Magmatic Fluids Research Articles

Metasomatism is a source of methane on Mars

The abundance of inactive Martian volcanic centres suggests that early Mars was more volcanically active than today. On Earth, volcanic degassing releases climate-forcing gases such as H2O, SO2, and CO2 into the atmosphere. On Mars, the volcanic carbon is likely to be more methane-rich than on Earth because the interior is, and was, more reducing than the present-day Terrestrial upper mantle. The reports of reduced carbon associated with high-temperature minerals in Martian igneous meteorites back up this assertion. Here, we undertake irreversible reaction path models of the fluid-rock interaction to predict carbon speciation in magmatic fluids at the Martian crust-mantle boundary. We find methane is a major carbon species between 300 and 800 °C where logfO2 is set at the Fayalite = Magnetite + Quartz redox buffer reaction (FMQ). When logfO2 is below FMQ, methane is dominant across all temperatures investigated (300–800 °C). Moreover, ultramafic rocks produce more methane than mafic lithologies. The cooling of magmatic bodies leads to the release of a fluid phase, which serves as a medium within which methane is formed at high temperatures and transported. Metasomatic methane is, therefore, a source of reduced carbonaceous gases to the early Martian atmosphere and, fundamentally, for all telluric planets, moons, and exoplanets with Mars-like low logfO2 interiors.

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

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

Mechanisms of fluid degassing in shallow magma chambers control the formation of porphyry deposits

Abstract Magmatic fluid degassing within shallow magma chambers underneath the ore bodies is critical to the formation of porphyry Cu-Au deposits (PCDs). Yet, it remains unclear that how the ways of fluid degassing influence on the development of PCDs. Here, geochemical data of apatite, amphibole and plagioclase from ore-forming and coeval barren porphyries have been analyzed in Sanjiang metallogenic belt, China. The ore-forming porphyries normally exhibit high and wide XF/XCl (31.76-548.12) and XF/XOH (0.779-7.370) ratios of apatites, which are evidently higher than those of the barren porphyries (XF/XCl of 1.03-26.58; XF/XOH of 0.686-3.602). Combined with the continuous variation features of Cl/OH ratios and H2O contents of melts calculated by amphiboles, as well as fluid migration models, we constrained the mechanisms of fluid degassing within shallow magma chambers underneath PCDs. There are three different ways of fluid degassing, while only fluid degassing via fluid channel stage can migrate and focus the metal-rich fluids effectively, conducive to the development of PCDs. The mechanisms of magmatic fluid degassing processes are further controlled by the storage depths of magma chambers and initial H2O contents of the magmas revealed by the compositions of amphibole, plagioclase and thermodynamic modelling. Magmas, with shallower storage depth and higher initial H2O content, are more likely to experience extensive and focused fluid degassing, leading to the generation of PCDs. This study demonstrates the potential utility of integrated mineral analyses, the thermodynamic modelling for investigating the mechanisms of magmatic fluid degassing in porphyry systems, as well as identifying prospective buried PCDs.

Ore-forming material sources of the Pakbeng gold deposit, Laos: Evidence from fluid inclusions, H-O-S isotopes, and trace elements

The Pakbeng gold deposit, located at the junction of the eastern Tethys and western Pacific tectonic domains, is part of the Phôngsali-Luang Prabang-Sayaboury polymetallic metallogenic belt. Its gold ore bodies are predominantly governed by fault structures, being vein-like and short-axis-veined in shape. The Pakbeng gold deposit primarily exhibits two types of mineralized alterations: the quartz-vein type and the schistositized altered rock type. The ore bodies are primarily distributed within cataclastic granites and altered andesite plutons, near their contact zone. The ore-forming process can be divided into four stages: quartz + rutile + pyrite (stage I), quartz + pyrite + coarse-grained arsenopyrite (stage II), quartz + polymetallic sulfides + native gold (stage III), and calcite + quartz (stage IV). Native gold primarily occurs as invisible gold in the quartz and pyrite of stages I and II, and as enclosed, intergranular, and interstitial gold within the quartz, pyrite, and other metal sulfides of stage III. The ore-forming materials of the Pakbeng gold deposit primarily originate from plagioclase granites and altered andesites, as indicated by investigations of gold-bearing quartz fluid inclusions, hydrogen and oxygen isotopes, the trace-element composition of pyrite, and in situ sulfur isotopes. The sulfur in the deposit is mainly derived from metamorphic sources, supplemented by late magmatic sulfur. The ore-forming fluids in the deposit were dominated by metamorphic fluids in the early stage, with magmatic fluids participating in the late stage. While ascending, the temperature of the ore-forming fluids decreased due to fluid boiling and mixing, but their salinity increased slightly. The ore-forming fluids exhibited a consistent decrease in homogenization temperatures from stages I to IV, with salinity initially increasing and then decreasing. This suggests that the ore-forming fluids are low-temperature, medium to low-salinity and low-density fluids.

Contrasting fluids and implications for ore genesis in the Jiawula-Chaganbulagen Porphyry Mo-epithermal Pb[sbnd]Zn metallogenetic system: Evidence from fluid inclusions and H-O-He-Ar isotopes

The Jiawula-Chaganbulagen (Jia-Cha) ore field is located in the part of the southern Erguna Block of Northeast China and has significant mineralization potential. It comprises three deposits: The Chaganbulagen hydrothermal vein-type PbZn (Ag) deposit in the southeast, the Jiawula hydrothermal vein-type PbZn (Ag) deposit in the northwest, and the blind porphyry Mo mineralization in between. Previous geochronological dates, including molybdenite ReOs, zircon UPb, sulfide RbSr, and sericite ArAr, indicate that the formation of hydrothermal molybdenite and the PbZn mineralization were coeval and that they originated from a porphyry-epithermal metallogenetic system that was related to Early Cretaceous magmatism. However, our comprehensive analysis of fluid inclusions and H-O-He-Ar isotopes reveals dissimilarities in the features and sources of the fluids that form three different deposits. Both the Jiawula deposit and porphyry Mo mineralization have three distinct types of fluid inclusions, which comprise liquid-rich two-phase aqueous inclusions (L-type), vapor-rich two-phase inclusions (V-type), and daughter mineral-bearing three-phase inclusions (S-type). The HeAr (3He/4He = 1.32–1.51 Ra; 40Ar/36Ar = 300 to 324) and HO (δ18OH2O = − 13.4 ‰ to 4.1 ‰; δD= − 155.1 ‰ to −129.9 ‰) isotope analysis results suggest that the trap fluids originated from an H2O-NaCl magmatic fluid system, which experienced Mo mineralization with high-temperature transformed into medium-temperature fluids that were primarily of meteoric water in the late-stage (Jiawula PbZn (Ag) deposit). The Chaganbulagen PbZn (Ag) deposit features L-type and V-type inclusions, along with aqueous‑carbonic inclusions (C-type). The results of Laser Raman analysis reveal that the gas phases of the fluid inclusions present in Chaganbulagen contain three different compositions: H2O, CO2, and CH4. The HO isotope compositions (δ18OH2O = −18.8 ‰ to −11.6 ‰; δD = −166 ‰ to −131 ‰) and HeAr (3He/4He = 0.034–0.041 Ra; 40Ar/36Ar = 296–298) in quartz of the Chaganbulagen PbZn (Ag) deposit indicate that the crustal fluids (MASW) were the main source of the ore-forming fluids, and belonged to a H2O-NaCl-CO2-CH4 system, which had low-temperature and low-salinity characteristics. By combining previously published geochronological dates, we proposed a model to explain the difference in the evolution of the fluids.

Re-distribution and upgrade of metals induced by the superimposition of later magmatic fluids in the Archean Hongtoushan VMS deposit, NE China

The Hongtoushan copper-zinc deposit is a highly metamorphosed Archean volcanogenic massive sulfide deposit (VMS) in China. After metamorphism, the deposit underwent later fluid superimposition, which is of significance for the re-distribution of metals and upgrading ores. However, the hydrothermal modification mechanism and fluid source remain unclear due to the difficulties in accurately recognizing the mineral textures and assemblages formed by hydrothermal modification. In this study, the mineral texture was investigated to identify the modification mechanism of later fluid and in situ sulfur isotope and trace elements of chalcopyrite were tested to track the source of later fluid and metals. The dominant assemblage formed by superimposed fluid consisted of pyrite, chalcopyrite, sphalerite, minor galena, magnetite, calcite, anhydrite, and hydrothermal alteration minerals, i.e. sericite and chlorite. These minerals infilled the fractures in early pyrite porphyroblasts or precipitated along the grain boundary. Additionally, the pre-existing sulfides were corroded by these minerals. They exhibited replacement and porous textures, indicating that the superimposed fluids resulted in a dissolution-reprecipitation process and formed new sulfides. The hydrothermal metasomatism produced the sericitization of plagioclase and chlorization of biotite, which concurrently liberated silica to form silicification. These interactions suggested that the hydrothermal fluid is acid fluid. The chlorite geothermometer defined the formation temperature of 226–279°C, implying that the superimposed fluid has a moderate temperature. The chalcopyrite precipitated from superimposed fluid either coexisted with pyrite (Ccp 2a) or magnetite (Ccp 2b). The sulfur isotope of Ccp 2a defined a closing zero range (0.75–2.41‰), demonstrating the superimposed fluids were derived from magmatic fluids. In contrast, the Ccp 2b enriched heavy sulfur with a δ34S range of 4.10–8.63‰, which was attributed to the oxidation of fluids. Partial ferrous ions were oxidized to ferric iron, and ferrous and ferric iron precipitated as magnetite. The mineral assemblage changed from chalcopyrite + pyrite, followed by magnetite + chalcopyrite + pyrite, to magnetite + pyrrhotite, representing the local increase of the oxidation state of hydrothermal systems. During the oxidation process, the oxygen fugacity of the superimposed fluid decreased, whereas the pH increased. These results provide crucial evidence on the re-distribution pattern of metals and the post-hydrothermal modification process in the Hongtoushan Cu-Zn deposit.

Ground deformations associated with an overpressurized hydrothermal systems at Azuma volcano (Japan) revealed by InSAR data

Inflations at active volcanoes are indicators of overpressure in the subsurface, which is known to be a phenomenon that precedes eruptions. Volcanic overpressure is induced by the injection of magmatic fluids, accumulated magma, or heat supply from greater depths. Azuma volcano (Japan) has experienced several episodes of volcanic unrest with increases in seismicity at the depth of the hydrothermal system, implying a potential increase in phreatic eruptions. The time series of interferometric synthetic aperture radar data, associated with the unrest episodes occurring in 2014–2015 and 2018–2019, revealed spatiotemporal variations of inflation episodes, centered around Oana crater, the most active fumarole of Azuma volcano. The modeled best-fit geometry of the elongated pressure source for the local deformation has the same dip as the overlying topographic slope direction and angle around Oana crater, suggesting the existence of topography-correlated layered structures within the hydrothermal system. In contrast, the broader deformation associated with the 2014–2015 unrest was explained by the overpressure of a horizontal flat source at 360–1500 m below sea level, showing the similar depth of the top as the conductive low-resistivity or low-viscosity body suggested by previous studies. The unrest episodes were thus interpreted as resulting mainly from the supply of magmatic fluids, or the transfer of heat from greater depths. Our study helps in understanding the shallow structure of this volcanic system and contributes to evaluating the potential for forthcoming eruptions in Azuma volcano.Graphical

The initial magma–fluid evolution of the Laochang porphyry molybdenum deposit in Lancang, Yunnan, SW China: Insights from the in-situ analysis of mica and titanite

The Laochang polymetallic deposit is the only large deposit in the Changning–Menglian Junction Zone. The deposit features by deep porphyry-skarn Mo–(Cu) and shallow vein Pb–Zn–(Ag) mineralization. Researches on the deposit have yielded extensive data, however, details about the initial evolution from magma to ore-forming fluid remain unclear. This study centers on the in-situ analysis of biotite from the porphyry, as well as phlogopite and titanite from the A vein, leading to the following insights: (1) The biotite geothermobarometer suggests the porphyry intruded in a moderate depth (2.57–4.27 km), with average parameters as P = 93 MPa, T = 697 °C, and logfO2 = -16.78. (2) The A vein in the deposit can be further subdivided into A1 K-feldspar vein and A2 quartz vein. The phlogopite in the A1 vein formed at P = 98 MPa, T = 681 °C, and logfO2 = -17.29. The pressure of the A1 vein is slightly higher than the static pressure of wall rock, attributed to pressure increment from the initial exsolved fluid. Conversely, the temperature and oxygen fugacity experience a slight decrease, due to buffering of the adjacent tuff. (3) The in-situ LA–ICP–MS U–Pb dating of the titanite in the A1 vein yields 44.4 ± 1.5 Ma (MSWD = 1.8, n = 48), comparable to the emplacement age of the porphyry (44.6–44.4 Ma). It is slightly older than the main mineralization age (43.78 Ma), further delineated the initial evolution sequence from magma to ore-forming fluid. Our research suggests that the in-situ analysis of titanite is crucial for preciously tracking the magma–fluid system, as titanite records both time and temperature information.

Rare earth element systematics of chimney anhydrite from seafloor hydrothermal vents

Comparative studies of sulphide chemistry have been conducted over the past few decades to characterise seafloor hydrothermal mineralisation, but few studies have been carried out on sulphate minerals. Here we report on a systematic study of the S isotopic composition and rare earth element (REE) chemistry of chimney anhydrite from various types of seafloor hydrothermal vent fields in the Central Indian Ridge, North Fiji Basin, and Tonga intra-oceanic arc. Our results show that sulphate δ34S values of anhydrite cluster around that of seawater sulphate, indicating a significant role for fluid–seawater mixing during anhydrite precipitation. However, some anhydrite has δ34S values lower than that of seawater. This likely reflects sulphate derived from magmatic SO2 disproportionation. Chondrite-normalised REE patterns of the anhydrite are not uniform on the scale of individual grains and/or between each type of hydrothermal vent field. The REE compositions of the anhydrite do not have a clear relationship with the REE compositions of the primary host rocks with which the hydrothermal fluids interacted. This indicates that the REEs are not sensitive indicators of the host rock compositions, even though the host rocks are the dominant source of REEs in the seafloor hydrothermal fluids. In contrast, anhydrite REE concentrations and Eu anomalies are correlated with δ34S values and the redox state of the hydrothermal fluids, respectively. We suggest that relatively REE-enriched anhydrite is formed by efficient leaching of REEs from host rocks by acidic magmatic fluids (i.e., a low pH), whereas a low redox potential of the hydrothermal fluids is the most important factor controlling Eu mobility. The original concentrations of REEs supplied to the hydrothermal fluids can also be modified by fluid boiling and fluid–seawater mixing. The former produces light REE-depleted anhydrite because the availability of chloride ligands decreases in low-density vapor-dominated boiled fluids. In situ geochemical analysis of anhydrite on the intra-grain scale shows that high degrees of fluid–seawater mixing contribute to the relatively low REE concentrations and positive Eu anomalies. As such, our results indicate that the REE systematics of anhydrite are mainly controlled by the combined effects of fluid conditions (i.e., redox state, pH, and Cl concentrations) and sub-seafloor geochemical processes (i.e., magmatic input, fluid boiling, and seawater mixing) rather than the nature of the source materials. In situ analysis of anhydrite grains is a useful tool for constraining variable hydrothermal mineralisation conditions during chimney growth, which cannot be solely inferred from geochemical studies of sulphide minerals, particularly in inactive and relict systems where the hydrothermal fluids cannot be sampled.

Timing and Mechanism of Ore Precipitation in Porphyry Cu Systems: Insight from LA-ICP-MS Analysis of Fluid Inclusions and In Situ Oxygen Isotope Analysis of Hydrothermal Quartz at Zhunuo Porphyry Cu Deposit, China

Abstract The timing and mechanism of ore precipitation in porphyry copper systems are hot topics and remain controversial. The large Miocene collision-related Zhunuo porphyry Cu deposit in the Gangdese belt of southern Tibet, China, was produced by multistage quartz veining and hydrothermal alteration, accompanied by Cu sulfide precipitation. In this study, we have combined cathodoluminescence (CL) petrography with in situ oxygen isotope analysis and fluid inclusion microthermometry and laser ablation-inductively coupled plasma-mass spectrometer microanalysis to constrain the growth history of individual quartz veins, the source and evolution of the hydrothermal fluids, and the timing and mechanism of ore precipitation at Zhunuo. Early quartz A veins associated with potassic alteration are composed of quartz, K-feldspar, biotite, Cu-Fe sulfides, and pyrite. Quartz B veins are composed of quartz, Cu-Fe sulfides, molybdenite, and pyrite. CL imaging shows that quartz grains in the A and B veins consist of abundant early generation of bright-luminescent quartz (QA and QB) with volumetrically minor later generation of dull-luminescent quartz (QA-crack and QB-crack) occurring in the voids or at the margins of the QA and QB veins with embayed contacts. Cu-Fe sulfides are generally in contact with the dull-luminescent quartz and locally in contact with the bright-luminescent quartz and K-feldspar in the A and B veins or occur as disseminations in the potassic-altered porphyries that have been overprinted by chlorite ± muscovite alteration. QA and QB contain single-phase intermediate-density inclusions and abundant brine and vapor-rich inclusions. A boiling assemblage in QA has a homogenization temperature of ~560°C and trapping pressure of ~530 bar. Two boiling assemblages in QB have homogenization temperatures of ~440°C with trapping pressures of ~230 and ~250 bar, indicating a transition from lithostatic to hydrostatic conditions at a paleodepth of ~2.0 to 2.5 km. QA-crack and QB-crack contain aqueous inclusions with lower homogenization temperatures of 340° to 400°C and salinities of 6 to 12 wt % NaCl equiv. In situ oxygen isotopes indicate that QA and QB have δ18O values of 7.6 to 11.4‰, whereas QA-crack and QB-crack have δ18O values of –7.2 to 6.7‰. Combined with fluid inclusion compositions, we propose that condensation of vapors into brines and mixing with 25 to 60% meteoric water can produce the salinity and oxygen isotopes of fluids that caused the dissolution of the early bright-luminescent quartz and the precipitation of the later dull-luminescent quartz. Zhunuo Cu-Fe sulfides are in contact with the bright-luminescent quartz and cut the growth bands. The dull-luminescent quartz in contact with the Cu-Fe sulfides has oscillatory growth banding. In addition, Cu-Fe sulfides in the A and B veins or in the potassic-altered rocks coexist with chlorite ± muscovite alteration minerals. These geologic observations, together with evidence that there is an abrupt drop in the Cu/(Na + K) ratio by more than one order of magnitude in the aqueous fluids within the dull-luminescent quartz compared to the brines within the bright-luminescent quartz, indicate that precipitation of Cu-Fe sulfides occurred after the potassic alteration stage and during the chlorite ± muscovite alteration stage. Ore precipitation was associated with mixing of magmatic fluids (brines + vapors) with meteoric water, accompanied by fluid cooling, salinity decrease, and retrograde quartz solubility as the rocks transitioned from lithostatic to hydrostatic conditions. During continued cooling in the latest stage, the hydrothermal fluids precipitated D veins that contain abundant pyrite with minor quartz. Quartz in the D veins (QD) contains aqueous inclusions with much lower temperatures and Cu/(Na + K) ratios, indicating that most of the Cu-Fe sulfides have been precipitated during this stage.

What controls Sn-W mineralization in granite batholith: A case study from the world-class Dulong Sn-Zn polymetallic ore deposit of SW China

Magmatic-hydrothermal ore deposits hosted in granitic batholiths are an important source of tungsten (W) and tin (Sn). However, it remains enigmatic whether and how the Sn-W mineralization is triggered by the spatially associated batholith because the Sn-W-bearing granitic rocks are more likely to occur as small intrusions. Here we used a combination of LA-ICP-MS cassiterite U-Pb dates, published whole-rock geochemical, and high-precision exploration data to evaluate a genetic link between the world-class Dulong Sn-Zn polymetallic ore deposit and its spatially associated batholith in SW China. Our new cassiterite U-Pb dates indicate that the Sn-Zn and Sn-Cu mineralization events were temporally associated with the emplacement of concealed granites and porphyritic dykes respectively, consistent with the spatial pattern between Sn-Zn-Cu mineralized zones and granitic rocks in the Dulong ore district as revealed by the high-precision exploration data. The compiled data presented in this study show that these granitic rocks throughout the batholith are of S-type and highly fractionated affinities, and their parent magmas might experience similar degrees of fractionation. Importantly, the low Nb/Ta ratios (most < ∼5) in granites of the Dulong ore district are markedly differentiated from highly variable values (∼2.0 to ∼ 9.4) in the batholith, which may be caused by the extensive sub-solidus interaction with late magmatic fluids. Furthermore, the granites of the Dulong ore district are significantly poorer in Sn-Zn contents than those of the Laojunshan batholith, suggesting the extensive Sn-Zn-rich fluids exsolved from highly evolved granitic magmas could lead to a significant decrease in Sn-Zn contents in consolidated granites and the formation of Sn-Zn ore deposit, due to the relatively high fluid/melt partition coefficients of Sn and Zn. In conjunction with evidence from previous numerical and mineralogical models, and the spatial pattern between Sn-Zn mineralized zones and apical parts of concealed pluton in the Dulong ore district as revealed by high-precision drill data, we propose a model involving highly evolved granitic magmas that formed batholith, apical portions of which as the emanative centers of Sn-Zn-rich fluids played a crucial role in the formation of the world-class ore deposit.

Mineral and S-Isotope Compositions of Cu-Sulfide Deposits in Southern Siberia (Kodar–Udokan Region), Russia

The Kodaro–Udokan region is a huge Cu metallogenic province in Southern Siberia, one of the largest on Earth. It contains world-class copper sandstone-hosted Udokan (Cu reserves of 26.7 Mt) and PGE-Ni-Cu Chineysky deposits related to gabbro–anorthosite pluton (Cu—10 Mt; Fe-Ti-V, 30 Gt of ore). Furthermore, there are many small deposits of sulfide ores in sedimentary and igneous rocks in this region as well. For many decades, their genesis has been hotly debated. We studied the mineral composition and the sulfur isotopes in several deposits located at different levels of the stratigraphic sequence and in gabbro intruded in sandstones of the Udokan complex. The differences in ore compositions were found. The Burpala and Skvoznoy deposits consisting of the chalcocite–bornite association are characterized only by negative δ34S. The δ34S values for the Udokan deposits are mostly &lt;0 (up to −28‰). The positive δ34S data characterize the ores of the Chineysky and Luktursky intrusions. Two Cu sandstone-hosted deposits are characterized by complex ore composition, i.e., the Krasny deposit, comprising chalcopyrite–pyrrhotite ores, is enriched in Co, Ni, Bi, Sb, Mo, Pb, Zn, Se, Te, and U and has a wide range of δ34S = −8.1–+13.5‰, and the Pravoingamakitsky deposit (Basaltovy section), consisting of quartz–chalcopyrite veins, has high PGE contents in ores with δ34S = +2.9–+4.0‰. These deposits are located near the gabbro massifs, and it is supposed that their ore compositions were influenced by magmatic fluids. The general regularities of the localization of the deposits in rift zones, and the proximity of mineral and isotopic composition allow us to conclude that the main source of copper could be rocks of basic composition because only they contain high Cu contents. Fluids from deep zones could penetrate to the surface and form Cu sandstone-hosted deposits.

Soil CO2 emission and stable isotopes (δ13C, δ18O) of CO2 and calcites reveal the fluid origin and thermal energy in the supercritical geothermal system of Krafla, Iceland

The Krafla geothermal system is located within a volcanic center that periodically erupts basaltic lavas, and has recently attracted an economic interest due to supercritical fluids forming near a shallow magma intrusion (∼ 2 km depth). Here, we discuss new soil CO2 flux and stable isotope data of the CO2 efflux (δ13C) and hydrothermal calcites (δ13C, δ18O) of drill cuttings to estimate both the current magmatic outgassing from soils and the thermal flows in the geothermal system. Soil CO2 emission is controlled by tectonics, following the NNE-SSW fissure swarm direction and a WSW-ENE trend, and accounts for ∼62.5 t d−1. While the δ18O of the H2O in equilibrium with deep calcites is predominantly meteoric, both the δ13C of the soil CO2 efflux and of the fluids from which calcite precipitated have a clear magmatic origin, overlapping the δ13C estimated for the Icelandic mantle (−2.5 ± 1.1 ‰). Estimates based on the soil CO2 emission from the southern part of the system show that these fluxes might be sustained by the ascent and depressurization of supercritical fluids with a thermal energy of ∼800 MW. Such significant amount of energy might reach 1.5 GW if supercritical conditions extended below the whole investigated area. Finally, we report an increase in the soil CO2 emission of about 3 times with respect to 14 years ago, likely due to recent changes in the fluid extracted for power production or magmatic activity. Pairing the soil CO2 emission with stable isotopes of the efflux and calcite samples has important implications for both volcano monitoring and geothermal exploration, as it can help us to track magmatic fluid upflows and the associated thermal energy.

2021–2023 Unrest and Geodetic Observations at Askja Volcano, Iceland

AbstractUnrest began in July 2021 at Askja volcano in the Northern Volcanic Zone (NVZ) of Iceland. Its most recent eruption, in 1961, was predominantly effusive and produced ∼0.1 km3 lava field. The last plinian eruption at Askja occurred in 1875. Geodetic measurements between 1983 and 2021 detail subsidence of Askja, decaying in an exponential manner. At the end of July 2021, inflation was detected at Askja volcano, from GNSS observations and Sentinel‐1 interferograms. The inflationary episode can be divided into two periods from the onset of inflation until September 2023. An initial period until 20 September 2021 when geodetic models suggest transfer of magma (or magmatic fluids) from within the shallowest part of the magmatic system (comprising an inflating and deflating source), potentially involving silicic magma. A following period when one source of pressure increase at shallow depth can explain the observations.

Subsurface anatomy of the Irazú–Turrialba volcanic complex, inferred from the integration of local and ambient seismic tomographic methods

SUMMARY Irazú and Turrialba are a twin volcanic complex that marks a distinct stop in volcanism along the Central America volcanic arc. We present a new traveltime velocity model of the crust beneath Irazú and Turrialba volcanoes, Costa Rica, and interpret it considering the results of previous ambient noise tomographic inversions. Data were acquired by a temporary seismic network during a period of low activity of the Irazú–Turrialba volcanic complex in 2018–2019. Beneath the Irazú volcano, we observe low P-wave velocities (VP = 5 km s−1) and low velocity ratios (VP/VS = 1.6). In contrast, below the Turrialba volcano, we observe low S-wave velocities (VS = 3 km s−1) and a high VP/VS (= 1.85) anomaly. We found that locations of low VP and VS anomalies (−15 %) correspond well with shear wave velocity anomalies retrieved from ambient noise tomography. At shallower depths, we observe high VP and VS anomalies (+15 %) located between the summits of the volcanoes. Subvertical velocity anomalies are also observed at greater depths, with high VP and VS anomalies appearing at the lower limits of our models. We propose a complex structure of an intermediate magmatic reservoir, presenting multiphase fluid states of a liquid-to-gas transition beneath Irazú and a juvenile store of magmatic fluid beneath Turrialba, while shallow fluid transport provides evidence of magmatic–hydrothermal interactions.

Skarn Formation and Zn–Cu Mineralization in the Dachang Sn Polymetallic Ore Field, Guangxi: Insights from Skarn Rock Assemblage and Geochemistry

The Dachang is a world-class, super-giant Sn polymetallic ore field mainly composed of Zn–Cu ore bodies proximal to the granitic pluton and Sn polymetallic ore bodies distal to the granitic pluton. In this study, we used petrographic studies and major and trace element geochemistry with calc-silicates from the Zn–Cu ore bodies to constrain the physicochemical conditions of hydrothermal fluids during skarn rock formation and the evolution of ore-forming elements. Two skarn stages were identified based on petrographic observations: Prograde skarn rocks (Stage I), containing garnet, vesuvianite, pyroxene, wollastonite, and retrograde skarn rocks (Stage II), containing axinite, actinolite, epidote, and chlorite. The retrograde skarn rocks are closely associated with mineralization. The geochemical results show that the garnets in the Dachang ore field belong to the grossular–andradite solid solution, in which the early generation of garnet is mainly composed of grossular (average Gro72And25), while the later generation of garnet is mainly composed of andradite (average Gro39And59); the vesuvianites are Al-rich vesuvianites; the pyroxenes form a diopside–hedenbergite solid solution with a composition of Di3–86Hd14–96; the axinites are mainly composed of ferroaxinite; and the actinolites are Fe-actinolite. The mineral assemblage of the skarn rocks indicates that the ore-forming fluid was in a relatively reduced state in the early prograde skarn stage. As the ore-forming fluid evolved, the oxygen fugacity of the ore-forming fluid increased. During the final skarn stage, the ore-forming fluid changed from a relatively oxidized state to a reduced state. The skarn rocks have evolved from early Al-rich to late Fe-rich characteristics, indicating that the early ore-forming fluid was mainly magmatic exsolution fluid, which may mainly reflect the characteristics of magmatic fluids, and the late Fe-rich characteristics of the skarn rocks may indicate that the late hydrothermal fluid was strongly influenced by country rocks. Trace element analyses showed that the Sn content decreased from the prograde skarn stage to the retrograde skarn stage, indicating that Sn mineralization was not achieved by activating and extracting Sn from prograde skarn rocks by hydrothermal fluids. The significant enrichment of Sn in the magmatic hydrothermal fluid is a necessary condition for Sn mineralization. There are various volatile-rich minerals such as axinite, vesuvianite, fluorite, and tourmaline in the Dachang ore field, indicating that the ore-forming fluid contained extensive volatiles B and F, which may be the fundamental reason for the large-scale mineralization of the Dachang ore field.

Characterization of an undocumented CO2 hydrothermal vent system in the Mediterranean Sea: Implications for ocean acidification forecasting.

A previously undocumented shallow water hydrothermal field from Sicily (Southern Tyrrhenian Sea, Italy) is here described, based on a multidisciplinary investigation. The field, covering an area of nearly 8000 m2 and a depth from the surface to -5 m, was explored in June 2021 to characterise the main physico-chemical features of the water column, describe the bottom topography and features, and identify the main megabenthic and nektonic species. Twenty sites were investigated to characterise the carbonate system. Values of pH ranged between 7.84 and 8.04, ΩCa between 3.68 and 5.24 and ΩAr from 2.41 to 3.44. Geochemical analyses of hydrothermal gases revealed a dominance of CO2 (98.1%) together with small amounts of oxygen and reactive gases. Helium isotope ratios (R/Ra = 2.51) and δ13CCO2 suggest an inorganic origin of hydrothermal degassing of CO2 and the ascent of heat and deep-seated magmatic fluids to the surface. Visual census of fishes and megabenthos (mainly sessile organisms) allowed the identification of 64 species, four of which are protected by the SPA/BIO Protocol and two by the International Union for Conservation of Nature. The macroalgae Halopteris scoparia and Jania rubens and the sponge Sarcotragus sp. were the dominant taxa in the area, while among fishes Coris julis and Chromis chromis were the most abundant species. This preliminary investigation of San Giorgio vent field suggests that the site could be of interest and suitable for future experimental studies of ocean acidification.

Magmatic-hydrothermal fluid evolution of the tin-polymetallic metallogenic systems from the Weilasituo ore district, Northeast China

The large Weilasituo Sn-polymetallic deposit is a recent exploration discovery in the southern Great Xing’an Range, northeast China. The ore cluster area shows horizontal mineralization zoning, from the inner granite body outward, consisting of high-T Sn–W–Li mineralization, middle-T Cu–Zn mineralization and peripheral low-T Pb–Zn–Ag mineralization. However, the intrinsic genetic relationship between Sn-W-Li mineralization and peripheral vein-type Pb–Zn–Ag–Cu mineralization, the formation mechanism and the deep geological background are still insufficiently understood. Here, we use fluid inclusions, trace elements concentrations in quartz and sphalerite, and H–O isotope studies to determine the genetic mechanism and establish a metallogenic model. Fluid inclusion microthermometry and Laser Raman spectroscopic analysis results demonstrates that the aqueous ore-forming fluids evolved from low-medium salinity, medium–high temperature to low salinity, low-medium temperature fluids. Laser Raman spectroscopic analysis shows that CH4 is ubiquitous in fluid inclusions of all ore stages. Early ore fluids have δ18OH2O (v–SMOW) values from + 5.5 to + 6.2‰ and δD values of approximately − 67‰, concordant with a magmatic origin. However, the late ore fluids shifted toward lower δ18OH2O (v–SMOW) (as low as 0.3‰) and δD values (~ − 136‰), suggesting mixing between external fluids derived from the wall rocks and a contribution from meteoric water. Ti-in-quartz thermometry indicates a magmatic crystallization temperature of around 700 °C at a pressure of 1.5 kbar for the magmatic ore stage. Cathodoluminescence (CL) imaging and trace element analysis of quartz from a hydrothermal vug highlight at least three growth episodes that relate to different fluid pulses; each episode begins with CL-bright, Al-Li-rich quartz, and ends with CL-dark quartz with low Al and Li contents. Quartz from Episode 1 formed from early Sn-(Zn)-rich fluids which were likely derived from the quartz porphyry. Quartz from episodes 2 and 3 formed from Zn-(Sn)-Cu-rich fluid. The early magmatic fluid is characterized by low fS2. The SO2 produced by magma degassing reacted with heated water to form SO42−, causing the shift from low fS2 to high fS2. The SO42− generated was converted to S2– by mixing with CH4-rich, Fe and Zn-bearing external fluid which led to late-stage alteration and dissolution of micas in vein walls, thus promoting crystallization of pyrrhotite, Fe-rich sphalerite and chalcopyrite and inhibiting the precipitation of anhydrite. This study shows that ore formation encompassed multiple episodes involving steadily evolved fluids, and that the addition of external fluids plays an important role in the formation of the later Cu–Zn and Ag–Pb–Zn mineralization in the Weilasituo ore district.

Degassing of Mantle‐Derived Helium From Hot Springs Along the India‐Asia Continental Collision Settings: Origins, Migration Velocity and Flux

AbstractMantle‐derived volatile degassing lacks quantitative evaluation in continental regions without active magmatism, such as the Tibetan Plateau. Ten new gas abundance and helium isotope data points combined with 286 hydrothermal volatile literature data points in India–Asia continental collision settings demonstrate widespread mantle‐derived volatiles across the thick (∼70 km) crust. The mantle‐derived 3He is best explained by direct mantle volatile input from subcontinental lithospheric mantle (1%–36.5%) or the asthenospheric wedge (1%–27.8%) instead of fossil residual magmatic fluids or Quaternary mantle‐derived melt intrusion into crustal depth. Mantle‐derived 3He is transported from the deep mantle to the surface at an upflow rate of 30–11,700 mm/year based on a newly developed steady‐state one‐dimensional flow model, corresponding to a mantle‐derived 3He flux of 17 to 1.5 × 107 atoms m−2 s−1 (81.7%–99.4% of the total 3He flux) and a mantle‐derived 4He flux from 2.0 × 106 to 1.8 × 1012 atoms m−2 s−1 (1.4%–36.5% of the total 4He flux). The mantle‐derived helium fluxes in the study area are comparable to those of other nonvolcanic hydrothermal systems in the tectonically active regions but lower than those of volcanic fields. The helium transit time ranges from 5.3 ka to 2.3 Ma, indicating that the spatial pattern of 3He/4He ratios in the India‐Asia continental collision settings can provide a snapshot of the state of the Indian mantle lithosphere between those revealed by potassic‐rich mafic rocks (25–8 Ma) and seismic methods (present).

Copper sulfide deposition and remobilisation triggered by non-magmatic fluid incursion in the single-intrusion Tongchang porphyry system, SE China

Porphyry ore deposits are a major source of base and precious metals. Likewise, they bear important fingerprints for understanding magmatic / hydrothermal processes in the convergent margin. For many decades, the sources of non-magmatic fluid and its role in sulfide mineralization in the porphyry hydrothermal systems have been equivocal. The Tongchang porphyry deposit, which is a single intrusive system with a well-established fluid history, is investigated to reconstruct its hydrothermal process that contributed to the ore formation. In-situ oxygen and strontium isotopes in hydrothermal quartz and anhydrite revealed a coexistence of magmatic and non-magmatic fluid reservoirs. The granodiorite—derived magmatic fluid and external groundwater were spatially separated by a hydrologically impermeable shell formed by retrograde mineral deposition (mainly quartz). The location of the impermeable shell coincided with a brittle-ductile transition (BDT) interface established in the host phyllite in response to latent heating by the cooling magmas. It is inferred that the ductile phyllite beneath the impermeable shell may have entrained some amounts of groundwater and remnant metamorphic fluid. The early fluid stage was dominated by the magmatic fluids, forming disseminated chalcopyrite and barren quartz veins in the potassic-altered ductile granodiorite at high temperatures (> 500 °C). The next stage (early-intermediate) was also driven by the circulation of the magmatic fluids, but in a largely brittle zone formed in-between the impermeable shell and the retreated BDT interface (similar to the so-called “carapace” in the orthomagmatic models). In this stage the formation of pyrite and chalcopyrite veins together with chloritic alteration at temperatures of 400–350 °C occurred. The late-intermediate stage was marked by incursion of the trapped non-magmatic fluids due to rupturing of the enlarged carapace. Mixing of the non-magmatic fluids and the magmatic fluids led to deposition of a major phase of vein-type Cu sulfide at temperatures of 350–300 °C. The late fluid stage was characterized by breaching of the impermeable shell in response to volumetric contraction of the fluid system, leading to excessive infiltration of groundwater and ore remobilization. Based on the Tongchang model, six generic fluid models are proposed for porphyry ore deposits that differ in availability of non-magmatic components as well as intrusive histories. The models can account for variabilities in ore and alteration styles found in porphyry ore deposits globally.