Genesis of fumarolic emissions as inferred by isotope mass balances: CO2 and water at Vulcano Island, Italy

We have developed a quantitative model of CO₂ and H₂O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H₂O and CO₂ and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H₂O and CO₂ content and the δD, δ¹⁸O, and δ¹³C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ¹³C_CO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO₂ concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ¹³C_CO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ¹³C of the entire hydrothermal system, including mixed H₂O-CO₂ vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO₂. On these grounds, we think that Mediterranean marine water (δD_H2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO₂ and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.     

Reactions governing the chemistry of crater fumaroles from Vulcano Island,Italy, and implications for volcanic surveillance

More than 200 chemical and isotope analyses of fumarolic fluids collected at the Fossa Grande crater, Vulcano Island, during the 1980s show that the main process controlling these fluids is mixing between the gas released by a magma body and the vapour produced through evaporation of brines of marine origin. Large variations in the relative contribution of these two sources have been observed during the last 10 a. The main species (H₂O and CO₂), the inert gases (He and N₂), and the D content of steam are fixed by the mixing processes; they are therefore the best tracers the fraction of the deep magmatic component in the fumarolic fluids discharged at the surface. In contrast, the “fast” species (H₂ and CO) equilibrate at T,P values close to the outlet temperature and atmospheric pressure, and under redox conditions governed by the SO₂H₂S buffer, as indicated by thermodynamic calculations.Acid gases (HCl, HF, H₂S and SO₂) are partly contributed by the magmatic component and partly produced by the reactions between hot rocks, steam and salts which take place in the “dry” zones surrounding the central magmatic gas column, as suggested by the good agreement between their analytical and theoretical contents.     

The origin of the fumaroles of La Solfatara (Campi Flegrei, South Italy)

The analysis of gaseous compositions from Solfatara (Campi Flegrei, South Italy) fumaroles since the early 1980s, clearly reveals a double thermobarometric signature. A first signature at temperatures of about 360 °C was inferred by methane-based chemical-isotopic geoindicators and by the H₂/Ar geothermometer. These high temperatures, close to the critical point of water, are representative of a deep zone where magmatic gases flash the hydrothermal liquid, forming a gas plume. A second signature was found to be at around 200-240 °C. At these temperatures, the kinetically fast reactive species (H₂ and CO) re-equilibrate in a pure vapor phase during the rise of the plume. A combination of these observations with an original interpretation of the oxygen isotopic composition of the two dominant species, i.e. H₂O and CO₂, shed light on the origin of fumarolic fluids by showing that effluents are mixture between fluids degassed from a magma body and the vapor generated at about 360 °C by the vaporization of hydrothermal liquids. A typical ‘andesitic’ water type (δD ∼ −20‰, δ¹⁸O ∼10‰) and a CO₂-rich composition (X_CO2∼0.4) has been inferred for the magmatic fluids, while for the hydrothermal component a meteoric origin and a CO₂ fugacity fixed by fluid-rock reaction at high temperatures have been estimated. In the time the fraction of magmatic fluids in the fumaroles increased (up to ∼0.5) at each seismic and ground uplift crisis (bradyseism) which occurred at Campi Flegrei, suggesting that bradyseismic crises are triggered by periodic injections of CO₂-rich magmatic fluids at the bottom of the hydrothermal system.     

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

Mantle-derived CO_2 in Hot Springs of the Rehai Geothermal Field,Tengchong,China

Gas concentrations and isotopic compositions of He and CO2 were determined on free gas samples from ten hot springs of the Rehai geothermal field, Tengchong, China. The results showed that hot-spring CO2 gas, together with He,was derived mainly from the mantle, indicating the accumulation of mantle-derived volatiles beneath the survey area. The δ^13C values of CO2, higher than those of the typical mantle-derived carbon and the isotopic composition of hot-spring-free CO2 in unequilibrium with dissolved CO2, are recognized only in the Rehai geothermal field, suggesting that there seems to be a still-degassing magmatic intrusion at depths, which provides mantle-derived volatiles to the hydrothermal system above. The accumulation of those volatiles has probably played an important role in triggering earthquakes in this region.In addition, the isotopic characteristics of He and C also indicate that the magmatic intrusion seems to have been derived from the MORB source, and could be contaminated by crustal materials during its upwelling through the continental crust.     

Subduction-related hot spring-type gold mineralization in the central Tengchong block,southwestern China

Numerous present-day hot springs and associated ancient Lianghe gold deposit occur in the central Tengchong block, SW China, associated with oceanic crust subduction. From the center outwards, the alteration zones in the hot spring of the Rehai consist of alunite and silica in a breccia zone, a kaolinite and illite zone, and a chlorite, illite, kaolinite zone. The gas phase in the hot spring is dominated by CO₂ with δ¹³C ranging from −4.5‰ to −7.2‰. These features indicate a major magmatic origin of the hot spring gas. The ³He/⁴He ratios in the gas from central Tengchong vary from 1.56 to 5.88, approaching to those of the MORB. This is probably related to the ongoing subduction of the Indian plate beneath the Tengchong block. The hot spring waters in the central Tengchong block have much higher content of Au and other elements, e.g., Ag, As, Sb, and Tl, than other typical hot springs, such as Hasbrouck, Sulfer, etc. in the world. The hot springs with more mantle gas contribution and higher water temperature show more elevated Au contents, which implies that the metal in the hot spring was most likely contributed from the magmatic gas. The compiled D-O isotopes of the hot spring waters from previous studies suggest that they are primarily derived from meteoric water. A genetic model for the hot spring system in the central of Tengchong has been tentatively established. The gold-charged hot spring is genetically connected to an active magma chamber, which was produced by subduction of oceanic crust. The chamber is driving long-term surface meteoric circulation and constantly releasing magmatic volatiles enriched with metals. As hot spring water mixed with magmatic volatiles, causing decompression-boiling and forming hydraulic fractures to penetrate the roof of siliceous sinter, which induced the continuing metal deposition and formed the Lianghe hot spring.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

An estimate of gas emissions and magmatic gas content from Kilauea volcano

Emission rates of CO₂ have been measured at Kilauea volcano, Hawaii, in the east-rift eruptive plume and CO₂ and SO₂ have been measured in the plume from the noneruptive fumaroles in the summit caldera. These data yield an estimate of the loading of Kilauean eruptive gases to the atmosphere and suggest that such estimates may be inferred directly from measured lava volumes. These data, combined with other chemical and geologic data, suggest that magma arrives at the shallow summit reservoir containing (wt.%) 0.32% H₂O, 0.32% CO₂ and 0.09% S. Magma is rapidly degassed of most of its CO₂ in the shallow reservoir before transport to the eruption site. Because this summit degassing yields a magma saturated and in equilibrium with volatile species and because transport of the magma to the eruption site occurs in a zone no shallower than the summit reservoir, we suggest that eruptive gases from Kilauea characteristically should be one of two types: a ‘primary’ gas from fresh magma derived directly from the mantle and a carbon-depleted gas from magma stored in the summit reservoir.     

Fluid inclusion and isotope geochemistry of the Yangla copper deposit,Yunnan, China

The Yangla copper deposit, with Cu reserves of 1.2 Mt, is located between a series of thrust faults in the Jinshajiang–Lancangjiang–Nujiang region, Yunnan, China, and has been mined since 2007. Fluid inclusion trapping conditions ranged from 1.32 to 2.10 kbar at 373–409 °C. Laser Raman spectroscopy confirms that the vapour phase in these inclusions consists of CO₂, CH₄, N₂ and H₂O. The gas phases in the inclusions are H₂O and CO₂, with minor amounts of N₂, O₂, CO, CH₄, C₂H₂, C₂H₄, and C₂H₆. Within the liquid phase, the main cations are Ca²⁺ and Na⁺ while the main anions are SO₄ ^2? and Cl^?. The oxygen and hydrogen isotope compositions of the ore-forming fluids (?3.05‰?≤?δ¹⁸O_H2O?≤?2.5‰; ?100‰?≤?δD?≤??120‰) indicate that they were derived from magma and evolved by mixing with local meteoric water. The δ³⁴S values of sulfides range from ?4.20‰ to 1.85‰(average on ?0.85‰), supporting a magmatic origin. Five molybdenite samples taken from the copper deposit yield a well-constrained ¹⁸⁷Re–¹⁸⁷Os isochron age of 232.8?±?2.4 Ma. Given that the Yangla granodiorite formed between 235.6?±?1.2 Ma and 234.1?±?1.2 Ma, the Cu metallogenesis is slightly younger than the crystallization age of the parent magma. A tectonic model that combines hydrothermal fluid flow and isotope compositions is proposed to explain the formation of the Yangla copper deposit. At first, westward subduction of the Jinshajiang Oceanic Plate in the Early Permian resulted in the development of a series of thrust faults. This was accompanied by fractional melting beneath the overriding plate, triggering magma ascent and extensive volcanism. The thrust faults, which were then placed under tension during a change in tectonic mode from compression to extension in the Late Triassic, formed favorable pathways for the magmatic ore-forming fluids. These fluids precipitated copper-sulfides to form the Yangla deposit.     

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius.Vesuvius groundwaters are dilute (mean TDS ∼ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. δD and δ¹⁸O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or ¹⁸O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO₂-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions.The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both ¹³C/¹²C and ³He/⁴He measurements indicate the contribution of a magmatic component with a δ¹³C ∼ 0‰ and R/R_a of ∼2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts.A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO₂ release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata-Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO₂ depleted, despite in some cases containing significant concentrations of magma-derived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.     

金属矿床的成矿流体成分和流体包裹体

自然界中的成矿流体按其主要成分,可分为:(1)岩浆,即形成岩浆矿床的岩浆;(2)以H2O为主的流体(含Na Cl);(3)以CO2为主的流体。地壳中的流体类型很多,只有含一定金属元素含量的,并且达到一定浓度时才称为金属矿床的成矿流体。基于对矿床中流体包裹体和天然成矿流体中金属种类和含量的测定,这些金属矿床的成矿流体按金属元素含量可以分为五组,成矿流体可以来自岩浆、岩浆热液、大气降水、盆地卤水和变质流体等地质环境。     

Fluid Inclusions and C?H?O?S?Pb Isotopes: Implications for the Genesis of the Zhuanshanzi Gold Deposit on the Northern Margin of the North China Craton

The Zhuanshanzi gold deposit lies in the eastern section of the Xingmeng orogenic belt and the northern section of the Chifeng‐Chaoyang gold belt. The gold veins are strictly controlled by a NW‐oriented shear fault zone. Quartz veins and altered tectonic rock‐type gold veins are the main vein types. The deposits can be divided into four mineralization stages, and the second and third metallogenic stages are the main metallogenic stages. In this paper, based on the detailed field geological surveys, an analysis of the orebody and ore characteristics, microtemperature measurement of fluid inclusions, the Laser Raman spectrum of the inclusions, determination of C? H? O? S? Pb isotopic geochemical characteristics, and so on were carried out to explore the origin of the ore‐forming fluids, ore‐forming materials, and the genesis of the deposits. The results show that the fluid inclusions can be divided into four types: type I – gas–liquid two‐phase inclusions; type II – gas‐rich inclusions; type III– liquid inclusions; and type IV – CO₂‐containing three‐phase inclusions. However, they are dominated by type Ib – gas liquid inclusions and type IV – three‐phase inclusions containing CO₂. The gas compositions are mainly H₂O and CO₂, indicating that the metallogenic system is a CO₂? H₂O? NaCl system. The homogenization temperature of the ore‐forming fluid evolved from a middle temperature to a low temperature, and the temperature of the fluid was further reduced due to meteoric water mixing during the late stage, as well as a lack of CO₂ components, and eventually evolved into a simple NaCl? H₂O hydrothermal system. C? H? O? S? Pb isotope research proved that the ore‐forming fluids are mainly magmatic water during the early stage, with abundant meteoric water mixed in during the late stage. Ore‐forming materials originated mostly from hypomagma and were possibly influenced by the surrounding rocks, suggesting that the ore‐forming materials were mainly magmatic hydrothermal deposits, with a small amount of crustal component. The fluid immiscibility and the CO₂ and CH₄ gases in the fluids played an active and important role in the precipitation and enrichment of Au during different metallogenic stages. The deposit is considered a magmatic hydrothermal deposit of middle–low temperature.     

Geochemistry of Ore Fluids and Rb-Sr Isotopic Dating for the Wulong Gold Deposit in Liaoning, China

On the basis of detailed geological studies of the Wulong gold deposit, three metallogenic stages can be identified. With quartz fluid inclusions as an object of study, the authors investigated phase characteristics, compositional variations, temperature and pressure changes, fluid evolution, Pb isotope tracing and Rb-Sr isotopic dating of fluid inclusions entrapped in the above three metallogenic stages. The results show that Na+ is decreased obviously with metallogenic evolution, while K+ and other cations and gas compositions (H2, CO, CH4 and CO2) are increased slightly, and that the temperature and salinity vary in a pulsating manner along with the metallogenic evolution. Inverse calculation of hydrogen and oxygen isotopes indicate that at the first metallogenic stage the fluids were magmatic water, at the second stage they were dominated by magmatic water with a minor amount of meteoric water involved, and at the third stage, i.e., the final stage of metallogenesis, the fluids were composed complete     

Coal seam gas distribution and hydrodynamics of the Sydney Basin,NSW, Australia

This paper reviews various coal seam gas (CSG) models that have been developed for the Sydney Basin, and provides an alternative interpretation for gas composition layering and deep-seated CO₂ origins. Open file CSG wells, supplemented by mine-scale information, were used to examine trends in gas content and composition at locations from the margin to the centre of the basin. Regionally available hydrochemistry data and interpretations of hydrodynamics were incorporated with conventional petroleum well data on porosity and permeability. The synthesised gas and groundwater model presented in this paper suggests that meteoric water flow under hydrostatic pressure transports methanogenic consortia into the subsurface and that water chemistry evolves during migration from calcium-rich freshwaters in inland recharge areas towards sodium-rich brackish water down-gradient and with depth. Groundwater chemistry changes result in the dissolution and precipitation of minerals as well as affecting the behaviour of dissolved gases such as CO₂. Mixing of carbonate-rich waters with waters of significantly different chemistries at depth causes the liberation of CO₂ gas from the solution that is adsorbed into the coal matrix in hydrodynamically closed terrains. In more open systems, excess CO₂ in the groundwater (carried as bicarbonate) may lead to precipitation of calcite in the host strata. As a result, areas in the central and eastern parts of the basin do not host spatially extensive CO₂ gas accumulations but experience more widespread calcite mineralisation, with gas compositions dominated by hydrocarbons, including wet gases. Basin boundary areas (commonly topographic and/or structural highs) in the northern, western and southern parts of the basin commonly contain CO₂-rich gases at depth. This deep-seated CO₂-rich gas is generally thought to derive from local to continental scale magmatic intrusions, but could also be the product of carbonate dissolution or acetate fermentation.     

中国大陆新生代典型火山区温室气体释放的规模及其成因

火山活动能够将地球深部的碳输送到大气圈,是地质碳排放和深部碳循环的重要形式.火山作用不仅在喷发期能够释放大量温室气体,而且在休眠期也能释放巨量的温室气体.在全球变暖的背景下,定量化地研究火山活动对大气圈温室气体含量增加的贡献具有至关重要的意义.本文利用密闭气室法等该领域国际先进的测试技术,测量并计算了长白山、腾冲、五大连池及青藏高原南部的羊八井等典型火山区的温室气体释放规模.结果显示,我国大陆新生代典型火山区向大气圈输送的温室气体总通量约为8.13×10⁶t·a^-1,接近10⁷t·a^-1级别,相当于全球火山活动导致的温室气体(主要为CO₂)释放总量的6%左右.太平洋构造域火山区的温室气体在释放通量与总量方面均低于特提斯构造域,并且太平洋构造域火山气体的地壳混染程度较低,显示出大洋俯冲带与大陆俯冲带火山区温室气体释放的成因差异.     

Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.     

Melt and fluid inclusion evidence for a genetic relationship between magmatism in the Shuangliao volcanic field and inorganic CO2 gas reservoirs in the southern Songliao Basin,China

We have studied melt and fluid inclusions in minerals from alkali basalts, mantle xenoliths, and dawsonite-bearing sandstones from the Shuangliao volcanic field in southern Songliao Basin, Northeast China. The inclusions have been investigated using petrographic, geochemical, and laser Raman spectroscopic techniques. Volcanic rocks of the Shuangliao field are predominantly alkali olivine basalts that contain rare mantle xenoliths. Silicate melt and fluid inclusions are common in both olivine phenocrysts and the mantle xenoliths. The fluid inclusions are mainly composed of CO₂ with small amounts of CO, CH₄, N₂, and H₂O, which is consistent with an upper mantle origin. CO₂ gas reservoirs in the southern Songliao Basin are mostly derived from a mantle–magmatic source. Coeval fluid-inclusion homogenization temperatures, coupled with the thermal burial history, show that the CO₂ gas reservoirs in the southern Songliao Basin are Cenozoic (40–63 Ma) and coeval with the magmatism in the Shuangliao volcanic field. Despite the relatively small scale of this volcanic activity, it released large amounts of CO₂. Much of the magma was not erupted, and CO₂- and H₂O-rich magma was probably intruded into the basin along deep faults, acting as a major source of inorganic CO₂ gas in the southern Songliao Basin.     

Mixing of magmatic CO2 into volcano groundwater flow at Aso volcano assessed combining carbon and water stable isotopes

To understand deep groundwater flow systems and their interaction with CO₂ emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ¹³C_DIC) and DIC concentrations of the sampled waters show that magma-derived CO₂ mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ¹³C_DIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ¹⁸O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ¹³C_DIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO₂ is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO₂ mixes into deeper groundwater flowing nearer the magma conduit or chamber.     

Sixty thousand years of magmatic volatile history before the caldera-forming eruption of Mount Mazama, Crater Lake, Oregon

The well-documented eruptive history of Mount Mazama, Oregon, provides an excellent opportunity to use pre-eruptive volatile concentrations to study the growth of an explosive silicic magmatic system. Melt inclusions (MI) hosted in pyroxene and plagioclase crystals from eight dacitic–rhyodacitic eruptive deposits (71–7.7?ka) were analyzed to determine variations in volatile-element concentrations and changes in magma storage conditions leading up to and including the climactic eruption of Crater Lake caldera. Temperatures (Fe–Ti oxides) increased through the series of dacites, then decreased, and increased again through the rhyodacites (918–968 to ~950 to 845–895?°C). Oxygen fugacity began at nickel–nickel-oxide buffer (NNO) +0.8 (71?ka), dropped slightly to NNO +0.3, and then climbed to its highest value with the climactic eruption (7.7?ka) at NNO +1.1 log units. In parallel with oxidation state, maximum MI sulfur concentrations were high early in the eruptive sequence (~500?ppm), decreased (to ~200?ppm), and then increased again with the climactic eruption (~500?ppm). Maximum MI sulfur correlates with the Sr content (as a proxy for LREE, Ba, Rb, P₂O₅) of recharge magmas, represented by basaltic andesitic to andesitic enclaves and similar-aged lavas. These results suggest that oxidized Sr-rich recharge magmas dominated early and late in the development of the pre-climactic dacite–rhyodacite system. Dissolved H₂O concentrations in MI do not, however, correlate with these changes in dominant recharge magma, instead recording vapor solubility relations in the developing shallow magma storage and conduit region. Dissolved H₂O concentrations form two populations through time: the first at 3–4.6 wt% (with a few extreme values up to 6.1 wt%) and the second at ≤2.4 wt%. CO₂ concentrations measured in a subset of these inclusions reach up to 240?ppm in early-erupted deposits (71?ka) and are below detection in climactic deposits (7.7?ka). Combined H₂O and CO₂ concentrations and solubility models indicate a dominant storage region at 4–7?km (up to 12?km), with drier inclusions that diffusively re-equilibrated and/or were trapped at shallower depths. Boron and Cl (except in the climactic deposit) largely remained in the melt, suggesting vapor–melt partition coefficients and gas fractions were low. Modeled Li, F, and S vapor–melt partition coefficients are higher than those of B and Cl. The decrease in maximum MI CO₂ concentration following the earliest dacitic eruptions is interpreted to result from a broadening of the shallow storage region to greater than the diameter of subjacent feeders, so that greater proportions of reservoir magma were to the side of CO₂-bearing vapor bubbles ascending vertically from the locus of recharge magma injection, thereby escaping recarbonation by streaming vapor bubbles. The Mazama melt inclusions provide a picture of a growing magma storage region, where chemical variations in melt and magma occur due to changes in the nature and supply rate of magma recharge, the timing of degassing, and the possible degree of equilibration with gases from below.     

新疆东准噶尔松喀尔苏铜金矿区斑岩型矿床成因研究

松喀尔苏铜金矿区位于卡拉麦里石炭纪陆相火山岩带。文章通过矿床地质、围岩蚀变、含矿斑岩、流体包裹体和同位素研究,探讨了矿床成因类型。研究表明,松喀尔苏矿床具斑岩型矿床的特征,铜金矿化体产于岩体接触带,围岩蚀变具有分带性,从岩体向围岩依次发育绢英岩化带、高岭石化带和青磐岩化带,绢英岩化带与成矿相关。含矿斑岩复式岩体系同期陆相火山活动产物,成矿作用在时间、空间和成因上与复式岩体中晚期花岗斑岩有关。花岗斑岩具有富水、富挥发性组分和岩浆爆破作用的氧化性岩浆特点,具有后碰撞花岗岩类的地球化学亲缘性,其岩浆起源于后碰撞挤压-伸展转换期的壳-幔岩浆过渡带。幔源岩浆注入、软流圈地幔底侵作用和壳-幔岩浆混合作用是形成含矿斑岩岩浆的主导因素。流体包裹体包括液相包裹体、气相包裹体和含子晶多相包裹体,激光拉曼探针分析表明,气相成分以CO₂和CH₄为主。成矿流体具有从高温、高盐度岩浆体系向低温、低盐度与大气降水混合的演化过程,流体沸腾或不混溶作用及温度、盐度降低是导致流体中成矿物质沉淀的主要因素。氢、氧同位素组成表明成矿流体以岩浆水为主,在成矿晚期混有大气降水。硫同位素具幔源硫的特征。铅同位素组成显示成矿作用起源于下地壳-上地幔过渡带的岩浆作用。综上所述,该矿床属于与陆相火山-侵入岩有关的斑岩型铜金矿床。