Fe Mn Oxyhydroxides Research Articles

Transfer of rare earth elements from clay-sized fraction to phosphate in East South Pacific Ocean: Implication for REY-rich sediment related to hydrothermal influence

Pelagic sediment enriched in critical metals (e.g. rare earth elements and yttrium, REY) has attracted much attention in recent years. Extensive research has focused on identifying the specific host mineral of REY in bulk pelagic sediment, however, research on clay-sized fraction of REY-rich sediment has not been fully understood yet. In this study, we aimed to investigate the host phase and migration mechanism of REY in clay-sized fractions from two cores, GC23 and GC17, located on the western and eastern sides of the East Pacific Rise (EPR), respectively. To the best of our knowledge, this is the first comprehensive investigation of the clay-sized fraction of REY-rich sediment associated with hydrothermal activity. Results show that GC23 contains negligible clay minerals but well-crystallized Fe oxyhydroxides, while GC17 is rich in smectite and poor-crystallized Fe oxyhydroxides. REY are predominantly hosted in poorly crystallized Fe-Mn oxyhydroxides, with some phosphorus selectively scavenged by Fe oxyhydroxides from seawater. In addition, fluorapatite nanocrystals were first observed within the matrix of Fe oxyhydroxides using transmission electron microscopy (TEM), indicating the formation of fluorapatite. The post-Archean average shale (PAAS)-normalized REY patterns show similar seawater-like patterns in both the clay-sized and silt-sized fraction. The clay-sized fractions primarily derived from hydrothermal plumes plays an important role in scavenging REY from ambient seawater. This study represents a significant step towards understanding the formation of REY-rich sediment related to hydrothermal activity. A two-stage mineralization process is proposed for the formation of REY-rich sediment near the EPR fields. Firstly, REY are initially scavenged by hydrothermal Fe-Mn oxyhydroxide particles from seawater during their lateral dispersion with hydrothermal plumes under low sedimentation rate until they are buried by newly formed precipitates. With the process of early diagenesis, poor crystallized Fe oxyhydroxides will be experienced recrystallization. Subsequently, REY would be released into porewater with the process of recrystallization due to their tendency to remain in a poorly crystallized phase. Ultimately, they are captured by biogenic apatite and/or fluorapatite. The case study indicates that REY-rich sediments may primarily formed within the dispersion area of hydrothermal plumes. Simultaneously, the necessity of slow sedimentation rates, greater water depth, and deep currents all accountable for the formation of REY-rich layers.

Mineralogy and environmental geochemistry of copper slag from Butte, Montana

Herein we characterize the mineralogy, chemical composition, and environmental geochemistry of slag formed by historic (1880s to circa 1910) smelting of the copper-rich lodes of Butte, Montana. The air-cooled slag exists as monolithic “walls” that border Silver Bow Creek, the headwaters of the upper Clark Fork River Superfund site. The slag is mainly comprised of fayalite, hedenbergite, wollastonite, magnetite, and glass. Zinc is present at per cent levels in all of these phases. The overall high zinc content of the slag is partly due to the polymetallic character of the Butte ore bodies. Copper occurs mainly as tiny spheres, or “prills”, which are remnants of the molten Cu-sulfide matte that failed to separate from the slag during smelting. Minerals in the prills include bornite, chalcopyrite, chalcocite, pyrrhotite, pyrite, sphalerite, galena, elemental copper, and elemental silver. The prills are variably oxidized along shrinkage cracks that penetrate into the enclosing slag matrix. Secondary minerals, including hydrous ferric oxide and ferric clay, coat the cracks. Where the cracks meet the surface of the slag, secondary encrustations of calcite, Fe-Mn oxyhydroxides, and mixed Ca-Cu-Zn-Mn-Al-Fe sulfates have locally accumulated. Acid-base accounting tests show that the unweathered slag is non-acid-generating, with the acid potential from Fe-Cu sulfides offset by the neutralization potential of the Ca-Fe silicates (olivine, pyroxene). Interaction of the slag with synthetic precipitation (SPLP tests) confirms the slag's ability to buffer pH to values >8. Nonetheless, the SPLP leachate solutions contain ppb levels of copper, arsenic, zinc, and lead that approach or exceed current regulatory standards for protection of aquatic life (Cu, Pb, Zn) and human health (As). Leaching experiments using Silver Bow Creek water show an increase in dissolved As and W, but variable results for Cu, Pb, and Zn. Leaching of the secondary sulfate-salt deposits produced much higher concentrations of dissolved metals and metalloids which could be a source of contamination to Silver Bow Creek during heavy rain events. Based on bulk analyses, some metals in the slag, including Fe, As, Co, Mn, Pb, Zn, and W, exceed USEPA screening levels for residential and/or urban soils. Leachates containing organic acids (TCLP tests) show Pb concentrations that approach levels for the slag to be classified as hazardous waste. Rather than removing the slag walls, which have value as a form of industrial architecture, an alternate remedy currently under evaluation is to divert Silver Bow Creek around the smelter site and preserve the slag as part of a non-motorized recreational trail system in the reclaimed Butte-Anaconda mine-scape.

Chemometric heavy metal contamination in tropical Indian estuaries: Implications for source identification

The impact of urban and industrial effluents in the tropical Indian estuaries (Ariankuppam backwater and Chunnambar River), east coast of India have been investigated in the present study by determining the degree of heavy metals contamination of the estuarine sediments. A total of 30 surface sediment samples were collected from both estuaries and were analyzed for trace metals, grain size and organic matter. The granulometric analysis reveals that both the estuaries are predominated by silty sand to sandy silt. The significant amount of organic matter (OM) in the Ariankuppam estuary sediment is due to natural (mangroves) and anthropogenic (pollution) organic input. Pearson correlation analysis reveals that there was a strong negative correlation of sand fraction with other sediment variables (silt, clay, and organic matter) and heavy metals, whereas a positive correlation was observed between silt+clay, organic matter, and heavy metals. The significant positive correlation of Fe with Ni, Cu, Pb and Zn presents Fe-Mn oxyhydroxides are the main controlling factor of heavy metals in both estuarine sediments. Cluster analysis and PCA helped to discriminate the station groups along both estuaries according to their sediment components and heavy metals. This study also revealed that sediment grain size is a key factor influencing organic matter and heavy metal accumulation in surface sediments. The calculated pollution indices such as Contamination factor (CF), Geoaccumulation Index (Igeo) and Pollution Load Index (PLI) values indicate that both estuaries are moderate to highly contaminated by Co and low to moderately contaminated by Pb and Zn. Based on the factor analysis, it is presumed that river runoff and industrial and untreated domestic wastes from lands are responsible for increased heavy metal concentration in both estuaries. Increased levels of metal contamination along the Union Territory of Puducherry coastline may increase the risk of human exposure to metals through the consumption of seafood, making the need for tougher regulations on the discharge of metals into the environment even more important.

Zinc isotope fractionation during the sorption of Zn to minerals and organic matter in sediment cores affected by anthropogenic pollution

Zinc stable isotopes (δ66Zn) serve as a widely fingerprinting tool for detecting anthropogenic Zn contamination. However, there is a limited understanding of δ66Zn behavior during the sorption of Zn to minerals and organic matter. In this study, we have determined the δ66Zn values in specific fractions to investigate their effectiveness in tracing anthropogenic Zn. The revised Community Bureau of Reference (BCR) extraction procedure was applied to a coastal marine core from Osaka Bay and from a lacustrine core from Lake Biwa, both with a history of anthropogenic metal pollution. The δ66Zn values varied from −0.14 ‰ to +1.00 ‰ across the four to five chemical fractions with up to 0.9 ‰ variation within a single horizon. The highest δ66Zn values in the acid-soluble fraction (up to +1.00 ‰) could be explained by the preferential sorption of 66Zn to carbonates and/or the preferential incorporation of 66Zn into calcite. The complex isotopic fractionation during the sorption of Zn to and co-precipitation with Fe–Mn oxyhydroxides likely resulted in an unclear pattern of the δ66Zn values of the reducible fraction. Low δ66Zn values in the oxidizable fraction (Osaka Bay) agree with the 64Zn enrichment in phytoplankton. Higher δ66Zn values of the reducible and oxidizable fractions of the Lake Biwa core indicate that environmental conditions (e.g. ionic strength) and for instance different phytoplankton species or dissolved and suspended particulate matter input drive the Zn isotope fractionation depending on the system (marine vs. lacustrine). The δ66Zn values of the acid-soluble fraction (Osaka Bay and Lake Biwa), of the reducible fraction (only Lake Biwa) and of oxidizable fraction (only Osaka Bay) better reflected the temporal changes in the Zn concentration than the bulk sediment, indicating that these fractions could be a sensitive fingerprinting tool for anthropogenic Zn contamination.

Influence of Organic Matter Thermal Maturity on Rare Earth Element Distribution: A Study of Middle Devonian Black Shales from the Appalachian Basin, USA

This study focuses on understanding the association of rare earth elements (REE; lanthanides + yttrium + scandium) with organic matter from the Middle Devonian black shales of the Appalachian Basin. Developing a better understanding of the role of organic matter (OM) and thermal maturity in REE partitioning may help improve current geochemical models of REE enrichment in a wide range of black shales. We studied relationships between whole rock REE content and total organic carbon (TOC) and compared the correlations with a suite of global oil shales that contain TOC as high as 60 wt.%. The sequential leaching of the Appalachian shale samples was conducted to evaluate the REE content associated with carbonates, Fe–Mn oxyhydroxides, sulfides, and organics. Finally, the residue from the leaching experiment was analyzed to assess the mineralogical changes and REE extraction efficiency. Our results show that heavier REE (HREE) have a positive correlation with TOC in our Appalachian core samples. However, data from the global oil shales display an opposite trend. We propose that although TOC controls REE enrichment, thermal maturation likely plays a critical role in HREE partitioning into refractory organic phases, such as pyrobitumen. The REE inventory from a core in the Appalachian Basin shows that (1) the total REE ranges between 180 and 270 ppm and the OM-rich samples tend to contain more REE than the calcareous shales; (2) there is a relatively higher abundance of middle REE (MREE) to HREE than lighter REE (LREE); (3) there is a disproportionate increase in Y and Tb with TOC likely due to the rocks being over-mature; and (4) the REE extraction demonstrates that although the OM has higher HREE concentration, the organic leachates contain more LREE, suggesting it is more challenging to extract HREE from OM than using traditional leaching techniques.

Sediment source variation using REEs, Sr, and Nd isotopic compositions: a case study in MD05-2901, northwestern South China Sea

The South China Sea (SCS) is the largest marginal sea in the western Pacific, fed by large Asian rivers, characterized by substantial volumes of sediment derived from surrounding Asian continents and islands. This study utilizes the rare earth elements (REEs), Sr isotopes (87Sr/86Sr), and Nd isotopes (ƐNd) in detritus fractions of MD05-2901 sediments in northwestern SCS, to evaluate the relative contribution among the Mekong River, the Red River, the Pearl River, and rivers in SW Taiwan over the last 32 ka. This deep-sea core is located off the coast of central Vietnam, an upwelling region with only minor continental inputs, and this study is important for a better understanding of the main sources of terrigenous material and their temporal variations in the region. In addition, potential particle exchange is examined using the same proxies in the Fe-Mn oxyhydroxide fractions. The obtained records are systematically compared with the available climatic archives in the region. The REEs in the Fe-Mn oxyhydroxides support the argument of water mass signature separation in bulk sediments by chemical leaching procedures. These 87Sr/86Sr in the Fe-Mn oxyhydroxides phase fall in a range between 0.709262 and 0.709313, deviating significantly from the modern seawater. ƐNd values vary >3Ɛ, being more radiogenic in the Fe-Mn oxyhydroxides, where the lowest value occurred in the Bølling/Allerød (B/A) and higher values occurred during the Younger Dryas (YD). The latter implies increased contribution of loess dusts or Taiwanese rivers under dry/cold climatic conditions, compared with the situation in modern times. The Red River and the Mekong River together may have contributed >60% during the Last Glacial Maximum (LGM) and YD. In contrast, the Pearl River components have increased sharply to ~60% during the warm B/A. These results demonstrate that the MD05-2901 sediments sensitively record changes in weathering intensity on land and transport pathways in the coastal regions in the Holocene.

Lattice Oxygen Exchange in Transition Metal Oxyhydroxides and Metal Hydroxide Organic Frameworks Elucidated for the Oxygen Evolution Reaction

To achieve the goal of climate neutrality by 2050, it is essential to increase the use of renewable fuels and carbon-neutral energy.1 The anodic oxygen evolution reaction (OER) is a key reaction not only in electrocatalytic production of many renewable fuels,2 but also for next generation of charge storage devices such as metal-air batteries.3 However, the slow kinetics of the OER process result in high energy losses and costs.4 Therefore, the development of more efficient electrocatalysts is critical for making renewable energy via electrocatalysis a viable option in emerging energy systems.Transition metal (TM) oxides are a promising alternative to expensive noble metals due to their high catalytic OER activity under alkaline conditions and wider earth-abundance. Despite extensive research, establishing structure-activity correlations and understanding mechanistic processes is challenging, given the intricate interplay between external and intrinsic parameters.In this study, we investigate the role of lattice oxygens in electrodeposited Ni-Fe, Co-Fe, and Mn-Fe oxyhydroxide (M(OH)xOy, M = TM) electrocatalysts using surface-enhanced Raman spectroscopy (SERS) in conjunction with secondary ion mass spectroscopy (SIMS). By taking advantage of the Raman shift that results from 16O/18O isotope exchange,5–7 we can track the participation of lattice oxygens in the electrocatalytic cycle. Our investigation reveals that, during OER, all the electrocatalysts display minimal exchange of lattice oxygens with the electrolyte (less than 5%). However, many of these electrocatalysts show partial or complete exchange when exposed to non-catalytic potential when in their more reduced states (see Figure 1).Apart from fully inorganic catalysts, we also present results from Ni-derived metal-hydroxide-organic frameworks (MHOFs), which are analogous to M(OH)xOy catalysts but with organic linkers separating the layers.8 Our findings indicate that MHOFs with linkers that have a high π-π stacking energy (and a high structural stability)8 undergo near complete 16O/18O exchange during OER, while MHOFs employing linkers with a low π-π stacking energy (and thus a low stability) show minor or no lattice exchange during OER.Our study suggests that participation oflattice oxygens is closely linked to the oxidation state of the transition metals rather than to the catalytic process. The work provides a detailed picture of the exchange mechanism and elucidates alternative processes involved in lattice oxygen participation and discusses their relation to the mechanisms of the OER process. References IEA (2023), Energy Technology Perspectives 2023, IEA, Paris https://www.iea.org/reports/energy-technology-perspectives-2023, License: CC BY 4.0.Wei, S. Z. et al. Combining theory and experiment in electrocatalysis: Insights into materials design. Science (80-. ). 355, eaad4998 (2017).Li, Y. & Lu, J. Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice? ACS Energy Lett. 2, 1370–1377 (2017).Song, F. et al. Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018).Lee, S., Banjac, K., Lingenfelder, M. & Hu, X. Oxygen Isotope Labeling Experiments Reveal Different Reaction Sites for the Oxygen Evolution Reaction on Nickel and Nickel Iron Oxides. Angew. Chemie Int. Ed. 58, 10295–10299 (2019).Moysiadou, A., Lee, S., Hsu, C.-S., Chen, H. M. & Hu, X. Mechanism of Oxygen Evolution Catalyzed by Cobalt Oxyhydroxide: Cobalt Superoxide Species as a Key Intermediate and Dioxygen Release as a Rate-Determining Step. J. Am. Chem. Soc. 142, 11901–11914 (2020).Diaz-Morales, O., Ferrus-Suspedra, D. & Koper, M. T. M. The importance of nickel oxyhydroxide deprotonation on its activity towards electrochemical water oxidation. Chem. Sci. 7, 2639–2645 (2016).Yuan, S. et al. Tunable metal hydroxide–organic frameworks for catalysing oxygen evolution. Nat. Mater. 21, 673–680 (2022). Figure 1

New advances on the carbon isotope and rare earth elements chemostratigraphy of the late Ediacaran Tamengo Formation (Corumbá Group, Brazil)

The Tamengo Formation (Corumbá Group, midwest Brazil) is a carbonate-dominated succession of major importance to unravel the environmental and biological changes during the Ediacaran–Cambrian transition in Gondwana. Although it has been extensively studied in terms of sedimentology, isotope geochemistry, biostratigraphy, and geochronology, these studies are constrained to the Corumbá region. This work presents new sedimentological, C and O isotope chemostratigraphy, and rare earth elements (REE) plus yttrium (REY) data of four sections of the Tamengo Formation in the Serra da Bodoquena region, approximately 200 km south of Corumbá, discussing how these new data are related to the type sections. The sections present ooid grainstones, with hummocky, swaley, and wavy structures, interbedded with mudstones and shales, indicating deposition of fine particles by suspension fallout in-between periods of high-energy, with reworking by storm waves. The δ13Ccarb curves show positive plateaus with minor, short-lived negative excursions linked to facies variations, which are related to a large δ13Ccarb depth gradient in a redox-stratified water column. The REY profiles present middle REE (MREE)-bulge patterns and absent to slightly positive Ce anomalies, consistent with MREE adsorption onto Fe–Mn oxyhydroxides in the water column followed by release in pore waters. Subsequently, REY remobilization during anoxic diagenetic stages resulted in the MREE-bulge pattern and overprinted some of the original seawater REY features, including the Ce anomalies. The Tamengo Formation in the Serra da Bodoquena region represents a storm-dominated carbonate ramp, as previously interpreted for this unit in the Corumbá region. Nevertheless, there is a significant shift of 2 ‰ in the peaks of δ13Ccarb data between both localities, which may be related to differences in the overall sector of the carbonate ramp. There are also substantial variations in the δ13Ccarb record of the Tamengo Formation and other coeval Gondwana basins, such as the Nama and Itapucumi groups, with different peak values, which may be related to latitudinal differences on the inorganic carbon isotope composition or to the degree of basin restriction.

REE + Y uptake in bioapatite revisited: Facies-controlled variability in coeval conodonts

REE + Y concentrations in bioapatite have been repeatedly shown to be ambiguous carriers of information for paleo-seawater reconstructions. The uptake of REE + Y begins rapidly after deposition, and bioapatite can, therefore, potentially record the pore water conditions during early diagenesis. In this study, we examined the REE + Y composition of conodonts belonging to a single species from three coeval facies across the Ordovician Baltic Paleobasin carbonate shelf. We show that the REE + Y concentrations, as well as Ce/Ce*, bell-shape index (BSI), Y/Ho and LaN/SmN ratios, vary systematically in conodonts from facies with different host rock compositions. Dissimilarly, REE + Y patterns and ratios of conodont dental elements from the same facies are uniform, indicating that the local depositional environment imposes principal control on the REE + Y uptake by bioapatite. Furthermore, our results show that even though REE + Y concentrations in different histological tissues of the same conodont vary significantly, no REE-specific fractionation occurs, resulting in similar REE + Y ratios in all tissue types. Our results illustrate that conodonts can record modified seawater-like characteristics of REE compositions if the input of FeMn oxyhydroxides and particulate organic carbon (POC) is low. In contrast, under elevated POC and FeMn oxyhydroxide loading, the conodonts show increasingly positive Ce anomalies and MREE enrichment. Collectively, these results suggest that, although primary seawater signatures are not captured in bioapatite, the conodont REE + Y patterns are controlled by local depositional environments and can record early diagenetic pore water conditions.

Heavy Metals in Sediments of Subarctic Meromictic Lakes of the White Sea as Possible Tracers of Environmental Changes

Meromictic lakes of the marine coast, quite widely distributed in the northern hemisphere, are the result of climate changes and glacier retreat. The bottom sediments of these lakes serve as a geological chronicle of the history of marine basin’s development with the geochemical occurrence forms of elements indicate various processes of their accumulation. This paper presents research results concerning the occurrence of forms of heavy metals in lake sediments along the coast of the White Sea. These results are based on a sequential seven step leaching procedure, followed by ICP-MS analysis and subsequent statistical data processing. To determine differences among the examined geochemical parameters, Pearson’s correlation analysis and Ward’s cluster analysis were utilized. The total content of Cr, Mn, Fe, Co, Ni, Zn, V, and Pb in the sediments did not exhibit significant differences based on their degree of isolation from the sea. The major contribution to deposition of these metals in sediments of the meromictic lakes studied is the residual form, encompassing the mineral matrix of the sediment. At the same time, the elevation of mobile forms for all the metals examined corresponds to an increase in the isolation of lakes from the White Sea. In the meromictic lake sediments, concentrations of Cu, Mo, and U demonstrated significant increases in forms tightly bound to organic matter, while Cd exhibited an association with Fe-Mn oxyhydroxides. Notably, a significant difference in the occurrence forms of Cu, Cd, Mo, and U was evident in the reduced sediments of meromictic lakes when compared to those of open sea bays. The meromictic lakes along the White Sea coast, positioned at various stages of isolation, hold promise for investigating the migration of metals in response to environmental changes.

Li isotopic variations of particulate non-silicate phases during estuarine water mixing

Lithium (Li) isotopes are widely used as a tracer of silicate weathering. However, Li isotopic compositions of non-silicate phases carried by sediments/suspended particulate matters (SPM) have not been systematically investigated, and their influences on the dissolved δ7Li variations remain poorly known. This study investigated Li geochemistry of different chemical fractions extracted by sequential leaching from SPM samples in the Changjiang (Yangtze River) Estuary. Our results demonstrate that Fe-Mn oxyhydroxide is the largest reservoir of non-silicate Li, accounting for ∼5% of Li in bulk SPM samples. The proportion of Li in exchangeable fraction is only 0.3 ± 0.1%, with δ7Li values ranging from 14.2‰ to 22.4‰. In response to seawater addition, the dissolved Na progressively replaces physically-adsorbed Li, and the chemically-adsorbed Li is isotopically fractionated with a factor of 0.9883. In the Changjiang Estuary, δ7Li of Fe-Mn oxyhydroxides responds rapidly to environmental variations. The isotope fractionation factors during Li uptake into authigenic Fe- and Mn-oxyhydroxides are 0.981 and 0.9735, respectively. Possibly due to short interaction time during SPM passing through the estuary, incorporation of Li into non-silicate phases cannot drive a detectable alteration of estuarine dissolved Li concentration. By contrast, this study highlights the possibility of oxyhydroxides affecting δ7Li values of river water. Further work may focus on determining Li isotopic behaviours of non-silicate phases and their applications on environment reconstruction.

Scientific mapping of the research in microbial and chemical contamination of potable water in Bangladesh: A review of literature.

Drinking water contamination is one of the most pressing concerns for the people of Bangladesh as they rely on groundwater to meet their water needs. The existing water sources of Bangladesh are losing potability due to natural, anthropogenic, and geogenic factors, resulting in acute to severe health consequences. To address the issue of safe drinking water, researchers are constantly examining potential sources that cause the pollution of drinking water. Through bibliometric and systematic research, the current work seeks to review the past research on microbiological and chemical contamination of drinkable water in Bangladesh. The bibliometric review provides insights into the research trends, notable authors, countries, and institutions, whereas the systematic review unfolds the key research areas, the contamination process, and the strategies used to mitigate the contamination process. The results show that arsenic and various coliform bacteria are the most commonly reported sources of chemical and microbiological contaminants that degrade water quality. The study demonstrates that the most crucial factors influencing arsenic mobilization include microbial decomposition of organic matter (biologically available organic matter, for example, peat), arsenic adsorption by metal-oxyhydroxides, Fe-Mn oxyhydroxide, chemical fertilizers, pond excavation, and altering of groundwater hydrology. The studies also indicated the sources that contribute to the microbiological quality decline. The current work has addressed the scope of future research.

Formation process of Pliocene cold seep carbonates from the southern Western Foothills, Southwestern Taiwan: A synthetical rare earth element and C–O–Sr–Nd isotope study

In this work, the Pliocene dolomitic carbonate concretions and pipes from Chiahsien of the Western Foothills, southwestern Taiwan were studied. We conducted a synthetical analysis of stable carbon and oxygen isotopes, rare earth element (REE) contents, and Sr and Nd isotopes, to trace the compositions and sources of pore fluids from which carbonates have precipitated and reconstruct the carbonate formation processes. The carbonates with low δ13C values (as low as −48.6‰) are promoted by the anaerobic oxidation of biogenic methane. The 87Sr/86Sr ratios of samples reflect the mixing of coeval bottom seawater and seep fluid enriched in 87Sr. The Nd isotopic signatures of studied carbonates indicate multiple Nd sources, including detrital components, Fe–Mn oxyhydroxides, organic matter, and seawater. The MREE-bulge patterns in samples are typical of anoxic conditions, which are supported by Ce anomalies. Our results demonstrate that the seepage intensity played a key role in the formation processes of concretions and pipes by controlling the depth of the sulfate-methane transition zone (SMTZ). The concretions characterized by the lowest δ13C values formed at a deeper depth in sediments under low methane flux, which suffered no/less influence of seawater. The representative pipe with obvious concentric lamination grew in a rim-to-core pattern. In the early stage, the variable flux of highly channelized seepage caused the fluctuation of carbon and oxygen isotopes. During the later stage, the modification of isotopic compositions in the core part were resulted from meteoric alteration. Our work provides insights into the formation process related to seepage evolution in ancient cold seeps on Taiwan Island.

Controls on Critical Metal Enrichments in Ferromanganese Nodules from the Philippine Sea, at Water Depths of 4400–6000 m

Enrichments of critical metals in ferromanganese (Fe–Mn) nodules have received increasing attention in both deep-sea research and mineral exploration. To better assess the controls on the resource potential of Fe–Mn nodules, we conducted a comprehensive and detailed study of twelve nodules from the Philippine Sea collected from water depths of 4400 to 6000 m by investigating their microstructures, bulk geochemistry, and in situ Fe–Mn oxyhydroxide geochemistry, using XRF, ICP-MS, EMPA, and LA-ICP-MS coupled with BSE images. We successfully resolved different controls on the element enrichments, of which significant selective enrichment of metal elements in seawater is similar to that of typical hydrogenetic nodules. An enhanced supply of iron hydroxide due to calcite dissolution resulted in a dilution effect on Co, Ni, and Mn but an enrichment effect on rare earth elements plus yttrium (REE + Y) and Fe in nodules near topographic highs close to the carbonate compensation depth. While the supply of diagenetic Mn resulted in a dilution on Co and REE + Y, it resulted in enrichment on Ni, Cu, Li, and Mn on nodules on the seafloor. Moreover, via micro-layer analyses we confirmed the growth rate is a major determinant for the correlations of Co and REE with Fe-oxyhydroxides in these Philippine Sea nodules.

Impacts of periodic saltwater inundation on heavy metals in soils from the Pearl River Delta, China

The alluvial plain delta is vulnerable to complex land–sea interactions as a result of rising sea levels and increasing storm surges due to global environmental change. Topsoil samples (0–20 cm) from the Pearl River Delta (PRD) were subjected to periodic artificial saltwater inundation treatments with varying salinities (0, 35‰, 40‰, 50‰) for 50 days to explore the impacts of saltwater inundation on heavy metals (Cd, Pb, Zn) in soils. The inundation treatments reached dynamic equilibrium in approximately 20 days, and heavy metals were promoted to release into leachate. The extraction rate of heavy metals was highest with artificial saltwater at 40‰ salinity, which was generally attributed to pH variation, increasing ionic strength and reductive dissolution of Fe–Mn oxyhydroxides. However, once the salinity reached 50‰, a higher SO2- 4concentration could depress the release of heavy metals by providing more negative adsorption sites. Cd in soils was most likely to leach, followed by Zn, but Pb showed higher retention. After saltwater inundation, the bioavailability of heavy metals decreased in the order Cd > Zn > Pb. Redundancy analysis (RDA) results demonstrated that Cd and Zn are more susceptible to soluble salt ions in soils than Pb. The retention of Pb could be attributed to its larger ionic radius and reduced hydrated radius as well as the stable species under the pH conditions of the treatments. This study suggests that the migration of heavy metals could reduce the water quality and increase the ecological risk of the interaction zone between land and sea.

High-Resolution Analysis of Fe–Mn Oxyhydroxide in Ferromanganese Nodules from the Northwestern Pacific Ocean and Insights on Element Mobility

Due to the multiple and poorly-crystallized phases in ferromanganese (Fe–Mn) nodules, research on the variability of micro-layers in nodules is limited and the accumulation of various elements with the growth of micro-layers have not been well documented. To address this gap, we examined the spatial distributions of elements in cross-sections of nodules from the Northwestern Pacific Ocean using in-situ electron microprobe analyses coupled with backscattered electron imaging and high-resolution X-ray elemental intensity mapping. Results suggest their significant selective enrichment of metal elements is similar to that of typical hydrogenetic nodules and diagenetic nodules. Moreover, WMn+Fe of Fe–Mn oxyhydroxide is equal to 50% after normalization and Co and Ni show positive relationships with Mn/Fe ratio, suggesting Fe oxyhydroxide would serve as a diluter at exposed surface during nodule growth. In suboxic conditions, Mn, Ni, and Co start to release, and the remaining Fe oxyhydroxide may react with the surrounding sediment to form Si-rich layers. Our studies reveal the diverse growth processes and show a much larger chemical heterogeneity of individual layers, which extend the models about the mechanisms of chemical precipitation and environmental conditions that existed during nodule growth.

Exotic REE behaviors of zircon in the Koktokay No. 3 granitic pegmatite, Xinjiang, northwest China

Rare earth elements (REEs) can be incorporated into zircon at significant concentrations that are controlled by the temperature, pressure, and composition of their growth environment. However, the distribution of REEs between zircon and melt does not always conform to the currently available partitioning data. This study presents evidence of exotic REE behaviors in zircon from the marginal zone of the Koktokay No. 3 granitic pegmatite in Xinjiang, northwest China. The behavior of the Koktokay REEs represents by large negative Ce anomalies, flat heavy REE patterns, and lanthanide tetrad effects. Two generations of zircon (Zrn-I and Zrn-II) are identified, which were formed by dissolution and re-precipitation processes. Zrn-I represents relic zircon domains with dissolution textures that formed from pegmatite melt during the late stage of the magmatic–hydrothermal transition. Zrn-II occurs as overgrowths and infilling fractures around or within Zrn-I, which formed by hydrothermal re-precipitation. From Zrn-I to Zrn-II, the zircon exhibits increasingly negative Ce anomalies and greater enrichment in light REEs and other non-stochiometric elements (e.g., Ca, Al, Fe, and Mg). Given the lack of Ce depletion in the host granite, the negative Ce anomalies in zircon can be attributed to Ce being sequestered into hydrothermal minerals (i.e., cerianite and/or Fe–Mn oxyhydroxides) as tetravalent Ce. In addition, the flat heavy REE patterns of both Zrn-I and Zrn-II likely resulted from the crystallization of heavy REE-enriched minerals, such as zircon and garnet, and were further enhanced by hydrothermal alteration. The two generations of zircon display identical M-type lanthanide tetrad effects in REE patterns, with similar TE3 values. This ubiquitous M-type tetrad effect of the REEs in garnet, zircon, and the host granite can be attributed to the exsolution and subsequent interaction with magmatically derived fluids containing F–aquo-complexes. Therefore, we conclude that such anomalous REE incorporation into zircon from a hydrous pegmatitic melt is controlled by the evolution of the hydrous melt and dissolution–re-precipitation processes. Our results suggest that the reliability of zircon REE partitioning data should be revaluated, and that further experimental studies are needed to fully understand the behavior of REEs in hydrothermal systems.

Hematite-mediated Mn(II) abiotic oxidation under oxic conditions: pH effect and mineralization

Interactions between manganese (Mn) and iron (Fe) are widespread processes in soils and sediments, however, the abiotic transformation mechanisms are not fully understood. Herein, Mn(II) oxidation on hematite were investigated at various pH under oxic condition. Mn(II) oxidation rates increased from 3 × 10−4 to 8 × 10−2 h−1 as pH increased from 7.0 to 9.0, whereas hematite enhanced Mn(II) oxidation rates to 1 h−1. During oxidation process, high pH could promote the oxidation of Mn(II) into Mn minerals, resulting in the rapid consumption of the newly-formed H+, and high pH facilitated Mn(II) adsorption and oxidation by altering Mn(II) reactivity and speciation. Only granule-like hausmannite was found on the hematite surface at pH 7.0, whereas hausmannite particles and feitknechtite and manganite nanowires were formed at pH from 7.5 to 9.0. Moreover, a co-shell structured nanowire composed of manganite and feitknechtite was observed owing to autocatalytic reactions. Specifically, electron transfers between Mn(II) and O2 occurred on the surface or through bulk phase of hematite, and direct electron transfers in the O2-Mn(II) complex and indirect electron transfers in the O2-Fe(II/III)-Mn(II) complex may both have contribution to the overall reactions. The findings provide a comprehensive interpretation of Fe-Mn interaction and have implications for the formation of soil Fe-Mn oxyhydroxides with unique properties in controlling element cycling.

Marine osmium isotopic composition reconstructed from the early Permian umber deposit in the Japanese accretionary complex

• Re-Os isotopes of early Permian umbers in Japan were analyzed. • Oxidative Mn-oxides prevented Re fixation into the Kunimiyama umbers. • 187 Os/ 188 Os values of early Permian seawater ranged from 0.523 to 0.676. Strata-bound ferromanganese (Fe–Mn) deposits (umbers) are thought to have formed by precipitation of Fe–Mn oxyhydroxides derived from seafloor hydrothermal activity at a mid-oceanic ridge. Fe–Mn oxyhydroxides effectively adsorb various elements (e.g., P, V, As, rare earth elements, and Os) dissolved in seawater. Of these elements, osmium (Os) is particularly important for reconstructing the Earth’s surface environment during formation of the deposits. Here we report the Os and rhenium (Re) contents and marine Os isotopic ratio ( 187 Os/ 188 Os) i of the early Permian reconstructed from the Kunimiyama umber deposit in the Northern Chichibu Belt, central Shikoku, southwest Japan. The Kunimiyama umbers exhibit comparable to slightly lower Os (42–183 ppt) and much lower Re (1.3–49 ppt) contents than other umbers in Japanese accretionary complexes and modern seafloor metalliferous sediments, the latter of which are regarded as umber precursors. The ( 187 Os/ 188 Os) i ratio of the Kunimiyama umbers is 0.523–0.676, which is comparable to or slightly higher than the values of the middle to Late Cretaceous and early Paleogene. This work is the first report of seawater Os isotope ratios in the Panthalassa Ocean of the early Permian, representing an important achievement in understanding the marine Os isotopic record of the Paleozoic Era.

Manganese carbonate minerals and their alteration products in Silurian metalliferous nodules from the region of Asaritsa peak, West Balkan Mountain

The studied Silurian nodules have hard light cores and dark shells. The cores consist of quartz with disseminated zonal carbonate mineral and pyrite. Zones in the carbonate have a variable composition from Mn-containing siderite, ankerite and dolomite to mixed Fe-Mn carbonate and Fe-containing rhodochrosite. The nodule shells are composed of quartz, chlorite, sericite, goethite, Mn-Fe oxyhydroxides and siderite. Fe-Mn oxyhydroxides in the nodule shells are formed due to an alteration of the carbonate minerals and inherited their composition. The formation of the nodules with Fe- and Mn-carbonates is related to diagenetic processes under reducing conditions of low Eh and high pH values. Later, carbonate minerals were altered into Fe-Mn oxyhydroxides. These alteration changes can be related to the influence of later magmatic activity in the area. An example of this activity is the presence of an igneous bodies established on both sides of the section.