Fe-Mn Oxides Research Articles

Evolution of continental inputs and watermass during cretaceous oceanic anoxic event 2 in the Neo-Tethyan region: Evidence from Nd-isotopes in southern Tibet

During the mid-Cretaceous extreme greenhouse (∼ 90 to 125 Ma), changes in continental inputs and water-mass circulation influenced nutrient distribution and set the stage for ocean anoxia. Investigation of these changes is critical for an understanding of contemporaneous global-ocean evolution. Previous studies on δ66Zn, δ15N, δ13C and 187Os/188Os isotopes in the Neo-Tethyan Ocean inferred both of these changes might be responsible for the continuous nutrient supply required to cause expansion of carbon burial during Oceanic Anoxic Event 2 (OAE2). Here, we applied the hydroxylamine hydrochloride (HH) extraction procedure to the analysis of Nd isotopic compositions of sediments collected from the mid-Cretaceous Dongshan and Lengqingre formations in southern Tibet. Our Nd isotope [εNd(t)] records exhibit a large negative excursion (from −9.8 to −6.1) during the Cenomanian-Turonian period, but little variation (−6.5 to −5.2) during the Aptian period. Major and trace elements as well as εNd(t) of residues indicate that the HH-extracted Nd in this study is mainly sourced from authigenic FeMn oxides. To evaluate the robustness of our εNd(t) records, we examined the potential influences of the detrital fraction. Our ɛNd(t) records reflect a mixing signal of surface currents from the Central Pacific and continental weathering inputs, and the corresponding negative excursion is triggered by the changes of continental weathering inputs in the Neo-Tethyan region, which was synchronous with the change of riverine systems during the drift of the Greater Indian Plate in the mid-Cretaceous greenhouse. Further, the enhanced continental weathering inputs, which supplied continuous nutrients to the Neo-Tethyan ocean, have likely caused OAE2 and extended the duration of OAE2. Our εNd(t) records shed new lights on our understanding of OAE2 during the mid-Cretaceous.

Geochemical (δ13C, δ18O, 87Sr/86Sr, REEs) characterization of travertine in Tengchong, China: Insights into travertine origin and reservoir conditions

Geochemical characterization is extensively employed in travertine research, yet few studies have explored the potential of travertine geochemistry for elucidating the subterranean details of spring systems. In this study, we systematically characterized the geochemical signatures (δ13C, δ18O, 87Sr/86Sr, REEs, Zr, Th, Sr, Mn) of travertine from six spring systems in Tengchong (SW China) and compared them with those of potential reservoir rocks, aiming to understand travertine origin and assess reservoir conditions. Our results revealed substantial variations in the δ13C and δ18O of travertine among the examined systems, but the water temperature and parent CO2 assessments suggest a hot spring thermogene origin of the travertine. The 87Sr/86Sr of the studied travertine also varies significantly among the systems and overlaps with that of potential reservoir rocks. However, only the springs systems with reservoir temperatures exceeding 150 °C are likely to have precipitated travertine with 87Sr/86Sr resembling the whole-rock 87Sr/86Sr of the reservoir rocks. REE contamination by exogenous detritus and FeMn (oxyhydr)oxides was noted, emphasizing the need for careful REE contamination evaluation in travertine research. The REE comparison reveals that the studied travertine does not fully replicate the REE signature of its potential reservoir rocks, but the REE pattern, (Eu/Eu*)SN, and (Ce/Ce*)SN characteristics of the travertine reveal informative reservoir conditions. In summary, this study shows that the geochemistry of the travertine offers valuable insights into its origin and reservoir conditions. These findings could assist in the geochemical interpretation of travertine and the exaction of hypogean reservoir conditions from travertine.

Mineral formation and element migration in fractures and pores of hydrogenetic ferromanganese nodules

Ferromanganese (Fe-Mn) nodules composed of nano-sized Fe-Mn (oxyhydr)oxides are significant mineral resources rich in multiple critical metals (e.g., Co, Ni, Cu, and REY). The ubiquitous high porosity, large pore size, and pore connectivity in hydrogenetic nodules enable the constant influx of seawater and/or porewater driving widespread diagenetic processes (i.e., mineral dissolution and recrystallization) in the abundant fractures and pores. These diagenetic processes are critical to understanding the migration, partitioning, and distribution of the critical metals, but remain unclear yet. In this study, high-resolution in-situ analyses were conducted to investigate the mineralogical and geochemical characteristics of diagenetic precipitates in fractures and pores of a hydrogenetic Fe-Mn nodule (MP5D33) from the central Pacific. Both oxic and suboxic processes were found in the fracture. The oxidized diagenetic products exhibit geochemical and mineralogical characteristics similar to those of hydrogenetic precipitates (e.g., vernadite), while the suboxic diagenetic processes primarily produced large-size 10 Å phyllomanganate. The diagenetic conditions within this studied fracture gradually shifted from oxic to suboxic, causing changes in the contents of multiple critical metals. The minerals in pores are mainly composed of 10 Å phyllomanganate that crystallized forms through heterogeneous nucleation on small-size vernadite in a suboxic environment. Additionally, minor todorokite likely transformed from 10 Å phyllomanganate undergoing long-term diagenesis. These findings shed some insights into the diagenetic process in the interior fractures and/or pores of Fe-Mn nodules and enhance the understanding of the migration of critical elements associated with Fe-Mn (oxyhydr)oxides during diagenesis in Fe-Mn deposits.

The fate of Cd in Soils with Various Particle Sizes: Characteristics, Speciation Distribution and Influencing Factors.

This study investigated the distribution of Cd in soil water-stable aggregate particles of varying sizes, revealing that smaller particles have higher total Cd content as well as different forms of Cd content, with the clay particle showing a greater tendency to accumulate Cd. However, the proportion of high activity Cd is lower in clay particles, posing a lower environmental risk of Cd transformation compared to silt particles. Adsorption experiments indicated that the clay particle exhibits the strongest adsorption capacity and highest adsorption rate. Additionally, correlation and principal component analyses identified Fe-Mn oxides and organic matter as the primary influencing factors on Cd distribution characteristics, with pH playing a secondary role. These findings provide valuable insights for the remediation of heavy metal-contaminated soil.

Do red marine carbonates represent oxic environments? New understanding from the Upper Ordovician marine limestone in Tarim Basin, China

Marine red beds (MRBs), typically colored by Fe- and Mn-rich minerals, are often interpreted as indicators of bottom water oxygenation. However, their continuous formation requires long-term input of aqueous derived Fe-Mn oxides and/or stable sources of Fe2+ and Mn2+ ions, challenging the traditional concept of “red equals oxic environment.” This study investigates two coeval Upper Ordovician Sandbian MRB carbonate intervals in the Tarim Basin. Previous studies attributed the pigment origin to hematite. Th/U values and total rare earth element and yttrium (REY) contents increased in the MRB interval, indicating a terrestrial source of iron. Hematite was observed within the intercrystal pores of calcite precipitating from porewater, consistent with high Nicarb abundance and MREE-enriched bulge pattern in the red intervals. Both sections exhibit high Fecarb and Mncarb, pointing to substantial reductive dissolution of Fe and Mn oxides. Simulation shows that isotopic discrimination (Δ13C) between carbonate and organic carbon could be biased by increasing benthic Fe-Mn flux, leading to decreased Δ13C values in MRB intervals. Ce/Ce∗ values in the high-Mncarb interval reflect the releasing of Ce by reductive dissolution of Mn oxides. The commonly used carbonate-based redox proxy I/(Ca + Mg) ratio is correlated positively with Mncarb in the shallower section and with TOC in the deeper section, while it is negatively correlated with TOC in the shallower horizon, suggesting that iodine behavior may be influenced by adsorption and releasing of Mn hydro-oxides and organic matter besides oxygen contents. This study links MRB coloring to Fe and Mn mineral cycling in pore water through reductive dissolution and oxidative precipitation, and highlights potential biases of carbonate-based redox proxies that might be susceptible to other electron acceptors/donors such as Fe-Mn oxides and organic matter, in addition to free oxygen in seawater.

Distribution Characteristics and Pollution Assessment of Soil Aggregates of Cr, Ni, and Cu in a Region of Northern Hebei Province

In order to understand the distribution, occurrence forms, and influencing factors of chromium (Cr), nickel (Ni), and copper (Cu) in soil aggregates, a five-step extraction method was used to determine their forms in soil aggregates of different sizes in a mountainous area of northern Hebei Province. The ecological risk was evaluated using the geo-accumulation index (Igeo) and primary and secondary comparison value method (RSP). Redundancy analysis (RDA) was used to identify the main factors affecting the distribution and morphology of Cr, Ni, and Cu in soil. The results showed that in vertical distribution, Cr, Ni, and Cu were concentrated in the surface soil, but there was no clear relationship between soil depth and heavy metal content. The distribution characteristics revealed that Cr, Ni, and Cu in soils mainly existed in relatively stable Fe-Mn oxides and residue states, and their morphology in aggregates did not vary considerably with particle size. Furthermore, the RSP results showed that the pollution risk of Cr, Ni, and Cu was higher, with Cr and Ni posing the highest risk in the 0.5–1 mm and 1–2 mm particle size ranges. The RDA results showed that available phosphorus and soil organic matter (SOM) were the main factors that caused the characteristic difference of 1–2 mm aggregate components. Additionally, hydrolyzed nitrogen, cation exchange capacity (CEC), and calcium exchange have positive effects on the residual state of Cr. For Ni, SOM, CEC and exchangeable calcium have positive effects on the binding state of Fe and Mn oxides and carbonate. For Cu, CEC and exchangeable calcium are the key factors that cause the morphological differences of aggregates. Based on the above results, a theoretical basis has been provided for the prevention and control of pollution in the subsequent research area.

Boosting Microbial CO2 Electroreduction by the Biocompatible and Electroactive Bimetallic Fe–Mn Oxide Cathode for Acetate Production

Boosting Microbial CO₂ Electroreduction by the Biocompatible and Electroactive Bimetallic Fe–Mn Oxide Cathode for Acetate Production

Excellent antibiotic degradation through PMS activation via bio derived Fe-Mn oxides with tunable defect concentration: Synergy between singlet oxygen oxidation and electron transfer

Regulating the defect sites and structural composition of metal-based metal catalysts is an effective strategy to improve the activity of activating PMS to degrade pollutants. Herein, bio derived Fe/Mn composite oxides (BFMO) rich in oxygen vacancy composed of crystalline manganese oxide coated with amorphous iron oxide was prepared through microbial mediation, and used for PMS activation in the degradation of tetracycline (TC). After 60 minutes reaction, the removal rate of TC achieved 92.4 %−98.8 % within wide pH range of 3–12. Besides, this system has outstanding anti-interference ability to common ions and humic acid (HA). The outstanding catalytic performance stemmed from the non-radical pathway for producing singlet oxygen (1O2) and electron transfer, facilitated by defect-rich polyvalent Mn and amorphous Fe species. Polyvalent Mn species accelerate the electron transfer process, and its surface defect structure further promotes the adsorption of pollutants on the surface of the materials. The redox cycle of Fe3+/Fe2+ was accelerate via electron-rich groups. This study explored the synergy triggered by microbe-mediated defect sites and structure-dependent, providing a design strategy for environmental remediation of PMS activated by Fe/Mn based bimetallic catalysts with strong resistance to environmental interference.

A biochar-based amendment improved cadmium (Cd) immobilization, reduced its bioaccumulation, and increased rice yield

Cadmium (Cd) contamination of soil threatens human health, food security, and ecosystem sustainability. The in situ stabilization of Cd has been recognized as a potentially economical technology for the remediation of Cd-contaminated soil. Recently, biochar (BC) and activated carbon (AC) have received widespread attention as eco-friendly soil amendments that are more beneficial for plant growth, soil health, and remediation of contaminated soil. An experiment was performed in a paddy field to investigate the effects of two different types of BC (maize straw biochar and bamboo biochar) and AC (coconut shell activated carbon) in combination with rape organic fertilizer (R), calcium magnesium phosphate fertilizer (P), and fulvic acid (F), respectively, on soil Cd immobilization, Cd accumulation in rice, and yield. The results indicated that the BC/AC-based amendments reduced soil bioavailable Cd (DTPA-Cd) and brown rice Cd by 9.58%–27.06% and 19.30%–71.77%, respectively. The transformation of exchangeable Cd (Ex-Cd) to carbonate-bound Cd (Ca-Cd), Fe-Mn oxide bond (Ox-Cd), and residual (Re-Cd) in soil accounted for the mitigation of Cd uptake and enrichment by rice. Additionally, BC-/AC-based amendments altered soil physicochemical properties, which significantly increased the soil pH and cation exchange capacity (CEC), total nitrogen (TN), total phosphorus (TP), soil organic carbon (SOC), and dissolved organic carbon (DOC), directly promoting soil health. All BC-/AC-based amendments significantly increased FeIMP and MnIMP concentrations by 47.31%–160.34% and 25.72%–73.09% in the Fe/Mn plaque (IMP), respectively. Maize straw and bamboo biochar-based amendments significantly increased rice yield by 10.46%–20.41% and 9.94%–16.17%, respectively, while coconut shell-activated carbon severely reduced rice yield by 65.06%–77.14%. The correlation analysis revealed that leaf Cd and IMP primarily controlled Cd uptake by rice, and soil pH, Eh, CEC, SOC, IMP, and TP influenced DTPA-Cd in soil. This field study demonstrated that maize straw and bamboo biochar-based amendments not only reduced soil DTPA-Cd in paddy fields but also decreased the accumulation of Cd in brown rice, as well as improved rice yield, which has potential application in Cd-contaminated agriculture fields. Coconut shell-activated carbon severely decreased rice yields, which is not appropriate for rice production.

Reconstructing the past environmental conditions of southwestern India using estuarine sediment core

Geological archives can be examined via multiple proxies to uncover significant information about historical environmental changes. In comparison to single proxy approach, the use of multiple proxies can provide better resolution of the paleoenvironmental record. Thus, in the present study, to understand the paleoenvironmental conditions in the Kali coast in southwestern India, sedimentological, geochemical and isotopic (210Pb, 137Cs) proxies were used. The findings demonstrated that, in previous decades, the sedimentation rate varied from 0.5 to 1.0 cm/year under conditions with relatively higher hydrodynamic energy that were more common and fluctuating, allowing for larger sand particle deposition. However, in more recent years, finer particle deposition towards the surface has been observed under conditions with lower and more stable hydrodynamic energy, with a sedimentation rate of 1.87 cm/year. Additionally, the finer fractions displayed a strong correlation with the metal distribution, which was mostly governed by Fe-Mn oxides. Furthermore, it can be revealed that the environment was warm, humid, and marine-like between 1995 and 2000 based on chemical weathering intensity values and Rb/K ratios. A subtle shift to a freshwater habitat with relatively less warm, less humid climate occurred between 2000 and 2020. Therefore, similar research with longer depositional histories coupled with multiple proxies can help predict the future climatic shifts in decadal time scales.

Optimizing Oxalic Acid Application Regime to Maximize Sunflower Remediation Efficacy in Cd-Contaminated Soils

The exogenous application of oxalic acid is a potential approach to amplifying phytoremediation performance on Cd-contaminated soils. However, few studies explore the optimal oxalic acid application regime from a perspective of coupling different concentrations and timings to maximize Cd removal rate. Given this, a pot experiment was conducted using oil sunflower (Helianthus annuus L.) as the test plant. Oxalic acid was added to the pots at concentrations of 1, 2, 3, 4, 5, and 6 mmol/kg at 20, 30, 40, and 50 days after emergence. A control (CK) without exogenous oxalic acid was also included. We examined the discrepancies in various soil Cd forms, sunflower height, plant non-protein thiol (NPT) levels, and soil Cd remediation efficiency under different oxalic acid application regimes. The results showed that applying oxalic acid at a concentration of 4 mmol/kg reduced the proportion of Fe-Mn oxide Cd and organic Cd compared to the control (CK), while increased the proportion of available Cd. The optimal application time is 30 or 40 days after emergence. The addition of exogenous oxalic acid promoted the growth of sunflowers, with the greatest increase in plant height observed when 4 mmol/kg oxalic acid was applied at 30 days after emergence. Exogenous oxalic acid enhanced the absorption of Cd by sunflower roots, with the total Cd accumulation in roots, stems, and leaves being higher than in the control (CK). When 4 mmol/kg oxalic acid was applied at 30 days after emergence, the total Cd accumulation in roots, stems, and leaves was highest. Under different application times and concentration levels of oxalic acid, Cd accumulation was highest in roots, followed by leaves, with stems showing the lowest accumulation. The NPT content in each part is as follows: root > stem > leaf. Applying 5 mmol/kg oxalic acid after 30 days of sunflower emergence resulted in relatively higher total NPT content in roots, stems, and leaves compared to the control (CK). The TOPSIS model was used for comprehensive evaluation, which showed that 4 mmol/kg oxalic acid application at 30 days after emergence could be used as the optimal oxalic acid application regime for phytoremediation. These findings indicate that the addition of oxalic acid effectively promoted the absorption of Cd by sunflower and increased the efficiency of Cd removal from the rhizosphere soil, with the optimal removal of soil Cd achieved by applying oxalic acid at a concentration of 4 mmol/kg 30 days after the emergence of oilseed sunflower seedlings.

A transformation and auxiliary extraction of Cr during electrokinetic removal of Cr-contaminated multilayer composite soil chamber.

Multilayer composite soil chamber was proposed to extract the Cr of contaminated site soil and insight into transformation of Cr fractionation associated with valence states. The variations of current, soil pH and moisture content were explored, as well as the migration of Cr fractionation and redistribution of Cr. Results indicated that duration of half peak current could be used to adjust treatment time and it varied among different composite ways. Moreover, extraction efficiency of Cr in soil near cathode was relatively higher and reached 60% when citric acid was used. Citric acid could promote the transformation between different Cr fractionations or different valence states. It could also improve the desorption of Cr, and could prevent excessive fluctuations of moisture content at the same time. Cr redistributed acrossed the soil chamber after extraction. When deionized water was used, Cr(VI) significantly migrated toward anode mainly in the form of exchangeable fractionation (EXC) while Fe-Mn oxides fractionation (Fe-Mn) which may be in the form of cationic Cr(III) hydroxides migrated toward cathode. When using citric acid, fractionations that were difficult to migrate of Cr, especially for Fe-Mn in site soils could be activated and became EXC and carbonate fractionation (CAR), then migrated to the anode or cathode. The migration of exchangeable Cr(III) was dramatically enhanced. But the use of citric acid could cause Cr(VI) transformation to Cr(III) near anode. In addition, during the migration process, EXC could go back to Fe-Mn again or transform to residue fractionation (RES).

Y-Ho fractionation during basalt alteration in hydrothermal system: An implication for superchondritic Y/Ho signature recorded in Precambrian banded iron formations

The concentration of rare earth elements (REE) in Precambrian sedimentary rocks is widely used to estimate their depositional environment. Specifically, superchondritic Y/Ho value is a powerful indicator for determining whether a sedimentary rock was deposited in a marine environment. Currently, superchondritic Y/Ho value in seawater is believed to result from the preferential adsorption of Y onto Fe-Mn oxides. In modern oceans, Fe-Mn oxides are considered the sink for subchondritic Y/Ho value. On the contrary, Precambrian banded iron formations (BIFs) display superchondritic Y/Ho value, suggesting that Precambrian seawater also possessed a superchondritic Y/Ho value. However, Precambrian BIFs cannot account for the sink of subchondritic Y/Ho value. Thus, other processes must have been responsible for maintaining the superchondritic Y/Ho value of Precambrian seawater. A hydrothermal experiment involving mid-ocean ridge basalt (MORB) and a Cl-rich fluid was conducted at 300 °C and 500 bars to assess the role of basalt-hosted hydrothermal systems on the Y/Ho value of seawater. Over time, the fluid's Ca concentration increased while Na decreased, suggesting plagioclase albitization occurred. The REE pattern of the reacted fluids exhibited superchondritic Y/Ho values up to 63.2. Based on the presence of positive Eu anomaly and the degree of light REE depletion, the REE in the hydrothermal fluids was mainly sourced from plagioclase during albitization. The superchondritic Y/Ho values in the fluids can be explained by the preferential leaching of these elements due to differences in chloride complexing strength between REE. Subchondritic Y/Ho values observed in Precambrian hydrothermally altered basalts may be interpreted as remnants generating superchondritic Y/Ho values in coexisting Precambrian hydrothermal fluids. Therefore, we believe that the superchondritic Y/Ho value of Precambrian seawater was maintained by basalt-hosted hydrothermal system.

Nano silica-mediated stabilization of heavy metals in contaminated soils

Soil contamination with heavy metals presents a substantial environmental peril, necessitating the exploration of innovative remediation approaches. This research aimed to investigate the efficiency of nano-silica in stabilizing heavy metals in a calcareous heavy metal-contaminated soil. The soil was treated with five nano-silica levels of 0, 100, 200, 500, and 1000 mg/kg and incubated for two months. The results showed that nano-silica had a specific surface area of 179.68 m2/g\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{m}}^{2}/\ ext{g}$$\\end{document}. At 1000 mg/kg, the DTPA-extractable concentrations of Pb, Zn, Cu, Ni, and Cr decreased by 12%, 11%, 11.6%, 10%, and 9.5% compared to the controls, respectively. Additionally, as the nano-silica application rate increased, both soil pH and specific surface area increased. The augmentation of nano-silica adsorbent in the soil led to a decline in the exchangeable (EX) and carbonate-bound fractions of Pb, Cu, Zn, Ni, and Cr, while the distribution of heavy metals in fractions bonded with Fe–Mn oxides, organic matter, and residue increased. The use of 1000 mg/kg nano-silica resulted in an 8.0% reduction in EX Pb, 4.5% in EX Cu, 7.3% in EX Zn, 7.1% in EX Ni, and 7.9% in EX Cr compared to the control treatment. Overall, our study highlights the potential of nano silica as a promising remediation strategy for addressing heavy metal pollution in contaminated soils, offering sustainable solutions for environmental restoration and ecosystem protection.

A New Find of Anorthoclase Crystals-lined Vug in a Deep-sea Basalt, Central Indian Ocean Basin

ABSTRACT We detail a new and first find of a vug in a deep-sea basalt that is lined with well-formed anorthoclase crystals. The specimen was dredged from the seafloor (water depth 4,440 m) near a seamount in the Central Indian Ocean Basin. The basalt has a thin veneer of glass covered with ferromanganese (FeMn) oxides while the interior is quite fresh. The geochemical analysis of the basalt depicts different degrees of alteration that vary from the outermost layer with FeMn oxides to the interior of the specimen. In general, the TiO2 (<1.5 wt%) and MgO (~5 wt%) contents are low while CaO, Na2O, K2O and P2O5 contents change within the specimen. The FeMn oxides have Fe2O3 (21 wt%) and MnO (8–27 wt%) and appear as botryoids and occur near and/or over the anorthoclase crystals. The trace and rare earth elements do not show significant variations from the outer to the interior of the specimen. Microscopy (binocular and scanning electron) and energy dispersive spectrometry of the vug revealed a dominance of drusy anorthoclase crystals. The formation of the anorthoclase crystals is ascribed to precipitation from hydrothermal solutions that seeped into the basalt through cracks. This is attested by the co-existing crystals of phillipsite and feldspar and FeMn oxides.

The Characteristics and Enrichment Process of Dabu Ion-Adsorption Heavy Rare-Earth Element (HREE) Deposits in Jiangxi Province, South China

Ion-adsorption rare-earth deposits supply over 90% of the global market’s heavy rare-earth elements (HREEs). The genesis of these deposits, particularly HREE deposits, has garnered significant attention. To elucidate the metallogenic mechanisms of HREE deposits, a comprehensive study of the weathering profile of granite was conducted in Jiangxi Province, South China. This study focuses on the following two aspects: the petrogeochemistry of HREE-rich granite and the enrichment and fractionation of rare-earth elements (REEs) during the weathering process. The results suggest that the Dabu granites are a typical peraluminous, high-K, calc-alkaline granite series with high silica content (SiO2: 74.5%–76.4%), relatively low phosphorus content (P2O5: <0.05%), and high HREE content (ΣLREE/ΣHREE: 0.16–0.66). Weathering advances the decomposition of minerals and the release of elements. REEs are mainly fixed in the regolith by scavengers, mainly clays, Fe–Mn oxides, and carbonates, and ΣREE can reach 799 ppm in the B horizon. However, HREEs tend to migrate further and preferentially combine with Fe–Mn oxides and carbonates as compared to LREEs, leading to a significant fractionation of REEs in the regolith (ΣLREE/ΣHREE = 0.2–1.1). Additionally, the differential weathering of REE-bearing minerals and the precipitation of secondary REE-bearing minerals are also vital for REE fractionation.

Vanadium doped Fe-Mn bimetallic oxides as cathodic materials for boosted heterogeneous electro-Fenton degradation of organic contaminants

The design of cathode materials with both sustainable H2O2 selectivity and accelerated recyclable regeneration remains a challenge for contaminants removal in heterogeneous electro-Fenton (HEF) process. Herein, a series of ternary Fe0.50Mn0.5−δVδOx (δ = 0.005, 0.01, 0.05) metal oxides have been synthesized and employed as cathodic materials for the degradation of various organic contaminants in water matrix. 99.7 % removal rate was achieved for carbamazepine (CBZ) in 60 min with 98.8 % mineralization rate. Simultaneously, the catalyst exhibited outstanding degradation efficiency (96.0–99.7 %) with other pollutants including sulfonamides (SMX), bisphenol A (BPA), 2,4-dichlorophenol (2,4-DPC) and ofloxacin (OFX), demonstrating its potential application. Factors affecting the EF process, including current density, pH, oxygen flow rate and compatibility of inorganic anions were thoroughly evaluated and the degradation mechanism was studied in detail. Density functional theory (DFT) calculations revealed that the improved catalytic efficiency was originated from vanadium doping to access optimized electronic structure, which endows enhanced 2e− ORR selectivity as well as excellent overall performance for the EF process. This work may enrich the study on EF system and offers a promising strategy for contaminants removal with FeMnVO materials in water treatment applications.

Polysulfone membranes decorated with Fe–Mn binary oxide nanoparticles and polydopamine for enhanced arsenate/arsenite adsorptive removal

Arsenic contamination of water is a global environmental concern, and membrane technology combined with nanotechnology contributes to more efficient removal of arsenic. In this study, Fe–Mn oxide (FM), Polydopamine (PDA), and PDA-modified FM (PFM) were incorporated into polysulfone (PSF) to prepare adsorption membranes (PFMP) for arsenic removal. The prepared nanoparticles and membranes were characterized using TEM, SEM, FTIR, TGA, contact angle, and pure water flux. The introduction of particles enhanced the hydrophilicity of the membranes and significantly enhanced the pure water flux of the membranes. Adsorption experiments indicated that the PFMP membrane exhibited the best arsenic removal performance, with maximum adsorption capacities for As(III) and As(V) were 11.57 mg/g and 12.39 mg/g, respectively. The Langmuir model fitted the adsorption isotherms well, and the kinetics followed the pseudo-second-order model. The filtration experiment revealed that the PFMP membrane was capable of reducing As(III) solution (915 L/m2) and As(V) solution (1075 L/m2) from a concentration of 100 μg/L to the safe limit of As (＜10 μg/L). The As-loaded membrane was regenerated using NaOH solution (pH = 11), and the filtration experiment was repeated. FTIR and XPS demonstrated that the mechanism of the reaction between the membrane and arsenic was ligand exchange, where the arsenic ions were bonded to the oxygen ions to form Mn–O–As and Fe–O–As.

Sedimentation and transformation of heavy metals during the transport from the Yellow River estuary to the sea: Evidence from surface sediments of the Yellow River subaqueous delta

Estuarine and coastal areas are one of the ultimate sinks for terrestrial heavy metals which play a vital role on the aquatic ecosystem. This study examined heavy metals contents and speciations in Yellow River subaqueous delta surface sediment, to characterize their sedimentation and transformation during transport from estuary to the sea. The results showed that higher concentrations were found in the seaward and the shear front affected areas. The surface sediments were generally not contaminated by heavy metals, except for Cd was highly enriched, while the post-standardization spatial distribution reflected the effect of estuarine processes as a “filter” that effectively intercepting heavy metals. The dominated phase was residual fraction for Cr, Cu, Zn, Cd, while reducible fraction for Ni and carbonate fraction for Pb. The transformation of heavy metal species was mainly influenced by the changes in the sediment components such as carbonate minerals, organic matter and FeMn oxides.

Formation of hydrothermal ferromanganese oxides in the Daini-Nishi-Yamato Seamount, Sea of Japan: Do they really contain critical-metal particles?

In submarine environments, ferromanganese (Fe–Mn) oxides are formed via various processes. Although hydrothermal Fe–Mn oxides are generally valueless as mineral resources because of their low critical metal content, they reflect temporal changes in hydrothermal activity. Metal particles, including native metals, have been observed in hydrothermal Fe–Mn oxides and associated igneous rocks that are extensively distributed in the Sea of Japan. This finding can have significant implications for metal transport in submarine hydrothermal systems. However, the existence of these metal particles requires verification because their thermodynamic coexistence with Mn oxides is challenging and has only been reported by one research team. Here, we show the growth structure and geochemistry of hydrothermal Fe–Mn oxides and volcanic rocks from the Daini-Nishi-Yamato Seamount in the Sea of Japan. The chemical and Nd–Sr isotopic compositions of the volcanic rock indicated that the Daini-Nishi-Yamato Seamount formed through magmatism after back-arc spreading in the Yamato Basin at 10–17 Ma. The hydrothermal Fe–Mn oxides consisted of Ti-rich layers that formed earlier and Ti-poor layers that formed later. The Ti-rich layers precipitated from Ti-rich hydrothermal fluids because of water–rock interactions at higher temperatures during the early stages of hydrothermal activity. During the late stages of hydrothermal activity, Ti-poor layers formed, likely because of a decrease in the temperature of the water–rock interactions and/or the depletion of Ti in the host rocks. However, unlike in previous studies, metal particles such as Ag and rare earth elements were not detected in our samples, which were impregnated with resin to prevent contamination during the polishing process. These results strongly suggest that the metal particles reported in the previous studies were contaminants.