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.     

Regime of carbon compounds in carbonatites in Uzbekistan: Evidence from carbon isotopic composition and thermodynamic simulations

Thermodynamic analysis of equilibria between minerals (with regard for their compositions) in carbonatites of the Chagatai complex, Uzbekistan, provides us with the possibility of estimating the oxygen fugacity at which carbonates could occur in equilibrium with elementary carbon. Isotopic studies and thermodynamic simulations show that graphite started to crystallize at 775°C and an oxygen fugacity value approximately one logarithmic unit below the QFM buffer and continued to crystallize with further cooling, simultaneously with a decrease in the Ti concentration in the equilibrium magnetite. Graphite crystallized from carbonatite melt at higher temperatures and likely precipitated from hydrothermal fluid at lower temperatures. The composition of gas in equilibrium with graphite in the C-H-O system was calculated for oxygen fugacity values evaluated for the Chagatai carbonatites. Inasmuch as the values of oxygen potential are almost identical in graphite- and diamond-bearing carbonatites, the presence of graphite in carbonatite dikes and diatremes can be regarded as a prospecting guide in exploration for diamondiferous carbonatites.     

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.     

Oxygen fugacity control in piston-cylinder experiments: a re-evaluation

Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) investigated a double capsule assembly for use in piston-cylinder experiments that would allow hydrous, high-temperature, and high-pressure experiments to be conducted under controlled oxygen fugacity conditions. Using a platinum outer capsule containing a metal oxide oxygen buffer (Ni–NiO or Co–CoO) and H₂O, with an inner gold–palladium capsule containing hydrous melt, this study was able to compare the oxygen fugacity imposed by the outer capsule oxygen buffer with an oxygen fugacity estimated by the AuPdFe ternary system calibrated by Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010). H₂O loss or gain, as well as iron loss to the capsule walls and carbon contamination, is often observed in piston-cylinder experiments and often go unexplained. Only a few have attempted to actually quantify various aspects of these changes (Brooker et al. in Am Miner 83(9–10):985–994, 1998; Truckenbrodt and Johannes in Am Miner 84:1333–1335, 1999). It was one of the goals of Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) to address these issues by using and testing the AuPdFe solution model of Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010), as well as to constrain the oxygen fugacity of the inner capsule. The oxygen fugacities of the analyzed melts were assumed to be equal to those of the solid Ni–NiO and Co–CoO buffers, which is incorrect since the melts are all undersaturated in H₂O and the oxygen fugacities should therefore be lower than that of the buffer by 2 log $a_{{{\text{H}}_{ 2} {\text{O}}}}$ .     

Diamond potential versus oxygen regime of carbonatites

Physicochemical conditions of graphite and diamond formation in the carbonate-rich melts were estimated. A large body of analytical data was obtained for compositions of coexisting minerals in the studied objects (Chernigovka Massif, Ukraine, and Chagatai carbonatite complex, Uzbekistan). The carbon isotopic composition of the coexisting carbonates and graphite from these carbonatites was analyzed. New thermodynamic methods were proposed to estimate the oxygen potential in graphite- and diamond-bearing carbonatites. Oxygen fugacity in the graphite-bearing carbonatites is slightly below the quartz-fayalite-magnetite buffer. It was proved that diamond is generated in the course of reduction of carbonate components arriving from plume material into the lower subcontinental lithosphere rather than owing to partial oxidation of methane fluids. As follows from the study of olivine and nominally anhydrous minerals in kimberlites, the limited role of methane in deep mantle is determined by low water activity. Methane is generated in mantle under special conditions such as extremely low oxygen fugacity (for instance, at the base of continental lithosphere) and elevated water activity. These conditions may occur during crystallization differentiation in deep-level chambers of kimberlite and proto-kimberlite magmas.     

Geology and geochemistry of Tertiary basalt in south Wadi Hodein area, South Eastern Desert, Egypt

Tertiary basalt is widespread in the area south of Wadi Hodein, south Eastern Desert, Egypt. It is the youngest unit in the basement rocks of the Central Eastern Desert classification of El Shazly (Proc 22nd Intl Geol Congr, New Delhi 10:88–101, 1964) and El Ramly (Ann Geol Surv Egypt II:1–17, 1972), traversed all the previous succession of the basement rocks as well as the Nubia Sandstone of Cretaceous age, forming sheets, small hills, ridges, and dikes. This Tertiary basalt is strongly associated with the opening of the Red Sea. Geologic, petrographic, and petrochemical studies as well as microprobe and X-ray analyses were performed on samples from Wadi Hodein Tertiary basalt. Field and petrographic studies classified the Tertiary basalt in south Wadi Hodein into porphyritic olivine basalt, plagiophyric basalt, and doleritic basalt. Opaque minerals (magnetite and ilmenite) constitute 6–7.5% of this basalt. Petrochemical studies and microprobe analyses reveal that they are low-TiO₂ basalt with low uranium and thorium contents, classified as being basaltic andesite to andesite, originated from calc-alkaline magma, and developed in within-plate tectonic environment. Scanning electron microscopy shows that magnetite and ilmenite are the prevalent opaque minerals in this Tertiary basalt. Field radiometric measurements of the Tertiary basalt in south Wadi Hodein reveals low uranium and thorium contents. Uranium contents range from 0.5 to 0.9 ppm, while thorium contents range from 1.2 to 3.2 ppm. Fractional crystallization and mass balance modeling indicate that the most-silica low-TiO₂ Tertiary basalt in south Wadi Hodein can be derived from the relatively less-silica low-TiO₂ Tertiary basalt of south Quseir and Gabal Qatrani through fractional crystallization of plagioclase, olivine, augite, and titanomagnetite oxides. Tertiary basalts in south Wadi Hodein and south Quseir have nearly the same age, 25 Ma (Sherif, The Fifth International Conference on the Geology of Africa, 2007), 24 Ma (Meneisy and Abdel Aal, Ain Shams Sci Bull 25(24B): 163–176, 1984), and 27 Ma (El Shazly et al., Egypt J Geol 1975), respectively. Finally, the fractionation modeling and geochemical characteristics of these basalts suggested their origination from one basaltic magma emplaced in late Oligocene.     

Accessory Fe-Ti oxides in the West-Carpathian I-type granitoids: witnesses of the granite mixing and late oxidation processes

Fe-Ti-oxides may reach hundreds ppm in I-type granitoids and close to microgranular mafic enclaves (MME) up to several thousands ppm. Western Carpathian I-type granitoids have magnetic susceptibility above 3?×?10^?4 SI units, whereas S-type granites are lower. Associated MMEs reach up to 160?×?10^?4 SI. The measurement of magnetic susceptibility in field appears a useful tool for regional mapping of I-type granites and searching enclaves. The increased contents of Fe-oxides around MME within host I-type granitoids are interpreted as result of hybridization with mafic magma. The hybridisation is manifested by occurrence of two Fe-Ti-oxide generations: (1) orthomagmatic titanomagnetite from pre-mixing stage, (2) late-magmatic magnetite of post-mixing stage. The titanomagnetites show composite textures with exsolved ilmenite. The oxybarometry (Sauerzapf et al. 2008; Ghiorso Evans 2009) yields temperatures 700?C750°C at fO₂ about NNO, and 650?C700°C below FMQ, respectively. Post-mixing pure magnetites originated from early titanomagnetite, annite and anorthite associated with titanite and apatite. The late oxidation seems to be responsible for high magnetic susceptibility of metaluminous I-type tonalites. Both post- and pre- mixing Fe-Ti oxides are locally converted to hematite.     

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.     

Applicability of different ground-motion prediction models for northern Iran

A total of 163 free-field acceleration time histories recorded at epicentral distances of up to 200 km from 32 earthquakes with moment magnitudes ranging from M _w 4.9 to 7.4 have been used to investigate the predictive capabilities of the local, regional, and next generation attenuation (NGA) ground-motion prediction equations and determine their applicability for northern Iran. Two different statistical approaches, namely the likelihood method (LH) of Scherbaum et al. (Bull Seismol Soc Am 94:341–348, 2004) and the average log-likelihood method (LLH) of Scherbaum et al. (Bull Seismol Soc Am 99:3234–3247, 2009), have been applied for evaluation of these models. The best-fitting models (considering both the LH and LLH results) over the entire frequency range of interest are those of Ghasemi et al. (Seismol 13:499–515, 2009a) and Soghrat et al. (Geophys J Int 188:645–679, 2012) among the local models, Abrahamson and Silva (Earthq Spectra 24:67–97, 2008) and Chiou and Youngs (Earthq Spectra 24:173–215, 2008) among the NGA models, and finally Akkar and Bommer (Seism Res Lett 81:195–206, 2010) among the regional models.     

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.     

Reply to ‘Comment on “The beginnings of hydrous mantle wedge melting” by Till et al.’ by Green, Rosenthal and Kovacs

The comment of Green et al. debates the interpretation of the temperature of the H₂O-saturated peridotite solidus and presence of silicate melt in the experiments of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) at <1,000?°C. The criticisms presented in their comment do not invalidate any of the most compelling observations of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) as discussed in the following response, including the changing minor element and Mg# composition of the solid phases with increasing temperature in our experiments with 14.5?wt% H₂O at 3.2?GPa, as well as the results of our chlorite peridotite melting experiments with 0.7?wt% H₂O. The point remains that Till et al. (Contrib Mineral Petrol 163:669–688, 2012) present data that call into question the H₂O-saturated peridotite solidus temperature preferred by Green (Tectonophysics 13(1–4):47–71, 1972; Earth Planet Sci Lett 19(1):37–53, 1973; Can Miner 14:255–268, 1976); Millhollen et al. (J Geol 82(5):575–587, 1974); Mengel and Green (Stability of amphibole and phlogopite in metasomatized peridotite under water-saturated and water-undersaturated conditions, Geological Society of Australia Special Publication, Blackwell, pp 571-581, 1989); Wallace and Green (Mineral Petrol 44:1–19, 1991) and Green et al. (Nature 467(7314):448–451, 2010).     

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.     

Sulphur isotope geochemistry of carbonatites

Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean $\text{δ}{}^{34}\text{S(0‰)}$.Classification of carbonatites in terms of T,?O₂ and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O₂ the mean δ³⁴S sulphide becomes increasing negative relative to the mean magma δ³⁴S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ^34S sulphide approaches the mean magmaδ³⁴S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ³⁴S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ³⁴S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ³⁴S is 0 to + 1‰     

A method for estimating the activity of titania in magmatic liquids from the compositions of coexisting rhombohedral and cubic iron–titanium oxides

A method is described for estimating the activity of titania (TiO₂) in a magmatic liquid from the compositions of coexisting cubic oxide (spinel) and rhombohedral oxide (ilmenite). These estimates are derived from the thermodynamic models of Ghiorso and Evans (Am J Sci 308:957–1039, 2008; see also Sack and Ghiorso in Contrib Mineral Petrol 106:474–505, 1991a; Am Mineral 76:827-847, 1991b) and may be computed self consistently along with temperature and oxygen fugacity for an assumed pressure. The method is applied to a collection of 729 naturally occurring oxide pairs from rhyolites and dacites. For this suite of oxides, values of titania activity relative to rutile saturation range from 0.3 to 0.9. Genetically related groups of oxide pairs display activity–temperature trends with negative slopes at higher activities (0.6–0.9) or positive slopes at lower activities (0.3–0.7). Thermodynamic analysis supports the assumption of two-oxide, liquid equilibrium for the former group, but suggests that such an interpretation for oxide sequences with positive activity–temperature trends may be problematic. Application of the estimation method to oxide pairs from the Shiveluch Volcano and the Bishop Tuff reveals that the former are consistent with having equilibrated with known matrix glass compositions, whereas the latter pairs are inconsistent with equilibration with pre-eruptive liquids trapped in quartz inclusions.     

Redox state of the upper mantle

The oxygen fugacity condition of equilibration has been carefully determined from a spinel lherzolite from Mongolia, olivine xenocrysts from chrome pyrope-bearing peridotite nodules from kimberlites of Yakutia, and basaltic samples from ocean floor, iron arcs and the continental areas. These indicate that the spinel lherzolites occurring within alkali basalts from Mongolia, equilibrated under an \(f_{O_2 } \) condition similar to that of WM buffer. The diamond and chrome pyrope-bearing peridotites from the kimberlite pipes equilibrated between IW and WM buffers. Some of the ilmenite-bearing peridotite crystallized under \(f_{O_2 } \) conditions similar to that between WM and QFM buffers and chondrites equilibrated below the QFI buffer. It is concluded that during geochemical processes in the upper mantle the \(f_{O_2 } \) conditions vary broadly, and are similar to that between FMQ and IW buffers. There is a dramatic change in the composition of the kimberlitic fluid, which is CH₄-bearing at an early stage, but is in equilibrium with H₂O and CO₂ at a later stage. This is related to mass transfer of fluids from the lower part of the mantle with a low oxidation state to the upper part having a higher \(f_{O_2 } \) condition.     

Hydrochemical characteristics of shallow groundwater in aquifer containing uranyl phosphate minerals, in the Köprübaşı (Manisa) area, Turkey

The concentrations of uranium, iron and the major constituents were determined in groundwater samples from aquifer containing uranyl phosphate minerals (meta-autunite, meta-torbernite and torbernite) in the Köprüba?? area. Groundwater samples from wells located at shallow depths (0.5–6 m) show usually near neutral pH values (6.2–7.1) and oxidizing conditions (Eh = 119–275 mV). Electrical conductivity (EC) values of samples are between 87 and 329 μS/cm^?1. They are mostly characterized by mixed cationic Ca dominating bicarbonate types. The main hydrogeochemical process is weathering of the silicates in the shallow groundwater system. All groundwater in the study area are considered undersaturated with respect to torbernite and autunite. PHREEQC predicted UO₂(HPO₄) ₂ ^2? as the unique species. The excellent positive correlation coefficient (r = 0.99) between U and PO₄ indicates the dissolved uranium in groundwater would be associated with the dissolution of uranyl phosphate minerals. The groundwater show U content in the range 1.71–70.45 μg/l but they are mostly lower than US EPA (2003) maximum contaminant level of 30 μg/l. This low U concentrations in oxic groundwater samples is attributed to the low solubility of U(VI) phosphate minerals under near neutral pH and low bicarbonate conditions. Iron closely associated with studied sediments, were also detected in groundwater. The maximum concentration of Fe in groundwater samples was 2837 μg/l, while the drinking water guidelines of Turkish (TSE 1997) and US EPA (2003) were suggested 200 and 300 μg/l, respectively. Furthermore, iron and uranium showed a significant correlation to each other with a correlation coefficient (r) of 0.94. This high correlation is probably related to the iron-rich sediments which contain also significant amounts of uranium mineralization. In addition to pH and bicarbonate controlling dissolution of uranyl phosphates, association of uranyl phosphates with iron (hydr) oxides seems to play important role in the amount of dissolved U in shallow groundwater.     

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.     

Primary and secondary niobium mineral deposits associated with carbonatites

This work reviews the character and origin of primary and supergene economic deposits of niobium associated with carbonatites. The Brazilian supergene deposits account for about 92% of the total worldwide production of Nb, with the primary St. Honoré carbonatite and other sources accounting for only for 7 and 1%, respectively. The emphasis of the review is upon the styles of Nb mineralization and the geological factors which lead to economic concentrations of Nb-bearing minerals. Primary economic deposits of Nb are associated principally with carbonatites found in diverse types of plutonic alkaline rock complexes. Primary magmas are principally those of the melilitite, nephelinite and aillikite clans. Although many primary niobium deposits are associated with carbonatites, ijolites and syenites in the same alkaline complexes can also contain significant Nb mineralization in the form of niobian titanite and diverse Nb–Zr-silicates (marianoite-wöhlerite); these potential sources of Nb have not as yet been explored or exploited. Primary Nb deposits can be regarded as large tonnage, low grade (typically < 1 wt.% Nb₂O₅) disseminated ore deposits. Niobium is hosted principally by diverse Na–Ca–U-pyrochlores, ferrocolumbite and fersmite. Every actual, and potential, primary Nb deposit is unique with respect to the varieties of pyrochlore present; extent of replacement by other minerals; and degree of alteration by deuteric/hydrothermal fluids. Within a given occurrence individual petrographically-defined units of carbonatite contain distinct suites of pyrochlore. Bulk rock analysis for Nb gives no indication of the style of mineralization and provides no information of use regarding beneficiation of the ore. Evaluation of any Nb deposit requires extensive definition drilling and detailed mineralogical studies. Primary Nb deposits result from the early crystallization of Nb-bearing minerals in magma chambers followed by crystal fractionation, magma mixing, and redistribution of Nb-minerals by density currents. Supergene Nb deposits occur in laterites formed by extensive weathering of primary carbonatites. The process results in the decomposition of apatite and magnetite, removal of soluble carbonates and physical concentration of resistant primary pyrochlore. Intense lateritization results initially in the replacement of primary pyrochlores by supergene, commonly Ba, Sr, K or Pb-bearing pyrochlores, and ultimately complete decomposition of pyrochlore and formation of Nb-bearing rutile, brookite, and anatase. The Nb contents of the laterites can be enriched up to 10 times or more above those of the primary carbonatite. Commonly, pyrochlores in laterites are fine grained and intimately intergrown with hematite, goethite and minerals of the crandallite group. The different styles of mineralization of primary and secondary Nb deposits require different methods of ore beneficiation.     

Perovskite alteration in kimberlites and carbonatites: the role of kassite,CaTi2O4(OH)2

A microbeam (electron microprobe, X-ray diffraction and Raman) study of pseudomorphs after magmatic perovskite from kimberlite (Iron Hill, Wyoming, USA) and carbonatite (Prairie Lake, Ontario, Canada) showed that the early product of perovskite replacement in these samples is kassite, a monoclinic (space group P2₁/a) polymorph of CaTi₂O₄(OH)₂. This mineral can be readily distinguished from its dimorph cafetite (space group P2₁/n) based on the presence of strong signals at ~120, 300, 330, 450, 470 and 690 cm^?1, and the absence or very low intensity of signals at ~250, 420, 600, 800 and 825 cm^?1 in its Raman spectrum. The strongest X-ray diffraction lines, measured for the Prairie Lake material, are [d _obs in Å (I) hkl]: ~3.29 (100) 022; 112, \( {\mathrm{11}}{\overline 2} \) ; 1.764 (61) \( {\mathrm{13}}{\overline 4} \) ; 2.284 (45) 132; 2.601 (24) 130; 2.050 (17) 222; 4.81 (16) 002; 2.034 (15) 042; 2.308 (14) 202; 1.778 (14) \( {\mathrm{20}}{\overline 4} \) . Diffraction lines at 3.60, 2.99, 2.79, 2.57, 2.56 and 1.91 Å, characteristic of cafetite, are not observed. The electron-microprobe analyses of kassite give formulae close to the stoichiometric composition. Progressive Ca leaching leads to replacement of kassite by anatase + calcite, which are also commonly observed as direct products of perovskite alteration in silica-undersaturated igneous rocks. Raman spectroscopy is the fastest and most reliable technique to identify submicroscopic anatase–calcite intergrowths that can be easily mistaken for kassite (cafetite) based on electron-microprobe data. Thermodynamic calculations indicate that conversion of perovskite into kassite and, subsequently, anatase requires initially high levels of f(H₂O) in the system, followed by an increase in f(CO₂) at either decreasing or constant T and f(H₂O). The implications of perovskite–kassite–anatase phase relations for deciphering the late-stage evolution of kimberlites and carbonatites are discussed.     

Rare metal mineralization of calcite carbonatites from the Cape Verde Archipelago

Rare metal mineralization of oceanic carbonatites was studied for the first time by the example of calcite carbonatite from Fogo Island in the Cape Verde Archipelago. The following evolutionary sequence of rare metal minerals was established: zirconolite-Th-calciobetafite-betafite + Th-pyrochlore-thorite + Ti-Zr-Nb silicates + zircon.Schematic reactions were proposed for zirconolite transformation to secondary phases: (Ca,Th,U)Zr(Ti,Nb)₂O₇ (zirconolite) + SiO₂ + Ca(F,OH)₂ → ZrSiO₄ (zircon) + (Ca,Th,U)₂(Ti,Nb)₂O₆(OH,F) (Th-calciobetafite) and (Ca,Th,U)₂(Ti,Nb)₂O₆(OH,F) + Na₂Si₂O₅ → ThSiO₄ (thorite) + (Ca,Na,Th)₂(Nb,Ti)₂O₆(OH,F) (Th-pyrochlore), where SiO₂, Ca(F,OH)₂, and Na₂Si₂O₅ are the components of melt-solution coexisting with the carbonatite.It was shown that the distribution and behavior of rare and radioactive elements in oceanic carbonatites show the same tendencies as in continental carbonatites. The contents and distribution of Ti, Ta, and Th in zirconolites and pyrochlores from oceanic and continental carbonatites are different: the minerals of oceanic carbonatites are enriched in Ti and Th and strongly depleted in Ta.