Redox-sensitive Elements Research Articles

In situ major and trace element compositions of apatite from the Yangla skarn Cu deposit, southwest China: Implications for petrogenesis and mineralization

The Yangla copper deposit is a rare Triassic intrusion-related Cu skarn system in the central part of the Jinshajiang tectonic belt, central Sanjiang orogenic belt, southwest China. Major- and trace-element compositions of apatites from ores, fertile calc-alkaline intrusions and its mafic microgranular enclaves, and barren calc-alkaline intrusions from the Yangla skarn copper deposit were measured by electron probe microanalysis and laser ablation–inductively coupled plasma–mass spectrometry. Results indicate that apatites grown within ores, fertile intrusions and its enclaves show similar features, but are different from that grown within barren intrusions. Apatite from fertile intrusions has higher Ca and correspondingly lower total trace-element contents, which partition onto the Ca sites, relative to that from barren intrusions. Apatites from the barren intrusions have high F and low Cl contents, and correspondingly high F/Cl ratios, which may have resulted from the assimilation of sediment. Apatites from fertile intrusions show relatively high Cl and low F contents, which may reflect crystallization from magmas with high water contents. Redox-sensitive elements in apatite can be used as indicators of the oxidation state of magmas. Apatites from the barren intrusion have lower V and As contents, higher Mn, Fe, and U contents, and more pronounced negative Eu anomalies than those from fertile intrusion, indicating that the barren magma was more reduced, consistent with its lower whole-rock Fe2O3/FeO and zircon Ce4+/Ce3+ ratios. These findings demonstrate that apatites are effective in distinguishing fertile from barren intrusions and can be used as a robust tool in mineral exploration.

Redox transfer at subduction zones: insights from Fe isotopes in the Mariana forearc

Subduction zones are active sites of chemical exchange between the Earth’s surface and deep interior and play a fundamental role in regulating planet habitability. However, the mechanisms by which redox sensitive elements (e.g., iron, carbon and sulfur) are cycled during subduction remains unclear. Here we use Fe stable isotopes (δ56Fe), which are sensitive to redox-related processes, to examine forearc serpentinite clasts recovered from deep sea drilling of mud volcanoes formed above the Mariana subduction zone in the Western Pacific. We show that serpentinisation of the forearc by slab-derived fluids produces dramatic δ56Fe variation. Unexpected negative correlations between serpentinite bulk δ56Fe, fluid-mobile element concentrations (e.g., B, As) and Fe3+/ƩFe suggest a concomitant oxidation of the mantle wedge through the transfer of isotopically light iron by slab-derived fluids. This process must reflect the transfer of either sulfate- or carbonate-bearing fluids that preferentially complex isotopically light Fe.

Visualizing the distribution of black carbon's electron storage capacity using silver

We have developed a method that combines chemical reduction, silver tagging, and electron microscopy (EM) for visualizing the electron storage capacity (ESC) of black carbon (BC). ESC is a BC's capacity to store and reversibly exchange electrons with abiotic and microbial agents, processes that are relevant to biochemistry, greenhouse gas production, contaminant fate, and remediation. In addition to the amount of electrons BC can store, the locations and spatial distribution of ESC on and inside biochar are critical for understanding the bioaccessibility of ESC and the kinetics of redox reactions involving BC. To locate the ESC in a BC particle, we fully reduced a BC, removed excess reductant, and applied silver ion (Ag+) as a tagging agent that diffused into BC to react with functional groups where electrons were stored (i.e., ESC) to form silver nanoparticles (nAg). The nAg deposited on and inside BC were then imaged using multiple EM techniques to visualize the locations and distribution of the ESC. The method is a new and potentially useful tool for investigating ESC production and for elucidating BC-mediated redox transformation.•Novel method to probe and assess the distribution of ESC on/within BC.•Visual confirmation of significant ESC both on the surface and in the interior of BC.•A new method to incorporate silver or other redox-sensitive elements into a carbon medium.

Aqueous leaching of ADOPT and standard UO2 spent nuclear fuel under H2 atmosphere

ABSTRACTLeaching results to compare the dissolution behavior of a new type of fuel with additives (Advanced Doped Pellet Technology, ADOPT) with standard UO2 fuel are presented. Both fuels were irradiated in the same assembly of a commercial boiling water reactor to a local burnup of ∼58 MWd/kgU. Fuel fragments are leached in simplified groundwater in two autoclaves under hydrogen atmosphere, representing conditions in a canister failure scenario resulting in water intrusion for a spent nuclear fuel repository. Preliminary results indicate the uranium concentration decreased to 3-4x10-8 M after 421 days, slightly above the solubility of amorphous UO2. Xe has been detected in the gas phase of both autoclaves. The concentration of Cs and I seems to gradually approach constant values, yet the redox sensitive elements continue to slowly increase with time. The preliminary data obtained supports the hypothesis that there is no major difference in leaching behavior between the two fuels.

АНОМАЛИИ РЕДКИХ ЭЛЕМЕНТОВ В МАРГАНЦЕВЫХ МИКРОКОНКРЕЦИЯХ ИЗ ЭТМОДИСКУСОВЫХ ИЛОВ БРАЗИЛЬСКОЙ КОТЛОВИНЫ АТЛАНТИЧЕСКОГО ОКЕАНА

The composition of manganese micronodules from miopelagic clays and Ethmodiscus oozes of the central part of the Brazil Basin (station 1537, R/V Akademik Sergei Vavilov) is considered. Micronodules were recovered from >50 μm fraction of sediments from the depth intervals of 300 to 305, 405 to 410 and 442 to 452 cm below seafloor. The composition of micronodules was determined in separate size fractions of 50–100, 100–250 and 250–500 μm after dissolution in 0.5N NH2OH × HCl + 25% CH3COOH. The contents of Co, Ni, Cu, Ce, Pb, W, Th, and Bi in micronodules of miopеlagic clays were found to be higher than in micronodules from Ethmodiscus oozes. In the latter, the positive anomalies of Li, As, Mo, Cd, Tl, and U were revealed. The REE composition of micronodules in miopelagic clays is similar to the composition of hydrogenous crusts with a maximum in middle REE and a positive cerium anomaly. Micronodules of Ethmodiscus oozes have a positive Ce anomaly 2.8–3.8 and a deficiency of light lanthanides, similar to the composition of dissolved REEs in pore and bottom ocean waters. High accumulation of redox-sensitive elements in micronodules (As, Mo, V, and Cd) indicates an anaerobic stage in the post-sedimentary period in Ethmodiscus ooze caused by high biological productivity of waters. The formation of micronodules began during the period when the reducing conditions changed to oxidizing ones. Elements with low mobility (As, Mo, V, and Cd) accumulated in sediments and pore water during the anaerobic stage were then sorbed on Mn oxyhydroxides during the oxidation stage.

Mineral composition and geochemical characteristics of sinking particles in the Challenger Deep, Mariana Trench: Implications for provenance and sedimentary environment

The properties of sinking particles in the ocean can reflect geochemical cycles of marine organisms and are related to oceanic mineralization. In this paper, sinking particles were collected with time-series sediment traps at three depths (2000 m, 4000 m and 6000 m) in the Challenger Deep in the Mariana Trench. The mineral compositions and geochemical characteristics of the sinking particles were analyzed in order to determine their provenance and the redox depositional environment of the surrounding seawater. The results reveal a total of 7 categories and 24 kinds of minerals (compounds) in the sinking particles, which are sourced mainly from volcanic materials eroded from surrounding ridges and oceanic basins, among which the West Mariana Ridge and Kyushu-Palau Ridge contribute the most. Terrestrial eolian dust and oceanic authigenic minerals contribute little. The particle flux is higher at 6000 m than at 2000 m and 4000 m, and the supply rates are higher in spring. Analytical results for DO data, redox-sensitive elements (Th/U and V/Sc) and rare earth elements show that there is an oxidative sedimentary environment and that the oxidation degree of seawater increases with the depth, which is affected by the oxidized bottom water. No systematic variation in depositional environment was observed in spring and in summer.

Sandstone-Hosted Uranium Deposits as a Possible Source for Critical Elements: The Eureka Mine Case, Castell-Estaó, Catalonia

The Eureka deposit in Castell-estaó in the Catalan Pyrenees is a Cu–U–V deposit, hosted by Triassic red-bed sandstones, and classified here as a low-temperature, sandstone-hosted stratabound metamorphite U deposit. The main mineralisation is stratabound, related to coal-bearing units and produced during the Alpine deformation by migration of hydrothermal fluids. In this stage, the original sedimentary and diagenetic components (quartz and calcite, micas, hematite and locally apatite) were replaced by a complex sequence of roscoelite, fine-grained REE phosphates, sulphides and Ni–Co arsenides and sulpharsenides, Ag–Pb selenides, bismuth phases, sulphosalts and uraninite. The black shales of the Silurian sediments underlying the deposit and the nearby Carboniferous volcanoclastic rocks are interpreted as the source of the redox-sensitive elements concentrated in Eureka. The sulphur source is related to leaching of the evaporitic Keuper facies. The REE transport would be facilitated by SO4-rich solutions. The reduction of these solutions by interaction with organic matter resulted in the widespread precipitation of REE and redox-sensitive elements, including many critical metals (V, Bi, Sb, Co), whereas barite precipitated in the oxidized domains. The occurrence of similar enrichments in critical elements can be expected in other similar large uranium deposits, which could be a source of these elements as by-products.

Evolution of a deep-water ferromanganese nodule in the South China Sea in response to Pacific deep-water circulation and continental weathering during the Plio-Pleistocene

The South China Sea (SCS) is connected to the West Pacific through a deep channel in the Luzon Strait. Thus the SCS deep water is sensitive to the evolution of Pacific Ocean circulation, which significantly influences the global climate system. Geochemical data (Pb isotope and redox-sensitive elements data) and magnetic data were determined for a Fe–Mn nodule obtained from Jiaolong seamount in the central SCS. These records reflect interactions between changes in ice sheets, deep Pacific circulation, and weathering inputs to the deep SCS during the Pliocene and Quaternary. Our results show that the SCS deep-water environment can be divided into three major Stages (Stages 1–3). Stage 1 (∼4.8–1.4 Ma) was characterized by a well-oxygenated Pacific Deep Water (PDW) and lower dust inputs; then moderate stable deep-water ventilation and greater inputs of Asian dust occurred during Stage 2 (1.4–0.9 Ma). During Stage 3 (<0.9 Ma), a more isolated PDW was accompanied by sluggish Pacific overturning circulation, probably due to the weakened southern-sourced deep-water formation. In general, the progressive intensification of northern hemisphere ice-sheet play an active role in controlling the variation of the deep-water environment in the SCS. Interestingly, the variation in deep-water ventilation lagged behind weathering and erosion around the Middle Pleistocene Transition, which strongly indicates that the ocean and continent environments had different sensitivities to the global paleoclimatic changes at the glacial climate boundary.

Mo-Ni and organic carbon isotope signatures of the mid-late Mesoproterozoic oxygenation

This study performed a redox sensitive trace element (RSTE) and organic carbon isotope investigation on the shallow section of ~1.2 Ga Bijaigarh Shale, Kaimur Group, Vindhyan Supergroup. The results demonstrate that unlike the coeval deeper section, in which Mo and Ni concentrations are several-folds higher compared to the upper continental crust (UCC), the shallow section contains Mo and Ni equivalent to the upper continental crust (UCC). This spatially heterogeneous burial of Mo and Ni is very similar to the modern stratified basins i.e., Black Sea and Cariaco Basin, where Ni and Mo composition of the sediments underlying a shallow oxic water column is comparable to the UCC however, the deeper sediments underlying the anoxic/euxinic contains several folds-higher Mo and Ni compared to the UCC. Bulk precipitation of Mo in a hydrosphere is mainly controlled by sulphide present in the anoxic/euxinic layers of the water column, on the other hand, Ni precipitation is generally controlled by oxygenic primary productivity. Though the shallow section of the Bijaigarh Shale is depleted in Ni, a significant correlation between Ni and TOC is still relevant and indicates an oxygen-rich surface water layer for the respective palaeohydrosphere. Furthermore, δ13C-org values (between −32.0 and −30.4‰) from the shallow section suggests that the organic carbon exported into the sediments during the Bijaigarh Shale deposition was primarily derived from oxygenic photosynthesis in the concurrent surface water layers.

Influence of soil redox state on mercury sorption and reduction capacity

We investigated the mechanisms of interactions between divalent aqueous Hg and rock samples originating from an outcropping rock formation, the Albian Tégulines Clay (France, Aube). Two solid samples collected at two different depths (7.7 and 21.2 m depth) in the rock formation were selected since, in situ, they had and were still experiencing contrasting redox conditions, and thus had different mineralogy with regards to the minerals containing redox-sensitive elements, in particular iron. The sample that was the closer to the surface was under oxidizing conditions and contained goethite and siderite, while the deeper one was under reducing conditions and had more siderite, together with pyrite and magnetite. The redox state of the samples was preserved throughout the present study by careful conditioning, preparation, and use them under O2-free conditions. The two samples had similar affinity for Hg, with a retention coefficient (RD) ranging between 102 and 106 mol·kg−1 when the aqueous Hg concentration ranged between 4.4 and 107 ng·L−1 with the lowest concentration for the highest RD. However, the mechanisms of interaction differed. In the oxidized sample, no change in Hg redox state was observed, and the retention was due to reversible adsorption on the mineral phases (including organic matter). In contrast, upon interaction with the deeper and reduced sample, Hg was not only adsorbed on the mineral phases, but part of it was also reduced to dissolve elemental Hg. This reduction was attributed to magnetite and siderite and highlights the influence of mineralogy on the geochemical cycle of Hg.

The pelagic archive of short-term sea-level change in the Cretaceous: a review of proxies linked to orbital forcing

Abstract Deep-time sea-level oscillations in the Milankovitch-band of orbital cyclicities govern deposition in the pelagic realm mainly by varying siliciclastic input. Pelagic sediments from the Cretaceous greenhouse climate phase provide a valuable archive for sea-level change. Although sea-level variations are of negligible amplitude compared with depositional water-depths, direct physical proxy data are based on higher and coarser siliciclastic input during sea-level lowstand and regressions, and include coarser grain size and grain-size parameters as well as the heavy mineral and clay content. Chemical proxies that relate to siliciclastics are manganese, titanium and zirconium, often normalized v. aluminium. Further proxies provide the ratios of strontium v. calcium, controlled by shelf carbonate erosion, and partly redox-sensitive elements like uranium and thorium. From a mineralogical point of view, the total amount of siliciclastics and their diversity relating to heavy minerals provides sea-level information in hemipelagites, as well as the phyllosilicate content v. biogenic pelagic background deposition of carbonate and siliceous microfossils in pelagites. In addition, measurements of gamma ray emission, linked to U, Th, K content and magnetic susceptibility may relate to sea-level cycles and various other more climate-dependent proxies like oxygen isotopes of fossil calcite and compositional maturity of hemipelagic sediments.

Geochemical studies of carbonates of the Tayiba Formation (Upper Eocene), Abu Zenima area, West Central Sinai

BackgroundTayiba Formation situated at the entrance of Wadi El-Tayiba. It unconformably overlies the Late Eocene Tanka Formation and unconformably underlies the Early Miocene Nukhul Formation. Severely authors studied this formation geologically, stratigraphically, and petrographically. But, geochemical studies on the rare earth elements to illustrate the depositional environments are seldom.ResultsResults were revealed that, mineralogically, the carbonate rocks in the Tayiba Formation are mainly composed of calcite, dolomite, quartz and clay minerals. The terminal parts of the studied Tayiba Formation are more dolomitized relative to the middle beds.Geochemical analysis revealed that the carbonates of Tayiba Formation were deposited under shallow, oxidizing, marine environment. The dolomitization process has taken place in marine environment. Carbonate rocks of the Tayiba Formation are highly enriched in trace elements and highly to moderately rare earth elements. The studied carbonate rocks characterized by light REE (LREE) enrichment than heavy REE (HREE).ConclusionsThe redox-sensitive and rare earth elements study indicates that the carbonate rocks in the Tayiba Formation were deposited under anoxic to oxic marine environment. Also, the trace and rare earth elements values indicated that the studied carbonate rocks are mainly hydrogenous sources. These elements may be derived from more mafic sources.

Formation of the Ce-Nd mantle array: Crustal extraction vs. recycling by subduction

We present new measurements of 138Ce/142Ce and 143Nd/144Nd isotopic ratios in terrestrial and extra-terrestrial samples. The mean value obtained from nine chondrites defines the 138Ce/142Ce ratio of the chondritic uniform reservoir (CHUR) as 0.02256577±66 (2sd). MORBs and OIBs define the mantle array in the εNd vs. εCe diagram to be εNd=−7.3(±0.5)×εCe+0.4(±0.3). From MORB measurements, we derive the isotopic composition of the depleted MORB mantle (DMM) to be εCe=−1.1±0.6 (2sd). Both CHUR and a modelled early-depleted mantle reservoir plot on the mantle array. Thus, the precise determination of the mantle array does not further constrain the La/Ce and Sm/Nd ratios of the bulk silicate Earth (BSE; i.e., primitive mantle). The composition of 1.8 Ga upper continental crust obtained from aeolian sediments is εCe=1.8±0.3 (2sd; εNd=−11.2), and that of its 2.2 Ga equivalent is εCe=2.3±0.3 (2sd; εNd=−17). Binary mixing models between depleted (DMM) and enriched (upper crust or mafic crust composition) components do not reproduce the linear Ce-Nd mantle array but plots close to the island arc basalt data. When the bulk Ce isotopic composition of the continental crust is calculated from the range of accepted Nd isotope values and a mass-balance budget of the BSE, the mixing curves are closer to the mantle array. However the calculated Ce isotopic composition for the bulk crust is always less radiogenic than measurements. Adjusting the Ce-Nd isotopic composition or the Ce/Nd ratio of the end-members to fully linearise the mixing curve leads to unrealistic values never measured in terrestrial samples. We propose a recycling model to reconstruct the mantle array with the participation of both oceanic crust and sediments in the mantle through time. Cerium is a redox sensitive element, making the La-Ce and Sm-Nd systematics an ideal combination to investigate sediment recycling through time. In this recycling model, the most extreme EM-like signatures require the involvement of oceanic sediments that formed under reduced conditions before the Great Oxygenation Event at 2.4 Ga, and which are devoid of Ce elemental anomalies.

Subtle Cr isotope signals track the variably anoxic Cryogenian interglacial period with voluminous manganese accumulation and decrease in biodiversity

Earth’s atmosphere experienced a step of profound oxygenation during the Neoproterozoic era, accompanied by diversification of animals. However, during the Cryogenian period (720–635 million years ago) Earth experienced its most severe glaciations which likely impacted marine ecosystems and multicellular life in the oceans. In particular, large volumes of Mn and Fe accumulated during the interglacial intervals of the Cryogenian glaciations, indicating large anoxic marine metal reservoirs. Here we present chromium isotope-, rare earth element-, and redox-sensitive trace element data of sedimentary rocks from the interglacial Datangpo Formation deposited between the Sturtian and Marinoan glaciations in South China, in an attempt to investigate the oxidation state of the oceans and atmosphere. Both the Cr isotope and trace element data indicate mainly anoxic water conditions with cryptic oxic surface water incursions after the Sturtian glaciation. Glacial-fed manganese precipitated as manganese carbonate in anoxic basins, and the non-fractionated δ53Cr record of −0.10 ± 0.06‰ identifies anoxic conditions with a cryptic component of slightly fractionated Cr isotope composition in manganese ore, in line with distinctly fractionated Mo isotope composition. Both the manganese carbonate ore and the black shales exhibit very low redox-sensitive element concentrations. Our study demonstrates that the oxygenation of the seawater, and inferably of the atmosphere, at the beginning of the Cryogenian interglacial interval was much subdued. The post-glacial rebound then allowed the Ediacaran biological diversity.

Comprehensive REE + Y and sensitive redox trace elements of Algerian phosphorites (Tébessa, eastern Algeria): A geochemical study and depositional environments tracking

The Algerian sedimentary phosphorites of marine origin are located mainly in the Tébessa region, which is part of the Eastern Saharan Atlas. These phosphorites are hosted by Paleocene-Eocene series and crop out in two main sedimentary areas: the northern sites (Djebel El Kouif, Djebel Dyr and Djebel Tazbant) and the southern sites, which include the Djebel Onk commercial world-class ore deposits that are represented in this study by the Kef Essenoun sector. This study reports a detailed investigation of these phosphorites at a regional scale and is aimed to characterizing the evolution of their depositional environments. Field and laboratory works consist of a systematic sampling of outcrops, petrographical (OM and SEM-EDS), mineralogical (XRPD) and chemical (major, trace and rare earth elements by ICP-MS) analyses associated with a PCA statistical treatment. The time-wise evolution of the depositional environments was constrained based on rare earth elements (REE) and selected redox sensitive element proxies, such as Ce, Eu, Y, Mn, U and V.The results show that the phosphorites have a granular fabric with variable grain sizes. The grains can contain micro-remains and impurities related to their origin, which was most often fecal pellets. Carbonate fluor-apatite is the main mineral phase in these phosphorites, where P2O5 contents show large variations between different outcrops (average from 18.39 to 30.16 wt%). A marked evolution of depositional environments is observed in their vertical trends from sub-reduced and sub-oxic in the lower beds to rather oxic conditions in the upper layers. This evolution shows a significant shift along the sedimentary profiles reflecting more open connection to Tethyan seawater towards younging trend. These results contrast remarkable changes of depositional conditions during Paleocene–Eocene transition.

Late Pleistocene oceanographic and depositional variations along the Wilkes Land margin (East Antarctica) reconstructed with geochemical proxies in deep-sea sediments

Abstract Water masses and depositional environments over the last 500 ka were reconstructed using absolute and relative abundances of lithogenous, biogenous and redox-sensitive elements in four sediment cores from two channel-levee systems of the Wilkes Land continental slope (East Antarctica). Sediments older than the Mid-Bruhnes event (MBE, 430 ka BP) show reduced glacial/interglacial variability in the abundance of elements associated to the terrigenous mineral phases (i.e. Al, Ti, Fe and partly Si). This suggests minor ice-sheet size changes occurred in the Antarctic margin during the pre-MBE “lukewarm” interval. Post-MBE sediments record instead a high variability between glacial and interglacial periods in the concentration of terrigenous and biogenous (i.e. Ca, Ba) elements suggesting larger amplitude changes in both ice-sheet size and ocean conditions toward the gradual establishment of last glacial cycle conditions. Moreover, a marked increase of Mn during the glacial to interglacial transitions, indicates a post-depositional migration of the redox front and re-oxidation of the surface sediment layers linked to major changes in bottom water oxygen conditions associated to Antarctic Bottom Water formation along the margin at the onset of deglaciations.

Accumulation patterns and species-specific characteristics of yttrium and rare earth elements (YREEs) in biological matrices from Maluan Bay, China: Implications for biomonitoring

The critical usage of rare earth elements (REEs) in a variety of industrial applications has increased their release to the environment as emerging contaminants, while little is known about the fate and transport of REEs in coastal aquatic biota. In the present study, seven common species were collected and the concentrations of 15 naturally occurring REEs (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) were determined. Significant differences in total REEs concentrations were found among species even in the same taxa or phylum, suggesting that REEs bioaccumulation patterns appeared to be species- and element-dependent even in the same taxa or phylum, but with limited potential for bio-magnification based on the nitrogen isotope signatures (δ15N). Except for occasional anomalies for redox-sensitive elements of Ce and Eu, the abundance patterns of REEs normalized to chondrite revealed similar REE distribution trends, indicating a common source of REEs in all samples. Additionally, the abundances of light REEs (from La to Eu) were much higher than those of heavy REEs (from Gd to Lu and Y), demonstrating the fractionation between the light and heavy REEs. Furthermore, REEs concentrations in molluscs were notably higher than other species, implying their potential as bio-indicators of REEs due to the habitat and specific feeding behavior. Overall, this is not only the first study to focus on distribution levels, accumulation characteristics, geochemical and fractionation patterns of REEs in coastal species from identical area, but quantifying and tracing REE behavior will contribute to better evaluating the possible environmental impacts of REEs enrichment for future biomonitoring research.

Depositional environments of redox-sensitive trace elements in the metalliferous black slates of the Okcheon Metamorphic Belt, South Korea

Metalliferous black slates consisting of black slates and interbedded coaly slates in the Okcheon Metamorphic Belt of South Korea were analyzed for redox-sensitive trace elements and rare earth elements (REEs) to examine their depositional conditions. Our data show that the coaly slates have elevated concentrations of redox-sensitive trace metals (U, V, Mo, and Cr), low Mn contents, high V/(V + Ni), V/Cr, and U/Th ratios, and high total organic carbon (TOC) contents. A general tendency of positive correlation between TOC and trace metals was established. The results suggest that the coaly slates were developed under a strongly reducing environment, while the black slates were deposited under a suboxic-oxic condition. The REE patterns of the coaly slates typically show positive Eu and negative Ce anomalies compared to the North American Shale Composite reference and they are essentially inherited from submarine hydrothermal fluids under high temperature reducing condition. The enrichment of the redox-sensitive elements including V (up to 3,564 ppm) and Mo (up to 358 ppm) may have been controlled by direct hydrothermal input of metals into the rift basin from hydrothermal vents, proximal from the vent sites, as supported by textural evidences, and the metals could have been fixed from seawater by means of scavenging process via exhalative oxide particles in a hydrothermal plume. The sorption of metals from seawater under anoxic conditions into organic-rich sediments occurred as well. The metal enrichments in the black slates seem to have been achieved in somewhat similar way to black shales in South China.

Tracking Fe mobility and Fe speciation in subduction zone fluids at the slab-mantle interface in a subduction channel: A tale of whiteschist from the Western Alps

Fluids released by subducting slabs are important to the geochemical evolution of Earth’s crust-mantle system. However, it is still not well constrained for the mobility of redox sensitive elements (like Fe, C or S) in subduction zone fluids, and its effect on the redox property of the overlying mantle wedge and its derived arc magmas. Iron isotope fractionation is sensitive to the redox state and speciation of Fe in fluids, which can potentially provide clues on the oxygen fugacity (fO2) of slab-derived fluids. Whiteschists at the Dora-Maira Massif in the Western Alps have experienced ultrahigh-pressure metamorphism at subarc depths. They are rich in both SiO2 (mostly >65 wt.%) and MgO (4–10 wt.%), and mainly composed of pyrope, quartz/coesite, talc, phengite and kyanite. They were demonstrated to have a granite protolith, but metasomatized by serpentinite-derived Mg-rich fluids at the slab-mantle interface in a subduction channel. Thus these rocks provide an excellent target to explore the fluid-rock interaction by Fe isotopes. The whiteschists show extremely high δ56Fe values of +0.32 to +1.22‰, being much higher than those of +0.10 to +0.38‰ for the surrounding metagranites. The Fe isotope composition of whiteschists significantly deviates from the igneous differentiation trend defined by rocks with basaltic to rhyolitic compositions. The heavy Fe isotope compositions must be produced by a metasomatic process. The much lower Fe2O3 and FeOt contents and Fe3+/∑Fe ratios but higher δ56Fe values for the whiteschists relative to their protolith suggest the reduction of Fe3+ to Fe2+ and the loss of isotopically light Fe, probably in the form of Fe(II)-Cl and/or Fe(II)-(HS) complexes, through saline fluids and/or HS- bearing fluids. The reduction of Fe3+ to Fe2+ and the possible presence of HS- suggests the occurrence of relatively reduced fluids. Such reduced fluids were probably derived from serpentinite dehydration at the slab-mantle interface in the subduction channel. Therefore, the Fe isotope results demonstrate that the fO2 at the slab-mantle interface can be locally highly heterogeneous, leading to various oxidation states in the mantle wedge and arc magmas.

Increasing hypoxia in the Changjiang Estuary during the last three decades deciphered from sedimentary redox-sensitive elements

Ranked as one of the world's largest seasonal hypoxic water bodies (Dissolved oxygen, DO≤2 mg l−1), the Changjiang hypoxia has been reported to grow rapidly worse in recent decades according to cruise observations, but it has been seldom studied by sedimentary records. In this paper, four gravity cores (E1-E4), retrieved from the Changjiang Estuary, were dated by excess 210Pb and analyzed with grain-size compositions, total organic carbon (TOC) contents, and RSEs (redox sensitive elements) compositions. We aim to decipher RSEs enrichment characteristics and controlling mechanisms in the Changjiang Estuary. The results show that Mo and V enrichment is highly promoted by particle absorption and FeMn redox cycling at the shallow estuarine environment (E1 and E2) with occasional hypoxic disturbances. Scavenging of Mo and V by organic complexation becomes significant at the hypoxic center (E3), together with great influence by FeMn redox cycling, but they do not work effectively for U enrichment because of its easy remobilization and abundant riverine input. Moreover, upcore increasing trends of Mo, V, and U in E3 match well with a general lowering trend of bottom water DO minima since the mid-1980s. There are two progressive hypoxic development stages intercalated with a less DO-depleted period 1991–1997 as shown by both cruise observations and RSEs/Al records. These findings are vital to better understanding coastal hypoxic development and RSEs enrichment mechanisms in the seasonal hypoxic settings, because hypoxia is predicted to increase in the near future due to intensifying human disturbances.