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.     

岩浆(型)碳酸岩研究进展

主要从岩石学，矿物学，岩石分类，C，O，Sr同位素，碳酸岩与矿化的关系等各方面对（碱性）碳酸岩的研究进行了较为全面的总结，并结合近20年来实验岩石等，流体包裹体研究，CO2^- H2O－NaCl流体体系的性质的研究，对碳酸岩岩浆的来源及成因，岩浆－热液的演化进行了分析和探讨，碳酸岩形成至少经历了三个阶段，即岩浆阶段，岩浆期后阶段（气相碳酸岩／岩浆热液阶段），交代碳酸岩阶段，而作为与碳酸岩在空间和成因上有密切联系的基性，超基性岩，碱性岩杂岩体，则经历了碳酸岩成岩阶段以前的岩浆不混熔作用，结晶分异作用，岩浆结晶作用以及碳酸岩形成之后的围岩蚀变（霓长岩化）作用。     

Genesis of the Khaluta alkaline-basic Ba-Sr carbonatite complex (West Transbaikala, Russia)

The Khaluta carbonatite complex comprizes fenites, alkaline syenites and shonkinites, and calcite and dolomite carbonatites. Textural and compositional criteria, melt inclusions, geochemical and isotopic data, and comparisons with relevant experimental systems show that the complex formed by liquid immiscibility of a carbonate-saturated parental silicate melt. Mineral and stable isotope geothermometers and melt inclusion measurements for the silicate rocks and carbonatite all give temperatures of crystallization of 915–1,000°C and 890–470°C, respectively. Melt inclusions containing sulphate minerals, and sulphate-rich minerals, most notably apatite and monazite, occur in all of the lithologies in the Khaluta complex. All lithologies, from fenites through shonkinites and syenites to calcite and dolomite carbonatites, and to hydrothermal mineralisation are further characterized by high Ba and Sr activity, as well as that of SO3 with formation of the sulphate minerals baryte, celestine and baryte-celestine. Thus, the characteristic features of the Khaluta parental melt were elevated concentrations of SO₃, Ba and Sr. In addition to the presence of SO₃, calculated fO₂ for magnetites indicate a high oxygen fugacity and that Fe⁺³>Fe⁺² in the Khaluta parental melt. Our findings suggest that the mantle source for Khaluta carbonatite and associated rocks, as well as for other carbonatites of the West Transbaikalia carbonatite province, were SO₃-rich and characterized by high oxygen fugacity.     

Geochronology and mineralogy of the Weishan carbonatite in Shandong province,eastern China

The Weishan REE deposit is located at the eastern part of North China Craton (NCC), western Shandong Province. The REE-bearing carbonatite occur as veins associated with aegirine syenite. LA-ICP-MS bastnaesite Th-Pb ages (129 Ma) of the Weishan carbonatite show that the carbonatite formed contemporary with the aegirine syenite. Based on the petrographic and geochemical characteristics of calcite, the REE-bearing carbonatite mainly consists of Generation-1 igneous calcite (G-1 calcite) with a small amount of Generation-2 hydrothermal calcite (G-2 calcite). Furthermore, the Weishan apatite is characterized by high Sr, LREE and low Y contents, and the carbonatite is rich in Sr, Ba and LREE contents. The δ¹³C_V-PDB (−6.5‰ to −7.9‰) and δ¹³O_V-SMOW (8.48‰–9.67‰) values are similar to those of primary, mantle-derived carbonatites. The above research supports that the carbonatite of the Weishan REE deposit is igneous carbonatite. Besides, the high Sr/Y, Th/U, Sr and Ba of the apatite indicate that the magma source of the Weishan REE deposit was enriched lithospheric mantle, which have suffered the fluid metasomatism. Taken together with the Mesozoic tectono-magmatic activities, the NW and NWW subduction of Izanagi plate along with lithosphere delamination and thinning of the North China plate support the formation of the Weishan REE deposit. Accordingly, the mineralization model of the Weishan REE deposit was concluded: The spatial-temporal relationships coupled with rare and trace element characteristics for both carbonatite and syenite suggest that the carbonatite melt was separated from the CO₂-rich silicate melt by liquid immiscibility. The G-1 calcites were crystallized from the carbonatite melt, which made the residual melt rich in rare earth elements. Due to the common origin of G-1 and G-2 calcites, the REE-rich magmatic hydrothermal was subsequently separated from the melt. After that, large numbers of rare earth minerals were produced from the magmatic hydrothermal stage.     

白云鄂博——一个典型的碱性-碳酸岩杂岩的厘定

在内蒙古白云鄂博地区发育着一套由碱性-碳酸岩杂岩(原H_8)、碳酸岩岩墙群、沉积—火山岩系(原H_9)、矿区浅成中基性岩岩墙群和角砾橄榄岩体群等组成的独具特色的大型杂岩。 白云鄂博Nb-Fe-RE超大型矿床其赋矿碳酸岩(H_8),长期被误认为沉积白云岩。根据综合对比研究表明,赋矿H_8同本区典型的火成碳酸岩岩墙群和世界同类碳酸岩存在着高度的相似性。而与本区典型沉积岩剖面中的腮林忽洞微晶丘和白云岩却完全迥异。故白云鄂博矿床赋矿H_8实为一典型的碱性—碳酸岩杂岩。在岩石分类学上,采用CaO-MgO-(FeO十Fe_2O_3+MnO)三端元组分分类图解,将本区碳酸岩类划分为两大独立的岩石分区,即:以方解石碳酸岩为代表的钙质碳酸岩类(Ⅰ类)和以含铁白云石或铁白云石碳酸岩为代表的镁质碳酸岩类(Ⅱ类)。前者岩浆成分属Ca Fe质系列,后者属Mg Fe质系列,两者均具有富铁演化趋势。 对世界上主要火成碳酸类(不含Na质碳酸岩)进行的统计结果,同样给出了两大独立的岩石类型分区(即Ⅰ类和Ⅱ类)和两大岩浆成分系列(Ca Fe质和Mg Fe质)。这一结果则与本区碳酸岩实际有着惊人地一致。它反映一个无可争辨的事实,即全球碳酸岩所固有的成岩成矿专属性,这一属性不受产地、成岩时代和产状等的约束,而表现一致共有的普遍规律。 赋矿碳酸岩体     

Micas from the Khaluta carbonatite deposit,western Transbaikal region

The Khaluta carbonatite deposit located in the western Transbaikal region was formed during the Late Mesozoic rifting in the southern framework of the Siberian Craton. Carbonatite is associated with shonkinite and syenite and is accompanied by fenitization. The composition of mica in more than 160 samples of country rocks, carbonatites, silicate rocks, and fenites was studied. The Fe³⁺ and Fe²⁺ contents, as well as oxygen isotopic composition, were determined. The Mg and Fe contents increase, whereas the Ti and Al contents decrease in micas when passing from silicate rocks and fenites to carbonatites. Micas from carbonatites are depleted in Al, enriched in Fe³⁺, and distinguished by high Si and F contents. According to our calculations, in some cases Al replaces Si in the tetrahedral site instead of replacement of Fe³⁺ as is characteristic of tetraferriphlogopite. Formally, the mica from carbonatites falls within the tetraferriphlogopite field, but typical inverse pleochroism is not always observable. The δ¹⁸O values of micas from carbonatite, shonkinite, syenite, and fenite are similar to those of mantle-derived silicate minerals. The δ¹⁸O values in the minerals coexisting with phlogopite testify to their isotopic equilibrium and make it possible to calculate the crystallization temperature of carbonatite.     

Carbon and oxygen isotopic compositions of Newania Dolomite Carbonatites, Rajasthan, India: implications for source of carbonatites

The Newania carbonatite complex of Rajasthan, India is one of the few dolomite carbonatites of the world, and oddly, does not contain alkaline silicate rocks thus providing a unique opportunity to study the origin and evolution of a primary carbonatite magma. In an attempt to characterize the mantle source, the source of carbon, and the magmatic and post-magmatic evolution of Newania carbonatites, we have carried out a detailed stable carbon and oxygen isotopic study of the complex. Our results reveal that, in spite of being located in a metamorphic terrain, these rocks remarkably have preserved their magmatic signatures in stable C and O isotopic compositions. The δ¹³C and δ¹⁸O variations in the complex are found to be results of fractional crystallization and low temperature post-magmatic alteration suggesting that like other carbonatites, dolomite carbonatites too fractionate isotopes of both elements in a similar fashion. The major difference is that the fractional crystallization of dolomite carbonatites fractionates oxygen isotopes to a larger extent. The modes of δ¹³C and δ¹⁸O variations in the complex, ?4.5?±?1‰ and 7?±?1‰, respectively, clearly indicate its mantle origin. Application of a multi-component Rayleigh isotopic fractionation model to the correlated δ¹³C versus δ¹⁸O variations in unaltered carbonatites suggests that these rocks have crystallized from a CO₂ + H₂O fluid rich magma, and that the primary magma comes from a mantle source that had isotopic compositions of δ¹³C ~ ?4.6‰ and δ¹⁸O ~ 6.3‰. Such a mantle source appears to be a common peridotite mantle (δ¹³C = ?5.0?±?1‰) whose carbon reservoir has insignificant contribution from recycled crustal carbon. Other Indian carbonatites, except for Amba Dongar and Sung Valley that are genetically linked to Reunion and Kerguelen plumes respectively, also appear to have been derived from similar mantle sources. Through this study we establish that dolomite carbonatites are generated from similar mantle source like other carbonatites, have comparable evolutionary history irrespective of their association with alkaline silicate rocks, and may remain resistant to metamorphism.     

New data on carbonatites of the Il’mensky-Vishnevogorsky alkaline complex,the southern Urals,Russia

Carbonatites that are hosted in metamorphosed ultramafic massifs in the roof of miaskite intrusions of the Il’mensky-Vishnevogorsky alkaline complex are considered. Carbonatites have been revealed in the Buldym, Khaldikha, Spirikha, and Kagan massifs. The geological setting, structure of carbonatite bodies, distribution of accessory rare-metal mineralization, typomorphism of rock-forming minerals, geochemistry, and Sr and Nd isotopic compositions are discussed. Dolomite-calcite carbonatites hosted in ultramafic rocks contain tetraferriphlogopite, richterite, accessory zircon, apatite, magnetite, ilmenite, pyrrhotite, pyrite, and pyrochlore. According to geothermometric data and the composition of rock-forming minerals, the dolomite-calcite carbonatites were formed under K-feldspar-calcite, albite-calcite, and amphibole-dolomite-calcite facies conditions at 575–300°C. The Buldym pyrochlore deposit is related to carbonatites of these facies. In addition, dolomite carbonatites with accessory Nb and REE mineralization (monazite, aeschynite, allanite, REE-pyrochlore, and columbite) are hosted in ultramafic massifs. The dolomite carbonatites were formed under chlorite-sericite-ankerite facies conditions at 300–200°C. The Spirikha REE deposit is related to dolomite carbonatite and alkaline metasomatic rocks. It has been established that carbonatites hosted in ultramafic rocks are characterized by high Sr, Ba, and LREE contents and variable Nb, Zr, Ti, V, and Th contents similar to the geochemical attributes of calcio-and magnesiocarbonatites. The low initial ⁸⁷Sr/⁸⁶Sr = 0.7044?0.7045 and εNd ranging from 0.65 to ?3.3 testify to their derivation from a deep mantle source of EM₁ type.     

Age and geochemistry of the Newania dolomite carbonatites, India: implications for the source of primary carbonatite magma

The Newania carbonatite complex of India is one of the few dolomite-dominated carbonatites of the world. Intruding into Archean basement gneisses, the rocks of the complex have undergone limited diversification and are not associated with any alkaline silicate rock. Although the magmatic nature of the complex was generally accepted, its age of emplacement had remained equivocal because of the disturbed nature of radioisotope systems. Many questions about the nature of its mantle source and mode of origin had remained unanswered because of lack of geochemical and isotopic data. Here, we present results of our effort to date the complex using ¹⁴⁷Sm–¹⁴³Nd, ²⁰⁷Pb–²⁰⁶Pb and ⁴⁰Ar–³⁹Ar dating techniques. We also present mineral chemistry, major and trace element geochemistry and Sr–Nd isotopic ratio data for these carbonatites. Our age data reveal that the complex was emplaced at ~1,473 Ma and parts of it were affected by a thermal event at ~904 Ma. The older ²⁰⁷Pb–²⁰⁶Pb ages reported here (~2.4 Ga) and by one earlier study (~2.3 Ga; Schleicher et al. Chem Geol 140:261–273, 1997) are deemed to be a result of heterogeneous incorporation of crustal Pb during the post-emplacement thermal event. The thermal event had little effect on many magmatic signatures of these rocks, such as its dolomite–magnesite–ankerite–Cr-rich magnetite–magnesio-arfvedsonite–pyrochlore assemblage, mantle like δ¹³C and δ¹⁸O and typical carbonatitic trace element patterns. Newania carbonatites show fractional crystallization trend from high-Mg to high-Fe through high-Ca compositions. The least fractionated dolomite carbonatites of the complex possess very high Mg# (≥80) and have similar major element oxide contents as that of primary carbonatite melts experimentally produced from peridotitic sources. In addition, lower rare earth element (and higher Sr) contents than a typical calcio-carbonatite and mantle like Nb/Ta ratios indicate that the primary magma for the complex was a magnesio-carbonatite melt and that it was derived from a carbonate bearing mantle. The Sr–Nd isotopic data suggest that the primary magma originated from a metasomatized lithospheric mantle. Trace element modelling confirms such an inference and suggests that the source was a phlogopite bearing mantle, located within the garnet stability zone.     

Sr and Nd isotope data of apatite,calcite and dolomite as indicators of source,and the relationships of phoscorites and carbonatites from the Kovdor massif,Kola peninsula,Russia

A detailed Sr−Nd isotopic study of primary apatite, calcite and dolomite from phoscorites and carbonatites of the Kovdor massif (380 Ma), Kola peninsula, Russia, reveals a complicated evolutionary history. At least six types of phoscorites and five types of carbonatite have been identified from Kovdor by previous investigators based on relative ages and their major and accessory minerals. Isotopic data from apatite define at least two distinct groups of phoscorite and carbonatite. Apatite from the earlier phoscorites and carbonatites (group 1) are characterized by relatively low⁸⁷Sr/⁸⁶Sr (0.70330–0.70349) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51230–0.51240) with F=2.01–2.23 wt%, Sr=2185–2975 ppm, Nd=275–660 ppm and Sm=31.7–96.2 ppm. Apatite from the second group has higher⁸⁷Sr/⁸⁶Sr (0.70350–0.70363) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51240–0.51247) and higher F (2.63–3.16 wt%), Sr (4790–7500 ppm), Nd (457–1074 ppm) and Sm (68.7–147.6 ppm) contents. This group corresponds to the later phoscorites and carbonatites. One apatite sample from a carbonatite from the earlier group fits into neither of the two groups and is characterized by the highest initial⁸⁷Sr/⁸⁶Sr (0.70385) and lowest¹⁴³Nd/¹⁴⁴Nd (0.51229) of any of the apatites. Within both groups initial⁸⁷Sr/⁸⁶Sr and¹⁴³Nd/¹⁴⁴Nd ratios show negative correlations. Strontium isotope data from coexisting calcite and dolomite support the findings from the apatite study. The Sr and Nd isotopic similarities between carbonatites and phoscorites indicate a genetic relationship between the two rock types. Wide variations in Sr and Nd isotopic composition within some of the earlier carbonatites indicate several distinct intrusive phases. Oxygen isotopic data from calcite and dolomite (δ¹⁸O=+7.2 to +7.7‰ SMOW) indicate the absence of any low-temerature secondary processes in phoscorites and carbonatites, and are consistent with a mantle origin for their parental melts. Apatite data from both groups of phoscorite plot in the depleted quadrant of an ε_Nd versus ε_Sr diagram. Data for the earlier group lie along the Kola Carbonatite Line (KCL) as defined by Kramm (1993) and data from the later group plot above the KCL. The evolution of the phoscorites and carbonatites cannot be explained by simple magmatic differentiation assuming closed system conditions. The Sr−Nd data can best be explained by the mixing of three components. Two of these are similar to the end-members that define the Kola Carbonatite Line and these were involved in the genesis of the early phoscorites and carbonatites. An additional component is needed to explain the isotopic characteristics of the later group. Our study shows that apatite from rocks of different mineralogy and age is ideal for placing constraints on mantle sources and for monitoring the Sr−Nd evolution of carbonatites. Editorial responsibility: W. Schreyer     

The Yungul carbonatite dykes associated with the epithermal fluorite deposit at Speewah, Kimberley, Australia: carbon and oxygen isotope constraints on their origin

The Yungul carbonatite dykes at Speewah in the Kimberley region of Western Australia were emplaced along a north-trending splay from the northeast-trending Greenvale Fault located at the western boundary of the Halls Creek Orogen. The Yungul carbonatite dykes intrude a thick composite sill of the Palaeoproterozoic Hart Dolerite (~1,790 Ma), consisting of tholeiitic dolerite and gabbro with its felsic differentiates that form the Yilingbun granophyres and associated granites. The carbonatite dykes consist of massive, calcite carbonatite that host very coarse, pegmatitic veins and pods of calcite, and have largely replaced (carbonatitized) and fenitized the country rock Hart Dolerite suite in a zone up to 150 m wide. Dykes of red-brown siliceous fluidized-breccia and epithermal-textured veins consisting of bladed quartz, adularia and fluorite are closely associated with the carbonatite dykes. The Yungul carbonatites are closely associated with fluorite occurrences with resources currently reported as 6.7 Mt at 24.6% CaF₂. The precise age of the Yungul carbonatite is not known, although it is believed to be post early Cambrian. The total REE content of the Yungul carbonatite is low (174.0–492.8 ppm; La/Yb 2.28–10.74) and thus atypical for calciocarbonatite. Chondrite-normalized REE patterns for the carbonatite are relatively flat compared to average calciocarbonatite, and show small negative Eu anomalies. These unusual geochemical features may have been acquired from the Hart Dolerite suite during emplacement of the carbonatite, a process that involved extensive replacement and fenitization of country rocks. Carbon and oxygen isotope compositions of massive calcite carbonatite and the coarse calcite veins and pods from the carbonatite suggest a deep-seated origin. The C and O isotope compositions show an overall positive correlation that can be attributed to both magmatic and magmatic-hydrothermal processes in their evolution. The magmatic δ¹³C-δ¹⁸O trend is also indicative of crustal contamination and/or low-temperature water/rock exchange. The carbon isotopic compositions have δ¹³C values that range from about ?5.2‰ to ?6.3‰ that support a mantle-derived origin for the Yungul carbonatites and are consistent with earlier conclusions based on whole-rock geochemistry and radiogenic isotopes studies.     

Evolution of bulk composition, mineralogy, strain style and fluid flow during an HT–LP metamorphic event: sillimanite zone of the Catalan Coastal Ranges Variscan basement, NE Iberia

Metamorphic rocks in the Osor complex (Guilleries massif, NE Iberian Peninsula) show the following structural and compositional features: strong differentiation into quartz-rich gneissic semipelitic and quartz-absent, mica-rich schistose bands, higher density of igneous (both basic and leucogranitic) and quartz veins in the schistose domains and strong strain partitioning in the pelitic bands. Garnet is present in both kinds of lithologies, showing also differential textural and chemical features interpreted to be dependent on bulk composition, deformation and fluid interaction histories. Textures, mineral composition and thermobarometry suggest the operation of concurrent mechanical, mass transfer and thermal phenomena such as: (1) variations in strain style, (2) fluid infiltration, (3) magmatic injection and (4) HT–LP metamorphic and metasomatic episodes. The following sequence of events is suggested: initially the cooling of syntectonic high-T basic quartz diorite sheets promoted high strain rates, low dP/dT thermobaric evolution, incipient anatexis in the pelitic bands and devolatilization through a pervasive to vein-channelized prograde fluid flow. The prograde flow enhanced an ongoing compositional tectono-metamorphic differentiation and produced metasomatism through depletion of the Osor rocks in alkalis and calcium. Later injection and cooling of peraluminous leucogranitoid sheets, preferentially along pelitic bands, increased the ratio of magmatic/metamorphic components in the fluids and strongly enriched them in alkalis producing a second metasomatic episode. During crystallization of quartz and leucogranitoid veins, the pelitic bands were strongly enriched back again in alkalis, promoting the blastesis of big crystals of post-peak muscovite and albite as well as the retrogression of garnet. The metasomatic mica-rich levels must have been the preferred locus for development of a new deformation style dominated by shear band fabrics in metapelites and related to a release of the gravitational instability originated previously due to crustal thickening. The increasing decompressional component of the retrograde P–T path also suggests that this style of deformation was prevalent during, if not responsible for, a phase of exhumation of the metamorphic complex. It is suggested that similar patterns of thermomechanical and mass transfer phenomena could well be a fundamental characteristic common to all HT–LP metamorphic belts.     

Fluid composition and origin in the hydrothermal system of the Nezhdaninsky gold deposit,Sakha (Yakutia), Russia

Petrochemical characteristics of igneous, sedimentary, and metasomatic rocks; chemical and isotopic compositions of minerals and fluids; and PT parameters of mineral formation at the Nezhdaninsky deposit are reported. A model of hydrothermal system formation is developed on this basis. In addition to decreasing Ba/Rb and Li/Mg ratios in the course of the hydrothermal process, resulting in the formation of ore-bearing metasomatic rocks, increasing K/Ba and diminishing K/Cs ratios indicate the probable participation of magmatic fluid in the ore deposition. The agreement of the K/Rb and K/Ba ratios with the values typical of the main trend of igneous rocks (MT) implies that the K, Rb, and Ba contents were distributed in the ore-forming hydrothermal fluid according to the ratios in the source magmatic chamber. The K/Rb ratios in metasomatic rocks correspond to the MT and approach the pegmatitic-hydrothermal trend and the composition of orthomagmatic fluid of Mo-W greisen. Similar REE patterns of igneous and terrigenous rocks do not allow the REE source to be constrained unequivocally. The lithological control of lithophile element distribution testifies to the supply of host rock components to the hydrothermal system. All studied rocks and minerals are enriched in LREE. The REE total and the contribution of HREE decrease from preore to synore metasomatic rocks, from preore to regenerated carbonates, and from older to younger scheelite. A similar tendency is noted in granitoids of the Kurum pluton. The δ¹⁸O values of quartz range from +10.3 to +12.6‰ in Au-Mo-W zones, from +15.9 to +16.4‰ in metasomatic rocks, from +14.8 to +16.6‰ in gold-ore veins, and from +13.5 to +16.9‰ in silver-base-metal ore mineralization. The estimates of \(\delta ^{18} O_{H_2 O} \) suggest that water was supplied from a magmatic source (δ¹⁸O = +(5.5?9.0‰)) and as a product of sedimentary rock dehydration. High-temperature (up to 390°C) and highly concentrated (up to 31 wt % NaCl equiv) fluids participated in the mineral formation. The phase separation of the fluid into H₂O-CO₂ liquid and predominantly carbon dioxide gas was combined with mixing of a high-temperature and relatively highly concentrated chloride solution with a low-temperature and poorly mineralized fluid. The redox conditions varied from equilibrium with CH₄-bearing fluid at the gold-molybdenum-tungsten stage to equilibrium with CO₂-bearing fluid during the gold-ore stage.     

Features of mineral and chemical composition of the Khamambettu Carbonatites, Tamil Nadu

The paper presents mineralogical features and EPMA results of the Khamambettu carbonatites. The mineralogical data suggest that these rocks have been generated in magmatic and hydrothermal stages. Mineral geothermometer for carbonatite give temperatures of 790°–980°C. Fluid inclusion measurements in monazite (hydrothermal stage) give temperatures of 220°–290°C. One of the features of the carbonatites is high content of magnesia that is defined by the presence of dolomite, olivine, spinel, phlogopite, Mg-rich ilmenite. Chloritization, serpentinization, amphibolization, silicification processes and occurrence of barite, monazite-(Ce), strontianite, celestine are related to hydrothermal stage. Hydrothermal minerals at the Khamambettu were formed by recrystallization of primary carbonatite minerals in the presence of Ba, (SO₄)^2?, REE and Si carried in solution by the hydrothermal fluid.     

Metasomatic processes in the lithospheric mantle beneath the V. Grib kimberlite pipe (Arkhangelsk diamondiferous province,Russia)

New data on metasomatic processes in the lithospheric mantle in the central part of the Arkhangelsk diamondiferous province (ADP) are presented. We studied the major- and trace-element compositions of minerals of 26 garnet peridotite xenoliths from the V. Grib kimberlite pipe; 17 xenoliths contained phlogopite. Detailed mineralogical, petrographic, and geochemical studies of peridotite minerals (garnet, clinopyroxene, and phlogopite) have revealed two types of modal metasomatic enrichment of the lithospheric-mantle rocks: high temperature (melt) and low-temperature (phlogopite). Both types of modal metasomatism significantly changed the chemical composition of the peridotites. Low-temperature modal metasomatism manifests itself as coarse tabular and shapeless phlogopite grains. Two textural varieties of phlogopite show significant differences in chemical composition, primarily in the contents of TiO₂, Cr₂O₃, FeO, Ba, Rb, and Cs. The rock-forming minerals of phlogopite-bearing peridotites differ in chemical composition from phlogopite-free peridotites, mainly in higher FeO content. Most garnets and clinopyroxenes in peridotites are the products of high-temperature mantle metasomatism, as indicated by the high contents of incompatible elements and REE pattern in these minerals. Fractional-crystallization modeling gives an insight into the nature of melts (metasomatic agents). They are close in composition to picrites of the Izhmozero field, basalts of the Tur’ino field, and carbonatites of the Mela field of the ADP. The REE patterns of the peridotite minerals make it possible to determine the sequence of metasomatic enrichment of the lithospheric mantle beneath the V. Grib kimberlite pipe.     

Non-magmatic Features in Carbonatitic Rocks: A Re-examination of Proterozoic “Carbonatites,” Southeast Rajasthan,Northwest Indian Craton

The Newania carbonatitic rocks (NCB), exposed as NW-trending, isolated linear bodies within Archean granitoids, are comprised mainly of Mg- and Fe-carbonate phases and volumetrically negligible Ca carbonate. The magmatic Mg-carbonatite shows partial metasomatic replacement by iron-rich solutions channelized along fractures. The C- and 0-isotopic compositions further document the magmatic lineage of the Mg-carbonatite (δ¹³C_PDB = ?4.0 to ?5.9% and δ¹⁸ O_SMOW = + 8.2 to 11.5%, barring one sample characterized by a high value of +25.6%). In contrast, the presumed ankeritic (Fe) and sovitic (Ca) carbonatites appear to be the result of metasomatism and hydrothermal activity, as indicated by corresponding enrichment in the heavier isotopes. The “atypical carbonatites” of Nayaphala, occurring as NW-trending dikes and veins of variable width (south of and colinear with the Newania trend), are nonmagmatic, and can be described as tectonic breccias. A nonmagmatic source for Nayaphala carbonates also is supported by the corresponding enrichment in the heavier C and O isotopes.     

Calculated silica activities in carbonatite liquids

Carbonatite magmas precipitate silicates, in addition to the abundant carbonates, oxides, and phosphates. Calculated silica activities for equilibria involving silicates and a silica component in magmatic liquids predict specific assemblages for silicate and oxide phases in carbonatites. These assemblages provide tests of alternative sources (carbonatite magma, coeval silicate magma, or older rock) for silicate minerals in carbonatites. Quartz, feldspars, and orthopyroxene are unlikely to be primary magmatic phases in carbonatites, because the silica activity in carbonatite magmas is too low to stabilize these minerals. Zircon and titanite should be unstable relative to baddeleyite and perovskite, respectively, but they do occur in carbonatites. Liquids dominated by carbonate are strongly nonideal with respect to dissolved silica. Consequently, activity coefficients for a silica component in carbonatite liquids are >>1, so that small mole fractions of SiO₂ translate into silica activities sufficient to stabilize phlogopite, clinopyroxene, amphibole, monticellite, and forsterite, among other silicates. Examination of silicate mineral assemblages in carbonatites in the light of silica activity indicates that many carbonatites are contaminated by solid silicate phases from external sources but these xenocrysts can be discriminated from magmatic minerals.     

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。     

Geochemical and petrological characteristics of Eppawala phosphate deposits,Sri Lanka

The apatite-bearing carbonate rocks at Eppawala, Sri Lanka occur as massive, discontinuous bodies in a Precambrian, high-grade metamorphic terrain, which weather to form economically important phosphate deposits. The ore bodies at Eppawala contain =42% P ₂O ₅, and citric acid solubility of different components varies from 4 to 6%. The parent rocks are mainly made up of calcite, dolomite and apatite, with lesser amounts of ilmenite, magnetite, pyrite, forsterite, phlogopite, enstatite, magnesite, diopside, tremolite and spinel. Most of minerals show an euhedral habit, with a wide range of crystal sizes (from a few millimetres to several decimetres). The Eppawala rocks are characterised by low silica (=0.41%), high phosphorous (=10.58%) and high strontium content (2,960–6,819 ppm). Concentrations of light rare-earth elements in these rocks are comparably higher than those of marbles. The REE fractionation of these rocks is pronounced, and La/Yb ratios vary between 14 and 43. Both apatite and calcite show markedly elevated strontium levels (=0.6%). The d ¹³C _PDB and d ¹⁸O _SMOW values of the carbonates are in the range of –3.4 to –2.2 and 7.7 to 16.4‰ respectively. The euhedral habit, as well as the presence of major quantities of apatite and considerable amounts of iron-bearing minerals suggest that the ore host rock has genetic links to an igneous source rather than to an intensely metamorphosed limestone. The higher light REE contents of the rocks, compared to marbles, also argue against a metamorphic or sedimentary origin. The Sr/Mn and Ce/La ratios in the apatite are ~40 and ~2 respectively, suggesting that they were formed in a carbonatite magma. The markedly increased REE concentrations in the bulk chemistry of the rocks have been shown to be mainly controlled by the content of phosphate minerals. Compared to most carbonatites, the Eppawala rocks are generally depleted in selected trace elements, particularly Ba, Nb, Th, V, U and Zr. This depletion may be due to either a primary infertility of the parent magma with regard to such trace elements, or it is a result of fractional crystallisation during the rock formation. The stable isotope ratios do not plot within the defined "mantle carbonatite box", but still lie within the broader range of carbonatitic rocks. With these data at hand, it can be readily argued that the mode of occurrence, petrography and geochemistry of the Eppawala apatite-bearing carbonates provide conclusive evidence of their carbonatitic origin.     

Geochemistry and petrogenesis of carbonatites from South Nam Xe,Lai Chau area,northwest Vietnam

This paper presents a study of the petrography, mineral chemistry, geochemistry, and Sr–Nd–Pb–C–O isotope systematics of carbonatite dykes and associated rocks from the northeastern part of the Song Da intracontinental rift in South Nam Xe (northwest Vietnam) aimed at constraining the origin of the carbonatite magmas. The carbonatites are characterized by SiO₂ < 12.18 wt.% and by wide ranges in FeO, MgO and CaO content that define them as calciocarbonatite and ferrocarbonatite. On U–Th–Pb isochron diagrams, whole rocks and mineral separates from the ferrocarbonatites form linear arrays corresponding to ages of 30.2–31.6 Ma (Rupelian, Oligocene). The South Nam Xe carbonatites are extremely enriched in Sr, Ba, and light rare earth elements (LREE), and depleted in high field strength elements (HFSE) (e.g. Ti, Nb, Ta, Zr and Hf). The age–corrected Sr–Nd–Pb isotope ratios and C isotope data are relatively uniform (⁸⁷Sr/⁸⁶Sr_(t) = 0.708193–0.708349; ¹⁴³Nd/¹⁴⁴Nd_(t) = 0.512250–0.512267; ε_Nd(t) = ?6.46 to ?6.80; ²⁰⁶Pb/²⁰⁴Pb_(t) = 18.26–18.79; ²⁰⁷Pb/²⁰⁴Pb_(t) = 15.62–15.64; ²⁰⁸Pb/²⁰⁴Pb_(t) = 38.80–39.38; δ¹³C_V-PDB = –2.7?‰ to ?4.1?‰). These isotopic compositions indicate source contamination that occurred before the production of the carbonatite magmas, and did not change noticeably during or after emplacement. The variation in oxygen isotopes is consistent with the change in mineral compositions and trace element abundances: the lower δ¹⁸O values (9.1–11.0?‰) coupled with Sr-rich, Mn-poor calcite, and igneous textures such as triple junctions among calcite grain boundaries, define a magmatic origin. However, the elevated δ¹⁸O values of the ferrocarbonatites (12.0–13.3?‰) coupled with a volatile-bearing mineral assemblages (including REE fluorcarbonates, sulfates, sulfides and fluorite) may be due to interaction with meteoric water during low-temperature alteration. High δ¹³C values and Sr–Pb ratios, and low Rb/Sr (0.00014–0.00301), Sm/Nd (0.089–0.141) and ¹⁴³Nd/¹⁴⁴Nd ratios, coupled with very high Sr-Nd concentrations, suggest the involvement of an enriched mantle component, which probably resulted from metasomatism due to the migration of subducted material. Because of the lack of tectonic data and the limited number of samples studied, this conclusion is still ambiguous and requires further study.