Sedimentary manganese metallogenesis in response to the evolution of the Earth system

The concentration of manganese in solution and its precipitation in inorganic systems are primarily redox-controlled, guided by several Earth processes most of which were tectonically induced. The Early Archean atmosphere-hydrosphere system was extremely O₂-deficient. Thus, the very high mantle heat flux producing superplumes, severe outgassing and high-temperature hydrothermal activity introduced substantial Mn²⁺ in anoxic oceans but prevented its precipitation. During the Late Archean, centered at ca. 2.75 Ga, the introduction of Photosystem II and decrease of the oxygen sinks led to a limited buildup of surface O₂-content locally, initiating modest deposition of manganese in shallow basin-margin oxygenated niches (e.g., deposits in India and Brazil). Rapid burial of organic matter, decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the Archean-Proterozoic transition. Concurrently, a massive drawdown of atmospheric CO₂ owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused Paleoproterozoic glaciations (2.45-2.22 Ga). The spectacular sedimentary manganese deposits (at ca. 2.4 Ga) of Transvaal Supergroup, South Africa, were formed by oxidation of hydrothermally derived Mn²⁺ transferred from a stratified ocean to the continental shelf by transgression. Episodes of increased burial rate of organic matter during ca. 2.4 and 2.06 Ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere. Black shale-hosted Mn carbonate deposits in the Birimian sequence (ca. 2.3-2.0 Ga), West Africa, its equivalents in South America and those in the Francevillian sequence (ca. 2.2-2.1 Ga), Gabon are correlatable to this period. Tectonically forced doming-up, attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric CO₂ drawdown causing glaciation on the Neoproterozoic Rodinia supercontinent. Tectonic rifting and mantle outgassing led to deglaciation. Dissolved Mn²⁺ and Fe²⁺ concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation. During the Sturtian glacial-interglacial event (ca. 750-700 Ma), interstratified Mn oxide and BIF deposits of Damara sequence, Namibia, was formed. The Varangian (≡ Marinoan; ca. 600 Ma) cryogenic event produced Mn oxide and BIF deposits at Urucum, Jacadigo Group, Brazil. The Datangpo interglacial sequence, South China (Liantuo-Nantuo ≡ Varangian event) contains black shale-hosted Mn carbonate deposits. The Early Paleozoic witnessed several glacioeustatic sea level changes producing small Mn carbonate deposits of Tiantaishan (Early Cambrian) and Taojiang (Mid-Ordovician) in black shale sequences, China, and the major Mn oxide-carbonate deposits of Karadzhal-type, Central Kazakhstan (Late Devonian). The Mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans. During the Early Jurassic OAE, organic-rich sediments host many Mn carbonate deposits in Europe (e.g., Úrkút, Hungary) in black shale sequences. The Late Jurassic giant Mn Carbonate deposit at Molango, Mexico, was also genetically related to sea level change. Mn carbonates were always derived from Mn oxyhydroxides during early diagenesis. Large Mn oxide deposits of Cretaceous age at Groote Eylandt, Australia and Imini-Tasdremt, Morocco, were also formed during transgression-regression in greenhouse climate. The Early Oligocene giant Mn oxide-carbonate deposit of Chiatura (Georgia) and Nikopol (Ukraine) were developed in a similar situation. Thereafter, manganese sedimentation was entirely shifted to the deep seafloor and since ca. 15 Ma B.P. was climatically controlled (glaciation-deglaciation) assisted by oxygenated polar bottom currents (AABW, NADW). The changes in climate and the sea level were mainly tectonically forced.     

Geochemical Characteristics and Genetic Significance of Datangpo‐Type Manganese Ore Deposits during the Cryogenian Period

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃^? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.     

Geochronology of unconformity-related uranium deposits in the Athabasca Basin,Saskatchewan, Canada and their integration in the evolution of the basin

The importance of geochronology in the study of mineral deposits in general, and of unconformity-type uranium deposits in particular, resides in the possibility to situate the critical ore-related processes in the context of the evolution of the physical and chemical conditions in the studied area. The present paper gives the results of laser step heating ⁴⁰Ar/³⁹Ar dating of metamorphic host-rock minerals, pre-ore and syn-ore alteration clay minerals, and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) U/Pb dating of uraninite from a number of basement- and sediment-hosted unconformity-related deposits in the Athabasca Basin, Canada. Post-peak metamorphic cooling during the Trans-Hudson Orogen of rocks from the basement occurred at ca 1,750 Ma and gives a maximum age for the formation of the overlying Athabasca Basin. Pre-ore alteration occurred simultaneously in both basement- and sandstone-hosted mineralizations at ca 1,675 Ma, as indicated by the ⁴⁰Ar/³⁹Ar dating of pre-ore alteration illite and chlorite. The uranium mineralization age is ca 1,590 Ma, given by LA-ICP-MS U/Pb dating of uraninite and ⁴⁰Ar/³⁹Ar dating of syn-ore illite, and is the same throughout the basin and in both basement- and sandstone-hosted deposits. The mineralization event, older than previously proposed, as well as several fluid circulation events that subsequently affected all minerals studied probably correspond to far-field, continent-wide tectonic events such as the metamorphic events in Wyoming and the Mazatzal Orogeny (ca 1.6 to 1.5 Ga), the Berthoud Orogeny (ca 1.4 Ga), the emplacement of the McKenzie mafic dyke swarms (ca 1.27 Ga), the Grenville Orogeny (ca 1.15 to 1 Ga), and the assemblage and break-up of Rodinia (ca 1 to 0.85 Ga). The results of the present work underline the importance of basin evolution between ca 1.75 Ga (basin formation) and ca 1.59 Ga (ore deposition) for understanding the conditions necessary for the formation of unconformity-type uranium deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Redistribution of REE, Pb and U by supergene weathering studied from in-situ isotopic analyses of the Bangombé natural reactor, Gabon

The isotopic analyses of rare earth elements (REE), Pb and U in several kinds of minerals from the clay and black shale layers above the Bangombé natural reactor, Gabon, were performed using a sensitive high-resolution microprobe (SHRIMP) to investigate the migration and retardation processes of fission products released from the reactor. REE isotopic data of the secondary minerals found in clays and black shales show that most of fission products were effectively trapped in the clays and not distributed into the black shales over the clays, which reveals that the clays play an important role in preventing fission products from spreading.Zircon crystals in the clays heterogeneously contain high-U regions (up to 28.3 wt%) with normal ²³⁵U/²³⁸U ratios (=0.00725) and significant amounts of fissiogenic REE, which suggest the occurrence of significant chemical fractionation between REE and U during the dissolution of reactor uraninite and the recrystallization of secondary U minerals. The Pb data suggest that galena grains in the clays were also formed by the mixing of the two components during a recent alteration event, and that a significant amount of Pb was derived from 2.05-Ga-old original uraninite rather than reactor uraninite. The U-Pb systematics of zircon provide chronological information on the old igneous activity associated with the basement rock formation at 2.8 Ga and geochemical evidence of the incomplete mixing of independent Pb and U sources. This result is consistent with previous chronological results in this area.     

U-Pb systematics of an Upper Carboniferous black shale from South Yorkshire, UK

Open-system behaviour of uraniferous shales, which has been known for many years, has discouraged attempts to use U-Pb geochronology to date sedimentary systems. Techniques now available can facilitate better understanding of their geochemical evolution and their possible use in geochronometry. For the U-rich Alton (G. listeri) Marine Band, a combined fission track mapping, electron optical and sequential chemical extraction study confirms that uranium is incorporated into francolite, an early diagenetic precipitate. U-Pb analyses of uranium-rich (>1000 ppm) francolite nodules are discordant and imply ages ∼50-150 Ma younger than the date of sedimentation. Pb isotopic analysis suggests that uranium daughters continually leaked from the francolite, ²³⁸U daughters being released more efficiently than those of ²³⁵U. Extrapolation of the U-Pb data to concordia produces an age consistent with the time of sedimentation. These features are also displayed by other uranium-rich shales such as the Swedish Kolm Measures, despite uranium being incorporated into different phases. Preferential loss of ²³⁸U daughters from fine-grained particles due to alpha recoil could explain the unusual U-Pb isotopic composition, in both examples. Further work would be justified to investigate the application of U-Pb isotopic analysis of such material to date sedimentary sequences.     

U-Pb systems and U isotopic composition of the sandstone-hosted paleovalley Dybryn uranium deposit, Vitim uranium district, Russia

The isotopic (U-Pb, ²³⁸U-²³⁵U, ²³⁴U-²³⁸U) and chemical study of whole-rock samples and finegrained fractions of rocks in a vertical section of the terrigenous sequence at the Dybryn uranium deposit in the Khiagda ore field shows that a wide U-Pb isotopic age range (26.9-6.5 Ma) is caused by oxidation and disturbance of the U-Pb isotopic system in combination with protracted uranium ore deposition. The oxidation of rocks resulted in the loss of uranium relative to lead and eventually to an overestimated ²⁰⁶Pb/²³⁸U age at sites with a low U content. The ²³⁸U/²³⁵U ratios in the studied samples are within the range of 137.74–137.88. Samples with a high uranium content are characterized by a decreasing ²³⁸U/²³⁵U ratio with a decrease in ²⁰⁷Pb/²³⁵U and ²⁰⁶Pb/²³⁸U ages. A nonequilibrium ²³⁴U/²³⁸U ratio in most studied samples furnishes evidence for young (<1.5 Ma) transformation of the Miocene uranium ore, which is responsible for uranium migration and its redeposition.     

No proof from carbon isotopes in the Francevillian (Gabon) and Onega (Fennoscandian shield) basins of a global oxidation event at 1980–2090 Ma following the Great Oxidation Event (GOE)

Highly depleted C isotope composition of organic matters from the Onega (Fennoscandian shield) and Francevillian (Gabon) basins are differently interpreted. Kump et al. (2011) suggested the occurrence of a massive and global oxidation event during the period of 1980–2090 Ma, which follows the Great Oxidation Event (2450–2320 Ma) (Bekker et al., 2004). Inversely, Gauthier-Lafaye and Weber (2003) invoke the possible action of methanotrophic microorganisms to explain the δ¹³C values as low as –46‰ measured in the Franceville basin. Here we present the isotope data available in the Franceville basin in order to discuss these two interpretations. The lack of any δ¹³C correlation between organic matter and carbonate in the Franceville basin does not allow the consideration of a massive and global oxidation event.     

相山铀矿田铀多金属成矿时代与成矿热历史

相山铀矿田的铀多金属矿化主要可划分为碱性铀矿化、酸性铀矿化、铅锌银铜矿化和金矿化四种类型。通过沥青铀矿和矿化岩石U-Pb等时线、黄铁矿Rb-Sr等时线、绢云母~(40)Ar-~(39)Ar同位素年龄测定,结合铀多金属成矿特征研究,厘定了相山铀矿田铀多金属成矿时代,确定铀多金属矿化的成矿时序为:碱性铀矿化、铅锌银铜矿化、金矿化、酸性铀矿化。锆石裂变径迹研究表明,相山矿田铀多金属矿化样品的锆石裂变径迹峰值年龄与U-Pb、Rb-Sr和~(40)Ar-~(39)Ar同位素年龄一致性良好,裂变径迹年龄(峰值年龄)可以限定热液铀多金属成矿热事件时代。碱性铀成矿热事件的锆石裂变径迹峰值年龄为119. 8～125. 6Ma;金成矿热事件和铅锌银铜多金属成矿热事件的锆石裂变径迹峰值年龄为106. 1～113. 8Ma;酸性铀成矿热事件的锆石裂变径迹峰值年龄为86. 7～100. 0Ma;新发现一期锆石裂变径迹峰值年龄为66. 4～78. 6Ma的热事件,该期热事件可能为相山矿田最晚一期酸性铀成矿热事件。相山矿田66. 4～78. 6Ma的铀成矿热事件,与华南花岗岩型热液铀矿床的区域成矿热事件时代耦合,该发现对华南火山岩型铀矿成矿时代的重新认识,对火山岩型、花岗岩型铀矿床成矿统一性认识具有重要意义。     

U–Th–Pb–REE systematics of organic-rich shales from the ca. 2.15 Ga Sengoma Argillite Formation, Botswana: Evidence for oxidative continental weathering during the Great Oxidation Event

The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere during deposition. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading even for drill core samples. Because both of these elements radioactively decay and produce lead isotopes, the Pb isotope composition may reflect the depositional Th/U ratio, although the Th/U ratios induced by changes shortly after deposition may not be distinguished from the true depositional Th/U ratios. In order to effectively evaluate the time-integrated Th/U ratio (κ_a), values for the initial depositional Pb isotope composition must be determined or accepted from the models for the whole Earth.While the timing for the rise of atmospheric oxygen is reasonably well constrained now, its effect on continental weathering and ocean redox state remains poorly constrained and debated. The ca. 2.15 Ga Sengoma Argillite Formation of Botswana contains organic-rich shales deposited during the Great Oxidation Event. The slope of the ²⁰⁷Pb/²⁰⁴Pb–²⁰⁶Pb/²⁰⁴Pb array of shales from the Sengoma Argillite Formation corresponds to a Pb–Pb age that is within analytical error of the depositional age and is, therefore, inferred to be the time by which the time-integrated thorogenic and uranogenic lead growth started. The time-integrated lead growth corresponds to an average κ_a of 2.63 (± 0.62, 1σ) for the organic-rich shales of the Sengoma Argillite Formation. This is lower than Th/U ratios measured in Archean shale suites or estimated for the Archean–Proterozoic average upper continental crust [Taylor, S.R. and McLennan, S.M., 1985. The Continental Crust: Its Composition and Evolution. Blackwell, Oxford, 312 pp.], which indicates that these samples were enriched in uranium with respect to thorium (and perhaps lead) at the time of deposition. In the modern ocean, sediments are enriched in uranium under reducing conditions by reduction of the water-soluble uranyl ion, which is delivered to the ocean by oxidative weathering of continental crust. To evaluate the potential mobility of Th, U, and Pb during post-depositional processes, the concentrations of the rare earth elements (REE) were also determined. Interelement ratios of the largely immobile REE (in this study, La/Nd and Gd/Er) can be used as a proxy for the Th/U ratio, as the geochemical behavior of the lanthanide and actinide elements is similar under a variety of conditions. Furthermore, close similarity in the chondrite-normalized REE patterns and small range in La/Nd and Gd/Er ratios in studied samples indicate that variations in κ_a values are not likely to have been controlled by mixing of one or more REE-, Th-, and U-rich heavy minerals from the multiple detrital sources. Our study of shales from the ca. 2.15 Ga Sengoma Argillite Formation indicates that decoupling of U from Th, most likely related to the oxidative continental weathering, began by 2.15 Ga, at the latest.     

Uraniferous Black Shale and Related Uranium Mineralization Features in South China

: Black shales are marine sediments with argillaceous, silty and siliceous compositions and high contents of organic materials, disseminated pyrite and uranium. Uraniferous black shale has uranium content of more than 20 ppm.Black shales are widely distributed in 17 provinces or autonomous regions in northwestern and southern-central China. Their sedimentary ages are from the Sinian to the Tertiary and uraniferous black shales are mainly exposed in Yunnan, Guizhou, Sichuan, Hunan, Hubei, Jiangxi, and Zhejiang provinces and Guangxi Zhuang Autonomous Region and the economically significant uranium deposits associated with black shale occur in Hunan and Jiangxi provinces and Guangxi Zhuang Autonomous Region.Uranium mineralization associated with black shale has the following main features: (1) forming stratabound deposits; (2) controlled by structures such as interlayer and intersected faults and fractures; (3) associated with different ore-forming processes such as leaching and hydrothermal reworking; (4)     

Magmatic and hydrothermal behavior of uranium in syntectonic leucogranites: The uranium mineralization associated with the Hercynian Guérande granite (Armorican Massif,France)

Most of the hydrothermal uranium (U) deposits from the European Hercynian belt (EHB) are spatially associated with Carboniferous peraluminous leucogranites. In the southern part of the Armorican Massif (French part of the EHB), the Guérande peraluminous leucogranite was emplaced in an extensional deformation zone at ca. 310 Ma and is spatially associated with several U deposits and occurrences. The apical zone of the intrusion is structurally located below the Pen Ar Ran U deposit, a perigranitic vein-type deposit where mineralization occurs at the contact between black shales and Ordovician acid metavolcanics. In the Métairie-Neuve intragranitic deposit, uranium oxide-quartz veins crosscut the granite and a metasedimentary enclave.Airborne radiometric data and published trace element analyses on the Guérande leucogranite suggest significant uranium leaching at the apical zone of the intrusion. The primary U enrichment in the apical zone of the granite likely occurred during both fractional crystallization and the interaction with magmatic fluids. The low Th/U values (< 2) measured on the Guérande leucogranite likely favored the crystallization of magmatic uranium oxides. The oxygen isotope compositions of the Guérande leucogranite (δ¹⁸O_{whole rock} = 9.7–11.6‰ for deformed samples and δ¹⁸O_{whole rock} = 12.2–13.6‰ for other samples) indicate that the deformed facies of the apical zone underwent sub-solidus alteration at depth with oxidizing meteoric fluids. Fluid inclusion analyses on a quartz comb from a uranium oxide-quartz vein of the Pen Ar Ran deposit show evidence of low-salinity fluids (1–6 wt.% NaCl eq.), in good agreement with the contribution of meteoric fluids. Fluid trapping temperatures in the range of 250–350 °C suggest an elevated geothermal gradient, probably related to regional extension and the occurrence of magmatic activity in the environment close to the deposit at the time of its formation. U-Pb dating on uranium oxides from the Pen Ar Ran and Métairie-Neuve deposits reveals three different mineralizing events. The first event at 296.6 ± 2.6 Ma (Pen Ar Ran) is sub-synchronous with hydrothermal circulations and the emplacement of late leucogranitic dykes in the Guérande leucogranite. The two last mineralizing events occur at 286.6 ± 1.0 Ma (Métairie-Neuve) and 274.6 ± 0.9 Ma (Pen Ar Ran), respectively. Backscattered uranium oxide imaging combined with major elements and REE geochemistry suggest similar conditions of mineralization during the two Pen Ar Ran mineralizing events at ca. 300 Ma and ca. 275 Ma, arguing for different hydrothermal circulation phases in the granite and deposits. Apatite fission track dating reveals that the Guérande granite was still at depth and above 120 °C when these mineralizing events occurred, in agreement with the results obtained on fluid inclusions at Pen Ar Ran.Based on this comprehensive data set, we propose that the Guérande leucogranite is the main source for uranium in the Pen Ar Ran and Métairie-Neuve deposits. Sub-solidus alteration via surface-derived low-salinity oxidizing fluids likely promoted uranium leaching from magmatic uranium oxides within the leucogranite. The leached out uranium may then have been precipitated in the reducing environment represented by the surrounding black shales or graphitic quartzites. As similar mineralizing events occurred subsequently until ca. 275 Ma, meteoric oxidizing fluids likely percolated during the time when the Guérande leucogranite was still at depth. The age of the U mineralizing events in the Guérande region (300–275 Ma) is consistent with that obtained on other U deposits in the EHB and could suggest a similar mineralization condition, with long-term upper to middle crustal infiltration of meteoric fluids likely to have mobilized U from fertile peraluminous leucogranites during the Late Carboniferous to Permian crustal extension events.     

Depositional setting of the 2·1 Ga Francevillian macrobiota (Gabon): Rapid mud settling in a shallow basin swept by high‐density sand flows

The depositional setting of the 2·1 Ga fill of the Franceville Basin of Gabon is important for understanding the habitat (energy and availability of light and oxygen) and taphonomy of recently discovered early macro‐organisms buried in black shales in Unit FB . The available data bearing on the stratigraphy and sedimentology of Unit FB provide new insight into processes acting on the palaeo‐sea floor. The shales are interpreted to have formed as fluid mud deposits interstratified with structureless sands. The latter (Poubara sandstones) were emplaced during a forced regression during the terminal infill of fault‐bounded sub‐basins following a stage characterized by a ferruginous to anoxic water column. The structureless sandstones were deposited from high‐density gravity currents along with a locally strong bottom oscillation of the water column. Tuft structures preserved in cyanobacterial mats, together with the position of the macro‐organisms at the top of the sandstone beds within associated black shales, point to a water depth of less than 80 m. The relative sea‐level fall that drove deposition of the Poubara sandstones controlled the rise of a phototrophic ecosystem and also possibly favoured the supply of oxygen and nutrients via density flows.     

Elemental geochemistry of the early Jurassic black shales in the Qiangtang Basin,eastern Tethys: constraints for palaeoenvironment conditions

The early Jurassic black shales are the most important source rocks in the Qiangtang Basin, Tibet. These black shales may provide a useful example for understanding the sedimentary conditions during the early Jurassic in the eastern Tethys. Thirty‐two black‐shale samples were collected from the Qiangtang Basin to reconstruct the depositional environments during the early Jurassic in the eastern Tethys. The palaeoclimate index Σ(Fe + Mn + Cr + Ni + V + Co)/Σ(Ca + Mg + Sr + Ba + K + Na) varies between 0.58 and 1.14, together with low Sr/Ba (0.20–0.60) and Sr/Cu (1.68–7.88) ratios, indicating a warm humid to semi‐humid climatic condition during black‐shale deposition. The early Jurassic black shales exhibit slight Ce anomalies (0.89–0.94) and Mn enrichment (EF = 1.2), suggesting a slightly oxic depositional environment. The conditions of the sedimentary water system during black‐shale deposition were apparently brackish as evidenced by middle B/Ga (3.96–5.73) and Th/U (3.96–6.51) ratios. Copyright © 2015 John Wiley & Sons, Ltd.     

Orogenesis vs. diagenesis: Can we use organic-rich shales to interpret the tectonic evolution of a depositional basin?

Black shales from the southern Appalachian Basin and the southwest Welsh Basin have anomalous U–Pb and Nd model ages suggesting syn- and post-depositional resetting of the Sm–Nd and U–Pb isotopic systems. This alteration to the primary detrital signature of these two shale sequences is indicative of black shale diagenetic/depositional processes that obscure paleo-environmental and provenance information recorded prior to and during deposition. The trace element and isotopic signatures of these two shale sequences reveal a syn-/post-depositional history that is de-coupled from the coeval orogenic history of the region making it difficult to reconstruct the tectonic and oceanographic conditions present at the time of deposition.Both the Ordovivian Welsh Basin and the Devonian Appalachian Basin sequences host REE- and U-bearing diagenetic phosphate minerals that play a critical role in the whole rock REE and U budgets. In the Welsh Basin shales, early diagenetic apatite and a later monazite phase dominate the REE budget and cause the redistribution of REE early in the basin's history (ca. 460 Ma). This redistribution is recorded by the Sm–Nd system (450 ± 90 Ma) and the Nd model ages that are anomalously old by as much as 20% (T_DM > 2.0 Ga). This early history is complicated by a Permo-Triassic fluid event affecting the whole rock U-budget and resetting the U–Pb isotopic system at 193 ± 45 Ma. The Appalachian Basin sequence appears to have a much less complicated history yet still records a significant disturbance in both the Sm–Nd isotopic system (392 ± 76 Ma) and the Pb isotopic system (340 ± 50 Ma) at about the time of deposition (ca. 365 Ma).These two sequences suggest a pattern of diagenetic disturbance common to black shales. These processes are unique to black shales and must be considered when interpreting provenance and paleo-environmental information from the black shale sequences. Although these rocks are susceptible to alteration, the alteration may provide extensive information on the post-depositional history of the basin while still retaining some primary depositional information. If black shale processes are considered during the interpretation of isotopic and trace element signatures from organic-rich shales, it may be possible to recover an extensive basin history.     

广西东平地区碳酸锰矿床Ga含量高异常的发现及成因初探

Ga是一种典型的稀有分散元素,主要产于铝土矿、闪锌矿及煤矿之中。最近,在广西东平地区下三叠统北泗组碳酸锰矿床中发现Ga高异常含量,w(Ga)介于5.16×10~(-6)~82.80×10~(-6)之间,平均为33.76×10~(-6),达到了Ga工业品位标准;锰矿层和围岩中w(Ga)平均分别为46.40×10~(-6)、19.31×10~(-6),高于国内外已报道的大部分锰矿床。文中根据北泗组碳酸锰矿床地球化学特征,揭示了该锰矿床为热水沉积;同时,结合现代大洋铁锰沉积有关Ga的最新报道,提出北泗组碳酸锰矿床中Ga的赋存与含锰矿物密切相关,其来源与海底热液活动有关。最后,文中还利用Mn/Fe-Ga、Co-Ga关系图判别了古代铁锰沉积的成因类型。     

The Ranger uranium deposit,northern Australia: Timing constraints,regional and ore-related alteration,and genetic implications for unconformity-related mineralisation

The Ranger 1 unconformity-related uranium deposit in the Northern Territory of Australia is one of the world's largest uranium deposits and has ranked in the top two Australian producers of uranium in recent years. Mineralisation at the Ranger, Jabiluka and other major unconformity-related deposits in the Alligator Rivers Uranium Field (ARUF) occurs in Paleoproterozoic metamorphic basement rocks immediately beneath the unconformity with the Paleo- to Mesoproterozoic McArthur Basin.The sites of uranium mineralisation and associated alteration at the Ranger 1 deposit (Number 3 orebody) were fundamentally controlled by reactivated shear zones that were initiated during the regional Nimbuwah tectonothermal event. The timing of shearing at medium metamorphic grade was constrained by ion microprobe U–Pb dating of zircons in two pegmatites, one weakly foliated (1867.0 ± 3.5 Ma) and another that is unfoliated and cuts the shear fabric (1862.8 ± 3.4 Ma). The younger age of ~ 1863 Ma represents the minimum age of D1 shearing during the Nimbuwah event at the Ranger 1 deposit (Number 3 orebody). Titanite within veins of amphibole-plagioclase-apatite yielded an ion microprobe U–Pb age of 1845.4 ± 4.2 Ma, which represents a previously unrecognised hydrothermal event in the ARUF. Based on previous data, retrograde hydrothermal alteration during D2 reactivation of D1 shear zones is interpreted to have occurred at ~ 1800 Ma during the regional Shoobridge tectonothermal event.Detailed paragenetic observations supported by whole-rock geochemical data from the Ranger 1 deposit (Number 3 orebody) reveal a sequence of post-D2 hydrothermal events, as follows. (1) Intense magnesium-rich chlorite alteration and brecciation, focussed within schists of the Upper Mine Sequence in the Cahill Formation. (2) Silicification of Lower Mine Sequence carbonate rock units and overlying schist units, comprising quartz ± Mg-foitite (tourmaline) ± muscovite ± pyrite ± marcasite, and rare uraninite (early U1). (3) Formation of main stage uranium ore and heterolithic breccias including clasts of olivine–phyric dolerite, with breccia matrix composed of uraninite (U1), Mg-chlorite ± Mg-foitite and minor pyrite and chalcopyrite. (4) A second generation of uraninite (U2) veinlets with disordered graphitic carbon and quartz of hydrothermal origin. (5) Late-stage veinlets of massive uraninite (U3). As inferred in a previous study and confirmed herein, olivine–phyric dolerite dykes at Ranger are mineralised and chloritised, and are geochemically similar to the regional Oenpelli Dolerite. A maximum age for uranium mineralisation at the Ranger 1 deposit is therefore set by the age of the Oenpelli Dolerite (~ 1723 Ma).In-situ ion microprobe U–Pb analysis of texturally oldest U1 uraninite yielded a discordia array with a ²⁰⁶Pb/²³⁸U-²⁰⁷Pb/²³⁵U upper intercept age of 1688 ± 46 Ma. The oldest individual ion microprobe ²⁰⁷Pb–²⁰⁶Pb age is 1684 ± 7 Ma whereas the oldest age determined by in-situ electron microprobe chemical dating of U1 uraninite is ~ 1646 Ma. Another sample containing both U1 and U2 uraninite yielded discordant data with a ²⁰⁶Pb/²³⁸U–²⁰⁷Pb/²³⁵U upper intercept age of 1421 ± 68 Ma. When the ²⁰⁷Pb/²⁰⁶Pb ages are considered the data are suggestive of U2 uraninite formation and possible resetting of the U1 age between ~ 1420 Ma and ~ 1040 Ma. All ion microprobe analyses of U1 and U2 uraninite indicate variable and possibly repeated lead loss. In contrast ion microprobe U–Pb dating of the third generation of uraninite (U3) yielded several near-concordant analyses and a ²⁰⁶Pb/²³⁸U–²⁰⁷Pb/²³⁵U upper intercept age of 474 ± 6 Ma. This age is supported by electron microprobe chemical ages of U3 uraninite between 515 Ma and 385 Ma.The new results constrain the timing of initial uranium mineralisation at the Ranger 1 deposit (Number 3 orebody) to the period ~ 1720 Ma to ~ 1680 Ma, which just overlaps with a previous U–Pb age of 1737 ± 20 Ma for uraninite-rich whole-rock samples. Our results are consistent with individual laser-ICPMS ²⁰⁷Pb/²⁰⁶Pb and chemical ages of uraninite as old as 1690–1680 Ma reported from other deposits and prospects in the ARUF.Whole-rock geochemical data in this study of the Ranger 1 deposit (Number 3 orebody) and in other studies in the ARUF demonstrate that zones of intense chloritisation associated with uranium mineralisation experienced large metasomatic gains of Mg, U, Co, Ni, Cu and S and losses of Si, Na, Ca, Sr, Ba, K, Rb, Y and the light REE. More broadly in the ARUF, a regionally extensive illite–hematite ± kaolinite-bearing ‘paleoregolith’ zone in basement beneath the McArthur Basin exhibits depletion of about half of its uranium as well as major losses in Na, Sr, Pb, Ba and minor losses of Mg. These features together with new petrographic observations suggest this zone is a regional sub-McArthur Basin alteration zone produced by interaction with diagenetic or hydrothermal fluids of primary basinal origin, rather than representing a low-temperature paleo-weathering zone before the deposition of the McArthur Basin, as previously suggested.Based on these results and a synthesis of previous work, a new multi-stage model is proposed for the Ranger 1 ore-forming mineral system that may apply to other major unconformity-related uranium deposits in the ARUF and which may be used for targeting new deposits in the region. As in most recent models, oxidised diagenetic brines within the McArthur Basin are envisaged as crucial in mobilising uranium. However, a different architecture of fluid flow is proposed involving the sub-unconformity regional basement alteration zone as a preferential source of leached uranium. Possibly driven by convection during regional magmatism at ~ 1725–1705 Ma, oxidised basinal brines were drawn downwards and laterally through fault networks and fractures in the regional sub-unconformity alteration zone, leaching uranium from hematite-altered basement rocks. Simultaneously within deeper and lateral parts of the hydrothermal system, Mg-metasomatism produced chloritic alteration and brines with increased acidity and silica content (from the desilicification of the basement rock), analogous to processes described in sub-seafloor hydrothermal systems. Silicification occurred locally (e.g., Ranger deposit) within upflow zones of convective systems due to decreases in temperature and/or pressure of the brines and/or CO₂ generation during carbonate dissolution. Interruptions to convection during transient regional extensional or strike-slip tectonic events resulted in generalised lateral and downwards flow of fluids from the McArthur Basin through deepened zones of sub-unconformity alteration, transferring leached uranium into reactivated shear zones within the basement. The main stage of uraninite precipitation at the Ranger deposit and elsewhere in the ARUF is proposed to have occurred between ~ 1720 Ma and ~ 1680 Ma as a result of reduction of oxidised and evolved basin-derived ore fluids during reaction with pre-existing Fe^2 +-bearing minerals and/or mixing of the ore fluids with basement-reacted silica-rich brines.A second, volumetrically minor but locally high-grade, stage of uraninite mineralisation was associated with hydrothermal disordered carbon and quartz of presently unknown origin. Available data suggest formation between ~ 1420 Ma and ~ 1040 Ma. Almost a billion years later at ~ 475 Ma, fluids capable of mobilising uranium again resulted in uraninite (U3) deposition as sparse veinlets in the Ranger deposit, representing the first documentation of uranium mineralisation of this age in the region.     

Weathering process at the natural fission reactor of Bangombé

 The uranium deposits in the basin of Franceville (Gabon) host the only natural fission reactors known in the world. Unique geological conditions favoured a natural fission reaction 2 Ga ago. This was detected by anomalous isotopic compositions of uranium and rare earth elements (REE), which are produced by the fission reaction. In total, 16 reactor zones were found. Most of them are mined out. The reactor zone of Bangombé, is only 10–11 m below the surface. This site has been influenced by surface weathering processes. Six drill cores have been sampled at the site of the reactor zone of Bangombé during the course of the study and only one drill core (BAX 08) hit the core of the reactor. From these data and previous drilling campaigns, the reactor size is estimated to be 10 cm thick, 2–3 m wide and 4–6 m long. The migration of fission products can be traced by the anomalous isotope ratios of REE because of the fission process. The ¹⁴⁹Sm/¹⁴⁷Sm ratio close to the reactor zone is only 0.28 (normal: 0.92) because of the intense neutron capture of ¹⁴⁹Sm and subsequent transmutation, whereas ¹⁴⁷Sm is enriched by the fission reaction. Similar changes in isotopic patterns are detectable on other REE. The isotope ratios of Sm and Nd of whole rock and fracture samples surrounding the reactor indicate that fission-genic REE migrated only a few decimetres above and mainly below the reactor zone. Organic matter (bitumen) seems to act as a trap for fission-genic REE. Additional REE-patterns show less intense weathering with increasing depth in the log profile and support a simple weathering model. Received: 26 November 1999 · Accepted: 2 May 2000     

铀的地球化学性质与成矿——以华南铀成矿省为例

铀是强不相容元素,随着岩浆演化而不断富集,在岩浆演化末期受结构氧增加影响进入独居石、磷钇矿等副矿物中。岩浆演化通常无法直接形成达到工业品位的铀矿床。铀是对氧逸度敏感的变价元素。在表生风化过程中岩体(层)中的铀被氧化为UO_2~(2+)而极易溶解进入水体中,并可在还原环境沉淀而富集成矿,氧化还原界面是找矿的理想选区。大气水可通过断裂构造系统进入一定深度,并受热源作用形成高氧逸度的热液而萃取出岩体(层)中的铀在还原位置沉淀富集形成矿床。新元古代氧化事件以及Marinoan冰期结束使得表生风化过程中更多的U进入水体;而寒武纪生命大爆发,易在沉积盆地底部形成还原环境,有利于U的沉淀富集。受上述三方面因素控制,在华南形成了广泛分布的富铀黑色页岩层,并被之后的沉积物覆盖,成为华南各型铀矿床的铀源层。印支期构造运动使部分富铀黑色页岩层发生部分熔融形成了富铀的S型花岗岩,该类岩石亦是之后铀成矿作用的铀源岩。燕山运动后期华南发生伸展构造背景下的岩浆热事件为以大气水为主的高氧逸度热液的形成并作用于铀源岩(层)提供了有利条件,促使华南各类型铀矿床开始在白垩纪集中形成。     

Re-Os and Mo isotope systematics of black shales from the Middle Proterozoic Velkerri and Wollogorang Formations, McArthur Basin, northern Australia

Joint application of the Mo isotope paleoredox proxy and Re-Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re-Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re-Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105-119 ppm) and degree of pyritization [DOP] values (0.90-0.92) implying quantitative conversion of molybdate (MoO₄²⁻) to thiomolybdate (MoS₄²⁻) in overlying bottom waters. The average δ^97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ^97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H₂S]_aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H₂S]_aq < 11 μM) marine deposition in the 1.4 Ga oceans. Mass-balance modelling suggests Mo removal into strongly euxinic and oxic sediments may have comprised 30-70% and less than 15%, respectively, of the oceanic Mo sink at 1.4 Ga as opposed to 5% and 35% today, respectively.The Re-Os radioisotope system in organic-rich shales serves as a test for post-depositional alteration that could affect the usefulness of paleoredox tracers such as Mo stable isotopes. Re-Os isotope data for the Wollogorang Formation black shales are scattered and yield a highly imprecise date of 1359 ± 150 Ma (2σ, n = 21, MSWD = 85, Model 3). This age is younger than U-Pb zircon ages from interbedded tuffs that constrain the age of deposition at ca. 1730 Ma. In conjunction with previous petrological, geochemical, and paleomagnetic data, the Re-Os isotope data suggest hydrothermal fluid flow through the Wollogorang Formation, possibly associated with formation of the ca. 1640 Ma McArthur River Pb-Zn-Ag sedimentary exhalative deposit, resulted in post-depositional mobilization of Re and Os. Based on the degree of deviation of the Re-Os data from a 1730 Ma reference line, open-system behavior of Re and Os was greatest near the base of the black shale unit. Wollogorang Formation black shales are enriched in Mo (41-58 ppm), but are characterized by variable δ^97/95Mo (0.3-0.8‰) and DOP (0.57-0.92). The lightest δ^97/95Mo values occur near the base of the black shale unit. Based on the Re-Os systematics, hydrothermal fluids have probably overprinted the authigenic δ^97/95Mo signature in those shales. However, the heaviest δ^97/95Mo values in the Wollogorang Formation come from stratigraphically higher shales, and are similar to those observed for the Velkerri Formation, and thus may reflect seawater δ^97/95Mo at 1.73 Ga.     

Provenance ages and alteration histories of shales from the Middle Archean Buhwa greenstone belt, Zimbabwe: Nd and Pb isotopic evidence

Shales of the ca. 3.0 Ga Buhwa Greenstone Belt, Zimbabwe, were derived from a compositionally diverse provenance whose ages, determined by ion probe analyses of detrital zircons in interbedded sandstones, range from 3.8 to 3.1 Ga. Geochemical data for the shales were previously interpreted to indicate that sediments had been derived from an intensely weathered source. REE concentrations in the shales were interpreted to suggest that the provenance was compositionally mixed, with components of felsic (tonalite and alkalic granitoid) and mafic rocks. Sm/Nd and Nd isotopic compositions of these rocks can be used to model initial Nd isotopic ratios at the time of sedimentation (ε_Ndsed), as well as model crustal formation ages (T_DM). The former, at the age of sedimentation, range from +0.6 to −10.8, consistent with a range of provenance ages. The latter range from 4.46 Ga to 2.99 Ga. The oldest crustal formation ages, up to 0.7 Ga older than known detrital components, are interpreted here to indicate that the Sm-Nd system of the sediments experienced open system behavior. The implied alteration would have included an increase in Sm/Nd by about 20-25 percent, probably in the form of preferential loss of Nd with respect to Sm. The Pb isotopic compositions of whole rock samples are quite radiogenic, with a range of ²⁰⁶Pb/²⁰⁴Pb from 25.5 to 154. An array of ten samples lies scattered about a line with a ²⁰⁷Pb/²⁰⁴Pb -²⁰⁶Pb/²⁰⁴Pb slope age of about 2.73 Ga. Five individual samples were sequentially leached to further test the timing and characteristics of this U-Th-Pb alteration event. These arrays of a whole rock, three leach steps, and a residue also form linear Pb-Pb arrays (one is more scattered) with ages ranging from 2260 ± 360 Ma to 2824 ± 170 Ma, suggesting that all samples experienced a latest Archean to earliest Proterozoic enrichment in U/Pb. This age range also may be the approximate age of Sm/Nd enrichment for the shales. All samples, both whole rocks and leached samples, lie grouped on a ²⁰⁸Pb/²⁰⁴Pb - ²⁰⁶Pb/²⁰⁴Pb diagram around a line with ²³²Th/²³⁸U = 3.5 (2.9 to 3.9). Because of the lack of large differences in the Th/U of the samples through large ranges of U/Pb, we interpret this consistency in Th/U to mean that the shales of the Buhwa belt experienced Pb loss, rather than U and Th gain. Circumstances that may be responsible for Pb loss in a sedimentary basin include loss of saline fluids during basin dewatering. Such an event would likely have been related to folding associated with the thrusting and magmatic intrusion of the adjacent Limpopo Belt, suggesting that uplift, dewatering, and geochemical and isotopic alteration can be genetically related.