“寨背式”离子吸附型稀土矿床多类型稀土矿化及其成因

赣南寨背离子吸附型稀土矿床产于寨背复式花岗岩体的风化壳中,自20世纪80年代发现以来一直以轻稀土型开采,近年在轻稀土型花岗岩风化壳中发现了重稀土矿。为了探讨轻稀土型花岗岩风化过程中重稀土元素的迁移、分馏和富集机制,本文选择了区内三个具有代表性的风化壳钻孔(ZK1、ZK2和ZK4)对其进行了全相和离子交换相稀土元素地球化学研究。结果显示：钻孔ZK4中离子交换相稀土含量介于14.90×10^-6～835.8×10^-6之间,并富集轻稀土(LREE/HREE=2.28～10.78);钻孔ZK1中离子交换相稀土含量达1470×10^-6(9件样品均值),具有从轻稀土型向重稀土型过渡的配分特征(LREE/HREE=1.30～1.65),并且剖面自上而下显示轻、重稀土逐渐富集的趋势;钻孔ZK2中离子交换相稀土含量为492.4×10^-6(8件样品均值),自上而下稀土配分类型从轻稀土型过渡至重稀土型(LREE/HREE=0.43～2.25),且轻稀土富集在全风化层上部而重稀土则富集在下部。三个钻孔的Nb/Ta和Zr/Hf...     

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.     

Genesis of the Yuanlingzhai porphyry molybdenum deposit,Jiangxi province,South China: Constraints from petrochemistry and geochronology

The newly discovered Yuanlingzhai porphyry molybdenum (Mo) deposit in southern Jiangxi province belongs to the group of Mo-only deposits in the Nanling region. The mineralization developed at contact zones between the Yuanlingzhai granite porphyry and Neoproterozoic metamorphic rocks of the Xunwu Formation. Precise LA–MC–ICPMS zircon U–Pb dating of the Yuanlingzhai porphyry, as well as the adjacent western Keshubei and eastern Keshubei granites, yielded ages of 165.49 ± 0.59 Ma, 159.68 ± 0.43 Ma, and 185.13 ± 0.52–195.14 ± 0.63 Ma, respectively. Molybdenite Re–Os isochron ages of the ores are 160 ± 1–162.7 ± 1.1 Ma, which is consistent with the age of large-scale W–Sn deposits in South China. The Yuanlingzhai porphyry is characterized by high K₂O, P₂O₅, and A/CNK (1.33–1.59), and low CaO and Na₂O. The rock shows relatively enriched LREE without significant Eu anomalies (Eu/Eu^* = 0.80–0.90). Geochemical and mineralogical characteristics indicate that the ore-hosting porphyry is a typical S-type granite generated from the partial melting of crustal material with only minor mantle contribution. Both Harker and evolutionary discrimination diagrams indicate that the Yuanlangzhai and western Keshubei granites are not products of co-magmatic evolution. The Keshubei granites and Xunwu Formation were not significant sources for the components in the porphyry mineralization, but the Yuanlangzhai granite may have supplied some ore-forming material. However, the main ore-forming material was carried by fluids from deep sources, as demonstrated by fluid inclusion and stable isotope data from the molybdenum deposit. The Mo porphyry deposit formed in an extensional setting, and was possibly associated with Jurassic subduction of the Izanagi Plate.     

REE mineralogy and geochemistry of the Western Keivy peralkaline granite massif,Kola Peninsula,Russia

The authors have studied the geology, geochemistry, petrology and mineralogy of the rare earth elements (REE) occurring in the Western Keivy peralkaline granite massif (Kola Peninsula, NW Russia) aged 2674 ± 6 Ma. The massif hosts Zr- and REE-rich areas with economic potential (e.g. the Yumperuaiv and Large Pedestal Zr-REE deposits), where 25% of ΣREE are represented by heavy REE (HREE). The main REE minerals are: chevkinite-(Ce), britholite-(Y) and products of their metamict decay, bastnäsite-(Ce), allanite-(Ce), fergusonite-(Y), monazite-(Ce), and others. The areas contain also significant quantities of zircon reaching potentially economic levels. We have discovered that behavior of REE and Zr is controlled by alkalinity of melt/solution, which, in turn, is controlled by crystallization of alkaline pyroxenes (predominantly aegirine) and amphiboles (predominantly arfvedsonite) at a late magmatic stage. Crystallization of mafic minerals leads to a sharp increase of K₂O content and decrease of SiO₂ content that cause a decrease of melt viscosity and REE and Zr solubility in the liquid. Therefore, REE and zirconium immediately precipitate as zircon and REE-minerals. There are numerous pod- and lens-like granitic pegmatites within the massif. Pegmatites in the REE-rich areas are also enriched in REE, but HREE prevails over light REE (LREE), about 88% of REE sum.     

Mesoproterozoic arc magmatism in SE India: Petrology,zircon U–Pb geochronology and Hf isotopes of the Bopudi felsic suite from Eastern Ghats Belt

The southern segment of the Eastern Ghats Mobile Belt (EGMB) in India was an active convergent margin during Mesoproterozoic, prior to the final collision in Neoproterozoic during the assembly of the Rodinia supercontinent. Here we present mineralogical, whole-rock geochemical, zircon U–Pb and Hf isotopic data from a granitoid suite in the Bopudi region in the EGGB. The granitoid complex comprises quartz monzodiorite with small stocks of rapakivi granites. The monzodiorite, locally porphyritic, contains K-feldspar megacrysts, plagioclase, quartz, biotite and ortho-amphibole. The presence of mantled ovoid megacrysts of alkali feldspar embaying early-formed quartz, and the presence of two generations of the phenocrystic phases in the rapakivi granites indicate features typical of rapakivi granites. The K-feldspar phenocrysts in the rapakivi granite are mantled by medium-grained aggregates of microcline (Ab₇ Or₉₃), which is compositionally equivalent to the rim of Kfs phenocryst and Pl (An_23–24 Ab₇₅). The geochemistry of both the granitoids shows arc-like features for REE and trace elements. LA-ICP-MS zircon analyses reveal ²⁰⁷Pb/²⁰⁶Pb ages of 1582 (MSWD = 1.4) for the rapakivi granite 1605 ± 3 Ma (MSWD = 3.9) for the monzodiorite. The zircons from all the granitoid samples show high REE contents, prominent HREE enrichment and a conspicuous negative Eu anomaly, suggesting a common melt source. The zircons from the monzodiorite have a limited variation in initial ¹⁷⁶Hf/¹⁷⁷Hf ratios of 0.28171–0.28188, with εHf(t) values of −2.2 to +2.8. Correspondingly, their two-stage Hf isotope model ages (T_DM2) ranging from 2.15 to 2.47 Ga probably suggest a mixed source for the magma involving melting of the Paleoproterozoic basement and injection of subduction-related juvenile magmas. The prominent Mesoproterozoic ages of these granitoids suggest subduction-related arc magmatism in a convergent margin setting associated with the amalgamation of the Columbia-derived fragments within the Neoproterozoic Rodinia assembly.     

Chronology,geochemistry and Sr–Nd isotope studies of Jurassic intrusions in the Diyanqinamu porphyry Mo mine,central Inner Mongolia,China

Available cores of porphyritic granite and aplitic granite from the Diyanqinamu porphyry Mo deposit in the north central Great Xing’an Range presented an opportunity to examine and analyze Mesozoic igneous rocks far from the Paleo-Pacific subduction zone. The Diyanqinamu granites are highly fractionated I-type, distinguished from the M-, A- or S-type granite by: high SiO₂, and Rb; low Zr, Nb, Y, and Ce; low Fe₂O₃^total/MgO and (K₂O + Na₂O)/CaO ratios; low alumina saturation index (<1.1); low initial I_Sr ratios (0.70137–0.70451); positive εNd(t) values (2.37–3.77); and negative correlation between P₂O₅ and SiO₂. The aplitic granites were generated by fractional crystallization of the porphyritic granite, as evidenced by: spatial proximity; consistent zircon U–Pb ages (156 Ma) within error; correlations between other oxides and SiO₂ in Haker diagrams; low Ba, Sr, Nb, P, Ti, Eu; linear relationship in both (La/Yb)_N vs. La and Sr vs. Ba diagrams; and, decreasing LREE and ∑REE with increasing SiO₂. The Diyanqinamu granites have young depleted-mantle two-stage model ages (avg. T_DM2 = 660 Ma) similar to those of most Mesozoic voluminous felsic magmas in northeastern China, and were likely sourced from pre-existent crustal components both “old” and juvenile that had been juxtaposed during the tectonic evolution of the Paleo-Asian Ocean. These granites project in the transitional field from syn-collision to post-collision tectonic settings on tectonic discrimination diagrams, implying emplacement in an extensional environment. Extensional volcanism and basin formation in the Great Xing’an Range region in Late Jurassic is coeval with the Diyanqinamu granites, demonstrating that post-orogenic lithospheric extension related to the closure of the Mongol-Okhotsk Ocean was the main driving force for Late Jurassic magmatism in this region.     

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 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.     

Petrogenesis of the Nanling Mountains granites from South China: Constraints from systematic apatite geochemistry and whole-rock geochemical and Sr–Nd isotope compositions

The widespread Mesozoic granitoids in South China (∼135,300 km²) were emplaced in three main periods: Triassic (16% of the total surface area of Mesozoic granitoids), Jurassic (47%), and Cretaceous (37%). Though much study has been conducted on the most abundant Jurassic Nanling Mountains (NLM) granites, their rock affinities relative to the Triassic Darongshan (DRS) and Cretaceous Fuzhou–Zhangzhou Complex (FZC) granites which are typical S- and I-type, respectively, and the issue of their petrogenetic evolution is still the subject of much debate. In this study, we discuss the petrogenesis of NLM granites using apatite geochemistry combined with whole-rock geochemical and Sr–Nd isotope compositions. Sixteen apatite samples from six granite batholiths, one gabbro, and three syenite bodies in the NLM area were analyzed for their major and trace element abundances and compared with those collected from DRS (n = 7) and FZC (n = 6) granites. The apatite geochemistry reveals that Na, Si, S, Mn, Sr, U, Th concentrations and REE distribution patterns for apatites from DRS and FZC granites basically are similar to the S and I granite types of the Lachlan Fold Belt (Australia), whereas those from NLM granites have intermediate properties and cannot be correlated directly with these granite types. According to some indications set by the apatite geochemistry (e.g., lower U and higher Eu abundances), NLM apatites appear to have formed under oxidizing conditions. In addition, we further found that their REE distribution patterns are closely related to aluminum saturation index (ASI) and Nd isotope composition, rather than SiO₂ content or degree of differentiation, of the host rock. The majority of apatites from NLM granites (ASI = 0.97–1.08 and εNd(T) = −8.8 to −11.6) display slightly right-inclined apatite REE patterns distinguishable from the typical S- and I-type. However, those from few granites with ASI > 1.1 and εNd(T) < −11.6 have REE distribution patterns (near-flat) similar to DRS apatites whereas those from granites with ASI < 1.0 and εNd(T) > −6.6 and gabbro and syenite are similar to FZC apatites (strongly right-inclined). In light of Sr and Nd isotope compositions, magmas of NLM intrusives, except gabbro and syenite, and few granites with εNd(T) > −8, generally do not involve a mantle component. Instead, they fit with a melt derived largely from in situ melting or anatexis of the pre-Mesozoic (mainly Caledonian) granitic crust with subordinate pre-Yanshanian (mainly Indosinian) granitic crust. We suggest that an application, using combined whole-rock ASI and εNd(T) values, is as useful as the apatite geochemistry for recognizing possible sources for the NLM granites.     

Mechanism of mineralization in the Changjiang uranium ore field,South China: Evidence from fluid inclusions,hydrothermal alteration,and H–O isotopes

The Changjiang uranium ore field, which contains >10,000 tonnes of recoverable U with a grade of 0.1–0.5%, is hosted by Triassic two-mica and Jurassic biotite granites, and is one of the most important uranium ore fields in South China. The minerals associated with alteration and mineralization can be divided into two stages, namely syn-ore and post-ore. The syn-ore minerals are primarily quartz, pitchblende, hematite, hydromica, chlorite, fluorite, and pyrite; the post-ore minerals include quartz, calcite, fluorite, pyrite, and hematite. The fluid inclusions of the early syn-ore stage characteristically contain O₂, and those of the late syn-ore and post-ore stage contain H₂ and CH₄. The fluid inclusions in quartz of the syn-ore stage include H₂O, H₂O–CO₂, and CO₂ types, and they occur in clusters or along trails. Homogenization temperatures (T_h) for the H₂O–CO₂ and two-phase H₂O inclusions range from 106 °C to >350 °C and cluster in two distinct groups for each type; salinities are lower than 10 wt% NaCl equiv. The ore-forming fluids underwent CO₂ effervescence or phase separation at ∼250 °C under a pressure of 1000–1100 bar. The U/Th values of the altered granites are lowest close to the ore, increase outwards, but subsequently decrease close to unaltered granites. From the unaltered granites to the ore, the lowest Fe₂O₃/FeO values become lower and the highest values higher. The REE patterns of the altered granites and the ores are similar to each other. The U contents of the ores show a positive correlation with total REE contents but a negative correlation with LREE/HREE ratios, indicating the pitchblende is REE-bearing and selectively HREE-rich. The δEu values of the ore show a positive correlation with U contents, indicating the early syn-ore fluids were oxidizing. The δCe values show a negative correlation, indicating the later mineralization environment became reducing. The water–rock interactions of the early syn-ore stage resulted in oxidization of altered granites and reduction of the ore-forming fluids, and it was this reduction that led to the uranium mineralization. During alteration in the early syn-ore stage, the oxidizing fluids leached uranium from granites close to faults, and Fe₂O₃/FeO ratios increased in the alteration zones. The late syn-ore and post-ore alteration decreased the Fe₂O₃/FeO ratios in the alteration zones. The δ¹⁸O_W–SMOW values of the ore-forming fluids range from −1.8‰ to 5.4‰, and the δD_W–SMOW values range from −104.4‰ to −51.6‰, suggesting meteoric water. The meteoric water underwent at least two stages of water–rock interaction: the first caused the fluids to become uranium-bearing, and the second stage, which was primarily associated with ore-bearing faults, led to uranium deposition as pitchblende, accompanied by CO₂ effervescence.     

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.     

Arc magmatism in the Delhi Fold Belt: SHRIMP U–Pb zircon ages of granitoids and implications for Neoproterozoic convergent margin tectonics in NW India

The northwestern region of Peninsular India preserves important records of Precambrian plate tectonics and the role of Indian continent within Proterozoic supercontinents. In this study, we report precise SHRIMP zircon U–Pb ages from granitoids from the Sirohi terrane located along the western fringe of the Delhi Fold Belt in Rajasthan, NW India. The data reveal a range of Neoproterozoic ages from plagiogranite of Peshua, foliated granite of Devala, and porphyritic granite of Sai with zircon crystallization from magmas at 1015 ± 4.4 Ma, 966.5 ± 3.5 and 808 ± 3.1 respectively. The plagiogranite shows high SiO₂, Na₂O and extremely low K₂O, Rb, Ba, comparable with typical oceanic plagiogranites. These rocks possess low LREE and HREE concentrations and a relatively flat LREE–HREE slope, a well-developed negative Eu-anomaly and conspicuous Nb and Ti anomalies. Compared to the plagiogranite, the foliated Devala granite shows higher SiO₂ and moderate Na₂O, together with high K₂O and comparatively higher Rb, Ba, Sr and REE, with steep REE profiles and a weak positive Eu anomaly. In contrast to the plagiogranite and foliated granite, the porphrytic Sai granite has comparatively lower SiO₂ moderately higher Na₂O, extremely high Y, Zr, Nb and elevated REE. The geochemical features of the granitoids [HFSE depletion and LILE enrichment, Nb- and Ta-negative anomalies], and their plots in the fields of Volcanic Arc Granites and those from active continental margins in tectonic discrimination diagrams suggest widespread Neoproterozoic arc magmatism with changing magma chemistry in a protracted subduction realm. Our results offer important insights into a long-lived active continental margin in NW India during early and mid Neoproterozoic, consistent with recent similar observations on Cryogenian magmatic arcs widely distributed along the margins of the East African Orogen, and challenge some of the alternate models which link the magmatism to extensional tectonics associated with Rodinia supercontinent breakup.     

Paleofluids circulation associated with the Gerês late-orogenic granitic massif,northern Portugal

The Hercynian late-orogenic granites from the Gerês massif, northern Portugal, underwent intense hydrothermal activity along tectonic structures striking N-S and NE-SW. The first hydrothermal stage is characterized by the albitization of feldspars (primary K-feldspar and plagioclase) followed by the dissolution of magmatic quartz, the chloritization of biotite, and the muscovitization of magmatic biotite and feldspars and occasionally of authigenic albite. Whole-rock geochemistry shows a decrease of SiO₂, K₂O and Rb and an increase of Na₂O, Al₂O₃ and Sr amounts during the albitization. The second hydrothermal stage is characterized by a mineral assemblage consisting of secondary quartz, albite, chlorite, hematite, apatite, muscovite, epidote, sphene and carbonates, which infilled the cavities produced by the early quartz leaching.Mass balance calculations demonstrate a noticeable element mobilization during the granite alteration. The average ∑REE of the Gerês granite is nearly constant at 154 ppm, but ranges from 91 to 163 ppm in the altered rocks. A relative LREE depletion and a slight HREE enrichment associated with a negative Eu anomaly characterize the feldspathization process of Gerês granite. The average ∑REE of the Carris granite is at 159 ppm but in the altered epidote + chlorite + hematite assemblage it reaches about 201 ppm with a slight HREE increase.Two different fluids were involved in the hydrothermal alteration. A first aqueous fluid (Lw₁), with a low to intermediate salinity (<10 wt.% eq. NaCl) circulated along the main structures (N-S, NE-SW and NW-SE), characterized by entrapment temperature lower than 350 °C and maximum pressure of 115 MPa followed by a later colder and more saline fluid (Lw₂) under a temperature of 220 °C and a pressure of about 27 MPa.Oxygen isotope data obtained on magmatic quartz indicate δ¹⁸O_quartz of + 9.3 and + 11.0‰, pointing to an interaction of magmatic fluids with others of meteoric origin. For the secondary quartz, δ¹⁸O_water of +0.5 and +0.7‰ were calculated for a temperature of 250 °C, suggesting a meteoric fluid with a possible seawater signature.The K-Ar data of K-feldspar from the altered rocks confirm an age of 273.6 ± 11.7 Ma, attributed to the first alteration process. Younger K-Ar ages between 155.8 ± 6.7 Ma and 124 ± 5.3 Ma were also obtained in the feldspathized rocks, confirming the late hydrothermal activity.Albitization and quartz dissolution of granitic rocks from the Gerês massif occurred at depths shallower than 5 km, induced by the circulation of fluids along brittle structures, during the orogenic uplift and extensional tectonics which affected the Iberian Massif in the Early Permian. A second major event is attributed to late hydrothermal circulations of aqueous brines until a depth of about 3 km, presumably derived from interaction with sub-surface evaporites throughout Late Jurassic to Early Cretaceous. These late hydrothermal events probably reflect the rifting episodes and the rising of geothermal gradient, associated with the opening of the Atlantic Ocean and Gulf of Biscay, respectively.     

Recurrent rare earth element mineralization in the northwestern Okcheon Metamorphic Belt,Korea: SHRIMP U–Th–Pb geochronology,Nd isotope geochemistry,and tectonic implications

Rare earth element (REE) mineralization is hosted within Neoproterozoic alkaline metaigneous rocks in the northwestern part of the Okcheon Metamorphic Belt (OMB), a polymetamorphosed fold-and-thrust belt transecting the Paleoproterozoic Gyeonggi and Yeongnam Massifs in the southern Korean Peninsula. The principal carrier phase of REEs is allanite. Allanite grains can be subdivided into several types based on the texture and mineral assemblage including quartz, K-feldspar, biotite, britholite, apatite, fergusonite, andradite, magnetite, zircon, titanite and fluorite. Electron microprobe analysis of allanite clearly distinguishes sample-to-sample variations in total REEs, Ca, Al, Fe and Y but the textural varieties from each rock sample do not show marked differences in those elements. Sensitive high-resolution ion microprobe dating of allanite and zircon reveals a complex history of multistage mineralization. Allanite grains from REE ores yielded Late Ordovician (444.6 ± 8.0 Ma), Permian to Triassic (ca. 300–220 Ma) and Early Jurassic (199–183 Ma) ²⁰⁸Pb/²³²Th ages. These multiple age components often coexist in single grains showing slight differences in backscattered electron brightness. The Ordovician components have distinctly higher Th/U than the younger domains in the same rock sample. The cores and rims of zircon from a syenite hosting REE ore bodies yielded Neoproterozoic (858.2 ± 6.3 Ma) and Early Jurassic (ca. 190 Ma) ²⁰⁶Pb/²³⁸U ages, respectively. The Early Jurassic ages (194–187 Ma) also obtained from zircon grains from granites taken from dykes occurring close to the ores and a drill core indicate the correspondence between granitic magmatism and REE mineralization. The Neoproterozoic zircon inheritance (weighted mean = 853.9 ± 3.8 Ma) in these granites is in sharp contrast to the dominant Paleoproterozoic inherited zircon from the widespread earliest Middle Jurassic granites enclosing the mineralized zone. The geotectonic significance of the Late Ordovician event recorded in the allanite, as well as in detrital zircon from the OMB, is still unclear but its temporal coincidence with intraplate volcanism and arc-related igneous activity, respectively, reported from the southwestern edge of the adjacent Taebaeksan Basin and the southwestern Gyeonggi Massif is noteworthy. The following Permian–Triassic and Early Jurassic mineralization events are probably linked to the continental suturing between the North and South China blocks and subsequent post-orogenic magmatism, and arc magmatism resulting from the paleo-Pacific plate subduction, respectively. Sub-grain Sm–Nd isotopic analyses of allanite by laser ablation multiple collector ICPMS yielded initial ε_Nd values plotting along the Nd isotopic evolution path of the Neoproterozoic metaigneous rocks, indicating that REEs originating from the host rock have been recycled during multistage mineralization events. The profound differences in inherited zircon ages and Nd isotopic compositions between the Early and Middle Jurassic granites may reflect the presence of a major thrust-bounded crustal structure beneath the OMB.     

Are South China granites special in forming ion-adsorption REE deposits?

Ion-adsorption REE deposits associated with clay minerals are the main global HREE producer. The majority of these deposits are formed by the weathering of granites in South China, but whether there is any fundamental difference between the granites in and outside South China is still unclear. Besides, an effective evaluation system of granite mineralization potential is urgently needed for HREE exploration.To answer this question, we compiled a global granite geochemical dataset from within (n = 1932) and outside (n = 6109) South China, together with a dataset of representative REE deposits in South China (n = 128). The geochemical comparation shows that the South China granites share similar REE contents with those of many granites from places outside South China. Such similarity has also been found between REE ore-related and ore-barren granites in South China. This shows that granites from outside South China could also have ore-forming potential. Warm humid climate and quasi-equalized crustal state promote chemical weathering to continuously leach REEs and store them in the weathering crust. The enrichment ratio (Rx) can be used to quantify the climatic effect between orebodies and parent rocks. The calculated average Enrichment Ratios (Rx) of LREE- and HREE-rich deposits are 2.41 and 2.68, respectively. Sufficient REE content in granite is the prerequisite for mineralization, and we propose that the combination of the minimum REE + Y (172 and 108 ppm in LREE- and HREE-rich parent rocks, respectively) and REE oxide ratio (1.32) can reveal the granite metallogenic potential. Together with the suitable tropical and temperate climate area with ion-adsorption REE deposits, we further identified certain regions with high REE mineralization potential outside South China to assist future exploration.     

Zircon U–Pb,molybdenite Re–Os and muscovite Ar–Ar isotopic dating of the Xitian W–Sn polymetallic deposit,eastern Hunan Province,South China and its geological significance

The Xitian tungsten–tin (W–Sn) polymetallic deposit, located in eastern Hunan Province, South China, is a recently explored region containing one of the largest W–Sn deposits in the Nanling W–Sn metallogenic province. The mineral zones in this deposit comprise skarn, greisen, structurally altered rock and quartz-vein types. The deposit is mainly hosted by Devonian dolomitic limestone at the contact with the Xitian granite complex. The Xitian granite complex consists of Indosinian (Late Triassic, 230–215 Ma) and Yanshanian (Late Jurassic–Early Cretaceous, 165–141 Ma) granites. Zircons from two samples of the Xitian granite dated using laser ablation-inductively coupled mass spectrometer (LA-ICPMS) U–Pb analysis yielded two ages of 225.6 ± 1.3 Ma and 151.8 ± 1.4 Ma, representing the emplacement ages of two episodic intrusions of the Xitian granite complex. Molybdenites separated from ore-bearing quartz-veins yielded a Re–Os isochron age of 149.7 ± 0.9 Ma, in excellent agreement with a weighted mean age of 150.3 ± 0.5 Ma. Two samples of muscovites from ore-bearing greisens yielded ⁴⁰Ar/³⁹Ar plateau ages of 149.5 ± 1.5 Ma and 149.4 ± 1.5 Ma, respectively. These isotopic ages obtained from hydrothermal minerals are slightly younger than the zircon U–Pb age of 151.8 ± 1.4 Ma of the Yanshanian granite in the Xitian area, indicating that the W–Sn mineralization is genetically related to the Late Jurassic magmatism. The Xitian deposit is a good example of the Early Yanshanian regional W–Sn ore-forming event (160–150 Ma) in the Nanling region. The relatively high Re contents (8.7 to 44.0 ppm, average of 30.5 ppm) in molybdenites suggest a mixture of mantle and crustal sources in the genesis of the ore-forming fluids and melts. Based upon previous geochemical studies of Early Yanshanian granite and regional geology, we argue that the Xitian W–Sn polymetallic deposit can be attributed to back-arc lithosphere extension in the region, which was probably triggered by the break-off of the flat-slab of the Palae-Pacific plate beneath the lithosphere.     

A crustal source for ca. 165 Ma post-collisional granites related to mineralization in the Jianglang dome of the Songpan-Ganzi Orogen,eastern Tiebtan Plateau

The Wenjiaping and Wulaxi granite plutons are located in the Jianglang dome, which is a key domain for providing deep insight into the tectonic evolution of the Songpan-Ganzi Orogen. Two granites are composed chiefly of K-feldspar, quartz, biotite with minor plagioclase and hornblende. This study presents zircon U-Pb chronology, geochemistry and Hf isotope data to explore their petrogenesis and metallogenic implications. Zircon U-Pb dating provides crystallization ages of 164.5 ± 0.9 Ma and 163.4 ± 0.9 Ma for the Wenjiaping granite, and 164.3 ± 1.7 Ma for the Wulaxi granite. This indicates that they were formed synchronously. They also contain inherited zircons related to the Rodinia and Gondwana supercontinents and the Emeishan large igneous province. Their mineral assemblages lack peraluminous (e.g., garnet and cordierite) and high-temperature (e.g., pyroxene and fayalite) minerals. They are characterized by low A/CNK (1.10–0.99), FeO^T/MgO (8.55–2.83) and K₂O/N₂O ratios (1.34–0.51) with low Zr + Nb + Ce + Y concentrations (average 258 ppm) and zircon saturation temperatures (781–651 °C). Their Al₂O₃, P₂O₅ and SiO₂ contents show negative correlations, and they thus fit the I-type granite definition. Some major and trace elements exhibit strong correlations, implying extensive fractional crystallization (e.g., hornblende and ilmenite) during the magma evolution. Two granites show enrichment in light rare earth elements and large ion lithophile elements, and depletion in high field strength elements. They have low Mg^# values (38.7–17.3) and Y/Nb ratios (0.45–0.16), and yield dominantly negative ε_Hf(t) values (1.4–−13.9), indicating a heterogeneous source and their derivation from remelting of ancient continental crust (e.g., Mesoproterozoic Liwu Group in this region) with minor juvenile crust. Combined with prior studies, we conclude that the Wenjiaping and Wulaxi granites were formed in a post-collisional extensional regime, and were responsible for the 163.7–151.1 Ma magmatic hydrothermal Cu-W mineralization in the Jianglang dome. In addition, two granite plutons intrude this dome and they are undeformed, implying that the doming was during the Early to Middle Jurassic.     

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.     

REE Mineralization of Weathered Crust and Clay Sediment on Granitic Rocks in the Sanyo Belt,SW Japan and the Southern Jiangxi Province,China

Rare earth element (REE) geochemistry and mineralogy have been studied in the weathered crusts derived from the Early Yanshanian (Jurassic) biotite granites of Dabu and Dingnan, as well as in the Indosinian (Permian) muscovite–biotite granite of Aigao in southern Jiangxi province, China, and the weathered crusts and clay sediments on biotite granites in the Sanyo belt, SW Japan, that is, Okayama, Tanakami, and Naegi areas. In all of the weathered crusts, biotite and plagioclase commonly tend to decrease toward the upper part of the profile, whereas kaolinite and residual quartz and K‐feldspar increase. The weathered crusts of the Dingnan granites and some Naegi granites, which are characterized by the enrichment in light REE (LREE) in C horizons, have higher total REE (ΣREE) content than the parent REE‐enriched granites. Weathering of LREE‐bearing apatite and fluorocarbonates in the Dingnan granites and allanite and apatite in some Naegi granites may account for the leaching of LREE at the B horizons. The leached LREE must result in subsequent enrichment of LREE in the C horizons. The enrichment is probably associated with mainly adsorption onto kaolinite and partly formation of possible secondary LREE‐bearing minerals. In Japan it was found that REE mineralization occurs not in the weathered granitic crusts but in reworked clay sediments, especially kaolinite‐rich layers, derived mainly from the weathering materials of REE‐enriched granitic rocks. The clay sediments are more enriched in LREE, which likely adsorbed onto kaolinite. Concentration of heavy REE within almost all the weathered crusts and clay sediments, however, may reflect mainly residual REE‐bearing minerals such as zircon, which originated in the parent granitic rocks. The findings of the present study support the three processes for fractionation of the REE during weathering: (i) selective leaching of rocks containing both stable and unstable REE‐bearing minerals; (ii) adsorption onto clay minerals; and (iii) presence of possible secondary LREE‐bearing minerals.     

In situ zircon U–Pb and Hf–O isotopic results for ca. 73 Ma granite in Hainan Island: Implications for the termination of an Andean-type active continental margin in southeast China

We report in the paper integrated analyses of in situ zircon U–Pb ages, Hf–O isotopes, whole-rock geochemistry and Sr–Nd isotopes for the Longlou granite in northern Hainan Island, southeast China. SIMS zircon U–Pb dating results yield a crystallization age of ∼73 Ma for the Longlou granite, which is the youngest granite recognized in southeast China. The granite rocks are characterized by high SiO₂ and K₂O, weakly peraluminous (A/CNK = 1.04–1.10), depletion in Sr, Ba and high field strength elements (HFSE) and enrichment in LREE and large ion lithophile elements (LILE). Chemical variations of the granite are dominated by fractional crystallization of feldspar, biotite, Ti–Fe oxides and apatite. Their whole-rock initial ⁸⁷Sr/⁸⁶Sr ratios (0.7073–0.7107) and ε_Nd(t) (−4.6 to −6.6) and zircon ε_Hf(t) (−5.0 to 0.8) values are broadly consistent with those of the Late Mesozoic granites in southeast China coast. Zircon δ¹⁸O values of 6.9–8.3‰ suggest insignificant involvement of supracrustal materials in the granites. These granites are likely generated by partial melting of medium- to high-K basaltic rocks in an active continental margin related to subduction of the Pacific plate. The ca. 73 Ma Longlou granite is broadly coeval with the Campanian (ca. 80–70 Ma) granitoid rocks in southwest Japan and South Korea, indicating that they might be formed along a common Andean-type active continental margin of east–southeast Asia. Tectonic transition from the Andean-type to the West Pacific-type continental margin of southeast China likely took place at ca.70 Ma, rather than ca. 90–85 Ma as previously thought.