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.     

我国东北小古里河-科洛-五大连池-二克山火山带钾质矿物成因及地质意义

东北黑龙江小古里河-科洛-五大连池-二克山火山岩带是我国近代保存最好的火山群之一,此带火山岩的岩石化学特点全都强碱富钾,K₂O/Na₂O>1.2,属于一套高钾过碱性火山岩。通过对东北钾质火山岩及金云母橄榄岩地幔捕虏体中钾质矿物金云母、白榴石的成分、结晶环境与岩浆成分及来源关系的研究,认为在岩石圈伸展构造背景下,地幔金云母橄榄岩的低度部分熔融形成钾质岩浆,钾质岩浆上升到地壳浅部经历了白榴石的结晶作用。岩浆演化晚期,因钾质矿物大量晶出导致岩浆相对富钠而出现他形霞石和方钠石等填隙矿物。火山岩及地幔捕虏体中富挥发分矿物金云母、白榴石、磷灰石、霞石和方钠石还提供了钾质岩浆富含H₂O、F、Cl、P等挥发分的证据。     

Nyerereite from carbonatite rocks at Vulture volcano: implications for mantle metasomatism and petrogenesis of alkali carbonate melts Research Article

Vulture volcano displays a wide range of mafic to alkaline, carbonate-, and/or CaO-rich volcanic rocks, with subvolcanic and plutonic rocks together with mantle xenoliths in pyroclastic ejecta. The roles of magmatic volatiles such as CO₂, S, and Cl have been determined from compositions and trapping temperatures of inclusions in phenocrysts, which include the Na-K-Ca-carbonate nyerereite within melilite. We surmise that this alkali carbonate crystallised from an appropriate carbonatitic melt at relatively high temperature. Carbonatitic metasomatic features are traceable throughout many of the mantle xenoliths, and various carbonatitic components are found in the late stage extrusive suite. There is no evidence that alkali carbonatite developed as a separate magma, but it may have been an important evolutionary stage. We compare the rare occurrence of nyerereite at Vulture with other carbonatites and with an unaltered kimberlite from the Udachnaya pipe. We review the evidence at Vulture for associated carbonatitic metasomatism in the mantle, and we suggest that low viscosity alkali carbonatitic melts may have a primary and much deeper origin than previously considered.     

Patent mantle-metasomatism: Inferences based on experimental studies

K, Na and Ca are the most common elements transported during mantle metasomatism and result in formation of phlogopite (K), amphibole (Na) and clinopyroxene (Ca) by various reactions. This review presents models for this type of metasomatism based on experiments on the pyrolite-K₂CO₃-H₂O, pyrolite-Na₂ CO₃-H₂O systems and on the pyrolite-CaCO₃ system. The addition of K₂CO₃ and Na₂CO₃ lowers the liquidus of pyrolite providing a low temperature, alkali-rich hydrous melt which may ascend and metasomatize overlying mantle regions. Several reactions are proposed for the formation of phlogopite and amphibole (pargasite-edenite) in these systems. The compositions of amphiboles correspond to those found in metasomatized mantle xenoliths. In contrast, Ca-metasomatism is considered to be mainly an anhydrous process in which orthopyroxene and carbonate react to produce clinopyroxene, olivine and CO₂. High pressure liquids in this model system are of carbonatitic composition and this low viscosity melt can ascend converting harzburgite mantle assemblages to olivine-rich wehrlite. Based on an inverse experimental approach, moderately high degrees of partial melting of a model metasomatized alkali clinopyroxenite xenolith yield liquids at 30kb which are very comparable in composition to the lavas enclosing such types of xenoliths. Experimental modelling of mantle metasomatism produces assemblages which are in good agreement with the mineral assemblages and textural relationships found in metasomatized mantle xenoliths from areas such as West Eifel and South-West Uganda.     

A geochemical traverse across the Eastern Carpathians (Romania): constraints on the origin and evolution of the mineral water and gas discharges

The inner sector of the Eastern Carpathians displays a large number of Na–HCO₃, CO₂-rich, meteoric-originated cold springs (soda springs) and bore wells, as well as dry mofettes. They border the southern part of the Pliocene–Quaternary Calimani–Gurghiu–Harghita (CGH) calc-alkaline volcanic chain. Both volcanic rocks and CO₂-rich emissions are situated between the eastern part of the Transylvanian Basin and the main east Carpathian Range, where active compression tectonics caused diapiric intrusions of Miocene halite deposits and associated saline, CO₂-rich waters along active faults. The regional patterns of the distribution of CO₂ in spring waters (as calculated pCO₂) and the distribution pattern of the ³He/⁴He ratio in the free gas phases (up to 4.5 R_m/R_a) show their maximum values in coincidence with both the maximum heat-flow measurements and the more recent volcanic edifices. Moving towards the eastern external foredeep areas, where oil fields and associated brines are present, natural gas emissions become CH₄-dominated. Such a change in the composition of gas emissions at surface is also recorded by the ³He/⁴He ratios that, in this area, assume ‘typical’ crustal values (R_m/R_a=0.02).In spite of the fact that thermal springs are rare in the Harghita volcanic area and that equilibrium temperature estimates based on geothermometric techniques on gas and liquid phases at surface do not suggest the presence of shallow active hydrothermal systems, a large circulation of fluids (gases) is likely triggered by the presence of mantle magmas stored inside the crust. If total ³He comes from the mantle or from the degassing of magmas stored in the crust, CO₂ might be associated to both volcanic degassing and thermometamorphism of recently subducted limestones.     

胜利油田火山岩单个包裹体碳同位素

近年来,在我国东部陆续发现了一些二氧化碳气藏,对其成因,不少学者有过讨论, 得出许多重要认识^①。     

Trace Element Geochemistry of Cenozoic Volcanic Rocks in Shandong Province

The Cenozoic volcanic rock of Shandong Province are mainly alkalic and strongly alkalic basaltic rocks.The Contents of major and trace elements including transitional,incompatible and rare-earth elements were determined.The chemical characterisitics of major and trace elements indicate that these basaltic rocks were derived from a mantle source and probably represent a primary magma,I,e.,unmodifiecd partical melts of mantle peridotite in terms of Mg values,correlatione between P2O5 and Ce,Sr,Ni and Rb concentrations,mantle xenoliths,etc.The abundances of trace elements vary systematically from west to east.The compatible transition elements such as Co,Ni,and Cr show a remarkable depletion,whereas the incompatible and rare-earth elements are abundant as viewed from the chondrite-nor-malized patterns.The chemical composition and correlation are consistent with the tectonic setting.According to the batch and fractional partial melting theory,the trace element contents of Shandong volcanic rocks can be calculated from the two-component mixing model.     

中昆仑造山带钾玄岩质火山岩的地质、地球化学和时代

 本文论述了中昆仑(北坡)4个地区第四纪火山岩的地质产状、岩石学、地球化学特征及时代。这一套岩石以安粗岩类为主,普遍含有普通辉石和斜长石斑晶,少数还有橄榄石、紫苏辉石或石英、透长石、黑云母斑晶。在化学上以富碱尤其富钾为突出特点,K₂O/Na₂O≥1,而且 Rb、Sr、Ba 等低场强元素和 LREE 也强烈富集,构成一个连续的钾玄岩系列(Shoshoaite Serics)。区域构造,地球化学和深源捕虏体的证据表明,本区钾玄质岩浆来自于上地幔的低度部分熔融,并受到地壳的同化和污染。火山活动大致从晚第三纪开始一直延续到第四纪,特别是中、晚更新世最为剧烈,是昆仑山及青藏高原快速隆升的新构造运动表现形式之一。     

滇东南建水地区高镁火山岩包体的成因和构造背景

在滇东南建水地区发现产于峨眉山玄武岩中的高镁火山岩包体,这对于地幔柱的形成演化具有重要研究意义.对这些包体进行了锆石U-Pb年代学、地球化学和岩矿分析.高镁火山岩包体具斑状结构,致密块状构造,斑晶主要为贵橄榄石和透辉石.13颗锆石U-Pb LA-ICP-MS加权平均年龄为259±2Ma(MSWD=1.9),显示与寄主岩石同期形成.包体岩石具有高镁(Mg~#=68～75)、低硅(SiO_2=45.11%～45.93%)特征,轻稀土元素(LREE)、高场强元素(HFSE)富集而重稀土元素(HREE)亏损,属于亚碱性、拉斑玄武岩系列,具有板内玄武岩(IPB)特征.火山岩包体的原始岩浆起源于石榴子石二辉橄榄岩低程度部分熔融的产物,岩浆演化过程中发生了橄榄石和单斜辉石的分离结晶作用,在侵位上升过程中未受明显的地壳混染作用.该高镁火山岩的存在,显示地幔柱除了垂直上升运动外,在地球深部不同的边界还有多次侧向扩展移动,表明滇东南晚二叠世存在峨眉山地幔柱的一个分支-地幔枝活动.     

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.     

松辽盆地含CO_2火山岩气藏的形成和分布

松辽盆地特有的深部构造背景和裂谷演化特征,造成盆地内含CO_2火山岩气藏的形成和富集。松辽裂谷盆地中新生代火山岩浆活动发育,总体上具有多期喷发、分布广泛和储集条件良好的特点。火山活动以中心式喷发为主,主要发育中基性-酸性火山岩,发育流纹岩、凝灰岩等多种岩石类型,爆发相和溢流相2种火山岩相。中生代火山岩在盆地内分布广泛,营域组构成深层有利储层,新生代火山岩在盆地外围出露较多,而在盆内出露较少。盆地高含量的二氧化碳为无机幔源成因,由青山口期和新生代幔源岩浆脱气形成。含CO_2火山岩气藏的形成主要受深部构造背景、深大断裂和中新生代火山岩控制。已发现含CO_2火山岩气藏主要分布于古中央隆起带及其两侧断陷的营城组火山岩中,具有点状、带状分布,局部富集的特点。根据主控因素分析,预测了5个CO_2富集区带。     

Carbon Enrichment in the Lithospheric Mantle: Evidence from the Melt Inclusions in Mantle Xenoliths from the Hainan Basalts

It is generally believed that the lithospheric mantle and the mantle transition zone are important carbon reservoirs. However, the location of carbon storage in Earth’s interior and the reasons for carbon enrichment remain unclear. In this study, we report CO₂-rich olivine-hosted melt inclusions in the mantle xenoliths of late Cenozoic basalts from the Penglai area, Hainan Province, which may shed some light on the carbon enrichment process in the lithospheric mantle. We also present ...     

Was the lethal eruption of Lake Nyos related to a double CO2/H2O density inversion?

The 1986 lethal eruption of Lake Nyos (Cameroon) was caused by a sudden inversion between deep, CO₂-loaded bottom lake waters and denser, gas-free surface waters. A deep CO₂ source has been found in fluid inclusions which occur predominantly in clinopyroxenes from lherzolitic mantle xenoliths, brought to the surface by the last erupted alkali basalts. P–T conditions of CO₂ trapping correspond to a gas density equal (or higher) than that of liquid water. It is suggested that this dense CO₂, found in many ultrabasic mantle xenoliths worldwide, has accumulated at km depth, below a column of descending lake water. It may remain in a stable state for a long period, as long as the temperature is above the density inversion temperature for pure H₂O/CO₂ systems. At an estimated depth of about 3 km, cooling by descending waters (to about 30 °C) induces a density inversion for the upper part of the CO₂ reservoir. This causes a constant, regular upstream of low-density CO₂ which, in its turn, feeds the shallower lake density inversion.     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

双辽火山活动与松辽盆地南部无机CO_2气藏的成因联系——来自火山岩中流体-熔融包裹体的证据

针对松辽盆地南部的双辽火山群中碱性玄武岩及包含其中的地幔捕掳体的普通薄片鉴定、岩石地球化学分析、流体包裹体显微岩相学和激光拉曼光谱分析,研究表明:双辽火山岩以碱性橄榄玄武岩为主,玄武岩中的地幔捕掳体比较发育;对玄武岩斑晶以及地幔捕掳体中的流体-熔融包裹体测试显示玄武岩中的橄榄石斑晶和地幔捕掳体中的流体-熔融包裹体十分发育,其成分主要是CO2,此外还含有少量的CO,CH4,N2和H2O,与上地幔中的自由流体相组分一致。松辽盆地南部的CO2气藏主要是幔源-岩浆成因,成藏时间较晚,主要在新生代,与双辽火山活动的时间接近。尽管双辽火山活动规模较小,但是具有很强的释出CO2的能力,这些富含CO2和H2O的碱性玄武质岩浆很可能并未喷出地表,而是沿着深大断裂进入盆地内部,从而成为松南无机CO2气藏气源体之一。     

Hf isotope compositions and HREE variations in off-craton garnet and spinel peridotite xenoliths from central Asia

Garnet-facies continental mantle is poorly understood because the vast majority of mantle xenoliths in continental basalts are spinel peridotite. Peridotite xenoliths from Vitim (southern Siberia) and Mongolia provide some of the best samples of garnet and garnet-spinel facies off-craton lithospheric mantle. Garnets in those fertile to moderately depleted lherzolites show a surprisingly broad range of HREE abundances, which poorly correlate with modal and major oxide compositions. Some garnets are zoned and have Lu-rich cores. We argue that these features indicate HREE redistribution after the partial melting, possibly related to spinel-garnet phase transition on isobaric cooling. Most peridotites from Vitim have depleted to ultra-depleted Hf isotope compositions (calculated from mineral analyses: ε_Hf(0) = +17 to +45). HREE-rich garnets have the most radiogenic ε_Hf values and plot above the mantle Hf-Nd isotope array while xenoliths with normal HREE abundances usually fall within or near the depleted end of the MORB field. Model Hf isotope ages for the normal peridotites indicate an origin by ancient partial melt extraction from primitive mantle, most likely in the Proterozoic. By contrast, an HREE-rich peridotite yields a Phanerozoic model age, possibly reflecting overprinting of the ancient partial melting record with that related to a recent enrichment in Lu. Clinopyroxene-garnet Lu-Hf isochron ages (31-84 Ma) are higher than the likely eruption age of the host volcanic rocks (∼16 Ma). Garnet-controlled HREE migration during spinel-garnet and garnet-spinel phase transitions may be one explanation for extremely radiogenic ¹⁷⁶Hf/¹⁷⁷Hf reported for some mantle peridotites; it may also contribute to Hf isotope variations in sub-lithospheric source regions of mantle-derived magmas.     

托云盆地新生代幔源岩浆源区起止深度的限定

在详细介绍了地幔熔融柱模型原理(Langmuir et al., 1992)的基础上,基于平衡熔融和分离熔融模型分别计算获得了上地幔橄榄岩源区在不同初始压力条件下发生绝热减压部分熔融时熔体相中FeO-MgO和FeO-Na₂O成分的演化轨迹。依据深源岩石包体与托云玄武岩之间的寄主关系将本次研究的16件托云火山岩样品划分成Group-1(深源岩石包体寄主岩)和Group-2(非寄主岩)两群,将收集前人的40件样品依据是否测试获得FeO的质量百分含量划分成Group-3群(具有实测的FeO质量百分含量)和Group-4群(无实测FeO质量百分含量数据)。分别对以上四群样品运用地幔熔融柱模型进行反演获得上地幔部分熔融源区的起止深度范围：Group-1和Group-3样品具有相同的初始熔融深度113.2km (34.1kbar),但它们的部分熔融作用终止深度分别为110.1km (33.1kbar) 和88.4km (26.2kbar);Group-2样品数据所反演的岩浆起源的初始深度和终止深度分别为111.6km (33.6kbar)和84.3.1km(24.9kbar);Group-4样品反演所获得的岩浆源区的起止深度分别为121.7km(36.8kbar)和106.0km(31.8kbar)。依据实测FeO百分含量的样品群反演的结果,将托云火山岩部分熔融源区的深度限定在113.2 km至84.3km,即48.1Ma前托云盆地所处的岩石圈厚度为84.3km,对梁涛(2005)运用熔融柱模型反演的托云盆地岩石圈深度进行了修正。此外,由地幔熔融柱模型反演获得的托云火山岩部分熔融源区熔体的温度压力条件与基于玄武岩中高压巨晶所反演的岩浆演化温压轨迹具有十分吻合的继承演化关系。地球物理探测表明现今西南天山岩石圈的厚度为71km,区域岩石圈演化历程中深度上13.3km的差异足以证明岩石圈拆沉这一地球动力学过程的存在,为由宽SHRIMP年龄谱识别出的岩石圈拆沉作用提供了另一个有力的证据。     

Multi-stage metasomatism in the lithosphere beneath the Veneto Volcanic Province (VVP, Northern Italy)

Mantle peridotites from the Veneto Volcanic Province (VPP) have been investigated in order to constrain P-T conditions of mantle events, determine the style of the metasomatic reactions, and the compositions of the metasomatic agents. Studied rocks show dominant protogranular and transitional textures; only one sample shows effect of pyrometamorphism. Clinopyroxenes in protogranular lherzolites show depleted LREE patterns, while those of transitional rocks are characterised by spoon-shaped REE patterns (La up to 60 times chondrite), and variable enrichments in LILE. Two generations of fluid inclusions are recognised: 1) Type I (CO₂ ± CO ± C fluid) found only in orthopyroxene of transitional xenoliths which may contain very small amphibole; 2) Type II (CO₂-rich fluid) found in all minerals of all xenoliths. Most of inclusions homogenize to liquid, with Th_L ranging between ?44 and 31°C. The densest CO₂ fluid inclusions (d?=?1.13?g/cm³), indicates a trapping pressure of ~10?kbar at 800°C. We propose that the mantle beneath the VVP equilibrated at pressures of 10?kbar, at about 800°C. Traces of an aqueous fluid preserved as fluid inclusions in orthopyroxene suggest the existence of an older subduction related metasomatic event and the occurrence of two stages metasomatism in the lithosphere beneath the SE Alps.     

Crustal growth in south-eastern Australia—evidence from lower crustal eclogitic and granulitic xenoliths

Mafic and ultramafic xenoliths in a basaltic cone at The Anakies in south-eastern Australia are geochemically equivalent to continental basaltic magmas and cumulates. The xenolith microstructures range from recognizably meta-igneous for intrusive rocks to granoblastic for garnet pyroxenites. Contact relationships between different rock types within some xenoliths suggest a complex petrogenesis of multiple intrusive, metamorphic and metasomatic events at the crust/mantle boundary during the evolution of south-eastern Australia. Unaltered spinel lher-zolite, typical of the uppermost eastern Australian mantle, is interleaved with or veined by the metamorphosed intrusive rocks of basaltic composition. Geothermobarometry calculations by a variety of methods show a concordance of equilibration temperatures ranging from 880°C to 980°C and pressures of 12 to 18 kbar (1200-1800 mPa). These physical conditions span the gabbro to granulite to eclogite transition boundaries. The water-vapour pressure during equilibration is estimated to be about 0.5% of the load pressure, using amphibole breakdown data. Large fluid inclusions of pure CO₂ are abundant in the mineral phases in the xenoliths, and it is suggested that flux of CO₂ from the mantle has been an important heat source and fluid medium during metamorphism of the mafic and ultramafic protoliths at the lower crust/upper mantle boundary. The calculated pressures and temperatures suggest that the south-eastern Australian crust has sustained a high geothermal gradient. In addition, the nature of the mineral assemblages and the contact relationships of granulitic rock with spinel lherzolite, characteristic of mantle material, suggest that the Moho is not a discrete feature in this region, but is represented by a transition zone approximately 20 km thick. These inferences are in agreement with geophysical data (including seismic, heat-flow and electrical resistivity data) determined for south-eastern Australia. Underplating at the crust/mantle boundary by continental basaltic magmas may be an important alternative or additional mechanism to the conventional andesite model for crustal accretion.