Is natrocarbonatite a cognate fluid condensate?

Natrocarbonatite flows in the crater of the volcano Oldoinyo Lengai (Tanzania) are the only carbonatite magmas observed to erupt and have provided strong arguments in favor of a magmatic origin for carbonatite. The currently favored explanation for the genesis of these carbonatites by liquid immiscibility between a silicate and a carbonatite melt is questioned based on the extremely low eruption temperatures of 544-593 °C and compositional and mineralogical characteristics not in agreement with experimental constraints. Experimental investigations of the relationship between Oldoinyo Lengai natrocarbonatite and related silicate rock compositions do indicate that alkali-bearing peralkaline carbonatite with liquidus calcite can form by liquid immiscibility. At the same time, these experiments result in evidence which speaks against a liquid immiscibility origin for the highly alkaline and peralkaline Oldoinyo Lengai natrocarbonatite. On the carbonatite side of the miscibility gap, fractional crystallization cannot account for a liquid evolution from alkali-bearing peralkaline carbonatite to highly alkaline natrocarbonatite. Such an evolution does not seem to be compatible with the liquidus mineral assemblages and the chemistry of Oldoinyo Lengai natrocarbonatite. No natural silicate magma is known to produce natrocarbonatite compositions by liquid immiscibility. The best interpretation of the Oldoinyo Lengai natrocarbonatite flows involves expulsion of a cognate, mobile, alkaline, and CO₂-rich fluid condensate. This conclusion is supported by recent studies of silicate and carbonatite melt inclusions in minerals of ultramafic alkaline complexes, trace element partitioning, isotopic constraints, and by experimental data on major element partitioning between coexisting H₂O-CO₂-rich fluid and carbonatitic melt. In contrast to all other suggested modes of formation, an origin of Oldoinyo Lengai natrocarbonatite from cognate fluid appears best to be in agreement with the field observations, the petrography, mineralogy, and geochemistry of Oldoinyo Lengai natrocarbonatite and the dynamics of the Oldoinyo Lengai natrocarbonatite extrusion.     

Liquid immiscibility in deep-seated magmas and the generation of carbonatite melts

This paper reviews the results of investigations of melt inclusions in minerals of carbonatites and spatially associated silicate rocks genetically related to various deep-seated undersaturated silicate magmas of alkaline ultrabasic, alkaline basic, lamproitic, and kimberlitic compositions. The analysis of this direct genetic information showed that all the deep magmas are inherently enriched in volatile components, the most abundant among which are carbon dioxide, alkalis, halides, sulfur, and phosphorus. The volatiles probably initially served as agents of mantle metasomatism and promoted melting in deep magma sources. The derived magmas became enriched in carbon dioxide, alkalis, and other volatile components owing to the crystallization and fractionation of early high-magnesium minerals and gradually acquired the characteristics of carbonated silicate liquids. When critical compositional parameters were reached, the accumulated volatiles catalyzed immiscibility, the magmas became heterogeneous, and two-phase carbonate-silicate liquid immiscibility occurred at temperatures of ≥1280–1250°C. The immiscibility was accompanied by the partitioning of elements: the major portion of fluid components partitioned together with Ca into the carbonate-salt fraction (parental carbonatite melt), and the silicate melt was correspondingly depleted in these components and became more silicic. After spatial separation, the silicate and carbonate-silicate melts evolved independently during slow cooling. Differentiation and fractionation were characteristic of silicate melts. The carbonatite melts became again heterogeneous within the temperature range from 1200 to 800–600°C and separated into immiscible carbonate-salt fractions of various compositions: alkali-sulfate, alkali-phosphate, alkali-fluoride, alkali-chloride, and Fe-Mg-Ca carbonate. In large scale systems, polyphase silicate-carbonate-salt liquid immiscibility is usually manifested during the slow cooling and prolonged evolution of deeply derived melts in the Earth’s crust. It may lead to the formation of various types of intrusive carbonatites: widespread calcite-dolomite and rare alkali-sulfate, alkali-phosphate, and alkali-halide rocks. The initial alkaline carbonatite melts can retain their compositions enriched in P, S, Cl, and F only at rapid eruption followed by instantaneous quenching.     

碳酸岩岩浆作用过程的包裹体研究

碳酸岩是一种富含碳酸盐矿物(方解石，白云石，铁白云石等＞50％以上)的火成岩。通常以侵入的方式，与超基性岩和碱性岩共生，位于环状侵人体的中心部位；或以喷出的方式，与碱性岩等构成环状杂岩体。碳酸岩在喷出或侵入过程中，与上部地壳围岩发生以富含碱质(钠或钾)为主的蚀变作用，形成特征性的蚀变岩石——霓长岩。通过对碳酸岩中的包裹体研究，可以获得包括成岩成矿时的温度、压力、密度、流体组分、流体演化等大量信息。碳酸岩矿物中包裹体的研究已取得很大进展，并为了解碳酸岩岩浆演化性质和特征提供了许多重要的信息：(1)碳酸岩可以形成于流体和熔体两种介质条件下；(2)碳酸岩矿物中包裹体富含CO2；(3)在碳酸岩的起源和演化过程中伴随有岩浆的不混溶作用发生；(4)碳酸岩岩浆具有的较低的粘度和密度。为了保证对从碳酸岩中获得的包裹体资料的合理解释，在研究过程中必须结合碳酸岩产出的大地构造背景、典型岩石组合、典型蚀变岩石(霓长岩)、赋存的矿产特征等方面的资料。虽然目前在包裹体研究方面尚有许多不足，但作为自然界唯一能够保存有原始成岩成矿流体的地质样品，包裹体的研究具有其他方法不可替代的作用。     

Oxygen isotope thermometry in carbonatites, Fuerteventura, Canary Islands, Spain

Summary Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960°C (average 710°C). The highest temperature is obtained from pyroxene–calcite pairs. The above range is in agreement with other carbonatite thermometric studies.This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite–carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar–Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite–carbonatite magmas.     

The bimodal composition of carbonatites: Reality or misconception?

The concept of compositional bimodality in carbonatites has become widely accepted and has been used to impose restrictions on the composition of carbonatite magmas. We agree that mineralogical bimodality exists in carbonatites (most are either calcitic or dolomitic/ankeritic), but we argue that there is no compositional bimodality. The idea of bimodality is based on the interpretation of a variety of element distribution diagrams which were compiled only from chemical analyses in which SiO₂ is < 10 wt.%. All others were rejected. Even with such a restricted data set the case for compositional bimodality is extremely weak, but the inclusion of analyses with higher SiO₂ content destroys it completely. Yet these more siliceous compositions must be included, for many carbonatites contain substantial amounts of Fe–Mg silicates which are an essential part of the magmatic mineralogy of the rocks. They account for much of the Mg in carbonatites that are otherwise calcitic. Many such carbonatites contain well in excess of 10 wt.% SiO₂. Supporters of the bimodality concept argue that liquids having compositions between calcite and dolomite can precipitate neither calcite nor dolomite because the minimum on the solid solution loops in the system calcite–dolomite permits only a carbonate of intermediate composition. Therefore, it is argued, liquids of such intermediate composition cannot be parental to calcitic and dolomitic carbonatites; their parent magmas must be calcitic and dolomitic. This deduction is incorrect. It is well established that dolomitic liquids have calcite as the liquidus phase over substantial temperature intervals, and that this is followed by dolomite precipitation. Mixed calcite–dolomite carbonatites are explicable in this way. Therefore, dolomitic liquids can be parental to calcitic carbonatites. However, dolomitic carbonatites cannot crystallize from a calcitic liquid. We suggest that intermediate composition carbonatite magmas are probably common. Bimodality in carbonatites is solely mineralogical, not compositional.     

Fluid–rock reactions in the 1.3 Ga siderite carbonatite of the Grønnedal–Íka alkaline complex,Southwest Greenland

Petrogenetic studies of carbonatites are challenging, because carbonatite mineral assemblages and mineral chemistry typically reflect both variable pressure–temperature conditions during crystallization and fluid–rock interaction caused by magmatic–hydrothermal fluids. However, this complexity results in recognizable alteration textures and trace-element signatures in the mineral archive that can be used to reconstruct the magmatic evolution and fluid–rock interaction history of carbonatites. We present new LA–ICP–MS trace-element data for magnetite, calcite, siderite, and ankerite–dolomite–kutnohorite from the iron-rich carbonatites of the 1.3 Ga Grønnedal–Íka alkaline complex, Southwest Greenland. We use these data, in combination with detailed cathodoluminescence imaging, to identify magmatic and secondary geochemical fingerprints preserved in these minerals. The chemical and textural gradients show that a 55 m-thick basaltic dike that crosscuts the carbonatite intrusion has acted as the pathway for hydrothermal fluids enriched in F and CO₂, which have caused mobilization of the LREEs, Nb, Ta, Ba, Sr, Mn, and P. These fluids reacted with and altered the composition of the surrounding carbonatites up to a distance of 40 m from the dike contact and caused formation of magnetite through oxidation of siderite. Our results can be used for discrimination between primary magmatic minerals and later alteration-related assemblages in carbonatites in general, which can lead to a better understanding of how these rare rocks are formed. Our data provide evidence that siderite-bearing ferrocarbonatites can form during late stages of calciocarbonatitic magma evolution.     

Geochemistry of radioactive elements in the rocks of the Guli Massif,Polar Siberia

The study of radioactive element distribution in the rocks of the Guli Complex revealed an increase of uranium and thorium contents in the final products of magmatic differentiation. In the carbonatite complex, the radioactive elements are mainly accumulated in the early rocks—phoscorites, while their contents in the late phases, dolomitic carbonatites, decrease. The Th/U ratio increases from near-chondritic values in the weakly differentiated highly-magnesian primary magmas to the late rocks—phoscorites, calcitic carbonatites, and dolomitic carbonatites. The majority of radioactive elements are hosted in rare-metal accessory minerals: perovskite, pyrochlore, calzirtite, and apatite. Rock-forming minerals are characterized by extremely low contents of radioactive elements.     

碳酸岩的地质地球化学特征及其大地构造意义

从已知碳酸岩的地质产状、岩石学特征、Nd-Sr-Pb-O-C同位素及痕量元素地球化学特征数据,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拉张岩石圈构造背景,也能够产生于挤压而派生的引张岩石圈构造背景。前者以产于裂谷环境、与硅酸不饱和过碱性岩构成环状碳酸岩—碱性杂岩为特征,主要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;后者产于碰撞造山过程中派生的引张岩石圈断裂带,以单一的透镜状、条带状和似层状碳酸岩体为标志,直接由导源岩石圈富集地幔的低程度部分熔融作用而产生的碳酸岩浆侵入或喷发所形成。     

成矿碳酸岩的实验岩石学研究现状与展望

火成碳酸岩及其风化产物是全球战略性关键金属稀土元素(REE)和铌(Nb)的主要来源。因此,对关键金属在火成碳酸岩中的超常富集机理研究具有重要的科学意义。研究表明成矿碳酸岩常常与碱性杂岩体存在密切的时空联系,因而母岩浆应属于碳酸盐化的硅酸盐岩浆,并以霞石岩岩浆为主。针对碳酸岩关键金属矿床的成岩成矿过程,已有实验发现母岩浆在地壳内的演化过程中,既可以通过分离结晶作用,也可以通过液态不混溶作用形成碳酸岩。然而,更加接近自然样品的多组分体系的实验均表明液态不混溶作用总是先于碳酸盐矿物分离结晶作用。因此,液态不混溶作用对关键金属成矿过程有着不可忽视的作用。尽管如此,已有不混溶实验表明当碳酸盐熔体和硅酸盐熔体发生不混溶之后,关键金属REE与Nb总是优先分配到硅酸盐熔体(碱性岩)中,但是在成矿杂岩体中,REE与Nb是高度富集在碳酸岩中。虽然不混溶实验表明REE与Nb在碳酸盐-硅酸盐熔体中的分配系数与含水量有关,即与熔体的聚合程度有关,但是绝大部分成矿碳酸岩成矿过程一般并不富水,所以碳酸岩中REE和Nb等关键金属元素超常富集的机理并不明确。因此未来的研究应重点关注在碳酸岩演化的过程中,除了水以外,其他配体对于关键金属元素在不混溶硅酸盐-碳酸盐熔体之间分配系数是否有影响,从而找到控制碳酸岩中关键金属成矿的关键。     

碳酸岩岩浆与地壳反应综述

碳酸岩是地表出露较少的地幔来源的岩石,其地幔交代作用已被广泛研究,而碳酸岩岩浆与地壳的反应过程却研究较少,目前已在中国草滩和丰镇地区、德国Kaiserstuhl地区、俄罗斯Petyayan-Vara地区和澳大利亚Nolans Bore矿床等各地被报道。碳酸岩岩浆与地壳反应的特征是可能形成大量富铁云母、辉石、榍石、钡冰长石等硅酸盐矿物并造成C-O和Sr-Nd同位素体系的扰动。实验岩石学研究发现碳酸岩岩浆在地幔与橄榄岩反应形成异剥橄榄岩,对应的在中下地壳反应形成反夕卡岩。碳酸岩岩浆与围岩的反应会造成局部Si的富集促使REE在早期岩浆阶段进入磷灰石,从而抑制稀土成矿。深部地壳的碳酸岩-硅酸岩反应在相同构造背景下通常不像浅部热液系统容易出露地表,并且其反应产物容易被误认为是夕卡岩矿物组合。因此,更多的高温高压实验研究以及对硅酸盐流体来源不是很清楚的高温夕卡岩矿物组合进行重新评估,将是揭示地壳深部反夕卡岩过程,特别是相关成矿作用的关键。     

Liquid Immiscibility in the Join NaAlSi3O8-CaCO3 to 2.5 GPa and the Origin of Calciocarbonatite Magmas

Field evidence from intrusive and effusive carbonatites supportsthe existence of calciocarbonatite magmas. Published experimentalevidence in the model system Na₂O–CaO–Al₂O₃–SiO₂–CO₂indicated the formation of nearly pure (99%) CaCO₃ immiscibleliquids from a carbonated silicate liquid. This evidence hasbeen used to support interpretations of extremely CaCO₃-richcalciocarbonatite magmas, and immiscible liquids with compositionsof almost pure CaCO₃ in metasomatized mantle peridotite andeclogite. Detailed phase relationships are constructed in themodel system, based on phase fields intersected by the joinNaAlSi₃O₈–CaCO₃ (Ab-CC) at 1.0, 1.5, and 2.5 GPa between1100 and 1500C, and analyzed immiscible liquids. The miscibilitygap between silicate-rich liquid and carbonate-rich liquid intersectedby the join Ab-CC contracts considerably with decreasing pressure:2.5 GPa, between Ab₁₀CC₉₀ (by wt%) and Ab₆₅CC₃₅ above 1310C;1.5 GPa, betweenAb₂₃CC₇₇ and Ab₄₃CC₅₇ above 1285C; 1.0 GPa,not intersected. The liquidus piercing point between calciteand silicates becomes enriched in CaCO₃ with decreasing pressure,from Ab₈₀CC₂₀ at 2.5 GPa to Ab₄₇CC₅₃ at 1.0 GPa. No immiscibleliquid contains more than 80% dissolved CaCO₃, and all containat least 5% Na₂CO₃. A round CaCO₃ phase exhibiting morphologysimilar to that displayed by immiscible liquid globules is determinedto be crystalline calcite under experimental conditions. Thetopology of the phase fields and field boundaries illustratesthe kinds of processes and controls existing in magmatic systems.Calciocarbonatite magmas cannot be produced by equilibrium immiscibilityprocess in the mantle. Carbonated silicate magmas in the crustyield residual calciocarbonatite magmas by fractionation alongthe silicate-calcite field boundary, reached either directlyfrom the silicate liquidus or more commonly via the miscibilitygap. Immiscible carbonaterich magmas when freed from the silicateparent cool down a sleep silicate liquidus until they reacha silicate-carbonate field boundary. There is no experimentalevidence for immiscible calciocarbonatite magmas with > 80%CaCO₃, and calcite lapilli cannot be formed from 99% CaCO₃ magmas.Sovites are surely cumulates. KEY WORDS: carbonatite; join NaAlSi₃O₈–CaCO₃; liquid immiscibility; sovite ^* Corresponding author. Telephone: (818)-395–6239. Fax: (818)-568–0935. e-mail: wjl{at}gpi.caltech.edu     

Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ⁵⁶Fe values for mantle-derived basaltic magmas (δ⁵⁶Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ⁵⁶Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ⁵⁶Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ⁵⁶Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ⁵⁶Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe³⁺-rich fluids at igneous or near-igneous temperatures; the expected δ⁵⁶Fe values for Fe²⁺-bearing fluids are too low to produced the observed positive δ⁵⁶Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe³⁺-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ⁵⁶Fe fenites, but this has yet to be tested.     

The ultramafic cumulate series,Gardiner complex,East Greenland

The ultramafic cumulate series of the ultramafic, alkaline and carbonatite bearing Gardiner complex in East Greenland is divided in: 1) Contact zone of plagio-clase-bearing alkaline rocks chilled to the surrounding gneisses and alkaline lavas; 2) a banded sequence of dunites to mt-pyroxenites; 3) a zoned dunite — cpx-dunite ring and 4) in the centre of the complex ol-pyroxenites and mt-pyroxenites.The zones and bands are superimposed with gradational contacts and are increasingly younger towards the centre of the complex. Primocrysts and intercumulus phases, which are equivalent to phenocryst phases in magmatic liquids show that these rocks accumulated from nephelinitic to nepheline-hawaiitic magmas and the contact rocks from less alkaline basanitic magma types similar to the regional alkaline magmas.The cumulates apparently formed in a magma chamber of a nephelinitic volcano, resting on the regional basalts of the Kangerdlugssuaq area.     

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.     

Ankerite carbonatite from Swartbooisdrif, Namibia: the first evidence for magmatic ferrocarbonatite

Although general accounts of carbonatites usually envisage Ca-Mg carbonate melts evolving by fractional crystallisation to Fe-rich residua, there is longstanding concern that ferrocarbonatites may actually be products of hydrothermal rather than magmatic processes. All previously published examples of ankerite- and/or siderite-carbonatites fail to show one or more of the isotopic criteria (all determined on the same sample) thought to be diagnostic of crystallised magmatic carbonate liquids. Ferrocarbonatite dykes cut Archaean-Proterozoic basement at Swartbooisdrif, adjacent to the NW Namibia-Angola border. Their age is uncertain but probably ~1,100 Ma and their associated fenites are rich in sodalite. Where unaffected by subsequent recrystallisation, their petrographic textures resemble those of silicate layered intrusions; ankerite, magnetite and occasionally calcite are cumulus phases, joined by trace amounts of intercumulus pyrochlore. Ankerite is zoned, from Ca(Mg, Fe²⁺)(CO₃)₂ cores towards ferroan dolomite rims. Calcite contains ~1.7% SrO, plus abundant, tiny exsolved strontianite grains. Magnetite is close to pure Fe₃O₄. Pyrochlore has fine-scale euhedral oscillatory zoning and light-REE-enriched rims. ICP-MS analysis of magnetite and pyrochlore from the carbonatite allows calculation of their modal amounts from mass-balance considerations. Sodalite from the fenite is REE poor. Geothermometry, using either the calcite-dolomite solvus or oxygen isotope fractionation between calcite and magnetite, gives temperatures in the range 420-460 °C. Initial Sr, Nd and Pb isotopic ratios of the ferrocarbonatites (⁸⁷Sr/⁸⁶Sr=0.7033; )Nd=0.2-1.0; ²⁰⁶Pb/²⁰⁴Pb=16.37; ²⁰⁷Pb/²⁰⁴Pb=15.42; ²⁰⁸Pb/²⁰⁴Pb=36.01) are appropriate for an ~1,100-Ma magmatic carbonatite. Likewise, carbonate '¹⁸O=8.0 and '¹³C=-7.36 indicate little or no subsequent shift from magmatic values. It appears that dense ankerite and magnetite dominated crystal accumulation from a melt saturated in these phases, plus calcite and pyrochlore, with prior fractionation of a silicate mineral and apatite. The resulting ferrocarbonatite lacks a silicate mineral (excluding fenite xenocrysts) and apatite. It has unusually low (basalt-like) REE abundances and (La/Lu)_n, and low concentrations of Ba, Rb, U, Th, Nb, Ta, Zr and Hf. Very high Nb/Ta and low Zr/Hf imply that the evolution of the parental magma involved immiscible separation of a carbonate from a silicate melt. The sodalite-dominated Swartbooisdrif fenites suggest that the parental melt also had a substantial Na content, in contrast with the ferrocarbonatite rock.     

火成碳酸岩的实验岩石学研究及对地球深部碳循环的意义

火成碳酸岩是地表出露较少的幔源岩石之一。实验岩石学研究表明碳酸盐化的橄榄岩和循环的地壳物质(如碳酸盐化榴辉岩或泥质岩)的低程度(<1%)部分熔融均可以产生碳酸岩质的熔体,其中碳酸盐化泥质岩具有最低的熔融温度且更加富碱质、CO2和不相容元素;富CO2的霞石质等硅酸盐岩浆也可以通过不混溶或分离结晶作用产生碳酸岩,用于解释碳酸岩在空间中常与碱性硅酸岩的共生关系。由于碳酸岩熔体具有极低的粘度和高的活性,形成后在上升过程中会将二辉橄榄岩转变为异剥橄榄岩,是引起地幔交代作用和地幔地球化学不均一性的重要介质之一。实验表明在俯冲作用过程中,大多数的碳酸盐在位于岛弧之下的含水熔融并不分解而是被带入到深部地幔并且稳定存在,含碳地幔的熔融又会形成碳酸岩质的熔体,这说明俯冲循环物质可能对碳酸岩的成因也起着重要的作用。然而,对于碳酸岩的初始熔体成分、岩浆演化、地幔交代作用、成矿特征以及碳从地球深部返回到地表的途径和过程等都存在着很大的争议。我国火成碳酸岩出露相对较多,分布广泛,因此,加强我国碳酸岩以及伴生硅酸岩的成因研究,同时开展与碳酸岩相关的实验岩石学工作,不仅可以检验现有的成因理论,而且有助于提高我国对火成碳酸岩的研究水平;由于其特殊的成因背景,还可为许多存在很大争议的重大地质事件提供新的科学依据。     

Petrology and composition of rare-metal alkaline rocks in the South Gobi Desert,Mongolia

Earlier, a belt of alkali-granite plutons and a carbonatite province were discovered in the South Gobi Desert, Mongolia. The Lugingol pluton of pseudoleucitic syenites with carbonatites was assigned to the alkali-granite belt. However, new dating showed that it is 40 Myr younger than the Khan-Bogdo pluton and a large fault separates it from the alkali-granite belt. In the same part of the South Gobi Desert, a dike series of alkaline K-shonkinites with a rare-metal carbonatite vein was found by V.I. Kovalenko west of the Lugingol pluton, near Mt. Baruun Hasar Uula, and a dike series of alkali and nepheline syenites was found by us northeast of the Lugingol pluton. These data give grounds to distinguish an intrusive complex of K-alkaline shonkinites and leucitic syenites with Late Paleozoic REE-bearing carbonatites. Thus, three alkaline-rock complexes of different ages are distinguished in the South Gobi Desert. We present refined geological maps of these complexes. The plutons of all three complexes are deposits of trace elements (REE, Nb, Zr, Y, P). The chemical composition of the silicate rocks of the complex, rare-metal agpaitic pegmatites, and carbonatite and apatite rare-metal ores was considered in detail. Shonkinites from Mt. Baruun Hasar Uula and the Mountain Pass mine (United States) and their carbonatites, along with the Lugingol carbonatites, belong to a single association of K-alkaline rocks and carbonatites, as evidenced by their identical chemical, mineral, and geochemical rare-metal compositions. Rare-earth element patterns and spidergrams show similarities and differences between the rare-metal rocks of three complexes as well as paragenetic differences between their rare-metal minerals. A rare process is described—the amorphization of rare-metal minerals, related to their high-temperature crystallization in a medium with abnormal silica contents of the Khan-Bogdo pegmatites. The parental magmas of the alkali-carbonatite complexes were generated from the EM-2 contaminated mantle that had undergone recycling, whereas the parental magmas of the Khan-Bogdo agpaitic alkali granites were produced from depleted mantle.     

Constraints of the formation of carbonatites in the Chernigovka Massif,Azov Region,Ukraine

Data on compositions of coexisting minerals in the graphite-bearing carbonatites of the Chernigovka massif are reported. Thermodynamic analysis of these results made it possible to establish that the temperature of equilibrium between graphite, dolomite, calcite, magnetite, and olivine for silica activity buffered by the (zircon + baddeleyite) assemblage is approximately 600°C. The minimal pressure of formation of these mineral assemblages is approximately 0.2 GPa, which is consistent with estimates of the erosion depth for the Chernigovka massif. The oxygen fugacity typical of the graphite-bearing carbonatite is 0.6–0.8 log units below the quartz-magnetite-fayalite buffer. Such values are typical of magmatic systems, e.g., basalts of the mid-ocean ridges (MORB). At 600°C, the gas phase in the C-H-O system equilibrated with the mineral assemblage of the carbonatite studied is dominated by CO₂ and H₂O, whereas methane-rich fluids appear at lower temperatures.     

四川冕宁包子山稀土矿床富Sr碳酸岩的发现及意义

全球范围内出露的碳酸岩大多为钙质、镁质、铁质碳酸岩,少量为钠质和硅质碳酸岩,极少有富Sr碳酸岩的报道,其岩石成因、资源意义及对碳酸岩岩浆演化的指示意义尚不清楚。本次在四川省牦牛坪稀土矿区南部包子山稀土矿床的露天采坑中发现了超级富Sr的碳酸岩,其呈不规则的脉状侵入到构造角砾岩中。岩石呈紫色-淡紫色,微晶-斑状结构,斑晶主要为萤石,基质主要为菱锶矿、方解石、氟碳铈矿、氟碳钙铈矿、金云母、重晶石并含少量的金属硫化物和氧化物。全岩的微量元素分析表明,其稀土元素总量(∑REE)达3.5%～6.1%,Sr含量达19.0%～27.7%,已超过稀土矿床和锶矿床的工业品位要求。岩石中的中、重稀土元素含量占稀土元素总量的1.14%～1.77%,一些高价值稀土元素含量较高,如Pr(939×10~(-6)～1399×10~(-6))、Nd(2783×10~(-6)～3937×10~(-6))、Gd(237×10~(-6)～320×10~(-6)),因此除轻稀土元素外,中、重稀土和锶元素也具有重要的资源意义。岩石强烈富集REE、Sr、Ba,而明显亏损P、Nb、Ta、Zr、Hf元素,可能与岩浆演化过程中锆石和其它基性矿物的结晶分离有关。全岩的Sr-Nd同位素组成与牦牛坪、里庄稀土矿床的碳酸岩相似,表明它们为同源岩浆产物。笔者认为,富Sr的碳酸岩代表了碳酸岩岩浆演化晚期的产物,REE、Sr、Ba、F和S元素均在岩浆演化晚期的碳酸岩中高度富集。碳酸岩岩浆超浅成侵位至构造角砾岩中,并与下渗的大气水相遇导致岩浆的淬冷和微晶-斑状结构的形成。早期基性矿物(如霓辉石、黑云母)及碳酸盐矿物(如方解石、白云石等)的结晶分离是造成晚期碳酸岩中稀土元素富集的重要原因。富Sr碳酸岩中石英斑晶的发现和其较低的SiO_2含量表明碳酸岩岩浆演化晚期可能是硅饱和的,且这种岩浆具有很低的SiO_2溶解能力。以菱锶矿(体积分数 50%)为主要碳酸盐矿物的稀土碳酸岩可能代表了一种新的碳酸岩类型,明显不同于已知的钙质、镁质、铁质和钠质碳酸岩。     

Isotopic and Geochemical Investigation of the Chilwa Island Carbonatite Complex, Malawi: Evidence for a Depleted Mantle Source Region, Liquid Immiscibility, and Open-System Behaviour

Initial Nd, Pb, and Sr isotopic data from carbonatites and associatedintrusive silica-undersaturated rocks from the early Jurassic,Chilwa Island complex, located in southern Malawi, central Africa,suggest melt derivation from a Rb/Sr- and Nd/Sm-depleted butTh/Pb- and U/Pb-enriched mantle source. Initial ¹⁴³Nd/¹⁴⁴Nd(0.51265–0.51270) isotope ratios from the Chilwa Islandcarbonatites are relatively constant, but their initial ⁸⁷Sr/⁸⁶Sr(0.70319–0.70361) ratios are variable. The ¹⁸O_smow (9.53–14.15%0)and ¹³C_PDB (–3.27 to –1.50%0) isotope ratios ofthe carbonates are enriched relative to the range of mantlevalues, and there is a negative correlation between ¹⁸O andSr isotope ratios. The variations in Sr, C, and O isotopic ratiosfrom the carbonatites suggest secondary processes, such as interactionwith meteoric groundwater during late-stage carbonatite activity.The initial ¹⁴³Nd/¹⁴⁴Nd (0.51246 0.51269) and initial ⁸⁷Sr/⁸⁶Sr(0.70344–0.70383) isotope ratios from the intrusive silicaterocks are more variable, and the Sr more radiogenic than thosefrom the carbonatites. Most of the Pb isotope data from Chilwa Island plot to the rightof the geochron and close to the oceanic regression line definedby MORBs and OIBs. Initial Pb isotopic ratios from both carbonatites(²⁰⁷Pb/²⁰⁴Pb 15.63–15.71; ²⁰⁶Pb/²⁰⁴Pb 19.13–19.78)and silicate rocks (²⁰⁷Pb/²⁰⁴Pb 15.61–15.72; ²⁰⁶Pb/²⁰⁴Pb18.18–20.12) show pronounced variations, and form twogroups in Pb-Pb plots. The isotopic variations shown by Nd, Pb, and Sr for the ChilwaIsland carbonatites and intrusive silicates suggest that thesemelts underwent different evolutionary histories. The chemicaldata, including isotopic ratios, from the carbonatites and olivinenephelinites are consistent with magmatic differentiation ofa carbonated-nephelinite magma. A model is proposed in whichdifferentiation of the carbonatite magma was accompanied byfenitization (metasomatic alteration) of the country rocks bycarbonatite-derived fluids, and subsequent alteration of thecarbonatite by hydrothermal activity. The chemical and isotopicdata from the non-nephelinitic intrusive silicate rocks reveala more complex evolutionary history, involving either selectivebinary mixing of lower-crustal granulites and a nephelinitemagma, or incremental batch melting of a depleted source andsubsequent crustal contamination.