Cobalt(II) sequestration on fungal biogenic manganese oxide enhanced by manganese(II) oxidase activity

We examined the ability of biogenic manganese oxide (BMO) formed in the cultures of a Mn(II) oxidizing fungus, Acremonium strictum strain KR21-2, to sequester Co(II) and found that the newly formed BMO effectively sequestered Co(II) under aerobic conditions with virtually no release of Mn(II). Under anaerobic conditions, smaller amounts of Co(II) were sequestered and a significant amount of Mn(II) was released. Similar trends were observed when the BMOs were poisoned with 50 mM NaN₃ or heated at 85 °C for 1 h. X-ray absorption near-edge structure spectroscopy and two-step extraction confirmed that oxidation of Co(II) to Co(III) occurs with BMOs with higher oxidation efficiency under aerobic conditions. These results demonstrate that BMOs can reoxidize Mn(II) through the Mn(II) oxidase associated with the BMO phase and can subsequently provide a new reaction site for Co sequestration. The ability of BMO to sequester Co(II) was also found to be long lasting in 20 mM 4-(2-hydroxyethyl)-1-piperazineethanesulphonic acid (HEPES) buffer (pH 7.0) containing no nutrients to maintain fungal growth, because sequential treatment of BMOs with the Co(II) solution every 24 h for at least 8 days led to Co(II) sequestration. In addition, Co accumulation in the solid phase was eventually 2.48-fold relative to the accumulation of Mn oxide (molar ratio). X-ray diffraction results suggest that the continuing Co(II) oxidation by newly formed BMOs results in the formation of heterogenite (β-CoOOH) aggregates. Assays using the concentrated Mn(II) oxidase crude solution showed that the preformed Mn oxide phase was important for further Mn(II) oxidation in coexisting Co(II). The fact that the coexisting Co(II) was less inhibitory to Mn(II) oxidation if the preformed Mn oxide phase was present suggests a possible electron path from Co(II) to the final electron acceptor O₂ through BMO and Mn(II) oxidase in BMO/enzyme aggregation. These results suggest that fungal BMOs supporting Mn(II) oxidase activity can serve as an effective Co(II) sequestering material, without the need for additional nutrients.     

Influence of extractable soil manganese on oxidation capacity of different soils in Korea

We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00–0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mn^d), NH₂OH·HCl (Mn^h), and hydroquinone (Mn^r) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH₂OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH₂OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mn^d, Mn^h, and Mn^r showed a relatively high correlation with the Cr tests (r = 0.655–0.851; P < 0.01). The concentrations of Mn^d and Mn^h were better correlated with the Cr oxidation tests than was the Mn^r concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mn^d and Mn^h than by Mn^r. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).     

Genesis of REE minerals in the karstic bauxite in western Guangxi,China, and its constraints on the deposit formation conditions

Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce^3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce^4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce^3 + was oxidized into Ce^4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.     

Mineralogy and geochemistry of laterites from the Morro dos Seis Lagos Nb (Ti,REE) deposit (Amazonas,Brazil)

The Morro dos Seis Lagos niobium deposit (2897.9 Mt at 2.81 wt% Nb₂O₅) is associated with laterites formed by the weathering of siderite carbonatite. This iron-rich lateritic profile (>100 m in thickness) is divided into six textural and compositional types, which from the top to the base of the sequence is: (1) pisolitic laterite, (2) fragmented laterite, (3) mottled laterite, (4) purple laterite, (5) manganiferous laterite, and (6) brown laterite. All the laterites are composed mainly of goethite (predominant in the lower and upper varieties) and hematite (predominant in the intermediate types, formed from goethite dehydroxylation). The upper laterites were reworked, resulting in goethite formation. In the manganiferous laterite (10 m thick), the manganese oxides (mainly hollandite, with associated cerianite) occur as veins or irregular masses, formed in a late event during the development of the lateritic profile, precipitated from a solution with higher oxidation potential than that for Fe oxides, closer to the water table. Siderite is the source for the Mn. The main Nb ore mineral is Nb-rich rutile (with 11.26–22.23 wt% Nb₂O₅), which occurs in all of the laterites and formed at expense of a former secondary pyrochlore, together with Ce-pyrochlore (last pyrochore before final breakdown), Nb-rich goethite and minor cerianite. The paragenesis results of lateritization have been extremely intense. Minor Nb-rich brookite formed from Nb-rich rutile occurs as broken spherules with an “oolitic” (or Liesegang ring structure). Nb-rich rutile and Nb-rich brookite incorporate Nb following the [Fe³⁺ + (Nb, Ta) for 2Ti] substitution and both contain up to 2 wt% WO₃. The laterites have an average Nb₂O₅ content of 2.91 wt% and average TiO₂ 5.00 wt% in the upper parts of the sequence. Average CeO₂ concentration increases with increasing depth, from 0.12 wt% in the pisolitic type to 3.50 wt% in the brown laterite. HREE concentration is very low.     

On the model of Mn,Fe, Ni,Co ore formation in recent basins: Experiments with the synthesis of Me-hydroxide phases on Mn3O4

Experiments on the sorption of dissolved Ni, Co, Mn, Fe from seawater by Mn₃O₄ reveal a sequence of reactions taking place: Ion exchange, hydrolysis, then autocatalytic oxidation and layer formation on the interface. The composition of the new compounds depends on the kinetics of i) sorption, and ii) interface oxidation. The highest oxidized Me ions accumulate at low sorption rates, i. e. when sorption does not inhibit interface oxidation: 60% Mn⁴⁺, 30% Ni³⁺ & 30% Co³⁺ are a representative example for that layer type. Iron is present in this layer as amorphous FeOOH·xH₂O according to Mössbauer spectra. Specific for the Me sorption by Mn₃O₄ is the interaction of Ni & Co with Mn²⁺ and Mn³⁺ of the sorbent lattice. Mn is found in the solute phase equivalent to 16, 14% of the adsorbed Co or 17, 96% of the adsorbed Ni. These results confirm the earlier presented model on the transition metal accumulation in recent basins as taking place in distinct stages with interface autocatalysis for the Me oxidation playing the main role.     

A Reliable Method for Determining the Oxidation State of Manganese at the Microscale in Mn Oxides via Raman Spectroscopy

Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X‐ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal‐chemical information at the local scale. In this work, we compare a large set of Raman data from well‐characterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co‐ordinated Mn²⁺ is recognised by a band around 530 cm^?1, Mn³⁺ by a band around 580 cm^?1 and Mn⁴⁺ by a band around 630 cm^?1, while tetrahedrally co‐ordinated Mn²⁺ is recognisable by a band around 650 cm^?1. Strongly distorted Mn³⁺ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.     

Energy transfer among Pb, Ce and Mn in fluorescent calcite from Kuerle, Xinjiang, China

Natural calcite from Kuerle, Xinjiang, China, shows orange-red fluorescence when exposed to short-wave ultraviolet (UV) light (Hg 253.7 nm). Photoluminescence (PL) emission and excitation spectra of the calcite are observed at room temperature in detail. The PL emission spectrum under 208 nm excitation consists of three bands: two UV bands at 325 and 355 nm and an orange-red band at 620 nm. The three bands are ascribed to Pb²⁺, Ce³⁺ and Mn²⁺, respectively, as activators. The Pb²⁺ excitation band is observed at 243 nm, and the Ce³⁺ excitation band at 295 nm. The Pb²⁺ excitation band is also observed by monitoring the Ce³⁺ fluorescence, and the Pb²⁺ and Ce³⁺ excitation bands, in addition to six Mn²⁺ excitation bands, are also observed by monitoring the Mn²⁺ fluorescence. These indicate that four types of the energy transfer can occur in calcite through the following processes: (1) Pb²⁺ → Ce³⁺, (2) Pb²⁺ → Mn²⁺, (3) Ce³⁺ → Mn²⁺ and (4) Pb²⁺ → Ce³⁺ → Mn²⁺.     

Sedimentary manganese metallogenesis in response to the evolution of the Earth system

The concentration of manganese in solution and its precipitation in inorganic systems are primarily redox-controlled, guided by several Earth processes most of which were tectonically induced. The Early Archean atmosphere-hydrosphere system was extremely O₂-deficient. Thus, the very high mantle heat flux producing superplumes, severe outgassing and high-temperature hydrothermal activity introduced substantial Mn²⁺ in anoxic oceans but prevented its precipitation. During the Late Archean, centered at ca. 2.75 Ga, the introduction of Photosystem II and decrease of the oxygen sinks led to a limited buildup of surface O₂-content locally, initiating modest deposition of manganese in shallow basin-margin oxygenated niches (e.g., deposits in India and Brazil). Rapid burial of organic matter, decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the Archean-Proterozoic transition. Concurrently, a massive drawdown of atmospheric CO₂ owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused Paleoproterozoic glaciations (2.45-2.22 Ga). The spectacular sedimentary manganese deposits (at ca. 2.4 Ga) of Transvaal Supergroup, South Africa, were formed by oxidation of hydrothermally derived Mn²⁺ transferred from a stratified ocean to the continental shelf by transgression. Episodes of increased burial rate of organic matter during ca. 2.4 and 2.06 Ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere. Black shale-hosted Mn carbonate deposits in the Birimian sequence (ca. 2.3-2.0 Ga), West Africa, its equivalents in South America and those in the Francevillian sequence (ca. 2.2-2.1 Ga), Gabon are correlatable to this period. Tectonically forced doming-up, attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric CO₂ drawdown causing glaciation on the Neoproterozoic Rodinia supercontinent. Tectonic rifting and mantle outgassing led to deglaciation. Dissolved Mn²⁺ and Fe²⁺ concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation. During the Sturtian glacial-interglacial event (ca. 750-700 Ma), interstratified Mn oxide and BIF deposits of Damara sequence, Namibia, was formed. The Varangian (≡ Marinoan; ca. 600 Ma) cryogenic event produced Mn oxide and BIF deposits at Urucum, Jacadigo Group, Brazil. The Datangpo interglacial sequence, South China (Liantuo-Nantuo ≡ Varangian event) contains black shale-hosted Mn carbonate deposits. The Early Paleozoic witnessed several glacioeustatic sea level changes producing small Mn carbonate deposits of Tiantaishan (Early Cambrian) and Taojiang (Mid-Ordovician) in black shale sequences, China, and the major Mn oxide-carbonate deposits of Karadzhal-type, Central Kazakhstan (Late Devonian). The Mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans. During the Early Jurassic OAE, organic-rich sediments host many Mn carbonate deposits in Europe (e.g., Úrkút, Hungary) in black shale sequences. The Late Jurassic giant Mn Carbonate deposit at Molango, Mexico, was also genetically related to sea level change. Mn carbonates were always derived from Mn oxyhydroxides during early diagenesis. Large Mn oxide deposits of Cretaceous age at Groote Eylandt, Australia and Imini-Tasdremt, Morocco, were also formed during transgression-regression in greenhouse climate. The Early Oligocene giant Mn oxide-carbonate deposit of Chiatura (Georgia) and Nikopol (Ukraine) were developed in a similar situation. Thereafter, manganese sedimentation was entirely shifted to the deep seafloor and since ca. 15 Ma B.P. was climatically controlled (glaciation-deglaciation) assisted by oxygenated polar bottom currents (AABW, NADW). The changes in climate and the sea level were mainly tectonically forced.     

Permanganate oxidation of arsenic(III): Reaction stoichiometry and the characterization of solid product

Permanganate (MnO₄⁻) has widely been used as an effective oxidant for drinking water treatment systems, as well as for in situ treatment of groundwater impacted by various organic contaminants. The reaction stoichiometry of As(III) oxidation by permanganate has been assumed to be 1.5, based on the formation of solid product, which is putatively considered to be MnO₂(s). This study determined the stoichiometric ratio (SR) of the oxidation reaction with varying doses of As(III) (3-300 μM) and MnO₄⁻ (0.5 or 300 μM) under circumneutral pH conditions (pH 4.5-7.5). We also characterized the solid product that was recovered ∼1 min after the oxidation of 2.16 mM As(III) by 0.97 mM MnO₄⁻ at pH 6.9 and examined the feasibility of secondary heterogeneous As(III) oxidation by the solid product. When permanganate was in excess of As(III), the SR of As(III) to Mn(VII) was 2.07 ± 0.07, regardless of the solution pH; however, it increased to 2.49 ± 0.09 when As(III) was in excess. The solid product was analogous to vernadite, a poorly crystalline manganese oxide based on XRD analysis. The average valence of structural Mn in the solid product corresponded to +III according to the splitting interval of the Mn3s peaks (5.5 eV), determined using X-ray photoelectron spectroscopy (XPS). The relative proportions of the structural Mn(IV):Mn(III):Mn(II) were quantified as 19:62:19 by fitting the Mn2p_3/2 spectrum of the solid with the five multiplet binding energy spectra for each Mn valence. Additionally, the O1s spectrum of the solid was comparable to that of Mn-oxide but not of Mn-hydroxide. These results suggest that the solid product resembled a poorly crystalline hydrous Mn-oxide such as (Mn^II_0.19Mn^III_0.62Mn^IV_0.19)₂O₃·nH₂O, in which Mn(II) and Mn(IV) were presumably produced from the disproportionation of aqueous phase Mn(III). Thermodynamic calculations also show that the formation of Mn(III) oxide is more favorable than that of Mn(IV) oxide from As(III) oxidation by permanganate under circumneutral pH conditions. Arsenic(III), when it remained in the solution after all of the permanganate was consumed, was effectively oxidized by the solid product. This secondary heterogeneous As(III) oxidation consisted of three steps: sorption to and oxidation on the solid surface and desorption of As(V) into solution, with the first step being the rate-limiting process as observed in As(III) oxidation by various Mn (oxyhydr)oxides reported elsewhere. We also discussed a potential reaction pathway of the permanganate oxidation of As(III).     

Structure of heavy metal sorbed birnessite. Part III: Results from powder and polarized extended X-ray absorption fine structure spectroscopy

The local structures of divalent Zn, Cu, and Pb sorbed on the phyllomanganate birnessite (Bi) have been studied by powder and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy. Metal-sorbed birnessites (MeBi) were prepared at different surface coverages by equilibrating at pH 4 a Na-exchanged buserite (NaBu) suspension with the desired aqueous metal. Me/Mn atomic ratios were varied from 0.2% to 12.8% in ZnBi and 0.1 to 5.8% in PbBi. The ratio was equal to 15.6% in CuBi. All cations sorbed in interlayers on well-defined crystallographic sites, without evidence for sorption on layer edges or surface precipitation. Zn sorbed on the face of vacant layer octahedral sites (□), and shared three layer oxygens (O_layer) with three-layer Mn atoms (Mn_layer), thereby forming a tridentate corner-sharing (TC) interlayer complex (Zn-3O_layer-□-3Mn_layer). ^TCZn complexes replace interlayer Mn²⁺ (Mn_inter²⁺) and protons. ^TCZn and ^TCMn_inter³⁺ together balance the layer charge deficit originating from Mn_layer⁴⁺ vacancies, which amounts to 0.67 charge per total Mn according to the structural formula of hexagonal birnessite (HBi) at pH 4. At low surface coverage, zinc is tetrahedrally coordinated to three O_layer and one water molecule (^[IV]TC complex: (H₂O)-^[IV]Zn-3O_layer). At high loading, zinc is predominantly octahedrally coordinated to three O_layer and to three interlayer water molecules (^[VI]TC complex: 3(H₂O)-^[VI]Zn-3O_layer), as in chalcophanite (^[VI]ZnMn₃⁴⁺O₇·3H₂O). Sorbed Zn induces the translation of octahedral layers from −a/3 to +a/3, and this new stacking mode allows strong H bonds to form between the ^[IV]Zn complex on one side of the interlayer and oxygen atoms of the next Mn layer (O_next): O_next…(H₂O)-^[IV]Zn-3O_layer. Empirical bond valence calculations show that O_layer and O_next are strongly undersaturated, and that ^[IV]Zn provides better local charge compensation than ^[VI]Zn. The strong undersaturation of O_layer and O_next results not only from Mn_layer⁴⁺ vacancies, but also from Mn³⁺ for Mn⁴⁺ layer substitutions amounting to 0.11 charge per total Mn in HBi. As a consequence, ^[IV]Zn,Mn_layer³⁺, and Mn_next³⁺ form three-dimensional (3D) domains, which coexist with chalcophanite-like particles detected by electron diffraction. Cu²⁺ forms a Jahn-Teller distorted ^[VI]TC interlayer complex formed of two oxygen atoms and two water molecules in the equatorial plane, and one oxygen and one water molecule in the axial direction. Sorbed Pb²⁺ is not oxidized to Pb⁴⁺ and forms predominantly ^[VI]TC interlayer complexes. EXAFS spectroscopy is also consistent with the formation of tridentate edge-sharing (^[VI]TE) interlayer complexes (Pb-3O_layer-3Mn), as in quenselite (Pb²⁺Mn³⁺O₂OH). Although metal cations mainly sorb to vacant sites in birnessite, similar to Zn in chalcophanite, EXAFS spectra of MeBi systematically have a noticeably reduced amplitude. This higher short-range structural disorder of interlayer Me species primarily originates from the presence of Mn_layer³⁺, which is responsible for the formation of less abundant interlayer complexes, such as ^[IV]Zn TC in ZnBi and ^[VI]Pb TE in PbBi.     

High-resolution parallel electron energy-loss spectroscopy of Mn L2,3-edges in inorganic manganese compounds

Parallel electron energy-loss spectroscopy (PEELS) in a scanning transmission electron microscope (STEM) was used to record the Mn L_2,3-edges from a range of natural and synthetic manganese containing materials, covering valences 0, II, III, IV and VII, with an energy resolution of ca. 0.5 eV. The Mn L_2,3 electron-loss near-edge structure (ELNES) of these edges provided a sensitive fingerprint of its valence. The Mn²⁺ L_2,3-edges show little sensitivity to the local site symmetry of the ligands surrounding the manganese. This is illustrated by comparing the Mn L_2,3-edges from 4-, 6- and 8-fold coordinated Mn²⁺. In contrast, the Mn L₃-edges from Mn³⁺ and Mn⁴⁺ containing minerals exhibited ELNES that are interpreted in terms of a crystal-field splitting of the 3d electrons, governed by the symmetry of the surrounding ligands. The Mn L₃-edges for octahedrally coordinated Mn²⁺, Mn³⁺ and Mn⁴⁺ showed variations in their ELNES that were sensitive to the crystal-field strength. The crystal-field strength (10Dq) was measured from these edges and compared very well with published optically determined values. The magnitude of 10Dq measured from the Mn L₃-edges and their O K-edge prepeaks of the manganese oxides were almost identical. This further confirms that the value of 10Dq measured at the Mn L₃-edge is correct. Selected spectra are compared with theoretical 2p atomic multiplet spectra and the differences and similarities are explained in terms of the covalency and site symmetry of the manganese. The Mn L₃-edges allow the valence of the manganese to be ascertained, even in multivalent state materials, and can also be used to determine 10Dq.     

Origin and metamorphic evolution of rocks with braunite and pyrophanite from the Iberian Massif (SW Spain)

Summary ?Rocks containing braunite from the Ossa-Morena central belt (Iberian Massif, SW Spain) have been studied; these include nodules and layers of braunite (association I), Mn-slates (association II) and Mn-metatuffs (associations III and IV). Geochemical features of braunite nodules such as Mn/Fe ratios around 2, positive Ce-anomalies and good correlations among Mn, Fe, Co, Cu and REE contents indicate that the protolith of the braunite-nodules was precipitated from oxidising sea water. Greenschist facies Hercynian metamorphism reduced initial Mn⁴⁺ to Mn³⁺ and Mn²⁺. High initial fO₂ of oxide beds (association I) limited reduction to the formation of braunite. Reduction continued until the formation of garnet + piemontite (associations II and III), and pyroxmangite + pyrophanite (association IV). Ti-rich braunites (up to 6.8% of TiO₂) occur in slates and metatuffs in which the (Mn + Fe)/Ti ratio of the whole rock is lower than 30, while braunites have lower Ti contents in slates and metatuffs with (Mn + Fe)/Ti ratios around 90. Fe-rich braunite crystallized in rocks with Mn²⁺ oxide and silicate where low Mn³⁺/Mn²⁺ in the whole rock facilitated substitution of Fe³⁺ for Mn³⁺. Received January 30, 2002; revised version accepted May 7, 2002 Published online November 22, 2002     

Geochemical modeling of coal mine drainage, Summit County, Ohio

 Geochemical modeling was used to investigate downstream changes in coal mine drainage at Silver Creek Metro-park, Summit County, Ohio. A simple mixing model identified the components that are undergoing conservative transport (Cl^–, PO₄ ^3–, Ca²⁺, K⁺, Mg²⁺ and Na⁺) and those undergoing reactive transport (DO, HCO₃ ^–, SO₄ ^2–, Fe²⁺, Mn²⁺ and Si). Fe²⁺ is removed by precipitation of amorphous iron-hydroxide. Mn²⁺ are removed along with Fe²⁺ by adsorption onto surfaces of iron-hydroxides. DO increases downstream due to absorption from the atmosphere. The HCO₃ ^– concentration increases downstream as a result of oxidation of organic material. The rate of Fe²⁺ removal from the mine drainage was estimated from the linear relationship between Fe⁺² concentration and downstream distance to be 0.126 mg/s. Results of this study can be used to improve the design of aerobic wetlands used to treat acid mine drainage. Received: 4 June 1996 · Accepted: 17 September 1996     

The uptake of cobalt into ferromanganese nodules,soils, and synthetic manganese (IV) oxides

Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO₂. Previously, it was suggested that Co³⁺ ions in these minerals replace either Mn³⁺ or substitute for Fe³⁺ in incipient goethite epitaxially intergrown with δ-MnO₂. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co³⁺ and high-spin Mn³⁺ or Fe³⁺ in oxide structures. The close agreement between the ionic radii of Co³⁺ and Mn⁴⁺ suggests that some cobalt substitutes for Mn⁴⁺ ions in edge-shared [MnO₆] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co²⁺ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO₆] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co²⁺ ions by Mn⁴⁺ and replacement of the displaced manganese by low-spin Co³⁺ ions in the [MnO₆] octahedra or vacancies.     

Oxidation of Mn(II): Initial mineralogy,oxidation state and ageing

The initial solid phase oxidation products formed during the oxidation of aqueous Mn(II) at 25°C were studied as a function of time. The analyses included morphology (TEM), mineralogy (x-ray diffraction), $\text{O}\text{Mn}$ ratio (iodometric method), oxidation state of manganese (XPS), and dissolved manganese. The initial solid formed under our conditions was Mn₃O₄ (hausmannite) which converted completely to γMnOOH (manganite) after eight months. βMnOOH (feitknechtite) appeared to be an intermediate in this transformation. The $\text{O}\text{Mn}$ ratio was initially 1.37 and increased to 1.49 over the same time span. Throughout the course of this study the XPS analyses showed that the surface of the solids (<50 Å) was dominated by Mn(III). The solution pH and dissolved manganese concentrations were consistent with disproportionation and oxidation reactions that favor the transformation of Mn₃O₄ to γMnOOH but not to γMnO₂.     

Divergent T–ƒO<Subscript>2</Subscript> paths during crystallisation of H<Subscript>2</Subscript>O-rich and H<Subscript>2</Subscript>O-poor magmas as recorded by Ce and U in zircon,with implications for TitaniQ and TitaniZ geothermometry

During solidification of magma chambers as systems closed to chemical exchange with environs, the residual siliceous melt may follow a trend of rising, constant, or decreasing oxidation state, relative to reference buffers such as nickel?+?nickel oxide (NNO) or fayalite?+?magnetite?+?quartz. Titanomagnetite–hemoilmenite thermometry and oxybarometry on quenched volcanic suites yield temperature versus oxygen fugacity arrays of varied positive and negative slopes, the validity of which has been disputed for several years. We resolve the controversy by introducing a new recorder of magmatic redox evolution employing temperature- and redox-sensitive trace-element abundances in zircon. The zircon/melt partition coefficients of cerium and uranium vary oppositely in response to variation of magma redox state, but vary in tandem as temperature varies. Plots of U/Pr versus Ce⁴⁺/Ce³⁺ in zircon provide a robust test for change in oxidation state of the melt during zircon crystallisation from cooling magma, and the plots discriminate thermally induced from redox-induced variation of Ce⁴⁺/Ce³⁺ in zircon. Temperature-dependent lattice strain causes Ce⁴⁺/Ce³⁺ in zircon to increase strongly as zircon crystallises from cooling magma at constant Ce⁴⁺/Ce³⁺ ratio in the melt. We examine 19 zircon populations from igneous complexes in varied tectonic settings. Variation of zircon Ce⁴⁺/Ce³⁺ due to minor variation in melt oxidation state during crystallisation is resolvable in 11 cases but very subordinate to temperature dependence. In many zircon populations described in published literature, there is no resolvable change in redox state of the melt during tenfold variation of Ce⁴⁺/Ce³⁺ in zircons. Varied magmatic redox trends indicated by different slopes on plots of zircon U/Pr versus Ce⁴⁺/Ce³⁺ are corroborated by Fe–Ti-oxide-based T–?O₂ trends of correspondingly varied slopes. Zircon and Fe–Ti-oxide compositions agree that exceptionally, H₂O-rich arc magmas tend to follow a trend of rising oxidation state of the melt during late stages of fluid-saturated magmatic differentiation at upper-crustal pressures. We suggest that H₂ and/or SO₃ and/or Fe²⁺ loss from the melt to segregating fluid is largely responsible. Conversely, zircon and Fe–Ti-oxide compositions agree in indicating that H₂O-poor magmas tend to follow a T–?O₂ trend of decreasing oxidation state of the melt during late stages of magmatic differentiation at upper-crustal pressures, because the precipitating mineral assemblage has higher Fe³⁺/Fe²⁺ than coexisting rhyolitic melt. We present new evidence showing that the Fe–Ti-oxide oxybarometer calibration by Ghiorso and Evans (Am J Sci 308(9):957–1039, 2008) retrieves experimentally imposed values of ?O₂ in laboratory syntheses of Fe–Ti-oxide pairs to a precision of ±?0.2 log unit, over a large experimental temperature range, without systematic bias up to at least log ?O₂?≈?NNO?+?4.4. Their titanomagnetite–hemoilmenite geothermometer calibration has large systematic errors in application to Ti-poor oxides that precipitate from very oxidised magmas. A key outcome is validation of Fe–Ti-oxide-based values of melt TiO₂ activity for use in Ti-in-zircon thermometry and Ti-in-quartz thermobarometry.     

Transient States in Diagenesis Following the Deposition of a Gravity Layer: Dynamics of O<Subscript>2</Subscript>, Mn,Fe and N-Species in Experimental Units

Biogeochemical processes induced by the deposition of gravity layer in marine sediment were studied in a 295-day experiment. Combining voltammetric microelectrode measurements and conventional analytical techniques, the concentrations of C, O₂, N-species, Mn and Fe have been determined in porewaters and sediments of experimental units. Dynamics of the major diagenetic species following the sudden sediment deposition of few cm-thick layer was explained by alternative diagenetic pathways whose relative importance in marine sediments is still a matter of debate. Time-series results indicated that the diffusion of O₂ from overlying waters to sediments was efficient after the deposition event: anoxic conditions prevailed during the sedimentation. After a few days, a permanent oxic horizon was formed in the top few millimetres. At the same time, the oxidation of Mn²⁺ and then Fe²⁺, which diffused from anoxic sediments, contributed to the surficial enrichment of fresh Mn(III/IV)- and Fe(III)-oxides. Vertical diffusive fluxes and mass balance calculations indicated that a steady-state model described the dynamic of Mn despite the transitory nature of the system. This model was not adequate to describe Fe dynamics because of the multiple sources and phases of Fe²⁺. No significant transfer of Mn and Fe was observed between the underlying sediment and the new deposit: Mn- and Fe-oxides buried at the original interface acted as an oxidative barrier to reduced species that diffused from below. Nitrification processes led to the formation of a NO₃⁻/NO₂⁻ rich horizon at the new oxic horizon. Over the experiment period, NO₃⁻ concentrations were also measured in the anoxic sediment suggesting anaerobic nitrate production.     

Manganiferous schists and their origin,Hidaka Mountains,Hokkaido, Japan

Manganiferous quartz-mica schists (4 m in stratigraphic thickness) overlie epidote amphibolite in the Chiroro River area, Hidaka Mountains, Hokkaido. The schist layers have a considerable range of A/F ratios and bulk oxidation ratios which vary from 21.5 to 100. Manganese contents are from 4 to 30 times higher than that of the average shale with 0.09% MnO. The schists are essentially quartz-white mica-biotite-Mn garnet-tourmaline-±epidote-magnetite assemblages. A highly oxidized layer (5–8 cm thick) 95 cm above the epidote amphibolite contact is characterized by viridine-piemontite-spessartine-Mn white mica-Mn tourmaline-Ti-Mn haematite indicative of both high initial manganese content and very high f _O2 conditions of recrystallization.Viridine contains up to 17 mol% Mn³⁺SiO₅ and coexists with piemontite with between 13.6 and 15.4 wt% Mn₂O₃. Mn-poor-Fe-rich (Ps₃₂) epidote occurs in the less oxidized schist enclosing the viridine-piemontite bearing seam. Garnets vary widely in composition with end member variations (mol%) of Spess_22.9–80.5; And_0.2–11.7; Alm_1.1–57.1; Pyr_2.0–12.2; Gross_7.0–49.0. The more manganiferous garnets occur in rocks with higher oxidation ratios while almandiferous varieties occur in schists with low oxidation ratios. Biotite ranges from green to red-brown varieties (increasing Ti and Fe) with Mg/ (Mg+Fe) ratios varying from 56 to 48. Ten to fifteen percent octahedral R²⁺ is replaced by Al indicating a trend towards eastonite-siderophyllite. The white micas deviate only slightly from dioctahedral stoichiometry but have up to 25% of octahedral sites occupied by Fe, Mg and to a lesser extent Mn and Ti as R²⁺ Si⁴⁺2Al³⁺ and in highly oxidized rocks as (Fe,Mn)³⁺Al³⁺. The white mica in the highly oxidized viridine-piemontite schist is pale pinkishorange, exhibits reverse pleochroism, and has between 0.30 and 0.43 wt% Mn₂O₃.There is a close comparison, both in terms of stratigraphic thickness and Fe-Mn variation, between the Chiroro schist sequence and many oceanic cores so that the bulk chemistry and mineralogy of the pelitic schists is largely an extension of the original Eh-pH conditions of hemipelagic sedimentation and post-depositional adjustments during diagenesis. The thin viridine-piemontite bearing schist is correlated with an oxidized, Fe-Mn rich layer commonly found in present day oceanic cores. The viridine presumably formed by reaction of original ferro-manganese microgranules and clay minerals. Halmrolytic alteration of the underlying metabasalt resulted in leaching of Mn and Fe (in particular) into the overlying sediments and the formation of concentrations of haematite — manganese oxide — Mn garnet along the schist-epidote amphibolite contact.Estimation of the P-T conditions of metamorphism from the phase relations and compositions in the epidote amphibolite associated with the manganiferous schist gives T °C = 530560 and a minimum P _fluid > 3 kb which corresponds to the epidote amphibolite facies of Barrovian-type terrains.This paper is dedicated to Professor Kenzo Yagi on the occasion of his retirement from the Chair of Mineralogy, Department of Geology and Mineralogy, Hokkaido University, Sapporo, Japan     

Inter-relationships of MnO2 precipitation, siderophore-Mn complex formation, siderophore degradation, and iron limitation in Mn-oxidizing bacterial cultures

To examine the pathways that form Mn^(III) and Mn^(IV) in the Mn^(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn^(IV)O₂ formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn^(III) complex or insoluble Mn^(IV)O₂ minerals - but not both simultaneously. PVD-Mn^(III) was present, and MnO₂ precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn^(III) arose by predominantly ligand-mediated air oxidation of Mn^(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn^(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn^(III), a process linked to the production of both MnO₂ and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn^(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO₂ to appear. These results suggest that P. putida cultures produce soluble Mn^(III) or MnO₂ by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO₂ under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn^(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn^(III) versus MnO₂) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.