Petrological and geochemical characteristics of Zhaibei granites in Nanling region,Southeast China: Implications for REE mineralization

Mineralization with ion adsorption rare earth elements (REEs) in the weathering profile of granitoid rocks from Nanling region of Southeast China is an important REE resource, especially for heavy REE (HREE) and Y. However, the Jurassic granites in Zhaibei which host the ion adsorption light REE (LREE) ores are rare. It is of peraluminous and high K calc-alkaline composition, which has similar geochemical features of high K₂O + Na₂O and Zr + Nb + Ce + Y contents and Ga/Al ratio to A-type granite. Based on the chemical discrimination criteria of Eby [Geology 20 (1992) 641], the Zhaibei granite belongs to A1-type and has similar source to ocean island basalts. The rock is enriched in LREE and contains abundant REE minerals including LREE-phosphates and halides. Minor LREE was also determined in the feldspar and biotite, which shows negligible and negative Eu anomalies, respectively. This indicates that the Zhaibei granite was generated by extreme differentiation of basaltic parent magmas. In contrast, granites associated with ion adsorption HREE ores contain amounts of HREE minerals, and show similar geochemical characteristics with fractionated felsic granites. Note that most Jurassic granitoids in the Nanling region contain no REE minerals and cannot produce REE mineralization. They belong to unfractionated M-, I- and S-type granites. Therefore, accumulation of REE in the weathering profile is controlled by primary REE mineral compositions in the granitoids. Intense fractional crystallization plays a role on REE enrichment in the Nanling granitoid rocks.     

黔西南高砷煤的元素地球化学特征

通过分析黔西南高砷煤的元素地球化学特征,探索高砷煤中微量元素、稀土元素的地球化学行为,从而揭示了高砷煤的形成机理。分析表明,高砷煤与非高砷煤在微量元素含量方面存在较大差异,金、汞、铊矿石与龙潭煤系中的砷具有同源性,龙潭煤系页岩与峨眉山玄武岩在稀土元素组成上具有继承性。     

黔西北上二叠统峨眉山玄武岩风化壳中铌富集机制初探

近年越来越多的研究显示,贵州西北一带的峨眉山玄武岩风化壳上存在一套富铌、锆、钛、镓、稀土的多金属矿层,主要与风化壳中的黏土岩有关,不过,其中有关铌的赋存状态和富集机制仍有待研究.文章对黏土岩物质来源做出厘定,认为风化壳黏土岩层主要来源于高钛的峨眉山玄武岩,铌、锆、稀土等元素也继承自玄武岩.铌主要赋存于铁铝质黏土岩中(w(Nb)100×10-6～250×10-6),含矿岩层中上部铌含量高,下部低,具体表现为w(Nb)自下而上,升高—(略微)降低—(再)升高的规律,尤以铁铝质黏土岩中铌含量最高.在峨眉山玄武岩喷发事件中,铌一方面随玄武岩喷出地表,在平缓低洼的盆地地带冷凝,另一方面酸性火山灰进入大气,形成酸雨并随之降落汇聚在先期成岩的低洼地区,形成酸性环境使原岩内的铌被侵蚀残留在原地.随着火山作用停止,酸雨不再产生,沉积环境中的水体因热水循环、海侵海退和大气降水与外界物质交换,酸性逐渐被中和乃至偏碱性,铌随黏土质沉积成岩,最终在玄武岩风化壳内富集.     

Geochemical and mineralogical characteristics of weathered ore in the Dalucao REE deposit,Mianning–Dechang REE Belt,western Sichuan Province,southwestern China

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.     

Nanhuan manganese deposits within restricted basins of the southeastern Yangtze Platform,China: Constraints from geological and geochemical evidence

The Nanhuan manganese deposits in the southeastern Yangtze Platform occur in the black shale series in the lower part of the Datangpo Formation. In order to constrain the genesis of the deposits, a detailed study was undertaken that involved field observations, major and trace element analyses, organic carbon analyses, and isotope analyses (C, O, S). The major findings are as follows. (1) The ore-bearing rock series, morphology of the ore bodies, and characteristics of ores in several deposits are similar. The ore minerals are rhodochrosite and manganocalcite. The gangue minerals are mainly quartz, feldspar, dolomite, and illite. Minor apatite and bastnaesite occur in the manganese ores. (2) The ores are enriched in Ca and Mg, whereas they are depleted in Si, Al, K, and Ti compared to wall rocks. The ores normalized to average Post-Archean Australian shale (PAAS) are enriched in Co, Mo, and Sr. The chondrite-normalized rare earth element (REE) patterns for ores and wall rocks are between those of typical hydrogenous and hydrothermal type manganese deposits. Additionally, the ores have positive Ce anomalies with an average Ce/Ce* of 1.23 and positive Eu anomalies with an average Eu/Eu* of 1.18 (normalized to PAAS). (3) The average content of organic carbon is 2.21% in the samples, and the average organic carbon isotopic value (δ¹³C_V-PDB) is − 33.44‰. The average inorganic carbon isotopic value (δ¹³C_V-PDB) of carbonates in Gucheng is − 3.07‰, while the values are similar in the other deposits with an average of − 8.36‰. The oxygen isotopic compositions (δ¹⁸O_V-PDB) are similar in different deposits with an average of − 7.72‰. (4) The sulfur isotopic values (δ³⁴S_V-CDT) of pyrite are very high and range from + 37.9‰ to + 62.6‰ (average of 52.7‰), which suggests that the pyrite was formed in restricted basins where sulfate replenishment was limited. The sulfate concentrations in the restricted basins were extremely low and enriched in δ³⁴S, which resulted in the very high δ³⁴S values for the pyrite that formed in the manganese deposits. Therefore, a terrigenous weathering origin for manganese can be excluded; otherwise, the sulfate would have been introduced into the basins together with terrigenous manganese, which would have decreased the δ³⁴S values of pyrites. The manganese, which originated from hydrothermal processes, was enriched in the restricted and anoxic basins, and then, it was oxidized to manganese oxyhydroxide in the overlying oxic waters whereby the products precipitated into the sediments. The manganese oxyhydroxide in the sediment was then reduced to Mn^2 + and released to the pore waters during the process of diagenesis. Some organic carbon was oxidized to CO₃^2 −, which made the depletion of ¹³C in manganese carbonates. Therefore, we suggest that the Nanhuan manganese deposits are hydrothermal–sedimentary/diagenetic type deposits.     

Nature and origin of the protolith succession to the Paleoproterozoic Serra do Navio manganese deposit,Amapa Province,Brazil

Until its closure in 1997, the Serra do Navio deposit, located in Amapá Province, Brazil, was one of the most important sources of high-grade manganese ore to the North American market. The high-grade manganese oxide ores were derived by lateritic weathering from metasedimentary manganese protoliths of the Serra do Navio Formation. The local geological context and nature of this protolith succession are not well understood, due to poor surface outcrop conditions, and intense deformation. However, based on similar age, regional tectonic setting and lithology the Paleoproterozoic volcanosedimentary succession that includes the Serra do Navio Formation is widely believed to be similar in origin and laterally equivalent to the Birimian Supergroup in West Africa. For the present investigation several diamond drill cores intersecting the protolith succession were studied. Detailed petrographic and whole rock geochemical studies permit distinction of two fundamental lithological groups comprising of a total of five lithotypes. Biotite schist and graphitic schist lithotypes are interpreted as former metapelites. A greywacke or pyroclastic protolith cannot be excluded for the biotite schist, whereas the graphitic schist certainly originated as a sulfide-rich carbonaceous mudstone. Rhodochrosite marble, Mn-calcite marble and Mn-silicate rock are grouped together as manganiferous carbonate rocks. Manganese lutite constitutes the most probable protolith for rhodochrosite marble, whereas Mn-calcite marble was derived from Mn-rich marl and Mn-silicate rock from variable mixtures of Mn-rich marl and chert.The sedimentary succession at the Serra do Navio deposit is similar to that encountered at many other black shale and chert-hosted Mn carbonate deposits. A metallogenetic model is proposed, predicting deposition of manganese and closely associated chert in intra-arc basins, in environments that were bypassed by distal siliciclastic (carbonaceous mud) and proximal pyroclastic/siliciclastic detritus. Positive Ce anomalies and δ¹³C_VPDB values of − 4.3 to − 9.4 per mill suggest that manganiferous carbonates derived during suboxic diagenesis from sedimentary Mn⁴⁺ oxyhydroxide precipitates. Metamorphic alteration of manganese carbonate–chert assemblages resulted in the formation of Mn-silicates, most importantly rhodonite and tephroite; porphyroblastic spessartine formed where Mn-carbonate reacted with aluminous clay minerals. Microthermometric studies of fluid inclusions in spessartine porphyroblasts suggests that peak metamorphic conditions reached the upper greenschist facies (1–2 kbars and 400–500 °C). Retrograde metamorphism is marked by partial re-carbonation, expressed by the formation of small volumes of rhodochrosite, and Mn-calcite that are closely associated with quartz, chlorite and minor amounts of sulfides related to post-metamorphic veinlets. It is this metamorphosed succession that sourced the high-grade manganese oxide ores during prolonged lateritic weathering.     

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.     

Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope,PGE, trace element,and REE geochemistry

The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ^98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ^98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 10⁷ compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.     

黔西北峨眉山玄武岩顶部Fe-Al岩系特征及其三稀元素富集特点

黔西北峨眉山玄武岩顶部普遍发育Fe-Al岩系。为查明峨眉山玄武岩顶部Fe-Al岩系特征,探讨其三稀元素富集特点,开展了针对峨眉山玄武岩顶部Fe-Al岩系的野外调查。调查结果显示: 当峨眉山玄武岩上覆地层分别为宣威组或龙潭组时,峨眉山玄武岩顶部风化壳Fe-Al岩系表现出明显差异。样品测试结果表明: Fe-Al岩系内Sc、Nb、REE等三稀元素含量丰富,具有很好的找矿前景,宣威组Fe-Al岩系内Sc、Nb、REE含量更高,尤其是Nb和REE。Fe-Al岩系内Sc、Nb、REE等三稀元素富集为峨眉山玄武岩风化初始富集和后期改造再次富集作用的结果。     

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.     

Importance of hydrogeological conditions during formation of the karstic bauxite deposits,Central Guizhou Province,Southwest China: A case study at Lindai deposit

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.     

Age and petrogenesis of Anisian magnesian alkali basalts and their genetic association with the Kafang stratiform Cu deposit in the Gejiu supergiant tin-polymetallic district,SW China

Gejiu is geographically located near Gejiu city, SW China. It is one of the largest tin-polymetallic districts in the world and contains approximately 3 million tons (Mt) of Sn and smaller quantities of Cu, Pb, and Zn. The deposit primarily yields three different types of ore: skarn-hosted ore, basalt-hosted stratiform ore, and carbonate-hosted stratiform ore. Kafang is one of the primary ore deposits in the Gejiu district and is an unusual occurrence hosted in basaltic rocks. Genetic models of the Kafang deposit suggest that it is related either to Anisian (Lower stage of Middle Triassic) Gejiu basalts or to Cretaceous Gejiu granite. In this study, we performed zircon SIMS U–Pb dating, major and trace element analyses, and Sr–Nd–Pb isotopic analyses for the Gejiu basalts and S isotopic analyses for stratiform Cu ore. Our results and previous studies are used to interpret the petrogenesis of the Gejiu basalts and the origin of the basalt-hosted stratiform Cu deposit. The SIMS zircon U–Pb analyses of the Gejiu basalts yield an age of 244.4 Ma. The trace element ratios of the Gejiu basalts are similar to those of ocean island basalt and have positive εNd(t) values (ranging from 0.6 to 2.5) and uniform (⁸⁷Sr/⁸⁶Sr)_i values (ranging from 0.70424 to 0.70488). These ratios are close to those of the Permian Emeishan flood basalt. Thus, the Gejiu basalts may represent coeval volcanisms within the plate involving remelting of the Emeishan plume head through a stress relaxation process after the main plume event. The Pb and S isotopic compositions of the Gejiu basalts and the stratiform Cu ores indicate that the source of Cu and S is primarily derived from the Gejiu basalts. However, the age of sulfide mineralization (84.2–79.6 Ma) and the age of hydrothermal alteration (85.5–81.9 Ma) are temporally consistent with the age of the Cretaceous granite emplacement (85.5–83.3 Ma). From a petrological and geochemical study, we determine that the Gejiu basalts may have been subjected to pervasive granite-related hydrothermal alteration during the emplacement of granite. These processes increase the K and Mg contents of basalt and probably caused the formation of the Cu ores. Thus, the Kafang stratiform Cu deposit can be considered as a granite-related hydrothermal deposit.     

Content and mode of occurrences of rare earth elements in the Zagrad karstic bauxite deposit (Nikšić area,Montenegro)

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.     

贵州威宁-赫章二叠系乐平统含铁、铝岩系的沉积环境及成矿元素富集特征

贵州威宁-赫章地区的二叠系乐平统宣威组第一段铁、铝岩系,是峨眉山玄武岩风化-沉积作用的产物.其中富集的稀土、稀有、稀散元素,与峨眉山玄武岩所处的构造位置和玄武岩风化的古地理位置有关.在六盘水裂陷槽区(B区),Cu、Ti、Sc、REE含量高,对应于六盘水裂陷槽复杂的地质环境;在裂陷槽边界西南,玄武岩剥蚀作用强烈,沉积层的厚度较薄,Nb、Ta和REE在强风化环境中富集;在裂陷槽边界北东,沉积厚度较大,Ga和V含量高,可能是沉积环境富集.风化作用是成矿有用组分富集的重要因素,它决定了稀土、稀有和稀散元素富集的趋势.有一些元素可以富集,达到工业利用价值,特别是Nb+ Ta,可能形成独立矿床.     

The pilot knob magnetite deposit in the Proterozoic St. Francois Mountains Terrane,southeast Missouri,USA: A magmatic and hydrothermal replacement iron deposit

The Pilot Knob magnetite deposit is located in southeast Missouri within the 1380–1480 Ma St. Francois Mountains terrane rhyolitic/trachytic volcanic rocks. The deposit is tabular, dips about 45°, and is sill-like in nature, being approximately parallel to the bedding in the host tuffs. The deposit was uncovered by erosion and exposed to weathering in the late Proterozoic, and is overlain in angular unconformity by the Cambrian Lamotte Sandstone. This Proterozoic weathering cycle apparently had little effect on the deposit with only the updip edge being converted to hematite. Textural and mineralogical features of the deposit suggest a combined magmatic and hydrothermal replacement origin. The magnetite-rich ores that make up the bulk of the deposit are interpreted as having crystallized from an iron-rich magma, and a surrounding envelope of lower- to moderate-grade ores where magnetite has clearly replaced the tuffaceous host rocks are interpreted as hydrothermal in origin. After the development of the higher-grade magnetite ores and the envelope of lower- to moderate-grade ores, late hydrothermal minerals were deposited as cross-cutting veins and breccia fill. The two most abundant minerals in the higher-grade portions of the deposit are magnetite and albitic plagioclase, and petrologically the higher-grade ores could be described as a magnetite sodic syenite. The most abundant gangue mineral within the lower-grade impregnated envelope of ores around the higher-grade ores is K-feldspar, apparently relict from the rhyolites/trachytes. Thin lenses within the higher-grade ores contain calcite as a matrix mineral to the magnetite and are considered to indicate carbonatitic affinity. Rare earth elements are elevated in one of five whole rock chemical analyses of the ores and the REE-bearing mineral ferriallanite has been identified. Minor portions of the deposit, below the Proterozoic weathering cap, consist of high-grade hematite ores having equilibrium textures. At depth, the deposit is intruded by the Shepherd Mountain gabbro, a 120 m thick, near-horizontal dike, which resulted in minor contact metamorphism of the ore.     

Development of unusual rock weathering features in the Cordillera Blanca,Peru

Mylonite textures in granodiorite boulders are responsible for higher rates of surface denudation of host rocks and the progressive development of unusual rock weathering features, termed weathering posts. These textures are characterized by smaller grain sizes, higher biotite content, and a higher biotite axial ratio in host rocks relative to weathering posts. Elemental concentrations do not show a significant difference between weathering posts and the host rocks in which they are found, and this reflects the absence of a weathering residue on the rock surfaces. Chemical weathering loosens the bonds between mineral grains through the expansion of biotite, and the loosened grains fall off or are blown off the boulder surface and continue their chemical alteration in the surrounding soil. The height of weathering posts on late Quaternary moraines increases at a linear rate of ~ 1.45 ± 0.45 cm (1000 yr)^? 1 until post heights reach the diameter of host rocks. Such a rate of boulder denudation, if unrecognized, would generate significant errors (> 20%) in cosmogenic exposure ages for Pleistocene moraines. Given the paucity of boulders with diameters that significantly exceed 1.5 m, the maximum age of utility of weathering posts as a numeric age indicator is ~ 100 ka.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: The Bayan Obo Fe-REE-Nb deposit,North China

The Bayan Obo Fe-REE-Nb deposit in northern China is the world's largest light REE deposit, and also contains considerable amounts of iron and niobium metals. Although there are numerous studies on the REE mineralization, the origin of the Fe mineralization is not well known. Laser ablation (LA) ICP-MS is used to obtain trace elements of Fe oxides in order to better understand the process involved in the formation of magnetite and hematite associated with the formation of the giant REE deposit. There are banded, disseminated and massive Fe ores with variable amounts of magnetite and hematite at Bayan Obo. Magnetite and hematite from the same ores show similar REE patterns and have similar Mg, Ti, V, Mn, Co, Ni, Zn, Ga, Sn, and Ba contents, indicating a similar origin. Magnetite grains from the banded ores have Al + Mn and Ti + V contents similar to those of banded iron formations (BIF), whereas those from the disseminated and massive ores have Al + Mn and Ti + V contents similar to those of skarn deposits and other types of magmatic-hydrothermal deposits. Magnetite grains from the banded ores with a major gangue mineral of barite have the highest REE contents and show slight moderate REE enrichment, whereas those from other types of ores show light REE enrichment, indicating two stages of REE mineralization associated with Fe mineralization. The Bayan Obo deposit had multiple sources for Fe and REEs. It is likely that sedimentary carbonates provided original REEs and were metasomatized by REE-rich hydrothermal fluids to form the giant REE deposit.     

Clay mineral variations in Holocene terrestrial sediments from the Indus Basin

We employed X-ray diffraction methods to quantify clay mineral assemblages in the Indus Delta and flood plains since ~ 14 ka, spanning a period of strong climatic change. Assemblages are dominated by smectite and illite, with minor chlorite and kaolinite. Delta sediments integrate clays from across the basin and show increasing smectite input between 13 and 7.5 ka, indicating stronger chemical weathering as the summer monsoon intensified. Changes in clay mineralogy postdate changes in climate by 5–3 ka, reflecting the time needed for new clay minerals to form and be transported to the delta. Samples from the flood plains in Punjab show evidence for increased chemical weathering towards the top of the sections (6–< 4 ka), counter to the trend in the delta, at a time of monsoon weakening. Clay mineral assemblages within sandy flood-plain sediment have higher smectite/(illite + chlorite) values than interbedded mudstones, suggestive of either stronger weathering or more sediment reworking since the Mid Holocene. We show that marine records are not always good proxies for weathering across the entire flood plain. Nonetheless, the delta record likely represents the most reliable record of basin-wide weathering response to climate change.     

Mineralogy,geochemistry and the origin of high-phosphorus oolitic iron ores of Aswan,Egypt

The Coniacian-Santonian high-phosphorus oolitic iron ore at Aswan area is one of the major iron ore deposits in Egypt. However, there are no reports on its geochemistry, which includes trace and rare earth elements evaluation. Texture, mineralogy and origin of phosphorus that represents the main impurity in these ore deposits have not been discussed in previous studies. In this investigation, iron ores from three localities were subjected to petrographic, mineralogical and geochemical analyses. The Aswan oolitic iron ores consist of uniform size ooids with snowball-like texture and tangentially arranged laminae of hematite and chamosite. The ores also possess detrital quartz, apatite and fine-grained ferruginous chamosite groundmass. In addition to Fe₂O₃, the studied iron ores show relatively high contents of SiO₂ and Al₂O₃ due to the abundance of quartz and chamosite. P₂O₅ ranges from 0.3 to 3.4 wt.% showing strong positive correlation with CaO and suggesting the occurrence of P mainly as apatite. X-ray diffraction analysis confirmed the occurrence of this apatite as hydroxyapatite. Under the optical microscope and scanning electron microscope, hydroxyapatite occurred as massive and structureless grains of undefined outlines and variable size (5–150 μm) inside the ooids and/or in the ferruginous groundmass. Among trace elements, V, Ba, Sr, Co, Zr, Y, Ni, Zn, and Cu occurred in relatively high concentrations (62–240 ppm) in comparison to other trace elements. Most of these trace elements exhibit positive correlations with SiO₂, Al₂O₃, and TiO₂ suggesting their occurrence in the detrital fraction which includes the clay minerals. ΣREE ranges between 129.5 and 617 ppm with strong positive correlations with P₂O₅ indicating the occurrence of REE in the apatite. Chondrite-normalized REE patterns showed LREE enrichment over HREE ((La/Yb)_N = 2.3–5.4) and negative Eu anomalies (Eu/Eu* = 0.75–0.89). The oolitic texture of the studied ores forms as direct precipitation of iron-rich minerals from sea water in open space near the sediment-water interface by accretion of FeO, SiO_2, and Al₂O₃ around suspended solid particles such as quartz and parts of broken ooliths. The fairly uniform size of the ooids reflects sorting due to the current action. The geochemistry of major and trace elements in the ores reflects their hydrogenous origin. The oolitic iron ores of the Timsha Formation represent a transgressive phase of the Tethys into southern Egypt during the Coniacian-Santonian between the non-marine Turonian Abu Agag and Santonian-Campanian Um Barmil formations. The abundance of detrital quartz, positive correlations between trace elements and TiO₂ and Al₂O₃, and the abundance mudstone intervals within the iron ores supports the detrital source of Fe. This prediction is due to the weathering of adjacent land masses from Cambrian to late Cretaceous. The texture of the apatite and the REE patterns, which occurs entirely in the apatite, exhibits a pattern similar to those in the granite, thus suggesting a detrital origin of the hydroxyapatite that was probably derived from the Precambrian igneous rocks. Determining the mode of occurrence and grain size of hydroxyapatite assists in the maximum utilization of both physical and biological separation of apatite from the Aswan iron ores, and hence encourages the use of these ores as raw materials in the iron making industry.     

A review of the genesis of the world class Bayan Obo Fe–REE–Nb deposits,Inner Mongolia,China: Multistage processes and outstanding questions

The Bayan Obo Fe–REE–Nb deposit is the world's largest rare earth element (REE) resource and with the increasing focus on critical metal resources has become a focus of global interest. The deposit is hosted in the Palaeoproterozoic Bayan Obo Group, mainly concentrated in the H8 dolomite marble. The ores consist of light REE enriched monazite and bastnäsite, with a wide array of other REE minerals. Niobium mineralisation is hosted primarily in aeschynite and pyrochlore, although there are a wide range of other Nb-minerals. The origin of the host dolomite and ore bodies has been a subject of intense debate. The host dolomite has been proposed to be both of sedimentary origin and an igneous carbonatite. Carbonatite dykes do occur widely in the area, and consideration of the textural, geochemical and isotopic composition of the dolomite suggests an origin via intrusion of magmatic carbonatite into meta-sedimentary marble, accompanied by metasomatism. The origin of the ore bodies is complex, indicated most strongly by an ~ 1 Ga range in radiometric age determinations. Compilation of available data suggests that the ores were originally formed around 1.3 Ga (Sm–Nd isochron ages; Th–Pb ages of zircon), close in time to the intrusion of the carbonatite dykes. The ores were subsequently subjected to several stages of deformation and hydrothermal overprint, culminating in deformation, metamorphism and fluid flow related to the Caledonian subduction of the Mongolian Plate under the North China Craton from ~ 450 to 420 Ma (Th–Pb ages of monazite). This stage resulted in the formation of the strong foliation (‘banding’) of the ore. The presence of undeformed veins with alkali mineral fills, and the overprinting of the foliation by Nb minerals suggest that secondary fluid flow events may also have contributed to the metal endowment of the deposits, as well as remobilising the original Fe and REE mineralisation. The alteration mineralogy and geochemistry of the ores are comparable to those of many REE mineralised carbonatites. Initial Nd isotope ratios at 450 Ma, however, suggest crustal sources for the metals. These conflicting lines of evidence can be reconciled if a (at least) two stage isotopic evolution is accepted for the deposits, with an original mantle-sourced, carbonatite-related metal accumulation forming around 1.3 Ga with εNd close to 0. The ore was remobilised, with associated re-equilibration of Th–Pb isotope systematics during deformation at ~ 450 Ma. A further stage of alkaline hydrothermal fluid was responsible for Nb mineralisation at this stage. The complex geological history, with multiple stages of alkaline, high field strength element-rich, metasomatic fluid flow, is probably the main reason for the exceptional metal endowment of the Bayan Obo area.