Mn Oxide Particles Research Articles

Does water transparency control the banding in shallow water iron formations?

Abstract Iron formations (IFs) are marine chemical sediments that are conined to the Precambrian rock record and provide unique insights into the co-evolution of the atmosphere-hydrosphere and biosphere through almost three billion years of Earth’s history. IFs commonly appear throughout the Archaean until the Palaeoproterozoic ca. 1.8 billion years ago and re-appear during the “Snowball Earth” epoch in the Neoproterozoic. The formation and deposition mechanism(s) of IFs are, however, still incompletely understood, hindering unique interpretations of palaeoenvironments. Many IFs are banded iron formations (BIFs) with layer thickness of alternating Fe- and Si-rich layers ranging over several orders of magnitude from the nanometre to the metre scale. A second textural type, so called granular iron formations (GIFs) that form above storm wave base become widespread in the Palaeoproterozoic. Understanding the fundamental mechanisms that are responsible for the textural types and the periodicity of banding in BIFs is crucial to link these features to the environmental and geochemical evolution of the Earth. We here provide a conceptual model that highlights the role of changing light conditions and water transparency for Iron Formation (IF) precipitation. We show that the model is particularly feasible for IFs deposited in shallow waters but may also be applicable for some IFs deposited in deeper water settings. The model builds on other primary Banded Iron Formation (BIF) precipitation models postulating that Fe(III)-(oxyhydr)oxide production can be dominated by anoxygenic photoautotrophic Fe2+-oxidising bacteria. These so called photoferrotrophs are adapted to very low light levels corresponding to about 1% of the light level required by oxygen-producing phototrophs allowing them to thrive deep down in the water column. The depth of Fe(III)-(oxyhydr)oxide production is mainly controlled by water turbidity which controls how deep photosynthetically available radiation (PAR) penetrates the water column. Eutrophic conditions result in relatively shallow Fe(III)-(oxyhydr)oxide production depth due to turbidity either induced by the biomass itself and/or by particles that are actively or passively produced by microorganisms (e.g., Fe(III) and Mn(IV)-(oxyhydr)oxides, sulphides), triggering the formation of Fe-rich bands. During oligotrophic stages, Fe(III)-(oxyhydr)oxides are only produced relatively deep down in the water column, so that only silica-rich bands form in the Fe(III)-(oxyhydr)oxide free upper water column. Reactive transport modelling adopted from Ozaki et al., (2019) shows that besides upwelling and nutrient supply, alternating Fe(III) production depth is mainly associated with changing light conditions as a result of water transparency. Periodicities reflected by alternating Fe- and Si-rich bands in IFs in our model can thus be associated with: (1) nutrient supply patterns; (2) additional sources of turbidity in the water column such as Fe(III) and Mn(IV) oxide particles, sulphides, and wind-blown silicate particles; or (3) formation and clearing of organic haze in the atmosphere. One or all of these reasons for low light conditions seem to become more important in the Palaeoproterozoic (<2.4 Ga) and could be partly responsible for the more widespread occurrences of shallow marine granular IFs relative to former epochs, which is often assigned to the gradual oxidation of the ocean. Our model shows that variable water transparency should be considered as additional factor for IF deposition especially for shallow marine settings. This model also reasonably explains the prominent layering in BIFs as syn-depositional feature.

Single atom manganese catalyst boosting selective oxidation of alcohols with activated peroxymonosulfate

Selective oxidations are important reactions in organic synthesis for fine chemical industry and conventional methods are expensive and produce a lot of toxic wastes. Herein, we demonstrate a facile and environmentally benign technique for liquid phase selective oxidation based on graphene-supported Mn single-atom-catalyst (SAMn-G) for efficient peroxymonosulfate (PMS) activation. The active Mn component in the developed SAMn-G catalyst reached single-atomic dispersion on graphene substrate via the coordination of individual Mn atoms with the doped N from the graphene framework. SAMn-G activated PMS via a nonradical-dominated pathway, which could convert aromatic alcohols into aldehydes or ketones at a mild temperature. The SAMn-G catalyst exhibited superior conversion and aldehyde selectivity in alcohol oxidation in comparison with their counterpart catalysts possessing either homogeneous Mn ions or oxide particles. The high activation efficiency of SAMn-G is due to the synergistic effect between Mn atoms and graphene substrate, as well as the dominated reaction pathway from nonradical oxidation, which is more selective than these free radicals to oxidize the alcohols. Concerted experimental evidence indicates that the non-radical oxidation process was highly possible to follow the electron transfer mechanism by PMS/organic adsorption on the surface of the catalyst. This study provides a fundamental understanding of PMS activation mediated by single atom catalyst for organic synthesis and the achieved insights can also help the catalyst design for other liquid phase selective oxidation processes.

Effects of Algal Extracellular Polysaccharides on the Formation of Filamentous Manganese Oxide Particles in the Near-Bottom Layer of Lake Biwa.

Filamentous manganese (Mn) oxide particles, which occur in the suboxic zone of stratified waterbodies, are important drivers of diverse elemental cycles. These particles are considered to be bacteriogenic; despite the importance of biogeochemical implications, however, the environmental factor responsible for their formation has not been identified. The aim of this study was to demonstrate the involvement of algal extracellular polysaccharides in Mn oxide particle formation. Based on this study of laboratory cultures of a model Mn(II)-oxidizing bacterium, the supply of algal extracellular mucilage was shown to stimulate Mn(II) oxidation and thus the production of filamentous Mn oxide particles. This observation was consistent with the results obtained for naturally occurring particles collected from a near-bottom layer (depth of approximately 90 m) in the northern basin of Lake Biwa, Japan, that is, most Mn particles resembling δ-MnO2 were associated with an extracellular mucilage-like gelatinous matrix, which contained dead algal cells and was lectin-stainable. In the lake water column, polysaccharides produced by algal photosynthesis sank to the bottom layer. The analysis of the quality of water samples, which have been collected from the study site for 18 years, reveals that the annual average total phytoplankton biovolume in the surface layer correlates with the density of filamentous Mn particles in the near-bottom layer. Among different phytoplankton species, green algae appeared to be the key species. The results of this study suggest that algal extracellular polysaccharides serve as an important inducer for the formation of filamentous Mn oxide particles in the near-bottom layer of the northern basin of Lake Biwa.

Carbon Nanofiber Decorated Ternary Transition Metal Oxide Anodes for Fast Charging Lithium‐Ion Batteries

Fast charging rate capability of electrochemically active ternary transition metal Ni–Co–Mn oxides (NCMO) anode incorporated with the carbon nanofibers (CNF‐NCMO) is prepared by a simple thermal decomposition of acetylene gas on spherical Ni–Co–Mn oxide particles, and the tap density of the particles is around 1.3 g cm−3. The CNF‐NCMO showed the reversible capacity of 447 mAh g−1 at 10C rate (10 A g−1) in lithium metal half‐cells at room temperature (loading level was 1.4 mg cm−2). However, pristine NCMO only shows a reversible capacity of 124 mAh g−1 at 10C rate. The improved lithium storage and rate capability are mainly ascribed to the conductive CNF networks, reducing the contact and charge transfer resistance between the NCMO samples. Also, these results suggest that the carbon nanofibers act as a buffer layer for preventing the volume expansion during the lithium conversion reactions with the improved structural integrity.

Activation of peroxymonosulfate by MnFe2O4@BC composite for bisphenol A Degradation: The coexisting of free-radical and non-radical pathways

In this study, novel metallic oxide catalyst MnFe2O4@biochar composite was synthesized by sol–gel pyrolysis loading of MnFe2O4 on biochar, and then used to activate peroxymonosulfate (PMS) to degrade bisphenol A (BPA). Characterization results demonstrated that the Fe and Mn oxide particles were homogeneously distributed on the surface of biochar, which avoided the aggregation of metal oxides. The strong magnetism of the composite was conducive to recycling during practical application. In the PMS system activated by MnFe2O4@biochar composite, the removal rate and mineralization rate of 20 mg/L BPA reached 100% and 95.9% within 30 min, respectively. The quenching experiments and electron paramagnetic resonance (EPR) study verified the coexistence of free-radical and non-radical pathways in the MnFe2O4@biochar/PMS system, with O2•- as the dominant active species, followed by singlet oxygen (1O2). The catalytic degradation process could adapt a wide pH range from weak acid to the alkaline matrix and showed negligible influence by anions and humic acid. The characterization results confirmed the synergistic effect of the bimetal, proving that the introduction of biochar and second metal source into iron-based catalyst played an important role in the composite. Overall, the MnFe2O4@biochar showed promising performance in activating PMS for organic pollutant degradation in water with high stability and safe performance.

Geochemistry and molybdenum isotopes of the basal Datangpo Formation: Implications for ocean-redox conditions and organic matter accumulation during the Cryogenian interglaciation

The basal Datangpo Formation in South China deposited in the Cryogenian interglacial period has gained increasing interest with the well development of organic-rich black shale and its hosted manganese (Mn) deposits (Mn carbonate), which contain important clues to the paleoclimate and ocean redox of this critical interval in Earth's history. The depositional environment of Mn deposits is still uncertain, as suggested by different suites of redox-indicating parameters. In addition, the Mn deposits are notable for their enrichment in organic matter (OM), despite the fact that the diagenetic origin for the Mn deposits would result in large consumption of OM. To gain insight into these issues, we present the geochemical and molybdenum (Mo) isotopic data of black shale and Mn carbonate samples from a new section. The Datangpo Mn carbonates are characterized by low Mo content (mostly <3.2 ppm) and slightly light Mo isotopic composition (mostly from +0.07‰ to +0.52‰), suggesting that Mo, once adsorbed in Mn-oxide particles, was released in suboxic or anoxic (non-sulfidic) pore water due to Mn-oxide reduction and then diffused back into the water column. Hence the extremely light Mo isotopic signatures might be rarely preserved in sediments. The Mn carbonate formation accompanied by OM re-mineralization within sediments may have caused lower total organic carbon (TOC) content relative to that in black shales. However, elevated nutrient input related with hydrothermal fluid activity probably enhanced primary productivity during the Mn deposition period. It is evidenced by: (1) the Mn-TOC-total inorganic carbon covariation displayed by the Datangpo section and (2) a positive correlation between TOC and Mn content when Mn content is higher than 10% in a large compiled dataset. A compilation of Mo concentration and Mo isotope data suggests that widespread anoxia prevailed during the Cryogenian interglaciation. Instead, Neoproterozoic ocean oxygenation was postponed to the Ediacaran.

Geochemistry of metacherts associated with continental margin volcanic seamount hydrothermal activity: metamorphic sole rocks of the UAE

The metacherts of the Asima Window, in northeastern U.A.E. at the southeastern corner of the Arabian Peninsula, are the dominant metamorphic sole lithologies of the Semail ophiolite that was obducted onto the Arabian continental margin at the end of the Cretaceous. There have been no previous geochemical studies of these metacherts. The Asima metachert samples of this study form four groups based on geochemistry, petrography and field association: (1) black hematitic, (2) green epidote-chlorite rich, (3) pink piedmontite-bearing and (4) grey micaceous metacherts. A continental margin setting for the parent cherts is indicated geochemically by Al2O3 to Fe2O3 and SiO2 ratios, low ΣREE, low La, moderate positive Ce/Ce* and Lan/Cen ~ 1. A significant terrigenous fraction was composed of illite, chlorite and Fe hydroxides. A hydrothermal component can be recognized in all of the metachert groups but is particularly evident in the black and green metacherts by low Al/(Al + Fe + Mn), high (Fe + Mn)/Ti, high Ba and Ba/Sr ratios, positive Eu/Eu* and left-leaning REE profiles. Most silica was biogenic. A hydrogenous component included REE’s, Cu, Ni, Zn, V, Ba and Co that were adsorbed onto clays, Fe hydroxide and Mn oxide particles. The Asima cherts were deposited in a marine basin adjacent to but separated from the continental margin by seamounts of the Al Hala Volcanics. These volcanics provided Fe,Mn-rich hydrothermal fluids that mixed with the oxygenated seawaters, leading to rapid hematite deposition (black metacherts) and slow Mn oxidation to form Mn oxide particles that accumulated in the pink metacherts. Grey metacherts were deposited farther from the vents. Green metacherts have similarities to the hydrothermal black metacherts.

Positive cerium anomalies imply pre-GOE redox stratification and manganese oxidation in Paleoproterozoic shallow marine environments

The Paleoproterozoic Koegas Subgroup (Transvaal Supergroup, South Africa) was deposited in the immediate prelude to the Great Oxidation Event (GOE), and can therefore shed light on oceanic paleoredox conditions just before atmospheric oxidation. Manganese enrichments of ~16 wt% in diagenetic kutnahorite horizons suggest that Mn2+ oxidation occurred, either by free O2 or by an ancient photosystem. Iron and molybdenum isotope trends also support the existence of a Mn4+ oxide sediment flux, suggesting that the Koegas basin may have been redox stratified. Evidence from detrital and authigenic pyrite with mass-independently fractionated sulfur isotopes, however, suggests that the atmosphere was devoid of oxygen. To resolve this contradiction, this paper presents new constraints on pathways of Mn2+ oxidation from field, petrographic, stable isotope, and rare earth element and yttrium (REYSN) analysis of stromatolitic carbonates from the upper Koegas Subgroup. Ferroan dolostones and limestones preserve marine REYSN arrays with positive CeSN anomalies. These differences are explained by a redox stratified basin, whereby Mn2+ and Ce3+ are oxidized at a redoxcline and Ce is adsorped onto sinking Mn oxide particles. Mn oxide particles and a negative Ce anomaly from the oxidized upper water column are transferred into carbonates accumulating above the redoxcline. Diagenetic fluids later reduce the Mn oxides to kutnahorite. Below the redoxcline, reduction of Mn oxides enriches carbonates in Mn and a positive Ce anomaly. This contribution adds evidence for the development of oxygen oases and redox-stratified basins before the GOE. Redox stratification was best developed during transgressions. During regressions, a deltaic system prograded into the Koegas Basin. High sedimentation rates likely allowed for preservation of detrital pyrite only in the deltaic sandstones, thus explaining the contradictory geochemical evidence. No previously unknown ancient photosystem of Mn oxidation is required to explain Mn oxidation.

Preliminary Assessment of Ferrate Treatment of Metals in Acid Mine Drainage.

We report a preliminary assessment of ferrate [Fe(VI)] for the treatment of acid mine drainage (AMD), focused on precipitation of metals (i.e., iron [Fe] and manganese [Mn]) and subsequent removal. Two dosing approaches were studied to simulate the two commercially viable forms of Fe(VI) production: Fe(VI) only, and Fe(VI) with sodium hydroxide (NaOH). Subsequent metal speciation was assessed via filter fractionation. When only Fe(VI) was added, the pH remained <3.6, and the precipitation of Mn and Fe was <30 and <70%, respectively, at the highest, stoichiometrically excessive Fe(VI) dose. When NaOH and Fe(VI) were added simultaneously, precipitation of Mn was much more complete, at doses near the predicted oxidation stoichiometric requirement. The optimal dosage of Fe(VI) for Mn treatment was 25 μM. The formation of Mn(VII) was noted at Fe(VI) dosages above the stoichiometric requirement, which would be problematic in full-scale AMD treatment systems. Precipitation of Fe was >99% when only NaOH was added, indicating that oxidation by Fe(VI) did not play a significant role when added. The Fe(III) and Al(III) particles were relatively large, suggesting probable success in subsequent removal through sedimentation. Resultant Mn-oxide particles were relatively small, indicating that additional particle destabilization may be required to meet Mn effluent goals. Ferrate seems viable for the treatment of AMD, especially when sourced through onsite generation due to the coexistence of NaOH in the product stream. More research on the use of Fe(VI) for AMD treatment is required to answer extant questions.

Removal and Oxidation of Arsenic from Aqueous Solution by Biochar Impregnated with Fe-Mn Oxides

We explored the preparation of Fe-Mn oxide-biochar composites and applied them for the removal of arsenic (As) from aqueous solutions. All composites exhibited high As removal efficiencies that increased with increasing pH within the investigated range (pH 3–7). According to the equation fitting for adsorption processes, F3M1BC18 (biochar:FeSO4:KMnO4, the weight ratios of 18:3:1) had the greatest sorption ability (Qm = 8.80 mg g−1), and the sorption process of F3M1BC18 was well fitted with Freundlich isotherm. In addition, FTIR and XPS analyses indicated that Fe oxides and Mn oxide particles on the outer sphere resulted in more oxidation of As(III) to As(V). The best-performing composite was characterized before and after adsorption using a range of instrumental techniques, which better identify the properties of F3M1BC18. Moreover, the physical properties, composition, and structures of the synthesized composites were investigated, and the As removal mechanism involving surface adsorption/oxidation was proposed with the high performance of Fe-Mn oxide-impregnated biochars, suggesting that these materials are well-suited for efficient water decontamination.

Impact of the Major Baltic Inflow in 2014 on Manganese Cycling in the Gotland Deep (Baltic Sea)

The deep basins of the Baltic Sea, including the Gotland and Landsort Deeps, are well known for the exceptional occurrence of sedimentary Mn carbonate. Although the details of the mechanisms of Mn carbonate formation are still under debate, a close relationship with episodic major Baltic inflows (MBIs) is generally assumed, at least for the Gotland Basin. However, the few studies on Mn cycling during MBIs suffer from a limited temporal resolution. Here we report on Mn dynamics in the water column and sediments of the Gotland Deep following an MBI that entered the Baltic Sea in December 2014. Water column profiles of dissolved Mn were obtained at a monthly to bi-monthly resolution between February 2015 and March 2017 and revealed an impact of the MBI on the Gotland Deep bottom waters beginning in March 2015. Water column profiles and budget estimates provided evidence for remarkable losses of dissolved Mn associated with the enhanced deposition of Mn oxide particles, as documented in sediment trap samples and surface sediments. In July 2015, subsequent to the nearly full oxygenation of the water column, clear signals of the re-establishment of bottom water anoxia appeared, interrupted by a second inflow pulse around February 2016. However, dissolved Mn concentrations of up to 40 µM in the bottom waters in June 2016 again indicated a pronounced reduction of Mn oxide and the escape of dissolved Mn back into the open water column. The absence of substantial amounts of Mn carbonate in the surface sediments at the end of the observation period suggested that the duration of bottom water oxygenation plays an important role in the formation of this mineral. Data from both an instrumental time series and a dated sediment core from the Gotland Deep supported this conclusion. Enhanced Mn carbonate formation occurred especially between the 1960s and mid-1970s, when several MBIs caused a long-lasting oxygenation of the water column. By contrast, Mn carbonate layers were much less pronounced or even missing after single MBIs in 1993, 2003, and 2014, each of which provided a comparatively short-term supply of O2 to the deeper water column.

Massive Mn carbonate formation in the Landsort Deep (Baltic Sea): Hydrographic conditions, temporal succession, and Mn budget calculations

The sediments of the Landsort Deep and Gotland Basin in the central Baltic Sea are strongly enriched in Mn carbonate. However, conceptual models attempting to explain the intense Mn carbonate precipitation in both basins are in part conflicting. In the Gotland Basin model, deposited Mn oxides are converted to Mn carbonate after the oxygenation of euxinic bottom waters enriched in dissolved Mn by major Baltic inflows (Huckriede and Meischner, 1996). By contrast, according to the Landsort Deep model, Mn carbonate precipitation occurs independent of oxygenation events below a euxinic water column (Lepland and Stevens, 1998; Lenz et al., 2015). In this study, we investigated Mn solid-phase signatures in recent/sub-recent well-dated sediments from the Landsort Deep and compared them to long-term observations to identify the hydrographic conditions favoring Mn carbonate formation. The comparisons of water column O2 and sulfide time series with sedimentary Mn carbonate enrichments identified long-lasting bottom water oxygenation as an important environmental factor in the enhancement of Mn carbonate precipitation (up to 32wt% Mn) in the Landsort Deep. Thus, by preventing the escape of dissolved Mn from still reducing sediments into the open water column, these conditions allow the accumulation of large amounts of Mn-oxide particles at the sediment/water interface, with their subsequent conversion to Mn carbonate. The euxinic conditions that have prevailed almost continuously in the Landsort Deep since roughly AD 2000 do not favor Mn enrichment (maximum 0.9wt% Mn), highlighting the importance of the recurring oxygenation of bottom water, most likely via medium-intensity inflows. The Mn abundances in seven sediment cores from water depths of 190–437m together with Mn balance calculations indicated that the Mn inventory in the water column in response to porewater Mn reflux and detrital Mn input is sufficient for Mn carbonate enrichment only in the deepest part of the basin.

The acceleration of dissolved cobalt's ecological stoichiometry due to biological uptake, remineralization, and scavenging in the Atlantic Ocean

Abstract. The stoichiometry of biological components and their influence on dissolved distributions have long been of interest in the study of the oceans. Cobalt has the smallest oceanic inventory of inorganic micronutrients and hence is particularly vulnerable to influence by internal oceanic processes including euphotic zone uptake, remineralization, and scavenging. Here we observe not only large variations in dCo : P stoichiometry but also the acceleration of those dCo : P ratios in the upper water column in response to several environmental processes. The ecological stoichiometry of total dissolved cobalt (dCo) was examined using data from a US North Atlantic GEOTRACES transect and from a zonal South Atlantic GEOTRACES-compliant transect (GA03/3_e and GAc01) by Redfieldian analysis of its statistical relationships with the macronutrient phosphate. Trends in the dissolved cobalt to phosphate (dCo : P) stoichiometric relationships were evident in the basin-scale vertical structure of cobalt, with positive dCo : P slopes in the euphotic zone and negative slopes found in the ocean interior and in coastal environments. The euphotic positive slopes were often found to accelerate towards the surface and this was interpreted as being due to the combined influence of depleted phosphate, phosphorus-sparing (conserving) mechanisms, increased alkaline phosphatase metalloenzyme production (a zinc or perhaps cobalt enzyme), and biochemical substitution of Co for depleted Zn. Consistent with this, dissolved Zn (dZn) was found to be drawn down to only 2-fold more than dCo, despite being more than 18-fold more abundant in the ocean interior. Particulate cobalt concentrations increased in abundance from the base of the euphotic zone to become ∼ 10 % of the overall cobalt inventory in the upper euphotic zone with high stoichiometric values of ∼ 400 µmol Co mol−1 P. Metaproteomic results from the Bermuda Atlantic Time-series Study (BATS) station found cyanobacterial isoforms of the alkaline phosphatase enzyme to be prevalent in the upper water column, as well as a sulfolipid biosynthesis protein indicative of P sparing. The negative dCo : P relationships in the ocean interior became increasingly vertical with depth, and were consistent with the sum of scavenging and remineralization processes (as shown by their dCo : P vector sums). Attenuation of the remineralization with depth resulted in the increasingly vertical dCo : P relationships. Analysis of particulate Co with particulate Mn and particulate phosphate also showed positive linear relationships below the euphotic zone, consistent with the presence and increased relative influence of Mn oxide particles involved in scavenging. Visualization of dCo : P slopes across an ocean section revealed hotspots of scavenging and remineralization, such as at the hydrothermal vents and below the oxygen minimum zone (OMZ) region, respectively, while that of an estimate of Co* illustrated stoichiometrically depleted values in the mesopelagic and deep ocean due to scavenging. This study provides insights into the coupling between the dissolved and particulate phase that ultimately creates Redfield stoichiometric ratios, demonstrating that the coupling is not an instantaneous process and is influenced by the element inventory and rate of exchange between phases. Cobalt's small water column inventory and the influence of external factors on its biotic stoichiometry can erode its limited inertia and result in an acceleration of the dissolved stoichiometry towards that of the particulate phase in the upper euphotic zone. As human use of cobalt grows exponentially with widespread adoption of lithium ion batteries, there is a potential to affect the limited biogeochemical inertia of cobalt and its resultant ecology in the oceanic euphotic zone.

Novel synthesis and shape-dependent catalytic performance of Cu–Mn oxides for CO oxidation

Transition metal oxides with large specific surface area are attractive for high-activity catalysts, and hierarchical structures of transition metal oxides with porous feature possess the structural advantage in the transfer of gaseous reactant and product. In this work, porous Cu–Mn oxides with high surface area were successfully obtained through low-temperature coprecipitation method in alcohol/water solvent and then post-annealing. The addition of alcohol showed great influences on the shape and catalytic performances for CO oxidation. Dumbbell-like Cu–Mn oxide particles with splitting ends displayed high catalytic activity and a complete conversion of CO was achieved at 45°C, suggesting a shape-dependent catalytic activity. The oxidative activity was attributed to a combination of factors including specific surface area, active surface oxygen species and Mn(IV) cations. The results may supply a new thought to design high-performance Cu–Mn oxide catalysts.

Rock varnish on architectural stone: microscopy and analysis of nanoscale manganese oxide deposits on the Smithsonian Castle, Washington, DC

The Smithsonian Institution Building, commonly referred to as the Castle, is located on the National Mall in Washington, DC, and was constructed in the mid-nineteenth century for the purpose of housing all museum and scientific functions for the newly formed institution. Matching gateposts designed by the Castle’s architect were erected more than a century later in the Enid A. Haupt Garden opposite the Castle. Black patches were recently noted on both structures, which are clad with locally quarried Seneca red sandstone. Portable x-ray fluorescence (XRF) spectrometry links the discoloration with elevated Mn concentrations. The discolored patches resemble rock varnish, a Mn-rich coating observed on rock surfaces formed in a variety of environments. Bulk rock and varnish chemistry, in addition to microscopy and microanalysis of the varnish, are presented here. On a bulk chemical basis, the Seneca sandstone is relatively poor in Mn, containing ~500 ppmw. In contrast, the rock varnish is greatly enriched in Mn relative to the stone and to a lesser degree in Pb, Ca, Zn, Cu and Ni. Cross sections of the black encrusted regions show that the stone’s red coloration has been modified by black pigmentation from the surface down to ~250 μm. X-ray diffraction of blackened particles produced no discernable pattern, indicating concentrations below the detection limit, poor crystallinity, or both. Scanning electron microscopy and EDS-based x-ray microanalysis of the uppermost portion of the cross section reveal nanometer scale (<20–200 nm) Mn-rich and clay particles concentrated in a thin film (≪1 μm) at the surface. Additionally, Mn oxide particles decorate the surfaces of fine-grained minerals in sandstone pores within the discolored zone. Imaging and microanalysis of the rock surface reveal that the Mn-rich varnish is a discontinuous film ≪1 μm in thickness with an estimated composition of Na0.2Ca0.1Mg0.1Al0.1Si0.5Mn1.9Fe0.5O6.7. This composition most likely represents a nanoscale mixture of a Mn oxide (e.g., birnessite or todorokite) and an Al-rich silicate mineral. Seneca sandstone on the Smithsonian Castle and gateposts is discolored in patches owing to the Mn-rich phase being deposited into two zones: (1) a vanishingly thin patina, and (2) nanoparticles coating grain boundaries and pores in the uppermost ~200–250 μm of the stone. While the mineralogy is similar to well-studied varnish formed in arid settings, rock varnish on the Smithsonian structures is significantly thinner. Because this architectural rock varnish is young, it may represent the earliest stages of formation of the more commonly described varnishes reported in the literature.

Ionic Strength-Controlled Mn (Hydr)oxide Nanoparticle Nucleation on Quartz: Effect of Aqueous Mn(OH)2.

The early formation of manganese (hydr)oxide nanoparticles at mineral-water interfaces is crucial in understanding how Mn oxides control the fate and transport of heavy metals and the cycling of nutrients. Using atomic force microscopy, we investigated the heterogeneous nucleation and growth of Mn (hydr)oxide under varied ionic strengths (IS; 1-100 mM NaNO3). Experimental conditions (i.e., 0.1 mM Mn(2+) (aq) concentration and pH 10.1) were chosen to be relevant to Mn remediation sites. We found that IS controls Mn(OH)2 (aq) formation, and that the controlled Mn(OH)2 (aq) formation can affect the system's saturation and subsequent Mn(OH)2 (s) and further Mn3O4 (s) nanoparticle formation. In 100 mM IS system, nucleated Mn (hydr)oxide particles had more coverage on the quartz substrate than those in 1 mM and 10 mM IS systems. This high IS also resulted in low supersaturation ratio and thus favor heterogeneous nucleation, having better structural matching between nucleating Mn (hydr)oxides and quartz. The unique information obtained in this work improves our understanding of Mn (hydr)oxide formation in natural as well as engineered aqueous environments, such as groundwater contaminated by natural leachate and acid mine drainage remediation.

Formation of Filamentous Mn Oxide Particles by the Alphaproteobacterium Bosea sp. Strain BIWAKO-01

Mn-rich filamentous particles present in stratified water environments are considered bacteriogenic; however, little is known about their causative agents. This study investigated the production of these particles by an alphaproteobacterium, Bosea sp. strain BIWAKO-01. Particle formation was promoted in static cultures with slightly viscous medium at pH 6.0−6.3 under low-O2 conditions. The Mn(II) oxidation in cultures was slower in higher O2 concentration. These results suggested that pH and O2 concentration are important factors affecting filamentous Mn particle formation in the Mn(II) oxidizer. Lectin staining followed by fluorescence microscopy revealed the presence of specific carbohydrates in the filamentous structures. In addition, transmission electron microscopy, high angle annular dark field scanning transmission electron microscopy, and electron energy loss spectroscopy revealed the structural and spatial associations of Mn with O and C on a nanometer scale in filaments. The results suggested the occurrence of sheet-type Mn oxide likely due to the catalytic activity in exopolymeric substances including acidic polysaccharides.

Fragments of layered manganese oxide are the real water oxidation catalyst after transformation of molecular precursor on clay.

A binuclear manganese molecular complex [(OH2)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](3+) (1) is the most prominent structural and functional model of the water-oxidizing Mn complex operating in plants and cyanobacteria. Supported on montmorillonite clay and using Ce(IV) as a chemical oxidant, 1 has been reported to be one of the best Mn-based molecular catalysts toward water oxidation. By X-ray absorption spectroscopy and kinetic analysis of the oxygen evolution reaction, we show that [(OH2)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](3+) is transformed into layered type Mn-oxide particles which are the actual water oxidation catalyst.

Mn(II)-Oxidizing Activity of &lt;i&gt;Pseudomonas&lt;/i&gt; sp. Strain MM1 is Involved in the Formation of Massive Mn Sediments around Sambe Hot Springs in Japan

There has been an increasing interest in the application of Mn(II) oxidizing microbes for Mn(II) containing waste water treatment, as well as biogenic Mn oxides for remediation of a number of toxic metals. Sambe hot spring in Shimane Prefecture, Japan is known for its Mn-rich spring water, and Mn oxide sediments are widely distributed over an area of 60m © 80m of this region. With an aim to find out Mn(II) oxidizing bacteria involved in this massive Mn(II) oxide deposit formation, culture enrichment was undertaken. Pseudomonas sp. strain MM1 was isolated as dominant Mn(II) oxidizing bacterium from the site. Biogenic Mn oxide formed by strain MM1 was shown to be poorly-crystalline birnessite, having the large specific surface area of 90m 2 ·g ¹1 . Mn(II) was readily oxidized by strain MM1 during the stationary phase and initial Mn(II) concentrations of up to 1.0mmol·dm ¹3 (55mg·dm ¹3 ) went well below the effluent standard of dissolved manganese (10mg·dm ¹3 ; set by Japanese Ministry of Environment). Strain MM1 grew heterotrophically and Mn(II) did not serve as the sole electron donor. Nano-sized (30­ 50nm) Mn oxide particles were produced by strain MM1, which later chained or aggregated to form larger Mn oxide minerals. Cells were observed eventually encrusted inside the Mn oxides. This study showed the important role of strain MM1 in the production of massive Mn oxide deposits at Sambe hot spring. The Mn(II) oxidizing ability of this strain is potentially applied for bioremediation of toxic metals. [doi:10.2320/matertrans.M-M2013825]

Zn sorption mechanisms onto sheathed Leptothrix discophora and the impact of the nanoparticulate biogenic Mn oxide coating

Zinc sorption on sheathed Leptothrix discophora bacterium, the isolated extracellular polymeric substances (EPS) sheath, and Mn oxide-coated bacteria was investigated with macroscopic and spectroscopic techniques. Complexation with L. discophora was dominated by the outer membrane phosphoryl groups of the phospholipid bilayer while sorption to isolated EPS was dominated by carboxyl groups. Precipitation of nanoparticulate Mn oxide coatings on the cell surface increased site capacity by over twenty times with significant increase in metal sorption. XAS analysis of Zn sorption in the coated system showed Mn oxide phase contributions of 18 to 43% through mononuclear inner-sphere complexes. The coordination environments in coprecipitation samples were identical to those of sorption samples, indicating that, even in coprecipitation, Zn is not incorporated into the Mn oxide structure. Rather, through enzymatic oxidation by L. discophora, Mn(II) is oxidized and precipitated onto the biofilm providing a large surface for metal sequestration. The nanoparticulate Mn oxide coating exhibited significant microporosity (75%) suggesting contributions from intraparticle diffusion. Transient studies conducted over 7 months revealed a 170% increase in Zn loading. However, the intraparticle diffusivity of 10 −19 cm 2 s −1 is two orders of magnitude smaller than that for abiotic Mn oxide which we attribute to morphological changes such as reduced pore sizes in the nanoparticulate oxide. Our results demonstrate that the cell-bound Mn oxide particles can sorb significant amounts of Zn over long periods of time representing an important surface for sequestration of metal contaminants.