PseudomonasputidaMnB1氧化分解菱锰矿的实验研究

自然界中,菱锰矿氧化形成锰的氧化物矿物是非常普遍的现象,在菱锰矿被氧化分解发生物相转变的过程中,碳酸 盐溶解和锰的氧化往往同时发生,微生物可能起着催化作用。选取锰氧化模式菌株PseudomonasputidaMnB1和广西梧州菱 锰矿,通过菱锰矿在该细菌作用下发生转变的实验,利用场发射扫描电镜、扫描透射X射线显微成像等分析方法,研究了 矿石表面形貌变化以及锰元素在细胞上的分布特征。结果表明细菌显著促进的菱锰矿的溶解,在此基础上,进一步探讨了 细菌在菱锰矿氧化过程中的贡献,本实验结果丰富了次生锰矿床的微生物成因研究。     

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.     

氧化锰矿物的生物成因及其性质的研究进展

土壤中的氧化锰矿物是原生矿物风化和成土过程的产物,是最具反应活性的一类矿物,决定着环境中许多物质的形态、迁移和转化,在元素生物地球化学循环中起着重要的作用,其形成机制和环境效应备受关注。已有的研究表明,环境中氧化锰的形成与微生物作用紧密相关,微生物作用可使自然环境中的Mn(Ⅱ)氧化速率提高105倍。参与Mn(Ⅱ)氧化的微生物在环境中广泛存在,已知的典型锰氧化细菌分布在变形菌门、放线菌门或厚壁菌门,它们均通过胞外聚合物中的多铜氧化酶来催化氧化Mn(Ⅱ)。细菌氧化Mn(II)成Mn(Ⅳ)是酶催化的两个连续的快速单电子传递过程,Mn(Ⅲ)在溶液中以与酶结合的瞬时中间态出现。生物形成氧化锰的最初形态为层状锰矿物,与δ-MnO2或酸性水钠锰矿很类似,且结晶弱,粒径小,锰氧化度高,结构中的八面体空穴多,因而比化学形成的氧化锰具有更强的吸附、氧化等表面活性。环境中Mn(Ⅱ)微生物氧化及形成的Mn(Ⅲ)中间体与碳、氮、硫等生命元素的地球化学循环的关系令人关注。     

Sorption of ferric iron from ferrioxamine B to synthetic and biogenic layer type manganese oxides

Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe-siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB⁺, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB⁺ at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron-siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.     

Magnesian andesite and basalt from Shodo-Shima Island,southwest Japan,and their bearing on the genesis of calc-alkaline andesites

Calc-alkaline andesites and olivine tholeiitic basalts are widely distributed on Shodo-Shima island, southwest Japan. The Fo content of olivine phenocrysts in the andesite is higher than in the basalt. The primary magma of the andesite, estimated on the basis of the olivine fractional crystallization model, is not basaltic but andesitic. The basalt contains both chromite and titanomagnetite as inclusions in olivine phenocrysts, while only chromite appears in the andesite. The Cr content of chromite in the andesite is higher than in the basalt. These facts again indicate that the andesite cannot be a fractionation product of the basalt, and that andesitic and basaltic primary magmas were generated independently.     

Coupled biotic-abiotic Mn(II) oxidation pathway mediates the formation and structural evolution of biogenic Mn oxides

Manganese (Mn) oxides are among the strongest oxidants and sorbents in the environment, impacting the transport and speciation of metals, cycling of carbon, and flow of electrons within soils and sediments. The oxidation of Mn(II) to Mn(III/IV) oxides has been primarily attributed to biological processes, due in part to the faster rates of bacterial Mn(II) oxidation compared to observed mineral-induced and other abiotic rates. Here we explore the reactivity of biogenic Mn oxides formed by a common marine bacterium (Roseobacter sp. AzwK-3b), which has been previously shown to oxidize Mn(II) via the production of extracellular superoxide. Oxidation of Mn(II) by superoxide results in the formation of highly reactive colloidal birnessite with hexagonal symmetry. The colloidal oxides induce the rapid oxidation of Mn(II), with dramatically accelerated rates in the presence of organics, presumably due to mineral surface-catalyzed organic radical generation. Mn(II) oxidation by the colloids is further accelerated in presence of both organics and light, implicating reactive oxygen species in aiding abiotic oxidation. Indeed, the enhancement of Mn(II) oxidation is negated when the colloids are reacted with Mn(II) in the presence of superoxide dismutase, an enzyme that scavenges the reactive oxygen species (ROS) superoxide. The reactivity of the colloidal phase is short-lived due to the rapid evolution of the birnessite from hexagonal to pseudo-orthogonal symmetry. The secondary particulate triclinic birnessite phase exhibits a distinct lack of Mn(II) oxidation and subsequent Mn oxide formation. Thus, the evolution of initial reactive hexagonal birnessite to non-reactive triclinic birnessite imposes the need for continuous production of new colloidal hexagonal particles for Mn(II) oxidation to be sustained, illustrating an intimate dependency of enzymatic and mineral-based reactions in Mn(II) oxidation. Further, the coupled enzymatic and mineral-induced pathways are linked such that enzymatic formation of Mn oxide is requisite for the mineral-induced pathway to occur. Here, we show that Mn(II) oxidation involves a complex network of abiotic and biotic processes, including enzymatically produced superoxide, mineral catalysis, organic reactions with mineral surfaces, and likely photo-production of ROS. The complexity of coupled reactions involved in Mn(II) oxidation here highlights the need for further investigations of microbially-mediated Mn oxide formation, including identifying the role of Mn oxide surfaces, organics, reactive oxygen species, and light in Mn(II) oxidation and Mn oxide phase evolution.     

Mn2+和Fe3+的致色作用:来自意大利白垩纪远洋红色灰岩的启示

本文首先详细研究了含Mn2 和Fe3 的致色矿物菱锰矿、鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收光谱及其一阶导数谱,鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收一阶导数谱的红光区的吸收谷的位置的变化表明随赤铁矿结晶度的降低,吸收谷由586.4nm移至577.4nm,而菱锰矿展示出了Mn2 的因电子跃迁产生的四个典型吸收及其一阶导数谱上577nm的吸收谷的强度比赤铁矿相应谷的强度低一个数量级,表明其电子跃迁的致色机理与赤铁矿的染色机理完全不同。依据赤铁矿的结晶度和鲕状赤铁矿与大洋红层中赤铁矿的沉积成因相似的原则遴选出鲕状赤铁矿为含Fe3 致色矿物,依据菱锰矿是和方解石具有相似结构且为红色的原则选取菱锰矿为含锰致色矿物,并佐以化学纯氧化镁为基体配制了一系列的含菱锰矿、鲕状赤铁矿和菱锰矿及鲕状赤铁矿的两相或三相混合物。详细研究了三类混合物的可见光吸收光谱的一阶导数谱,发现含菱锰矿和含鲕状赤铁矿在573nm附近均存在一吸收谷,鲕状赤铁矿的重量分数低至0.05%时仍可见一明显吸收谷且该吸收谷移至565nm附近,菱锰矿在低至0.50%时也可见这一吸收且在低至0.11%时仍可显示出菱锰矿的信息,其575nm的吸收峰未见偏移;混合物可见光一阶导数吸收谱上鲕状赤铁矿的575nm附近的吸收谷的强度随鲕状赤铁矿的重量分数的升高而增强,而所有的配制混合物中该吸收谷的位置低于577.4nm的事实也表明为使致色矿物和氧化镁混合均匀的研磨降低了赤铁矿的结晶度。本研究表明Mn2 的电子跃迁激发和细小、结晶差的赤铁矿的染色共同造就了意大利白垩纪远洋红色灰岩的红色。     

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick × 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-Å basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments.     

Geochemistry of an oceanite-ankaramite-basalt suite from East Island,Crozet Archipelago

The petrology and geochemistry of East Island have been investigated for the first time. The island is a deeply dissected remnant of a Pleistocene shield volcano, one of several emerging from an oceanic rise forming part of the southwest branch of the Indian Ocean ridge system. The lavas form a flat-lying sequence of oceanites, ankaramites, olivine basalts and feldsparphyric basalts, the ankaramites containing 1 cm phenocrysts of diopsidic clinopyroxene. X-Ray fluorescence analyses were made of 43 lavas for the major elements plus Cr, Ni, Rb, Sr, Ba, Pb, and Th and the minerals were analysed by electron microprobe. The elements Mg, Cr, and Ni are strongly concentrated in spinel, olivine and clinopyroxene phases and in the ankaramites and oceanite lavas with maximum concentrations of 18% MgO, 1,000 ppm Cr, 380 ppm Ni, while Al, Ti, K, Rb, Ba, Th, Na, P, Sr concentrate in the groundmass and in the feldspathic and aphyric basalts. The elements Si, Ca, Fe and Mn remain virtually constant throughout the series.Correlations of +0.95 or better exist between the concentrations of elements within the two groups given above, and negative correlations between elements in different groups. The fractionation trends are unique with respect to the constant Al/Ti ratio and K/Sr ratio, but all trends may be reproduced by calculating the effect of subtraction of suitable amounts of chromite, olivine and low Ti clinopyroxene from an alkaline olivine basalt parent. Either fractionation has taken place involving these three phases under low pressure conditions or it is the result of different degrees of partial melting of mantle material.A complex magnesian chrome spinel is found in the ankaramites and is often jacketed by a chromian titanomagnetite. A complete series of intermediate compositions appears to exist between the two end members.     

黔东北黑色泥岩盆地含锰岩系的铁锰地球化学特征

黑色泥岩盆地内的菱锰矿矿床中常伴生大量黄铁矿,由于菱锰矿和黄铁矿的沉积过程难以直接观察,铁锰的富集关系尚不明确。为了探讨二者的相互关系,以黔东北西溪堡锰矿的典型剖面为例,根据岩石薄片、TOC分析和元素分析等手段,分析了含锰岩系及其顶底板的岩性序列、矿物组合和铁锰地球化学特征,与现代沉积的菱锰矿进行了对比分析。研究表明,在黄铁矿和菱锰矿富集关系上,西溪堡锰矿与现代波罗的海具有类似特征。含锰岩系顶板和底板的锰含量较低;含锰岩系内部的Mn含量波动很大,与铁含量呈负相关。黄铁矿和菱锰矿的沉淀析出具有先后顺序,通常黄铁矿从溶液中析出在先,菱锰矿沉淀在后。     

西昆仑玛尔坎苏石炭纪大型锰矿带构造背景与成矿条件

西昆仑北段玛尔坎苏地区探明的大型碳酸锰成矿带,是我国近年最重要的找矿成果之一。该锰矿带构造上属北昆仑晚古生代弧后伸展盆地,其构造动力学背景为古特提斯洋向北俯冲于塔里木地块之下形成的弧盆体系。锰矿体主要发育于晚石炭世喀拉阿特河组含炭泥质灰岩夹薄层灰岩中。矿石中主要金属矿物为菱锰矿（75%~95%）,次为软锰矿、硫锰矿及少量黄铁矿等。含锰岩系岩性和岩相学研究表明,玛尔坎苏锰矿带属典型的海相沉积锰矿床,其矿床成因可能与晚古生代半局限盆地沉积和海底热液活动有关。海底热液活动可能为成矿提供了丰富的物质来源。含锰岩系元素和同位素地球化学特征表明,玛尔坎苏锰矿沉淀时的水体环境为常氧条件,而矿层下盘（部分）岩系的岩性及地球化学特征反映其沉积时的水体环境为低氧—贫氧条件。玛尔坎苏锰矿带锰矿石具有负的δ¹³C值（-23.3‰~-10.0‰）,推测有机质导致的还原作用是该锰矿由原生氧化锰在成岩期转化为菱锰矿和形成富锰矿的重要机制。     

Enzymatic microbial Mn(II) oxidation and Mn biooxide production in the Guaymas Basin deep-sea hydrothermal plume

Microorganisms play important roles in mediating biogeochemical reactions in deep-sea hydrothermal plumes, but little is known regarding the mechanisms that underpin these transformations. At Guaymas Basin (GB) in the Gulf of California, hydrothermal vents inject fluids laden with dissolved Mn(II) (dMn) into the deep waters of the basin where it is oxidized and precipitated as particulate Mn(III/IV) oxides, forming turbid hydrothermal “clouds”. Previous studies have predicted extremely short residence times for dMn at GB and suggested they are the result of microbially-mediated Mn(II) oxidation and precipitation. Here we present biogeochemical results that support a central role for microorganisms in driving Mn(II) oxidation in the GB hydrothermal plume, with enzymes being the primary catalytic agent. dMn removal rates at GB are remarkably fast for a deep-sea hydrothermal plume (up to 2 nM/h). These rapid rates were only observed within the plume, not in background deep-sea water above the GB plume or at GB plume depths (∼1750-2000 m) in the neighboring Carmen Basin, where there is no known venting. dMn removal is dramatically inhibited under anoxic conditions and by the presence of the biological poison, sodium azide. A conspicuous temperature optimum of dMn removal rates (∼40 °C) and a saturation-like (i.e. Michaelis-Menten) response to O₂ concentration were observed, indicating an enzymatic mechanism. dMn removal was resistant to heat treatment used to select for spore-forming organisms, but very sensitive to low concentrations of added Cu, a cofactor required by the putative Mn(II)-oxidizing enzyme. Extended X-ray absorption fine structure spectroscopy (EXAFS) and synchrotron radiation-based X-ray diffraction (SR-XRD) revealed the Mn oxides to have a hexagonal birnessite or δ-MnO₂-like mineral structure, indicating that these freshly formed deep-sea Mn oxides are strikingly similar to primary biogenic Mn oxides produced by laboratory cultures of bacteria. Overall, these results reveal a vigorous Mn biogeochemical cycle in the GB hydrothermal plume, where a distinct microbial community enzymatically catalyzes rapid Mn(II) oxidation and the production of Mn biooxides.     

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

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

Genesis of carbonates from the Parnok ferromanganese deposit,Polar Urals

The Parnok deposit is made up of stratiform lodes of iron (magnetite) and manganese (oxide-carbonate, carbonate, and carbonate-silicate) ores localized among terrigenous-carbonate sediments (black shales) on the western slope of the Polar Urals. The lithological study showed that ore-bearing sediments were accumulated in a calm hydrodynamic setting within a relatively closed seafloor area (trap depressions). Periodic development of anaerobic conditions in the near-bottom seawater was favorable for the accumulation of dispersed organic matter in the terrigenous-carbonate sediments. Carbon required to form calcium carbonates in the ore-bearing sediments was derived from carbon dioxide dissolved in seawater. In the organic-rich sediments, carbonates were formed with the participation of carbon dioxide released by the destruction of organic matter. However, δ¹³C values (from 0.5 to ?4.4‰ PDB) suggest a relatively low fraction of the isotopically light biogenic carbon in the host calcite. The most probable sources of Fe and Mn were hydrothermal seepages at the seafloor. The Eh-pH conditions during stagnation were favorable for the precipitation of Fe and accumulation of Mn in a dissolved state. Transition from the stagnation regime to the concentration of oxygen in near-bottom waters was accompanied by oxidation of the dissolved Mn and its precipitation. Thus, fluctuations in Eh-pH parameters of water led to the differentiation of Fe and Mn. Initially, these elements were likely precipitated as oxides and hydroxides. During the subsequent lithification, Fe and Mn were reduced to form magnetite and rhodochrosite. The texture and structure of rhodochrosite aggregates indicate that manganese carbonates already began to form at the diagenetic stage and were recrystallized during the subsequent lithogenetic stages. Isotope data (δ¹³C from ?8.9 to ?17.1‰ PDB) definitely indicate that the oxidized organic matter of sediment served as the main source of carbon dioxide required to form manganese carbonates. Carbonates from host rocks and manganese ores have principally different carbon isotopic compositions. Unlike carbonates of host rocks, manganese carbonates were formed with an active participation of biogeochemical processes. Further processes of metagenesis (T ≈ 250–300°C, P ≈ 2 kbar) resulted in the transformation of textures, structures, and mineral composition of all rocks of the deposit. In particular, increase in temperature and pressure provided the formation of numerous silicates in manganese ores.     

Ferromanganese carbonate metasediments of the Sob area,Polar Urals: Bedding conditions,composition, and genesis

The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO₂ + Fe₂O ₃ ^tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe₂O ₃ ^tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module Al_M = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ¹³C_carb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.     

Oxidation of aqueous Cr(III) at birnessite surfaces: constraints on reaction mechanism

X-ray Photoelectron Spectroscopy (XPS) was used to investigate oxidation of aqueous Cr(III) at the surface of 7 Å-birnessite [MnO_1.75(OH)_0.25]. Special emphasis was placed on detection of intermediate oxidation states of chromium due to their critical environmental significance. No previous studies have been able to identify these intermediate oxidation states of chromium (namely, Cr[IV] and Cr[V]) on mineral surfaces or in natural solutions. Mn(2p_3/2), Cr(2p_3/2) and O(1s) spectra of the reacted surfaces reveal that Mn(IV) of synthetic birnessite undergoes reductive dissolution in two steps. The first step involves Mn(IV) reduction to Mn(III),that forms at the oxide surface probably as an oxyhydroxide (MnOOH), and in the second step Mn(III) is reduced to Mn(II) that is subsequently taken into solution. Each reductive reaction step involves transfer of only one electron to the Mn ion. After Cr(III)_aq is adsorbed onto the MnO₂ surface, it undergoes oxidation in three separate steps, each involving the loss of one electron to Mn ions, so that Cr(IV), Cr(V) and Cr(VI) are produced. The intermediate reaction products, namely Mn(III), and Cr(V) were positively identified by XPS spectral analyses. Similarity in XPS binding energy values of Cr(III) and Cr(IV) as well as that of Cr(V) and Cr(VI), however, preclude separate identification of Cr(III) from Cr(IV) and Cr(VI) from Cr(V) multiplets on the near-surface of the solid. A parallel reaction scheme (exclusive of sorption reactions) best describes the birnessite-Cr(III)_aq redox reactions. The two parallel reactions proceed by separate mechanisms with a monodentate complex formed in one mechanism and a bidentate complex in another. The bulk of Cr(IV) probably is formed via the monodentate complex and Cr(V) via the bidentate complex. The rate expressions associated with these reactions display near-perfect correlation with changing surface abundances of Cr(IV) and Cr(V) as a function of reaction time. Copyright © 1999 Elsevier Science Ltd.     

鄂东北早元古代沉积变质锰矿元素矿物组合特征

鄂东北早元古代沉积变质锰矿是我国时代最古老的锰矿之一,是由早元古代锰质碳酸盐岩经区域变质作用而成,后又经风化富集形成工业矿床。由于特殊的地质构造背景和成矿作用的多阶段性,元素和矿物组合复杂,具有独特性。本文研究了各种组分的演变关系和元素集散因素,为锰质碳酸盐岩在高压绿片岩相区域动力变质及其后表生作用中的演变提供了一个实例。     

冀东秦家峪中元古界高于庄组锰矿成因: 来自矿物学和地球化学的制约

冀东秦家峪锰矿赋存于中元古界蓟县系高于庄组二段底部含锰岩系内,其成因尚不明确.以秦家峪锰矿ZK58-2钻孔样品为研究对象,通过显微薄片观察、电子探针分析及全岩地球化学分析等方法,探讨了高于庄组锰矿的锰质来源和沉积环境对成矿的贡献.显微薄片观察、电子探针分析表明,原生矿带中含锰矿物主要为菱锰矿、铁镁菱锰矿、钙菱锰矿、锰方...     

湘西南南华系大塘坡组锰矿地球化学特征与沉积环境分析:以湖南靖州照洞锰矿床为例

为了分析湘西南南华系大塘坡组照洞锰矿的沉积环境,对照洞锰矿床进行了岩石学和地球化学研究.分析认为:照洞锰矿赋存于大塘坡组底部碳酸锰层中,包括条纹状菱锰矿和块状菱锰矿两种矿石类型.湘西南照洞锰矿的常量元素TiO₂、SiO₂、K₂O、Fe₂O₃、S与Al₂O₃之间呈现良好的正相关关系,CaO、MgO、MnO、P₂O₅和Al₂O₃之间呈负相关关系,常量元素之间的相关性与黔东、湘西的典型锰矿之间存在一致性,反映这些锰矿可能具有相似的成矿背景.照洞锰矿的Fe/Mn值低,Th/U、Ni/Co、V/Cr、V/（V+Ni）等沉积环境古氧相的指标显示,湘西南照洞锰矿形成时的水体处于常氧-贫氧的条件下.湘西南照洞锰矿稀土元素总量较高,PAAS标准化稀土元素配分模式呈现轻、重稀土亏损,中稀土富集的特征,具有弱的Ce正异常,类似现代海底铁锰结核的稀土元素配分特征.      

A 200–300 year cyclicity in sediment deposition in the Gotland Basin,Baltic Sea,as deduced from geochemical evidence

During the EU funded project BASYS (Baltic Sea System Study) short (Niemistö-type) and long (box and piston cores) sediment cores were taken which cover sedimentation during the past 8 ka. The uppermost part of the sedimentary sequence was chosen for a detailed geochemical study and freeze dried samples were analysed for about 20 elements but only the elements Mn and Ca are discussed. An age model was constructed using radiometric dating results by ²¹⁰Pb/¹³⁷Cs and ¹⁴C AMS. Significant correlation exists along the cores between very high Mn and moderately high Ca due to occrrences of the mineral rhodochrosite (kuthnahorite), a complex Mn(Ca) carbonate. This mineral is thought to be produced when salt water meets the pool of dissolved Mn at the bottom of the Gotland Basin. During favourable hydrographic conditions, e.g. strong northwesterly winds, salt water from the North Sea invades even the deepest parts of the central Baltic. Mn²⁺ which is produced mainly by the dissolution of ferromanganse oxides/oxyhydroxides in the water colum and in the course of destruction of organic matter in the sediments, combines with HCO₃^2- and Ca²⁺ in the seawater to form rhodochrosite. After burial, this mineral stays in the sediment and is seen as light-coloured layers. A certain cyclicity in the upper 1.5 m of the cores was observed in that about 200–300 a periods of elevated Mn–Ca are followed by periods with lower Mn–Ca of similar duration. An explanation for the observed cyclicity may be sea level variations: during rising sea level (transgression) more and more saline water is pushed into the deep basin of the Baltic Sea and if conditions are favourable (high dissolved Mn) the mineral rhodochrosite is precipitated.