Anatoly N. Zaitsev
Saint Petersburg State University
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Geochimica et Cosmochimica Acta | 2002
Yuri Amelin; Anatoly N. Zaitsev
We present the results of a comparative study of several geochronometer minerals (baddeleyite, zircon, apatite, phlogopite and tetraferriphlogopite) and isotopic systems (U-Pb, Th-Pb and Rb-Sr) from phoscorites (magnetite-forsterite-apatite-calcite rocks) and carbonatites of the Kovdor ultramafic-alkaline-carbonatite massif, Kola Peninsula, Russia. Uranium, thorium and their decay products are extremely fractionated by minerals that crystallise from carbonatite and phoscorite magma. We obtain high-precision ages from different chronometers, compare their accuracy, and evaluate the role of geochronological pitfalls of initial radioactive disequilibrium, differential migration of radiogenic isotopes, and inaccurate decay constants. Apatite yielded concordant U-Th-Pb ages between 376 and 380 Ma. The accuracy of the apatite 238U-206Pb ages is, however, compromised by uncertainty in the amount of radiogenic 206Pb produced from initial excess 230Th. The 235U-207Pb ages are relatively imprecise due to large common Pb correction and the uncertainty in the initial Pb isotopic composition. The Th-Pb system yields a more precise age of 376.4 ± 0.6 Ma. Zircon from two carbonatite samples is characterised by moderate to low U contents, high Th contents, and very high Th/U ratios up to 9000. The 206Pb*/238U systems in the zircon are strongly affected by the presence of excess 206Pb*, produced by decay of initial 230Th. The 208Pb*/232Th ages of zircon from both carbonatite samples are uniform and yield a weighted average of 377.52 ± 0.94 Ma. Baddeleyite U-Pb analyses are 3 to 6% normally discordant and have variable 207Pb*/206Pb* apparent ages. Eleven alteration-free baddeleyite fractions from three samples with no evidence for Pb loss yield uniform 206Pb*/238U ages with a weighted average of 378.54±0.23 Ma (378.64 Ma after correction for initial 230Th deficiency), which we consider the best estimate for age of the phoscorite-carbonatite body of the Kovdor massif. The 206Pb*/238U ages of baddeleyite fractions from five other samples spread between 378.5 and 373 Ma, indicating a variable lead loss up to 1.5%. The anomalously old 207Pb/235U and 207Pb/206Pb ages are consistent with the presence of excess radiogenic 207Pb* in the baddeleyite. We interpret this as a result of preferential partitioning of 231Pa to baddeleyite. Fifteen phlogopite and tetraferriphlogopite fractions from five carbonatite and phoscorite samples yielded precise Rb-Sr isochron age of 372.2 ± 1.5 Ma, which is 5 to 7 m.y. younger than our best estimate based on U-Th-Pb age values. This difference is unlikely to be a result of the disturbance or late closure of Rb-Sr system in phlogopite, but rather suggests that the accepted decay constant of 87Rb is too high. Comparative study of multiple geochronometer minerals from the Kovdor massif has revealed an exceptional complexity of isotopic systems. Reliable ages can be understood through systematic analysis of possible sources of distortion. No single geochronometer is sufficiently reliable in these rocks. Th-Pb and Rb-Sr can be a very useful supplement to U-Pb geochronometry, but the routine use of these geochronometers together will require more precise and accurate determination of decay constants for 232Th and 87Rb.
Lithos | 2002
Anatoly N. Zaitsev; Attila Demény; Sven Sindern; Frances Wall
The 370–380 Ma Khibina and Vuoriyarvi complexes on the Kola Peninsula, Russia, which form part of the Palaeozoic Kola Alkaline Province, contain REE-rich carbonatites with burbankite (Na,Ca)3(Sr,Ca,REE,Ba)3(CO3)5 or calcioburbankite (Na,Ca)3(Ca,Sr,REE,Ba)3(CO3)5 as the principal primary REE mineral. Within each complex the C–O and Sr–Nd isotopic data are similar for burbankite group minerals and co-existing calcite or dolomite (Khibina: δ13C(V-PDB)=−6.4 to−5.8‰, δ18O(V-SMOW)=7.3–7.7‰, (87Sr/86Sr)370=0.70390–0.70404 and (143Nd/144Nd)370=0.51230–0.51235; Vuoriyarvi: δ13C=−4.2 to −3.0‰, δ18O=8.1–9.4‰, (87Sr/86Sr)370=0.70313–0.70315 and (143Nd/144Nd)370=0.51243–0.51245). This indicates that the REE mineralization and its host carbonatites in each complex are derived from the same source and are co-genetic. There is, however, a great difference between the Sr, Nd and C isotopic signatures from Khibina and Vuoriyarvi, whereas the δ18O ranges are similar. This suggests that the REE carbonatites of the two complexes originate from sources with different isotopic signatures. At least three mantle components are needed to explain the variations in Sr and Nd compositions in the carbonatites from Kola. The δ13C ranges of primary carbonatites with low δ18O values are quite different for Khibina and Vuoriyarvi and show correlation with the radiogenic isotope compositions. The data may be best explained by subduction-related source contamination that caused δ13C variations in different mantle components. During late-stage processes burbankite and calcioburbankite have been replaced by various assemblages of REE–Sr–Ba minerals. The alteration of burbankite group minerals is an open-system hydrothermal process leading to multiple element transfer. It has produced mineral assemblages which are characterized by high δ18O values (Khibina: δ18O(V-SMOW)=11.4–13.9‰ and Vuoriyarvi: δ18O=17.1–18.0‰) compared to primary burbankite and calcioburbankite. Co-existing calcite and dolomite have retained their original C and O isotope compositions, and one calcite sample from Khibina shows strong positive δ13C–δ18O shifts similar to those of the pseudomorph. The high δ18O and sometimes high δ13C values can be attributed to low-temperature isotope exchange between minerals and fluid with variable CO2/H2O ratio taking place during and/or after crystallization as usually observed in carbonatites. The Sr and Nd isotope compositions of pseudomorphs and associated calcite/dolomite in general are identical to those of burbankite/calcioburbankite and associated carbonates suggesting that the fluids which caused burbankite alteration are from the same source, i.e. carbonatitic. Small variations in the Sr and Nd isotope signatures point to interaction of the pseudomorph-forming fluid with alkali silicate wall rocks.
Geology of Ore Deposits | 2009
Anatoly N. Zaitsev; Jörg Keller; John Spratt; Teresa Jeffries; Victor V. Sharygin
Alkali carbonates nyerereite, ideally Na2Ca(CO3)2 and gregoryite, ideally Na2CO3, are the major minerals in natrocarbonatite lavas from Oldoinyo Lengai volcano, northern Tanzania. They occur as pheno- and microphenocrysts in groundmass consisting of fluorite and sylvite; nyerereite typically forms prismatic crystals and gregoryite occurs as round, oval crystals. Both minerals are characterized by relatively high contents of various minor elements. Raman spectroscopy data indicate the presence of sulfur and phosphorous as (SO4)2− and (PO4)3− groups. Microprobe analyses show variable composition of both nyerereite and gregoryite. Nyerereite contains 6.1–8.7 wt % K2O, with subordinate amounts of SrO (1.7–3.3 wt %), BaO (0.3–1.6 wt %), SO3 (0.8–1.5 wt %), P2O5 (0.2–0.8 wt %) and Cl (0.1–0.35 wt %). Gregoryite contains 5.0–11.9 wt % CaO, 3.4–5.8 wt % SO3, 1.3–4.6 wt % P2O5, 0.6–1.0 wt % SrO, 0.1–0.6 wt % BaO and 0.3–0.7 wt % Cl. The content of F is below detection limits in nyerereite and gregoryite. Laser ablation ICP-MS analyses show that REE, Mn, Mg, Rb and Li are typical trace elements in these minerals. Nyerereite is enriched in REE (up to 1080 ppm) and Rb (up to 140 ppm), while gregoryite contains more Mg (up to 367 ppm) and Li (up to 241 ppm) as compared with nyerereite.
Geology of Ore Deposits | 2010
Anatoly N. Zaitsev
The extinct Quaternary Kerimasi volcano located in the southern part of the Gregory Rift, northern Tanzania, contains both intrusive and extrusive calciocarbonatites. One carbonate mineral with a high content of Na and Ca has been found in a sample of volcanic carbonatite, which is probably a cumulate rock. On the basis of Raman spectroscopy and SEM/EDS, this mineral was identified as nyerereite, ideally Na2Ca(CO3)2. It occurs as solid inclusions up to 300 × 200 μm in size in magnetite and contains (wt. %) 25.4–27.4 Na2O, 26.0–26.8 CaO, 1.6–1.9 K2O, 0.6–1.8 FeO, 0.3–0.6 SrO, <0.4 BaO, 1.4–2.3 SO3, and 0.6–0.9 P2O5. The average mineral formula is (Na1.84K0.08)Σ1.92(Ca1.00Fe0.03Sr0.01)Σ1.04[(CO3)1.91(SO4)0.05(PO4)0.02]Σ1.98. A few inclusions in magnetite also contain calcite, which is considered here to be a late-stage, subsolidus mineral. The occurrence of nyerereite in carbonatite supports Hay’s (1983) idea that some of the extrusive carbonatites at the Kerimasi volcano were originally alkaline rich and contained both calcite and nyerereite as primary minerals.
Mineralogical Magazine | 2013
Anatoly N. Zaitsev; Thomas Wenzel; Torsten Vennemann; Gregor Markl
Abstract The Tinderet volcano (19.9 to 5.5 Ma), located within the Kavirondo rift in Kenya, contains blocks of carbonatite lavas with calcite, minor apatite, fluorite, spinel-group minerals, accessory perovskite and ‘plumbopyrochlore’; nyerereite is present as inclusions in the perovskite. At least four types of calcite are present in the carbonatite lavas; they differ in morphology, composition and origin. The dominant variety is secondary type-II calcite, which is enriched in sodium (up to 1.1 wt.% Na2O) and strontium (up to 1.3 wt.% SrO). The spinel-group minerals are manganese-bearing and include Mn-rich magnetite, magnesioferrite and jacobsite. Oxygen isotope data for bulk carbonatite samples (δ18O = +16.2‰ to +22.6‰ VSMOW) support a low crystallization temperature for the secondary calcite. Petrographic, mineralogical and isotopic data indicate that the Tinderet carbonatites are similar to natrocarbonatites from the Oldoinyo Lengai and Kerimasi volcanoes that have altered and recrystallized to form calcite carbonatites. These data support the hypothesis that some of the Tinderet carbonatites were originally alkali-rich rocks which contained primary nyerereite.
Mineralogical Magazine | 2009
Daniel Wiedenmann; Anatoly N. Zaitsev; Sergey N. Britvin; Sergey V. Krivovichev; Jörg Keller
Abstract Alumoåkermanite, (Ca,Na)2(Al,Mg,Fe2+)(Si2O7), is a new mineral member of the melilite group from the active carbonatite-nephelinite-phonolite volcano Oldoinyo Lengai, Tanzania. The mineral occurs as tabular phenocrysts and microphenocrysts in melilite-nephelinitic ashes and lapilli-tuffs. Alumoåkermanite is light brown in colour; it is transparent, with a vitreous lustre and the streak is white. Cleavages or partings are not observed. The mineral is brittle with an uneven fracture. The measured density is 2.96(2) g/cm3. The Mohs hardness is ~4.5−6. Alumoåkermanite is uniaxial (−) with ω = 1.635(1) and e = 1.624−1.626(1). In a 30 mm thin section (+N), the mineral has a yellow to orange interference colour, straight extinction and positive elongation, and is nonpleochroic. The average chemical formula of the mineral derived from electron microprobe analyses is: (Ca1.48Na0.50Sr0.02K0.01)∑2.01(Al0.44Mg0.30Fe2+0.17Fe3+0.07Mn0.01)∑0.99(Si1.99Al0.01O7). Alumoåkermanite is tetragonal, space group P4̅. 21m with a = 7.7661(4) Å, c = 5.0297(4) Å, V = 303.4(1) Å3 and Z = 2. The five strongest powder-diffraction lines [d in Å, (I/Io), hkl] are: 3.712, (13), (111); 3.075, (25), (201); 2.859, (100), (211); 2.456, (32), (311); 1.757, (19), (312). Single-crystal structure refinement (R1= 0.018) revealed structure topology typical of the melilite-group minerals, i.e. tetrahedral [(Al,Mg)(Si2O7)] sheets interleaved with layers of (CaNa) cations. The name reflects the chemical composition of the mineral.
Mineralogy and Petrology | 2016
Anton R. Chakhmouradian; Ekaterina P. Reguir; Anatoly N. Zaitsev
Carbonatites are nominally igneous rocks, whose evolution commonly involves also a variety of postmagmatic processes, including exsolution, subsolidus re-equilibration of igneous mineral assemblages with fluids of different provenance, hydrothermal crystallization, recrystallization and tectonic mobilization. Petrogenetic interpretation of carbonatites and assessment of their mineral potential are impossible without understanding the textural and compositional effects of both magmatic and postmagmatic processes on the principal constituents of these rocks. In the present work, we describe the major (micro)textural characteristics of carbonatitic calcite and dolomite in the context of magma evolution, fluid-rock interaction, or deformation, and provide information on the compositional variation of these minerals and its relation to specific evolutionary processes.
Mineralogical Magazine | 2010
Anatoly N. Zaitsev; C. T. Williams; Sergey N. Britvin; I. V. Kuznetsova; John Spratt; Sergey V. Petrov; Jörg Keller
Abstract Kerimasite, ideally Ca3Zr2(Fe23+Si)O12, is a new calcium zirconium silicate-ferrite member of the garnet group from the extinct nephelinitic volcano Kerimasi and surrounding explosion craters in northern Tanzania. The mineral occurs as subhedral crystals up to 100 μm in size in calcite carbonatites, and as euhedral to subhedral crystals up to 180 μm in size in carbonatite eluvium. Kerimasite is light to dark-brown in colour and transparent with a vitreous lustre. No cleavage or parting was observed and the mineral is brittle. The calculated density is 4.105(1) g/cm3. The micro-indentation, VHN25, ranges from 1168 to 1288 kg/mm2. Kerimasite is isotropic with n = 1.945(5). The average chemical formula of the mineral derived from electron microprobe analyses (sample K 94-25) and calculated for O = 12 and all Fe as Fe2O3 is (Ca3.00Mn0.01Ce0.01Nd0.01)∑3.03(Zr1.72Nb0.14Ti0.08Mg0.02Y0.02)∑1.98(Fe1.233+Si0.86Al0.82Ti0.09)∑3.00O12. The largest Fe content determined in kerimasite is 21.6 wt.% Fe2O3 and this value corresponds to 1.66 a.p.f.u. in the tetrahedral site. Kerimasite is cubic, space group Ia3̄d with a = 12.549(1) Å, V = 1976.2(4) Å3 and Z = 8. The five strongest powder-diffraction lines [d in Å, (I/Io), hkl] are: 4.441 (49) (220), 3.140 (91) (400), 2.808 (70) (420), 2.564 (93) (422) and 1.677 (100) (642). Single-crystal structure refinement revealed the typical structure of the garnet-group minerals. The name is given after the locality, Kerimasi volcano, Tanzania.
Mineralogical Magazine | 2014
Oleg I. Siidra; Lidiya P. Vergasova; Sergey V. Krivovichev; Yuri L. Kretser; Anatoly N. Zaitsev; Stanislav K. Filatov
Abstract Markhininite, ideally TlBi(SO4)2, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975-1976), Kamchatka Peninsula, Russia. Markhininite occurs as white pseudohexagonal plates associated with shcherbinaite, pauflerite, bobjonesite, karpovite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Markhininite is triclinic, P1̄ , a = 7.378(3), b = 10.657(3), c = 10.657(3) Å , α = 61.31(3), β = 70.964(7), γ = 70.964(7)°, V = 680.2(4) Å3, Z = 4 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 68/4.264/111, 100/3.441/113, 35/3.350/222, 24/3.125/122, 23/3.054/202, 45/2.717/022, 20/2.217/331, 34/2.114/204. Chemical composition determined by electron microprobe analysis is (wt.%): Tl2O 35.41, Bi2O3 38.91, SO3 25.19, total 99.51. The empirical formula based on 8 O a.p.f.u. is Tl1.04Bi1.05S1.97O8. The simplified formula is TlBi(SO4)2, which requires Tl2O 35.08, Bi2O3 38.48, SO3 26.44, total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.055 on the basis of 1425 independent observed reflections. The structure contains four Tl+ and two Bi3+ sites in holodirected symmetrical coordination. BiO8 tetragonal antiprisms and SO4 tetrahedra in markhininite share common O atoms to produce [Bi(SO4)2]- layers of the yavapaiite type. The layers are parallel to (111) and linked together through interlayer Tl+ cations. The mineral is named in honour of Professor Yevgeniy Konstantinovich Markhinin (b. 1926), Institute of Volcanology, Russian Academy of Sciences, Kamchatka peninsula, Russia, in recognition of his contributions to volcanology. Markhininite is the first oxysalt compound that contains both Tl and Bi in an ordered crystal structure.
Mineralogical Magazine | 2011
Anatoly N. Zaitsev; Anton R. Chakhmouradian; Oleg I. Siidra; John Spratt; C. T. Williams; C. J. Stanley; Sergey V. Petrov; Sergey N. Britvin; E. A. Polyakova
Abstract Cerianite-(Ce), ideally CeO2, occurs as rounded grains up to 5 μm across in a block of highly altered calcite carbonatite lava from the Kerimasi volcano, and as euhedral crystals up to 200 μm across in carbonatite-derived eluvial deposits in the Kisete and Loluni explosion craters in the Gregory Rift, northern Tanzania. X-ray powder diffraction data (a = 5.434(5) Å ) and Raman spectroscopy (minor vibration modes at 184 and 571 cm-1 in addition to a strong signal at 449 cm-1) suggest the presence of essential amounts of large cations and oxygen vacancies in the Kisete material. Microprobe analyses reveal that the mineral contains both light and heavy trivalent rare earth elements (REE) (7.9-15.5 wt.% LREE2O3 and 4.9-9.7 wt.% HREE2O3), and that it is enriched in yttrium (7.1-14.5 wt.% Y2O3) and fluorine (2.2-3.5 wt.%). Single-crystal structure refinement of the mineral confirms a fluorite-type structure with a cation anion distance of 2.3471(6) Å. The cerianite-(Ce) is considered to be a late-stage secondary mineral in the carbonatitic rocks.