壳源碳酸岩特征、成因及意义

自1999年Lentz David R.重新提出碳酸岩壳源成因以来,已有越来越多壳源成因碳酸岩实例的报道。本文对近二十年来发现的壳源成因碳酸岩的时空分布、产出特征、岩石矿物学特点、地球化学特征以及成因机制进行了总结,对该类碳酸岩成因研究的意义和研究方向进行了展望。壳源碳酸岩在空间上均分布于造山带内部,并以克拉通边缘的造山带为主,在特提斯造山带和中亚造山带中分布最为集中;时代上从元古代到新生代均有发育,不同时代的岩体在地球化学组成上有所差异;其围岩多为经历过高级变质的花岗片麻岩和大理岩组成的混合岩;成分上多为钙质,微量元素具较弱的轻重稀土分异,显著的Eu、Nb、Ta、Zr和Hf负异常及Pb和Sr正异常,Sr-Nd同位素组成介于球粒陨石和大陆地壳演化线之间,C-O同位素介于原生碳酸岩浆与沉积碳酸盐岩之间。这些特征在一定程度上异于克拉通内的碳酸岩,而多与造山带内的碳酸岩相似。实验岩石学工作揭示方解石和白云石在地壳深度、温度低至650℃以及有足够多水参与的情况下可发生部分熔融而形成碳酸盐岩浆,而高级区域变质作用过程中释放的变质流体或热液卤水有助于碳酸盐矿物的部分熔融。这种方式形成的碳酸岩在矿物组合及某些地球化学特征方面与其母岩大理岩、灰岩或白云岩具有相似性。因此,鉴于壳源碳酸岩规模较小且多与其母岩共存,厘定是否发生过部分熔融尚存在一定难度,其成因机制亦存在较多争议。壳源碳酸岩浆的成因机制包括中酸性侵入体引起碳酸盐岩熔融、基性岩浆高温热流引起碳酸盐岩熔融、强烈区域变质作用造成碳酸盐岩部分熔融和大理岩深熔作用。壳源成因碳酸岩的发现对以往碳酸岩成因上的疑惑给出了合理解释,亦对主流的碳酸岩幔源成因观点提出了挑战;对碳酸岩用于反演地幔演化、深部碳循环乃至板块俯冲提出了质疑,亦为探索造山过程、变质作用、地壳深熔作用及碳酸岩成矿多样性提供了重要的研究窗口。

     

碳酸盐岩干酪根催化降解生烃过程及动力学研究

以甘肃平凉地区奥陶系碳酸盐岩干酪根为对象,利用热模拟实验方法和化工催化原理,从热解生烃组成特征、生烃量及生烃动力学等方面考察了不同介质对干酪根热解生烃过程的影响。结果表明,碳酸盐岩对干酪根生烃过程具有反催化作用,随着温度的增加,反催化作用越明显。膏岩CaSO4则表现出正催化作用,各种盐类对干酪根生烃过程影响较小。干酪根热解动力学研究表明,生烃动力学参数活化能E与视频率因子A之间不是独立变化的,它们之间存在一定的关系,即:E与lnA呈线形关系,这对于认识碳酸盐岩干酪根的化学结构及热解生烃机理具有一定的参考价值。     

甘肃西秦岭新生代钾霞橄黄长岩和碳酸岩的微量、稀土和Sr，Nd，Pb同位素地球化学：地幔柱-岩石圈交换的证据

西秦岭新生代钾霞橄黄长岩和碳酸岩具有强烈富集LILE和LREE的特征,经球粒陨石标准化的REE分配模式与OIB十分相似。钾霞橄黄长岩和碳酸岩的(^87Sr／^86Sr)i分别在0．70381～0．70940和0．70529～0．71332之间,^144Nd／^143Nd分别介于0．512404～0．512924和0．512210～0．512928之间。经计算获得多数样品的εNd落在-3．4～5．58范围内,与OIB的εNd值一致。这两类岩石的^208Pb／^204Pb、^207Pb/^204Pb和^206Pb／^204Pb分别为37．613～39．330和38．060～38．995,15．842～16．441和15.545～15．677,以及18．418～22．4和18．149～19．062。采用主量元素MgO—Ni和ε(Nd)-(^87Sr/^86Sr)相关图,以及高场强元素比值Zr／Nb—La／Nb和Ba／La—Ba／Nb相关图以及。^208Pb／^204Pb-^206Pb/^204Pb,^207Pb／^204Pb-^206Pb／^204Pb相关图,一致证明本区火山岩具有与洋岛玄武岩(OIB)相似的地球化学特征,且源区具有EM1和EM11富集端员的混合。但是本区火山岩高的Nb／Ta比和强烈富集Nb等高场强元素,以及较高的^144Nd／^143Nd值,表明该火山岩地球化学具有某种特殊性。结合对西秦岭深部地球物理资料及地质构造背景和演化历史的分析,提出西秦岭新生代钾霞橄黄长岩和碳酸岩的成因与地幔柱的活动有关,源区包含了EM1和EM11富集端员的组分。EM1和EM11富集端员的成因与地幔柱/软流圈流体的作用有关,也与大洋板片的脱水作用和大陆岩石圈的拆层作用有关。该区特殊的大地构造背景和演化历史为上述几种作用的联合提供了可能。它不仅较好地解释了该火山岩地球化学方面的特殊性,及钾霞橄黄长岩与碳酸岩共生的事实,同时也证明新生代火山岩的成因是地幔柱．岩石圈相互作用的产物。     

白云鄂博地区碳酸岩墙及岩墙旁侧石英岩中的包裹体研究

白云鄂博的碳酸岩墙中包裹体类型有多子晶包裹体、两相水溶液包裹体、含CO_2三相包裹体和含子晶三相包裹体,岩相学和显微测温结果表明,这些包裹体与国外典型的碳酸岩中的包裹体具有很大程度的一致性,反映了其岩浆成因特点;碳酸岩墙中旁侧的白云鄂博H2石英岩中含有大量的流体包裹体,主要类型为NaCl-H_2O包裹体、CO_2包裹体和H_2O±CO_2±固体的包裹体。包裹体的岩相学、显微测温、阴极发光特征、包裹体成分ICP-MS测定,激光拉曼研究等,揭示出石英岩中的包裹体捕获了来自碳酸岩墙的碳酸岩浆流体,提供了一种不可多得的直接研究碳酸岩流体的手段。     

Columbitization of fluorcalciopyrochlore by hydrothermalism at the Saint-Honoré alkaline complex,Québec (Canada): New insights on halite in carbonatites

Niobium (Nb) in carbonatite is mainly hosted in fluorcalciopyrochlore and columbite-(Fe). Information related to Nb petrogenesis is useful for understanding the processes related to Nb mineralization and carbonatite evolution. The Saint-Honoré, Quebec, alkaline complex offers a rare opportunity for studying these processes as the complex is not affected by post-emplacement deformation, metamorphism nor weathering. Columbite-(Fe) is shown to be an alteration product of fluorcalciopyrochlore (columbitization). Columbitization is characterized by the leaching of Na and F from the A- and Y-sites of the pyrochlore crystal structure. As alteration increases, Fe and Mn are slowly introduced while Ca is simultaneously leached. Leached Ca and F then crystallize as inclusions of calcite and fluorite within the columbite-(Fe). A-site cations and vacancies in the crystal structure of fresh and altered pyrochlores demonstrate that pyrochlore alteration is hydrothermal in origin. Moreover, halite is a ubiquitous mineral in the Saint-Honoré alkaline complex. Petrographic evidence shows that halite forms in weakly altered pyrochlores, suggesting halite has a secondary origin. As alteration increases, halite is expelled by the hydrothermal fluid and is carried farther into the complex, filling factures throughout the carbonatite. The hydrothermal hypothesis is strengthened by significant enrichments in Cl and HREEs in columbite-(Fe). Chlorine is most likely introduced by a hydrothermal fluid that increases the solubility of REEs.     

The Catalão I niobium deposit, central Brazil: Resources, geology and pyrochlore chemistry

The Catalão I alkaline–carbonatite–phoscorite complex contains both fresh rock and residual (weathering-related) niobium mineralization. The fresh rock niobium deposit consists of two plug-shaped orebodies named Mine II and East Area, respectively emplaced in carbonatite and phlogopitite. Together, these orebodies contain 29 Mt at 1.22 wt.% Nb₂O₅ (measured and indicated). In closer detail, the orebodies consist of dike swarms of pyrochlore-bearing, olivine-free phoscorite-series rocks (nelsonite) that can be either apatite-rich (P2 unit) or magnetite-rich (P3 unit). Dolomite carbonatite (DC) is intimately related with nelsonite. Natropyrochlore and calciopyrochlore are the most abundant niobium phases in the fresh rock deposit. Pyrochlore supergroup chemistry shows a compositional trend from Ca–Na dominant pyrochlores toward Ba-enriched kenopyrochlore in fresh rock and the dominance of Ba-rich kenopyrochlore in the residual deposit. Carbonates associated with Ba-, Sr-enriched pyrochlore show higher δ¹⁸O_SMOW than expected for carbonates crystallizing from mantle-derived magmas. We interpret both the δ¹⁸O_SMOW and pyrochlore chemistry variations from the original composition as evidence of interaction with low-temperature fluids which, albeit not responsible for the mineralization, modified its magmatic isotopic features. The origin of the Catalão I niobium deposit is related to carbonatite magmatism but the process that generated such niobium-rich rocks is still undetermined and might be related to crystal accumulation and/or emplacement of a phosphate–iron-oxide magma.     

Change in carbonate budget and composition during subduction below metal saturation boundary

It is generally accepted that carbonates can be subducted to the mantle depths, where they are reduced with iron metal to produce a diamond. In this work, we found that this is not always the case. The mantle carbonates from inclusions in diamonds show a wide range of cation compositions (Mg, Fe, Ca, Na, and K). Here we studied the reaction kinetics of these carbonates with iron metal at 6–6.5 GPa and 1000–1500 °C. We found that the reduction of carbonate with Fe produces C-bearing species (Fe, Fe-C melt, Fe₃C, Fe₇C₃, C) and wüstite containing Na₂O, CaO, and MgO. The reaction rate constants (k = Δx²/2t) are log-linear relative to 1/T and their temperature dependences are determined to bek_MgCO3 (m²/s) = 4.37 × 10^?3 exp [?251 (kJ/mol)/RT]k_CaMg(CO3)2 (m²/s) = 1.48 × 10^?3 exp [?264 (kJ/mol)/RT]k_CaCO3 (m²/s) = 3.06 × 10^?5 exp [?245 (kJ/mol)/RT] andk_Na2CO3 (m²/s) = 1.88 × 10^?10 exp [?155 (kJ/mol)/RT].According to obtained results at least, 45–70 vol% of carbonates preserve during subduction down to the 660-km discontinuity if no melting occurs. The slab stagnation and warming, subsequent carbonate melting, and infiltration into the mantle saturated with iron metal are accompanied by a reduction of carbonate melt with Fe. The established sequence of reactivity of carbonates: FeCO₃ ≥ MgCO₃ > CaMg(CO₃)₂ > CaCO₃ ? Na₂CO₃, where K₂CO₃ does not react at all with iron metal, implies that during reduction carbonate melt with Fe evolves toward alkali-rich. The above conclusions are consistent with the findings of carbonates in inclusions in diamonds from the lower mantle and high concentrations of alkalis, particularly K, in mantle carbonatite melts entrapped by diamonds from kimberlites and placers worldwide.     

碳酸岩是大陆岩石圈构造背景和地幔交代作用的指示岩石

根据已知碳酸岩的地质产状、岩石学特征、Nd-Sr-Pb同位素及痕量元素地球化学特征,结合高温高压实验岩石学资料,论述了其地幔源区的物质成分、交代过程、软流圈地幔部分熔融机制和碳酸岩岩浆的演化模型碳酸岩既可以产生于裂谷环境,由起源于软流圈地幔的霞石质超基性-基性岩浆经液态不混溶作用而形成,与硅酸不饱和过碱性杂岩构成环状碳酸岩-碱性杂岩;也能够产生于碰撞造山过程中派生的引张岩石圈断裂带,直接导源于岩石圈地幔的低程度部分熔融作用,形成单一的透镜状、条带状和似层状碳酸岩体     

The role of carbonate-fluoride melt immiscibility in shallow REE deposit evolution

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements(REE). Both carbonatites and nepheline syenite-fluorite-calcite veinlets are host to a previously unreported macroscale texture involving pseudo-graphic intergrowths of fluorite and calcite. The inclusions within calcite occur as either pure fluorite, with associated REE minerals within the surrounding calcite, or as mixed calcite-fluorite inclusions, with associated zirconosilicate minerals. Consideration of the nature of the texture, and the proportions of fluorite and calcite present(～29 and 71 mol%,respectively), indicates that these textures most likely formed either through the immiscible separation of carbonate and fluoride melts, or from cotectic crystallization of a carbonatefluoride melt. Laser ablation ICP-MS analyses show the pure fluorite inclusions to be depleted in REE relative to the calcite. A model is proposed, in which a carbonate-fluoride melt phase enriched in Zr and the REE, separated from a phonolitic melt, and then either unmixed or underwent cotectic crystallization to generate an REE-rich carbonate melt and an REE-poor fluoride phase. The separation of the fluoride phase(either solid or melt) may have contributed to the enrichment of the carbonate melt in REE, and ultimately its saturation with REE minerals. Previous data have suggested that carbonate melts separated from silicate melts are relatively depleted in the REE, and thus melt immiscibility cannot result in the formation of REE-enriched carbonatites. The observations presented here provide a mechanism by which this could occur, as under either model the textures imply initial separation of a mixed carbonate-fluoride melt from a silicate magma. The separation of an REEenriched carbonate-fluoride melt from phonolitic magma is a hitherto unrecognized mechanism for REE-enrichment in carbonatites, and may play an important role in the formation of shallow magmatic REE deposits.     

Petrogenetic processes in the ultramafic, alkaline and carbonatitic magmatism in the Kola Alkaline Province: A review

Igneous rocks of the Devonian Kola Alkaline Carbonatite Province (KACP) in NW Russia and eastern Finland can be classified into four groups: (a) primitive mantle-derived silica-undersaturated silicate magmas; (b) evolved alkaline and nepheline syenites; (c) cumulate rocks; (d) carbonatites and phoscorites, some of which may also be cumulates. There is no obvious age difference between these various groups, so all of the magma-types were formed at the same time in a relatively restricted area and must therefore be petrogenetically related. Both sodic and potassic varieties of primitive silicate magmas are present. On major element variation diagrams, the cumulate rocks plot as simple mixtures of their constituent minerals (olivine, clinopyroxene, calcite, etc). There are complete compositional trends between carbonatites, phoscorites and silicate cumulates, which suggests that many carbonatites and phoscorites are also cumulates. CaO / Al₂O₃ ratios for ultramafic and mafic silicate rocks in dykes and pipes range up to 5, indicating a very small degree of melting of a carbonated mantle at depth. Damkjernites appear to be transitional to carbonatites. Trace element modelling indicates that all the mafic silicate magmas are related to small degrees of melting of a metasomatised garnet peridotite source. Similarities of the REE patterns and initial Sr and Nd isotope compositions for ultramafic alkaline silicate rocks and carbonatites indicate that there is a strong relationship between the two magma-types. There is also a strong petrogenetic link between carbonatites, kimberlites and alkaline ultramafic lamprophyres. Fractional crystallisation of olivine, diopside, melilite and nepheline gave rise to the evolved nepheline syenites, and formed the ultramafic cumulates. All magmas in the KACP appear to have originated in a single event, possibly triggered by the arrival of hot material (mantle plume?) beneath the Archaean/Proterozoic lithosphere of the northern Baltic Shield that had been recently metasomatised. Melting of the carbonated garnet peridotite mantle formed a spectrum of magmas including carbonatite, damkjernite, melilitite, melanephelinite and ultramafic lamprophyre. Pockets of phlogopite metasomatised lithospheric mantle also melted to form potassic magmas including kimberlite. Depth of melting, degree of melting and presence of metasomatic phases are probably the major factors controlling the precise composition of the primary melts formed.