Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Immiscibility of high salinity fluids in volcanic rocks and the mechanism of magma degassing in the Dongying sag, eastern China

Fluid inclusions that bear halite daughter minerals were discovered in volcanic rocks at Pingnan area in the Dongying sag. The samples of the fluid inclusions collected from the BGX-15 well drill cores are hosted in quartz of diorite-porphyrite. The daughter minerals are identified as NaCl crystals after being observed under a microscope and analyzed by in situ Raman spectroscopy at −185°C. The results of micro-thermal analysis show that the homogenization temperatures of primary fluid inclusions are between 359 and 496°C, and the salinities of fluid inclusions are from 43.26 to 54.51 wt-%. All fluid inclusions in the studied samples can be divided into five types including primary fluid inclusions and secondary fluid inclusions. The fact that five types of fluid inclusions were symbiotic in the same quartz grain implies that immiscibility happened in magma. Due to the decrease in temperature and pressure during the ascent of magma, the fluids became intensively immiscible. This process accelerates the degassing of CO₂ from magma, but the remnant fluids with high salinity are preserved in fluid inclusions. Thus, the primary fluid inclusions are mainly in NaCl-H₂O fluids and poor in CO₂. The results of our study indicate that the degassing of magma and accumulation of CO₂ gas at the Pingnan area are relative to the immiscibility of high salinity fluids. This discovery is important because it can help us have a further understanding of the mechanism of magma degassing and accumulation of the inorganic CO₂ in eastern China. Translated from Acta Geologica Sinica, 2006, 80(11): 1699–1705 [译自: 地质学报]     

The 1783 Lakagigar eruption in Iceland: geochemistry,CO2 and sulfur degassing

About 12.3 km³ of basaltic magma were erupted from the Lakagigar fissure in Iceland in 1783, which may have been derived from the high-level reservoir of Grimsvotn central volcano, by lateral flow within the rifted crust. We have studied the petrology of quenched, glassy tephra from sections through pyroclastic cones along the fissure. The chemical composition of matrix glass of the 1783 tephra is heterogeneous and ranges from olivine tholeiite to Fe–Ti rich basalt, but the most common magma erupted is quartz tholeiite (Mg#43.6 to 37.2). The tephra are characterized by low crystal content (5 to 9 vol%). Glass inclusions trapped in plagioclase and Fo₈₆ to Fo₇₅ olivine phenocrysts show a large range of compositions, from primitive olivine tholeiite (Mg#64.3), quartz tholeiite (Mg#43–37), to Fe–Ti basalts (Mg#33.5) which represent the most differentiated liquids and are trapped as rare melt inclusions in clinopyroxene. Both matrix glass and melt inclusion data indicate a chemically heterogeneous magma reservoir, with quartz tholeiite dominant. LREE-depleted olivine-tholeiite melt-inclusions in Mg-rich olivine and anorthitic-plagioclase phenocrysts may represent primitive magma batches ascending into the reservoir at the time of the eruption. Vesicularity of matrix glasses correlates with differentiation, ranging from 10 to 60 vol.% in evolved quartz-tholeiite glasses, whereas olivine-tholeiite glasses contain less than 10 vol.% vesicles. FTIR analyses of olivine-tholeiite melt-inclusions indicate concentrations of 0.47 wt% H₂O and 430 to 510 ppm for CO₂. Chlorine in glass inclusions and matrix glasses increases from 50 ppm in primitive tholeiite to 230 ppm in Fe–Ti basalts, without clear evidence of degassing. Melt inclusion analyses show that sulfur varies from 915 ppm to 1970 ppm, as total FeO^* increases from 9 to 13.5 wt%. Sulfur degassing correlates both with vesicularity and magma composition. Thus sulfur in matrix glasses decreases from 1490 ppm to 500 ppm, as Mg # decreases from 47 to 37 and vesicularity of the magma strongly increases. These results indicate loss of at least 75% of sulfur during the eruption. The correlation of low sulfur content in matrix glasses with high vesicularity is regarded as evidence of the control of a major exsolving volatile phase on the degassing efficiency of the magma. Our model is consistent a quasi-permanent CO₂ flux through the shallow-level magmatic reservoir of Grimsvotn. Following magma withdrawal from the reservoir and during eruption from the Lakagigar fissure, sulfur degassing was controlled by inherent CO₂-induced vesicularity of the magma.     

Pre- and syn-eruptive degassing and crystallisation processes of the 2010 and 2006 eruptions of Merapi volcano,Indonesia

The 2010 eruption of Merapi (VEI 4) was the volcano’s largest since 1872. In contrast to the prolonged and effusive dome-forming eruptions typical of Merapi’s recent activity, the 2010 eruption began explosively, before a new dome was rapidly emplaced. This new dome was subsequently destroyed by explosions, generating pyroclastic density currents (PDCs), predominantly consisting of dark coloured, dense blocks of basaltic andesite dome lava. A shift towards open-vent conditions in the later stages of the eruption culminated in multiple explosions and the generation of PDCs with conspicuous grey scoria and white pumice clasts resulting from sub-plinian convective column collapse. This paper presents geochemical data for melt inclusions and their clinopyroxene hosts extracted from dense dome lava, grey scoria and white pumice generated during the peak of the 2010 eruption. These are compared with clinopyroxene-hosted melt inclusions from scoriaceous dome fragments from the prolonged dome-forming 2006 eruption, to elucidate any relationship between pre-eruptive degassing and crystallisation processes and eruptive style. Secondary ion mass spectrometry analysis of volatiles (H₂O, CO₂) and light lithophile elements (Li, B, Be) is augmented by electron microprobe analysis of major elements and volatiles (Cl, S, F) in melt inclusions and groundmass glass. Geobarometric analysis shows that the clinopyroxene phenocrysts crystallised at depths of up to 20 km, with the greatest calculated depths associated with phenocrysts from the white pumice. Based on their volatile contents, melt inclusions have re-equilibrated during shallower storage and/or ascent, at depths of ~0.6–9.7 km, where the Merapi magma system is interpreted to be highly interconnected and not formed of discrete magma reservoirs. Melt inclusions enriched in Li show uniform “buffered” Cl concentrations, indicating the presence of an exsolved brine phase. Boron-enriched inclusions also support the presence of a brine phase, which helped to stabilise B in the melt. Calculations based on S concentrations in melt inclusions and groundmass glass require a degassing melt volume of 0.36 km³ in order to produce the mass of SO₂ emitted during the 2010 eruption. This volume is approximately an order of magnitude higher than the erupted magma (DRE) volume. The transition between the contrasting eruptive styles in 2010 and 2006 is linked to changes in magmatic flux and changes in degassing style, with the explosive activity in 2010 driven by an influx of deep magma, which overwhelmed the shallower magma system and ascended rapidly, accompanied by closed-system degassing.     

Geology and fluid evolution of the Wangfeng orogenic-type gold deposit,Western Tian Shan,China

The Wangfeng gold deposit is located in Western Tian Shan and the central section of the Central Asian Orogenic Belt (CAOB). The deposit is mainly hosted in Precambrian metamorphic rocks and Caledonian granites and is structurally controlled by the Shenglidaban ductile shear zone. The gold orebodies consist of gold-bearing quartz veins and altered mylonite. The mineralization can be divided into three stages: quartz–pyrite veins in the early stage, sulfide–quartz veins in the middle stage, and quartz–carbonate veins or veinlets in the late stage. Ore minerals and native gold mainly formed in the middle stage. Four types of fluid inclusions were identified based on petrography and laser Raman spectroscopy: CO₂–H₂O inclusions (C-type), pure CO₂ inclusions (PC-type), NaCl–H₂O inclusions (W-type), and daughter mineral-bearing inclusions (S-type). The early-stage quartz contains only primary CO₂–H₂O fluid inclusions with salinities of 1.62 to 8.03 wt.% NaCl equivalent, bulk densities of 0.73 to 0.89 g/cm³, and homogenization temperatures of 256 °C–390 °C. Vapor bubbles are composed of CO₂. The middle-stage quartz contains all four types of fluid inclusions, of which the CO₂–H₂O and NaCl–H₂O types yield homogenization temperatures of 210 °C–340 °C and 230 °C–300 °C, respectively. The CO₂–H₂O fluid inclusions have salinities of 0.83 to 9.59 wt.% NaCl equivalent and bulk densities of 0.77 to 0.95 g/cm³, with vapor bubbles composed of CO₂, CH₄, and N₂. Fluid inclusions in the late-stage quartz are NaCl–H₂O solution with low salinities (0.35–3.87 wt.% NaCl equivalent) and low homogenization temperatures (122 °C–214 °C). The coexistence of inclusions of these four types in middle-stage quartz suggests that fluid boiling occurred in the middle-stage mineralization. Trapping pressures estimated from CO₂–H₂O inclusions are 110–300 MPa and 90–250 MPa for the early and middle stages, respectively, suggesting that gold mineralization mainly occurred at depths of about 10 km. In general, the Wangfeng gold deposit originated from a metamorphic fluid system characterized by low salinity, low density, and enrichment of CO₂. Depressurized fluid boiling caused gold precipitation. Given the regional geology, ore geology, fluid-inclusion features, and ore-forming age, the Wangfeng gold deposit can be classified as a hypozonal orogenic gold deposit.     

CO<Subscript>2</Subscript> fluid inclusions in Jack Hills zircons

The discovery of Hadean to Paleoarchean zircons in a metaconglomerate from Jack Hills, Western Australia, has catalyzed intensive study of these zircons and their mineral inclusions, as they represent unique geochemical archives that can be used to unravel the geological evolution of early Earth. Here, we report the occurrence and physical properties of previously undetected CO₂ inclusions that were identified in 3.36–3.47 Ga and 3.80–4.13 Ga zircon grains by confocal micro-Raman spectroscopy. Minimum P–T conditions of zircon formation were determined from the highest density of the inclusions, determined from the density-dependence of the Fermi diad splitting in the Raman spectrum and Ti-in-zircon thermometry. For both age periods, the CO₂ densities and Ti-in-zircon temperatures correspond to high-grade metamorphic conditions (≥5 to ≥7 kbar/~670 to 770 °C) that are typical of mid-crustal regional metamorphism throughout Earth’s history. In addition, fully enclosed, highly disordered graphitic carbon inclusions were identified in two zircon grains from the older population that also contained CO₂ inclusions. Transmission electron microscopy on one of these inclusions revealed that carbon forms a thin amorphous film on the inclusion wall, whereas the rest of the volume was probably occupied by CO₂ prior to analysis. This indicates a close relationship between CO₂ and the reduced carbon inclusions and, in particular that the carbon precipitated from a CO₂-rich fluid, which is inconsistent with the recently proposed biogenic origin of carbon inclusions found in Hadean zircons from Jack Hills.     

http://www.sciencedirect.com/science/article/pii/S1674987114000590

This paper reviews the origin and evolution of fluid inclusions in ultramafic xenoliths,providing a framework for interpreting the chemistry of mantle fluids in the different geodynamic settings.Fluid inclusion data show that in the shallow mantle,at depths below about 100 km,the dominant fluid phase is CO_2±brines,changing to alkali-,carbonate-rich(silicate) melts at higher pressures.Major solutes in aqueous fluids are chlorides,silica and alkalis(saline brines;5-50 wt.%NaCl eq.).Fluid inclusions in peridotites record CO_2 fluxing from reacting metasomatic carbonate-rich melts at high pressures,and suggest significant upper-mantle carbon outgassing over time.Mantle-derived CO_2(±brines) may eventually reach upper-crustal levels,including the atmosphere,independently from,and additionally to magma degassing in active volcanoes.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Fluid and silicate glass inclusions in ultramafic and mafic xenoliths from Hierro,Canary Islands: implications for mantle metasomatism

Fluid and solid inclusions have been studied in selected samples from a series of spinel-bearing Crdiopside-and Al-augite-series ultramafic (harzburgites, lherzolites, and olivine-clinopyroxene-rich rocks), and gabbroic xenoliths from Hierro, Canary Islands. In these samples several generations of fluid inclusions and ultramafic-and mafic-glass inclusions may be texturally related to different stages of crystal growth. The fluid inclusions consist of pure, or almost pure, CO₂. The solid inclusions in the ultramafic xenoliths comprise early inclusions of devitrified ultramafic glass, sulphide inclusions, as well as polyphase inclusions (spinel+clinopyroxene±glass±other silicates) believed to have formed from trapped basaltic melts. Vitreous basaltic glass±CO₂±sulphide±silicates are common as secondary inclusions in the ultramafic xenoliths, and as primary inclusions in the gabbroic xenoliths. Microthermometry gives minimum trapping temperatures of 1110° C for the early ultramafic-and mafic-glass inclusions, and a maximum of 1260–1280° C for late inclusions of host basaltic glass. In most samples the CO₂ inclusions show a wide range in homogenization temperatures (-40 to +31° C) as a result of decrepitation during ascent. The lowest homogenization temperatures of about-40° C, recorded in some of the smallest CO₂ inclusions, indicate a minimum depth of origin of 35 km (12 kbar) for both the Cr-diopside-and Al-augite-series xenoliths. The gabbroic xenoliths originate from a former magma chamber at a depth of 6–12 km.Contribution no. 100 of the Norwegian programme of the International Lithosphere Project     

Mixing and differentiation in the Oruanui rhyolitic magma, Taupo, New Zealand: evidence from volatiles and trace elements in melt inclusions

Large pyroclastic rhyolites are snapshots of evolving magma bodies, and preserved in their eruptive pyroclasts is a record of evolution up to the time of eruption. Here we focus on the conditions and processes in the Oruanui magma that erupted at 26.5 ka from Taupo Volcano, New Zealand. The 530 km³ (void-free) of material erupted in the Oruanui event is comparable in size to the Bishop Tuff in California, but differs in that rhyolitic pumice and glass compositions, although variable, did not change systematically with eruption order. We measured the concentrations of H₂O, CO₂ and major and trace elements in zoned phenocrysts and melt inclusions from individual pumice clasts covering the range from early to late erupted units. We also used cathodoluminescence imaging to infer growth histories of quartz phenocrysts. For quartz-hosted inclusions, we studied both fully enclosed melt inclusions and reentrants (connecting to host melt through a small opening). The textures and compositions of inclusions and phenocrysts reflect complex pre-eruptive processes of incomplete assimilation/partial melting, crystallization differentiation, magma mixing and gas saturation. ‘Restitic’ quartz occurs in seven of eight pumice clasts studied. Variations in dissolved H₂O and CO₂ in quartz-hosted melt inclusions reflect gas saturation in the Oruanui magma and crystallization depths of ∼3.5–7 km. Based on variations of dissolved H₂O and CO₂ in reentrants, the amount of exsolved gas at the beginning of eruption increased with depth, corresponding to decreasing density with depth. Pre-eruptive mixing of magma with varying gas content implies variations in magma bulk density that would have driven convective mixing. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

A Fluid Inclusion Study of Vein-type Copper Mineralization in the East Wulasigou Pb–Zn–Cu Deposit, Altay, Northwestern China

The Wulasigou Cu-Pb-Zn deposit,located 15 km northwest of Altay city in Xinjiang,is one of many Cu-Pb-Zn polymetallic deposits in the Devonian Kelan volcanic-sedimentary basin in southern Altaids.Two mineralizing periods can be distinguished:the marine volcanic sedimentary PbZn mineralization period,and the metamorphic hydrothermal Cu mineralization period,which is further divided into an early bedded foliated quartz vein stage(Q1) and a late sulfide-quartz vein stage(Q2) crosscutting the foliation.Four types of fluid inclusions were recognized in the Q1 and Q2 quartz from the east orebodies of the Wulasigou deposit:H_2O-CO_2 inclusions,carbonic fluid inclusions,aqueous fluid inclusions,and daughter mineral-bearing fluid inclusions.Microthermometric studies show that solid CO_2 melting temperatures(T_(m,CO2)) of H_2O-CO_2 inclusions in Ql are from-62.3℃ to-58.5C,clathrate melting temperatures(T_(m,clath)l) are from 0.5 C to 7.5 C,partial homogenization temperatures(T_(h,CO2)) vary from 3.3℃ to 25.9℃(to liquid),and the total homogenization temperatures(T_(h,tot)) vary from 285℃ to 378℃,with the salinities being 4.9%-15.1%NaCl eqv.and the CO_2-phase densities being 0.50-0.86 g/cm~3.H_2O-CO_2 inclusions in Q2 have T_(m,CO_2) from-61.9℃ to-56.9℃,T_(m,clath)from 1.3℃ to 9.5℃,T_(h,CO2) from 3.4℃ to 28.7℃(to liquid),and T_(h,tot) from 242℃ to 388℃,with the salinities being 1.0%-15.5%NaCl eqv.and the CO_2-phase densities being 0.48-0.89 g/cm~3.The minimum trapping pressures of fluid inclusions in Q1 and Q2 are estimated to be 260-360 MPa and180-370 MPa,respectively.The δ~(34)S values of pyrite from the volcanic sedimentary period vary from2.3‰ to 2.8‰(CDT),and those from the sulfide-quartz veins fall in a narrow range of-1.9‰ to 2.6‰(CDT).The δD values of fluid inclusions in Q2 range from-121.0‰ to-100.8‰(SMOW),and theδ~(18)O_(H2O) values calculated from δ~(18)O of quartz range from-0.2‰ to 8.3‰(SMOW).The δD-δ~(18)O_(H2O)data are close to the magmatic and metamorphic fields.The fluid inclusion and stable isotope data documented in this study indicate that the vein-type copper mineralization in the Wulasigou Pb-Zn-Cu deposit took place in an orogenic-metamorphic enviroment.     

The melt inclusion record from the rhyolitic Kos Plateau Tuff (Aegean Arc)

The >60 km³ rhyolitic Kos Plateau Tuff provides an exceptional probe into the behavior of volatile components in highly evolved arc magmas: it is crystal-rich (30–40 vol% crystals), was rapidly quenched by the explosive eruptive process, and contains abundant homogeneous melt inclusions in large quartz crystals. Several methods for measuring major, trace and volatile element concentrations (SIMS, FTIR, Raman spectroscopy, electron microprobe, LA–ICPMS) were applied to these melt inclusions. We found a ~2 wt% range of H₂O contents (4.5–6.5 wt% H₂O, measured independently by SIMS, FTIR, and Raman spectroscopy) and relatively low CO₂ concentrations (15–140 ppm measured by FTIR, with most analyses <100 ppm). No obvious correlations between H₂O, CO₂, major and trace elements are observed. These observations require a complex, protracted magma evolution in the upper crust that included: (1) vapor-saturated crystallization in a chamber located between 1.5 and 2.5 kb pressure, (2) closed-system degassing (with up to 10 vol% exsolved gas) as melts percolated upwards through a vertically extensive mush zone (2–4 km thick), and (3) periodic gas fluxing from subjacent, more mafic and more CO₂-rich magma, which is preserved as andesite bands in pumices. These processes can account for the range of observed H₂O and CO₂ values and the lack of correlation between volatiles and trace elements in the melt inclusions.     

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.     

Fluid Inclusions in the Gold—Bearing Quartz Veins at Um Rus Area,Eastern Desert,Egypt

Fluid inclusions in the gold-bearing quartz veins at the Um Rus area are of three types: H₂O, H₂O−CO₂ and CO₂ inclusions. H₂O inclusions are the most abundant, they include two phases which exhibit low and high homogenization temperatures ranging from 150 to 200°C and 175 to 250°C, respectively. The salinity of aqueous inclusions, based on ice melting, varies between 6.1 and 8 equiv. wt% NaCl. On the other hand, H₂O−CO₂ fluid inclusions include three phases. Their total homogenization temperatures range from 270 to 325°C, and their salinity, based on clathrate melting, ranges between 0.8 and 3.8 equiv. wt% NaCl. CO₂ fluid inclusions homogenize to a liquid phase and exhibit a low density range from 0.52 to 0.66 g/cm³. The partial mixing of H₂O−CO₂ and salt H₂O−NaCl fluid inclusions is the main source of fluids from which the other types of inclusions were derived. The gold-bearing quartz veins are believed to be of medium temperature hydrothermal convective origin.     

Fluid inclusions in quartz from deep-seated granitic intrusions,south Norway

H₂O, CO₂, and H₂OCO₂ inclusions were observed in quatz from deep-seated granitic intrusions belonging to the Precambrian Farsund plutonic complex, south Norway. These inclusions represent solidus and/or sub-solidus fluids that were present in these rocks at some period between the initial melt and the present. Early CO₂ and H₂OCO₂ inclusions with about 20 mole% CO₂ contain up to 10 mole% CH₄ in the CO₂ phase and have densities from 0.96 to 0.85 g/cc. These inclusions are considered to most nearly approximate solidus vapour phases and suggest conditions of final solidification of the magma at 5 to 6 Kb and 700°C to 800°C. The H₂O inclusions have salinities between 2 and 60 wt%; the majority contain 5 to 20 equivalent wt.% NaCl and have densities from 1.05 to 0.85 g/cc. Microthermometry indicates that other cations such as K⁺, Ca²⁺ and / or Mg²⁺ are present in these aqueous fluids. The H₂O inclusions primarily represent fluids present at a post-magmatic stage of fracturing and healing of these rocks during uplift.     

A new view of the He-Ar-CO2 degassing at mid-ocean ridges: Homogeneous composition of magmas from the upper mantle

Deep-sea exploration is rapidly improving our understanding of volatiles geochemistry in mid-ocean-ridge igneous products. It is also placing greater constraints on degassing processes of the Earth’s mantle, with the result that degassing models based on vapour-melt equilibrium are no longer able to explain the increasing number of data. In fact, such models force to postulate an upper mantle strongly heterogeneous at any scale, and cannot account for the widespread carbon supersaturation of the recovered igneous products. Here we review the global He-Ar-CO₂ dataset of fluid inclusions in mid-ocean-ridge glasses using the framework of advanced modelling of multicomponent bubble growth in magmas. We display that non-equilibrium fractionations among He, Ar and CO₂, driven by their different diffusivities in silicate melts, are common in most of the natural conditions of magma decompression and their signature strongly depends on pressure of degassing. Due to the comparable Ar and CO₂ diffusivity, magma degassing at low pressure fractionates both the He/Ar and He/CO₂ ratio by a similar extent, while the slower CO₂ diffusion at high pressure causes early kinetic effects on Ar/CO₂ ratio and dramatically changes the degassing path. On this ground, the very different geochemical signatures among suites of data coming from different ridge segments mainly depend on the depth of the magma chamber where the melt was stored. Besides, the variations inside a single suite highlight variable ascent speed and cooling rate of the emplaced lava. The large variations in both the He/CO₂ and Ar/CO₂ ratios at almost constant He/Ar, displayed in glasses coming from the Mid-Atlantic Ridge 24-30°N segment and the Rodriguez Triple Junction, are therefore interpreted as a high-pressure signature. In contrast, the simultaneous increase in both He/CO₂ and He/Ar of the East Pacific Rise, Pito Seamount and South-East Indian Ridge data sets suggests the dominance of low-pressure fractionation, implying that the shallow magma chambers are at a lower depth than those of the Mid-Atlantic Ridge 24-30°N and Rodriguez Triple Junction. Our conclusions support the presence of a relationship between spreading rate and depth of high-temperature zones below ridges, and are consistent with the depth of magma chambers as suggested from seismic studies. Non-equilibrium degassing explains the volatile systematics of mid-ocean-ridge basalts by starting from a single mantle-derived magma, dispensing with the supposed need for heterogeneities in abundance ratios of volatiles in the mantle below oceanic ridges.     

Silicate melt inclusions in the Qiushuwan granitoids,northern Qinling belt,China: Implications for the formation of a porphyry Cu–Mo deposit as a reduced magmatic system

Melt inclusions (MIs) in quartz from granitoids in the northern Qinling belt were studied using microthermometry and laser Raman spectroscopy. The total homogenization of melt inclusions occurs in a mean range between 1050 and 1100 °C. Laser Raman experiments reveal H₂O, C₂H₆, C₄H₆ and CH₄ as the dominant volatile compounds. Our results provide insights into the temperatures of magma crystallization and the dominantly reducing environment during the early magmatic stage. Based on ore mineralogy, and on the volatile species content in the MIs, we evidence firstly that the Qiushuwan porphyry Cu–Mo deposit in the Qinling–Dabie–Sulu orogenic belt was derived from a reduced magmatic system, emplaced at relatively deep domains more than 10 km deep, and secondly, that the magmas that are responsible for the generation of Qiushuwan were either derived from an inherently reduced source, or reduced during ascent and emplacement. The mechanism might have involved the assimilation of sedimentary material with minimal crustal interaction. The parental magmas likely underwent reduction essentially by loss of all of their SO₂ by degassing, as evidenced by the low S content in melt inclusions. These reduced materials provided adequate sulfur source for the formation of the porphyry Cu–Mo deposits with obvious zonation, which plays a key role in the mineralization; finally, we conclude that the reduced environment and the relatively deep domain of magma emplacement probably limited the extent of mineralization, generating only a relatively small Cu–Mo deposit in Qiushuwan, located within the northern Qinling accretionary belt.     

Abundance of CO<Subscript>2</Subscript>-rich fluid inclusions in a sedimentary basin-hosted Cu deposit at Jinman,Yunnan, China: implications for mineralization environment and classification of the deposit

The Jinman Cu deposit is hosted in sandstones and slates of the Jurassic Huakaizuo Formation in the Mesozoic to Cenozoic Lanping basin in western Yunnan, China. Despite the fact that Cu mineralization occurs mainly in quartz–carbonate veins controlled by faults and fractures, the Jinman deposit was classified as a sediment-hosted stratiform Cu deposit, mainly because it is hosted in a sedimentary basin characterized by abundant red beds with many stratiform Cu deposits. A detailed petrographic and microthermometric study of fluid inclusions from the Jinman deposit reveals the presence of abundant CO₂-rich fluid inclusions, together with aqueous inclusions. The CO₂-rich inclusions have CO₂ melting temperatures mainly from −58.0°C to −56.6°C, homogenization temperatures of the carbonic phase (mostly into the liquid phase) mainly between 22°C and 30°C, clathrate melting temperatures from 1.8°C to 9.2°C, with corresponding salinities from 1.6 to 13.4 wt.% NaCl equivalent, and total homogenization temperatures from 226°C to 330°C. The aqueous inclusions have first melting temperatures from −60°C to −52°C, ice melting temperatures from −41.4°C to −2.3°C, with salinities from 3.9 to 29.0 wt.% NaCl equivalent, and total homogenization temperatures mainly from 140°C to 250°C. These fluid inclusion characteristics are comparable to those of orogenic or magmatic mineralization systems and are uncharacteristic of basinal mineralization systems, suggesting that it is inappropriate to classify the Jinman deposit as a sediment-hosted stratiform Cu deposit. The results of this study, together with geochemical data reported previously, suggest that the Jinman deposit formed in a hydrothermal system that involved both extra-basinal, deeply sourced CO₂-rich fluid and basinal, aqueous fluid.     

Origin of xenoliths in the trachyte at Puu Waawaa,Hualalai Volcano,Hawaii

Rare dunite and 2-pyroxene gabbro xenoliths occur in banded trachyte at Puu Waawaa on Hualalai Volcano, Hawaii. Mineral compositions suggest that these xenoliths formed as cumulates of tholeiitic basalt at shallow depth in a subcaldera magma reservoir. Subsequently, the minerals in the xenoliths underwent subsolidus reequilibration that particularly affected chromite compositions by decreasing their Mg numbers. In addition, olivine lost CaO and plagioclase lost MgO and Fe₂O₃ during subsolidus reequilibration. The xenoliths also reacted with the host trachyte to form secondary mica, amphibole, and orthopyroxene, and to further modify the compositions of some olivine, clinopyroxene, and spinel grains. The reaction products indicate that the host trachyte melt was hydrous. Clinopyroxene in one dunite sample and olivine in most dunite samples have undergone partial melting, apparently in response to addition of water to the xenolith. These xenoliths do not contain CO₂ fluid inclusions, so common in xenoliths from other localities on Hualalai, which suggests that CO₂ was introduced from alkalic basalt magma between the time CO₂-inclusion-free xenoliths erupted at 106±6 ka and the time CO₂-inclusion-rich xenoliths erupted within the last 15 ka.     

CO_2 Density-Raman Shift Relation Derived from Synthetic Inclusions in Fused Silica Capillaries and Its Application

Abstract: The densities of CO2 inclusions in minerals are commonly used to determine the crystallizing conditions of the host minerals. However, conventional microthermometry is difficult to apply for inclusions of small size (< 5–10 μm) or low density. Raman analysis is an alternative method for determining CO2 density, provided that the CO2 density–Raman shift relation is known. This study aims to establish this CO2 density–Raman shift relation by using CO2 inclusions synthesized in fused silica capillaries. By using this newly-developed synthetic technique, we formed pure CO2 inclusions, and their densities were determined by microthermometry. The Raman analysis showed that the relation between CO2 density (D in g/cm3) and the separations (Δ in cm?1) between the two main bands (i.e. Fermi diad bands) in CO2 Raman spectra can be represented by a cubic equation: D (g/cm3)=0.74203(?0.019Δ3+5.90332Δ2?610.79472Δ+21050.30165)?3.54278 (r2=0.99920). Our calculated D value for a given Δ is between those obtained from two previously-reported equations, which were derived from different experimental methods. An example was given in this study to demonstrate that the densities of natural CO2 inclusions that could not be derived from microthermometry could be determined by using our method.