Geochemical constraints on depth of origin of oceanic carbonatites: The Cape Verde case

We present new Sr-Nd isotope compositions together with major- and trace element concentrations measured for whole rocks and mineral separate phases (apatite, biotite and calcite) from fifteen Cape Verde oceanic carbonatites (Atlantic Ocean). Trace element patterns of calcio- and magnesio-carbonatites present a strong depletion in K, Hf, Zr and Ti and an overall enrichment in Sr and REE relative to Cape Verde basalts, arguing for distinct source components between carbonatites and basalts. Sr and Nd isotopic ratios show small, but significant variations defining a binary mixing between a depleted end-member with unradiogenic Sr and radiogenic Nd values and a ‘‘enriched’’ end-member compatible with old marine carbonates. We interpret the depleted end-member as the Cape Verde oceanic lithosphere by comparison with previous studies on Cape Verde basalts. We thus propose that oceanic carbonatites are resulting from the interaction of a deep rooted mantle plume carrying a lower ⁴He/³He signature from the lower mantle and a carbonated metasomatized lithosphere, which by low degree melting produced carbonatite magmas. Sr-Nd compositions and trace element patterns of carbonatites argue in favor of a metasomatic agent originating from partial melting of recycled, carbonated oceanic crust. We have successfully reproduced the main geochemical features of this model using a Monte-Carlo-type simulation.     

Newania carbonatites, Western India: example of mantle derived magnesium carbonatites

The key mineralogical features of the Newania carbonatites, that illustrate their derivation from primary mantle melts (Gruau et al. Terra Nova, Abstract Suppl 1:336, 1995; Viladkar Petrology 6(3):272–283, 1998; Basu and Murty Abstracts of Goldschmidt Conference A40, 2006), are the presence of magnesite, graphite and Cr-rich magnetite. Magnesite is an early crystallizing phase. Cr-rich magnetite and graphite coexist with carbonatite minerals and precipitated from carbonate magma. Graphite, as well as gaseous CO₂ and carbonate minerals such as dolomite and magnesite, can be stable in peridotite mantle. Coexistence of these minerals is controlled by fO ₂ and PT-conditions. Mineral geothermometers for the Newania carbonatite give temperatures from 463 to 950°C. The parental source for Newania carbonatites was characterized by a relatively high log (fHF/fH₂O) level which increased during the crystallization history of Newania. The estimated oxygen fugacity (for ilmenite–magnetite pairs) varies from ?1.5 to +3.5 (log-bar unit deviation from FMQ buffer), which is supported by the presence of Fe-columbite, and the composition of phlogopite, amphibole and pyroxene that have an elevated concentration of Fe³⁺. However, the oxygen fugacity range represented by co-existing early-crystallized graphite and magnesite is below that of the FMQ buffer and lies on the CCO buffer.     

Thermoluminescence of carbonates from carbonatites

The Gejiu tin field in southern China consists of six major deposits and many minor ones containing more than 120 million tons (pre-mining resource) at 1% Sn and significant amounts of Cu, Ag, Zn, and Pb. It is one of the largest tin fields of primary deposits in the world. Mineralization is the result of the intrusion of granitic plutons into Permian and Triassic sedimentary rocks, which are dominantly limestone, dolomitic limestone, and dolomite. Five (mostly peraluminous) granitic intrusives (64-115 Ma) are present in the area. The largest orebodies are spatially and temporally related to the Laoka (principally), Beipaotai, and Marsong granites. Tin mineralization is mainly within greisens developed at the outermost zone of a skarn zonal sequence and are mineralogically dominated by fluorite, quartz, and micas.

The deposits are the result of volatile-rich ore solutions that evolved late in the plutonic crystallization history. The solutions produced metamorphic skarns as well as ore skarns, both of which later became “greisenized” skarns. Gejiu is the largest example of what has been, up to now, a style of mineralization reported only in minor amounts.     

An exsolution silica-pump model for the origin of myrmekite

Myrmekite, as defined here, is the microscopic intergrowth between vermicular quartz and modestly anorthitic plagioclase (calcic albite-oligoclase), intimately associated with potassium feldspar in plutonic rocks of granitic composition. Hypotheses previously invoked in explanation of myrmekite include: (1) direct crystallization; (2) replacement; (3) exsolution. The occurrence of myrmekite in paragneisses and its absence in rocks devold of discrete grains of potassium feldspar challenge those hypotheses based on direct crystallization or replacement. However, several lines of evidence indicate that myrmekite may in fact originate in response to kinetic effects associated with the exsolution of calcic alkali feldspar into discrete potassium feldspar and plagioclase phases. Exsolution of potassium feldspar system projected from [AlSi₂O₈] involves the exchange CaAlK_-1Si_-1, in which the AlSi_-1 tetrahedral couple is resistant to intracrystalline diffusion. By contrast, diffusion of octahedral K proceeds relatively easily where it remains uncoupled to the tetrahedral exchange. We suggest here that where the ternary feldspar system is open to excess silica, the exchange reaction that produces potassium feldspar in the ternary plane is aided by the net-transfer reaction K+Si=Orthoclase, leaving behind indigenous Si that reports as modal quartz in the evolving plagioclase as the CaAl component is concomitantly incorporated in this same phase. Thus silica is pumped into the reaction volume from a silica reservoir, a process that enhances redistribution of both Si and Al through the exsolving ternary feldspar.     

Aeromagnetic prospecting for carbonatites (East Sayan)

A whole series of new and promising anomalies are revealed by airborne magnetic studies in the articulation belt of the East Sayan marginal uplift and the Siberian Platform proper. Possessing all the specific features of anomalies over carbonatite massifs, they coincide with sectors where zones of northwesterly faults and sublatitudinal faults intersect. --IGR Staff.     

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‰     

Geochemistry of oceanic carbonatites compared with continental carbonatites: mantle recycling of oceanic crustal carbonate

Major and trace element and Sr-Nd-Pb-O-C isotopic compositions are presented for carbonatites from the Cape Verde (Brava, Fogo, Sáo Tiago, Maio and Sáo Vicente) and Canary (Fuerteventura) Islands. Carbonatites show pronounced enrichment in Ba, Th, REE, Sr and Pb in comparison to most silicate volcanic rocks and relative depletion in Ti, Zr, Hf, K and Rb. Calcio (calcitic)-carbonatites have primary (mantle-like) stable isotopic compositions and radiogenic isotopic compositions similar to HIMU-type ocean island basalts. Cape Verde carbonatites, however, have more radiogenic Pb isotope ratios (e.g. ²⁰⁶Pb/²⁰⁴Pb=19.3-20.4) than reported for silicate volcanic rocks from these islands (18.7-19.9; Gerlach et al. 1988; Kokfelt 1998). We interpret calcio-carbonatites to be derived from the melting of recycled carbonated oceanic crust (eclogite) with a recycling age of ~1.6 Ga. Because of the degree of recrystallization, replacement of calcite by secondary dolomite and elevated ‘¹³C and ‘¹⁸O, the major and trace element compositions of the magnesio (dolomitic)-carbonatites are likely to reflect secondary processes. Compared with Cape Verde calcio-carbonatites, the less radiogenic Nd and Pb isotopic ratios and the negative Ɨ/4 of the magnesio-carbonatites (also observed in silicate volcanic rocks from the Canary and Cape Verde Islands) cannot be explained through secondary processes or through the assimilation of Cape Verde crust. These isotopic characteristics require the involvement of a mantle component that has thus far only been found in the Smoky Butte lamproites from Montana, which are believed to be derived from subcontinental lithospheric sources. Continental carbonatites show much greater variation in radiogenic isotopic composition than oceanic carbonatites, requiring a HIMU-like component similar to that observed in the oceanic carbonatites and enriched components. We interpret the enriched components to be Phanerozoic through Proterozoic marine carbonate (e.g. limestone) recycled through shallow, subcontinental-lithospheric-mantle and deep, lower-mantle sources.     

The Petrogenetic Grid and Subfacies for Middle-temperature Metapelites

All a priori possible types of PT diagrams for medium-temperaturequartz- and muscovite- bearing metapelites, are deduced theoreticallyon the base of analysis of the concentration diagram for thesystem SiO₂-AI₂O₃-Fe₂O₃-FeO-MgO-CaO-K₂O-Na₂O-H₂O. Comparisonswith all known mineralogic observations permitted one to choosethe most probable type of diagram for all those derived. PTcalibration of this paragenetic grid is given as based on experimentaldata. It is established, that the Fe/Mg ratio decreases in mineralsof all the univariant associations with increase of pressure.The same is true of divariant associations at constant temperature. The suggested new scheme of subfacies permits the detailingof estimates of the PT conditions for the medium-temperatureregion (in the first place with respect to pressure).     

白云鄂博碳酸岩的方解石-白云石地质温度计

利用方解石-白云石地质温度计对白云鄂博地区碳酸岩的平衡温度进行了测定。出露于东矿下盘的白云岩质火山岩和出露于尖山的方解石-白云石型火山岩获得了较高的温度,分别为681℃和648℃。这些样品中的方解石呈二十微米左右晶形较完整的小片,被稍大粒度的白云石颗粒包裹,未受交代作用影响,推测这种碳酸岩在快速冷却的情况下保存下了其岩浆侵位时的成分特点,从而指示出接近碳酸岩浆侵位时的温度。但本区多数碳酸岩的平衡温度在400～500℃之间,有下列三种情况:(1)具有自形-半自形中粗粒粒状变晶结构的碳酸岩最后的平衡温度为415～496℃;(2)产自东矿的其余样品(火山岩),所测最后平衡温度为431～485℃,在测温的微区范围内可见极细粒白云石方解石与稀土等矿物共生的现象;(3)为交代重结晶结构的碳酸岩明显受到后期热液流体的交代,在流体的作用下共生方解石和白云石在成分上达到新的平衡,平衡温度为432～507℃。本文所分析的样品多数结果(371～507℃)与用白云石(方解石)和磁铁矿氧同位素温度计对白云鄂博碳酸岩的计算结果(360～546℃)十分一致。虽然有研究者对方解石-白云石温度计用于火成碳酸岩表示过质疑,但本文资料表明火成碳酸岩最后的平衡温度是可以运用方解石-白云石温度计法来计算的。     

Economic aspects of carbonatites of India

Among the 20 carbonatite–alkaline rock associations known from India, eight contain economic deposits that are either being presently exploited or likely to become workable resources. These include deposits of fluorite (Ambadongar, Gujarat), apatite, (Newania, Rajasthan; Kutni and Beldih, West Bengal) and vermiculite (Sevattur, Tamil Nadu). Carbonatite complexes of Sevattur, Sung Valley and Samchampi hold considerable potential for Nb, P, and Fe. The Samchampi Complex, Assam contains an estimated reserve of some 300 million tons of hematite ore, besides Nb (10,970 tons), Ta (3740 tons), Y (1894 tons) and apatite (10 million tons of ore with 35% P₂O₅) and thus appears to be the most promising complex among the new discoveries. Recovery of pyrochlore±apatite, magnetite, zircon, and monazite have been evaluated for the soils at Sevattur, Sung Valley and Samchampi. A variety of elements either alone or in combination such as REE, Ba, Sr, V, Ti, Zr, Th, and U could become important co-products from these complexes.     

The main geochemical features of carbonatites

A great deal of data is available on the geochemistry of the carbonatite family as well as diverse sedimentary, metamorphic and endogenic carbonate rocks. The distinctive geochemical features of carbonatites are expressed first of all in their simultaneous enrichment in Sr, Ba, ree and V. Since the carbonatite family is related both to alkaline petrogenesis and a mantle origin, these associations allow distinction of carbonatites from the large variety of other carbonate rocks. At the same time, carbonatites associated with different types of alkaline rocks under different geologic-tectonic settings differ in contents of a number of elements (Sr, Ba, Nb, ree, Pb, Zn, P). These differences permit the geochemical classification of various rock associations of carbonatites. This geochemical classification is of practical interest because the ore productivity of the various associations is different.     

Geochemical multi-element prospecting for carbonatites by energy-dispersive x-ray fluorescence

A radionuclide-excited energy-dispersive X-ray fluorescence (EDXRF) device has been used for geochemical mapping of soils over the Orberg deposit of the Kaiserstuhl carbonatite near Schelingen. About 500 samples were collected from an area of 0.2 km². The mobile EDXRF equipment was used in field laboratories to determine twelve trace elements (Cu, Zn, As, Rb, Sr, Y, Zr, Nb, Ba, La, Ce and Pb) quantitatively, and the major components K₂O, CaO, TiO₂, MnO and Fe₂O₃ semiquantitatively. Additional information on bulk chemistry was obtained by determining the average atomic number from scattered radiation. An attempt is made to identify the different carbonatite subcrops in this area by use of trace element patterns and inter-element relationships. Since part of the survey area is covered with loess, relations and ratios between elements were used to estimate the dilution effect due to loess.     

Mantle(?) xenoliths in the carbonatites of northern Transbaikalia

The composition and nature of high-Cr minerals in lithic clasts from the carbonatites of the Veseloe occurrence, northern Transbaikalia, were considered. In order to determine their source, the Cr-bearing phases were compared with chromite, magnetite, and rutile from ultrabasic rocks, mantle xenoliths, and eclogites. It was suggested that the xenoclasts studied were formed at great depths, whereas the carbonatites were directly derived from the mantle rather than formed by the crustal differentiation of a silicate-carbonate melt.     

Geochemical characteristics of Cretaceous carbonatites from Angola

The Early Cretaceous (138–130 Ma) carbonatites and associated alkaline rocks of Angola belong to the Paraná-Angola-Etendeka Province and occur as ring complexes and other central-type intrusions along northeast trending tectonic lineaments, parallel to the trend of coeval Namibian alkaline complexes. Most of the Angolan carbonatite-alkaline bodies are located along the apical part of the Moçamedes Arch, a structure representing the African counterpart of the Ponta Grossa Arch in southern Brazil, where several alkaline-carbonatite complexes were also emplaced in the Early Cretaceous. Geochemical and isotopic (C, 0, Sr and Nd) characteristics determined for five carbonatitic occurrences indicate that: (1) the overall geochemical composition, including the O---C isotopes, is within the range of the Early and Late Cretaceous Brazilian occurrences from the Paraná Basin; (2) the La versus relationships are consistent with the exsolution of CO_i2-rich melts from trachyphonolitic magmas; and (3) the and initial ratios are similar to the initial isotopic ratios (129 Ma) of alkaline complexes in northwest Namibia. In contrast, the Lupongola carbonatites have a distinctly different initial ratio, suggesting a different source.The Angolan carbonatites have Sr---Nd isotopic compositions ranging from bulk earth to time-integrated depleted sources. Since those from eastern Paraguay (at the western fringe of the Paraná-Angola-Etendeka Province) and Brazil appear to be related to mantle-derived melts with time-integrated enriched or B.E. isotopic characteristics, it is concluded that the carbonatites of the Paraná-Angola-Etendeka Province have compositionally distinct mantle sources. Such mantle heterogeneity is attributed to ‘metasomatic processes’, which would have occurred at ca 0.6–0.7 Ga (Angola, northwest Namibia and Brazil) and ca 1.8 Ga (eastern Paraguay), as suggested by Nd-model ages.     

Chrome-bearing mineral phases in the carbonatites of northern Transbaikalia

This paper presents the results of a study of the Vesely carbonatite occurrence in a new carbonatite-bearing area of northern Transbaikalia. The REE patterns, oxygen and carbon isotope compositions of carbonates and magnetites, and strontium isotope composition of dolomite allow us to classify the rocks as carbonatites. This study focused on minerals from xenoliths that were identified as mantle-derived on the basis of structure and mineral composition. The compositions of Cr-bearing chlorite, phengite, magnetite, rutile, ilmenite, and titanite are reported. Aggregates of closely intergrown magnetite and rutile occurring in the xenoliths resemble exsolution structures. A possible origin of these aggregates is discussed.     

Petrogenesis of carbonate-bearing nepheline syenites and carbonatites from Southern Victoria Land, Antarctica: origin of carbon and the effects of calcite-graphite equilibrium

Chemically-evolved carbonate-bearing nepheline syenites are intruded into basement metasediments of the Koettlitz Group on Dismal and Radian Ridges in the Pipecleaner Glacier region of Southern Victoria Land, Antarctica. Whole rock XRF data from the Dismal Nepheline Syenite defines a broad trend which is consistent with the removal of a cumulate fraction of approximate composition 70% hedenbergite, 15% nepheline, 10% titanite and 5% apatite. Stable isotope, major and trace element and mineralogical characteristics of the syenites are very similar to those of cross-cutting calcite-rich dykes indicating derivation from closely-related source magmas. The general association of carbonatites and nepheline syenites with extensional environments, suggests that the Dismal and Radian Ridge nepheline syenites and carbonatite dykes indicate a period of early Paleozoic (531 Ma) rifting or intrusion into localised tensional structures in an overall compressional regime. Assimilation of marble by the syenite magmas is evidenced by abundant rafts and xenoliths within the Dismal Nepheline Syenite, however, carbon and oxygen isotopic ratios from syenite and carbonatite calcites are distinctly lighter than values from the marble country rock indicating a magmatic source. Graphite and calcite commonly occur as aggregates in the Dismal Nepheline Syenite suggesting equilibrium between these two carbon-bearing phases. Isotopic fractionation between calcite and graphite, via the equilibrium: C + O₂ = CO₂ has resulted in enrichment of the ¹³C isotope in calcites from the Dismal Nepheline Syenite.