbite-tantalite is observed in greisens, expressed by a higher W concentration and coeval or even younger crystallization compared to the associated cassiterite. Fractionation trend in a crystal scale includes an extreme increase in Ta/(Ta + Nb) ratio with little or no change in Mn/(Mn + Fe), mainly caused by the high Ta solubility in the silicate melt during fractionation. On a regional scale, the pegmatites follow Fe-Mn fractionation trend towards high Mn/(Mn + Fe) compositions. This is due to fractional crystallization of CGM and crystallization of other Fe competing minerals shifting the melt composition towards Mn enrichment. In the outermost pegmatites, the final crystallization stage is characterized by a rapid increase in Fe. Fe enrichment in the residual melt was due to infiltration of meteoric/metamorphic fluids. Tapiolite and wodginite crystallised from the B and H2O undersaturated, Na-rich residual melt carrying Ta mixed with Sn- and Fe-rich hydrous fluids. The difference in fractionation patterns and styles of mineralization between different deposits within Kibara metallogenic province provides the evidence of the complexity of magmatic-hydrothermal systems which developed by partial melting of heterogenous crustal material.