EARLY MAGMATIC AND REACTION-INDUCED TRENDS IN MAGNETITE FROM THE CARBONATITES OF KERIMASI, TANZANIA
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We examined the mode of occurrence, pattern of zoning and composition of magnetite and associated spinel-group minerals in three types of calciocarbonatite from the Kerimasi volcano, in Tanzania. In all samples, magnetite is one of the earliest phases to have crystallized, and shows an appreciable compositional variation. The majority of compositions correspond to magnetite with low to moderate proportions of magnesioferrite and ulvospinel components (10–28 and 2–28 mol.%, respectively) and 2 O 4 ). The two trace elements consistently present in appreciable amounts are V (400–2000 ppm) and Zn (700–3300 ppm); the abundances of other trace elements are much lower and very variable (≤15 ppm Cr, 170 ppm Ni, 220 ppm Co, 490 ppm Zr, 14 ppm Hf, 95 ppm Nb, 3 ppm Ta, and 80 ppm Ga). Magnetite is thus a minor host of Zr, Hf, Nb and Ta in carbonatites. The composition of magnetite crystallizing from carbonatitic magma evolves by becoming depleted in Mg and Ti, whereas its Al content inversely correlates with the V content and, thus, is sensitive to variations in f (O 2 ). The compatibility of V is interpreted to decrease, and that of Mn to increase, with increasing f (O 2 ). Covariation between the Mn and Zn contents suggests that the partitioning behavior of Zn is controlled by the coupled substitution Zn 2+ Mn 3+ Fe 2+ −1 Fe 3+ −1 . The Mg–Ti depletion trend is accompanied by a decrease in Zr and Ta contents at constant or decreasing levels of Nb and Hf, which has implications for the partitioning behavior of high-field-strength elements in carbonate melts. In addition to the magmatic evolutionary trend, the Kerimasi magnetite exhibits a previously unrecognized trend arising from a reaction of the magnetite with the carbonatitic magma. This trend involves enrichment of the peripheral parts of magnetite crystals in Mg, Al, Mn, Zr and Nb, and their mantling by Fe-rich spinel. This trend requires that a (Mg 2+ ) and a (Al 3+ ) in the magma increase with evolution, whereas a (SiO 2 ) remains low to impede the precipitation of Mg–Al silicates.Keywords:
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Carbonatite
Ultramafic rock
Mantle plume
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We present in situ major element, trace element, and Sr–Nd isotope data of apatite from an alkaline–carbonatite intrusion in the South Qinling Belt (SQB) to investigate their magma evolution and mantle sources. The Shaxiongdong (SXD) complex consists predominantly of the early Paleozoic hornblendite, nepheline syenite, and subordinate Triassic carbonatite. Apatites from all lithologies are euhedral to subhedral and belong to fluorapatite. Elemental substitution varies from REE3+ + Na+ + Sr2+ ↔ 3Ca2+ in carbonatite and syenite apatite to Si4+ + 2Na+ + 2S6+ + 4REE3+ ↔ 4P5+ + 5Ca2+ in hornblendite apatite. Apatites are characterized by enriched rare earth elements (REEs) and depleted high field strength elements (HFSEs). They record the distinct evolution of their parental magmas. The weak, negative Eu anomaly in hornblendite apatite, together with the lack of Eu anomalies in the bulk rocks, indicates a relatively reduced magma. The Sr–Nd isotope data of the apatite in SXD carbonatite, falling on the East African carbonatite line (EACL) and close to the field of Oldoinyo Lengai carbonatite, indicate that the SXD carbonatite is derived from a mixed mantle source consisting of the HIMU component and subducted sedimentary carbonates. The similarity in Sr and Nd isotopic compositions between the SXD hornblendite and syenite apatites and the early Paleozoic mafic-ultramafic dykes in the SQB suggests that they may share a common metasomatized lithospheric mantle source.
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Rare-earth element
Nepheline syenite
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Electron microprobe analyses of magnetites from five carbonatite intrusions (C_1, oldest,
to C_5, youngest) constituting the carbonatite plug in the Jacupiranga complex confirm
previous results from Jacupiranga giving compositions in the magnesioferrite-magnetite
series very close to Fe_3O_4. Magnetites from other carbonatites are similar with somewhat
more Ti and less Mg. MgO in Jacupiranga magnetites reaches no more than 10 wt.%. All
analyzed grains are zoned, with Fe_3O_4 increasing toward the rim. In magnetites from C_2 to
C_5, Fe_2O_3 replacement is mainly by Al_2O_3 and less by TiO_2; in C_1 magnetites TiO_2
replacement is more important. Despite their limited range of compositions, the cores of
magnetites in each of the five intrusions are chemically distinct and distinguishable from
each other as indicated by projections from within the Cr-free spinel prism, MgFe_2O_4-Mg_2TiO_4-MgAl_2O_4-Fe_3O_4-Fe_2TiO_4-FeAl_2O_4, and a plot of Mn ys. Mg. Magnetites from
special locations such as dikes, banded reaction zones between carbonatite and jacupirangite,
and in intergrowths with pyrite, are chemically related but distinct from the
carbonatite magnetites. The systematic chemical variation and zoning of magnetites in the
five carbonatite intrusions indicate magmatic origin. Magnetite crystals nucleated throughout
the crystallization interval of the carbonatites, but most of them show evidence of
marginal resorption. The oldest carbonatite, C_1, was probably derived from a magma
somewhat different chemically from those producing carbonatites C_2 through C_5. The
precipitation of carbonatite C_2 probably went to completion independently of C_3 through
C_5, whereas carbonatites C_3 through C_5 probably were precipitated from successive
batches of magma representing a continuum in time and magmatic evolution.
Carbonatite
Cassiterite
Columbite
Wolframite
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홍천 카보나타이트-포스코라이트 복합체를 형성하는 주 구성광물인 자철석은 각각 세 시기에 걸쳐 정출되었으며 후기로 가면서 함량이 점차 감소한다. 자철석에 대한 전자현미분석결과 Ti, V은 미량 검출되지만 초기에서 후기로 가면서 증가하는 경향을 보여준다. 반면, Mg, Mn은 뚜렷이 감소하는데 이는 일반적인 카보나타이트질 마그마 분화특성을 잘 나타낸다. Al 또한 카보나타이트와 포스코라이트에서 감소하는 경향을 보여주며, Cr은 대부분 검출한계 미만을 나타내나 후기 포스코라이트에 와서는 미량 정출된다. 자철석은 초기에는 $Fe^{2+}$ 가 주로 $Mg{2+}$ 와 $Mn^{2+}$ 에 의해 치환되고, $Fe^{3+}$ 는 $Al^{3+}$ 에 의한 치환되는 양상이 주를 이루었으나 후기에 와서는 감소하면서 거의 순수한 자철석 조성을 갖게 된다. V의 증가와 Mn의 감소는 마그마 분화가 산소분압이 점차 감소하는 환경에서 진행되었음 나타내고, 감람석, 금운모의 부재와 더불어 자철석의 Mg, Al, Cr 및 Ti 원소들의 함량이 낮은 것은 홍천 카보나타이트-포스코라이트 복합체가 결핍된 모마그마로부터 생성되었음을 지시한다. 특히, 후기로 가면서 철질 탄산염광물과 석영의 산출이 두드러지면서 전형적인 카보나타이트-포스코라이트 복합체에 비해 연구지역 자철석의 Mg 함량이 적게 산출되는 것은 마그마 분화가 최후기까지 진행되었음을 시사한다. Magnetite, a major constituent mineral of the Hongcheon carbonatite-phoscorite complex, was produced over three stages in each rock type and decreased in quantity toward the late stage. Electron microprobe analyses for magnetite revealed that Ti and V were detected in traces, but showed increasing tendency from early to late stage. On the contrary, Mg and Mn decreased distinctly, and it is the general differentiation trend of carbonatitic magma. Al also showed decreasing tendency in carbonatite and phoscorite, and Cr was mostly below detection limit except late phoscorite. In early stage, $Fe^{2+}$ was largely replaced by $Mg{2+}$ and $Mn^{2+}$ , and $Fe^{3+}$ by $Al^{3+}$ in magnetite, but it has nearly pure composition in late stage. Tendency of increase in V and decrease in Mn toward late stage represents that magma differentiation progressed under the condition of decreasing oxygen fugacity. Low concentrations of Mg, Al, Cr and Ti, as well as the absence of olivine and phlogopite, suggest that the Hongcheon carbonatite-phoscorite complex was generated from depleted magma. Especially, lower concentrations of Mg in magnetite compared to other typical carbonatite-phoscorite complex, and abundant occurrence of Fe-carbonate minerals and quartz in late stage, suggest that magma differentiation of the Hongcheon carbonatite-phoscorite proceeded to the latest stage.
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Mineral redox buffer
Phlogopite
Columbite
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Carbonatite
Metasomatism
Aegirine
Allanite
Phlogopite
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Abstract Mountain Pass is the site of the most economically important rare earth element (REE) deposit in the United States. Mesoproterozoic alkaline intrusions are spatiotemporally associated with a composite carbonatite stock that hosts REE ore. Understanding the genesis of the alkaline and carbonatite magmas is an essential scientific goal for a society in which critical minerals are in high demand and will continue to be so for the foreseeable future. We present an ion microprobe study of zircon crystals in shonkinite and syenite intrusions to establish geochronological and geochemical constraints on the igneous underpinnings of the Mountain Pass REE deposit. Silicate whole-rock compositions occupy a broad spectrum (50–72 wt % SiO2), are ultrapotassic (6–9 wt % K2O; K2O/Na2O = 2–9), and have highly elevated concentrations of REEs (La 500–1,100× chondritic). Zircon concordia 206Pb/238U-207Pb/235U ages determined for shonkinite and syenite units are 1409 ± 8, 1409 ± 12, 1410 ± 8, and 1415 ± 6 Ma (2σ). Most shonkinite dikes are dominated by inherited Paleoproterozoic xenocrysts, but there are sparse primary zircons with 207Pb/206Pb ages of 1390–1380 ± 15 Ma for the youngest grains. Our new zircon U-Pb ages for shonkinite and syenite units overlap published monazite Th-Pb ages for the carbonatite orebody and a smaller carbonatite dike. Inherited zircons in shonkinite and syenite units are ubiquitous and have a multimodal distribution of 207Pb/206Pb ages that cluster in the range of 1785–1600 ± 10–30 Ma. Primary zircons have generally lower Hf (<11,000 ppm) and higher Eu/Eu* (>0.6), Th (>300 ppm), Th/U (>1), and Ti-in-zircon temperatures (>800°C) than inherited zircons. Oxygen isotope data reveals a large range in δ18O values for primary zircons, from mantle (5–5.5‰) to crustal and supracrustal (7–9‰). A couple of low-δ18O outliers (2‰) point to a component of shallow crust altered by meteoric water. The δ18O range of inherited zircons (5–10‰) overlaps that of the primary zircons. Our study supports a model in which alkaline and carbonatite magmatism occurred over tens of millions of years, repeatedly tapping a metasomatized mantle source, which endowed magmas with elevated REEs and other diagnostic components (e.g., F, Ba). Though this metasomatized mantle region existed for the duration of Mountain Pass magmatism, it probably did not predate magmatism by substantial geologic time (>100 m.y.), based on the similarity of 1500 Ma zircons with the dominantly 1800–1600 Ma inherited zircons, as opposed to the 1450–1350 Ma primary zircons. Mountain Pass magmas had diverse crustal inputs from assimilation of Paleoproterozoic and Mesoproterozoic igneous, metaigneous, and metasedimentary rocks. Crustal assimilation is only apparent from high spatial resolution zircon analyses and underscores the need for mineral-scale approaches in understanding the genesis of the Mountain Pass system.
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Dike
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In Mongolia, rare earth element (REE) mineralization of economic significance is related either to the Mesozoic carbonatites or to the Paleozoic peralkaline granitoid rocks. Carbonatites occur as part of alkaline silicate-carbonatite complexes, which are composed mainly of nepheline syenites and equivalent volcanic rocks. The complexes were emplaced in the Gobi-Tien Shan rift zone in southern Mongolia where carbonatites usually form dikes, plugs or intruded into brecciated rocks. In mineralized carbonatites, REE occur mainly as fluorocarbonates (bastnäsite, synchysite, parisite) and apatite. Apatite is also present in the carbonatite-hosted apatite-magnetite (mostly altered to hematite) bodies. Alkaline silicate rocks and carbonatites show common geochemical features such as enrichment of light REE but relative depletion of Ti, Zr, Nb, Ta and Hf and similar Sr and Nd isotopic characteristics suggesting the involvement of the heterogeneous lithospheric mantle in the formation of both carbonatites and associated silicate rocks. Hydrothermal fluids of magmatic origin played an important role in the genesis of the carbonatite-hosted REE deposits. The REE mineralization associated with peralkaline felsic rocks (peralkaline granites, syenites and pegmatites) mainly occurs in Mongolian Altai in northwestern Mongolia. The mineralization is largely hosted in accessory minerals (mainly elpidite, monazite, xenotime, fluorocarbonates), which can reach percentage levels in mineralized zones. These rocks are the results of protracted fractional crystallization of the magma that led to an enrichment of REE, especially in the late stages of magma evolution. The primary magmatic mineralization was overprinted (remobilized and enriched) by late magmatic to hydrothermal fluids. The mineralization associated with peralkaline granitic rocks also contains significant concentrations of Zr, Nb, Th and U. There are promising occurrences of both types of rare earth mineralization in Mongolia and at present, three of them have already established significant economic potential. They are mineralization related to Mesozoic Mushgai Khudag and Khotgor carbonatites in southern Mongolia and to the Devonian Khalzan Buregtei peralkaline granites in northwestern Mongolia.
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Peralkaline rock
Nepheline syenite
Rare-earth element
Petrogenesis
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Abstract Magnetite is present in most carbonatites, and in the most abundant and best-known form of carbonatite, coarse-grained intrusions, it typically falls in a narrow composition range close to Fe 3 O 4 . A fine-grained carbonatite from Zambia contains magnetites with an extraordinary array of compositions (from 18–1% TiO 2 , 10–2% Al 2 O 3 , and 16–4% MgO) outranging previously-reported examples. Zoning trends are from high TiO 2 to high Al 2 O 3 and MgO. No signs of exsolution are seen. Checks on similar rocks from Germany, Uganda and Tanzania reveal magnetites with comparable compositions, ranges, and zoning. Magnetites from alkaline and alkaline ultramafic silicate volcanic rocks cover only parts of this array. Magnetite analyses from some other fine-grained carbonatites, reported in the literature, fall in the same composition field, suggesting that this form of carbonatite may be distinctive. The chemistry and zoning would be consonant with rapid high-temperature crystallization in the carbonatite melts, with the lack of exsolution pointing to fast quenching: this contrasts with coarse-grained intrusive carbonatites, in which the magnetite compositions are attributed to slow cooling, with final equilibration at low temperature. In some complexes, both forms of carbonatite, with their different magnetite compositions, are represented.
Carbonatite
Ultramafic rock
Melilite
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