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1.
Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce3 + was oxidized into Ce4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.  相似文献   

2.
The Mandan and Deh-now bauxite deposits are located 40 km northeast of the Dehdasht city in the Zagros simply fold belt. These deposits occur in eroded major NW–SE trending anticlines and occupy karst cavities near or at the boundary between the Sarvak and Ilam Formations. Local uplifts at the end of the Cenomanian and the mid-Turonian caused erosion and karstification of the Sarvak Formation. These unconformities in the Upper Cretaceous favoured the formation and enrichment of bauxite deposits in the Zagros fold belt. The bauxite sequence in the Mandan deposit consists of white, gray, black, pisolitic, red, and yellow bauxites. This sequence was repeated in the Deh-Now area, but without gray and black bauxites. The present mineralogical studies of the Sarvak Formation and the Mandan and Deh-now bauxite deposits indicate oxidizing to reducing conditions during the Upper Cretaceous in the Zagros fold belt, which had a significant effect on the compositions of the bauxites. At least two phases of bauxitization can be distinguished in the study area: (i) an oxidizing phase represented by boehmite, diaspore, hematite and kaolinite; and (ii) a reducing phase represented by pyrite and chlorite. Geochemical data show that trace elements, like Zr, Hf, Nb, Ta, Th, and U, were enriched during bauxitization. The bauxite deposits and carbonate rocks show similar REE patterns, namely they are enriched in REEs although the LREEs are more enriched than the HREEs. Mass change calculations demonstrate that Mg, Mn, Ca, K, and P2O5 were leached out of the weathered system whereas Al, Fe, and Si become concentrated in the residual system. This study indicates that the Mandan and Deh-now deposits are karst-type bauxites formed by karstification and weathering of the Sarvak Formation.  相似文献   

3.
Bauxite deposits, traditionally the main source of aluminum, have been recently targeted for their remarkable contents in rare earth elements (REE). With ∑REE (lanthanoids + Sc + Y) concentrations systematically higher than ∼1400 ppm (av. = 1530 ppm), the Las Mercedes karstic bauxites in the Dominican Republic rank as one of the REE-richest deposits of its style.The bauxitic ore in the Las Mercedes deposit is mostly unlithified and has a homogeneous-massive lithostructure, with only local cross-stratification and graded bedding. The dominant arenaceous and round-grained texture is composed of bauxite particles and subordinate ooids, pisoids and carbonate clasts. Mineralogically, the bauxite ore is composed mostly of gibbsite and lesser amounts of kaolinite, hematite, boehmite, anatase, goethite, chromian spinel and zircon. Identified REE-minerals include cerianite and monazite-Ce, whose composition accounts for the steady enrichment in light- relative to medium- and heavy-REE of the studied bauxites.Considering the paleo-geomorphology of the study area, we propose that bauxites in the Las Mercedes deposit are the product of the erosion and deposition of lithified bauxites located at higher elevations in the Bahoruco ranges. Based on the available data, we suggest a mixed lithological source for the bauxite deposits at the district scale: bedrock carbonates and an igneous source of likely mafic composition.  相似文献   

4.
Three vertical sections through the Zagrad deposit of Jurassic karst bauxite in central Montenegro have provided knowledge of the vertical distribution of major and some selected trace elements, including rare earth elements (REE). Variations in the mineralogy, particularly those hosting REE, have been studied. This has revealed the presence of authigenic mineral phases such as xenotime, mottramite and monazite (best proved using Raman microprobe analysis) as well as residual phases such as zircon, titanite and monazite. The mobility of the elements during bauxitization processes has been studied to show that the REE minerals ensure progressive concentration of these elements during removal of major elements through weathering. The similarity of normalized REE in the bauxite to the typical Post-Archean Australian Shales (PAAS) and Upper Continental Crust (UCC) profile, and the preserved Eu anomaly, are evidence that the bauxite was not derived from carbonates and represents alteration of shale, marly limestone and volcanogenic or proximal igneous sourced detritus that accumulated in the original karst landform. Mass change during bauxitization, using Ti as “index” element and compared to PAAS composition, revealed almost 100% depletion of Si and weak enrichment in Al. Deeper parts of the deposit with authigenic minerals exhibit very strong enrichment in all REE. The bauxite ores have high ΣREE contents (693.5–6953.4 ppm), especially ΣLREE contents (582.8–4882.9 ppm), while ΣHREE contents (106.6–2070.5 ppm) are much lower.  相似文献   

5.
The Dalucao deposit, located in western Sichuan Province, southwestern China, in the western part of the Yangtze Craton, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE belt. Moreover, the Dalucao deposit is the only deposit identified in the southern part of the belt. The Dalucao deposit contains the No. 1, 2, and 3 orebodies; the No. 1 and 3 orebodies are both hosted in two breccia pipes, located in syenite–carbonatite host rocks. Both pipes have elliptical cross-sections at the surface, with long-axis diameters of 200–400 m and short-axis diameters of 180–200 m; the pipes extend downwards for > 450 m. No. 1 and No. 3 have total thickness varying between 55 and 175 m and 14 to 58 m respectively. The REE mineralization is associated with four brecciation events, which are recorded in each of the pipes. The ore grades in the No. 1 and 3 orebodies are similar, and consist of 1.0%–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a Type I mineral assemblage (fluorite + barite + celestite + bastnäsite), whereas the No. 3 orebody is characterized by a Type II assemblage (fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite). Argon (40Ar/39Ar) dating of hydrothermal muscovite intergrown with REE minerals in typical ores from the No. 1 and 3 orebodies yielded similar ages of 12.69 ± 0.13 and 12.23 ± 0.21 Ma, respectively, which suggest that both mineral assemblages formed coevally, rather than in paragenetic stages. Both ages are also similar to the timing of intrusion of the syenite–carbonatite complex (12.13 ± 0.19 Ma). The ore-mineral assemblages occur in breccias, veinlets, and in narrow veins. The ore veinlets, which usually show a transition to mineralized breccia or brecciated ores, are commonly enveloped by narrow veins and stringer zones with comparable mineral assemblages. The brecciated ores form 95% of the volume of the deposit, whereas brecciated ores are only a minor constituent of other deposits in the Mianning–Dechang REE belt. The carbonatite in the syenite–carbonatite complexes contains high concentrations of S (0.07–2.32 wt.%), Sr (16,500–20,700 ppm), Ba (3600–8400 ppm), and light REEs (LREE) (2848–10,768 ppm), but is depleted in high-field-strength elements (HFSE) (Nb, Ta, P, Zr, Hf, and Ti). The syenite is moderately enriched in large-ion lithophile elements (LILE), Sr (155–277 ppm), and Ba (440–755 ppm). The mineralized, altered, and fresh syenites and carbonatites exhibit similar trace element compositions and REE patterns. Brecciation events, and the Dalucao Fault and its secondary faults around the deposit, contributed to the REE mineralization by facilitating the circulation of ore-forming fluids and providing space for REE precipitation. Some hydrothermal veins composed of coarse-grained fluorite and quartz are distributed in the syenite–carbonatite complex. The oxygen isotope compositions of ore-forming fluids in equilibrium with quartz at 215 °C are − 4.95‰ to − 7.45‰, and the hydrogen isotope compositions of fluid inclusions in coarse-grained quartz are − 88.4‰ to − 105.1‰. The syenite–carbonatite complex and carbonatite are main contributors to the mineralization in the geological occurrence. Thus, the main components of the ore-forming fluids were magmatic water, meteoric water, and CO2 derived from the decarbonation of carbonatite. According to the petrographic studies, bastnäsite mineralization developed during later stages of hydrothermal evolution and overprinted the formation of the brecciated fluorite–quartz hydrothermal veins. As low-temperature isotope exchange between carbonates of the carbonatite and water-rich magmatic fluids will lead to positive shifts in δ18O values of the carbonates, C–O isotopic compositions from the bulk primary carbonatite to hydrothermal calcite and bastnäsite changed (δ18OV-SMOW from 8.0‰ to 11.6‰, and δ13C V-PDB from − 6.1 to − 8.7‰). According to the chemical composition of syenite and carbonatite, REE chloride species are the primary complexes for the transport of the REEs in the hydrothermal fluids, and the presence of bastnäsite and parisite means the REE were precipitated as fluorocarbonates. High contents of Sr, Ba and S in the syenite–carbonatite complex led to the deposition of large amount of barite and celestite.  相似文献   

6.
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.  相似文献   

7.
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.  相似文献   

8.
The major and trace element characteristics of black shales from the Lower Cretaceous Paja Formation of Colombia are broadly comparable with those of the average upper continental crust. Among the exceptions are marked enrichments in V, Cr, and Ni. These enrichments are associated with high organic carbon contents. CaO and Na2O are strongly depleted, leading to high values for both the Chemical Index of Alteration (77–96) and the Plagioclase Index of Alteration (86–99), which indicates derivation from a stable, intensely weathered felsic source terrane. The REE abundances and patterns vary considerably but can be divided into three main groups according to their characteristics and stratigraphic position. Four samples from the lower part of the Paja Formation (Group 1) are characterized by LREE-enriched chondrite-normalized patterns (average LaN/YbN = 8.41) and significant negative Eu anomalies (average Eu/Eu1 = 0.63). A second group of five samples (Group 2), also from the lower part, have relatively flat REE patterns (average LaN/YbN = 1.84) and only slightly smaller Eu anomalies (average Eu/Eu1 = 0.69). Six samples from the middle and upper parts (Group 3) have highly fractionated patterns (average LaN/YbN = 15.35), resembling those of Group 1, and an identical average Eu/Eu1 of 0.63. The fractionated REE patterns and significant negative Eu anomalies in Groups 1 and 3 are consistent with derivation from an evolved felsic source. The flatter patterns of Group 2 shale and strongly concave MREE-depleted patterns in two additional shales likely were produced during diagenesis, rather than reflecting more mafic detrital inputs. An analysis of a single sandstone suggests diagenetic modification of the REE, because its REE pattern is identical to that of the upper continental crust except for the presence of a significant positive Eu anomaly (Eu/Eu1 = 1.15). Felsic provenance for all samples is suggested by the clustering on the Th/Sc–Zr/Sc and GdN/YbN–Eu/Eu1 diagrams. Averages of unmodified Groups 1 and 3 REE patterns compare well with cratonic sediments from the Roraima Formation in the Guyana Shield, suggesting derivation from a continental source of similar composition. In comparison with modern sediments, the geochemical parameters (K2O/Na2O, LaN/YbN, LaN/SmN, Eu/Eu1, La/Sc, La/Y, Ce/Sc) suggest the Paja Formation was deposited at a passive margin. The Paja shales thus represent highly mature sediments recycled from deeply weathered, older, sedimentary/metasedimentary rocks, possibly in the Guyana Shield, though Na-rich volcanic/granitic rocks may have contributed to some extent.  相似文献   

9.
The Karoo volcanic sequence in the southern Lebombo monocline in Mozambique contains different silicic units in the form of pyroclastic rocks, and two different basalt types. The silicic units in the lower part of the Lebombo sequence are formed by a lower unit of dacites and rhyolites (67–80 wt.% SiO2) with high Ba (990–2500 ppm), Zr (800–1100 ppm) and Y (130–240 ppm), which are part of the Jozini–Mbuluzi Formation, followed by a second unit, interlayered with the Movene basalts, of high-SiO2 rhyolites (76–78 wt.%; the Sica Beds Formation), with low Sr (19–54 ppm), Zr (340–480 ppm) and Ba (330–850 ppm) plus rare quartz-trachytes (64–66 wt.% SiO2), with high Nb and Rb contents (240–250 and 370–381 ppm, respectively), and relatively low Zr (450–460 ppm). The mafic rocks found at the top of the sequence are basalts and ferrobasalts belonging to the Movene Formation. The basalts have roughly flat mantle-normalized incompatible element patterns, with abundances of the most incompatible elements not higher than 25 times primitive mantle. The ferrobasalt has TiO2  4.7 wt.%, Fe2O3t = 16 wt.%, and high Y (100 ppm), Zr (420 ppm) and Ba (1000 ppm). The Movene basalts have initial (at 180 Ma) 87Sr/86Sr = 0.7052–0.7054 and 143Nd/144Nd = 0.51232, and the Movene ferrobasalt has even lower 87Sr/86Sr (0.70377) and higher 143Nd/144Nd (0.51259). The silicic rocks show a modest range of initial Sr-(87Sr/86Sr = 0.70470–0.70648) and Nd-(143Nd/144Nd = 0.51223–0.51243) isotope ratios. The less evolved dacites could have been formed after crystal fractionation of oxide-rich gabbroic cumulates from mafic parental magmas, whereas the most silica-rich rhyolites could have been formed after fractional crystallization of feldspars, pyroxenes, oxides, zircon and apatite from a parental dacite magma. The composition of the Movene basalts imply different feeding systems from those of the underlying Sabie River basalts.  相似文献   

10.
Karstic bauxite deposits are widespread in Central Guizhou Province, SW China, and high-grade ores are frequently sandwiched with overlying coal and underlying iron-rich layers and form a special “coal–bauxite–iron” structure. The Lindai deposit, which is one of the most representative karstic bauxite deposits in Central Guizhou Province, was selected as a case study. Based on textural features and iron abundances, bauxite ores in the Lindai deposit are divided into three types of ores, i.e., clastic, compact, and high-iron. The bauxite ores primarily comprise diaspore, boehmite, kaolinite, illite, and hematite with minor quartz, smectite, pyrite, zircon, rutile, anatase, and feldspar. The Al2O3 (53–76.8 wt.%) is the main chemical contents of the bauxite ore samples in the Lindai district, followed by SiO2, Fe2O3, TiO2, CaO, MgO, S, and P etc. Our geological data on the Lindai deposit indicated that the ore-bearing rock series and its underlying stratum have similar rare earth elements distribution pattern and similar Y/Ho, Zr/Hf, and Eu/Eu1 values; additionally, all ore-bearing rock samples are rich in MgO (range from 0.16 wt.% to 0.68 wt.%), and the plots of the dolomites and laterites lie almost on or close to the weathering line fit by the Al-bearing rocks in Zr vs. Hf and Nb vs. Ta diagrams; suggesting that the underlying Middle Cambrian Shilengshui Formation dolomite is the parent rock of bauxite resources in the Lindai district.Simulated weathering experiments on the modern laterite from the Shilengshui Formation dolomite in the Lindai bauxite deposit show that hydrogeological conditions are important for karstic bauxite formation: Si is most likely to migrate, its migration rate is several magnitudes higher than those of Al and Fe under natural conditions; the reducing inorganic acid condition is the most conducive to Al enrichment and Si removal; Fe does not migrate easily in groundwater, Al enrichment and Fe removal can occur only in acidic and reducing conditions with the presence of organic matter.The geological and experimental studies show that “coal–bauxite–iron” structure in Lindai deposit is formed under certain hydrogeological conditions, i.e., since lateritic bauxite or Al-rich laterite deposited upon the semi-closed karst depressions, Si can be continuously removed out under neutral/acidic groundwater conditions; the coal/carbonaceous rock overlying the bauxitic materials were easily oxidized to produce acidic (H2S, H2SO4, etc.) and reductant groundwater with organic materials that percolated downward, resulting in enrichment of Al in underlying bauxite; it also reduced Fe3+ to its easily migrating form Fe2+, moving downward to near the basal carbonate culminated in precipitating of ferruginous (FeS2, FeCO3, etc.) strata of the “coal–bauxite–iron” structure. Thus, the bauxitic materials experienced Al enrichment and Si and Fe removal under above certain hydrogeological conditions forming the high-quality bauxite.  相似文献   

11.
Phosphorites in Egypt occur in the Eastern Desert, the Nile Valley and the Western Desert at Abu Tartur area and present in Duwi Formation as a part of the Middle Eastern to North African phosphogenic province of Late Cretaceous to Paleogene age (Campanian–Maastrichtian). The Maghrabi-Liffiya phosphorite sector is considered as the most important phosphorite deposits in the Abu Tartur area due to its large reserve thickness and high-grade of lower phosphorite bed beside high content of REE. Back scattered electron (BSE) images show framboidal pyrite filling the pores of the phosphatic grains, suggesting diagenetic reducing conditions during phosphorites formation.Electron Probe Micro Analyzer (EPMA) chemical mapping was conducted to examine the variation and distributions of selected elements (P, F, La, Fe, Yb, Si, Ce, W, Eu, S, Ca, Y and Er) within the shark teeth, coprolites and bone fragments. In the teeth W, S, Fe are concentrated along the axis of the teeth, the bone fragments show high concentration of W, Yb, Er and Eu, whereas coprolites are nearly homogenous in composition contains S, Er with some Si as micro-inclusions. Fluorapatite is considered as main phosphate mineral whereas pyrite occurs as pore-filling within the phosphatic grains and cement materials. Maghrabi-Liffiya samples show a wide range in the P2O5 content, between 19.8 wt.% and 29.8 wt.% with an average of 24.6 wt.% and shows low U content ranging from 15 ppm to 34 ppm with an average of 22 ppm. The total REE content in nine samples representing the Maghrabi-Liffiya ranges from 519 to 1139 ppm with an average of about 879 ppm. The calculation of LREE (La–Gd) show indeed a marked enrichment relative to the HREE (Tb–Lu) where LREE/HREE ratio attains 8.4 indicating a strong fractionation between the LREE and HREE. Chondrite-normalized REE patterns of the studied phosphorite samples show a negative Eu anomaly.  相似文献   

12.
The Beiligaimiao magmatic Ni-Cu sulfide deposit is located in the northern rim of the North China Block, which was an active continental margin related to the southward subduction of the Paleo-Asian oceanic plate to the north in the Paleozoic. This deposit has never been studied before but is an excellent example of sulfide mineralization in arc settings that have been commonly overlooked by exploration geologists worldwide. Sulfide mineralization in the deposit is hosted in a mafic-ultramafic complex that consists of a small ultramafic body surrounded by an older and much larger gabbroic intrusion. Disseminated sulfide zones are present in both intrusive bodies but only those close to the surface within the ultramafic body have been mined in the past. The sulfide-mineralized ultramafic body is composed of olivine websterite and orthopyroxenite with a gradational contact between them. SIMS U-Pb dating of zircon crystals from a large olivine websterite sample yields a crystallization age of 269.4 ± 2.1 Ma, which is ∼25 Ma younger than the Erbutu subduction-related magmatic Ni-Cu sulfide deposit that occurs ∼50 km to the north. Orthopyroxene crystals in the Beiligaimiao ultramafic rocks have Mg# [100 Mg/(Mg + Fe), molar] of 77–78, significantly lower than those in the ultramafic rocks of the Erbutu deposit. Olivine crystals in the Beiligaimiao ultramafic rocks have forsterite (Fo) contents from 72 to 75 mol%, which are also significantly lower than those in the ultramafic rocks of the Erbutu deposit (Fo, 86–88 mol%). The mineral chemical data indicate a more fractionated parental magma for the former. Ca-depletion in olivine (i.e., <1000 ppm Ca), which is common for ultramafic cumulates in arc settings worldwide, is present in both deposits. Like Erbutu, the host rocks of the Beiligaimiao deposit are characterized by enrichments in light rare earth elements (REE) relative to heavy REE and pronounced negative Nb-Ta anomalies, consistent with ultramafic rocks in arc settings. The δ34S values of sulfide separates from the Beiligaimiao deposit are 1.7 to 2.5‰, significantly lower than those for the Erbutu deposit but still slightly higher than the MORB value (−1.5 to 0.5‰). Olivine websterites in the Beiligaimiao deposit have εNd from −8.9 to −9.5 and (87Sr/86Sr)i close to 0.7075, which are similar to those of an enriched lithospheric mantle. An orthopyroxenite sample from the deposit has much lower εNd (−12.6) coupled with much higher (87Sr/86Sr)i ratio (0.7132), indicating ∼25% crustal contamination. The Sr-Nd-S isotope data support the premise that both crustal contamination and addition of crustal sulfur played a role in triggering sulfur saturation in the parental magma of the Beiligaimiao deposit. Since the immediate country rocks are exclusively gabbros, these processes likely took place at depth. The close temporal and spatial association of the Beiligaimiao and Erbutu deposits points to the possibility that more Permian arc-type magmatic sulfide deposits are yet to be discovered in the region.  相似文献   

13.
Rare-earth elements abundance in black shales of the Upper Jurassic (Tithonian Stage)–Lower Cretaceous (Berriassian Stage) Bazhenov Formation is discussed. This formation is the principal oil source rocks of West Siberia. The deposits within the formation can be subdivided into two main marine groups: (a) moderately hemipelagic deposits (clayey-siliceous, including phosphatic and carbonate rocks) and low-density distal clayey turbidites (argillites), both are considered as normal and (b) silty argillites and clayey-silt rocks, which are channel deposits and considered as anomalous. The hemipelagic rocks of normal sections, which are enriched in the rare-earth elements (REE), accumulated under both slow rates of sedimentation (clayey-siliceous rocks) and faster rates of sedimentation (argillites). The channel deposits of anomalous sections, which are impoverished in the REE, accumulated exclusively under fast rates of sedimentation.Within the hemipelagic group the rate of sedimentation of the argillites was faster than of the clayey-siliceous rocks, but the REE concentration in the former rocks (140.4 ppm) is higher than in the latter group (97.4 ppm). The argillites are more than twice enriched in clayey material than clayey-siliceous rocks. It is likely that the clay fraction was the main carrier of REE in these rocks. In the channel group of rocks, the REE abundance in clayey-silt rocks (21.2 ppm) is lower than in the silty argillite (84.6 ppm), in which the clay content is elevated.With respect to redox potential the Bazhenov Formation rocks can be subdivided further into three groups, based on the degree of pyritization index (DOP): (1) the highly reducing clayey-siliceous rocks of normal sections, with high DOP; (2) the substantially reducing argillites and carbonate rocks of normal sections, with intermediate DOP; (3) the moderately reducing rocks of anomalous sections with low DOP. The rocks with the high DOP (group 1) are characterized by ΣLREE/Σ(M+H)REE ratios between 7.37 and 7.5, whereas the rocks with the lower DOP (group 2 and 3) are characterized by ΣLREE/Σ(M+H)REE ratios between 12.8 and 13.5. Negative Ce anomalies are either small or absent in all deposits, which is typical for reducing conditions.Thus, the Bazhenov Formation exemplifies the complex depositional conditions that influence the REE concentration in black shale. However, it is this very complexity that has contributed to the development of six separate depositional models (REE contents in ppm are given in brackets). (1) Phosphatic clayey-siliceous rocks of normal sections (367.95); (2) argillites of normal sections (130.73); (3) clayey-siliceous rocks of normal sections (85.97); (4) carbonate rocks, largely dolomites of normal sections (23.23); (5) silty argillites of anomalous sections (78.7) and (6) clayey-silt rocks of anomalous sections (19.66).  相似文献   

14.
The Upper Cretaceous Nakhlak epigenetic vein-type Pb(Ag) deposit is located 55 km northeast of the town of Anarak in Isfahan Province, Iran. The deposit contains 7 Mt of galena-barite ore with an average grade of 8.33% Pb, 0.38% Zn, and 72 ppm Ag. The ore mineralization occurs as stratabound, epigenetic, steeply dipping, east-west–trending veins in faulted- or fracture-controlled Upper Cretaceous Sadar carbonates. Galena and barite are the primary minerals. Minor sphalerite, tennantite-tetrahedrite, pyrite, and chalcopyrite occur as inclusions in galena. Cerussite with minor amounts of anglesite and plattnerite formed in the oxidized supergene zone. The ore and ore-related minerals were deposited in the hydrothermally dolomitized carbonate host rock containing saddle-shaped dolomite. Geochemically, the dolomitized carbonate host rocks are enriched in MgO, Fe2O3, MnO, Pb, Zn, and Ba, but depleted in CaO. The galena concentrate contains high values of Ag (932 ppm), Sb (342 ppm), Cu (422 ppm), As (91 ppm), and Zn (296 ppm); the presence of these trace elements indicates a low-temperature type of galena mineralization. This interpretation is corroborated by fluid inclusions containing 12.98 wt.% NaCl equivalent salinity; the inclusions homogenize at the low temperature of about 152.1 °C. The similarity between δ34S(V-CDT) values in Nakhlak barite and Permian–Triassic δ34S marine sulfate values indicates that the Nakhlak sulfur was probably provided from evaporates of Permian–Triassic age. The δ34S(V-CDT) values of galena and barite samples occupy the ranges of − 1.04‰ to + 8.62‰ and + 10.95‰ to + 13.71‰, respectively, and are similar to Mississippi Valley–type (MVT) deposits. The low-temperature basinal fluids, evaporate-originated sulfur, and fault- or fracture-controlled galena-rich veins in the Nakhlak deposit resemble the type of geological features documented in Pb-rich MVT deposits.  相似文献   

15.
Thick horizons of iron formations including Banded Iron Formations (BIFs) and Banded Silicate Formations (BSFs) occur as E–W trending bands in the eastern part of Cauvery Suture Zone (CSZ) in the Sothern Granulite Terrane of India. Some of these occur in close association with the Neoarchean-Neoproterozoic suprasubduction zone complexes, where as some others are associated with metamorphosed accretionary sequences including pyroxene granulites and other high grade rocks. The iron formations are highly deformed and metamorphosed under amphibolite to granulite facies conditions and are composed of quartz–magnetite–hematite–goethite–garnet–pyrite together with grunerite and pyroxene. Here we report the geochemical characteristics of twenty representative samples from the iron formations that reveal a widely varying composition with Fe2O3(t) (22–65 wt.% as total iron) total- Fe2O3/TiO2 (205–6532), MnO/TiO2 (0.25–12.66) and SiO2 (33–85 wt.%), broadly representing the two types of iron formations. These formations also show very low Al/(Al + Fe + Mn) ratio (0.001–0.01), Al2O3 (0.07–0.76 wt.%), Al2O3/TiO2 ratio (2.7–21), MgO (0.01–4.41 wt.%), CaO (0.1–1.24 wt.%), Na2O (0.01–0.05 wt.%) and K2O (0.01 wt.%) together with low total REE (3.38–31.63 ppm). The trace and REE elemental distributions show wide variation with high Ni (274 ppm), and Zn contents (up to 87 ppm) when compared to mafic volcanics of the adjoining areas. Tectonic discrimination plots indicate that the iron formations of the Cauvery Suture Zone are of hydrothermal origin. Their chondrite normalized patterns show slight positive Eu anomaly (Eu/Eu* = up to 1.77) and relatively less fractionation of REE with slight LREE enrichment compared to HREE. However, the PAAS (Post Archean Average of Australian Sediments) normalized REE patterns display significant positive Eu anomaly (Eu/Eu* up to 2.32) with well represented negative Ce anomalies (Ce/Ce* = 0.66–1.28). The above results together with petrological characteristics and available geochronology of the associated lithologies suggest that the iron formations can be correlated to Algoma-type. The Fe and Si were largely supplied by medium to high temperature sub-marine hydrothermal systems in Neoarchean and Neoproterozoic convergent margin settings.  相似文献   

16.
Through detailed studies we have delineated a suite of banded TTG gneisses from the Zanhuang Complex. The protolith of the gneisses, predominantly tonalite, has undergone intensive metamorphism, deformation and anatexis and in a banded structure is intimately associated with melanocratic dioritic gneiss and leucocratic trondhjemitic veins. SHRIMP Zircon U–Pb data show that the tonalite was formed ca. 2692 ± 12 Ma ago. The tonalitic gneiss has the features of high SiO2 (67.76–73.31%), high Al2O3 (14.38–15.83%), rich in Na2O (4.48–5.07%) and poor in K2O (0.77–1.93%). The gneiss is strongly fractioned in REE ((La/Yb)N = 12.02–24.65) and shows a weak positive Eu anomaly (Eu/Eu* = 1.05–1.64). It has high contents of Ba (199–588 ppm) and Sr (200–408 ppm), low contents of Yb (0.32–1.00 ppm) and Y (3.41–10.3 ppm) with high Sr/Y ratios (21.77–96.77) and depletion in HFSE Nb, Ta and Ti. These characteristics are similar to those of the high-Si adakitic rocks. The melanocratic dioritic gneiss has low SiO2 (59.81%), high MgO (6.34%), high Al2O3 (14.02%) contents, rich in Na2O (3.7%) and poor in K2O (1.79%), with high Mg index (Mg# = 67). REE and trace elements are on the whole similar to that of the tonalitic gneiss, but compatible element abundances V (116 ppm), Cr (249 ppm), Co (37 ppm) and Ni (179 ppm) are higher. The leucocratic felsic bands (approximating trondhjemite in composition) have major oxides similar to that of the TTG gneisses but the REE and compatible elements are extremely low, which are indicative of the products of anatexis. The tonalitic gneiss has positive εNd(t) (2.37–3.29) and low initial Sr (0.69719–0.70068) values with depleted mantle Nd model age of ca. 2.8 Ga, suggesting its generation from partial melting of mantle-derived juvenile crust. The dioritic gneiss was also derived from subduction environment, but has undergone significant metasomatism of mantle wedge. The delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex further proves that the North China Craton experienced large-scale continental crustal accretion in early Neoarchean, and gives new constraints on the subdivision of the early blocks and greenstone belts of the craton.  相似文献   

17.
The Dalucao deposit in western Sichuan Province, southwest China, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE Belt. Moreover, this is the only deposit identified in the southern part of the belt. The deposit contains the No. 1, 2, and 3 orebodies. The No. 1 and 3 orebodies are hosted in two breccia pipes within syenite–carbonatite rocks that intrude a Proterozoic quartz–diorite pluton. Both breccia pipes have elliptical horizontal cross-sections at the surface, being 200–400 m long, 180–200 m wide, and extending to > 450 m depth. The No. 1 and No. 3 orebodies have total thicknesses of 55–175 m and 14–58 m, respectively. REE mineralization is associated with four brecciation events that are recorded in both pipes. The ore grades in the No. 1 and 3 orebodies are similar, with the rocks containing 1.0–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a mineral assemblage comprising fluorite + barite + celestite + bastnäsite (i.e., Type I), whereas the No. 3 orebody is characterized by an assemblage comprising fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite (i.e., Type II). Significant amounts of weathered high-grade REE ore (up to 60 wt.% of the rock mass) is mainly present in the No. 1 orebody. This is the main ore-type targeted for exploration within the Dalucao deposit, but is rarely present in other deposits in the Mianning–Dechang REE Belt.Faulting and cryptoexplosive breccia events, possibly linked to movement on the Panxi Fault, were more common in the No. 1 orebody than in the No. 3 orebody. This facilitated the introduction of ore-forming hydrothermal fluids and provided space for the precipitation of REE minerals. Based on the present results, we infer that the Dalucao deposit was the product of multiple stages of ore formation. REE minerals formed in envelopes around, or fractures within, quartz, fluorite, calcite, barite, and celestite in the brecciated ores. The main REE minerals were deposited from hydrothermal fluids within cryptoexplosive breccia, followed by weathering that increased the ore grade. Petrographic studies and X-ray powder diffraction (XRD) analyses indicate that the weathered ore contains 5–60% REE minerals (including bastnäsite, parisite, and monazite), together with gangue (quartz, barite, celestite, and fluorite), large amount of clay minerals (smectite, illite, kaolinite, and sepiolite), and relict igneous minerals (quartz, albite, and K-feldspar). The weathered samples are strongly enriched in La (up to 92,390 ppm), Ce (up to 103,500 ppm), Pr (up to 8006 ppm), and Nd (up to 16,690 ppm) compared with the unweathered brecciated ores. Conversely, Sr concentrations are significantly more enriched in the brecciated ores (up to 256,500 ppm) than in the weathered ores (generally less than 2671 ppm with one exception of 37,850 ppm) due to less celestite. Calcite is largely absent from the weathered ores (except one sample with up to 30% mode), which contrasts with the brecciated ores that contain up to 75% calcite. The effects of weathering, oxidation, loss of ions, and hydration on the brecciated ores led to the refertilization of the REEs and an increase in the grade of the ore deposit.  相似文献   

18.
Copper, gold and molybdenum mineralization of the Kalmakyr porphyry deposit in Uzbek Tien Shan occurs as stockworks, veinlets and disseminations in the phyllic and K-silicate alteration zones developed predominantly in a middle to late Carboniferous intrusive complex composed of monzonite and granodiorite porphyry. Zircon U–Pb dating yielded an age of 327.2 ± 5.6 Ma for the ore-hosting monzonite and an age of 313.6 ± 2.8 Ma for the ore-bearing granodiorite porphyry. Re–Os dating of seven molybdenite samples from stockwork and veinlet ores yielded model ages from 313.2 to 306.3 Ma, with two well-constrained isochron ages of 307.6 ± 2.5 Ma (five stockwork ores) and 309.1 ± 2.2 Ma (five stockwork ores and two veinlet ores), respectively. These results indicate that Cu–Au mineralization post-dated the emplacement of the monzonite, started right after the emplacement of the granodiorite porphyry, and lasted for ca. 7 Ma afterward. The geochronological and geochemical data suggest that the Kalmakyr deposit was formed in a late Carboniferous mature magmatic arc setting, probably related to the latest subduction process of the Turkestan Ocean beneath the Middle Tien Shan. The εHf(t) values of zircon grains from the monzonite vary from +11 to +1.7, with an average of +5.1, and those of zircon grains from the granodiorite porphyry range from +5.7 to −1.8, with an average of +2.4. These data indicate that the magma of both monzonite and granodiorite porphyry was derived from partial melting of a thickened lower crust with input of mantle components and variable crustal contamination, and that there was more mantle contribution to the formation of the monzonite than the granodiorite porphyry. The high rhenium concentrations of molybdenite (98–899 ppm) also indicate major mantle contribution of rhenium and by inference ore metals. The relatively high EuN/EuN1 values (average 0.68), Ce4+/Ce3 values (average 890) and Ce/Nd values (average 36.8) for zircon grains from the granodiorite porphyry than those from the monzonite (average EuN/EuN1 = 0.33, average Ce4+/Ce3 = 624, average Ce/Nd = 3.9) suggest that the magma for the syn-mineralization granodiorite porphyry has higher oxygen fugacity than that for the pre-mineralization monzonite. Based on these data, it is proposed that while the monzonite was emplaced, the oxygen fugacity and volatile contents in the magma were relatively low, and ore metals might disperse in the intrusive rock, whereas when the granodiorite porphyry was emplaced, the oxygen fugacity and volatile contents in the magma were increased, favoring copper and gold enrichment in the magmatic fluids. The Kalmakyr deposit formed from a long-lived magmatic-hydrothermal system connected with fertile magmatic sources in relation to the subduction of the Turkestan Ocean beneath the Middle Tien Shan.  相似文献   

19.
The newly discovered Dadaoshan Sn deposit is located in the eastern Guangdong Sn–W province, coastal SE China. The Sn mineralization, hosted in Jurassic porphyritic granite and the Lower Jurassic Jinji Formation sedimentary wall rocks, is considered to be granite-related. In this study, the porphyritic granite was LA–ICP–MS zircon U–Pb dated to be 153.2 ± 1.2 Ma, consistent with the syn-mineralization molybdenite Re–Os age of 152.6 ± 1.8 Ma. The porphyritic granite samples are weakly peraluminous (A/CNK = 1.0–1.1) and high-K calc-alkaline. The rocks contain high SiO2 (72.9–75.6 wt%), moderate Rb/Sr (5–9) and low ΣREE (136–223 ppm). They are enriched in F, Li, Rb and Sn, depleted in Ba, Sr, P, Zr, Th, Nb and Y, and have distinct negative Eu anomalies (δEu = 0.09–0.18), suggesting that the porphyritic granite is highly fractionated I-type granite. The calculated initial 87Sr/86Sr (0.711582–0.715173), relatively low ɛNd(t) (−9.48 to −8.54; TDM2 = 1638–1814 Ma), and the zircon εHf(t) (−14.2 to −5.1; two-stage model ages = 1528–2103 Ma) all suggest that the granite was mainly crustal-derived with little mantle input. Sulfur isotopic compositions for the sulfides (arsenopyrite and chalcopyrite: δ34S = −1.1 to 1.4‰, average = −0.1) imply a dominantly magmatic sulfur source. The calculated zircon Ce4+/Ce3+ and EuN/EuN1 ratios of the Dadaoshan granite range from 1.0 to 112 (mean = 31.7) and from 0.04 to 0.37 (mean = 0.14), respectively, indicating a low oxygen fugacity for the magma. The reducing and highly fractionated nature of the Dadaoshan granitic magma may have played a key role in the Sn mineralization.It was previously argued that the Jurassic Sn–W mineralization and its causative magmatism were largely confined in the South China interior, e.g., the Nanling Range. Our new data suggest that the Late Jurassic Sn–W mineralization and its causative magmatism actually extended to the SE China coastal area. The Dadaoshan granite may have been generated from partial crustal melting led by underplating of mantle-derived magmas in an extensional environment. Regional extension may have been related to the west-directed, flat-slab subduction and delamination of the Paleo-Pacific (Izanagi) plate beneath the South China block. Another suite of Early Cretaceous Sn–W-bearing granitic rocks in eastern Guangdong may have mainly been crustal-derived with minor mantle input, and likely occurred under back-arc extensional setting led by the Paleo-Pacific subduction rollback.  相似文献   

20.
The Tieshan Fe–Cu deposit is located in the Edong district, which represents the westernmost and largest region within the Middle–Lower Yangtze River Metallogenic Belt (YRMB), Eastern China. Skarn Fe–Cu mineralization is spatially associated with the Tieshan pluton, which intruded carbonates of the Lower Triassic Daye Formation. Ore bodies are predominantly located along the contact between the diorite or quartz diorite and marbles/dolomitic marbles. This study investigates the mineral chemistry of magnetite in different skarn ore bodies. The contrasting composition of magnetite obtained are used to suggest different mechanisms of formation for magnetite in the western and eastern part of the Tieshan Fe–Cu deposit. A total of 178 grains of magnetite from four magnetite ore samples are analyzed by LA–ICP–MS, indicating a wide range of trace element contents, such as V (13.61–542.36 ppm), Cr (0.003–383.96 ppm), Co (11.12–187.55 ppm) and Ni (0.19–147.41 ppm), etc. The Ti/V ratio of magnetite from the Xiangbishan (western part of the Tieshan deposit) and Jianshan ore body (eastern part of the Tieshan deposit) ranges from 1.32 to 5.24, and 1.31 to 10.34, respectively, indicating a relatively reduced depositional environment in the Xiangbishan ore body. Incorporation of Ti and Al in magnetite are temperature dependent, which hence propose that the temperature of hydrothermal fluid from the Jianshan ore body (Al = 3747–9648 ppm, with 6381 ppm as an average; Ti = 381.7–952.0 ppm, with 628.2 ppm as an average) was higher than the Xiangbishan ore body (Al = 2011–11122 ppm, with 5997 ppm as an average, Ti = 302.5–734.8, with 530.8 ppm as an average), indicating a down–temperature precipitation trend from the Jianshan ore body to the Xiangbishan ore body. In addition, in the Ca + Al + Mn versus Ti + V diagram, magnetite is plotted in the skarn field, consideration with the ternary diagram of TiO2–Al2O3–MgO, proposing that the magnetite ores are formed by replacement, instead of directly crystallized from iron oxide melts, which provide a better understanding regarding the composition of ore fluids and processes responsible for Fe mineralization in the Tieshan Fe–Cu deposit.  相似文献   

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