Mn Oxide Minerals Research Articles

Isolation, characterization, and genetic manipulation of cold-tolerant, manganese-oxidizing Pseudomonas sp. strains.

Manganese-oxidizing bacteria (MnOB) produce Mn oxide minerals that can be used by humans for bioremediation, but the purpose for the bacterium is less clear. This study describes the isolation and characterization of cold-tolerant MnOB strains isolated from a compost pile in Morris, Minnesota, USA: Pseudomonas sp. MS-1 and DSV-1. The strains were preliminarily identified as members of species Pseudomonas psychrophila by 16S rRNA analysis and a multi-locus phylogenetic study using a database of 88 genomes from the Pseudomonas genus. However, the average nucleotide identity between these strains and the P. psychrophila sp. CF149 type strain was less than 93%. Thus, the two strains are members of a novel species that diverged from P. psychrophila. DSV-1 and MS-1 are cold tolerant; both grow at 4°C but faster at 24°C. Unlike the mesophilic MnOB P. putida GB-1, both strains are capable of robustly oxidizing Mn at low temperatures. Both DSV-1 and MS-1 genomes contain homologs of several Mn oxidation genes found in P. putida GB-1 (mnxG, mcoA, mnxS1, mnxS2, and mnxR). Random mutagenesis by transposon insertion was successfully performed in both strains and identified genes involved in Mn oxidation that were similar to those found in P. putida GB-1. Our results show that MnOB can be isolated from compost, supporting a role for Mn oxidation in plant waste degradation. The novel isolates Pseudomonas spp. DSV-1 and MS-1 both can oxidize Mn at low temperature and likely employ similar mechanisms and regulation as P. putida GB-1.IMPORTANCEBiogenic Mn oxides have high sorptive capacity and are strong oxidants. These two characteristics make these oxides and the microbes that make them attractive tools for the bioremediation of wastewater and contaminated environments. Identifying MnOB that can be used for bioremediation is an active area of research. As cold-tolerant MnOB, Pseudomonas sp. DSV-1 and MS-1 have the potential to expand the environmental conditions in which biogenic Mn oxide bioremediation can be performed. The similarity of these organisms to the well-characterized MnOB P. putida GB-1 and the ability to manipulate their genomes raise the possibility of modifying them to improve their bioremediation ability.

Insights on the formation of layered ferromanganese precipitates from the southern Mariana Arc, West Pacific, from micron-scale major, minor, and trace element variations

A combined laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy dispersive X-ray spectroscopy (EDS) study was used to map 49 elements in four FeMn precipitates produced from three different genetic processes (hydrogenetic, hydrothermal, and mixed-type hydrogenetic-hydrothermal) in samples obtained from the southern Mariana Arc. Results show Mn-oxide minerals are consistently found to be associated with Ba, Mo, Sb, V, Zn, and the rare earth elements and yttrium (REY), excluding Ce, whereas Fe-oxyhydroxide minerals are primarily associated with Ti, Co, Cr, Cu, Nb, and Pb. Element distributions in FeMn precipitates from the southern Mariana Arc differ from deposits formed in other environments; notably, there is a decoupling of As and Sb, and redox-sensitive elements are more variable than non-redox-sensitive elements. Samples previously classified as either hydrogenetic or hydrothermal in origin, based on bulk geochemical data, show characteristics of both at higher resolution. Combining high resolution in-situ data with genetic classification discrimination diagrams reveals more ambiguity in metal and metalloid origin than previously thought. Mariana Arc FeMn precipitates can be separated into two formation sub-types (hydrothermal or mixed hydrothermal/hydrogenetic) based on textural and compositional differences, e.g., differences in Ce/Ce and Y/Ho values and relative variations in (Zr + Y + Ce) versus (Co + Ni) versus (Mn + Fe). Improved classification and knowledge of how fast-growing hydrothermal FeMn precipitates form may help us identify a relatively renewable critical metal resource.

The adsorption of cerium on synthetic δ-MnO2: Implications for Ce uptake behavior of hydrogenetic and early diagenetic ferromanganese nodules from the Western Pacific

Cerium (Ce) anomalies can be used to distinguish diagenetic and hydrogenetic nodules, making them an important discriminator for the genesis of marine ferromanganese nodules. To understand the enrichment and adsorption mechanisms of Ce in different types of ferromanganese nodules, we conducted mineralogical and geochemical studies on ferromanganese nodule layers formed through both hydrogenetic and early diagenetic processes as well as adsorption experiments on synthetic δ-MnO2 to monitor the Ce uptake during the different processes. The major and trace element contents of natural ferromanganese nodule layers were investigated by SEM, EPMA and LA-ICP-MS analysis. The marine nodule studied in this study consisted of a core of fish tooth and a rim that could be divided into the hydrogenetic (type I) and early diagenetic (type II) layers based on their mineralogy and Mn/Fe ratios. The Mn oxide mineral assemblage is composed of todorokite, buserite, birnessite, and vernadite (δ-MnO2) and occurred in both type I and II layers. The type I layer has laminated structures with a low Mn/Fe ratio (1.1–3.2; averaging at 1.7), and low Cu, Ni and Mg contents consistent with a hydrogenetic genesis. The type II layer has a columnar and stromatolitic structure with a high Mn/Fe ratio (5.1–54.0; averaging at 23.3) and high Cu, Ni and Mg contents that are similar to early diagenetic nodules. The ΣREE contents in type I and type II layers are 1405–3506 ppm (averaging at 2091 ppm) and 199–1232 ppm (averaging at 674 ppm), respectively, indicating that the REE is enriched in the hydrogenetic type I layers. Strong positive Ce anomalies are present type I layers ranging from 1.2 to 2.5 (averaging 1.9), but only slightly positive are seen in type II ranging from 0.4 to 2.4 (averaging at 1.0). Synthetic experiments to monitor the Ce uptake process show that Ce can be adsorbed onto δ-MnO2 with the XRD and FTIR patterns suggesting that the structure of δ-MnO2 did not change significantly, consistent with Ce behavior in hydrogenetic nodules. The results suggest that Ce is predominantly concentrated in hydrogenetic nodules in an oxic environment, whereas in the early diagenetic layer, there is less oxidation and fixation of Ce due to the suboxic conditions. Our findings are consistent with Ce anomalies in marine Fe-Mn nodules being the result of Mn oxide oxidation adsorption and then fixation (oxidation) after adsorption.

Biological Mn(II) oxidation under organic substrate-limited conditions and its application in mine drainage remediation

Manganese (Mn)-oxidizing bacteria are considered promising tools for remediation of Mn-containing mine drainage. However, whether such microorganisms function in an environment rich in metals and poor in organic substrate remains largely unexplored. In repeated batch experiments, we found that suspensions of mine drainage sediment showed heat-labile, azide-sensitive, and Mn(II) concentration-dependent removal of dissolved Mn(II), consistent with the contribution of biological activity to the Mn(II) oxidation. In limestone-packed bioreactors, most Mn(II) and zinc (Zn) (II) ions added at 20 or 60 mg L−1 and 6 mg L−1, respectively, were removed at hydraulic retention times ranging from 0.5 days to 3.0 days. The Mn oxide deposits in the reactors showed network structures of nanosheets, which structurally incorporated most parts of Mn and Zn to form a Zn-bearing Mn(IV) oxide mineral resembling woodruffite. The Mn deposit suspensions incubated with 13C-labeled bicarbonate assimilated the inorganic carbon and this process enhanced the Mn(II) oxidation. The preferential growth of oligotrophs or methylotrophs might provide organic carbon within Mn(II)-oxidizing microbial communities. This study first demonstrates the important role of inorganic carbon assimilation in heterotrophic Mn(II)-oxidizing community maintained under metal-rich, organic substrate-limited conditions and reinforces the advantage of use of biological Mn(II) oxidation for mine drainage remediation.

Photocatalytic Generation of Reactive Oxygen Species on Fe and Mn Oxide Minerals: Mechanistic Pathways and Influence of Semiconducting Properties

Photocatalytic Generation of Reactive Oxygen Species on Fe and Mn Oxide Minerals: Mechanistic Pathways and Influence of Semiconducting Properties

The role of depositional environment and chemical composition on the triple oxygen isotope ratios of ferromanganese precipitates and their endmember components

Ferromanganese precipitates - crusts, nodules, and hydrothermal deposits – typically exhibit negative Δ'17O values. These deviations are thought to reflect partial incorporation of dissolved atmospheric O2, a component with strongly negative Δ'17O values, seawater oxygen, and deep sea O2 into Mn-oxide minerals, in combination with the other major mineralogical endmember components (Fe-oxyhydroxide and silicate minerals), and kinetic processes such as oxidation at mineral surfaces and biological respiration. Our understanding of the triple oxygen isotope systematics of these materials are limited, however; in the current body of literature, triple oxygen isotope data has only been generated for marine hydrogenetic (i.e., metals accrete directly from seawater) Fe-Mn crusts and Mn nodules. This study evaluates the underlying chemical and environmental factors contributing to the bulk triple oxygen isotopic composition of Fe-Mn precipitates of different genetic types (i.e., hydrothermal, hydrogenetic, mixed-type) from a variety of formation environments (e.g., volcanic arc, pull-apart basin, hotspot, freshwater lake). To improve our understanding of the triple oxygen isotope systematics of natural Fe-Mn precipitates and better constrain the endmember components, we isolate and measure close approximations of the Mn-oxide, Fe-oxyhydroxide, and silicate fractions. Hydrothermal Fe-Mn deposits show greater variation in δ'18O and Δ'17O values (6.0 to 29.6 ‰ and −0.286 to 0.007 ‰, respectively) than hydrogenetic Fe-Mn crusts (5.1 to 11.9 ‰ and −0.200 to −0.086 ‰, respectively). Lacustrine Mn nodule δ'18O and Δ'17O values (5.1 to 8.8 ‰ and −0.230 to −0.090 ‰, respectively) are similar to marine hydrogenetic Fe-Mn crusts, primarily reflecting tropospheric O2. The triple oxygen isotope ratios of nearly pure Mn-oxide samples cluster into distinct groups based on oxygen source, and mass-balance mixing models suggest a significant proportion of incorporated oxygen was photosynthetic in origin. The layered Fe-Mn precipitates in this study show irregular to rhythmic patterns of δ'18O and Δ'17O values depending on formation environment that mostly do not correlate with Mn, Fe, and Si contents. Shale-normalized rare earth element and yttrium (REYSN) patterns and anomalies (CeSN/CeSN*, EuSN/EuSN*, and YSN/HoSN), which can provide insight on formation conditions (e.g., redox, oxygen fugacity, and REY speciation of fluids), are compared with the triple oxygen isotope data. The REYSN anomalies increase from the bottom to the top of the profile of the layered marine sample, suggesting conditions became more oxic over time. Although the triple oxygen isotope ratios correlate with the Eu anomaly in most Fe-Mn precipitates, hydrothermal input can limit their utility as indicators of oxygen fugacity. The triple oxygen isotope ratios of Fe-Mn precipitates reflect complex processes and mixing of multiple sources. Constraining these oxygen sources will assist future studies in interpreting paleoenvironmental conditions (e.g., the saturation state and triple oxygen isotope ratios of dissolved O2 in bottom water) at the time of Fe-Mn precipitate formation.

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.

Geochemical and mineralogical characterization of mine tailings at the Rautuvaara mine site and aspects to environmental conditions and resource potential

Mining industry generates a significant amount of waste including waste rock and tailings. The disposal of mine tailings has environmental impacts, such as the releasing of heavy metals to surface and underground waters. Therefore, adequate rehabilitation of mining waste storage facilities is essential. Abandoned tailings ponds may contain significant amounts of valuable minerals, including critical raw materials, and offer opportunities as secondary mineral resources. In this study geochemical and mineralogical characterization were made for the diverse mine tailings of the Rautuvaara tailings pond which was the final disposal site for different ore deposits. The samples were collected from two different locations in the tailings pond, preconcentrated and analysed with several methods including PSA, XRD, FE-SEM, EPMA, pXRF, WD-XRF and AAS. The geochemical results indicate substantially elevated Cu, As, Ni and Zn concentrations in the tailings. Mineralogical investigations revealed that the tailings contain valuable minerals such as gold, cobaltite, and W-bearing rutile. The last could be used as an indicator mineral in tailings classification and possibly also in future ore exploration. The study of secondary mineralogy revealed that the most weathered top layers of the tailings show secondary alteration rims on the surfaces of mineral particles, and the enrichment of As and Ni in the Fe- and Mn-oxide minerals.

Mineralogy and geochemistry of ferromanganese nodules in semiarid calcareous soils from Northeastern Brazil

Fe/Mn nodules are important records of pedogenesis, weathering processes, and pedoenvironmental conditions. However, data regarding the morphology and mineralogy of Fe/Mn nodules are limited due to difficulties concerning the identification of their low crystallinity Fe/Mn oxides. The hypothesis is that nodules in calcareous soils in Northeastern Brazil present crystalline forms of Mn oxides, whose mineralogy and chemical composition are linked to slight variations in relief. This study investigated the mineralogy and geochemistry of Fe/Mn nodules of soils on different relief surfaces (convex, flat, and concave). The nodules were analyzed using sequential selective dissolution procedure (SSDP), X-ray diffraction, elemental analyses, micromorphology scanning electron microscopy, and energy dispersive spectroscopy. Improvements of the SSDP were needed to identify Mn oxide minerals (birnessite and lithiophorite) in nodules. The relief features are determinants for the distribution and formation of minerals in nodules. The occurrence of calcite silt-sized on the convex and straight surfaces indicates pedogenetic genesis. An increase in kaolinite, highly crystalline lithiophorite, and the absence of calcite in the nodules close to the concave surface also indicates synchronism with pedogenesis. Pseudo-hexagonal lithiophorite and birnessite with plate-like habits are important scavengers of Ce, Co, V, and Ba. This research represents the first record of the detailed morphology and identification of Mn minerals in Fe/Mn nodules using SSDP in semiarid calcareous soils from Northeastern Brazil.

Aqueous Co removal by mycogenic Mn oxides from simulated mining wastewaters

Naturally occurring manganese (Mn) oxide minerals often form by microbial Mn(II) oxidation, resulting in nanocrystalline Mn(III/IV) oxide phases with high reactivity that can influence the uptake and release of many metals (e.g., Ni, Cu, Co, and Zn). During formation, the structure and composition of biogenic Mn oxides can be altered in the presence of other metals, which in turn affects the minerals’ ability to bind these metals. These processes are further influenced by the chemistry of the aqueous environment and the type and physiology of microorganisms involved. Conditions extending to environments that typify mining and industrial wastewaters (e.g., increased salt content, low nutrient, and high metal concentrations) have not been well investigated thus limiting the understanding of metal interactions with biogenic Mn oxides. By integrating geochemistry, microscopic, and spectroscopic techniques, we examined the capacity of Mn oxides produced by the Mn(II)-oxidizing Ascomycete fungus Periconia sp. SMF1 isolated from the Minnesota Soudan Mine to remove the metal co-contaminant Co(II) from synthetic waters that are representative of mining wastewaters currently undergoing remediation efforts. We compared two different applied remediation strategies under the same conditions: coprecipitation of Co with mycogenic Mn oxides versus adsorption of Co with pre-formed fungal Mn oxides. Co(II) was effectively removed from solution by fungal Mn oxides through two different mechanisms: incorporation into, and adsorption onto, Mn oxides. These mechanisms were similar for both remediation strategies, indicating the general effectiveness of Co(II) removal by these oxides. The mycogenic Mn oxides were primarily a nanoparticulate, poorly-crystalline birnessite-like phases with slight differences depending on the chemical conditions during formation. The relatively fast and complete removal of aqueous Co(II) during biomineralization as well as the subsequent structural incorporation of Co into the Mn oxide structure illustrated a sustainable cycle capable of continuously remediating Co(II) from metal-polluted environments.

The Formation and Transformation of Manganese Oxide Minerals on the Surface of Kaolinite

AbstractThe formation of manganese (Mn) oxides is influenced by environmental conditions and, in some red soils, Mn oxides occur as coatings on the surface of kaolinite particles in the form of colloidal films or fine particles. The present study aimed to explore the types of formation mechanisms of Mn oxide minerals on the surface of kaolinite. Mn oxide minerals synthesized by reducing the Mn in KMnO4 with a divalent Mn salt (MnSO4) were examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of various initial molar ratios of Mn2+/Mn7+ (R = 1:0.67, 1:1, 1:2, and 1:4), cationic species (Na+ or Mg2+), synthesis temperatures (30, 60, and 110°C), and amount of added kaolinite (0.25, 0.5, 1.0, 2.0, and 5.0 g) on the formation of Mn oxides were studied. The results showed that Mn oxide mineral types were affected by the initial R value and the background cation. With decreases in the initial R value, the synthesized minerals transformed from cryptomelane to birnessite. The relative mass ratios of kaolinite to Mn oxide were calculated as 1:0.92, 1:0.63, 1:1.15, and 1:1.63. The sodium cation (Na+) had a greater role than Mg2+ in promoting the dissolution–recrystallization of birnessite to cryptomelane. The synthesis temperature had no effect on mineral types, but Mn content increased as temperature increased. When the amount of added kaolinite was increased from 0.25 to 5.0 g, Mn oxide minerals formed gradually and transformed from birnessite to cryptomelane. This work revealed a possible formation process and reaction mechanism on the surface of kaolinite particles in some red soils.

Oxidised gold lode stains black: the historical Encardideira (Chico Rei) deposit, Ouro Preto, Brazil

ABSTRACT The historical Encardideira gold mine, currently known as Chico Rei, represents a rare case of gold mine owned by a freed slave in Brazil’s colonial times. The term ‘encardideira’ alludes to the property of ingraining dirt on the surface of something. Here, we provide chemical and mineralogical evidence that the Encardideira mine likely had its name from the begriming character of its ore shoots. Gold-mineralised samples are enriched in graphite C, identified as tourmaline-enclosed euhedral graphite, and Mn-oxide minerals, mostly pyrolusite and cryptomelane-like material. Measurements for Au by atomic absorption spectrometry returned Au values above 1 ppm only after cupellation, suggesting the existence of graphite-bound gold in pervasively oxidised rocks. It is hypothesised that graphite-rich ore shoots, with superposition of Mn-oxide minerals, could account for enough gold and softness for manual removal by enslaved miners and their characteristic begriming.

Microbial communities contribute to the elimination of As, Fe, Mn, and NH4+ from groundwater in household sand filters

Household sand filters (SFs) are widely applied to remove iron (Fe), manganese (Mn), arsenic (As), and ammonium (NH4+) from groundwater in the Red River delta, Vietnam. Processes in the filters probably include a combination of biotic and abiotic reactions. However, there is limited information on the microbial communities treating varied groundwater compositions and on whether biological oxidation of Fe(II), Mn(II), As(III), and NH4+ contributes to the overall performance of SFs. We therefore analyzed the removal efficiencies, as well as the microbial communities and their potential activities, of SFs fed by groundwater with varying compositions from low (3.3 μg L−1) to high (600 μg L−1) As concentrations. The results revealed that Fe(II)-, Mn(II)-, NH4+-, and NO2−-oxidizing microorganisms were prevalent and contributed to the performance of SFs. Additionally, groundwater composition was responsible for the differences among the present microbial communities. We found i) microaerophilic Fe(II) oxidation by Sideroxydans in all SFs, with the highest abundance in SFs fed by low-As and high-Fe groundwater, ii) Hyphomicropbiaceae as the main Mn(II)-oxidizers in all SFs, iii) As sequestration on formed Fe and Mn (oxyhydr)oxide minerals, iv) nitrification by ammonium-oxidizing archaea (AOA) followed by nitrite-oxidizing bacteria (NOB), and v) unexpectedly, the presence of a substantial amount of methane monooxygenase genes (pmoA), suggesting microbial methane oxidation taking place in SFs. Overall, our study revealed diverse microbial communities in SFs used for purifying arsenic-contaminated groundwater, and our data indicate an important contribution of microbial activities to the key functional processes in SFs.

X-ray absorption spectroscopy study of Mn reference compounds for Mn speciation in terrestrial surface environments

Abstract X-ray absorption spectroscopy (XAS) offers great potential to identify and quantify Mn species in surface environments by means of linear combination fit (LCF), fingerprint, and shell-fit analyses of bulk Mn XAS spectra. However, these approaches are complicated by the lack of a comprehensive and accessible spectrum library. Additionally, molecular-level information on Mn coordination in some potentially important Mn species occurring in soils and sediments is missing. Therefore, we investigated a suite of 32 natural and synthetic Mn reference compounds, including Mn oxide, oxyhydroxide, carbonate, phosphate, and silicate minerals, as well as organic and adsorbed Mn species, by Mn K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The ability of XAS to infer the average oxidation state (AOS) of Mn was assessed by comparing XANES-derived AOS with the AOS obtained from redox titrations. All reference compounds were studied for their local (<5 Å) Mn coordination environment using EXAFS shell-fit analysis. Statistical analyses were employed to clarify how well and to what extent individual Mn species (groups) can be distinguished by XAS based on spectral uniqueness. Our results show that LCF analysis of normalized XANES spectra can reliably quantify the Mn AOS within ~0.1 v.u. in the range +2 to +4. These spectra are diagnostic for most Mn species investigated, but unsuitable to identify and quantify members of the manganate and Mn(III)-oxyhydroxide groups. First-derivative XANES fingerprinting allows the unique identification of pyrolusite, ramsdellite, and potentially lithiophorite within the manganate group. However, XANES spectra of individual Mn compounds can vary significantly depending on chemical composition and/or crystallinity, which limits the accuracy of XANES-based speciation analyses. In contrast, EXAFS spectra provide a much better discriminatory power to identify and quantify Mn species. Principal component and cluster analyses of k2-weighted EXAFS spectra of Mn reference compounds implied that EXAFS LCF analysis of environmental samples can identify and quantify at least the following primary Mn species groups: (1) Phyllo- and tectomanganates with large tunnel sizes (2 × 2 and larger; hollandite sensu stricto, romanèchite, todorokite); (2) tectomanganates with small tunnel sizes (2 × 2 and smaller; cryptomelane, pyrolusite, ramsdellite); (3) Mn(III)-dominated species (nesosilicates, oxyhydroxides, organic compounds, spinels); (4) Mn(II) species (carbonate, phosphate, and phyllosilicate minerals, adsorbed and organic species); and (5) manganosite. All Mn compounds, except for members of the manganate group (excluding pyrolusite) and adsorbed Mn(II) species, exhibit unique EXAFS spectra that would allow their identification and quantification in mixtures. Therefore, our results highlight the potential of Mn K-edge EXAFS spectroscopy to assess bulk Mn speciation in soils and sediments. A complete XAS-based speciation analysis of bulk Mn in environmental samples should preferably include the determination of Mn valences following the “Combo” method of Manceau et al. (2012), EXAFS LCF analyses based on principal component and target transformation results, as well as EXAFS shell-fit analyses for the validation of LCF results. For this purpose, all 32 XAS reference spectra are provided in the Online Materials1 for further use by the scientific community.

Shale Heavy Metal Isotope Records of Low Environmental O2 Between Two Archean Oxidation Events

Evidence of molecular oxygen (O2) accumulation at Earth’s surface during the Archean (4.0–2.5 billion years ago, or Ga) seems to increase in its abundance and compelling nature toward the end of the eon, during the runup to the Great Oxidation Event. Yet, many details of this late-Archean O2 story remain under-constrained, such as the extent, tempo, and location of O2 accumulation. Here, we present a detailed Fe, Tl, and U isotope study of shales from a continuous sedimentary sequence deposited between ∼2.6 and ∼2.5 Ga and recovered from the Pilbara Craton of Western Australia (the Wittenoom and Mt. Sylvia formations preserved in drill core ABDP9). We find a progressive decrease in bulk-shale Fe isotope compositions moving up core (as low as δ56Fe = –0.78 ± 0.08‰; 2SD) accompanied by invariant authigenic Tl isotope compositions (average ε205TlA = –2.0 ± 0.6; 2SD) and bulk-shale U isotope compositions (average δ238U = –0.30 ± 0.05‰; 2SD) that are both not appreciably different from crustal rocks or bulk silicate Earth. While there are multiple possible interpretations of the decreasing δ56Fe values, many, to include the most compelling, invoke strictly anaerobic processes. The invariant and near-crustal ε205TlA and δ238U values point even more strongly to this interpretation, requiring reducing to only mildly oxidizing conditions over ten-million-year timescales in the late-Archean. For the atmosphere, our results permit either homogenous and low O2 partial pressures (between 10−6.3 and 10−6 present atmospheric level) or heterogeneous and spatially restricted O2 accumulation nearest the sites of O2 production. For the ocean, our results permit minimal penetration of O2 in marine sediments over large areas of the seafloor, at most sufficient for the burial of Fe oxide minerals but insufficient for the burial of Mn oxide minerals. The persistently low background O2 levels implied by our dataset between ∼2.6 and ∼2.5 Ga contrast with the timeframes immediately before and after, where strong evidence is presented for transient Archean Oxidation Events. Viewed in this broader context, our data support the emerging narrative that Earth’s initial oxygenation was a dynamic process that unfolded in fits-and-starts over many hundreds-of-millions of years.

Mechanisms of efficient As(III) and As(V) removal by Ni-coprecipitated hausmannite nanocomposites

Being one of the low-valence manganese oxides ubiquitous in surficial environments, hausmannite has high adsorption and redox reactivities towards various contaminants. Natural hausmannite often contains various other cations, such as Ni2+, but it is unclear yet on the crystal chemistry of the foreign cations in the hausmannite structure and as-induced changes in the mineral physicochemical properties and reactivities. In this study, Ni-containing hausmannites were synthesized by Ni2+ coprecipitation with Mn2+, and then were characterized by powder XRD, FTIR, HRTEM, Ni K-edge XAFS, and wet chemical analysis. Then As(V) adsorption and As(III) oxidation behaviors on these nanocomposites were investigated by batch experiments and reaction mechanisms were deciphered by As K-edge XAFS. These nanocomposites have higher points of zero charges and larger specific surface areas than the pristine hausmannite. The dopant mainly exists as α-Ni(OH)2 coatings on the hausmannite surfaces. Compared to the pure hausmannite, these Ni-containing nanocomposites have enhanced As(V) adsorption capacity per unit mass but reduced adsorption affinity and density; while they can also quickly remove As(III) from waters by oxidation, adsorption and fixation, though the initial oxidation rate is slightly reduced. Arsenic immobilized on the mineral surfaces is As(V) and binds with active Mn/Ni sites with an average As-Mn/Ni distances of 3.28–3.30 Å, which can be assigned to bidentate binuclear complexes. These results not only provide new insights into the mediations of As geochemical behaviors by low valence Mn oxide minerals, but also deepen our understanding of the interaction mechanisms of various transition metals with these minerals.

Effects of cobalt doping on the reactivity of hausmannite for As(III) oxidation and As(V) adsorption

Hausmannite is a common low valence Mn oxide mineral, with a distorted spinel structure, in surficial sediments. Although natural Mn oxides often contain various impurities of transitional metals (TMs), few studies have addressed the effect and related mechanism of TM doping on the reactivity of hausmannite with metal pollutants. Here, the reactivity of cobalt (Co) doped hausmannite with aqueous As(III) and As(V) was studied. Co doping decreased the point of zero charge of hausmannite and its adsorption capacity for As(V). Despite a reduction of the initial As(III) oxidation rate, Co-doped hausmannite could effectively oxidize As(III) to As(V), followed by the adsorption and fixation of a large amount of As(V) on the mineral surface. Arsenic K-edge EXAFS analysis of the samples after As(V) adsorption and As(III) oxidation revealed that only As(V) was adsorbed on the mineral surface, with an average As-Mn distance of 3.25–3.30 Å, indicating the formation of bidentate binuclear complexes. These results provide new insights into the interaction mechanism between TMs and low valence Mn oxides and their effect on the geochemical behaviors of metal pollutants.

Mineralogical Characterization of Manganese Oxide Minerals of the Devonian Xialei Manganese Deposit

The Guangxi Zhuang Autonomous Region is an important manganese ore district in Southwest China, with manganese ore resource reserves accounting for 23% of the total manganese ore resource reserves in China. The Xialei manganese deposit (Daxin County, Guangxi) is the first super-large manganese deposit discovered in China. The Mn oxide in the supergene oxidation zone of the Xialei deposit was characterized using scanning electron microscopy (SEM), energy spectrometer (EDS), transmission electron microscopy (TEM, HRTEM), and X-ray diffraction analysis (XRD). The Mn oxides have a gray-black/steel-gray color, a semi-metallic-earthy luster, and appear as oolitic, pisolitic, banded, massive, and cellular textures. Scanning electron microscopy images show that the manganese oxide minerals are present as fine-spherical particles with an earthy surface. TEM and HRTEM indicate the presence of oriented bundled and staggered nanorods, and nanopores between the crystals. The Mn oxide ore can be classified into two textural types: (1) oolitic and pisolitic (often with annuli) Mn oxide, and (2) massive Mn oxide. Pyrolusite, cryptomelane, and hollandite are the main Mn oxide minerals. The potassium contents of cryptomelane and pyrolusite are discussed. The unit cell parameters of pyrolusite are refined.

Mineralogy and petrogenesis of fracture coatings in Athabasca Group sandstones from the McArthur River uranium deposit

ABSTRACT The McArthur River unconformity-related uranium deposit, located in the Athabasca Basin of Saskatchewan, Canada, is structurally hosted near the unconformity between Archean to Paleoproterozoic metasedimentary basement and the Proterozoic Athabasca Group sandstones. In this study, the mineralogy and geochemistry of fracture materials within the entire ca. 550 m thickness of the Athabasca Group sandstones and the metasedimentary (host) rocks from the McArthur River area were used to determine the paragenetic sequence and origin of minerals in and near the fractures. Our work sought to determine if the host minerals record elements associated with the uranium deposit at depth and if they could be used to guide exploration (vectoring). Fracture orientations indicate that most are moderately dipping (<50°) and provided permeable pathways for fluid movement within the basin, from below, and through the overlying sedimentary rocks. Many of the fractures and adjacent wall rocks record evidence of multiple distinct fluid events. Seven types of fracture fillings were identified from drill core intersecting the Athabasca Basin and present distinct colors, mineralogy, and chemical features. Brown (Type 1) and pink (Type 7) fractures host paragenetically late botryoidal goethite, Mn oxide minerals, and poorly crystallized kaolinite that formed from relatively recent low-temperature meteoric fluids, as indicated by poor crystallinity and low δ2H values of –198 to –115‰. These minerals variably replaced higher temperature minerals that are rarely preserved on the fractures or in wall rock near the fractures. Hydrothermal alteration associated with the mineralizing system at ca. 200 °C is recorded in assemblages of dickite, well-crystallized kaolinite, and spherulitic dravite in some white and yellow (Type 2) and white (Type 3) fractures, as reflected by the crystal habits and variable δ2H values of –85 to –44‰. Fibrous goethite in white and yellow (Type 2) and black and orange (Type 5) fractures and microfibrous Mn oxy-hydroxide minerals in black (Type 4) fractures also crystallized from hydrothermal fluids, but at temperatures less than 200 °C. White and yellow fractures (Type 2) containing fibrous goethite reflect fracture networks indicative of hydrothermal fluids associated with the mineralizing system during primary dispersion of pathfinder elements and therefore extend the deposit footprint. Brown (Type 1) and pink (Type 7) fractures have low δ2H values in botryoidal goethite and poorly crystallized kaolinite and are indicative of the movement of meteoric waters. Secondary dispersion of elements from the deposit to the surface on some fractures is evidence that fractures are pathways for element migration from the deposit to the surface, over distances exceeding ∼500 m.

Photocatalytic oxidation of dissolved Mn(II) on natural iron oxide minerals

The energy conversion in Earth’s surface environments over geological history heavily involves the redox reactions of natural minerals. Natural Mn(III/IV) oxides and Mn2+(aq) is one of the most important redox couples that significantly dictate the electron flow in nature. Elucidating their formation and redox reactions is of critical importance for understanding numerous elemental cycles and the evolution of redox environments on Earth and other planets. Previous studies generally consider biotic processes as the dominant oxidation pathway for Mn2+(aq) in natural environments. In this study, we demonstrate rapid abiotic oxidation of Mn2+(aq) through photocatalytic reactions in the presence of natural Fe oxide minerals at rates comparable to those of currently known biotic/abiotic oxidation processes. Fe oxide minerals not only facilitate the electron transfer, but also serve as templates for the heterogeneous nucleation of tunnel structured Mn oxides. This finding highlights an important yet previously overlooked abiotic process on the formation of Mn oxides, which offers a new pathway for explaining the commonly observed co-occurrence of Fe and Mn oxide minerals in nature and the origin of diverse structures of Mn oxides.