Oxidation and Mineralization of Mn2+ Ions Mediated by Pseudomonas putida: Insights from an Experimental Study

The formation of manganese oxides in nature is commonly mediated by microorganisms.In this study,the mineralization of biogenic manganese oxidation mediated by Pseudomanas putida has been experimentally investigated by employing various characterization techniques,including SEM,FESEM,TEM,XRD,and STXM-NEXAFS.The results indicate that Mn~(2+) ions can be oxidized into Mn(Ⅳ) minerals(birnessite and pyrolusite) and Mn(Ⅲ) minerals(hausmannite and feitknechtite),successively.The primary products(birnessite and pyrolusite) further transformed into hausmannite and feitknechtite under Mn~(2+) ion-enriched conditions.However,birnessite and pyrolusite are the endproducts of the continuous microbial oxidation processes.These biogenic Mn oxides are poorly crystallized,which provides them with a high potential for usage in environmental restoration of contaminated soils and waters contaminated with heavy metals.The approaches employed in this study will also enrich genesis research of biological oxidation of Mn(Ⅱ) species in nature.     

Electron Microscopic Study of Manganese Minerals in the Polymetallic Nodules from the Central Pacific Ocean

Manganese minerals in the polymetallic nodules from the Central Pacific Ocean were studied using electron microscopy. The principal Mn minerals, being vernadite and todorokite, exhibit different electron diffraction patterns and morphological features. According to its morphological feature, todorokite shows three phases: fibrous, lamellar and lath-shaped. Both vernadite and todorokite are authigenic minerals. While vernadite was mainly precipitated directly from the relevant solution by microbiological oxidation, todorokite was separated from the solution chemically without the help of microbe. Hence, these two minerals show a close genetic relation.     

A Study of Chromium Adsorption on Natural Goethite Biomineralized with Iron Bacteria

Goethite, especially biogenic goethite, has high specific surface area and great capacity for the adsorption of many contaminants including metal ions and organic chelates. Chromium is a redox actively toxic metal ion that exists as either Cr^Ⅲ or Cr^Ⅵ in nature, and as such it is essential to understand its behavior of adsorption on natural goethite mineralized by iron bacteria, as Gallionella and Leptothrix in water body. The adsorption of Cr^3＋ and Cr^Ⅵ on naturally biomineralized goethite is studied in this paper. The results show that both Langmuir and Freundlich adsorption isothermal models are able to accurately describe the adsorption of these two ions. Investigation of SEM/EDS, TEM/EDS indicates that the two ions do not adsorb homogeneously on goethite owing to the different microstructures of goethite, and that the microspherical goethite has a greater adsorption capacity for chromium ions than the helical one. XPS data show that redox reaction of chromium on the surface of biomineralized goethite takes place in the adsorption of both Cr^3＋ and Cr^Ⅵ. The CrvI adsorbed on biogoethite is much easier to transform into CrIII than the oxidization of Cr^Ⅲ on the bio-goethite.     

Adsorption and stabilization of organic carbon by mineral surfaces in soils

Soils are the largest carbon reservoir in the terrestrial system. Soils contain about three times more carbon than vegetation and twice as much as that present in the atmosphere. Soil organic matter （SOM） is very complex in composition and structure, formed of heterogeneous substances and generally associated with minerals in soils. SOM is classified as labile and stable fractions on the basis of residence time, determined not only by the chemical composition of SOM, but also by types of protection or bonds within soils. The stable carbon fraction is protected either physically or chemically. To understand the process of SOM stabilization, physicochemical properties of organic-mineral complexes were determined by Fourier transformed infrared （FTIR） with attenuated total reflectance （ATR） and diffuse reflectance （DRIFT）, atomic force microscopy （AFM）, and nuclear magnetic spectroscopy （NMR）. Humic acids and carboxylic acids with relatively short carbon chains were used as sorbates, and goethite, kaolinite, and montmorillonite as adsorbents. Humic acid was fractionated during adsorption on the minerals, which was highly influenced by the characteristics of minerals. For instance, long-chain aliphatic carbon was likely to be adsorbed onto the surface of kaolinite and montmorillonite, while goethite surface attracted carboxylic functional groups of humic acid.     

Characteristics and genesis of hematite in Chinese loess and paleosol sequences： Mineral genetic restriction for magnetic susceptibility as paleoclimate proxy and iron geochemistry

Hematite is an important iron oxide mineral in loess-paleosol sequences in central China. Investigation of the mineralogical characteristics, genetic mechanism and relationship of hematite with other iron oxides and Fe-bearing minerals will help understand the geochemical process before and after eolian deposit, paleocliamte significance of magnetic susceptibility and reconstruct paleoclimate in central China. So, hematite and related minerals of the loess and paleosol units from Chinese Loess Plateau were investigated using optical microscope, X-ray powder diffraction （XRD）, scanning electron microscopy （SEM）, and high-resolution transmission microscopy （HRTEM）. The results show that there are five genetic types of hematite in loess-paleosol sequences of central China： （1） weathering of Fe-bearing silicate minerals, for instance, chlorite, will release iron that is precipitated as aggregates of hematite nano-crystals on mineral surfaces; （2） hematite combined with eolian magnetite grains that resulted from partial oxidation of magnetite, even though the partial oxidation may occur in the original area; （3） phase transformation from eolian goethite to hematite; （4） hematite formed on the edge and surface of maghemite because of dissolution and hematite recrystallization; and （5） eolian detrial hematite. The hematite formed from chemical weathering of Fe-bearing silicates with nanoporous texture because of dehydration from iron hydroxide is the most important genetic mechanism. It is proposed that the fact that hematite was formed from chemical weathering of Fe-bearing silicates is a main reason for the redness in paleosol units. However, too intense pedogenesis and high amounts of precipitation will promote oxidation of eolian magnetite and maghemite dissolution, which may result in the decreasing of magnetic susceptibility.     

Ferruginous Microspherules in Bauxite at Maochang, Guizhou Province, China： Products of Microbe-Pyrite Interaction？

The Maochang bauxite in Guizhou Province is one of the important aluminum ore deposits in southwestern China. Ferruginous spherules, measuring about a few microns across, were found in the transitional layer of the deposit. The EDS and XRD results show that the microspherules are composed mostly of iron （hydr）oxide minerals （goethite） with only weak presence of aluminum and silicon. Occasionally, some pyrite micrograins with dissolved surface are found associated with goethite within the spherules. It is thus suggested that microspherules are linked to pyrite oxidization. It is also thought that microbial activities contribute not only to pyrite oxidization, but also to ball-like assemblage of the iron （hydr）oxides. The mechanism of the formation of ferruginous microspherules is also believed to be important in studying geomicrobiology of bauxite.     

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

Comparison of components and distribution of heavy metals in sediments, suspended particulate matter and surface coatings in natural waters

Solid phases, such as surface coatings （SC）, suspended particulate matter （SPM） and deposited sediments （DS）, contribute to the pool of heavy metals in natural waters. Their existing and forming conditions lead to potential differences in enrichment capacity of pollutants, chemical compositions and crystals. In this study, the contents of heavy metals in SC, SPM and DS were determined by GF-AAS after digestion with a mixture of concentrated HNO3 and HClO4. The selective extraction method was employed to remove Fe, Mn oxides and organic matters and associated heavy metals （Cu, Pb, Zn）. X-ray diffraction analyses were performed to characterize the crystals in the samples. The results showed that no significant difference in the contents of Fe-oxides in DS, SPM and SC was found, but the contents of Mn-oxides and organic matter follow the order of SC〉SPM〉DS. The significant crystal characters were observed in DS, SPM and SC, and the kinds of minerals and crystallization degree follow the order of DS〉SC〉SPM. In addition, quartz was the most important matter of crystals in the solid phases. Enrichment capacity follows the order of SPM〉SC〉DS for Pb, Cu and Zn. Organic matter was the major sorbent for Cu, and Mn oxides and organic matter played an important role in the enrichment of Zn. However, Pb was absorbed mainly by Fe oxides. Moreover, compared with Fe oxides and organic matter, Mn oxides had a great enrichment capacity for these metals. Although DS, SPM and SC were formed in the same water system, contents of chemical components, crystals and enrichment capacities to heavy metals were obviously different.     

Natural mineral photoelectric effect: mineral non-classical photosynthesis

Under the ever-present solar radiation, photosynthetic organisms on Earth evolved structurally-sophisticated photosynthetic systems. However, little attention has been paid to the inherent impact of sunlight illumination on the inorganic minerals widespread on the Earth surface. We discovered for the first time the solar energy conversion system of the “mineral coatings” on the Earth's surface (aka“mineral membrane”), which exerts potential oxygen-production and carbon-sequestration functions on the Earth surface. Our finding shed a light on the photoelectric effect and non-classical photosynthesis involving natural semiconducting minerals. In this contribution, we studied the semiconducting property and photoelectron energy of typical minerals in the “mineral membrane”, focusing primarily on the photoelectric effect in and oxygen-production/carbon-sequestration function of ferromanganese oxides, as well as relevant geological records. We propose that birnessite, goethite and hematite, the semiconducting minerals commonly found in the “mineral membrane”, can perform sensitive and stable photon-to-electron conversion under solar radiation. The non-classical mineral photosynthetic function we put forth is as follows: Solar energy utilization by inorganic minerals resembles photosynthesis in regarding to oxygen evolution and carbon fixing, and the “mineral membrane” may take part in both photocatalytic water-oxidation reaction and transformation of atmospheric CO₂into marine carbonate. In addition, minerals might as well have promoted photosynthesis in photosynthetic organisms. During the water-oxidation reaction, the inorganic cluster Mn₄CaO₅of photosystem II cycles through redox intermediates that are analogous to birnessite both in structure and component. Thus, it is fair to postulate that birnessites could play a role in the initiation of the photosynthesis in cyanobacteria, as minerals could weaken the hydrogen bond strength and alter water properties, thus facilitating water oxidation and photosynthesis. This observation offers further insights into the molecular mechanism of mineral participation in photosynthesis in photosynthetic organisms.     

Forms of Iron in the Phosphorites of Abu—Tartur Area,Egypt

The Campanian-Maastrichtian phosphatic deposits in Egypt,called the Duwi Forma-tion,comprise a part of the extensive Middle East to North African phosphogenic province of Late Cretaceous to Paleogene age.The province holds the greatest accumulation of phosphorites in the geological history,possibly in excess of 70 billion metric tons.The phosphate resources in Egypt alone exceed 3 billion metric tons.Two-third of these three billions occur only in the Abu-Tartur area.Among the phosphorite deposits in Egypt,the phosphorites of the Abu-Tartur area are characterized by high contents of iron ranging from 3% to 7% with an average of 5%.The detailed mineralogical and geochemical studies on the Abu-Tartur phosphorites revealed that iron is found in the form of pyrite,ankerite,clay minerals,microinclusions,and iron oxide.Pyrite,which is the major fraction,occurs as filling cement and partial to complete teplacement of phosphatic grains and confined to the fresh phosphorites while iron oxide occurs as cryp-tocrystalline aggregates of red to brown particles and is confined to the weathered outcrops.Ex-clusive relations between pyrite in the fresh phosphorite samples inside the Abu-Tartur mine and iron oxide in the equivalent horizon of the weathered exposure indicated that iron oxide was formed by the oxidation of pyrite as a result of weathering.All of these forms harm the quality of ore,manufacturing processes,and the produced phosphoric acid and fertilizers.     

模拟表生环境水钠锰矿亚结构转化及钙锰矿的形成

水钠锰矿是土壤与沉积物中最为常见的氧化锰矿物, 依据其MnO₆层对称特点分为六方和三斜两种亚结构类型.六方水钠锰矿在表生环境中可通过Mn2+的化学或生物氧化形成, 而环境中三斜水钠锰矿的形成及进一步转化为钙锰矿的途径尚不清楚.以两种六方水钠锰矿(酸性水钠锰矿和水羟锰矿)为前驱物, 采用X射线吸收光谱(EXAFS)、X射线衍射(XRD)、电镜(FESEM/TEM)及化学组成分析等技术方法模拟表生环境研究了水钠锰矿从六方向三斜的亚结构转化及生成钙锰矿的化学条件和矿物学机制.结果表明, 适当Mn(Ⅱ)浓度和弱碱性条件(pH≥8)可使六方水钠锰矿逐渐转化为三斜水钠锰矿, 继而经Mg2+交换、常压回流得到了长纤维状的钙锰矿, 其晶体生长以溶解-结晶为主.Mn(Ⅱ)与六方水钠锰矿MnO₆八面体层内的Mn(Ⅳ)反应生成Mn(Ⅲ)并填充层内空位, 使水钠锰矿对称型由六方向三斜转变.与酸性水钠锰矿相比, 水羟锰矿结晶弱、层状堆积混乱度高, 与Mn(Ⅱ)反应迅速, 层结构向三斜水钠锰矿转化快.pH升高, 促进六方水钠锰矿对Mn(Ⅱ)的吸附和Mn(Ⅱ)与Mn(Ⅳ)间的反应, 六方水钠锰矿转化为三斜水钠锰矿的速率加快."六方水钠锰矿→三斜水钠锰矿"可能是环境中三斜水钠锰矿的重要来源, 及进一步形成钙锰矿的重要化学生成机制.      

Manganese-reducing Pseudomonas fluorescens-group bacteria control arsenic mobility in gold mining-contaminated groundwater

Previous studies show the importance of iron- and arsenate-reducing bacteria in mobilizing arsenic in groundwater. Here the authors present experimental evidence of arsenic mobilization in connection with bacterially mediated manganese reduction in groundwater affected by mining activities. Manganese-reducing Pseudomonas species were enriched, isolated and identified by 16S rRNA gene phylogeny from groundwater containing high co-dissolved arsenic (as As^III) and manganese. Enrichment cultures dissolved synthetic birnessite and hausmannite efficiently, but Mn reduction by isolates was reduced at the upper range of environmental levels of dissolved As^III. Results suggest either a self-limiting release of arsenic coupled to bacterial manganese reduction, in the absence of other electron donors like sulfide, or increased arsenic resistance conferred to Mn-reducing bacteria in consortia.     

Ion exchange properties of manganese and iron minerals in oceanic micronodules

The results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules (MN) from diverse bioproductive zones of the World Ocean are considered. It was found that the sorption behavior of these minerals is similar to that of ore minerals from ferromanganese nodules (FMN) and low-temperature hydrothermal crusts. The exchange complex of minerals in the MN includes the major (Na⁺, K⁺, Ca²⁺, Mg²⁺, and Mn²⁺) and the subordinate (Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, and others) cations. Reactivity of theses cations increases from Pb²⁺ and Co²⁺ to Na⁺ and Ca²⁺. Exchange capacity of MN minerals increases from the alkali to heavy metal cations. Capacity of iron and manganese minerals in the oceanic MN increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite Fe-vernadite + Mn-feroxyhyte. The data obtained supplement the available information on the ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in the redistribution of metal cations at the bottom (ooze) water-sediment interface during the MN formation and growth.     

Deposition of deep-sea manganese nodules

Manganese at equilibrium in seawater occurs dominantly as Mn²⁺ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O₂ and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 10⁸ ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn²⁺ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)₃⁰ and Fe(OH)₄^?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)₃.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.     

MnO2-UV联用光化学降解苯酚废水的初步研究

探讨了人工合成的高价锰氧化物与紫外光(UV)联用时降解苯酚废水的特性。结果表明,氧化锰矿物在无UV时对苯酚的降解能力差异大,1 g/L的氧化锰4 h对200 mg/L苯酚废水的降解率和COD去除率分别为:锰钾矿97.51%、酸性水钠锰矿89.07%、碱性水钠锰矿11.36%、钙锰矿9.67%;锰钾矿87.79%、酸性水钠锰矿53.11%、碱性水钠锰矿6.42%、钙锰矿1.43%。UV光照下,氧化锰矿物对苯酚的降解率有不同程度的提高,且表现出显著的表面光催化性质,增加了苯酚的深度降解,COD去除率显著提高。UV下氧化锰4 h对苯酚的降解率分别为:锰钾矿99.48%、酸性水钠锰矿91.86%、碱性水钠锰矿40.15%、钙锰矿35.95%);COD的去除率分别为:锰钾矿98.11%、酸性水钠锰矿68.45%、钙锰矿27.57%、碱性水钠锰矿24.27%。MnO2-UV联用时降解苯酚可能包括两种主要作用机制:氧化锰矿物的直接化学氧化降解和UV下MnO2的表面光催化降解。     

Manganese oxide mineralogy,petrography and genesis,Pilbara Manganese Group,Western Australia

Supergene manganese oxides, occurring in shales, breccias and dolomites of Proterozoic Age, in the Western Australian Pilbara Manganese Group, have Mn/Fe ranging from 1.9 to 254 and Mn⁴⁺ to Mn (Total) of 0.49–0.94. The manganese mineralogy is dominated by tetravalent manganese oxides, especially by cryptomelane, with lesser amounts of pyrolusite, nsutite, manjiroite, romanechite and other manganese oxide minerals. The manganese minerals are commonly associated with iron oxides, chiefly goethite, indicating incomplete separation of Mn from Fe during Tertiary Age arid climate weathering of older, manganiferous formations. These manganese oxides also contain variable amounts of braunite and very minor hausmannite and bixbyite. The braunite occurs in three generations: sedimentary-diagenetic, recrystallised sedimentary-diagenetic, and supergene. The mode of origin of the hausmannite and bixbyite is uncertain but it is possible that they resulted from diagenesis and/or low-grade regional metamorphism. The supergene manganese deposits appear to have been derived from manganiferous Lower Proterozoic banded iron formations and dolomites of the Hamersley Basin and overlying Middle Proterozoic Bangemali Basin braunite-containing sediments.     

Composition and characteristics of the ferromanganese crusts from the western Arctic Ocean

Layered ferromanganese crusts collected by dredge from a water depth range of 2770 to 2200 m on Mendeleev Ridge, Arctic Ocean, were analyzed for mineralogical and chemical compositions and dated using the excess ²³⁰Th technique. Comparison with crusts from other oceans reveals that Fe-Mn deposits of Mendeleev Ridge have the highest Fe/Mn ratios, are depleted in Mn, Co, and Ni, and enriched in Si and Al as well as some minor elements, Li, Th, Sc, As and V. However, the upper layer of the crusts shows Mn, Co, and Ni contents comparable to crusts from the Atlantic and Indian Oceans. Growth rates vary from 3.03 to 3.97 mm/Myr measured on the uppermost 2 mm. Mn and Fe oxyhydroxides (vernadite, ferroxyhyte, birnessite, todorokite and goethite) and nonmetalliferous detrital minerals characterize the Arctic crusts. Temporal changes in crust composition reflect changes in the depositional environment. Crust formation was dominated by three main processes: precipitation of Fe-Mn oxyhydroxides from ambient ocean water, sorption of metals by those Fe and Mn phases, and fluctuating but large inputs of terrigenous debris.     

The formation of todorokite and birnessite in sea water pumped from under ground

Manganese oxides precipitated from aerated well sea water at the Marine Science Museum, Tokai University, have been analyzed chemically and mineralogically. The $\text{O}\text{Mn}$ ratios are lower in todorokite than in birnessite but these minerals have similar contents of minor transition metals, which can be taken up additionally from sea water after the precipitation of Mn oxides. On the basis of these results, the genesis of Mn minerals is discussed in relation to marine Mn nodules.     

Fe-Mn oxide indications in the feeder and mound zone of the Jurassic Mn-carbonate ore deposit, Úrkút,Hungary

The Úrkút manganese deposit, one of the World's largest, is located in the central part of the Transdanubian Range, western Hungary. The deposit is interbedded with Mesozoic limemarlstone. The Fe-Mn-oxide indications of a feeder and mound zone embedded in limemarlstone at the footwall of the Mn-carbonate ore deposit were studied using 45 samples (Úrkút Mine, Shaft III, deep level). Microstructural and textural (optical microscopy, SEM-EDS) observations, mineralogy (XRD-μXRD), and geochemistry (ICP, C and O by IR-MS) were used to characterize the host marlstone and the Fe-Mn oxides of the feeder and mound zone. High-resolution in situ and bulk organic matter analyses were performed for the first time using GC–MS, FTIR-ATR, and Raman spectroscopy. Stromatolite-like, filamentous and coccoid microstuctures built up of Fe-Mn-oxides (ferrihydrite, goethite, manganite, pyrolusite, hollandite, birnessite, hausmannite) and silica occur in the micritic marlstone host rock among common calcite biodebris (microfossils and Echinozoa fragments) and rare detrital clasts (quartz, feldspar). The clay minerals occur as greenish patches in the limemarlstone and show boring traces. The calcite matrix of the limemarlstone and idiomorphic dolomite are authigenic. δ¹³C_PDB values of the carbonate in the host limemarlstone reflect greater organic matter contributions approaching the mineralized areas (0.64 to − 21.35‰). Temperature calculation based on δ¹⁸O_SMOW values of the carbonate, assuming equilibrium conditions, show elevated temperatures toward the mineralized areas (9.93 to 29.87‰). In places, the Mn oxides appear with Fe oxides in laminated, micro-stromatolite-like structures. In these oxide zones, variable kinds of organic compounds occur as intercalated microlaminae identified by FTIR and Raman line-profile analyses as aromatic hydrocarbons. Results indicate that metal-bearing fluids infiltered the unconsolidated micritic limemarl. Fe-oxide enrichment occurred most probably through iron oxidizing microbes under suboxic, neutrophilic conditions, while Mn oxide formed most probably by active surface catalyses. At the sediment/water interface, Fe-Mn-oxide stromatolite mounds (chimneys) formed in rift zones from the discharge of fluids of elevated temperature. The host marl itself may have originated by microbially mediated reactions (clay minerals and calcite micrite).