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The genesis of calcite and dolomite carbonatite-forming magma by liquid immiscibility: a critical appraisal
- John Gittins, Roger H. Mitchell
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- Journal:
- Geological Magazine / Volume 160 / Issue 8 / August 2023
- Published online by Cambridge University Press:
- 15 September 2023, pp. 1463-1480
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Liquid immiscibility has become the preferred mode of genesis for the carbonatite rocks, which commonly, but not exclusively, accompany silicate rocks in alkaline-rock complexes. This concept has been universally based on the presumption that nephelinitic and phonolitic magmas can evolve to a stage where two conjugate immiscible liquids separate. It is assumed that these two liquids separate quickly, or even instantaneously, into discrete bodies of magma capable of being intruded or extruded with subsequent independent crystallization. Supporting evidence generally given is: alleged consanguinity as discrete occurrence of the two rock types; similarity of radiogenic isotope ratios; trace element contents similar to those predicted from experimentally derived partition coefficients. We do not accept that a general case for liquid immiscibility has been demonstrated; although we do accept that silicate and carbonate liquids are inherently immiscible, we maintain that they are not conjugate in a petrogenetic context. We have reviewed and critically examined the experimental data purporting to establish liquid immiscibility and find that when applied to natural rocks, they are based on inappropriate experimental designs, which are not relevant to the genesis of calcite or dolomite carbonatites, although they might have some relevance to Oldoinyo Lengai nyerereite–gregoryite lavas. The design of these experiments guarantees immiscibility and ensures that the carbonate liquids formed will be calcitic or sodium-rich. We dispute the validity of comparing the trace element contents of natural rocks, which in many instances do not represent liquid compositions, to experimentally determine partition coefficients. We consider that experimental design inadequacies, principally assuming but not proving, that the liquids involved are conjugate, indicate that these coefficients are merely an expression of the preference of certain elements for particular liquids, regardless of how the liquids formed. Proof of consanguinity in alkaline complexes requires more accurate age determinations on the relevant rock types than has generally been the case, and in most complexes, consanguinity can be discounted. We dispute the contention that melt inclusions represent parental melts, although they might elucidate the character of magmas undergoing fractional crystallization from magmatic to carbothermal stages. Radiogenic isotope data are shown to be too widely variable to support a case for liquid immiscibility. We address the contention that calcite cannot crystallize from a dolomitic liquid formed by direct mantle melting, and must therefore have crystallized from a calcite carbonate liquid generated by liquid immiscibility, and demonstrate that it is an unsupported hypothesis as calcite can readily crystallize from dolomitic liquids. We observe that, because immiscible dolomite liquids have never been produced experimentally, the liquid immiscibility proposition could at best be applied only to calcite carbonatites, thus leaving unexplained the large number of dolomite carbonatites and those of either type, which are not accompanied by alkaline silicate rocks. The assumed bimodality of alkaline-rock carbonatite complexes is considered to be fallacious and no actual geological or petrographic evidence for immiscibility processes is evident in these complexes. Several examples of alkaline rock carbonatite complexes for which immiscibility has been proposed are evaluated critically and shown to fail in attempts to establish them as exemplifying immiscibility. We conclude that no actual geological or experimental data exist to establish liquid immiscibility being involved in the genesis of calcite or dolomite carbonatite-forming magmas.
Conversion of nepheline to sodalite during subsolidus processes in alkaline rocks
- Adrian A. Finch
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- Journal:
- Mineralogical Magazine / Volume 55 / Issue 380 / September 1991
- Published online by Cambridge University Press:
- 05 July 2018, pp. 459-463
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Cathodoluminescence (CL) petrography of nepheline syenites of the Igaliko complex, Gardar province, South Greenland shows that sodalites possess embayed contacts against nepheline, and have formed by a process of metasomatic replacement. This texture is demonstrated clearly by CL, since sodalite luminesces bright orange and nepheline is poorly luminescent. The transformation from nepheline to sodalite results in a volume change which leads to a network of fractures in which deep-blue luminescent fluorite is precipitated. Fluorite is formed since the chlorination process involved in the transformation causes localised reductions of the salinity of the fluid and therefore a decrease in the solubility of fluorite. Sodalite-fluorite textures observed using CL allow sodalites of secondary origin in alkaline igneous rocks to be identified.
Nephelines and sodalites, when observed using scanning electron microscopy, possess small micropores. By analogy with recent work on alkali feldspars, pervasive alteration of nephelines may occur by fluid flow assisted by a permeable micropore network.
Some aspects of the crystal-chemistry of apatites
- Yu Liu, Paola Comodi
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- Journal:
- Mineralogical Magazine / Volume 57 / Issue 389 / December 1993
- Published online by Cambridge University Press:
- 05 July 2018, pp. 709-719
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Twenty-four apatite (Ap) samples mainly from carbonatite and alkaline rocks were studied by electron microprobe, IR spectroscopy and X-ray powder diffraction. The crystal structures of six were refined using single crystal X-ray diffraction data to R = 1.7-2.5%. The generally high Si content of Ap from carbonatite and alkaline rock has been related to the presence of characteristic Si-O absorptions in IR spectra. Bands, whose intensities change with Si content, were observed at 520, 650, 930 and 1160 cm-1. The IR absorption features of v3 CO3 mode of Ap from carbonatite are different from those of v3 CO3 mode of Ap from sedimentary rock. This phenomenon is probably due to the different effects of F and OH on the CO3 substitution for PO4. The structural refinements yield more information on the CO3=PO4 substitution, which is now supported also by the geometrical evolution of the tetrahedron with increasing CO3 content: the tetrahedral size decreases and the angle distortion increases with C-content. It is likely that the triangular planar CO3 group is disordered on the four faces of PO43-tetrahedron. It was observed also that Ap from early-stage carbonatite is OH-dominant with considerable LREE, Si, CO3 and negligible Mn, Fe, Mg, K, S and C1 contents. They have high Sr/Mn, Si/S and C/S ratios.
Modelling of dissolution–reprecipitation ion-exchange reactions for the development of flame perthite in a suite of sheared alkaline rocks: an example from Chimakurthy, Eastern Ghats, India
- Sudip Bhattacharyya, P. Sengupta
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- Mineralogical Magazine / Volume 78 / Issue 5 / October 2014
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- 05 July 2018, pp. 1301-1323
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A suite of sheared syenites occurring along the western margin of the Eastern Ghats Belt, India have developed extensive flame perthite in K-feldspar. Albite flames show large variation in size, shape and abundance. Field, petrographic and chemical evidence suggests complex interplay between differential stress, recycling of K-Na-Ca and supply of Na by infiltration for the development of flame perthite. Partial replacement of pyroxenes, plagioclase and alkali feldspar by amphibole, biotite, nepheline and calcite causes internal recycling of Na-Ca-K in a closed system. Representative compositions of the minerals are used to constrain the model dissolution–reprecipitation ion-exchange reactions involving Na and K either as reactants and/or as products. A substantial proportion of Na+ required for the development of the albite flames, originates from Na metasomatism accompanied by ductile shearing in the feldspathic rocks, providing an ideal open system wherein both the differential stress and Na+ are made available for the development of the flame perthites. This process probably augmented the replacement of K-feldspar grains by flame albite and the K+ released was carried away by the fluid or, possibly, augmented the biotite-forming reactions in the associated quartz-poor syenites and, hence, trigger the Na-K cycle in these rocks.
Magmatic and metasomatic processes during formation of the Nb-Zr-REE deposits Khaldzan Buregte and Tsakhir (Mongolian Altai): Indications from a combined CL-SEM Study
- U. Kempe, J. Götze, S. Dandar, D. Habermann
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- Mineralogical Magazine / Volume 63 / Issue 2 / April 1999
- Published online by Cambridge University Press:
- 05 July 2018, pp. 165-177
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Cathodoluminescence (CL) imaging and spectroscopy, as well as backscattered electron imaging, were used to assign the occurrence of several mineral phases and rock structures in altered nordmarkites and calcite-bearing granites from the Nb-Zr-REE deposits from Khaldzan Buregte and Tsakhir (Mongolian Altai) to three events: (1) intrusion of barren nordmarkites; (2) intrusion of small bodies of calcite-bearing granites with metasomatic alteration of the wall-rocks; and (3) alteration by F-rich fluids.
Unusual red and yellow CL caused by Fe3+ and Mn2+ emission centres were detected in microcline and albite. Fe3+ centres were also established (along with others) in quartz, zircon, and possibly in fluorite.
Magmatic and metasomatic rock structures and internal structures of the minerals coexist in the samples. The primary magmatic features were in part preserved during alteration. In contrast, the internal and the centre structures may be changed during alteration even in non-replaced mineral phases. Euhedral minerals may be formed by secondary processes as shown for lath-shaped albite. The occurrence of pseudomorphs, the inheritance of elements during replacement, and the mechanical effects of secondary minerals on earlier mineral phases during metasomatic growth are proposed as criteria for the reconstruction of the mineral succession in altered rocks. Snowball structures may be formed as a result of metasomatic alteration rather than as a magmatic intergrowth.
Khvorovite, Pb2+4Ca2[Si8B2(SiB)O28]F, a new hyalotekite-group mineral from the Darai-Pioz alkaline massif, Tajikistan: Description and crystal structure
- Leonid A. Pautov, Atali A. Agakhanov, Elena Sokolova, Frank C. Hawthorne, Vladimir Y. Karpenko, Oleg I. Siidra, Viktor K. Garanin, Yassir A. Abdu
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- Journal:
- Mineralogical Magazine / Volume 79 / Issue 4 / August 2015
- Published online by Cambridge University Press:
- 02 January 2018, pp. 949-963
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Khvorovite, ideally Pb42+Ca2[Si8B2(SiB)O28]F, is a new borosilicate mineral of the hyalotekite group from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, Tajikistan. Khvorovite was found in a pectolite aggregate in silexites (quartz-rich rocks). The pectolite aggregate consists mainly of pectolite, quartz and fluorite, with minor aegirine, polylithionite, turkestanite and baratovite; accessory minerals are calcite, pyrochlore-group minerals, reedmergnerite, stillwellite-(Ce), pekovite, zeravshanite, senkevichite, sokolovaite, mendeleevite-(Ce), alamosite, orlovite, leucosphenite and several unknown Cs-silicates. Khvorovite occurs as irregular grains, rarely with square or rectangular sections up to 150 μm, and grain aggregates up to 0.5 mm. Khvorovite is colourless, rarely white, transparent with a white streak, has a vitreous lustre and does not fluoresce under ultraviolet light. Cleavage and parting were not observed. Mohs hardness is 5–5.5, and khvorovite is brittle with an uneven fracture. The measured and calculated densities are 3.96(2) and 3.968 g/cm3, respectively. Khvorovite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.659(3), βcalc. = 1.671(2), γ = 1.676(3); 2Vmeas. = 64(3)°, medium dispersion: r < v. Khvorovite is triclinic, space group I1¯, a = 11.354(2), b = 10.960(2), c = 10.271(2) Å, α = 90.32(3), β = 90.00(3), γ = 90.00(3)°, V = 1278(1) Å3, Z = 2. The six strongest lines in the powder X-ray diffraction pattern [d (Å), I, (hkl)] are: 7.86, 100, (110); 7.65, 90, (101); 7.55, 90, (011); 3.81, 90, (202); 3.55, 90, (301); 2.934, 90, (312, 312). Chemical analysis by electron microprobe gave SiO2 36.98, B2O3 6.01, Y2O3 0.26, PbO 40.08, BaO 6.18, SrO 0.43, CaO 6.77, K2O 1.72, Na2O 0.41, F 0.88, O=F –0.37, sum 99.35 wt.%. The empirical formula based on 29 (O+F) a.p.f.u. is (Pb2.762+Ba0.62K0.56Na0.16)Σ4.10(Ca1.86Sr0.06Y0.04Na0.04)Σ2[Si8B2(Si1.46B0.65)Σ2.11O28](F0.71O0.29), Z = 2 , and the simplified formula is (Pb2+, Ba, K)4Ca2[Si8B2(Si,B)2O28]F. The crystal structure of khvorovite was refined to R1 = 2.89% based on 3680 observed reflections collected on a four-circle diffractometer with MoKα radiation. In the crystal structure of khvorovite, there are four [4]-coordinated Si sites occupied solely by Si with <Si–O>= 1.617 Å. The [4]-coordinated B site is occupied solely by B, with <B–O> = 1.478 Å. The [4]-coordinated T site is occupied by Si and B (Si1.46B0.54), with <T–O> = 1.605 Å; it ideally gives (SiB) a.p.f.u. The Si, B and T tetrahedra form an interrupted framework of ideal composition [Si8B2(SiB)O28]11–. The interstitial cations are Pb2+, Ba and K (minor Na) [A(11–22) sites] and Ca [M site]. The two A sites are each split into two subsites ∼0.5 Å apart and occupied by Pb2+ and Ba + K. The [8]-coordinated M site is occupied mainly by Ca, with minor Sr, Y and Na. Khvorovite is a Pb2+ analogue of hyalotekite, (Ba,Pb2+,K)4(Ca,Y)2[Si8(B,Be)2(Si,B)2O28]F and a Pb2+-, Ca-analogue of kapitsaite-(Y), (Ba,K)4(Y,Ca)2[Si8B2(B,Si)2O28]F. It is named after Pavel V. Khvorov (b. 1965), a Russian mineralogist, to honour his contribution to the study of the mineralogy of the Darai-Pioz massif.
Mendeleevite-(Nd), (Cs,□)6 (□,Cs)6 (□,K)6 (REE,Ca)30(Si70O175)(OH,H2O,F)35, a new mineral from the Darai-Pioz alkaline massif, Tajikistan
- Atali A. Agakhanov, Leonid A. Pautov, Elena Sokolova, Frank C. Hawthorne, Vladimir Yu Karpenko, Oleg I. Siidra, Viktor K. Garanin
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- Journal:
- Mineralogical Magazine / Volume 81 / Issue 1 / February 2017
- Published online by Cambridge University Press:
- 02 January 2018, pp. 135-141
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Mendeleevite-(Nd), (Cs,□)6(□,Cs)6(□,K)6(REE,Ca)30(Si70O175)(OH,H2O,F)35 is a new mineral from the Darai-Pioz alkaline massif, Tajikistan. Mendeleevite-(Nd) was found in a pectolite aggregate in silexites (quartz-rich rocks) which consist of fine to medium pectolite grains, quartz, aegirine and fluorite, with minor khvorovite, mendeleevite-(Ce), sokolovaite, hyalotekite, orlovite, kirchhoffite, pekovite, neptunite, zeravshanite, senkevichite, nordite-(Nd), alamosite, pyrochlore-group minerals and baratovite. Mendeleevite-(Nd) forms colourless cubic crystals 10–40 μm in size; it has a vitreous lustre and a Mohs hardness of 5–5.5; Dmeas. = 3.20(2) g/cm3, Dcalc. = 3.155 g/cm3. Mendeleevite-(Nd) is optically isotropic, with the refractive index n = 1.582(2). Mendeleevite-(Nd) is cubic, space group Pm3̄, a = 21.9106(4) Å; Z = 2. The six strongest reflections in the powder X-ray diffraction pattern are [d (Å), I (%), (h k l)] are: 11.01, 100, (0 0 2); 15.63, 55, (0 1 1); 3.47, 42, (2 0 6); 3.099, 42, (3 4 5); 2.192, 42, (0 0 10); 1.819, 41, (3 6 10). Chemical analysis by electron microprobe gave SiO2 42.30, Ce2O3 10.12, La2O3 3.60, Nd2O3 16.19, Pr2O3 2.79, Sm2O3 4.19, Gd2O3 1.69, Eu2O3 0.47, SrO 2.99, CaO 2.20, Cs2O 8.50, K2O 0.85, H2O 3.85, F 1.25, –O = F2 –0.53, sum 100.46 wt.%, with H2O calculated by analogy with mendeleevite-(Ce). The empirical formula based on 210 (O + F) apfu, with F + OH + H2O = 35 pfu, is Cs6(□4.20K1.80)∑6{[(Nd9.57Ce6.13Sm2.39La2.20Pr1.68Gd0.93Eu0.27)∑23.17(Ca3.90Sr2.87)∑6.77]∑29.94□0.06}∑30(Si70.03O175)(OH14.47F6.54)∑21.01 (H2O)14, Z = 2. The simplified and ideal formulae are (Cs,□)6 (□,Cs)6(□,K)6 (REE,Ca)30 (Si70O175)(OH, H2O,F)35 and Cs6(REE23Ca7)(Si70O175)(OH,F)19(H2O)16, respectively. The compatibility index (from measured density) = – 0.039 (excellent). Mendeleevite-(Nd) is a Nd analogue of mendeleevite-(Ce), (Cs,□)6(□,Cs)6(□,K)6(REE,Ca,□)30(Si70O175)(H2O,OH,F,□)35. Both minerals are named after Dmitri Mendeleev (1834–1907), the great Russian chemist, author of the periodic table of chemical elements, who has had a significant impact on the development of natural sciences and industry, both in Russia and around the world.
Proterozoic mountain building in Peninsular India: an analysis based primarily on alkaline rock distribution
- C. LEELANANDAM, K. BURKE, L. D. ASHWAL, S. J. WEBB
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- Geological Magazine / Volume 143 / Issue 2 / March 2006
- Published online by Cambridge University Press:
- 16 March 2006, pp. 195-212
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Peninsular India was assembled into a continental block c. 3 million km2 in area as a result of collisions throughout the length of a 4000 km long S-shaped mountain belt that was first recognized from the continuity of strike of highly deformed Proterozoic granulites and gneisses. More recently the recognition of a variety of tectonic indicators, including occurrences of ophiolitic slivers, Andean-margin type rocks, a collisional rift and a foreland basin, as well as many structural and isotopic age studies have helped to clarify the history of this Great Indian Proterozoic Fold Belt. We here complement those studies by considering the occurrence of deformed alkaline rocks and carbonatites (DARCs) in the Great Indian Proterozoic Fold Belt. One aim of this study is to test the recently published idea that DARCs result from the deformation of alkaline rocks and carbonatites (ARCs) originally intruded into intra-continental rifts and preserved on rifted continental margins. The suggestion is that ARCs from those margins are transformed into DARCs during continental, or arc–continental, collisions. If that idea is valid, DARCs lie on rifted continental margins and on coincident younger suture zones; they occur in places where ancient oceans have both opened and closed. Locating sutures within mountain belts has often proved difficult and has sometimes been controversial. If the new idea is valid, DARC distributions may help to reduce controversy. This paper concentrates on the Eastern Ghats Mobile Belt of Andhra Pradesh and Orissa, where alkaline rock occurrences are best known. Less complete information from Kerala, Tamil Nadu, Karnataka, West Bengal, Bihar and Rajasthan has enabled us to define a line of 47 unevenly distributed DARCs with individual outcrop lengths of between 30 m and 30 km that extends along the full 4000 km length of the Great Indian Proterozoic Fold Belt. Ocean opening along the rifted margins of the Archaean cratons of Peninsular India may have begun by c. 2.0 Ga and convergent plate margin phenomena have left records within the Great Indian Proterozoic Fold Belt and on the neighbouring cratons starting at c. 1.8 Ga. Final continental collisions were over by 0.55 Ga, perhaps having been completed at c. 0.75 Ga or at c. 1 Ga. Opening of an ocean at the Himalayan margin of India by c. 0.55 Ga removed an unknown length of the Great Indian Proterozoic Fold Belt. In the southernmost part of the Indian peninsula, a line of DARCs, interpreted here as marking a Great Indian Proterozoic Fold Belt suture, can be traced within the Southern Granulite Terrain almost to the Achankovil-Tenmala shear zone, which is interpreted as a strike-slip fault that also formed at c. 0.55 Ga.