Sr–Nd–Pb isotopic compositions of the Kovdor phoscorite–carbonatite complex, Kola Peninsula, NW Russia

The Sr, Nd and Pb isotopic compositions for the Kovdor phoscorite–carbonatite complex (PCC), Kola Peninsula, NW Russia, have been determined to characterize the mantle sources involved and to evaluate the relative contributions of a plume and subcontinental lithospheric mantle in the formation of the complex. The Kovdor PCC is a part of the Kovdor ultramafic–alkaline–carbonatite massif, and consists of six intrusions. The initial isotopic ratios of the analyzed samples, calculated at 380 Ma, display limited variations: ε_Nd, + 2.0 to + 4.7; ⁸⁷Sr/⁸⁶Sr, 0.70319 to 0.70361 (ε_Sr, − 12.2 to − 6.2); ²⁰⁶Pb/²⁰⁴Pb, 18.38 to 18.74; ²⁰⁷Pb/²⁰⁴Pb, 15.45 to 15.50; ²⁰⁸Pb/²⁰⁴Pb, 37.98 to 39.28. The Nd and Sr isotope data of the Kovdor PCC generally fit the patterns of the other phoscorites and carbonatites from the Kola Alkaline Province (KAP), but some data are slightly shifted from the mixing line defined as the Kola Carbonatite Line, having more radiogenic ⁸⁷Sr/⁸⁶Sr ratios. However, the less radiogenic Nd isotopic compositions and negative Δ7/4 values of Pb isotopes of the analyzed samples exclude crustal contamination, but imply the involvement of a metasomatized lithospheric mantle source. Isotopic variations indicate mixing of at least three distinct mantle components: FOZO-like primitive plume component, EMI-like enriched component and DMM-like depleted component. The isotopic nature of the EMI- and DMM-like mantle component observed in the Kovdor samples is considered to be inherited from metasomatized subcontinental lithospheric mantle. This supports the previous models invoking plume–lithosphere interaction to explain the origin of the Devonian alkaline carbonatite magmatism in the KAP.     

Fluid–rock interaction at a carbonatite-gneiss contact, Alnö, Sweden

We evaluate balanced metasomatic reactions and model coupled reactive and isotopic transport at a carbonatite-gneiss contact at Alnö, Sweden. We interpret structurally channelled fluid flow along the carbonatite-gneiss contact at ～640°C. This caused (1) metasomatism of the gneiss, by the reaction: ${\hbox{biotite} + \hbox{quartz} + \hbox{oligoclase} + \hbox{K}_{2} \hbox{O} +\,\hbox{Na}_{2}\hbox{O} \pm \hbox{CaO} \pm \hbox{MgO} \pm \hbox{FeO} = \hbox{albite} + \hbox{K-feldspar} + \hbox{arfvedsonite} + \hbox{aegirene-}\hbox{augite} + \hbox{H}_{2} \hbox{O} + \hbox{SiO}_{2}}We evaluate balanced metasomatic reactions and model coupled reactive and isotopic transport at a carbonatite-gneiss contact at Aln?, Sweden. We interpret structurally channelled fluid flow along the carbonatite-gneiss contact at ∼640°C. This caused (1) metasomatism of the gneiss, by the reaction: , (2) metasomatism of carbonatite by the reaction: calcite + SiO₂ = wollastonite + CO₂, and (3) isotopic homogenization of the metasomatised region. We suggest that reactive weakening caused the metasomatised region to widen and that the metasomatic reactions are chemically (and possibly mechanically) coupled. Spatial separation of reaction and isotope fronts in the carbonatite conforms to a chromatographic model which assumes local calcite–fluid equilibrium, yields a timescale of 10²–10⁴ years for fluid–rock interaction and confirms that chemical transport towards the carbonatite interior was mainly by diffusion. We conclude that most silicate phases present in the studied carbonatite were acquired by corrosion and assimilation of ijolite, as a reactive by-product of this process and by metasomatism. The carbonatite was thus a relatively pure calcite–H₂O−CO₂–salt melt or fluid.     

碳酸岩型稀土矿床成矿流体演化机制研究现状及展望

与碱性岩有关的碳酸岩型内生稀土矿床在中国乃至世界上轻稀土资源储量中占有极为重要的地位,诸如我国内蒙古的白云鄂博稀土矿床、川西冕宁—德昌稀土成矿带中的牦牛坪、大陆槽等稀土矿床、山东微山县郗山稀土矿床以及美国的Mountain Pass稀土矿床等都属于这种类型的稀土矿床.当前,对于这类稀土矿床的成矿流体演化机制,学界主要存...     

碳酸盐岩干酪根催化降解生烃过程及动力学研究

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

Peralkaline syenite autoliths from Kilombe volcano, Kenya Rift Valley: Evidence for subvolcanic interaction with carbonatitic fluids

Mineral chemistry, textures and geochemistry of syenite autoliths from Kilombe volcano indicate that they crystallized in the upper parts of a magma chamber from peralkaline trachytic magmas that compositionally straddle the alkali feldspar join in the “residuum system” (ne = 0–1.03; qz = 0–0.77). Mineral reaction and/or overgrowth processes were responsible for the replacement of (i) Mg–hedenbergite by aegirine–augite, Ca–aegirine and/or aegirine, (ii) fayalite by amphiboles, and (iii) magnetite by aenigmatite. Ti–magnetite in silica-saturated syenites generally shows ilmenite exsolution, partly promoted by circulating fluids.

By contrast, the Fe–Ti oxides in the silica-undersaturated (sodalite-bearing) syenites show no signs of deuteric alteration. These syenites were ejected shortly after completion of crystallization. Ilmenite–magnetite equilibria indicate fO₂ between − 19.5 and − 23.1 log units (T 679–578 °C), slightly below the FMQ buffer. The subsequent crystallization of aenigmatite and Na-rich pyroxenes suggests an increase in the oxidation state of the late-magmatic liquids and implies the influence of post-magmatic fluids.

Irrespective of silica saturation, the syenites can be divided into (1) “normal” syenites, characterized by Ce/Ce ratios between 0.83 and 0.99 and (2) Ce-anomalous syenites, showing distinct negative Ce-anomalies (Ce/Ce 0.77–0.24). “Normal” silica-saturated syenites evolved towards pantelleritic trachyte. The Ce-anomalous syenites are relatively depleted in Zr, Hf, Th, Nb and Ta but, with the exception of Ce, are significantly enriched in REE.

The silica-saturated syenites contain REE–fluorcarbonates (synchysite-bastnaesite series) with negative Ce-anomalies (Ce/Ce 0.4–0.8, mean 0.6), corroded monazite group minerals with LREE-rich patches, and hydrated, Fe- and P-rich phyllosilicates. Each of these is inferred to be of non-magmatic origin. Fractures in feldspars and pyroxenes contain Pb-, REE- and Mn-rich cryptocrystalline or amorphous material. The monazite minerals are characterized by the most prominent negative Ce-anomalies (Ce/Ce_mean = 0.5), and in the most altered and Ca-rich areas (depleted in REE), Ce/Ce is less than 0.2.

It is inferred that carbonatitic fluids rich in F, Na and lanthanides but depleted in Ce by fractional crystallization of cerian pyrochlore, percolated into the subvolcanic system and interacted with the syenites at the thermal boundary layers of the magma chamber, during and shortly after their crystallization.

Chevkinite–(Ce), pyrochlore, monazite and synchysite-bastnaesite, occurring as accessory minerals, have been found for the first time at Kilombe together with eudialyte, nacareniobsite–(Ce) and thorite. These latter represent new mineral occurrences in Kenya.     

The mineral isotope composition of two Precambrian carbonatite complexes from the Kola Alkaline Province – Alteration versus primary magmatic signatures

We investigated the isotope composition (O, C, Sr, Nd, Pb) in mineral separates of the two Precambrian carbonatite complexes Tiksheozero (1.98 Ga) and Siilinjärvi (2.61 Ga) from the Karelian–Kola region in order to obtain information on Precambrian mantle heterogeneity. All isotope systems yield a large range of variations. The combination of cathodoluminescence imaging with stable and radiogenic isotopes on the same samples and mineral separates indicates various processes that caused shifts in isotope systems. Primary isotope signatures are preserved in most calcites (O, C, Sr, Pb), apatites (O, Sr, Nd), amphiboles (O), magnetites (O), and whole rocks (Sr, Nd).

The primary igneous C and O isotope composition is different for both complexes (Tiksheozero: δ¹³C = − 5.0‰, δ¹⁸O = 6.9‰; Siilinjärvi: δ¹³C = − 3.7‰, δ¹⁸O = 7.4‰) but very uniform and requires homogenization of both carbon and oxygen in the carbonatite melt. The lowest Sr isotope ratios of our carbonates and apatites from the Archaean Siilinjärvi (0.70137) and the Palaeoproterozoic Tiksheozero (0.70228) complexes are in the range of bulk silicate earth (BSE). Positive ε_Nd values of the two carbonatites point to very early Archaean enrichment of Sm/Nd in the Fennoscandian mantle. No HIMU components could be detected in the two complexes, whereas Tiksheozero carbonatites give the first indication of Palaeoproterozoic U depletion for Fennoscandia.

Sub-solidus exchange processes with water during emplacement and cooling of carbonatites caused an increase in the oxygen isotope composition of some carbonates and probably also an increase of their ⁸⁷Sr/⁸⁶Sr ratio. A larger increase of initial Sr isotope ratios was found in carbonatized silicic rocks compared to carbonatite bodies. The Svecofennian metamorphic overprint (1.9–1.7 Ga) caused reset of Rb/Sr (mainly mica) and Pb/Pb (mainly apatite) isochron systems.     

白云鄂博超大型REE-Nb-Fe矿区碳酸岩墙的侵位年龄--兼答Le Bas博士的质疑

对白云鄂博稀土-铁-铌矿矿区一号碳酸岩墙内锆石U-Pb年龄进行了测定,三颗锆石测定数据点拟合直线与谐合线的上交点年龄为1416±77 Ma,它可能表明了白云鄂博矿区火成碳酸岩墙的侵入时代,而另外1颗锆石的表面年龄(1925±8 Ma)则可能是来自围岩的捕获锆石年龄.     

The carbonate fraction in carbonatitic Italian lamprophyres

Alkaline and ultramafic lamprophyres represent the majority of pre-Pleistocene alkaline mafic magmatic activity in Italy and have been described from several localities. The age of magmatism ranges from Triassic to Lower Oligocene. Some contain appreciable amounts of carbonate. The primary carbonate of the Italian carbonatitic lamprophyres is mainly Sr- or Mn-rich calcite that occurs mostly as immiscible ocelli or as groundmass. Its textural occurrence, composition, and relationship with co-precipitating silicate phases is taken as evidence of an igneous origin. Low BaO and REE contents in the carbonate are explained by early crystallization of essential mica and subordinate apatite. Whole rock analyses and isotopic data (Rukhlov, A.S., Bell, K., Vichi, G., Stoppa, F., submitted for publication. The heterogeneous deep mantle: the Sr, Pb and Nd isotopic evidence from Early Cretaceous alkaline lamprophyres of Southern Tuscany, Italy. Lithos.) suggest a mantle origin for these rocks and rule out contamination in either high or low pressure regimes. The bulk compositions of the carbonatitic lamprophyres have high HFSE / LILE and LREE / HREE ratios and although the abundances of these elements are generally lower than for carbonatites s.s., they are comparable with the abundances in other ‘carbonate-free’ Italian lamprophyres and Italian carbonatites, suggesting similar mantle sources. Moreover, the age of the Italian lamprophyres, ranging from Middle Triassic to Lower Oligocene, is much greater than the Pleistocene age of Italian carbonatites and indicates that the source remained similar over a long time span.     

Geochemistry of carbonatite–silicate pairs in nature: A case history from Central Italy

At Oricola (Aquila-Abruzzo, Italy) carbonatite is associated with phonolitic foidite tuff. The Oricola carbonatite contains fresh silicate glass of kamafugitic foidite composition which, compared with carbonate, shows similar trace element patterns but lower concentrations. As a whole, the mineralogy of the Oricola rocks matches that of the neighbouring Grotta del Cervo kamafugitic foidite and carbonatitic foidite and is in the range of the Intramountain Ultralkaline Province (IUP) of melilitites and carbonatites of Italy.

The IUP carbonatites and kamafugitic foidites definitely form intra-outcrop conjugate pairs. All these co-eruptive rocks have parallel trace element patterns, namely REE, which implies a dilution–concentration relationship among them but always with higher contents in primary calcite. Based on current textural and compositional criteria, as well as comparable experimental data, we attribute this feature to liquid immiscibility dominant over crystal fractionation at crustal pressure. This relatively late immiscibility phenomenon is superimposed on co-magmatic features shown by inter-outcrop conjugate rock couples. In fact if we consider San Venanzo kamafugite and Polino Ca-carbonatite, or Grotta del Gervo kamafugite and Oricola Ca-carbonatite, we note couple by couple that they are chemical heteromorphs erupted in isolation in different place. The REE distribution is another distinctive feature of these couples and shows a marked crossover at MREE level. A fact we interpret as produced by near mantle-solidus immiscibility. After this early phenomenon the two members of the couple can erupt in a near primary state carrying mantle xenoliths or undergo some evolution including settling out mantle xenoliths and crystals and fractionation and finally exsolve a carbonatitic residuum by immiscibility.     

Magmatic evolution of the differentiated ultramafic, alkaline and carbonatite intrusion of Vuoriyarvi (Kola Peninsula, Russia). A LA-ICP-MS study of apatite

The nature of the petrogenetic links between carbonatites and associated silicate rocks is still under discussion (i.e., [Gittins J., Harmer R.E., 2003. Myth and reality of the carbonatite–silicate rock “association”. Period di Mineral. 72, 19–26.]). In the Paleozoic Kola alkaline province (NW Russia), the carbonatites are spatially and temporally associated to ultramafic cumulates (clinopyroxenite, wehrlite and dunite) and alkaline silicate rocks of the ijolite–melteigite series [(Kogarko, 1987), (Kogarko et al., 1995), (Verhulst et al., 2000), (Dunworth and Bell, 2001) and (Woolley, 2003)]. In the small (≈ 20 km²) Vuoriyarvi massif, apatite is typically a liquidus phase during the magmatic evolution and so it can be used to test genetic relationships. Trace elements contents have been obtained for both whole rocks and apatite (by LA-ICP-MS). The apatites define a single continuous chemical evolution marked by an increase in REE and Na (belovite-type of substitution, i.e., 2Ca²⁺ = Na⁺ + REE³⁺). This evolution possibly reflects a fractional crystallisation process of a single batch of isotopically homogeneous, mantle-derived magma.The distribution of REE between apatite and their host carbonatite have been estimated from the apatite composition of a carbonatite vein, belonging to the Neskevara conical-ring-like vein system. This carbonatite vein is tentatively interpreted as a melt. So, the calculated distribution coefficients are close to partition coefficients. Rare earth elements are compatible in apatite (D > 1) with a higher compatibility for the middle REE (D_Sm : 6.1) than for the light (D_La : 4.1) and the heavy (D_Yb : 1) REE.