Primary and secondary niobium mineral deposits associated with carbonatites

This work reviews the character and origin of primary and supergene economic deposits of niobium associated with carbonatites. The Brazilian supergene deposits account for about 92% of the total worldwide production of Nb, with the primary St. Honoré carbonatite and other sources accounting for only for 7 and 1%, respectively. The emphasis of the review is upon the styles of Nb mineralization and the geological factors which lead to economic concentrations of Nb-bearing minerals. Primary economic deposits of Nb are associated principally with carbonatites found in diverse types of plutonic alkaline rock complexes. Primary magmas are principally those of the melilitite, nephelinite and aillikite clans. Although many primary niobium deposits are associated with carbonatites, ijolites and syenites in the same alkaline complexes can also contain significant Nb mineralization in the form of niobian titanite and diverse Nb–Zr-silicates (marianoite-wöhlerite); these potential sources of Nb have not as yet been explored or exploited. Primary Nb deposits can be regarded as large tonnage, low grade (typically < 1 wt.% Nb₂O₅) disseminated ore deposits. Niobium is hosted principally by diverse Na–Ca–U-pyrochlores, ferrocolumbite and fersmite. Every actual, and potential, primary Nb deposit is unique with respect to the varieties of pyrochlore present; extent of replacement by other minerals; and degree of alteration by deuteric/hydrothermal fluids. Within a given occurrence individual petrographically-defined units of carbonatite contain distinct suites of pyrochlore. Bulk rock analysis for Nb gives no indication of the style of mineralization and provides no information of use regarding beneficiation of the ore. Evaluation of any Nb deposit requires extensive definition drilling and detailed mineralogical studies. Primary Nb deposits result from the early crystallization of Nb-bearing minerals in magma chambers followed by crystal fractionation, magma mixing, and redistribution of Nb-minerals by density currents. Supergene Nb deposits occur in laterites formed by extensive weathering of primary carbonatites. The process results in the decomposition of apatite and magnetite, removal of soluble carbonates and physical concentration of resistant primary pyrochlore. Intense lateritization results initially in the replacement of primary pyrochlores by supergene, commonly Ba, Sr, K or Pb-bearing pyrochlores, and ultimately complete decomposition of pyrochlore and formation of Nb-bearing rutile, brookite, and anatase. The Nb contents of the laterites can be enriched up to 10 times or more above those of the primary carbonatite. Commonly, pyrochlores in laterites are fine grained and intimately intergrown with hematite, goethite and minerals of the crandallite group. The different styles of mineralization of primary and secondary Nb deposits require different methods of ore beneficiation.     

Petrology,geochemistry, and geochronology of Paleoproterozoic volcanic and granitic rocks (1.89–1.88 Ga) of the Pitinga Province,Amazonian Craton,Brazil

This paper presents geochemical, petrographic, and geochronological data on the Uatumã magmatism in the Pitinga Province, where it is represented by volcanic rocks from the Iricoumé Group and granitic rocks from the Mapuera Suite. The Iricoumé Group (1.89–1.88 Ga) is constituted of the Divisor Formation (intermediate volcanic rocks), Ouro Preto Formation (acid effusive rocks), and Paraiso Formation (acid crystal-rich ignimbrites, surge deposits, and basic rocks). The volcanic sequence is intruded by granitoids from the Mapuera Suite (1.88 Ga), mainly represented by monzogranites and syenogranites. Structural and field relations suggest that caldera complex collapse controlled the emplacement of volcanics and granitoids of the Mapuera Suite. Subsequent structure reactivations allowed the younger Madeira Suite (1.82–1.81 Ga) to be emplaced in the central portion of the caldera complex. The felsic Iricoumé magmatism is mainly composed of rhyolites, trachydacites and latites, with SiO₂ contents between 64 wt% and 80 wt%. The plutonic rocks from the Mapuera Suite present SiO₂ between 65 wt% and 77 wt%. Volcanic and granitic rocks present identical geochemical characteristics and that is attributed to their co-magmatic character. The felsic volcanic rocks and granites are metaluminous to slightly peraluminous and show affinity with silica-saturated alkaline series or with A-type magmas. They have Na₂O + K₂O between 6.6% and 10.4%, FeO^t/(FeO^t + MgO) varying between 0.76 and 0.99, Ga/Al ratios between 1.5 and 4.9, like typical A-type rocks; and plot in the within-plate or post-collisional fields in the (Nb + Y) vs. Rb diagram. The Nb/Y ratios indicate that these rocks are comparable to A2-type granites. This magmatism can be related to the (i) potassic alkaline series, with low Sr content in the felsic rocks explained by plagioclase fractionation at low pressure and high temperature or, alternatively, (ii) a bimodal association where magma had high crustal influence. The similarity of the Iricoumé felsic magmatism with A2-type granitoids and their high ETRL/Nb ratios suggest its relation with mantle sources previously modified by subduction, probably in a post-collision environment. Alternatively, this can be interpreted as bimodal within-plate magmatism with contamination by crustal melts. In this context, the extreme F, Nb and Zr enrichment of Madeira Suite could be explained by the presence of a thin crust which favored the presence and continuity of convective systems in the upper mantle.     

Paleogene magmatism and gold metallogeny of the Jinping terrane in the Ailaoshan ore belt,Sanjiang Tethyan Orogen (SW China): Geology,deposit type and tectonic setting

The Jinping terrane is situated in the southern segment of the Ailaoshan ore belt, Sanjiang Tethyan Orogen (SW China). The Paleogene intrusions in Jinping consist of syenite porphyry, fine-grained syenite and biotite granite stocks/dikes, and contain relatively low TiO₂ (0.21–0.38 wt%), P₂O₅ (0.01–0.35 wt%), and high Na₂O (2.00–4.62 wt%) and K₂O (4.48–7.06 wt%), belonging to high-K alkaline series. Paleogene gold mineralization in Jinping comprises four genetic types, i.e., orogenic, alkali-rich intrusion-related, porphyry and supergene laterite. The NW–NNW-trending faults and their subsidiaries are the major ore-controlling structures. The orogenic Au mineralization, dominated by polymetallic sulfide-quartz veins, occurs in the diorite and minor in Silurian-Devonian sedimentary rocks. It contains a CO₂-rich mesothermal fluid system generated from the mixing of mantle-derived fluids with crustal-derived metamorphic fluids, and the ore-forming materials were upper crustal- or orogenic-derived. The alkali-rich intrusion-related Au mineralization is hosted in the Ordovician-Silurian sedimentary rocks and minor in the Paleogene alkaline intrusions, and the Au orebodies occur predominantly in the alteration halos. It contains a CO₂-bearing, largely metamorphic-sourced mesothermal fluid system, and the ore-forming materials were derived from the ore-hosting rocks and minor from the alkali-rich intrusions. The porphyry Cu-Mo-Au mineralization occurs in the granite/syenite porphyries and/or along their contact skarn, with the mineralizing fluids being magmatic-hydrothermal in origin. The former two hypogene Au mineralization types in Jinping were mainly formed in the late Eocene (ca. 34–33 Ma) and slightly after the porphyry Cu-Mo-Au mineralization (ca. 35–34 Ma), which is coeval with the regional Himalayan orogenic event. Subsequent weathering produced the laterite Au mineralization above or near the hypogene Au orebodies.     

Carbonatite-hosted niobium deposit at Aley,northern British Columbia (Canada): Mineralogy,geochemistry and petrogenesis

The Aley Nb deposit in northern British Columbia, Canada, is hosted by metamorphosed calcite and dolomite carbonatites of anorogenic affinity emplaced in Lower Paleozoic sedimentary carbonate rocks in the Devonian. Primary Nb mineralization consists of pyrochlore (commonly comprising a U–Ta-rich and F-poor core) and ferrocolumbite developed as discrete crystals and replacement products after the pyrochlore. These phases and associated heavy minerals (apatite ± magnetite ± zircon ± baddeleyite) precipitated early in the magmatic history and probably formed laterally extensive cumulate layers up to at least 1.5 m in thickness. Fractionation of copious amounts of pyrochlore is reflected in the chemical composition of the carbonatites and their constituent minerals, which show large variations in Nb/Ta value, but a near-chondritic Zr/Hf ratio. Alkali-rich metasomatic rocks (in particular, fenites and glimmerites) associated with the carbonatites are barren; the bulk of Nb in these rocks is contained in rutile, phlogopite and, to a much lesser extent, amphibole. When the passive margin of North America became the zone of plate convergence in the Cretaceous, the host carbonatites were strongly deformed, which is manifested in structures and textures indicative of grain comminution, ductile flow, folding and, locally, brecciation. The structure and continuity of the cumulate units enriched in Nb minerals were profoundly affected by these processes. Interaction of the carbonatites with crustal fluids of complex chemistry resulted in extensive dolomitization, replacement of the pyrochlore and ferrocolumbite by fersmite, and development of hydrothermal parageneses consistent with the lower greenschist-facies conditions. At these late evolutionary stages, Nb was mobilized only to a very limited extent and sequestered in a variety of minerals (fersmite, euxenite, Mg-rich ferrocolumbite and Nb-bearing rutile) typically occurring as scarce minute crystals associated with hydrothermal dolomite, quartz and chlorite. Progressive enrichment of the deformed dolomite carbonatites in heavy C and O isotopes relative to primary calcite, coupled with changes in the trace-element composition of Nb phases, indicate that the fluids were equilibrated with the wall-rock sedimentary rocks hosting the Aley deposit and were capable of transporting F⁻, (PO₄)^3 −, U, Th and rare-earth elements, but not Nb.     

Geochemical features of nickel-laterite deposits from the Balkan Peninsula and Gordes,Turkey: The genetic and environmental significance of arsenic

Iron–nickel-laterite deposits in the Balkan Peninsula and Turkey, located in the Mirdita–Sub-Pelagonian and Pelagonian geotectonic zones, extending into the Anatolides zone are a major source of nickel. Repeated marine transgression and regression, and the multistage development of allochthonous laterite deposits by re-working and re-deposition in a shallow sea environment are demonstrated by the alternation of Fe–Ni-laterite layers within marine sequences.Geochemical study of these Fe–Ni laterite deposits shows that arsenic contents are generally low, ranging from less than 2 to a few tens of ppm. However, in the Aghios Ioannis deposit, Lokris, Central Greece As varies significantly and attains values up to 0.26 wt.% As and in the Gordes deposit of W. Turkey, the As content ranges from 0.004 to 1.07 wt.% As (average 0.34), reaching values up to 1.94 in the hematite zone. Investigation of the mineral chemistry (SEM-EDS) shows that goethite is the main host of As, ranging between 0.5 and 1.2 wt.% As₂O₃ in the Aghios Ioannis deposit, and between 1.2 to 6.9 wt.% As₂O₃ in the Gordes deposit, whereas, in co-existing calcite As was not detectable. Goethite occurs in fine-grained porous and concretionary, concentric textures. As values are higher in concretionary goethite. Positive correlation (r > 0.74) between As and Al₂O₃, TiO₂ and ∑ REE contents in the laterite deposits of Greece, coupled with the As-enrichment only in certain laterite deposits points to post depositional As-enrichment.Assuming that high pH facilitates the adsorption of As by goethite, due to its high surface area and low values of the activation energy of adsorption (literature data) As-adsorption by goethite is considered to play an important role in its retention. Elevated As-contents in goethite (Fe-oxides) in Fe–Ni-laterites of Greece and Turkey, due to its absorption capacity, are considered to be of particular significance in the remediation of aquifer and soil contamination rather than being a source of environmental risk.     

REE fractionation,mineral speciation,and supergene enrichment of the Bear Lodge carbonatites,Wyoming, USA

The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ¹⁸O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO₄³⁻/CO₃²⁻ and F⁻/CO₃²⁻ ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.     

Geochemical features of the Matomb alluvial rutile from the Neoproterozoic Pan-African belt,Southern Cameroon

The Matomb region constitutes an important deposit of detrital rutile. The rutile grains are essentially coarse (> 3 mm), tabular and elongated, due to the short sorting of highly weathered detritus. This study reports the major, trace, and rare-earth element distribution in the bulk and rutile concentrated fractions. The bulk sediments contain minor TiO₂ concentrations (1–2 wt%), high SiO₂ contents (∼77–95 wt%) and variable contents in Al₂O₃, Fe₂O₃, Zr, Y, Ba, Nb, Cr, V, and Zn. The total REE content is low to moderate (86–372 ppm) marked by high LREE-enrichment (LREE/HREE ∼5–25.72) and negative Eu anomalies (Eu/Eu^* ∼0.51–0.69). The chemical index of alteration (CIA) shows that the source rocks are highly weathered, characteristic of humid tropical zone with the development of ferrallitic soils. In the concentrated fractions, TiO₂ abundances exceed 94 wt%. Trace elements with high contents include V, Nb, Cr, Sn, and W. These data associated with several binary diagrams show that rutile is the main carrier of Ti, V, Nb, Cr, Sn, and W in the alluvia. The REE content is very low (1–9 ppm) in spite of the LREE-abundance (LREE/HREE ∼4–40). The rutile concentrated fractions exhibit anomalies in Ce (Ce/Ce^* ∼0.58 to 0.83; ∼1.41–2.50) and Eu (Eu/Eu^* ∼0.42; 1.20–1.64). The high (La/Sm)_N, (La/Yb)_N and (Gd/Yb)_N ratios indicate high REE fractionation.     

Relationships between major and trace elements during weathering processes in a sedimentary context: Implications for the nature of source rocks in Douala,Littoral Cameroon

In Douala (Littoral Cameroon), the Cretaceous to Quaternary formation composed of marine to continental sediments are covered by ferrallitic soils. These sediments and soils have high contents of SiO₂ (≥70.0 wt%), intermediate contents of Al₂O₃ (11.6–28.4 wt%), Fe₂O₃ (0.00–20.5 wt%) and TiO₂ (0.04–4.08 wt%), while K₂O (≤0.18 wt%), Na₂O (≤0.04 wt%), MgO (≤0.14 wt%) and CaO (≤0.02 wt%) are very low to extremely low. Apart from silica, major oxides and trace elements (REE included) are more concentrated in the fine fraction (<62.5 μm) whose proportions of phyllosilicates and heavy minerals are significant. The close co-associations between Zr, Hf, Th and ∑REE in this fraction suggest that REE distribution is controlled by monazite and zircon. CIA values indicate intense weathering. Weathering products are characterized by the association Al₂O₃ and Ga in kaolinite; the strong correlation between Fe₂O₃ and V in hematite and goethite; the affinity of TiO₂ with HFSE (Hf, Nb, Th, Y and Zr) in heavy minerals. The ICV values suggest mature sediments. The PCI indicates a well-drained environment whereas U/Th and V/Cr ratios imply oxic conditions. La/Sc, La/Co, Th/Cr, Th/Sc and Eu/Eu* elemental ratios suggest a source with felsic components. Discrimination diagrams are consistent with the felsic source. The REE patterns of some High-K granite and granodiorite of the Congo Craton resemble those of the samples, indicating that they derive from similar source rocks.     

Mineralogical and geochemical investigations of the Mombi bauxite deposit,Zagros Mountains,Iran

The Mombi bauxite deposit is located in 165 km northwest of Dehdasht city, southwestern Iran. The deposit is situated in the Zagros Simply Fold Belt and developed as discontinuous stratified layers in Upper Cretaceous carbonates (Sarvak Formation). Outcrops of the bauxitic horizons occur in NW-SE trending Bangestan anticline and are situated between the marine neritic limestones of the Ilam and Sarvak Formations. From the bottom to top, the deposit is generally consisting of brown, gray, pink, pisolitic, red, and yellow bauxite horizons. Boehmite, diaspore, kaolinite, and hematite are the major mineral components, while gibbsite, goethite, anatase, rutile, pyrite, chlorite, quartz, as well as feldspar occur to a lesser extent. The Eh–pH conditions during bauxitization in the Mombi bauxite deposit show oxidizing to reducing conditions during the Upper Cretaceous. This feature seems to be general and had a significant effect on the mineral composition of Cretaceous bauxite deposits in the Zagros fold belt. Geochemical data show that Al₂O₃, SiO₂, Fe₂O₃ and TiO₂ are the main components in the bauxite ores at Mombi and immobile elements like Al, Ti, Nb, Zr, Hf, Cr, Ta, Y, and Th were enriched while Rb, Ba, K, Sr, and P were depleted during the bauxitization process. Chondrite-normalized REE pattern in the bauxite ores indicate REE enrichment (ΣREE = 162.8–755.28 ppm, ave. ∼399.36 ppm) relative to argillic limestone (ΣREE = 76.26–84.03 ppm, ave. ∼80.145 ppm) and Sarvak Formation (ΣREE = 40.15 ppm). The REE patterns also reflect enrichment in LREE relative to HREE. Both positive and negative Ce anomalies (0.48–2.0) are observed in the Mombi bauxite horizons. These anomalies are related to the change of oxidation state of Ce (from Ce³⁺ to Ce⁴⁺), ionic potential, and complexation of Ce⁴⁺ with carbonate compounds in the studied horizons. It seems that the variations in the chemistry of ore-forming solutions (e.g., Eh and pH), function of carbonate host rock as a geochemical barrier, and leaching degree of lanthanide-bearing minerals are the most important controlling factors in the distribution and concentration of REEs. Several lines of evidences such as Zr/Hf and Nb/Ta ratios as well as similarity in REE patterns indicate that the underlying marly limestone (Sarvak Formation) could be considered as the source of bauxite horizons. Based on mineralogical and geochemical data, it could be inferred that the Mombi deposit has been formed in a karstic environment during karstification and weathering of the Sarvak limy Formation.     

Geology,mineralization, and fluid inclusion characteristics of the Lermontovskoe reduced-type tungsten (±Cu,Au, Bi) skarn deposit,Sikhote-Alin,Russia

The Lermontovskoe deposit (∼48 Kt WO₃; average 2.6% WO₃, 0.24% Cu, 0.23 g/t Au) is situated in a W-Sn-Au metallogenic belt that formed in a collisional tectonic environment. This tungsten skarn deposit has a W-Au-As-Bi-Te-Sb signature that suggests an affinity with reduced intrusion-related Au deposits. The deposit is associated with an intrusion that is part of the ilmenite-series, high-K peraluminous granitoid (granodiorite to granite) suite. These rocks formed via mantle magma-induced melting of crustal sources.The deposit comprises reduced-type, pyroxene-dominated prograde and retrograde skarns followed by hydrosilicate (amphibole-chlorite-pyrrhotite-scheelite-quartz) and phyllic (muscovite/sericite-carbonate-albite-quartz-scheelite-sulfide, with abundant apatite) alteration assemblages. Fluid inclusions from the skarn assemblages indicate high-temperature (>500 °C), high-pressure (1400–1500 bars) and high-salinity (53–60 wt% NaCl-equiv.) magmatic-hydrothermal fluids. They were post-dated by high-carbonic, methane-dominate, low-salinity fluid at the hydrosilicate alteration stage. These fluids boiled at 360–380 °C and 1300–1400 bars. The subsequent phyllic alteration started again with a high-temperature (>450 °C), high-pressure (1000–1100 bars) and high-salinity (42–47 wt% NaCl-equiv.) fluid, with further incursion of high-carbonic, methane-dominated, low-salinity fluid that boiled at 390–420 °C and 1150–1200 bars. The latest phyllic alteration included the lower-temperature (340–360 °C), lower pressure (370–400 bars) high-carbonic, methane-dominated (but with higher CO₂ fraction), low-salinity fluid, and then the low-temperature (250–300 °C) H₂O-CO₂-CH₄-NaCl fluid, with both fluids boiled at the deposit level. The high-salinity aqueous fluids are interpreted to have come from crystallizing granitoid magma, whereas the reduced high-carbonic fluids probably came from a deeper mafic magma source. Both of these fluids potentially contributed to the W-Au-As-Bi-Te-Sb metal budget. Decreasing temperatures coupled with high aCa²⁺ and fluid boiling promoted scheelite deposition at all post-skarn hydrothermal stages.The deposit is characterized by limited downdip extent of mineralized zones and abundant coarse-grained muscovite-quartz (+apatite, scheelite) aggregates that formed at the phyllic alteration stage. Together with presence of high-temperature, high-pressure and high-salinity fluids directly exsolving from crystallizing magma, this suggests a root level of the mineralized magmatic-hydrothermal system of reduced W skarn deposits.     

Mafic xenoliths in Proterozoic kimberlites from Eastern Dharwar Craton,India: Mineralogy and P–T regime

Mafic xenoliths of garnet pyroxenite and eclogite from the Wajrakarur, Narayanpet and Raichur kimberlite fields in the Archaean Eastern Dharwar Craton (EDC) of southern India have been studied. The composition of clinopyroxene shows transition from omphacite (3–6 wt% Na₂O) in eclogites to Ca pyroxene (<3 wt% Na₂O) in garnet pyroxenites. Some of the xenoliths have additional phases such as kyanite, enstatite, chromian spinel or rutile as discrete grains. Clinopyroxene in a rutile eclogite has an X_Mg value of 0.70, which is unusually low compared to the X_Mg range of 0.91–0.97 for all other samples. Garnet in the rutile eclogite is also highly iron-rich with an end member composition of Prp_26.5Alm_52.5Grs_14.7Adr_5.1TiAdr_0.3Sps_1.0Uv_0.1. Garnets in several xenoliths are Cr-rich with up to 8 mol% knorringite component. Geothermobarometric calculations in Cr-rich xenoliths yield different P–T ranges for eclogites and garnet pyroxenites with average P–T conditions of 36 kbar and 1080 °C, and 27 kbar and 830 °C, respectively. The calculated P–T ranges approximate to a 45 mW m^?2 model geotherm, which is on the higher side of the typical range of xenolith/xenocryst geotherms (35–45 mW m^?2) for several Archaean cratons in the world. This indicates that the EDC was hotter than many other shield regions of the world in the mid-Proterozoic period when kimberlites intruded the craton. Textural and mineral chemical characteristics of the mafic xenoliths favour a magmatic cumulate process for their origin as opposed to subducted and metamorphosed oceanic crust.     

Ultramafic xenoliths from Lake Nyos area,Cameroon volcanic line,West-central Africa: Petrography,mineral chemistry,equilibration conditions and metasomatic features

Spinel-bearing mantle xenoliths have been recovered in the pyroclastic breccia surrounding the Lake Nyos maar. These include spinel lherzolites, spinel harzburgites and olivine websterites. They exhibit coarse granular or protogranular to weakly porphyroclastic textures, and show variations in mineral chemistry, modal compositions and equilibrium temperature. The xenoliths consist of four mineral phases typical of upper mantle origin: olivine (Fo₈₉–Fo_91.5, NiO = 0.29–0.38 wt%, CaO = 0.02–0.17 wt%), enstatite (Mg# = 90–92, Cr₂O₃ = 0.35 ± 0.04 wt%), Cr-diopside (Mg# = 92–98, Cr₂O₃ = 0.7–1.65 wt%, TiO₂ = 0.26–0.6 wt%) and spinel (high Mg# of 70–80, low TiO₂ ≤ 0.4 wt%). Spinels are aluminous (Cr# = 9.7–11) in most lherzolites, and become increasingly chromiferous from websterites (Cr#_Sp = 15.3–19.8) to harzburgites (Cr#_Sp = 19–33.6). The lherzolites are composed of olivine (48–58%), orthopyroxene (22–30%), and clinopyroxene (8–15%). The harzburgites modes are olivine (60–81%), orthopyroxene (11–29%), and clinopyroxene (<5%). The websterites are mainly composed of pyroxene (～62%) with variable amounts of olivine (23–31%). Temperatures of mineral equilibration in the xenoliths have been estimated from the two-pyroxene thermometer of Wells (1977) and range between 850 and 1050 °C, corresponding to about 10–30 kbar at a depth mantle of 30 km at least. These P–T conditions show significant variations between different petrographical types, the maximum conditions being recorded in two spinel lherzolites (NY-05 and NY-23) that have atypical chemical compositions and textures suggesting that they were initially formed in an environment close to the garnet stability field, then re-equilibrated within the spinel stability field prior to their incorporation in the host magma. With the exception of minerals from these two lherzolite nodules, all the minerals exhibit depletion of light REE, a typical feature of abyssal peridotites implying that some xenoliths from the Cameroon volcanic line were probably sampled in a part of the sub-continental mantle that is chemically similar to sub-oceanic mantle. The variations observed in the mineral chemistry and modal compositions of xenoliths suggest that the spinel harzbugite nodules which represent residues of a significant degree of partial melting of lherzolitic mantle were affected by infiltration of alkali-enriched metasomatizing melts (or fluids) within the uppermost mantle to produce pargasitic amphiboles prior to their sampling by the host lava. The features of this metasomatism event occur in the rocks of all three petrographical facies xenoliths from Lake Nyos.     

The volcanic succession of Baoligaomiao,central Inner Mongolia: Evidence for Carboniferous continental arc in the central Asian orogenic belt

The Baoligaomiao Formation, within the Hegenshan ophiolite-arc-accretion complex is an important segment to understand the tectonic evolution of the Central Asian Orogenic Belt (CAOB), world's largest Phanerozoic orogenic belt. In this study, we present an integrated study of zircon U-Pb isotopic ages, whole rock major-trace elements, and Sr-Nd-Pb isotopic data from the volcanic succession in the Baoligaomiao Formation. The volcanic succession can be divided into the lower sequence with zircon U-Pb ages in the range of 326.3 Ma–307.4 Ma and the upper sequence of 305.3 Ma. The succession belongs to two suites: calc-alkaline volcanics and high-Si rhyolites. The calc-alkaline volcanic rocks include basaltic andesite through andesite and dacite to rhyolite and their pyroclastic equivalents. These rocks exhibit a well-defined compositional trend from basaltic to rhyolitic magma, reflecting continuous fractional crystallization. These rocks show obvious enrichment in LILEs and LREEs and relative depletion of HFSEs, typical of subduction-related magma. The calc-alkaline rocks have low initial ⁸⁷Sr/⁸⁶Sr (0.7023–0.7052), positive ɛNd(t) values (2.75–4.80), and their initial Pb isotopic compositions are 17.875–18.485 of ²⁰⁶Pb/²⁰⁴Pb, 15.481–15.520 of ²⁰⁷Pb/²⁰⁴Pb and 37.467–37.764 of ²⁰⁸Pb/²⁰⁴Pb, respectively. Geochemical and isotopic results suggest that the volcanic succession represents Carboniferous subduction-related, mature, continental arc volcanism. The outcrops of high-Si rhyolites are restricted to the northern edge of the continental arc, marking a transition zone between volcanic arc and back-arc basin, where they are interbedded with the calc-alkaline rocks in the lower sequence, and the upper sequence is composed only of high-Si rhyolites. The high-Si rhyolites have high SiO₂ (71.12–81.76 wt%) and varied total alkali contents (K₂O + Na₂O = 5.46–10.58 wt%), low TiO₂ (0.06–0.27 wt%), MgO (0.09–0.89 wt%) and CaO (0.08–0.72 wt%). Based on the presence of mafic alkali phenocrysts, such as arfvedsonite and siderophyllite, high Zr/Nb ratios (> 10) and peralkalinity index (PI) near unity, the high-Si rhyolites can be classified as peralkaline comendites. The high-Si rhyolites are characterized by unusually low Sr and Ba, and high abundance of Zr, Th, Nb, HREEs and Y. They show geochemical characteristics similar to those of typical A₂-type granites including their high K₂O + Na₂O, Nb, Zr and Y, and high ratios of FeO^T/MgO, Ga/Al and Y/Nb. Our study suggests that the high-Si rhyolites were derived from discrete trachytic parent magma with fractional crystallization within shallow magma reservoirs. Their Nd-Pb isotopic characteristics are similar to those of the calc-alkaline arc rocks and are compatible with partial melting of pre-existing juvenile continental arc crust. We observe that the widespread eruptions of A₂-rhyolitic magmas (305.3 Ma–303.4 Ma) following a short period of magmatic quiescence was temporally and spatially associated with voluminous intrusion of the bimodal magmas (304.3 Ma–299.3 Ma) in the pre-existing arc volcanic-plutonic belt (329 Ma–307 Ma). We envisage northward subduction and slab breakoff process resulting in an obvious change of the regional stress field to extensional setting within the Carboniferous continental arc running E-W for thousands of kilometers. Therefore, we propose the existence of an east-west-trending Carboniferous continental arc in the Hegenshan ophiolite-arc-accretion complex, with the slab breakoff event suggesting that the age of the upper sequence (305.3 ± 5.5 Ma) likely indicates the maximum age for the cessation of the northward subduction of the Hegenshan oceanic lithosphere.     

U–Pb dating,geochemistry, and Sr–Nd isotopic composition of a granodiorite porphyry from the Jiadanggen Cu–(Mo) deposit in the Eastern Kunlun metallogenic belt,Qinghai Province,China

The Jiadanggen porphyry Cu–(Mo) deposit is newly discovered and located in the Eastern Kunlun metallogenic belt of Qinghai Province, China. Here, we present a detailed study of the petrogenesis, magma source, and tectonic setting of the mineralization causative granodiorite porphyry. The new data indicate that the granodiorite porphyry is characterized by high SiO₂ (68.21–70.41 wt.%) and Al₂O₃, relatively high K₂O, low Na₂O, and low MgO and CaO concentrations, and is high-K calc-alkaline and peraluminous. The granodiorite porphyry has low Mg^# (38–46) values that are indicative of no interaction between the magmas and the mantle. The samples that we have examined have low Nb/Ta (9.17–10.3) and Rb/Sr (0.28–0.39) ratios, which are indicative of crustal-derived magmas. Source region discrimination diagrams indicate that the magmas that formed the granodiorite porphyry were derived from melting of a mixed amphibolite source in the lower crust. The samples have I_Sr values of 0.70954–0.70979, ε_Nd(t) values of − 8.3 to − 7.9, and t_2DM ages ranging from 1644 to 1677 Ma. These indicate that the magmas that formed this intrusion were generated by melting of Mesoproterozoic lower crustal material. Higher K(Rb) contents of the samples indicate that the magma source is high potassium basaltic material in the lower crust, which could be derived from an enriched mantle source. LA-ICP-MS zircon U–Pb dating of the granodiorite porphyry yields a late Indosinian age (concordia age of 227 ± 1 Ma; MSWD = 0.31), which is close to the molybdenite Re–Os isochron age (227.2 ± 1.9 Ma), indicating further the close relationship between the granodiorite porphyry and the Cu–(Mo) mineralization. These samples are LREE and LILE (e.g., Rb, K, Ba, and Sr) enriched, and HFSE (e.g., Nb, Ta, P, and Ti) depleted, especially in P and Ti, similar to the characteristics of volcanic arc magmas. This intrusion most likely formed during the later stage of Indosinian deep subduction of oceanic slab. This was associated with underplating of mantle-derived magmas, which provided heat for crustal melting. Similar to the Jiadanggen granodiorite porphyry, Indosinian hypabyssal intermediate-felsic intrusive rocks, formed under subduction tectonism or a transitional regime from subduction to syn-collision, make up the most important targets for porphyry Cu(Mo) deposits in the Eastern Kunlun metallogenic belt.     

Mobility of elements in a continental subduction zone: evidence from the UHP metamorphic complex of the Kokchetav massif

We studied clastics of high-alumina garnet-kyanite-mica schists and garnet-kyanite-quartz granofelses, including diamond-bearing ones, found in the eluvial sediments near Lake Barchi. In contents of major elements the studied rocks correspond to argillaceous shales. The garnet-kyanite-quartz granofelses are poorer in K (0.49-1.35 wt.% K₂O) than the garnet-kyanite-mica schists (4.9-2.2 wt.% K₂O) but have the same contents of other major components. The REE patterns of most of the garnet-kyanite-phengite schists are similar to those of the Post-Archean Australian Shale (PAAS) (xLa/Yb = 13). All garnet-kyanite-quartz rocks are much stronger depleted in LREE (x_La/Yb = 1.4) and other incompatible elements. Our studies show that allanite and monazite are the main concentrators of LREE and Th in the garnet-kyanite-phengite rocks of the Barchi site. Monazite, occurring as inclusions in garnet, contains not only LREE but also Th, U, and Pb. Rutile of the nondepleted rocks is enriched in Fe and Nb impurities only. The garnet-kyanite-quartz granofelses bear rutile, apatite, and xenotime as accessory phases. Rutile of the depleted rocks shows wide variations in contents of Nb, Ta, and V impurities. In places, the contents of Nb and Ta reach 10.5 and 2.3 wt.%, respectively. The rutile decomposes into rutile with Nb (1.4 wt.%) and Fe (0.87 wt.%) impurities and titanium oxide rich in Fe (6.61 wt.%), Nb (up to 20.8 wt.%), and Ta (up to 2.81%) impurities. Based on the measured contents of incompatible elements in differently depleted high-alumina rocks, the following series of element mobility during UHP metamorphism has been established: Th > Ce > La > Pr > Nd > K > Ba > Rb > Cs > Sm > Eu. The contents of U, P, and Zr in the depleted rocks are similar to those in the nondepleted rocks. The studies have shown that metapelites subducted to the depths with diamond stability conditions can be depleted to different degrees. This might be either due to their exhumation from different depths of the subduction zone or to the presence of an external source of water controlling the temperature of dissolution of phengite and the formation of supercritical fluid/melt.     

Bulk chemical compositions of Al-rich objects from Rumuruti (R) chondrites: Implications for their origin

R chondrites are a distinct group of chondritic meteorites with unique mineralogical and chemical compositions. They contain various types of Al-rich objects [Ca,Al-rich inclusions (CAIs), Al-rich chondrules and fragments], whose mineralogical compositions and classifications were previously determined by Rout and Bischoff (2008). Here, we report on the bulk compositions of 126 such Al-rich objects determined by broad-beam electron probe microanalysis.Most of the CAIs, except a few, are significantly altered by complex nebular and/or parent body processes and the determination of their pristine composition is difficult. We found that the simple concentric spinel-rich inclusions have high Al₂O₃ (21–72 wt%) correlated with their high modal spinel. The subgroup of simple concentric spinel-rich CAIs have a high Al₂O₃ (21–57 wt%) and also sometimes high FeO (up to 36 wt%), due to a high hercynitic component in the spinel. One simple concentric spinel- and hibonite-rich CAI H030/L, identified as a HAL-type CAI by isotopic studies reported elsewhere, has a highly refractory composition (Al₂O₃～72 wt%). Most of the simple concentric spinel- and fassaite-rich CAIs have consistently high CaO (～2.5–17 wt%) compared to other simple concentric spinel-rich inclusions group, where only some inclusions have high CaO (up to 15 wt%). Simple concentric spinel- and Na,Al-alteration product-rich CAIs are heavily altered and have high Na₂O (up to ～12.5 wt%).The three analyzed fassaite-rich spherules have high CaO and Al₂O₃, and complex spinel- and fassaite-rich CAIs have high CaO (up to 23 wt%) and SiO₂ (up to 41 wt%). Most of the complex spinel- and plagioclase-rich CAIs are altered and contain high amounts of secondary oligoclase. However, a few are less affected by secondary alteration and these are characterized by relatively high CaO (up to 24 wt%) and Al₂O₃ (18–33 wt%); complex spinel and Na,Al-alteration product-rich CAIs are similar to the concentric spinel- and Na,Al-alteration product-rich CAIs. Due to Fe- and alkali-metasomatism, the vast majority of the inclusions in this subgroup were heavily altered, either in a nebular or parent body environment. As a result of this alteration, they contain high FeO and Na₂O+K₂O+Cl.Almost all inclusions have a Ca/Al-ratio below the solar ratio. This suggests that significant Ca/Al fractionation occurred during the formation of most CAIs, most probably due to disequilibrium condensation of spinel prior to melilite. However, a distillation process cannot be ruled out for some CAIs in producing the spinel enrichment. Some porous and fine grained CAIs may have been produced by agglomeration of refractory dust rich in spinel and fassaite. The HAL-type CAI, H030/L, most likely formed by distillation, similar to most of the HAL-type inclusions. Phase equilibrium analysis, in the CMAS system, shows that the fassaite-bearing spherules most likely formed by metastable crystallization and disequilibrium processes. Al-rich chondrules are characterized by >10 wt% Al₂O₃, and most of these also have high FeO and Na₂O. Considering their bulk compositions, their precursors seem to have been a mixture of a ferromagnesian chondrule component rich in olivine and an anorthite–spinel–pyroxene–nepheline-rich CAI component. The mineral assemblages of some of the less altered Al-rich chondrules conform to those predicted by phase equilibrium studies.     

Petrography,mineralogy and geochemistry of the Late Eocene oolitic ironstones of the Jebel Ank,Southern Tunisian Atlas

The oolitic ironstones ore deposit of Jebel Ank (central Tunisia), is a simply folded stratiform ore body of about 2.5–8 m thickness located in the upper part of the epicontinental Souar Formation (Late Eocene) and is covered by the continental Segui Formation (Mio-Pliocene). The deposit contains about 20 Mt of ore with an average grade of 50% Fe. Generally, oolitic iron deposition occurs in shallow water lagoonal environments. The Jebel Ank deposit lies between two regional disconformities (Late Eocene and Miocene), and is evidence of a transitional stage at the end of regional regression before renewed transgression. The footwall of the oolitic iron ore-bearing bed consists of a fine-grained sandstone bed (10–20 cm-thick) pinching out laterally westward into green clays. The hanging wall is composed of thin-bedded limestone and clay alternations (2–3.5 m-thick).Iron occurs in the form of cryptocrystalline goethite with limited Al-Fe substitution. The goethite contains around 48% Fe, 5% Al and up to 1.5% P. Jarosite, alunite and manganese minerals (cryptomelane, psilomelane and manjiorite) are supergene secondary minerals, probably related to descending surface fluids. These manganese minerals occur as accessory minerals with the goethite and are most abundant at the lowermost part of the succession showing varied morphologies (local cement, space filling and free centimeter sized nodules). Fe-oolites in the deposit are similar to those documented in many other oolitic ironstone deposits. The dominant Fe-oolite type (>90%) has a concentrically laminated cortex with no nucleus. The nuclei of the oolites that do have a nucleus are most commonly detrital quartz grains.Major elements in high grade samples (Fe₂O₃ > 65%) vary within a limited range and show higher concentrations of SiO₂ (average 7.85%) and Al₂O₃ (average 5.1%), with minor TiO₂, MnO, MgO, Na₂O, K₂O, and SO₃ (less than 1%). PAAS-normalized trace elements of bulk samples and Fe-oolite generally show similar behavior, both are enriched in V, Co, Ni, Mo, As, Zn, and Y and are depleted in Cu, Rb, Zr, Nb, Ba, and Hf. Anomalous V, Cr, Ni, Zn, and REE-Y are correlated with goethite. PAAS-normalized REE-Y patterns of both bulk samples and Fe-oolite show slight HREE enrichment, positive Ce with negative Y anomalies.The mineralogy (goethite and cryptomelane) along with the geochemistry (Si vs. Al; As + Cu + Mo + Pb + V + Zn vs. Ni + Co binary plots; Zn–Ni–Co triangular diagram, REE-Y content and patterns and Ce/Ce¹ vs. Nd and Ce/Ce¹ vs. Y_N/Ho_N binary plots) of the studied oolitic ironstone are congruent with a hydrogenetic type. While two possible sources of iron for Jebel Ank ironstone can be proposed: (i) submarine weathering of glauconite-rich sandstone and (ii) detrital iron from adjacent continental hinterland, the later is the more plausible source of iron, based on paleogeographic setting, the occurrence of fine sandstone underlying the iron level, occurrence of Mn-ores in the lower part of the Fe-ores succession, high phosphorous, zinc, ∑REE-Y concentrations and Y/Ho ratios, and low La/Ce ratios.     

New evidence of mantle heterogeneity beneath the Hyblean Plateau (southeast Sicily,Italy) as inferred from noble gases and geochemistry of ultramafic xenoliths

We analyzed major and trace elements, Sr and Nd isotopes in ultramafic xenoliths in Miocenic age Hyblean diatremes, along with noble gases of CO₂-rich fluid inclusions hosted in the same products. The xenoliths consist of peridotites and pyroxenites, which are considered to be derived from the upper mantle. Although the mineral assemblage of peridotites and their whole-rock abundance of major elements (e.g., Al₂O₃ = 0.8–1.5 wt.%, TiO₂ = 0.03–0.08 wt.%) suggest a residual character of the mantle, a moderate enrichment in some incompatible elements (e.g., La_N/Yb_N = 9–14) highlights the presence of cryptic metasomatic events. In this context a deep silicate liquid is considered the metasomatizing agent, which is consistent with the occurrence of pyroxenites as veins in peridotites. Both the Zr/Nb and ¹⁴³Nd/¹⁴⁴Nd ratios of the investigated samples reveal two distinct compositional groups: (1) peridotites with Zr/Nb ≈ 4 and ¹⁴³Nd/¹⁴⁴Nd ≈ 0.5129, and (2) pyroxenites with Zr/Nb ≈ 20 and ¹⁴³Nd/¹⁴⁴Nd ≈ 0.5130. The results of noble-gas analyses also highlight the difference between the peridotite and pyroxenite domains. Indeed, the ³He/⁴He and ⁴He/⁴⁰Ar* ratios measured in the fluid inclusions of peridotites (respectively 7.0–7.4 ± 0.1 Ra and 0.5–8.2, where Ra is the atmospheric ³He/⁴He ratio of 1.38 × 10^? 6) were on average lower than those for the pyroxenites (respectively 7.2–7.6 Ra and 0.62–15). This mantle heterogeneity is interpreted as resulting from a mixing between two end-members: (1) a peridotitic layer with ³He/⁴He ≈ 7 Ra and ⁴He/⁴⁰Ar* ≈ 0.4, which is lower than the typical mantle ratio (~ 1–4) probably due to melt extraction events, and (2) metasomatizing mafic silicate melts that gave rise to pyroxenites characterized by ³He/⁴He ≈ 7.6 Ra, with a variable ⁴He/⁴⁰Ar* due to degassing processes connected with the ascent of magma at different levels in the peridotite wall rock. The complete geochemical data set also suggests two distinct mantle sources for the xenolithic groups highlighted above: (1) a HIMU (high-μ)-type source for the peridotites and (2) a DM (depleted mantle)-type source for the pyroxenites.     

Geology,mineralogy and fluid inclusion data of the Kizilcaören fluorite–barite–REE deposit,Eskisehir, Turkey

The Kizilcaören fluorite–barite–Rare Earth Element (REE) deposit occurs as epithermal veins and breccia fillings in altered Triassic metasandstones and Oligocene–Miocene pyroclastics adjacent to alkaline porphyritic trachyte and phonolite. This deposit is the only commercial source of REE and thorium in Turkey. Most of the fluorite–barite–REE mineralisation at Kizilcaören has been formed by hydrothermal solutions, which are thought to be genetically associated with alkaline volcanism. The occurrence of the ore minerals in vuggy cavities and veins of massive and vuggy silica indicate that the ore stage postdates hydrothermal alteration. The deposit contains evidence of at least three periods of hypogene mineralisation separated by two periods of faulting. The mineral assemblage includes fluorite, barite, quartz, calcite, bastnäsite, phlogopite, pyrolusite and hematite as well as minor amounts of plagioclase feldspar, pyrite, psilomelane, braunite, monazite, fluocerite, brockite, goethite, and rutile. Fluid inclusion microthermometry indicates that the barite formed from low salinity (0.4–9.2 equiv. wt% NaCl) fluids at low temperatures, between 105 and 230 °C, but fluorite formed from slightly higher salinity (<12.4 equiv. wt% NaCl) fluids at low and moderate temperatures, between 135–354 °C. The depositional temperature of bastnäsite is between 143–286 °C. The local coexistence of liquid- and vapour-rich inclusions suggests boiling conditions. Many relatively low-salinity (<10.0 equiv. wt% NaCl), low and moderate temperature (200–300 °C) inclusions might be the result of episodic mixing of deep-saline brines with low-salinity meteoric fluids. The narrow range of δ³⁴S (pyrite and barite) values (2.89–6.92‰ CDT)suggests that the sulphur source of the hydrothermal fluids are the same and compatible with a volcanogenic sulphate field derived from a magmatic sulphur source.     

Rutile geochemistry and thermometry of eclogites and associated garnet-mica schists in the Biga Peninsula,NW Turkey

In northwest Turkey, high-pressure metamorphic rocks occur as exotic blocks within the Çetmi mélange located on the south of the Biga Peninsula. Rutile chemistry and rutile thermometry obtained from the eclogite and associated garnet-mica schist in the Çetmi mélange indicate significant trace element behaviour of subducted oceanic crust and source-rock lithology of detrital rutiles. Cr and Nb contents in detrital rutile from garnet-mica schist vary from 355 to 1026 μg/g and 323 and 3319 μg/g, respectively. According to the Cr-Nb discrimination diagram, the results show that 85% of the detrital rutiles derived from metapelitic and 15% from metamafic rocks. Temperatures calculated for detrital rutiles and rutiles in eclogite range from 540 °C to 624 °C with an average of 586 °C and 611 °C to 659 °C with an average of 630 °C at P = 2.3 GPa, respectively. The calculated formation temperatures suggest that detrital rutiles are derived from amphibolite- and eclogite-facies metamorphic rocks. Amphibolite-facies rocks of the Kazdağ Massif could be the primary source rocks for the rutiles in the garnet-mica schist from the Çetmi mélange. Nb/Ta ratios of metapelitic and metamafic rutiles fall between 7–24 and 11–25, respectively. Nb/Ta characteristics in detrital rutiles may reflect a change in source-rock lithology. However, Nb/Ta ratios of rutiles in eclogite vary from 9 to 22. The rutile grains from eclogites are dominated by subchondritic Nb/Ta ratios. It can be noted that subchondritic Nb/Ta may record rutile growth from local sinks of aqueous fluids from metamorphic dehydration.