Minerals Mn Research Articles

Simulation of rapid sand filters to understand and design sequential iron and manganese removal using reactive transport modelling

Iron (Fe2+), manganese (Mn2+), and ammonium (NH4+) oxidation processes were studied in three single media and three dual media full-scale rapid sand filters (RSFs) using reactive transport modelling (RTM) in PHREEQC and parameter estimation using PEST. Here, we present the insights gained into the spatial distribution of Fe and Mn mineral coatings in RSFs and its influence on the oxidation sequence and rates. Fe2+ and Mn2+ oxidation predominantly occurred simultaneously in the RSFs, contrary to the expected sequential oxidation based on Gibbs free energy calculations. During backwashing, RSF grains become fully mixed, which initiates heterogeneous Mn2+ oxidation on Mn-coated grains that end up in the top layer. The resulting grains have a mixed Fe/Mn mineral coating, which is limiting heterogeneous Mn2+ oxidation due to the limited Mn mineral surface available. Mixed coatings did not seem to affect Fe2+ oxidation rates, instead oxidation rates were increasing at lower pH. We found that RSFs can be designed to spatially separate Fe2+ and Mn2+ oxidation, which results in optimal conditions for Mn2+ oxidation. The RSF needs to consist of two layers with varying density to inhibit mixing and complete Fe2+ oxidation should occur in the top layer. The developed RTM can be used to estimate the depth at which Fe2+ oxidation is complete, and thus the ideal intersection depth of the two layers. A novel perspective is provided on how mineral coating distribution in single and dual media filters influence removal rates and the sequence of oxidation, which contributes to the design of more efficient groundwater filters.

Manganese(III) dominants the mobilization of phosphorus in reducing sediments: Evidence from Aha reservoir, Southwest China

Eutrophication has become one of the greatest threats to aquatic ecosystems. The release of phosphorus (P) from sediments exerts a critical role on eutrophication level. Both manganese (Mn) and iron (Fe), sensitive to redox conditions, own strong affinity for P. Numerous works have demonstrated that Fe was a key factor to drive P cycle in sediments. However, the role of Mn on P mobilization remains largely unexplored. Herein, the mechanism of P mobilization driven by Mn were investigated in a seasonal anoxic reservoir. Diffusive gradients in thin films (DGT) results, from both field investigations and laboratory incubations, showed P was synchronously distributed and significantly positive correlated (r2 ≥ 0.40, p < 0.01) with Mn, suggested that P cycle was associated with Mn. X-ray photoelectron spectroscopy (XPS) results showed that in the outer layers at the top 1 cm sediment pellet the contents of Mn and P occurred significantly synchronize changed, while that of Fe remains virtually unchanged when oxygen conditions changed. This demonstrated that Mn is likely to be the key factor affect P cycle. Most importantly, the relative content of Mn(III) changed the most (≈20 %) interpreted that Mn(III) is the key Mn species dominants the P mobilization. Furthermore, Dual-Beam scanning electron microscope (DB-SEM) maps clearly showed the co-enrichment of P and Mn in oxic sediments, confirmed P was mainly hosted by Mn minerals. In contrast, the random distributions and weak or negative correlations between P and Fe implied that P cycle was decouple with Fe, this resulted from that Fe was almost deposited as inert Fe fractions (>99.2 %) in reducing sediments. This study significantly expanded our knowledge on the geochemical behavior of P influenced by Mn in aquatic sediments.

Cerium(III)-induced structural transformation of hexagonal birnessite: Effect of mineral phase transition on arsenite transport and valence changes

The widespread mining and application of rare earth elements (REEs) have led to their continuous accumulation in the environment, with increasing concentrations in soil. The interaction between the most abundant REEs, cerium (Ce), and the prevalent hexagonal birnessite (HB) in the environment is worth attention. HB is one of the most effective metal oxides for the oxidation of arsenite [As(III)] and subsequent adsorption, and thus for arsenic (As) immobilization. Therefore, in this study, we investigated the effect of the presence of Ce(III) ion on the HB formation process and the influence of generating minerals on the oxidation and removal of As(III). Research has found that the interfacial reactions of REEs in manganese (Mn) minerals not only affect their cycling but also alter the properties of the Mn minerals, thereby affecting the environmental fate of As. The results indicated that the presence of Ce ions affected the structure of HB during mineral synthesis and reduced the crystallinity of the conversion products. Their substitution for Mn(IV) in the lattice increased the specific surface area of minerals, reduced particle size, and produced more hydroxyl groups that were conducive to the immobilization of As(III). Meanwhile, Ce(III) was oxidized to Ce(IV) during the formation of Ce-bearing hexagonal birnessite (Ce-HB), and CeO2 nanoparticles were formed on the mineral surface and the removal rate of As(III) by Ce-HB was greatly improved. When the As concentration was lower than 6 mg·L−1, the removal effect of Ce-HB could reach the drinking water standard. However, the oxidation rate decreased due to the decrease in the proportion of Mn(IV). This study fundamentally reveals the behavior of HB coexisting with Ce in the migration and transformation of As(III) in the environment.

Mineralisation controls for the diverse Cape manganese occurrences, South Africa

Abstract The Cape Fold Belt, comprising folded sedimentary sequences from predominantly the Palaeozoic Cape Supergroup, hosts a multitude of manganese occurrences and mineral deposits, many of which were subject to historical mining activity. Although size, grade and quality issues negate their modern-day exploitation for the steel-making process, the mechanisms by which Mn has enriched at these sites holds scientific value for our understanding of low-temperature Mn (bio-)geochemical cycling. Deposits located within the Cape Fold Belt comprise structure-hosted Mn deposits and a little described class of Mn mound deposits associated with chalybeate thermal springs (temperature = 41 to 48°C). Although the relationships between the two remain tenuous, detailed study of both classes provides insight into the conditions that favour Mn accumulation in the near-surface and sub-aerial environments. Comparisons between the physicochemistry of manganiferous- and non-manganiferous thermal springs suggest that manganese solubility is favoured by warm, acidic and slightly reducing fluids with elevated salinity. Transport, and associated fluid focusing typically within highly permeable sandstone units, serves to locate Mn mineralisation in near-surface structurally-complex trap sites that provide both accommodation space and conditions that are sufficiently oxidising. Where manganiferous spring waters spill out at surface, oxidation is caused by contact with atmospheric O2 to form Mn mound deposits, and ambient Mn-oxidising microbiota (e.g., genus Ramlibacter, and members of Burkholderiales, Rhodocyclaceae, and Oxalobacteraceae) are likely to play a role in enhancing the kinetics of this process. Relative to the structure-hosted deposits, these Mn mound deposits are typically lower grade (higher iron content) and relatively friable (high porosity and fine grain sizes). Supergene and diagenetic processes can lead to localised upgrade of the Mn mound material, although typically not to ore grade.

Multiple effects of iron oxides on the adsorption and oxidation of dissolved organic matter by manganese oxides

Adsorptive fractionation and oxidation of dissolved organic matter (DOM) on manganese (Mn) oxide surfaces alter the molecular composition and stability of DOM, but the impact of iron (Fe) oxides on the coupled adsorption-oxidation processes of DOM by Mn oxides is largely unknown. In this study, the underlying mechanisms of molecular transformation of DOM on birnessite (Bir) in the presence of ferrihydrite (Fh), with varying Fh/Bir mass ratios, were investigated at both molecular levels and microscopic scales with a suite of characterization techniques, including Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and spherical aberration corrected scanning transmission electron microscopy (Cs-STEM). We found that higher Fh/Bir mass ratio impeded the adsorption of DOM by birnessite and the reductive dissolution of birnessite to release dissolved Mn, and the impediment on the reductive dissolution of birnessite was proportional to Fh/Bir mass ratio. Overall, during the interactions of DOM with ferrihydrite and birnessite, phenolic compounds were preferentially adsorbed by Fe and Mn minerals, and compounds with higher oxygen contents and polymeric substances were formed. FT-ICR-MS analysis further suggested that higher Fh/Bir mass ratio inhibited the occurrence of aromatic ring-opening and carboxylation of substituted groups on aromatic rings, but promoted polymerization of phenolic compounds. Cs-STEM analysis revealed that DOM distributions on ferrihydrite, birnessite, and their mixtures were regulated by their microscopic structures and reactivity. Compared with aromatic carbon (C), carboxylic and phenolic C were more likely to associate with birnessite. Our results highlighted the significance of organo-mineral associations with the mixed minerals in regulating the distribution and reactivity of organic C. This study has provided molecular evidences for molecular transformation of DOM mediated by both Mn and Fe oxides, which contributed to advancing our understanding on coupled reactions of organic C at the mineral–water interfaces in the environment.

Microbial contribution to the formation of the Carboniferous sedimentary manganese deposits in northwestern China

There is an increasing consensus that microbes play a critical role in the genesis of sedimentary manganese (Mn) carbonate deposits. However, compelling evidence for the microbial involvement during sedimentary Mn metallogenesis remains insufficient, and the specific effects of microbial mediation need to be further elucidated. To advance our understanding of the microbial Mn metallogenesis, multi-scale petrographic observations and high-resolution mineralogical analyses (mainly based on Fourier transform infrared spectrometer and Raman spectroscopy) were conducted on the Carboniferous black shale-hosted Malkansu and limestone-hosted Zhaosu Mn ore deposits in northwestern China. Results show that the Mn ore samples are characterized by finely laminated texture with μm-scale cyclic variations of microbe-associated minerals including rhodochrosite, apatite, quartz, and organic matter as well. These features indicate the ubiquity of microbial mats during Mn mineralization. Microbial involvement is also supported by Mn carbonate aggregates with variable morphologies (filamentous with pearl necklace-like inner forms resembling vermiform morphologies and spheroidal, coccoid-like forms), as well as the annular organic matter that resembles bacterial cells. The cyclic occurrence of trace amounts of remnant Mn oxides verify that primary Mn accumulation took place under oxic bottom waters. The negative co-variation between Mn carbonates and organic matter on Raman profiles suggests that the former was formed during diagenesis via organic matter decomposition coupled with Mn oxide reduction. Combined with previous experimental simulations and natural observations, a two-step microbially mediated Mn metallogenic model is tentatively proposed for the studied Mn deposits: (1) Mn(II)-oxidizing bacteria effectively catalyzed the deposition of considerable Mn oxides under oxygenated bottom water columns, a process that was simultaneously sustained by oxygenic microbial mats such as cyanobacteria; (2) Buried Mn oxides were reduced by highly reactive organic matter sourced from dead biomats of Mn(II)-oxidizing bacteria and benthic phototrophs, a process mediated by Mn(IV)-reducing bacteria which not only promoted the reaction rate but also served as nucleation sites for Mn carbonate minerals. This model can also help to explain the occurrence of diverse authigenic accessory minerals (e.g., quartz, apatite, and talc) and remarkable enrichments of several specific elements (e.g., Co, Ce, and Mo) in the studied Mn ores, which were closely linked to the decomposed cells and extracellular polymeric substance (EPS). By comparing with previous microbial investigations on Mn deposits over geological history, we further highlight the fundamental role of microorganisms in regulating the formation of economic Mn carbonate deposits.

Discovery of Late Carboniferous high-grade carbonate-hosted manganese mineralization in the Maerkansu area of the Western Kunlun Orogen, Northwest China

The Aoertuokanashi deposit located in the Western Kunlun Orogen is the first known Late Carboniferous large high-grade carbonate-hosted Mn deposit in the world and it has been mined since 2018. The deposit is considered to have formed in a back-arc basin developed during the northward subduction of the Paleo-Tethys Ocean beneath the Tarim Block. The Re-Os isotope isochron age of Mn ore at the Aoertuokanashi deposit is 302 ± 9 Ma. The minimum initial 187Os/188Os values obtained from the deposit is 0.28, which indicates the presence of a mantle source for the mineralization. The Aoertuokanashi deposit is similar in age to the 301 ± 5 Ma Wajilitag kimberlite in the Tarim Block, which is considered to be the initial magmatic pulse triggered by the Tarim mantle plume. The Late Carboniferous Aoertuokanashi Mn deposit was likely promoted by igneous activity from the Tarim mantle plume.The Aoertuokanashi deposit shows geochemical characteristics of hot water activity in a back-arc basin. The Mn mineralization is hosted in the restricted platform facies. Framboidal pyrite, typical biomat, and authigenic quartz are observed in the Mn deposit, indicating the influence of microbial processes. The sedimentary facies show a starving basin feature that can enhance microbial mediation. The δ13CV-PDB values of mineralized rocks (from −19.5 to −8.2 ‰) are more negative than those of wall rocks (from −5.3 to + 4.2 ‰), whereas the δ13CV-PDB values (around −29 ‰) of kerogen for the Mn ore are significantly lower than those of the whole rock. These compositions indicate that the reducing function of organic matter played an important role in Mn mineralization. In the inferred extensional tectonic environment, under the influence of a mantle plume, the stratum with strong hot water activities and a large amount of organic matter becomes the focal point for the formation of carbonate type manganese ore deposit.

Review of soil form and wetness indicators for wetland delineation in South Africa

Wetland delineation in South Africa incorporates soil form and soil wetness indicators, requiring formal soil classification and description of soil redox morphology. The current wetland definition used administratively in South Africa focuses on saturated (hydric) soil signatures within plant root zones. Saturated soil horizons deeper than plant root zones fall outside the 50 cm criterion in the local approach as well as the accepted zone in USA literature. The field of hydropedology accommodates the classification of the various hydrologically active horizons and provides a tool for the handling of horizons with ephemeral wetness. This approach has been variably accepted by mandated authorities in South Africa. The South African soil classification system has evolved through three editions over the past 50 years while retaining the same redox morphology understanding. However, despite the concepts and context of redox morphology having been thoroughly technically adopted by soil scientists, this is not the case within the wetland research and management environment. This especially because the classification system is structured differently from other international systems, and the South African landscape is geologically ancient with mature soils, introducing challenges to resource assessment specialists who rely on international norms and approaches for wetland assessment. This paper reviews the various components of soil classification and redox morphology based on Fe and Mn minerals within the context of the South African soil classification system, the field of hydropedology and wetland delineation indicators. We provide a qualitative correlation between the various diagnostic horizons and materials in the system and their related redox morphology contexts that are relevant to wetland assessment, delineation, and protection in South Africa. This paper therefore aims to serve as a reference point for the description and correlation of various soil hydrological parameters used in formal assessments.

Mineral Chemistry of Olivine, Oxy-Spinel, and Clinopyroxene in Lavas and Xenoliths from the Canary, Azores, and Cape Verde Islands (Macaronesia, North Atlantic Ocean): New Data and Comparisons with the Literature

An electron microprobe study was carried out on olivine, clinopyroxene, and oxy-spinel occurring in basalts and dunite xenoliths from the archipelagos of the Azores, the Canary Islands, and Cape Verde. By comparing our results with previously published data from the volcanic islands of Macaronesia, we confirmed the validity of the compositions of olivine, clinopyroxene, and oxy-spinel as geochemical tracers. The origin of olivine, i.e., crystallized in the lithospheric mantle or in volcanic rocks, was successfully discriminated. Olivine from Lanzarote dunite xenoliths, which represent fragments of the mantle transported to the surface by host magmas, exhibited higher Fo% values (Fo91.02 to Fo91.94) and a different distribution of minor elements Ca, Ni, and Mn (CaO up to 0.42 wt%, NiO 0.07–0.41 wt%, MnO 0.06–0.3 wt%) when compared with olivine occurring as phenocrysts in basaltic lavas from the Macaronesian islands. The highly variable forsterite contents (Fo75.1 to Fo94.4) in olivine from gabbro and peridotite xenoliths found across the islands of Macaronesia were attributed to fractional crystallization that started in a deep magma reservoir, suggesting that these xenoliths represent cumulate rocks and not mantle fragments. Alternatively, these xenoliths may have been affected by the interaction with metasomatic fluids. The composition of clinopyroxene phenocrysts was used to decipher formation conditions under extensional tectonics. Their composition suggests that the host lavas have an alkaline to calc-alkaline signature. Furthermore, clinopyroxene euhedral shapes and compositions suggest an origin by fractional crystallization in a closed magmatic system. The composition alone of oxy-spinel from Macaronesian basalts and xenoliths was not sufficient to draw conclusions about the geodynamic environment where they were formed. Nevertheless, the relationship between oxy-spinel and olivine crystallized in equilibrium was successfully used as oxybarometers and geothermometers. The oxy-spinel–olivine pairs show evidence that the basaltic lavas were crystallized from melts with higher oxygen fugacity and different cooling histories than those of the mantle xenoliths, as the latter crystallized and re-equilibrated much slower than the basalts.

The effect of minor Ti and Mn additions on the microstructure and mechanical properties of additive manufactured Al–Ce–Mg alloys

The effect of minor Ti and Mn additions on the microstructure and mechanical properties of additive manufactured Al–Ce–Mg alloys

New insight into genesis of the Maojun laterite Fe–Mn deposit in the Lanshan area, Hunan Province, South China: Evidence from detailed mineralogical and geochemical studies

Laterite Fe–Mn deposits are widespread in South China, with the majority of Fe–Mn ore being present in residual quaternary clay beds. However, detailed geological data on the lateritization of low-iron-content carbonate rocks are rare. In this study, we present new results on the mineralogy and geochemistry, as well as a genetic model, of the Maojun laterite Fe–Mn deposit in the Lanshan area, Hunan Province, South China. The profile sequence of laterite consists of an eroded bedrock horizon at its base, an intermediate black–brown clay layer containing earthy Fe–Mn ore, and a reddish-brown clay layer with nodular ferromanganese ore in contact with reddish-brown or yellowish-brown clay on top. Field evidence and chemical analysis indicated that during lateritization, the Mn-Fe-containing carbonate rocks of the Huanggongtang (D2h) and Shetianqiao formations (D3s) saw a more significant removal of mobile elements (Mg, Ca, and Na) whilst insoluble elements (Fe, Mn, Si, Al, Pb, and Zn) exhibited persistent enrichment in situ. Discriminative diagrams of Fe–Mn mineralization, as well as the assemblage-related enrichment of Y, U, Mo, Pb, and Zn and depletion of high-field-strength elements Zr, Nb, and Th, imply that subsequent hydrothermal circulation overprinted on the previously formed hydrogenous deposit. Mineralogical studies conducted using XRD, EPMA, HR-TEM, and TIMA indicated the predominance of iron and manganese oxides; hematite, goethite, limonite, and hollandite were identified as major oxide phases and cryptomelane, pyrolusite, and coronadite were present in minute quantities. Similar minerals constitute the upper ferromanganese nodule horizons, although they possess distinct textures and concentrations. The mineralogy, geochemical associations, and Ti mass balance show a continuous vertical evolution from top to bottom in the lateritic profile. Ferromanganese concretions from the drenching zone with poorly crystallized Al–goethite, Al–hematite, limonite, Fe–kaolinite, Fe–Mn oxides and hollandite predominate in shallow parts, and microcrystalline hematite, goethite and hollandite were found in deeper layers. Mn2+ can be rapidly oxidized and precipitated on the surface of hematite and limonite as high-valence-state (Mn4+) manganese oxides and binds strongly with mobile elements (Ba, K, Pb, Zn, Ca, and Ni). Petrographical, mineralogical, and geochemical studies show that three stages comprised the formation of the Maojun laterite Fe–Mn deposit.

The Boumaadine Fe–Mn–Pb–Cu (± Au) ore deposit (Jbel Skindis, eastern High Atlas, Morocco): New insights from geological, hydrothermal alteration and geochemical investigations

Petrographic, structural and geochemical analysis combined with SEM and XRD were performed on the Boumaadine Fe–Mn–Pb–Cu (±Au) mineralization of Jbel Skindis in the eastern High Atlas, (Morocco). The results indicate a polyphasic process of mineralization, which produced orebodies with distinct features and different chemical conditions formation. The earliest mineralization formed replacement and disseminated Fe–Mn–Pb orebodies under oxidizing conditions, with a mineral assemblage composed of coronadite, plumboferrite, cesarolite, specularite and calcite, in association with a large-scale hydrothermal alteration consisting essentially of Fe–Mn minerals, i.e., ferroan dolomite, hematite, jacobsite and limonite. The second event was formed under reducing conditions that generate some veins filled mainly by sulfides (galena, with minor pyrite and chalcopyrite), in addition of calcite and dolomite.The mineralization is hosted in Lower Liassic dolostones and is linked to the structural evolution of the study area. Fractures related to the displacement of the Boumaadine fault seem to control the disposition and the localization of the alteration and the mineralization: (i) the Fe–Mn–Pb oxides are related to a NE-SW conjugate fault system generated during the first phase of deformation, with a horizontal principal stress striking NNW-SSE, and (ii) the sulfide mineralization occurs mainly as filling conjugate fractures of two preferentially directions striking N80–90 and N150-165 with a slight dip (15–40°) to the NE. These latter were caused by a dextral movement along the Boumaadine fault, generated during the late phase of deformation with a NW-SE bearing horizontal principal stress.The deep-seated Boumaadine fault has acted as pathways for the rising fluids, and supports the origin of lead and other metals from the Paleozoic basement. The Triassic evaporitic sequence along the Boumaadine fault has also contributed to the chemical composition of the fluid, and represents the potential source of both the salinity and sulfur. The oxide-sulfide mineralogical assemblage and its associated alteration emphasize a polyphasic hydrothermal activity with distinct physicochemical conditions; an iron-manganese rich, and highly oxidizing brine is considered to be responsible for the Fe–Mn alteration and for the deposit of the oxide assemblage. Furthermore, a mixing of the oxidizing fluid with a meteoric reducing fluid could have resulted in the sulfide-rich ore.

Sulfur isotopic characteristics of the Gaobanhe deposit in East Hebei Province and their constraints on the processes of sulfide and Mn mineralization from the Gaoyuzhuang Formation

Sulfur isotopic characteristics of the Gaobanhe deposit in East Hebei Province and their constraints on the processes of sulfide and Mn mineralization from the Gaoyuzhuang Formation

Radon Concentration and its Indices in Bulak (Mencilis) Cave

The Bulak cave is in the village of Bulak near Safranbolu city. It’s one of the longest caves in Türkiye, which goes 6 kilometers into the inside, but approximately 400 meters are accessible to visitors. You require a professional guide and special equipment to travel further into the cave with lakes, a waterfall, and rivers which are essential for cavers, tourists, and researchers. However, there are possible several health problems for cave visitors. This study mainly aims to measure the radon concentrations with the nuclear track CR-39 detector in the cave environment. Twenty-two detectors were distributed inside the tourist’s area, and another six detectors were in the cave’s deeper region. The exposure time was one month on 24 September 2020, in addition to two soil samples collected from the cave used for medical purposes. These detectors are collected after 30 days and then etched with a chemical solution. The radon concentrations were calculated, which ranged between 16.437 (Bq/m3) and 48.652 (Bq/m3) using an optical microscope from the track density in detectors. The minimum and maximum values of radiation indices AED (mSv/y), LCR (WLM), PAEC (mWL), Dsoft (nGy/h), Dlung (nGy/h) and Heff (nSv/h) are presented, and all results for the radon and radiation indices are within the global limit. Radon concentrations for two soil samples were 26.956 (Bq/m3) and 59.172 (Bq/m3), and all the results were within the acceptable limits recommended by ICRP and UNSCEAR. The XRF examination was performed, which indicated the presence of Fe, Cu, Zn, As, and Mn minerals with high concentrations of 101607, 552, 1337, 237, and 1601 ppm, respectively, which are all more than the world permissible limits. The XRD analyses for the soil sample indicated the presence of clay and non-clay minerals such as Feldspar, Quartz, Gypsum, Calcite, Palygorskite, Kaolinite, and Montmorillonite.

Recovery of critical battery metals from cobalt-rich deep-sea polymetallic nodules: Selective carbothermal reduction based on kinetics

Metal recovery from deep-sea polymetallic nodules (DPN) is a promising option to ensure the future supply of critical battery metals due to terrestrial resource constraints. In this study, the leaching efficiency of Mn and critical metals (Co, Ni, and Cu) that hosted in the crystal lattice of Mn(IV) mineral is significantly enhanced by selective carbothermal reduction. The reduction kinetics of Mn(Ⅳ) is consistent with the CO gas diffusion-controlled mechanism, and the kinetic equation can be expressed as 1−23R−1−R23=0.024e−10.06RT∙t. Under the optimal conditions of 600 °C, 60 min, and 3 wt% carbon addition, 61.54 % of Mn(IV) minerals are reduced to Mn(Ⅱ) and the rest was converted to Mn(Ⅲ), while the leachable metal oxides (CoO, NiO, and CuO) are hardly reduced, therefore, the leaching efficiency of Co and Mn increased from 8.18 % and 5.12–98.03 % and 96.23 %, respectively. In order to limit the leaching of the impurities Fe and Al, high-pressure acid leaching was carried out after selective carbothermal reduction, and the leaching parameters were optimized to 160 °C, H2SO4/DPN 0.77 wt%, and leaching for 4 h with a liquid/solid ratio of 5:1 mL/g. As a result, only 2.35 % Fe and 3.34 % Al were leached, and the leaching efficiencies of Co, Ni, Mn and Cu were 98.47 %, 95.72 %, 97.24 % and 94.99 %, respectively.

Characterisation of hot isostatically pressed (HIPed) hollandite wasteform-canister interaction zone

A potential hollandite wasteform for immobilising waste containing Cs, Ba, Sr, and Rb, projected from a solvent extraction process that separates Cs/Sr from spent nuclear fuel, was fabricated via hot isostatic pressing (HIPing) within a stainless-steel (SS) canister at 1250 °C / 30 MPa / 2 h. Before HIPing, 2 wt.% Ti metal was added to the precursor, as a redox control additive. Detailed elemental profiling and microstructural analysis at the interaction zone between the wasteform and the SS HIP canister were thoroughly investigated with transmission electron microscopy (TEM) using a lamella extracted by focused ion beam (FIB) milling, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The interaction zone towards the wasteform was ∼20–30 µm in distance and in this region, a hollandite composition with varying chemistry was observed relative to the bulk wasteform. Moreover, the regular Cr-oxide layer, often observed previously for HIPed Synroc-type materials, was not present due to the achievement of reducing condition by adding Ti-metal as redox additive and simultaneous diffusion of canister material towards the ceramic. Predominant Cr-diffusion was observed with incorporation in the hollandite phase along with minor Fe, Mn and Co from the SS canister. This study provides a detailed understanding of the HIP canister – wasteform interaction zone for a hollandite-rich wasteform design for the first time. Importantly, no deleterious phases were formed that may otherwise reduce the performance of the wasteform. This study further demonstrates the flexibility of HIPing as a consolidation process for the treatment of radioactive wastes.

Solid solution softening at room temperature and hardening at elevated temperatures: a case by minor Mn addition in a (HfNbTi)85Mo15 refractory high entropy alloy

To address the conflict between room-temperature (RT) ductility and high-temperature (HT) strength in single phase bcc-structured refractory high entropy alloys, here we propose to use minor alloying to achieve solid solution softening at RT and simultaneously, solid solution hardening at HT. Our strategy was manifested by minor Mn additions in a RT brittle (HfNbTi)85Mo15 refractory high entropy alloy, where nominal Mn additions ranging from 2 at. % down to 0.03 at. % were seen to soften the base (HfNbTi)85Mo15 alloy at RT, while to harden the base alloy at the temperature range from 400 to 800 °C. The yield stress in all studied alloys showed a three-stage pattern, characterized by a temperature dependent stage at temperatures below 400 °C, followed by a temperature independent stage at intermediate temperatures ranging from 400 to 800 °C, and finally another temperature dependent stage at temperatures higher than 800 °C. The mechanisms for solid solution softening and solid solution hardening in single phase bcc-structured refractory high entropy alloys were discussed, together with their temperature dependence.

Manganese Mineralization of Pathogenic Viruses as a Universal Vaccine Platform.

Biomimetic viral mineralization improves viral vaccine stability and immunogenicity using inorganic metals such as Ca, Al, or Fe. Mn is a metal found in high concentrations in mammalian tissues; however, under natural or laboratory conditions, Mn mineralization by medical viruses has yet to be established. Herein, a single IAV particle is successfully encapsulated with manganese phosphate (MnP) under specific conditions using the human influenza A virus (IAV). MnP-mineralized IAVs (IAV@Mn) exhibited physiochemical and in vitro properties similar to Ca-mineralized IAVs. In animal models, IAV@Mn shows limited replication in immune-competent cells and a significant attenuation compared to naïve cells. Moreover, a single-dose vaccination with IAV@Mn induced robust humoral and cellular immune responses and conferred significant protection against a wild-type IAV challenge in mice. Thus, Mn mineralization in pathogenic viruses provides a rapid and universal strategy for generating an emergency vaccine in response to emerging viruses.

Insights on the Formation Conditions of Manganese Oxides from Crimora, VA (USA)

Many regions of the United States contain manganese deposits economically valuable in New England, Appalachian, and Piedmont regions in the Eastern United States, in Northern Arkansas, and, to a small extent, in Central–Western California. Mn oxide/hydroxide (commonly referred to as Mn oxide minerals) are found in a wide variety of geological settings and occur as fine-grained aggregates, veins, marine and freshwater nodules and concretions, crusts, dendrites, and coatings on rock surfaces (e.g., desert varnish). How manganese oxides form and what mechanisms determine which oxides are likely to form are limited and still debated. This paper focuses on Mn oxides collected at the southern bound of the abandoned open-pit site called Crimora Mine (Augusta County, Virginia). This study uses mineralogical and chemical features to shed light on the origin of manganese deposits in Crimora along the western foot of the Blue Ridge in South–West Virginia. We report the first detailed study on the genesis of the Crimora manganese deposit conducted since the mine was closed in the 1950s. Crimora Mine sample is dark black fine- to medium-grained round and oblong nodules coated with a fine-grained intermix of yellowish earthy limonite, clays, and quartz. Scanning electron microscopy (SEM) revealed that the Crimora Mn-oxides exhibit concentric layering, breccia-like matrices, and veins. X-ray powder diffraction (XRPD) identified the set of Mn minerals as hollandite and birnessite. The concentration and range of dissolved chemical species in freshwater, seawater, and hydrothermal depositional fluids impart a geochemical signature to the Mn-oxides, providing a diagnostic tool to shed light on their genetic origin. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis of the Crimora manganese oxides shows Mn, Fe, and Ti, as well as trace elements such as Co, Ba, Y, Zn, Cr, Ni, Tl, La, V, and Li. A bivariate analysis based on the geochemical correlation of Mn and other common substituting cations (e.g., Fe, Co, Ti) shows a mixed genesis in different environments with varying biological and sedimentary supergene (freshwater and marine) conditions. These data suggest that the Mn-rich deposit in Crimora, VA, was formed in a continental margin environment of surficial deposits and reprecipitated in mixed biogenic and supergene conditions.

Mineralogy of the 1.45 Ga Wafangzi manganese deposit in North China: Implications for pulsed Mesoproterozoic oxygenation events

Abstract Ancient manganese (Mn) deposits are primarily characterized by the presence of Mn(II) carbonates that likely formed by the diagenetic reduction of precursor Mn(IV) oxides. As such, Precambrian sedimentary Mn deposits have been used as a line of evidence for the evolution of oxygen in Earth’s surface environments. However, recent studies have shown that these Mn(II)-carbonates have the ability to directly accumulate within anoxic water columns, where free oxygen does not play a role in their formation. This alternative pathway casts uncertainty on the robustness of using ancient Mn deposits to constrain the redox fabric of the past marine water columns. Here, we investigate the Wafangzi Mn and Fe ore deposit from the 1.45 billion-year-old Tieling Formation, North China. The deposit contains Mn(II, III) mineral phases (hausmannite, braunite) as inclusions, or unreacted residues, trapped within Mn(II) carbonate (Ca-rhodochrosite). Some nodules and oolites of Mn(II) and Fe(II)-carbonate phases are also present and display a banded structure with concentric rings. Mn(III) oxide (manganite) is present in a paragenetic assemblage along with hematite and replacement textures with braunite. The negative carbon isotope composition (δ13C, –7‰ to –4‰) from Mn(II) carbonate samples in the Wafangzi Mn deposit which are distinct from that of contemporaneous seawater (~0‰), along with petrographic and speciation analyses, collectively suggest that the Mn(II, III)- and Fe(II)-bearing mineral phases formed through the diagenetic reduction of primary Mn(IV)/Fe(III) minerals coupled to the oxidation of organic matter. Therefore, the Wafangzi Mn deposit suggests the presence of sufficiently oxygenated marine waters, overlying anoxic ferruginous deeper waters with a transitional manganous water layer that could have driven the redox cycling of Mn, Fe, and C. Given the contemporaneous economic Mn deposits in the 1.45 Ga Ullawarra Formation in Western Australia, our findings imply the existence of a transient, and perhaps widespread, pulsed oxygenation event in the mid-Proterozoic oceans.