Negative Ce Anomalies Research Articles

A carbonate molybdenum isotope and cerium anomaly record across the end-GOE: Local records of global oxygenation

Earth’s Great Oxidation Event (GOE), ca. 2.5–2.0 Ga, was one of the most extreme environmental perturbations in the history of the planet. In addition to the first sustained accumulation of O2 in the atmosphere, the latter half of the GOE is associated with a very large positive carbon isotope excursion, both in terms of magnitude and inferred duration. The end of the GOE may have been associated with a decrease in atmospheric oxygen levels, although this transition remains poorly understood. We test if this suggested decline in atmospheric O2 is reflected in the molybdenum stable isotope compositions (δ98Mo) and Ce anomalies of a large number (N = 299) of carbonate sedimentary rocks collected from Finnish Lapland and the Canadian Labrador Trough and Belcher Group, which collectively span ca. 2.1–1.88 Ga. Clear evidence for a shift in redox conditions across the end-GOE is obscured by coupled stratigraphic variations in δ98Mo values, Ce anomalies, and Mn concentrations, suggesting local controls on these redox proxies as a function of depositional environment, likely as a result of particulate shuttling of Mo and Ce associated with Mn redox cycling across a chemocline. The most negative Ce anomalies recorded in the Belcher Group (<0.6) are among the lowest reported in literature from the mid-late Paleoproterozoic to early Neoproterozoic; however, the strong local controls on these proxies hinder direct evaluation of secular trends. These findings highlight the critical role of stratigraphic and paleobasinal context for the robust interpretation of δ98Mo values and Ce anomalies for the evolution of marine redox conditions.

Metallogenetic Mn-model of the Rhyacian-aged Buritirama Formation, Carajás domain (Amazon Craton)

The Mn-bearing Buritirama Formation is composed of clastic and chemical metasedimentary rocks representing a Rhyacian platformal basin (ca. 2.18–2.06 Ga) that limits the northern border of the Archean-Paleoproterozoic Carajás domain with the Paleoproterozoic Bacajá domain in the southern Amazon Craton, northern Brazil. The Buritirama Formation is divided into three main stratigraphic units. The Lower and Upper units consist of a basal quartzite followed by carbonate–silicate rocks (marls), dolomitic marbles (dolostone) and minor biotite schist while the Intermediate Unit consists of Mn-carbonate rocks topped by a supergene Mn-oxide deposit (Cenozoic age). These rocks were deformed and metamorphosed during the Transamazonian event (ca. 2.06 Ga).Geochemical data from dolomitic marbles (Lower Unit) exhibit negative Ce anomalies, high Y/Ho ratios (ca. 48) and seawater-like REE + Y patterns that reinforce an open platform setting for the Buritirama basin. Positive δ13C values (+3.2‰ to +5.0‰ V-PDB) for dolomitic marbles are considered to be an expression of the Lomagundi Carbon Isotopic Excursion. The metallogenesis of Mn-carbonate rocks is evaluated based on redox-sensitive trace elements (e.g. Zn and Ni), PAAS-normalized REE + Y patterns and δ13C values (−2.56‰ to +0.15‰ V-PDB) and point out to a classical multi-stage redox-controlled Mn-model involving: i) a primary hydrothermal fluid source related to ocean vents and/or normal faults; ii) microbially-mediated reduction of Mn-oxides particles at the ocean bottom; and iii) reactions between Mn2+ and CO32− (organic matter and seawater related), giving rise to diagenetic Mn-carbonates. The Rhyacian age, Mn deposits, and presence of Lomagundi-like δ13C allows to correlate the Buritirama Formation with the Águas Claras Formation within the Carajás domain further south, thus establishing an important metalliferous event that was up to now largely overlooked within the southern Amazon Craton.

Middle Jurassic–Lower Cretaceous glendonites from the eastern Barents Shelf as a tool for paleoenvironmental and paleoclimatic reconstructions

Glendonites are carbonate pseudomorphs after ikaite which use as indicators of near-freezing temperatures. We describe the first glendonites of Middle–Late Jurassic to Early Cretaceous age from the Barents Shelf, including the first glendonites of Late Barremian–Early Aptian age ever discovered on Earth and provide the detailed mineralogical-geochemical and isotopic studies. Mesozoic glendonites are well-known across the Arctic realm, however the ikaite-calcite transformation and implication of glendonite findings are still debatable. Pseudomorphs are mainly composed of calcite. Cathodoluminescence and scanning electron microscopy studies reveal three types (I-III) of calcite: type I - elongated, rounded and irregular calcite; type II - blocky, fibrous and needle-like calcite/siderite; type III - blocky calcite in pores. Elemental analyses distinguish geochemical differences between the calcite types: type I comprises pure CaCO3; type II calcite contains Mg and P (in all studied samples), Fe (Bajocian–Callovian), S (Middle Volgian) or Sr (Upper Barremian–Lower Aptian); type III calcite is depleted in Mg, P and Fe. Concentrations of Mn, Fe, Sr and calculated Mn/Ca, Fe/Ca and Sr/Ca ratios are suggestive of diagenetic alteration. Bulk δ18O values range from −5.39 to −1.71‰ VPDB, supporting overprinting of primary values during burial diagenesis, while bulk δ13C values range from −33.3 to −22.6‰ VPDB, providing the influence of organic matter on ikaite-glendonite formation. However, 87Sr/86Sr values range from 0.7070 to 0.7110, mainly corresponding to Jurassic–Cretaceous seawater. Rare-earth elements characterize porewater REE-patterns, with slight middle REE-enrichment and depletion in light and heavy REE. Weak positive and negative Ce anomalies indicate fluctiating from anoxic to oxic conditions during ikaite-glendonite formation. Our new biostratigraphic data refine the ages of glendonite-bearing horizons in the Barents Shelf region, allowing a more definitive correlation with coeval glendonite occurrences across the Arctic realm and with global climatic changes during the Jurassic–Cretaceous.

Fault-controlled carbonate-hosted barite-fluorite mineral systems: The Shuanghe deposit, Yangtze Block, South China

Fault-controlled carbonate-hosted Ba-F deposits occur in many major orogenic belts of the world and are important repositories of fluorine production required in various fields of chemical, metallurgical glass, ceramic, and cement industries. Here we investigate the poorly documented Shuanghe barite-fluorite deposit in the Yangtze Block of South China. This deposit offers an excellent case for studying the processes of formation of fault-controlled carbonate-hosted barite-fluorite mineral system. The orebodies in Shuanghe are hosted in carbonate rocks belonging to the early Ordovician Honghuayuan Formation and are dominantly controlled by NE-trending faults. Fluorite and barite exhibit similar rare earth element patterns with positive Eu anomalies and negative Ce anomalies. We report fluorite Sm–Nd isotopic data which yielded an isochron age of 103.1 ± 1.3 Ma. The δ18OV‐SMOW values range from +0.2‰ to +1.1‰ and the δDV‐SMOW values show a range of –33.1‰ to −26.3‰. The δ34SV-CDT values for barite range from 31.1‰ to 38.2‰. The bulk and in-situ Sr values for fluorite and barite show a range of 0.709081 to 0.712258. The petrological and geochemical data reported in this study suggest the following processes: (1) derivation of the ore-forming fluid from basinal water mixed with meteoric water; and (2) origin of the ore-forming components from Cambrian carbonate rocks, black shale, and Ordovician limestone. We propose a model that correlates the tectonic background of mineralisation with the Late Cretaceous subduction of the Paleo-Pacific Oceanic plate.

Geochemistry of lower Ordovician microbialites on the Yangtze Platform, South China: Implications for oceanic oxygenation at the onset of the GOBE

The causes of the Great Ordovician Biodiversification Event (GOBE) remain a topic of debate. Recent studies indicate that global and regional oceanic oxygenation was a plausible trigger of the GOBE. The Ce anomaly of rare earth and yttrium (REY) elements in shallow marine carbonates is thought to be a powerful indicator of marine redox conditions of local waters. In this study, we analyzed REY, major and trace element compositions, and C and O isotopes of the Lower Ordovician microbial-dominant reefs on the Yangtze Platform, South China. We evaluate which carbonate components within the reefs most reliably record the seawater REY composition. The elemental correlations show that the REY elements of oncoids, stromatoporoids, sponges and carbonate infillings were affected by clastic influence, diagenetic processes, and the vital effects of carbonate secreting organisms; whereas the microbialites REY were partially modified by synsedimentary terrigenous and little diagenetic modification. Such introduction of synsedimentary terrigenous REY increased ΣREY and flattened the REY patterns of the microbialites, but the redox signals (Ce anomalies) of input source of the water column might still preserved in microbialites formed in situ. Although the magnitude of Ce anomalies is small, variation might still reflect authentic redox history of primary local seawater. In the middle Tremadocian, microbialites have positive Ce anomalies which were coeval to positive δ13Ccarb shifts. The positive δ13Ccarb shifts were documented from other sections of central Yangtze Platform, North American and Argentina, which might indicate global anoxic event. In the late Tremadocian to early Floian, microbialites have more visible negative Ce anomalies, which might indicate regional oceanic oxygenation event. The negative Ce anomalies provide direct local-geochemical evidence of oceanic oxygenation in the late Tremadocian-early Floian on the Yangtze Platform of South China, which might facilitate the first acme of biodiversification of local faunas predating the main pulse of the GOBE on the other palaeoplates.

Geochemical evidence for a multi-source origin of manganese in the Montaña de Manganeso deposit, central Mexico

The Montaña de Manganeso is a manganese vein-type deposit spatially associated with back-arc basin remnants of the Guerrero tectonostratigraphic terrane. The study of major- and trace-element geochemical characteristics of the deposit provides insight into the controls on ore-forming processes within the area. The deposit is characterized by low Co, Cu and Ni abundances, and high Ba (>10,000 ppm) contents and Mn/Fe ratios (<500), typical of hydrothermal Mn deposits. In addition, the low ∑REE abundances (18.7 to 103 ppm), negative Ce anomalies (0.2 to 0.6), and positive Y (1.00 to 2.34) and Eu anomalies (0.6 to 4.4) also suggest a hydrothermal source for the deposit. Discrimination plots involving ∑REE and Zr vs. (Cu + Ni + Co) and Ce/Ce* vs. Nd and Y/Ho further indicate a hydrothermal source in an oxidizing depositional environment. The Mn-Fe-(Ni + Cu + Co), MnO2-MgO-Fe2O3, (Cu/Zn)/Fe2O3 vs. (Zn/Ni)/MnO2 and Na/Mg diagrams display intermediate signatures between marine and terrestrial environments. This suggest that the Montaña de Manganeso deposit is the result of two metallogenic stages: (I) the earliest stage, which involved the formation of Mn oxides by hydrothermal/diagenetic processes in the Arperos back-arc basin during the Cretaceous; and (II) the latest stage took place subsequent to accretion the Guerrero tectonostratigraphic terrane onto the continent and involved the remobilization of the Cretaceous submarine Mn oxides (and associated trace elements) and subsequent redepositation by Tertiary continental hydrothermal activity.

Effects of topography and soil properties on the distribution and fractionation of REEs in topsoil: A case study in Sichuan Basin, China

In order to investigate how topographic factors and soil physicochemical properties influenced the distribution and fractionation of rare earth elements (REEs) in soil, Jiangjin district of Sichuan Basin, an area with mountainous topography, was selected as a study area. The concentration of REEs, pH and organic matter (OM) and major elements in 156 topsoil samples were measured and analyzed. The topographic factors considered were elevation, slope, and topographic wetness index (TWI), which were extracted by using the digital elevation model (DEM). The median concentration of total REEs in topsoil of the study area was 147 mg/kg, lower than the Chinese soil background value (164 mg/kg). The concentration of LREEs and HREEs, and the ratio of LREEs/HREEs and LaN/YbN indicated that the distribution and fractionation patterns of REEs in topsoil were LREEs-enriched. Significant Eu negative anomalies and weak Ce negative anomalies were observed in topsoil according to the median values of δEu (0.57) and δCe (0.89). The coefficient of weathering and eluviation (BA), an important factor affecting the distribution and fractionation of REEs, was substantially correlated with δEu (r = 0.344, p < 0.01), δCe (r = −0.252, p < 0.01), ∑REEs (r = 0.135, p < 0.01), and LREEs/HREEs (r = −0.281, p < 0.01) in topsoil. Soil pH and OM had some influence on the distribution and fractionation of REEs. Under the geographical environment of the study area, Ce was positive anomaly with the elevation and slope increasing. The enrichment of LREEs was more significant than HREEs as elevation increased. The findings revealed that topographical attributes and soil physicochemical properties integratedly influenced the distribution and fractionation of REEs in topsoil.

The transfer of rare earth elements during early diagenesis in REY-rich sediments: An example from the Central Indian Ocean Basin

Rare earth element and ytterbium (REY)-rich deep-sea sediments are recently discovered potential undersea rare earth element (REE) resources. Here, we present the results of the mineralogical and geochemical characterization of REY-rich sediments collected from the Central Indian Ocean Basin (CIOB). These data were used to provide a jigsaw puzzle for the investigation of REY transfer during early diagenesis and to discuss the formation mechanism of REY-rich sediments. The research results show that the REY-rich sediments distributed in the CIOB mainly consist of phillipsite-bearing pelagic clay and pelagic clay, and are characterized by enrichments in middle REEs (MREEs) and heavy REEs (HREEs), negative Ce anomalies and positive Y anomalies. The REY in these sediments are mainly captured dirtcely from overlying seawater by bioapatite and micronodules at the water-sediment interface. After burial, driven by the redox reaction between organic matter and an oxidizer (free O2 and Mn and Fe oxides), the REY-rich sediments experienced weak early diagenesis, and the REY released from hydrogenetic micronodules were captured by the bioapatite.

Carbon, oxygen and strontium isotope geochemistry of the late Neoproterozoic carbonate platform deposit Hyangsanni Dolomite of the Okcheon metamorphic belt, Korea

The age-unknown Hyangsanni Dolomite is distributed in the northeastern part of the Okcheon metamorphic belt in central South Korea. It has been claimed as Early to Middle Cambrian because of the misidentified Archaeocyatha fossil in the past, but the time of sedimentation has not yet been confirmed. We performed elemental and isotopic analyses for the Hyangsanni Dolomite. The REE + Y patterns of the samples of the Hyangsanni Dolomite are generally flat and Ce negative anomaly is generally negligible to the extent that it appears only weakly in some samples. Y/Ho values are in the range of 29–43, which is fairly lower than typical Y/Ho ratio of seawater, indicating the influence of terrigenous materials. REE and trace element geochemical discrimination diagrams indicate that the Hyangsanni Dolomite was deposited in a continental margin environment rather than an open ocean. We suggest that the Hyangsanni Dolomite was deposited in a rift basin connected to the ocean rather than in the passive continental margin, considering occurrence of magmatism related to continental rifting within the Okcheon metamorphic belt. Carbon and oxygen isotope analysis was performed on dolomite powders scraped off from polished surfaces unstained with Alizarin-Red-S in order to avoid the recrystallized calcite. The Hyangsanni Dolomite has δ13C(V-PDB) values between +2.9‰ and + 6.2‰, and δ18O(V-SMOW) values between +11.3‰ and + 24.5‰. These δ13C values are markedly higher than the Cambro-Ordovician values, and are consistent with the Neoproterozoic values. The minimum value of 87Sr/86Sr ratio obtained from the Hyangsanni Dolomite also refers to Neoproterozoic, not Phanerozoic. We suggest that the Hyangsanni Dolomite belongs to the sedimentary sequence of the Neoproterozoic, along with other sediments of the northeastern Okcheon metamorphic belt.

Characteristics and genesis of ion adsorption type REE deposits in the weathering crusts of metamorphic rocks in Ningdu, Ganzhou, China

Over the past few decades, numerous ion adsorption type rare earth element (REE) deposits have been discovered in the weathering crusts of granitic and volcanic rocks, and a great deal of studies have been conducted on their characteristics and genesis. Recently, ion adsorption type REE deposits in the weathering crusts of metamorphic rocks were discovered for the first time in Ningdu County, China. Unlike the extensively studied weathering crusts of granitic rocks, the geochemical and mineralogical characteristics of the weathering crusts of metamorphic rocks and the mobility of REEs during weathering processes remain unclear. Our research shows that the bedrocks in the Ningdu area are primarily metamorphic sandstone that contain ~ 200 ppm of total REEs. REEs in the metamorphic rocks are primarily hosted in hydrothermal REE-epidote and rhabdophane-(Ce), implying that hydrothermal fluids, which might have introduced REEs and provided the materials for REE mineralization, are likely one of the most critical factors for mineralization in the weathering crusts of metamorphic rocks. The weathered products of fine-grained metamorphic bedrocks are significantly less permeable than those of granitic rocks; consequently, the weathering crusts are rather thin, usually less than 20 m. The degree of weathering is relatively low, with chemical index of alteration (CIA) values of less than 80. Clay minerals consist primarily of illite, kaolinite, and hydrobiotite. The low permeability of the weathered products causes a short migration distance for water medium carrying REE ions, and the ore bodies in the weathering crusts of metamorphic rocks are primarily located in the middle and upper parts of the completely weathered horizon. Average REE concentrations in the ore bodies are ~ 1000 ppm, of which 70%–80% are ion-exchangeable. The REE distribution patterns of the weathering crusts are largely similar to that of the bedrocks, except for the strong negative Ce anomalies in the topsoils that are caused by the pre-existing positive Ce anomaly layer above the ore body that is thin and removed due to weathering and erosion. Our research results deepen the understanding of the genesis of ion adsorption type REE deposits in the weathering crusts of metamorphic rocks and indicate that the hydrothermal process is the key mineralization factor.

Marine diagenesis of ikaite: Implications from the isotopic and geochemical composition of glendonites and host concretions (Palaeogene–Neogene sediments, Sakhalin Island)

AbstractGlendonites represent pseudomorphs after calcium carbonate hexahydrate (ikaite) and can be used as indicators of past cold climates, because ikaite only naturally occurs in cold environments (&lt;7°C) in the modern. The results of a multi‐proxy study of 11 glendonite and host concretion samples from Palaeogene (Gennoishi Formation) and Neogene (Bora and Vengeri formations) sediments from Sakhalin Island, Russian Far East are reported here. Petrographic, cathodoluminescence, powder X‐ray diffraction and scanning electron microscope analyses reveal that glendonites are composed of several successive mineralogical phases: low‐magnesium ikaite‐derived calcite, high‐magnesium acicular cement (calcite and dolomite) and blocky calcite or authigenic quartz filling the remaining pore space. Host concretions comprise sandy limestones cemented by high‐magnesium calcite. The δ13C and δ18O values for host concretions and enclosed glendonites are very similar, with δ13C ranging from –20.3 to +1.9‰ Vienna Pee‐Dee Belemnite and δ18O ranging from –3.4 to +3.4‰ Vienna Pee‐Dee Belemnite. Such isotopic values suggest that seawater was the main source of oxygen, while dissolved inorganic carbon and decaying organic matter were the main carbon sources for ikaite growth, concretion and glendonite cementation. The 87Sr/86Sr values within the glendonites and host concretions are significantly lower compared with coeval Palaeogene–Neogene marine carbonates, suggesting an influence of continental runoff on their isotopic composition. Post Archean Australian Shale normalized rare earth element patterns display negative Ce anomalies and positive Eu anomalies, with a depletion in light rare earth elements or bulge in middle rare earth elements. Such spectra of rare earth elements indicate that ikaite growth and replacement occurred very close to the aerobic–anaerobic boundary, with pore waters derived from trapped seawater and/or ikaite dehydration. Since Mg/Ca ratios and alkalinity increase with depth below the sediment–water interface, subsequent mineral phases show enrichment in Mg, while the lack of diagenetic alteration by basinal fluids enabled preservation of the primary isotopic and geochemical characteristics of ikaite within the recrystallized pseudomorph.

Geochronology, geochemistry and mineral chemistry of Malayer–Boroujerd–Shazand pegmatite dikes, Sanandaj–Sirjan zone, NW Iran

Pegmatite dikes in the Malayer–Boroujerd–Shazand magmatic complex, located in the Sanandaj-Sirjan zone of the Zagros orogen, are hosted in both granitoid rocks and their contact and regional metamorphic aureoles. In this study, we report the geochronology, geochemistry and mineral chemistry of these pegmatite dikes. The granitoid rocks in the Malayer–Boroujerd–Shazand magmatic suites are mainly monzogranite, quartz diorite, granodiorite and quartz monzonite characterized by metaluminous to peraluminous I-type compositions of the calc-alkaline series and display the geochemical characteristics of volcanic arc granites related to an active continental margin. The pegmatite dikes mainly consist of quartz, feldspar (albite and orthoclase), tourmaline, muscovite and less common biotite and garnet. The tourmaline content in the igneous-hosted pegmatite dikes is higher than those of metamorphic rocks, whereas the muscovite content is lower in the igneous-hosted pegmatite dikes. The K/Rb ratio and the Rb content of pegmatite dikes and their minerals (K-feldspar and muscovite) indicate that they are less evolved. Pegmatite dikes display a typical calc-alkaline affinity of I-type granites and are classified as peraluminous Lithium-Caesium-Tantalum (LCT) family (barren sub-type) to muscovite class. The tourmaline is a schorl-foitite type, which is common in the early crystallization stage of less evolved pegmatites. U–Pb zircon dating of the Boroujerd and Shazand pegmatite dikes yield weighted mean 206Pb/238U ages of 160.2 ± 1.8 and 121.8 ± 1.5 Ma, respectively. In contrast, U–Pb zircon dating of the Malayer pegmatite dike gives a mean 206Pb/238U age of 43.2 ± 1.5 Ma. Our new geochronological data indicate that the first group of pegmatite dikes (older pegmatite dikes) in the Boroujerd district (160.2 ± 1.8 Ma) shows an overlap with the main and first magmatic episode in the Sanandaj–Sirjan zone during Jurassic times, simultaneous with the Middle Cimmerian Orogenic phase, and formed during the subduction initiation. The second group of pegmatite dikes in the Shazand district (121.8 ± 1.5 Ma) formed in the Early Cretaceous and shows a temporal overlap with previously reported ages (ca. 130–114 Ma) during the early Alpine tectonic movements (Late Cimmerian Orogenic phase). Finally, the younger group of pegmatite dikes in the Malayer district (43.2 ± 1.5 Ma) formed in the Eocene overlapping with previously reported ages (ca. 34–52 Ma) which is equivalent to the Laramian phase. These data reveal that the magmatism in the Malayer–Boroujerd–Shazand magmatic complex started in the Early-Middle Jurassic resembling adjacent areas in the Sanandaj–Sirjan zone (e.g., Hamedan region) by melting of crustal protoliths in a subduction tectonic setting. The second and third groups of pegmatite dikes formed during the late subduction to syn-collisional process, respectively. These pegmatite generation marked the subduction initiation to syn-collisional span in the region. The zircon geochemistry (negative Ce anomalies and positive Eu anomalies) is indicative of the relatively oxidized conditions of the parent magma and shows characteristics of continental crust zircon.

The origin of early-Paleozoic banded iron formations in NW China

There is growing evidence that the earliest Paleozoic ocean experienced fluctuations in ocean redox chemistry, with anoxic ferruginous conditions being a prevalent feature at certain times. However, the general absence of early Paleozoic banded iron formations (BIFs) means that direct supporting evidence for ferruginous conditions inferred from geochemical proxy data is currently limited. Here, we describe an early-Paleozoic BIF (Tiande No.2) from the late Silurian Habahe Group in Altay, NW China. The BIF is hosted in meta-volcano-sedimentary rocks, and is characterized by alternating iron-rich and silica-rich laminae. In addition to abundant magnetite and quartz, Fe-silicates (garnet and amphibole) are dominant minerals in the BIF. Like most earlier Precambrian examples, the BIF horizons are dominated by high Si and Fe contents, but also contain significant Al, Ti and rare earth element concentrations, consistent with a dominant chemical origin, but with significant terrigenous contribution. We observe slightly positive Eu anomalies (1.17 to 1.57) and low εNd(t) values (−4.2 to −0.8) in BIF samples, indicating a mixed seawater and submarine hydrothermal source for the iron. The BIF also generally displays negative Ce anomalies, and homogeneous and slightly negative δ56Fe values. This suggests near-quantitative oxidation of dissolved Fe(II) from the water column, likely following upwelling into oxygenated surface waters as sea level decreased, in a region where the terrigenous input was low relative to the dissolved Fe2+ flux. The Tiande No.2 BIF is conformably bedded within schist, which also has high concentrations of Fe (up to 12.67 wt%), generally elevated Fe/Al ratios (>1.0), and no Ce anomaly, while magnetite in the schist has heavy and variable δ56Fe values. This suggests that the schist precursor, which likely comprised a significant contribution from deposited marine sediment, was also deposited from ferruginous waters, but with only partial oxygenation of dissolved Fe2+ in a dominantly anoxic water column. The occurrence of this late Silurian BIF and associated ferruginous rocks provides new constraints on the nature of ocean redox chemistry at this time, and supports continued dynamic Fe cycling and at least intermittent ferruginous deeper water conditions in this location during the late Silurian.

Geochemistry and detrital zircon geochronology of the Lower Jurassic clastic rocks of the northern Qiangtang Basin, northern Tibet: Implications for palaeoenvironment, provenance, and tectonic setting

The Lower Jurassic clastic rocks in the Qiangtang Basin, northern Tibet, are generally regarded as the early sediments of the new Mesozoic Qiangtang Basin (Late Triassic to Early Cretaceous). However, little attention has been paid to the palaeoenvironment, provenance, and tectonic setting of this unit. The QZ‐16 well, located in the east of the northern Qiangtang Basin, firstly recovered the Lower Jurassic strata (Quemo Co Formation) in the Qiangtang Basin. In this paper, the whole‐rock major‐trace elemental characteristics of 34 mudstone samples and detrital zircon geochronology of one sandstone, collected from the Quemo Co Formation of the QZ‐16 well, are reported in order to infer the palaeoenvironment, provenance, and tectonic setting. Quemo Co mudstones are dominated by SiO2 and Al2O3, while Fe2O3, CaO, K2O, and MgO are the second most abundant oxides. They are generally characterized by high REE concentrations, enrichment in light rare earth elements (LREEs), marked negative Eu and Ce anomalies. The REE contents of the mudstones are mainly controlled by terrigenous detrital minerals input. The Lower Jurassic mudstones have relatively high chemical index of alteration (79.1–83.6) values, indicating moderate to high degree of chemical weathering conditions of the source area. Sr/Ba and Rb/K ratios reflect that the marine transgression impact was limited and the mudstones were generally deposited in a brackish water environment. Major, trace, and REE contents indicate that the mudstones were mainly derived from intermediate igneous rocks with subordinate felsic igneous rocks. Prominent age peaks at ca. 200 ~ 400 Ma, 700 ~ 970 Ma, 1,700 ~ 1,900 Ma, and 2,100 ~ 2,700 Ma of the detrital zircon grains suggest that the Lower Jurassic clastic rocks were derived from the Central Qiangtang and Songpan–Ganzi complex. Moreover, tectonic discrimination diagrams based on major and trace elements show that the source of the Lower Jurassic sediments were most likely derived from a collision tectonic setting.

Contrasting Depositional Environment of Iron Formation at Endengue Area, NW Congo Craton, Southern Cameroon: New Insights from Trace and Rare Earth Elements Geochemistry

The Endengue Banded Iron Formation (BIF) is located in the northwestern edge of the Congo craton in Cameroon. Here, we report geochemical data of trace and rare earth elements (REE) of the Endengue BIF samples from the Archean Ntem complex and investigate their environmental setting. Two types of BIF occur at Endengue area, both containing minimal contamination from terrestrial material. Total REE (ΣREE) contents in the Type 1 BIF are extremely low, ranging from 0.34 to 1.83 ppm, similarly to pure chemical sediments while Type 2 BIF displays ΣREE contents ranging from 2.98 to 24.26 ppm. The PAAS-normalized REE + Y patterns of the two BIF types display LREE enrichment relative to HREE and weak positive Eu anomaly, most likely suggesting that the source of iron and siliceous of the Endengue BIFs is mainly from the contribution of low-temperature hydrothermal alteration of the crust. Type 1 BIF shows very low Nd content (* and positive Ce anomalies which suggests suboxic or anoxic seawater similar to the depositional environment of Elom BIF in Archean Ntem complex. In contrast, Type 2 BIF displays low to moderate Nd contents (1 and 100 ppm with the exception of sample LBR65) with negative correlation between Nd and Ce/Ce* and negative Ce anomalies. These features indicate precipatation of Type 2 BIF from oxic iron-rich solution that changed to oxidized surface by rapid precipitation of the hydrothermal Fe. The Endengue BIFs were deposited in the continental margin ocean in presence of low-temperature hydrothermal fluids mixed with seawater, similar to Paleoproterozoic Kpwa-Atog Boga BIFs within the Nyong group and other Paleoproterozoic Superior-type BIFs worldwide.

Geochemical Behaviors of Rare Earth Elements (REEs) in Karst Soils under Different Land-Use Types: A Case in Yinjiang Karst Catchment, Southwest China.

The geochemical characteristics of rare earth elements (REEs) can be employed to identify the anthropogenic and natural influence on the distributions of REEs in soils. A total of 47 soil samples from the three soil profiles of the secondary forest land, abandoned cropland, and shrubland in the Yinjiang county of Guizhou province, southwest China, were collected to determine the contents and distribution of REEs in the soil environment. The total REEs (ΣREE) contents in different soil profiles are in the following sequence: secondary forest land (mean: 204.59 mg·kg−1) > abandoned cropland (mean: 186.67 mg·kg−1) > shrubland (mean: 139.50 mg·kg−1). The ratios of (La/Gd)N and (Gd/Yb)N ranged from 0.62 to 1.00 and 1.18 to 2.16, which indicated that the enrichment of the medium rare earth elements (MREEs) was more obvious than that of the light rare earth elements (LREEs) and the heavy rare earth elements (HREEs). The phenomenon could be attributed to the preferential absorption of MREEs by fine particles and the substitution of Ca2+ by MREEs. Most soil samples were characterized by the negative Ce anomalies (anomalies values: 0.30–1.10) and positive Eu anomalies (anomalies values: 0.43–2.90). The contents of REEs in the profiles of secondary forest land and shrubland were mainly regulated by soil pH and Fe contents while clay content and agricultural activities were the main controlling factors in the soil profile of abandoned cropland. This study highlights the role of agricultural activities in affecting the distributions of REEs in karst soils, which could provide some insights for the protection of the soil environment.

Discovery of Permian crustal carbonatite in the northwestern margin of Tarim Basin and its geological significance

碳酸岩是自然界较为特殊的一类火成岩，由于其在上侵过程中不易受到地壳物质的混染，可以很好地保留源区原始特征，因而在揭示岩浆源区属性和地球深部碳循环等方面具有重要的研究价值。塔里木盆地西北缘阿克苏-乌什南部地区发育多条侵位到新元古界南华系中的火成碳酸岩岩墙或岩脉。这些岩脉的锆石U-Pb测年结果显示出多个年龄峰值，其中最年轻一组（3颗）岩浆锆石的谐和加权年龄为272±4Ma，另外还有400Ma、450Ma、790Ma、850Ma等年龄峰，而这些锆石可能均为碳酸岩岩浆捕获成因。结合区域上发育大量早二叠世辉绿岩岩床及岩墙等侵入事件，推测这些碳酸岩很可能形成于早二叠世（~270Ma）。碳酸岩主要由方解石（90%以上）构成，并含少量的白云石、重晶石、天青石、赤铁矿等其它矿物，可见方解石与白云石之间明显的出溶结构以及野外宏观上碳酸岩包裹围岩等现象。元素地球化学分析显示，碳酸岩CaO含量高（44.40%~50.40%），SiO₂含量低（1.83%~7.97%）；稀土元素总量很低（ΣREE=21.67×10^-6~91.32×10^-6），轻重稀土分异明显（LREE/HREE=3.90~8.40），具有中等负铕异常（δEu=0.61~0.68）和中等至弱负铈异常（δCe=0.59~0.98）；大离子亲石元素Sr、Rb、Ba等相对富集，Nb、Ta、Ti等高场强元素相对亏损；稳定同位素δ¹³C_V-PDB值高（-2.69‰~-2.93‰）、δ¹⁸O_V-SMOW值高（17.33‰~17.86‰）。这些特征与壳源碳酸岩特征相似，而与幔源碳酸岩差别较大。Sr-Nd同位素结果显示高的（⁸⁷Sr/⁸⁶Sr）_i值（0.710106~0.710558），低的ε_Nd（t）值（-8.46~-12.80），也进一步证实碳酸岩为地壳来源。综合分析认为这些碳酸岩很可能是塔里木二叠纪大火成岩省晚期岩浆事件的组成部分，系由塔里木西北缘地幔柱减压熔融后形成高温的基性岩浆向上侵位运移时，导致下地壳的碳酸盐储库部分熔融形成碳酸岩岩浆，并沿着断裂快速向上侵位形成。本文研究不仅丰富了塔里木大火成岩省的岩石组成认识，而且有助于增进对二叠纪深部复杂壳幔作用过程的理解。;Igneous carbonatites is a kind of special igneous rock in nature. Because they are not easily contaminated by crustal materials in the process of upwelling, they can well retain the original characteristics of the magma source. Therefore, they have important research value in revealing the properties of the magma source and the carbon cycle of the deep earth. Several carbonatite dikes or dykes are found intruded into the Neoproterozoic Nanhua System in the southern Aksu-Wushi area, the northwestern margin of Tarim Basin. Zircon U-Pb geochronology dating of these carbonatites yield multiple peak ages, including a youngest one at 272±4Ma obtained by three zircons, and other ones at 400Ma, 450Ma, 790Ma, 850Ma, respectively. However, all these zircons were probably captured by carbonate magma. Considering the intrusive events of massive Early Permian diabase sills and dikes in the region, we speculate that these carbonatite dikes were probably formed in the Early Permian (~270Ma). The carbonatites are mainly composed of calcite (over 90%) and a small amount of dolomite, barite, celestite, hematite and other minerals. In addition, the carbonatites have obvious exsolution structures between calcite and dolomite, and the country rock breccias are found wrapped by the carbonatites in the field. The element geochemistry analysis results show that carbonatites have high CaO content (44.40%~50.40%), low SiO₂ content (1.83%~7.97%), extremely low total rare earth elements content (21.67×10^-6~91.32×10^-6) with obvious differentiation of LREE and HREE (LREE/HREE=3.90~8.40) and weak negative Eu and Ce anomalies (δEu=0.61~0.68; δCe=0.59~0.98). And the large ion lithophile elements like Sr, Rb, Ba are relatively enriched, and high field-strength elements such as Nb, Ta, Ti are relatively depleted. The stable isotope of δ¹³C_V-PDB and δ¹⁸O_V-SMOW are high (-2.69~-2.93‰ and 17.33~17.86‰, respectively). All these characteristics are similar to the crustal carbonatite, but quite different from the mantle carbonatite. The Sr-Nd isotopic results of high (⁸⁷Sr/⁸⁶Sr)_i values (0.710106~0.710558) and low ε_Nd(t) values (-8.46~-12.80) also confirm that the Aksu carbonatites are derived from the crust. After comprehensive analysis, we propose that these carbonatites are probably the components of the late magmatic event in the Permian Tarim Large Igneous Province. When the mantle plume in the northwestern margin of Tarim was decompressed, it would form high-temperature basic magma and emplaced upward. These basic magma would heated the carbonate reservoir in the lower crust and partially melted it to form carbonatites magma, which was rapidly emplaced upward along the extension fault. This study not only enriched the petrological compositions of the Permian Tarim Large Igneous Province, but also promoted the understanding of the complex crust-mantle interaction processes in the deep area of Permian Tarim Basin.

Evidence of Paleoproterozoic phosphogenesis in the Salvador-Curaçá Orogen (Tanque Novo-Ipirá Complex), northeastern São Francisco Craton, Brazil

Abstract This paper analyzes mineralogical, geochemical, and geochronological aspects, along with the effect of hydrothermal/metasomatic overprints, to identify the presence of primary phosphate as well as depositional and paleoenvironmental conditions in marble and calcsilicate sequences recrystallized under transitional amphibolite-granulite metamorphic conditions in the Tanque Novo-Ipira Complex within the Salvador-Curaca Orogen, northeastern Sao Francisco Craton, state of Bahia, Brazil. Petrographic studies have identified up to 10 vol.% disseminated apatite and whole-rock P2O5 contents up to 3.2 wt.%. Post-depositional events affected the lithofacies to varying degrees. Late hydrothermalism did not modify the rare earth element and yttrium (REEY) patterns considerably. When normalized to Post-Archean Australian Shale (PAAS), these lithofacies are marked by flat pattern REEY, true negative Ce anomalies, and positive Y and Gd. The highly variable Eu anomalies were inherited from the source composition but may have been affected by interaction with fluids. U-Pb LA-ICP-MS (laser ablation multicollector inductively coupled plasma mass spectrometry) ages indicate a maximum depositional age of 2128 Ga, as well as Paleoproterozoic and Neoarchean sources. Samples with anomalous phosphorus show Y/Ho ratios >30 and Ce/Ce* anomalies between 0.53 and 1.0 with an average of 0.70, suggesting a sub-oxic environment for phosphate precipitation.

Rare earth and yttrium elements (REY) patterns of mesostructures of Miaolingian (Cambrian) thrombolites at Jiulongshan, Shandong Province, China

The relationship between the thrombolitic mesostructures and their depositional environments is still poorly understood due to inconsistent results by sedimentary investigation. Rare earth elements plus yttrium (REY) in ancient microbialites have been extensively applied to paleoenvironmental studies owing to their fractionation in different depositional environments. In order to investigate the environmental controls on thrombolitic mesostructures, we present the REY concentrations and patterns of four types of mesostructures of the Miaolingian (Cambrian) thrombolites in the Changhia Formation at the Jiulongshan section, Shandong Province, China. The REY compositions of those thrombolites show two distinctive groups: (1) light REY depleted patterns with negative Ce anomalies in spotted (SM) and layered mesostructures (LM) of thrombolites; and (2) flat patterns with weak Ce anomalies in dendritic (DM) and meshed mesostructures (MM) of thrombolites. Controlling factors analysis reveals that terrigenous detritus inputs have stronger influence on REY in SM and LM. In contrast, early diagenetic porewaters from underlying sediments have more serious impacts on REY concentrations and patterns in DM and MM. Our results clearly indicate that SM and LM were formed under oxic marine settings with minor terrigenous inputs, whereas DM and MM formed under suboxic marine settings suffered from early diagenetic porewater from underlying sediments. This new geochemical evidence suggests that thrombolitic mesostructures were strongly influenced by paleoenvironment, and REY of thrombolites with controlling factors analysis can be utilized as effective proxies for paleoenvironments.

A transient swing to higher oxygen levels in the atmosphere and oceans at ~1.4 Ga

The mid-Proterozoic (1.8–0.8 Ga) may have witnessed persistent and predominant anoxia at the Earth’s surface. However, recent studies suggest that there was a period around ~1.4 Ga where oxygen levels might have been transiently elevated, both in the atmosphere and oceans. In order to shed light on this debated topic, we analyzed rare earth elements plus Y (REY) and Cr isotope profiles of the carbonate rocks from the ~1.44-Gyr-old Tieling Formation consisting of the lower Daizhuangzi (DZZ) and upper Laohuding (LHD) Members at the Jixian section, North China. The DZZ samples are characterized by middle REE enriched, hump-shaped REY distribution patterns, while those of the LHD Member display seawater-like REY patterns with slightly negative Ce anomalies (0.67 < Ce/Ce* < 0.87). Although differing greatly, the REY profiles both in the DZZ and LHD Members indicate the presence of Mn oxyhydroxides and thus an oxygenation at least locally in the shallow seawater of the North China Platform at ~1.44 Ga. The middle LHD Member records positive authigenic δ53Cr up to 0.48‰, indicating an enhanced continental oxidative weathering transiently occurred at ~1.44 Ga with pO2 higher than 1% of the present atmospheric level, and extending the mid-Proterozoic sedimentary record of positive Cr isotope fractionation to as early as ~1.44 Ga. Combining the investigations in this study with other published geochemical evidence from the North China Platform and elsewhere, we suggest that there was a transient and global swing to higher oxygen levels in the atmosphere and oceans at ~1.4 Ga.