Impact of former mining activities on the uranium distribution in the River Saale (Germany)

In the lower part of the River Saale, Germany, U shows concentrations of up to 4 μg/L. Former mining activities and their still existing dewatering systems in the drainage basin of the River Saale are responsible for the high salt and trace metal concentrations in the water of some tributaries. An old adit from the Mansfeld mining district flowing into the Schlenze Stream with mean U concentrations of about 60 μg/L increases the U concentration of the River Saale by 0.5 μg/L. The U concentrations in the running waters of the study area can be explained by mixing processes. Uranium from the adit and the Schlenze is mainly transported in the <0.45 μm fraction as a carbonate complex.     

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

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

Post-collisional carbonatite-hosted rare earth element mineralization in the Hongcheon area,central Gyeonggi massif,Korea: Ion microprobe monazite U‐Th‐Pb geochronology and Nd‐Sr isotope geochemistry

The Hongcheon area in the central Gyeonggi massif is a unique carbonatite locality in South Korea. The age and petrogenesis of this uncommon rock type and associated rare earth element (REE) mineralization still remain uncertain. The NNE trending, 20–50 m wide and ~ 2 km long Fe-REE ore bodies are hosted within a swarm of carbonatite dykes intruding Precambrian basement gneisses. The intrusive nature of the dykes, fenite alteration halos, exsolution intergrowths of constituent minerals and stable isotope data in the literature collectively attest to the ore formation by crystallization of carbonatite magma. The carbonatites are composed primarily of dolomite, ankerite, siderite, magnetite, monazite, apatite, strontianite and pyrite with subordinate quartz, barite, columbite, fergusonite and calcite. The principal carrier phase of REEs is monazite. The REE contents of monazite vary narrowly (TREO = 66.1–69.4 wt.%) irrespective of the textural occurrence. Although the monazite shows a sample-to-sample variation in La/Nd ratio, the textural varieties from each rock sample are similar with respect to this ratio. Thorium contents in monazite are consistently low (average = ca. 2500 ppm) with unusually high (average = ca. 2200) Th/U ratios. Sensitive high-resolution ion microprobe (SHRIMP) dating of monazite yielded a weighted mean ²⁰⁸Pb/²³²Th age of 232.9 ± 1.6 Ma, which agrees with a weighted mean ²⁰⁶Pb/²³⁸U age of 227.2 ± 8.3 Ma within uncertainties. This age, coupled with comparable intrusion ages documented for kimberlites and monzonite-syenite-gabbro-mangerite suite from central Korea, demonstrates the occurrence of mantle-derived alkaline igneous activities and associated REE mineralization following the North and South China collision. The intrusion of the Hongcheon carbonatite and potassic or ultrapotassic suite in central Korea may have resulted from the post-collisional detachment of the subducted slab and consequent upwelling of hot asthenosphere and melting of the overriding lithospheric mantle. Initial Nd‐Sr isotopic ranges of the Hongcheon carbonatite (ε_Nd = ca. − 26, ⁸⁷Sr/⁸⁶Sr = 0.703–0.706) and previous trace element data deny a petrogenetic linkage with the coeval silicate magmas. The metasomatism in the lithospheric mantle source of the Hongcheon carbonatite must have occurred in the distant past (> 1.7 Ga) to generate significantly negative ε_Nd values.     

Monazite stability,composition and geochronology as tracers of Paleoproterozoic events at the eastern margin of the East European Craton (Taratash complex,Middle Urals)

The Precambrian Taratash complex (Middle Urals) is one of the rare windows into the Palaeoproterozoic and earlier history of the eastern margin of the East European Craton. Monazite from intensively deformed rocks within a major amphibolite-facies shear zone in the Taratash complex has been investigated by means of electron-probe microanalysis and laser-ablation SF-ICP-MS.Metamorphic and magmatic cores of monazite from metasedimentary and metagranitoid rocks yield U–Pb ages of 2244 ± 19 and 2230 ± 22 Ma (± 2 σ) and record a previously unknown pre-deformational HT-metamorphic event in the Taratash complex. Subsequent dissolution–reprecipitation of monazite, during shear zone formation under amphibolite-facies conditions, caused patchy zonation and chemical alteration of the recrystallised monazite domains, leading to higher cheralite and huttonite components. This process, which was mediated by a probable (alkali + OH)-bearing metamorphic fluid also caused a total resetting of the U–Pb-system. The patchy domains yield concordant U–Pb-ages between 2052 ± 16 and 2066 ± 22 Ma, interpreted as the age of the shear zone. In line with previously published ages of high grade metamorphism and migmatisation, the data may point to a Palaeoproterozoic orogenic event at the eastern margin of the East European Craton.Post-deformational fluid-induced greenschist-facies retrogression caused partial to complete breakdown of monazite to fluorapatite, REE + Y-rich epidote, allanite and Th-orthosilicate.The retrograde assemblages either form coronas around monazite, or occur as dispersed reaction zones, indicating that the REE, Y, and Th were mobile at least on the thin section scale. The greenschist-facies metamorphic fluid was aqueous and rich in Ca. Monazite affected by advanced breakdown responded to the retrogression by incorporating the cheralite or huttonite components during a fluid-induced dissolution–reprecipitation process. This event did not reset the U–Pb-system but caused partial Pb loss reflected by discordant U–Pb-dates.     

CHIME dating of monazite,xenotime, zircon and polycrase: Protocol,pitfalls and chemical criterion of possibly discordant age data

This paper outlines the CHIME (chemical Th–U-total Pb isochron method) dating method, which is based on precise electron microprobe analyses of Th, U and Pb in Th- and U-bearing accessory minerals such as monazite, xenotime, zircon and polycrase. The age-mapping technique that is applicable to young monazite and zircon is also described. CHIME dating consists of analyzing multiple spots within homogeneous age domains that show sufficient compositional variation, and then these data are used to construct a “pseudo-isochron” from which an age can be obtained via regression. This method, when coupled with discrimination of possibly concordant age data by chemical criteria such as the (Ca + Si)/(Th + U + Pb + S) ratio for monazite and Ca and S contents for zircon, has the potential advantage of significant precision, and the ability to work with minerals that have a significant initial common Pb component. This technique can identify two or more homogeneous domains that are separated by age gaps smaller than the error on individual spot age analysis. Many features that are insignificant in major element analysis can have major impact in the acquisition of trace element data. Critical factors include the roles of collimator slit, detector gas, background estimation, accelerating voltage, probe current, X-ray interferences and count rate in affecting the accuracy, and a way to apply the Th and U interference correction without pure Th- and U-oxides or synthesized pure ThSiO₄. The age-mapping procedure for young monazite and zircon includes acquiring PbMα (or PbMβ) intensity of individual pixels with multiple spectrometers, correcting background with background maps computed from a measured background intensity by the intensity relationships determined in advance of the measurement, calibrating of intensity with standards and calculating of ages from the Th, U and Pb concentrations. This technique provides age maps that show differences in age domains on the order of 20 Ma with in monazite as young as 100 Ma. The effect of sample damage by irradiation of intense and prolonged probe measurement is also described.     

An improved EPMA analytical protocol for U-Th-Pbtotal dating in xenotime: Age constraints from polygenetic Mangalwar Complex,Northwestern India

EPMA U-Th-Pb_total dating in U- and Th bearing minerals (e.g., monazite, zircon, and xenotime) is a low-cost and reliable technique used for retrieving age information from detrital, diagenetic and low to high-T metamorphic, as well as magmatic rocks. Although, the accuracy on measured ages obtained using EPMA is considered to be poor compared to isotopic ages, the superior spatial resolution, ability to integrate textural and age information by in-situ measurement, lack of sample damage and easier and cheaper data generation in EPMA make chemical dating a very valuable tool to decipher diverse petrological processes.This contribution presents an improved analytical protocol to obtain precise estimates of U, Th and Pb concentrations in xenotime. Results were tested on monazite standard (Moacyr pegmatite, Brazil; TIMS age: 487 ± 1 Ma) as the reference material. The proposed analytical protocol has been successfully applied to achieve an analytical uncertainty of less than 10% in U, Th and Pb measurements in xenotime. The protocol was further used to resolve polygenetic xenotime ages (ca. 1.82, 1.28 and 0.93 Ga) in metapelite samples from the Mangalwar Complex, Northwestern India. Monazites in the same samples were also analyzed and found to preserve the two younger ages (i.e., ca. 1.28 and 1.0 Ga). The obtained ages from the xenotime and monazite very well corroborate with the earlier published ages from the area validating the proposed analytical protocol.     

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.     

Assessment of trace metal and rare earth elements contamination in rivers around abandoned and active mine areas. The case of Lubumbashi River and Tshamilemba Canal,Katanga, Democratic Republic of the Congo

Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (I_geo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg⁻¹ for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.     

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.     

Source,transport, and fate of rhenium,selenium, molybdenum,arsenic, and copper in groundwater associated with porphyry–Cu deposits,Atacama Desert,Chile

We collected groundwaters in and around a large (313 Mt at 1.08% Cu and 0.3% cutoff) undisturbed porphyry copper deposit (Spence) in the hyperarid Atacama Desert of northern Chile, which is buried beneath 30–180 m of Miocene piedmont gravels. Groundwaters within and down-flow of the Spence deposit have elevated Se (up to 800 μg/l), Re (up to 31 μg/l), Mo (up to 475 μg/l) and As (up to 278 μg/l) concentrations compared to up-flow waters (interpreted to represent regional groundwater flow). In contrast, Cu is only elevated (up to 2036 μg/l) in groundwaters recovered from within the deposit; Cu concentrations are low down gradient of the deposit. The differential behavior of the metals/metalloids occurs because the former group dissolves as anions, enhancing their mobility, whereas the base metals dissolve as cations and are lost from solution most likely through adsorption to clay surface exchange sites and through formation of secondary copper chlorides, carbonates, and oxides. Most groundwaters within and down-flow of the deposit have Eh–pH values around the Fe^II/Fe^III phase boundary, limiting the impact of Fe-oxyhydroxides on oxyanions mobility. Se, Re, Mo, and As are all mobile (with filtered/unfiltered samples ～ 1) to the limit of sampling 2 km down gradient from the deposit. The increase in ore-related metals, metalloids, and sulfate and decrease in sulfate–S isotope ratios (from values similar to regional salars, + 4 to + 8‰ δ³⁴S_CDT to lower values closer to hypogene sulfides, + 1 to + 4‰ δ³⁴S_CDT) is consistent with active water–rock reactions between saline groundwaters and the Spence deposit. It is likely that hypogene and/or supergene sulfides are being oxidized under the present groundwater conditions and mineral saturation calculations suggest that secondary copper minerals (antlerite, atacamite, malachite) may also be actively forming, suggesting that supergene and exotic copper mineralization is possible even under the present hyperarid climate of the Atacama Desert.     

Dehydration and melting during continental collision: Constraints from element and isotope geochemistry of low-T/UHP granitic gneiss in the Dabie orogen

A combined study of petrography, whole-rock major and trace elements as well as Rb?Sr and Sm?Nd isotopes, and mineral oxygen isotopes was carried out for two groups of low-T/UHP granitic gneiss in the Dabie orogen. The results demonstrate that metamorphic dehydration and partial melting occurred during exhumation of deeply subducted continent. Zircon δ¹⁸O values of ? 2.8 to + 4.7‰ for the gneiss are all lower than normal mantle values of 5.3 ± 0.3‰, consistent with ¹⁸O depletion of protolith due to high-T meteoric-hydrothermal alteration at mid-Neoproterozoic. Most samples have extremely low ⁸⁷Sr/⁸⁶Sr ratios at t₁ = 780 Ma, but very high ⁸⁷Sr/⁸⁶Sr ratios at t₂ = 230 Ma. This suggests intensive fluid disturbance due to the hydrothermal alteration of protoliths during Neoproterozoic magma emplacement and the metamorphic dehydration during Triassic continental collision. Rb–Sr isotopes, Th/Ta vs. La/Ta and Th/Hf vs. La/Nb relationships suggest that Group I gneiss experienced lower degrees of hydrothermal alteration, but higher degrees of dehydration, than Group II gneiss. The two groups of gneiss have similar patterns of REE and trace element partition. Group I gneiss displays good correlations between Nb and LREEs but no correlations between Nb and LILEs (Rb, Ba, Pb, Th and U), indicating differential mobilities of LILEs during the dehydration. Thus the correlation between Nb and LREEs is inherited from protolith rather than caused by metamorphic modification. Relative to Group I gneiss, Group II gneiss has stronger negative Eu anomaly, lower contents of Sr and Ba but higher contents of Rb, Th and U. In particular, Nb correlates with LILEs (e.g., Rb, Sr, Ba, Th and U), but not with LREEs (La and Ce). This may indicate decoupling between the dehydration and LILEs transport during continental collision. Furthermore, dehydration melting may have occurred due to breakdown of muscovite during “hot” exhumation. Group II gneiss has extremely low contents of FeO + MgO + TiO₂ (1.04 to 2.08 wt.%), high SiO₂ contents of 75.33 to 78.23 wt%, and high total alkali (Na₂O + K₂O) contents (7.52 to 8.92 wt.%), comparable with compositions predicted from partial melting of felsic rocks by experimental studies. Almost no UHP metamorphic minerals survived; felsic veins of fine-grain minerals occurs locally between coarse-grain minerals, resulting in a kind of metatexite migmatites due to dehydration melting without considerable escape of felsic melts from the host gneiss. In contrast, Group I gneiss only shows metamorphic dehydration. Therefore, the two groups of gneiss show contrasting behaviors of fluid–rock interaction during the continental collision.     

Integrated U–Pb and Sm–Nd geochronology for a REE-rich carbonatite dyke at the giant Bayan Obo REE deposit,Northern China

The Bayan Obo deposit in North China contains the largest rare-earth element (REE) resources in the world, but its forming time remains controversial. Nearly one hundred carbonatite dykes occur around the Bayan Obo deposit, including dolomite, calcite and calcite–dolomite carbonatite varieties. Zircons from a REE-rich carbonatite dyke and wallrock quartz conglomerate at Bayan Obo have been analyzed for U–Pb to determine the age of the dyke. Zircon from the carbonatite dyke, analyzed by conventional isotope dilution thermal ionization mass spectrometry (ID-TIMS), yielded an upper intercept age of 1417 ± 19 Ma. This age is confirmed by SHRIMP U–Pb analysis of zircon from the same carbonatite dyke, which gave a ²⁰⁷Pb/²⁰⁶Pb weighted mean age of 1418 ± 29 Ma. In situ Nd isotope measurements of monazite collected from the carbonatite dyke gave an isochron age of 1275 ± 87 Ma. These results demonstrate that the dyke intruded ~ 1400 Ma. In view of predecessor's results, it is clarified that the REE mineralization at Bayan Obo occurred at ca. 1400 Ma, consistent with the timing of carbonatite dyke intrusion in the region. The youngest detrital zircons from the quartz conglomerate yielded a ²⁰⁷Pb/²⁰⁶Pb weighted mean age of 1941 ± 7 Ma using LA ICP-MS U–Pb method. Detrital zircons in the carbonatite dyke also gave a mean apparent age of 1932 ± 3 Ma using ID-TIMS U–Pb method and 1914 ± 14 Ma using SHRIMP U–Pb method. These ages constrain the beginning active time of the Zha'ertai–Bayan Obo rift in the northern margin of the North China Craton after ~ 1900 Ma.     

Ion microprobe U–Th–Pb geochronology and study of micro-inclusions in zircon from the Himalayan high- and ultrahigh-pressure eclogites,Kaghan Valley of Pakistan

We report ion microprobe U–Th–Pb geochronology of in situ zircon from the Himalayan high- and ultrahigh-pressure eclogites, Kaghan Valley of Pakistan. Combined with the textural features, mineral inclusions, cathodoluminescence image information and the U–Th–Pb isotope geochronology, two types of zircons were recognized in Group I and II eclogites. Zircons in Group I eclogites are of considerably large size (>100 μm up to 500 μm). A few grains are euhederal and prismatic, show oscillatory zoning with distinct core–rim luminescence pattern. Several other grains show irregular morphology, mitamictization, embayment and boundary truncations. They contain micro-inclusions such as muscovite, biotite, quartz and albite. Core or middle portions of zircons from Group I eclogites yielded concordant U–Th–Pb age of 267.6 ± 2.4 Ma (MSWD = 8.5), have higher U and Th contents with a Th/U ratio > 1, indicating typical magmatic core domains. Middle and rim or outer portions of these zircons contain inclusions of garnet, omphacite, phengite and these portions show no clear zonation. They yielded discordant values ranging between 210 and 71 Ma, indicating several thermal or Pb-loss events during their growth and recrystalization prior to or during the Himalayan eclogite-facies metamorphism. Zircons in Group II eclogites are smaller in size, prismatic to oval, display patchy or sector zoning and contain abundant inclusions of garnet, omphacite, phengite, quartz, rutile and carbonates. They yielded concordant U–Th–Pb age of 44.9 ± 1.2 Ma (MSWD = 4.9). The lower U and Th contents and a lower Th/U ratio (<0.05) in these zircons suggest their formation from the recrystallization of the older zircons during the Himalayan high and ultrahigh-pressure eclogite-facies metamorphism.     

Nd–Hf–Sr–Pb isotopes and trace element geochemistry of Proterozoic lamproites from southern India: Subducted komatiite in the source

The probable sources of some of the famous Indian diamonds are the 1.2 Ga old Krishna lamproites of Southern India, a rare Proterozoic occurrence of lamproites which are usually Cretaceous or younger in age. In this study we report Nd, Sr, Pb and Hf isotopes and multiple trace element concentrations of the Krishna lamproites. The goals are to evaluate mantle-processes and the petrogenesis of these ultrapotassic rocks of extreme chemical composition in light of these geochemical data, including their major element compositions.The Krishna lamproites show nearly uniform, parallel rare earth element (REE) distribution patterns with high concentrations and extreme light-REE enrichment (La/Yb_(N) = 41–88), high average concentrations of Ba (∼ 1200 ppm), Sr (∼ 1200 ppm), Zr (∼ 930 ppm), La (∼ 230 ppm), high U/Pb and Th/U ratios with notable absence of any Eu-anomaly. These rocks are typically porphyritic without any evidence of crystal accumulation, and have moderately high Mg-numbers (59–73) along with high Ni (average ∼ 301 ppm, highest 819 ppm) and Cr (average ∼ 183 ppm, highest 515 ppm) concentrations that show a positive correlation with MgO (wt.%), implying a role of olivine in the melt source. The low SiO₂ content (lowest 37.8%, average 49%) and high Nb (average 147 ppm), Zr, Sr, as well as Ni and Cr in these rocks indicate lack of upper continental crustal contribution in the genesis of these rocks. The initial Pb-isotopic composition of these lamproites is unusual in that in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb plot, these rocks plot to the left of the 1.2 Ga geochron (age of emplacement), unlike most mantle-derived rocks. This Pb-isotopic signature and the superchondritic Nb/Ta ratios (average 23.6) of these rocks rule out their derivation from a metasomatized sub-continental lithospheric mantle. The high ²⁰⁷Pb/²⁰⁴Pb at low ²⁰⁶Pb/²⁰⁴Pb indicates an Archean component in the source of these rocks. We argue that this Archean crustal component, which produced the low-SiO₂ lamproites along with the high Ni and Cr must have been ultrabasic, and we propose a model in which these lamproites formed by partial melting of metasomatized, subducted Archean komatiite in a peridotite mantle-source assemblage. In addition, these rocks display initial Hf isotopic compositions similar to Al-depleted komatiites, and high Nb/U, Nb/Th, and TiO₂ as well as low Al₂O₃/TiO₂ ratios (1.1–4.2) and average CaO/Al₂O₃ of ∼ 1.6 that are also similar to Archean komatiites. This is also supported by the initial Pb isotopic composition of the Krishna lamproites, requiring evolution in a variably high U/Pb, Th/Pb reservoir early in earth history, possibly resulting from preferential segregation of Pb relative to U and Th in the sulfides of the komatiite.The Al-depleted subducted komatiitic component was enriched by carbonate metasomatism in the peridotitic mantle. This metasomatism was responsible for the observed Nd–Hf isotope characteristics, specifically variable ε_Nd(T) at relatively constant ε_Hf(T) in the lamproites. This Nd–Hf-isotopic characteristic seems to be common in global lamproites of all ages. Our proposed model for the genesis of the Krishna lamproites involving a subducted komatiitic source may also be applicable for other global lamproites from cratonic settings, as older komatiite-bearing subducted crustal components were possibly ubiquitous in the architecture of ancient cratonic mantle.     

Geochemical and mineralogical evidence for a coal-hosted uranium deposit in the Yili Basin,Xinjiang, northwestern China

The petrological, geochemical, and mineralogical compositions of the coal-hosted Jurassic uranium ore deposit in the Yili Basin of Xinjiang province, northwestern China, were investigated using optical microscopy and field emission-scanning electron microscopy in conjunction with an energy-dispersive X-ray spectrometer, as well as X-ray powder diffraction, X-ray fluorescence, and inductively coupled plasma mass spectrometry. The Yili coal is of high volatile C/B bituminous rank (0.51–0.59% vitrinite reflectance) and has a medium sulfur content (1.32% on average). Fusinite and semifusinite generally dominate the maceral assemblage, which exhibits forms suggesting fire-driven formation of those macerals together with forms suggesting degradation of wood followed by burning. The Yili coals are characterized by high concentrations of U (up to 7207 μg/g), Se (up to 253 μg/g), Mo (1248 μg/g), and Re (up to 34 μg/g), as well as As (up to 234 μg/g) and Hg (up to 3858 ng/g). Relative to the upper continental crust, the rare earth elements (REEs) in the coals are characterized by heavy or/and medium REE enrichment. The minerals in the Yili coals are mainly quartz, kaolinite, illite and illite/smectite, as well as, to a lesser extent, K-feldspar, chlorite, pyrite, and trace amounts of calcite, dolomite, amphibole, millerite, chalcopyrite, cattierite, siegenite, ferroselite, krutaite, eskebornite, pitchblende, coffinite, silicorhabdophane, and zircon. The enrichment and modes of occurrence of the trace elements, and also of the minerals in the coal, are attributed to derivation from a sediment source region of felsic and intermediate petrological composition, and to two different later-stage solutions (a U–Se–Mo–Re rich infiltrational and a Hg–As-rich exfiltrational volcanogenic solution). The main elements with high enrichment factors, U, Se, As, and Hg, overall exhibit a mixed organic–inorganic affinity. The uranium minerals, pitchblende and coffinite, occur as cavity-fillings in structured inertinite macerals. Selenium, As, and Hg in high-pyrite samples mainly show a sulfide affinity.     

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.     

Geochemistry of Archean Radioactive Quartz Pebble Conglomerates and Quartzites from western margin of Singhbhum-Orissa Craton,eastern India: Implications on Paleo-weathering,provenance and tectonic setting

Lenses of radioactive Quartz Pebble Conglomerates (QPC) and associated quartzites are exposed along western margin of Archean Bonai Granite in Singhbhum-Orissa Craton, eastern India intermittently spreading over a strike length of 8–10 km. QPCs are radioactive while quartzites are mostly non-radioactive in nature. The purpose of the research is to investigate and characterize the radioactive QPC and quartzites geochemically to decipher their paleo-weathering conditions, provenance characteristics and possible tectonic setting of deposition. Geochemical data suggest moderate to high chemical weathering conditions in the provenance areas of QPC and quartzites. Major, trace and REE data indicate predominantly felsic to partly mafic-ultramafic sources for the deposition of radioactive Quartz Pebble Conglomerates from the surrounding Archean terrain.Elevated values of Th, U, Pb, La, Ce, Y and low Sc with high critical trace elemental ratios of Th/Sc, La/Sc, Th/Cr and Zr/Sc in radioactive QPC indicate their derivation from felsic igneous source. Low concentration of Th and Sc in quartzites compared to QPC and their variable Th/Sc ratios indicate both felsic and mafic sources for quartzites, albeit their preferential felsic affiliation. Higher Cr/Th ratios in quartzites (18.4), moderate Cr/Th in QPC (5.42), low to moderate Y/Ni in QPC (0.36–12.4) and quartzite (0.29–1.88), along with Au ranging from 30 to 1527 ppb, Pt up to 188 ppb and 682 ppb in QPC and quartzites respectively point towards some contribution from mafic-ultramafic source as well. REE patterns and in particular negative Eu anomalies for both QPC and quartzites further support their derivation from felsic rocks and could possibly linked to some of the phases of Archean Singhbhum Granite and Bonai Granite. Granitic to pegmatitic source for QPC is also revealed by the presence of rounded to sub-rounded monazite, zircon and thorian-uraninite grains in their matrix. Study indicates that QPC and quartzites were deposited in a passive margin tectonic setting developed during Archean between a span of 3.3 and 3.16 Ga along the western margin of Bonai Granite when the reducing condition was prevalent as indicated by their low Th/U ratios (<4.0) and presence of detrital grains of uraninite and pyrite in QPC. Radioactive QPC from western margin of Archean Singhbhum-Orissa Craton bears broad resemblance with QPC from Witwatersrand basin of South Africa and Elliot Lake, Canada and thus appears to be ideal sites for exploring QPC hosted U (+Au-PGE) mineralization in the analogous areas.     

Relationship among titanium,rare earth elements,U–Pb ages and deformation microstructures in zircon: Implications for Ti-in-zircon thermometry

A zircon grain in an orthopyroxene–garnet–phlogopite–zircon–rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal–plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U–Pb ages from more deformed zones (mean age of 1799 ± 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 ± 65 Ma, n = 7), and indicate that open system behaviour of Ti–Th–U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (< 5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U–Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.     

Contributions of zircon U–Pb geochronology to understanding the volcanic and sedimentary history of some Purāna basins,India

In this century, U–Pb ages of magmatic and detrital zircons, together with a few less accurate but fairly robust ages determined on monazite and baddeleyite, in the Purāna successions in India have established a few firm timelines that constrain the opening, closure, inversion, and provenance of the Purāna basins. The Cuddapah basin opened shortly before ca. 1900 Ma, the Vindhyan basin opened before ca. 1630 Ma, the Khariar basin likely opened ca. 1500 Ma, and the Chhattisgarh basin opened ca. 1400 Ma. The Marwar basin opened after ca. 750 Ma. The Chhattisgarh basin began to invert at ca. 1000 Ma and closed shortly thereafter. The Indravati and the Vindhyan basins closed ca. 1000 Ma. There are no other defensible geochronologic data to adequately constrain the opening and closure of other Purāna basins (e.g., Kaladgi, Badami, Bhima, Kurnool, Mallampalli, Albaka, Ampani, Sabari, and Kolhan). Neither the fossil record nor the biostratigraphy of these basins necessarily correspond to the chronology determined through radiometric measurements.The discovery of ca. 1000 Ma volcanic events in the Indravati and Chhattisgarh basins adds to the growing list of ca. 1000 Ma thermal disturbances in the Indian shield. Most of these events were likely the far field effects of the final assembly of Rodinia.     

Monazite CHIME/EPMA dating of Erinpura granitoid deformation: Implications for Neoproterozoic tectono-thermal evolution of NW India

The in-situ “chemical” Th–U–Pb dating of monazite with the electron microprobe is used to unravel the Neoproterozoic tectono-thermal history of the “Erinpura Granite” terrane in the foreland of the Delhi Fold Belt (DFB) in the NW Indian craton. These granitoids are variably deformed and show effects of shearing activity. Monazites from the Erinpura granitoids recorded two main events; (1) protolith crystallization at 863 ± 23 Ma and (2) recrystallization and formation of new Th-poor monazite at 775 ± 26 Ma during shear overprint. Some components of the Erinpura granitoids, such as the Siyawa Granite and granites exposed near Sirohi town, show evidence of migmatization. This migmatization event is documented by anatexis and associated monazite crystallization at 779 ± 16 Ma. The age data indicate an overlap in timing between anatectic event and ductile shear deformation. The end of the tectono-thermal event in the Sirohi area is constrained by a 736 ± 6 Ma Ar–Ar muscovite age data from the ductile shear zone.