Mn Carbonate Research Articles

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

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

A distinct manganese deposit on a Middle Permian carbonate platform in South China

During the Middle Permian, Earth experienced a period of profound environmental changes, including the final stages of the Late Paleozoic Ice Age (LPIA), global seawater regression, the Guadalupian mass extinction event, and the eruption of the Emeishan Large Igneous Province (ELIP) in South China. These events collectively induced significant shifts in both the environment and biosphere, yielding several geochemical anomalies, including deposition of manganese (Mn) deposits. The link between Middle Permian Mn deposits and the prevailing environmental conditions, however, remains unclear. Here, four sections spanning the Middle Permian Maokou Formation to the Late Permian Longtan Formation in the Zunyi area of northern Guizhou, South China are investigated. Through sedimentological and geochemical analyses, this work aims to elucidate the evolution of sedimentary environments over the Middle to Late Permian. During this period, a transition from a shallow-water carbonate platform in the 1st Member of the Maokou Formation to a deeper, siliceous deposit in its 2nd Member was recorded. This shift results in a pronounced paleogeographic differentiation in the 3rd Member, juxtaposing the shallow-water carbonate platform against a deeper Mn-enriched basin. A number of geochemical proxies indicate a strong hydrothermal signal in the Mn deposits. Combined with positive Eu anomalies and low Sr isotopes, the data underscore the profound influence of hydrothermal input linked with early subaqueous eruptions from the ELIP on the nearby marine environment. A detailed examination of carbon isotope profiles from the Maokou Formation indicates that volcanic influences, shifts in marine ecosystems, and changes in primary production caused the fluctuations of δ13Ccarb and δ13Corg. Moreover, the formation of Mn carbonate in deeper waters effectively sequestered organic C. Collectively, our new data demonstrate that the essential conditions for the development of the carbonate-hosted Mn deposits include drowning of the carbonate platform through an increase in sea level, the availability of a sufficient Mn source, and the presence of a redox-stratified water column.

Hydrological dynamics and manganese mineralization in the wake of the Sturtian glaciation

The Cryogenian Sturtian and Marinoan glaciations stand as the most extreme climate events in Earth history. Intriguingly, large-scale Mn carbonates characterize the nonglacial interlude of this period in South China. The formation mechanism of Mn carbonates and the potential correlation underlying this temporal association remain elusive. Here, we present an integrated petrographic and geochemical study of drill core materials intercepting the Mn-bearing Datangpo Formation. Rare earth element patterns of these Mn carbonates exhibit positive Ce anomalies and a lack of Y anomalies, which differ from those of modern seawater but resemble marine Mn-Fe oxides. These features, combined with negative carbonate carbon isotope compositions (δ13Ccarb as light as −9.9 ‰ VPDB), indicate the presence of oxide precursors and the incorporation of light carbon during Mn-carbonate precipitation. Phosphate oxygen isotope ratios (δ18Op) of HCl-extractable apatite reveal a ∼4 ‰ difference in the average δ18Op between Mn-rich and Mn-poor rocks. We propose that the more positive δ18Op of Mn-rich samples may result from the dominance of phosphate released by reductive dissolution of metal oxides or a heavier oxygen isotope signal of surrounding waters with which isotopic equilibrium has been reached. We further illustrate how marine invasions into coastal anoxic basins could have triggered the formation of Mn oxides and highlight the role of glaciation–deglaciation in the development of giant Mn deposits.

Methanogen‐Mediated Precipitation of Mn Carbonates at the Expense of Mn Oxides

AbstractWhether Mn carbonates can be used as a proxy for the oxygenation event is debated. Here we examined the Early Cretaceous lacustrine Mn carbonates from North China, which contain abundant microbial fossils. The extremely positive δ13C (up to +15‰ relative to Vienna Peedee belemnite) and micro‐area enrichment of Ni strongly indicate a methanogenic archaea origin of these microorganisms. Transmission electron microscope and electron energy loss spectroscopy show the nanoscale transformation of Mn‐oxides (Mg‐exchanged phyllomanganate) to Mn carbonates (kutnohorite), on extracellular polymeric substances. The reaction of the Mn oxides with organic matter resulted in increasing pH and alkalinity, together with the fluctuating pH, offering a suitable micro‐environment for the transformation processes. These Mn carbonates are therefore indicative of an oxidized, sulfate‐absent environment. The depicted scenario serves as a reference to ocean of the early Earth and provides a referable Mn oxide tracer for determining the emergence of the Great Oxidation Event.

Controls on the formation of Mn carbonates in mudrocks of the Datangpo Formation, Northern Margin Rift Basin, Yangtze Block

Deglaciation following the Sturtian Ice Age led to widespread manganese carbonate precipitates within marine mudrocks, reflecting unique climatic and oceanographic changes. The Mn carbonates hold economic importance in the Datangpo Formation, Yangtze Block, South China. Although their genesis in the Nanhua Rift Basin is well understood, little is known regarding their formation mechanism in the North Margin Rift Basin (NMRB). With growing interest in Mn ore exploration in this region, this study examines the weathering trend, climate patterns and watermass conditions using a variety of geochemical proxies. The results reveal two phases of climate variation during the deglaciation. Climate during the early phase (Phase I) was unstable, characterized by fluctuating values of Chemical Index of Alteration (CIA = 65 ± 4) and elevated Li isotope (8.8 ± 3.0‰) patterns. The degree of chemical weathering during the later stage (Phase II) was relatively stable (CIA = 65 ± 1, δ7Li = 5.4 ± 2.7‰), but the weathering intensity increased due to the reduced denudation rate, possibly related to a shift in the basin development. Fe speciation data indicate euxinia prevailing much of the section. However, Mo and U enrichment (> 1) and fluctuating ratios of Mo versus total organic content (0–40) suggest that pulses of freshwater influx associated with climate variation during Phase I caused the fluctuation of the chemocline along the continental shelf, facilitating the formation of Mn carbonates through the particulate Fe-Mn-hydroxide shuttle. With the establishment of stabilized climate, basin tectonics, and watermass circulation during Phase II, the accumulation of Mn carbonates in the sediments became less significant. The accumulation of Mn carbonates in the NMRB conforms to the “bathtub ring model”, distinct from the metallogenic model in the NRB, providing valuable guidance for Mn ore prospecting within this area and elsewhere with similar settings.

Efficient degradation of acetaminophen by activated peroxymonosulfate using Mn/C composites: Performance and mechanism

The synthesis of manganese oxide (MnOx) composites often leads to particle aggregation and the formation of larger metal nanoparticles, which greatly reduces the efficient use of manganese (Mn) as catalyst. Additionally, the structurally unstable Mn matrix composites increase the risk of metal precipitation during the reaction process. To address these issues, a series of Mn-carbon (Mn/C) co-doped composites (Mn@CA400, Mn@CA500, and Mn@CA600) were synthesized using potassium permanganate (KMnO4) and citric acid (CA) as precursors. The Mn@CA400 exhibited exceptional catalytic activity towards peroxymonosulfate (PMS) resulting in complete removal of 10 mg/L acetaminophen (ACT) within 10 min. Furthermore, Mn@CA400 demonstrated significant selectivity and resistance in complex matrices to interference for pollutant degradation. The results showed that Mn@CA400 exhibited higher catalytic activity and better stability compared with the reported Mn-based composites. Quenching experiments, electron paramagnetic resonance (EPR), solvent exchange experiments, and electrochemical analysis confirmed that singlet oxygen (1O2) and electron transfer pathways were responsible for ACT degradation. The mechanism analysis revealed that ACT could be degraded under three pathways. The current study not only presents an effective method to solve the problem of metal agglomeration and precipitation in the synthesis of MnOx composites but also establishes an efficient and selective oxidation system. In addition, it greatly improves the understanding of PMS activation and ACT degradation mechanisms.

Distribution of In, Sn, Ga, Ge, and other critical metals in sulfide ores from epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposit (Kosovo): Insights from mineralogy and geochemistry

This work presents a mineralogical and geochemical study of sulfide ores from the epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposit, which is located in the central part of the Kizhnica-Hajvalia-Badovc ore field, in the Trepça Mineral Belt (TMB) in Kosovo. Badovc is an example of one of many base-metal Pb–Zn–Ag deposits associated with the Serbo-Macedonian metallogenic province. There are three types of ores, the first two associated with polymetallic epithermal IS veins (massive-banded Pb–Zn–Sb and rhodochrosite-stibnite breccia) and disseminated ores associated with listvenites, which are hydrothermally altered mafic and ultramafic rocks. The mineralogy of these ores was described using EPMA in combination with reflected and transmitted light microscopy. The mineralogy of massive-banded Pb–Zn–Sb and rhodochrosite-stibnite breccia ores is relatively limited: sphalerite + rhodochrosite-siderite + pyrite/marcasite ± Pb–Sb sulfosalts ± stibnite. Listvenite Pb–Zn–Sb–Ni ores are more mineralogically variable due to the multi-stage formation of these rocks and the overprint of polymetallic mineralization. Apart from typical base-metal sulfides such as sphalerite, pyrite, galena, and chalcopyrite, the listvenite ores contain Fe–Mn carbonates, quartz, and Ni–Fe ± As ± Sb association (gersdorffite, ullmannite, millerite, and Ni–Fe thiospinels), Sn minerals (stannite and cassiterite). The LA-ICP-MS technique was used to determine critical metals occurring as minor and trace elements and substitution mechanisms in sphalerite, pyrite, stibnite, chalcopyrite and stibnite. The main critical metals, such as In, Sn, Ga, and Ge, are hosted by sphalerite in all types of ores. The highest concentrations of tin in sphalerite are observed in massive-banded Pb–Zn–Sb ores, which substitutes within the 3Zn2+ ↔ 2(Cu, Ag)+ + Sn4+ mechanism. The highest concentrations of indium are observed in sphalerites from listvenites, indicating the 2Zn2+ ↔ Cu+ + In3+ substitution. Low-temperature sphalerites from rhodochrosite-stibnite breccia exhibit elevated concentrations of Ga, Ge, and Ag, which incorporate into the structure through 2Zn2+ ↔ (Ag, Cu)+ + Ga3+, and 3Zn2+ ↔ 2(Cu, Ag)+ + Ge4+ mechanisms. The specific crystallization temperatures using GGIMFis for sphalerite are: 248–332 °C for massive-banded Pb–Zn–Sb ores, 208 °C for rhodochrosite-stibnite breccia, and 2112–344 °C for listvenite Pb–Zn–Sb–Ni ores. Additionally, stibnite from Badovc exhibits substitutions such as As3+ ↔ Sb3+ and (Cu+ + Ag+) + Pb2+ ↔ Sb3+ + □, and can incorporate various monovalent elements other than copper, including Ag+ and Tl+. Studies of epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposits suggest that similar deposits spread across the Balkans may hold considerable prospectivity.

Manganese cycling and transport in boreal estuaries impacted by acidic Mn-rich drainage

As critical transition zones between the land and the sea, estuaries are not only hotspots of hydrogeochemical and microbial processes/reactions, but also play a vital role in processing and transferring terrestrial fluxes of metals and nutrients to the sea. This study focused on three estuaries in the Gulf of Bothnia. All of them experience frequent inputs of acidic and Mn/metal-rich creek waters due to flushing of acid sulfate soils that are widespread in the creekś catchments. Analyzing existing long-termwaterchemistrydata revealed a strong seasonal variation of Mn loads, with the highest values in spring (after snow melt) and autumn (after heavy rains). We sampled surface waters, suspended particulate matter (SPM), and sediments from the estuarine mixing zones and determined the loads and solid-phase speciation of Mn as well as the composition and metabolic potentials of microbial communities. The results showed that the removal, cycling, and lateral transport of Mn were governed by similar phases and processes in the three estuaries. Manganese X-ray absorption spectroscopy data of the SPM suggested that the removal of Mn was regulated by silicates (e.g., biotite), organically complexed Mn(II), and MnOx (dominated by groutite and phyllomanganates). While the fractional amounts of silicate-bound Mn(II) were overall low and constant throughout the estuaries, MnOx was strongly correlated with the Mn loadings of the SPM and thus the main vector for the removal of Mn in the central and outer parts of the estuaries, along with organically complexed Mn(II). Down estuary, both the fractional amounts and average Mn oxidation state of the MnOx phases increased with (i) the total Mn loads on the SPM samples and (ii) the relative abundances of several potential Mn-oxidizing bacteria (Flavobacterium, Caulobacter, Mycobacterium, and Pedobacter) in the surface waters. These features collectively suggested that the oxidation of Mn, probably mediated by the potential Mn-oxidizing microorganisms, became more extensive and complete towards the central and outer parts of the estuaries. At two sites in the central parts of one estuary, abundant phyllomanganates occurred in the surface sediments, but were converted to surface-sorbed Mn(II) phases at deeper layers (>3–4 cm). The occurrence of phyllomanganates may have suppressed the reduction of sulfate in the surface sediments, pushing down the methane sulfate transition zone that is typically shallow in estuarine sediments. At the outermost site in the estuary, deposited MnOx were reduced immediately at the water–sediment interface and converted most likely to Mn carbonate. The mobile Mn species produced by the Mn reduction processes (e.g., aqueous Mn(II) and ligand complexed Mn(III)) could partly diffuse into the overlying waters and, together with the estuarine Mn loads carried by the surface waters, transfer large amounts of reactive Mn into open coastal areas and subsequently contribute to Mn shuttling and inter-linked biogeochemical processes over the seafloor. Given the widespread occurrence of acid sulfate soils and other sulfidic geological materials on many coastal plains worldwide, the identified Mn attenuation and transport mechanisms are relevant for many estuaries globally.

Dynamic deep-water oxygenation of marginal seas in the aftermath of the Sturtian Snowball Earth: Insights from redox-hydrological reconstructions of the Nanhua basin (South China)

The Cryogenian interglacial period, separated by the Sturtian and Marinoan icehouses, witnessed early radiations of eukaryotic algae and the first emergence of putative metazoans. To date, the detailed oceanic redox state in the aftermath of the Sturtian glaciation remains obscure, limiting our understanding of the causal linkage, if any, between environmental changes and biological evolution during this critical interval. In order to gain further insights into the marine redox framework following the Sturtian Snowball glaciation, here we present high-resolution geochemical results of an integrated study on the basal Datangpo Formation from the Daotuo area (South China), and also provide a systematically compiled dataset of counterparts in other profiles from the Nanhua Basin. The basal Datangpo Formation is characterized by black shales intercalated with Mn carbonate ore layers in the lower (Member I), and only black shales in the upper (Member II). The Member I black shales have relatively high abundances of Mo and Re, and display a MoEF-UEF pattern typical of Mn-oxide shuttle, indicating that the Nanhua basin was redox-stratified with the oxic-euxinic chemocline fluctuating above the deep-basin floor. Multiple lines of evidence, including positive PAAS-normalized Ce anomalies, negative δ13Ccarb values, and marked authigenic enrichments of manganophile elements (Co, Ni, Cu), imply that the Mn carbonate ore beds were generated through the diagenetic transformation of Mn oxides originally deposited under oxic bottom waters. Therefore, these Mn ore layers hosted by the Member I black shales reflect episodic benthic oxygenation. By contrast, the Nanhua basin was more stagnant during deposition of Member II black shales, as supported by their rather low Mo/TOC ratios, as well as the relatively lower abundances of Mo and Re compared to Member I black shales. Moreover, the Mo isotope data of the basal Datangpo Formation indicate that the global ocean remained pervasively anoxic. Taken together, this study reveals a more holistic redox landscape in the wake of the Sturtian Snowball Earth—that is, extensive anoxia in the global ocean with episodic deep-water oxygenation in the marginal seas such as the Nanhua Basin. These epicratonic seas with dynamic redox variations might promote the ecological revolution during the interglacial period immediately after the Sturtian glaciation.

Phosphorus mobilization in sulfidic sediments in the Baltic Sea

It is well-known that the geochemical behavior of phosphorus (P) in sediments is closely related to that of Fe and Mn, but their relations remain unclear in long-term sulfidic sediments such as those of the Gotland Basin in the Baltic Sea. Therefore, P mobilization in these sediments at both shallow and deep sites was investigated in relation to that of Fe, Mn, and S. To achieve that aim, classic sediment slicing and subsequent solid phase sequential extraction were combined with in situ DGT (Diffusive Gradients in Thin-films) sampling, DIFS (DGT induced flux in sediments) modelling, and Visual MINTEQ calculations. Correlations between total dissolved and labile dissolved concentrations of P, Mn, and Fe in porewater, and the associations between labile fractions of these elements in the solid phase suggested two kinds of sources for P: The dissolution of P-bearing Fe oxides and/or Mn carbonates was observed in the shallower sites, while P and Mn release from different solid sources was observed in the deepest sites. Although the formation of Fe sulfides leads to extremely low dissolved Fe level in porewater, the simultaneous release of P with Mn/Fe was confirmed by theoretical calculations with Visual MINTEQ. The DIFS model showed that the resupply ability of P from sediment solids is determined by labile pool size. The application of experimental and theoretical methods made it possible to clarify the relationships between P, Fe, Mn and S in sulfidic sediments which may contribute to a better understanding of the P cycle in other sulfidic regions.

Carbonate-hosted manganese deposits and ocean anoxia

Late Devonian (ca. 360 Ma), Early Carboniferous (ca. 330 Ma), and Early Triassic (ca. 250 Ma) manganese deposits in the South China Block support an emerging view that some Mn carbonates form through direct synsedimentary (authigenic) precipitation. These Mn carbonates accumulated on distal shelves and are interbedded with lime mudstone and heterozoan carbonates that accumulated in coastal upwelling environments. Lithofacies, Ce anomalies combined with vanadium, uranium, and molybdenum enrichments indicate that the Mn carbonates were primarily precipitated under anoxic conditions. We provide a robust dataset to clarify the precipitation pathway of these Mn carbonates and explore the implications of using them as proxies of regional shallow water and deep-ocean anoxia. In the studied deposits, Mn calcite encases dolomite rhombs (<10 μm) or aggregates, indicating heterogenous nucleation, which is supported by similar lattice parameters of both minerals with a small lattice mismatch (<2.1%). The presence of micro-sized euhedral rhombs and subhedral aggregates of rhombs, the non-stoichiometric compositions, and characteristic organic matter Raman spectroscopy peaks near the D and G bands in the dolomite nuclei suggest an organogenic origin. Authigenic organogenic dolomite precipitation is interpreted to have preconditioned the sediment with nucleation sites for the subsequent precipitation of Mn carbonates in the shallow seafloor. This is consistent with δ13C values (−2.61‰) of Mn carbonate bulk samples that are slightly lower than coeval seawater (0.31‰, from host rocks), suggesting incorporation of 12C during microbial respiration of sedimentary organic matter during the precipitation of organogenic dolomite and hydrothermal sourced inorganic carbon. The absence of Mn in shallow facies suggests terrestrial input of Mn was minimal. Geochemical and sedimentologic evidence suggests that coastal upwelling delivered manganous anoxic deep waters to the shelves. Eu/Eu⁎ ratios (<1.5) and decoupling of Fe and Mn imply long-range transport of hydrothermal Mn, during which hydrothermal fingerprints were muted through mixing with ambient seawater. The transport of hydrothermal Mn to shelves indicates that the regional deep oceans at the time must have been anoxic, as Mn2+ would be easily oxidized and become insoluble under oxygen-rich conditions, preventing its long-distance transport. This precipitation pathway and depositional model implies that Mn carbonates are a largely unrecognized proxy for tracking ancient oceanic redox fluctuations, particularly during times of well-oxygenated global oceans. Hence, these Mn deposits record at least transient regional deep-ocean oxygen depletion in the generally well-oxygenated Late Paleozoic and Early Triassic oceans. The recognition that this periodic anoxia was broadly coeval with the anoxia-related Hangenberg, Serpukhovian, and Permian-Triassic biotic crises suggests a potential relationship between Mn carbonate accumulation and extinction events.

Geochemistry of Cryogenian Datangpo manganese deposits in the southeastern Yangtze Platform of South China: implications for the origin of metallogenesis and depositional environment

ABSTRACT Sedimentary manganese (Mn) deposits in the southeastern Yangtze Platform of China have been newly discovered with considerable potential for resource exploration. Such deposits formed due to dynamic changes in the global environment, including the break-up of the supercontinent Rodinia, Snowball Earth glaciation, and the Neoproterozoic Oxygenation Event. The Mn-bearing sequences are hosted in the basal Datangpo Formation and are interbedded with black carbonaceous shale in a series of graben sub-basins in the Nanhua Rift Basin. We investigated the origin of these Mn deposits by analysing the major and trace elements, total organic carbon, and stable carbon and oxygen isotopes. Positive Eu anomalies were observed, indicating that the Mn was derived from a hydrothermal system. Redox-related elements, including Ce, Mo, U, V, S, and P, indicated that the depositional environment of the Mn layers was oxidative and that Mn2+ was initially oxidized to Mn oxides. However, the host rock (i.e. black carbonaceous shale) was deposited under dysoxic – anoxic and even sulfidic water conditions. The alternating distribution of Mn ore and host rock suggested alternating redox conditions in the sub-basins. A negative correlation between the Mn content and δ 13Ccarb values (−10‰–−7‰) and a deficiency of sulphide minerals indicate that the diagenetic degradation of organic matter (δ 13Corg from − 34‰ to − 31.9‰) took place through Mn oxide reduction rather than microbial sulphate reduction and can contribute to a considerable source of bicarbonates. The approximately homogeneous δ 13Ccarb depletion and their apparent discrepancy with δ 13Corg indicate that the post-depositional genesis of the Mn carbonate ore occurred in a relatively open early diagenetic pore water system with a considerable contribution from seawater-derived carbon sources.

Revisiting the multipath elimination of contaminants by carbonyl-containing manganese-carbon composites in the peroxymonosulfate system: A new way of constructing C-Mn-PMS complexes to distinguish the stages of active species production

The use of value-added effects of composite catalysts to enhance the practical application of peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) has been one of the hot topics in the field of environmental remediation. However, the complex structure of the composite catalyst/PMS systems has hindered the exploration of the origin and generation stages of active species. To clarify the relationship between active sites and active species, Mn carbon-based composite/PMS systems with structured active sites were constructed to achieve an effective strategy for organic conversion. This paper investigates the correlation between C = O-Mn and reactive species generation by developing Mn carbon composites with structured active sites (C = O) to activate PMS for the degradation of TCH. Additionally, a pre-oxidation experiment was proposed to divide the whole catalytic degradation process into two stages: oxidation and degradation. The results show that the C = O–Mn–PMS composite intermediate can still effectively degrade Tetracycline after being separated from the solution. The study also revealed the structure–function relationship of different active sites in the C = O-Mn catalyst was revealed by density functional theory (DFT) calculations. The Mn-O, Mn-O-Mn and C = O structures achieved efficient utilization of PMS and rapid degradation of TCH through the adsorption of PMS and single electron transfer generation SO4−, OH, O2−, 1O2. This paper provides new ideas for the reaction mechanism and rational design of catalysts based on the Mn-carbon composite/PMS system.

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

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

Co-existing two distinct formation mechanisms of micro-scale ooid-like manganese carbonates hosted in Cryogenian organic-rich black shales in South China

Manganese-rich deposits in the lower member of the Datangpo Formation (DTP) (ca. 663–654 Ma) in South China formed in the aftermath of the Cryogenian Sturtian glaciation. The Mn in the DTP occurs dominantly as rhodochrosite and Ca-rhodochrosite. A hydrothermal origin of the Mn2+ is shown by the rare earth element distribution and significantly high Mn/Fe ratios (3–19, average = 10.1). Previous studies suggested a microbially-mediated process for controlling the DTP black-shale hosted Mn carbonate deposits. However, detailed reports on the formation mechanisms of micro-scale (<2–5 μm) ooid-like Mn carbonates in the DTP have rarely been published. Systematic petrography and geochemical analyses in this study demonstrate the coexistence of two types of micro-scale ooidal-like Mn carbonates formed through two distinct mechanisms, either dominated by microbially-mediated or physiochemically-forced pathways. The Type I Mn carbonate has relatively larger grain size of 2–5 μm and exhibits a radial-concentric microfabric that shows signs of growth banding in the form of alternating light and dark laminae, which mainly express variation in Ca and Mn concentrations. The initial precipitation phase of the Type I Mn carbonate is interpreted to be Mn oxide/hydroxide, based on positive Ce anomalies and selective enrichments of particular trace elements. Novel evidence indicates that the capture of Mn as a carbonate phase directly from the water column by primarily precipitated calcite, which is referred to as the Type II Mn carbonate, has also contributed to the DTP Mn-rich deposits. Multiple roles of organic matter in Mn carbonate formation have been established: (1) catalysed Mn-redox cycling; (2) trapping and transportation of initial mineral precipitates to sediments; (3) serving as a carbon source; (4) regulating the morphology of the Mn carbonate. As a key link for understanding Cryogenian carbon and Mn cycling, specific formation pathways for the DTP Mn-carbonates are likely to have been controlled by given atmospheric-oceanic compositions (including oxygen level, pCO2, and redox conditions) in response to major geological and biological events during the interglacial period. In turn, massive storage of inorganic carbon and phosphorous in Mn carbonate phases would have had a substantial influence on biogeochemical carbon cycling during the Cryogenian.

Sedimentary Mn Metallogenesis and Coupling among Major Geo-Environmental Events during the Sturtian Glacial–Interglacial Transition

The Sturtian (720–670 Ma) glacial–interglacial transition period was an important interval for sedimentary manganese metallogenesis, including the Mn oxide deposit in the Otjosondu region in Namibia and Mn carbonate deposits in the Datangpo Formation in the south-eastern Yangtze Platform, South China. During this period, Earth experienced the breakup of Rodinia, the Sturtian glaciation, and the Neoproterozoic oxygenation event. In this study, we investigate scenarios that might have provided geologically and geochemically favorable conditions for Mn metallogenesis. In these scenarios, the global recovery of microorganisms enhanced marine primary productivity and O2 levels of the hydrosphere and atmosphere during the Sturtian glacial–interglacial transition. However, the water column was not completely oxidized, maintaining redox stratification. Transgression–regression cycles or O2-rich downwelling drove the exchange of oxygenated topwater and anoxic deep water in rift-related basins that developed due to Rodinia’s breakup. The coupling of these processes precipitated existing dissolved Mn(II) at the margins of basins (Otjosondu region) or at their centers (Yangtze Platform). In the latter case, precursor Mn oxides were further converted into Mn carbonates via the reduction of Mn oxides coupled with organic matter oxidation during early diagenesis. A brief review of Mn metallogenesis in the geological record reveals that Mn metallogenic processes typically occur under geo-environmental conditions that, in concert, produce favorable conditions for Mn sourcing, concentration, and sedimentation.

Episodic ventilation of euxinic bottom waters triggers the formation of black shale-hosted Mn carbonate deposits

Many manganese (Mn) carbonate deposits over geologic history are often closely associated with black shales. However, the mechanism(s) by which the Mn entered the sediments remains controversial because on one hand oxygenated waters are required for primary Mn(IV) oxide formation but on the other hand black shales generally form under reducing conditions. China hosts some of the world’s largest black shale-hosted Mn deposits, for example, the Carboniferous Ortokarnash and Malkantu Mn deposits in the Malkansu region, offering a good opportunity to revisit the genesis of black shale-hosted Mn carbonate deposits. Here, we present the first coupled, systematic paleoredox and hydrographic reconstruction of those deposits with the aim of elucidating the redox-state of the depositional basin at the time of their initial deposition. The Mn ore beds in this region are hosted within laminated, organic-rich mudstones (i.e., black shales) reflective of a relatively deep-water depositional environment. The Mn ores are comprised of the Mn(II) carbonate minerals (rhodochrosite and Ca-rhodochrosite), with minor alabandite, pyrite, and monazite. Multiple independent lines of evidence, including positive shale-normalized Ce anomalies (average 3.0), negative δ13CVPDB values (average −11.55 ‰), and negative δ98MoNIST+0.25 values (average −1.07 ‰), indicate that the Mn(II) carbonate ores were formed during diagenesis via the coupled oxidation of organic matter and reduction of Mn(IV) oxides originally deposited from an oxygenated water column. However, in apparent contradiction, highly reactive iron to total iron (FeHR/FeT; average 0.66) and pyrite iron to highly reactive iron (FePy/FeHR; average 0.71) ratios, combined with a high abundance of small framboidal pyrites (mean diameter ∼5 μm) with narrow size ranges (standard deviations <2 μm), suggest that the associated black shales were deposited in euxinic (H2S-bearing) bottom waters. Euxinia resulted from sluggish water mass circulation, with sedimentary Mo/TOC ratios indicating a relatively strong hydrologic restriction. During this stage, dissolved Mn(II) would have accumulated in euxinic waters but not become permanently fixed into sediments, as indicated by higher degrees of enrichment for Mo over U and lower Mo isotope values than coeval seawater recorded in the black shales. These reveal an active Mn(IV) oxide shuttle across a redox-stratified water column. Combined, the Mn ore intervals document sharp benthic oxygenation of euxinic bottom waters, a process that might be induced by the periodic incursions of oxic seawater associated with eustatic sea level rises. This model is supported by the Mo isotopic characteristics of the Mn carbonate ores, which indicate original Mn oxide precipitation from an overlying water with Mo isotopic composition close to coeval open seawater (minimum δ98MoNIST+0.25 of 1.9 ‰). In contrast to the generalized “bathtub ring” model envisaging that the black shale-hosted Mn deposits were formed at shallow basin margins, our results highlight that they were more likely formed by in-situ ventilation of anoxic (especially euxinic) deep waters of basin center settings. In this regard, we suggest that the ventilation model better explains the close association of Mn carbonate ores with black shales, and has profound implications for understanding the paleoredox framework of otherwise Mn-rich black shale successions.

Microbially-mediated Mn redox cycling and Mn carbonate precipitation in the Marinoan glacial aftermath, South China

Carbonate-type Mn deposits developed at the top of the Ediacaran Doushantuo Formation (Marinoan glacial aftermath) along the northern margin of the Yangtze Block, South China, provide an exceptional opportunity to study Mn redox cycling in deep time, which remains a controversial topic of Mn biogeochemistry. To address this issue, here we conduct integrated petrological and geochemical work. Results show that Mn oxidizing microorganisms may fix CO2 into organic matter by oxidizing Mn(II). This process provides energy for metabolism of the microorganisms under obligatory oxidation conditions in natural geological environments. At the same time, Mn(II) is oxidized to unstable todorokite, with accompanying Co and Ce oxidation and enrichment. Under suboxic conditions, heterotrophic Mn-reducing bacteria use organic matter as an electron donor and Mn bio-oxide as a terminal electron acceptor to generate Mn(II) and 12C-rich dissolved inorganic carbon (DIC; carbonate and/or bicarbonate). Furthermore, microorganisms and macroalgae also provide nucleation sites for the precipitation of Mn carbonate minerals with structures consistent with microbially precipitated carbonates. Spherical and ellipsoidal Ca-rich rhodochrosite was formed in the syngenetic stage and cemented by Mg-rich kutnohorite in the early diagenetic stage. Microorganisms thus play an important role in Mn redox cycling and precipitation of Mn carbonate minerals, in a possibly universal phenomenon in geological evolution. The bloom of microorganisms and associated formation of mineral deposits may be a general phenomenon in the aftermath of a glaciation.

Mesoproterozoic surface oxygenation accompanied major sedimentary manganese deposition at 1.4 and 1.1Ga.

Manganese (Mn) oxidation in marine environments requires oxygen (O2 ) or other reactive oxygen species in the water column, and widespread Mn oxide deposition in ancient sedimentary rocks has long been used as a proxy for oxidation. The oxygenation of Earth's atmosphere and oceans across the Archean-Proterozoic boundary are associated with massive Mn deposits, whereas the interval from 1.8-1.0Ga is generally believed to be a time of low atmospheric oxygen with an apparent hiatus in sedimentary Mn deposition. Here, we report geochemical and mineralogical analyses from 1.1Ga manganiferous marine-shelf siltstones from the Bangemall Supergroup, Western Australia, which underlie recently discovered economically significant manganese deposits. Layers bearing Mn carbonate microspheres, comparable with major global Mn deposits, reveal that intense periods of sedimentary Mn deposition occurred in the late Mesoproterozoic. Iron geochemical data suggest anoxic-ferruginous seafloor conditions at the onset of Mn deposition, followed by oxic conditions in the water column as Mn deposition persisted and eventually ceased. These data imply there was spatially widespread surface oxygenation ~1.1Ga with sufficiently oxic conditions in shelf environments to oxidize marine Mn(II). Comparable large stratiform Mn carbonate deposits also occur in ~1.4Ga marine siltstones hosted in underlying sedimentary units. These deposits are greater or at least commensurate in scale (tonnage) to those that followed the major oxygenation transitions from the Neoproterozoic. Such a period of sedimentary manganogenesis is inconsistent with a model of persistently low O2 throughout the entirety of the Mesoproterozoic and provides robust evidence for dynamic redox changes in the mid to late Mesoproterozoic.

Photoactivatable properties of water-soluble fac-Mn(CO)3 bearing N∧O bidentate pyridine ligands

Two water-soluble fac-Mn(CO)3 based complexes of the general formula fac-[MnBr(CO)3(N∧O)] (N∧O = pyridine-2-carboxaldehyde (A), and 2-acetylpyridine (B)) were described for their potential CO releasing properties upon illumination at 468 nm, solvatochromism features and cytotoxicity against different malignant cell lines in both the dark and upon the exposure to light source. Negative solvatochromism may be responsible for the red shift of the metal-to-ligand charge transfer band in increasingly less polar solvents. Compound B, which had been functionalized with 2-acetylpyridine, released CO in water faster than complex A, suggesting the role of the methyl group in regulating the CO release kinetics. According to myoglobin assay, the CO release pathway in water is slower than in DMSO revealing to the role of the solvent in controlling the CO release kinetics of Mn(I) carbon monoxide releasing molecules.