微生物在锰的氧化富集过程中的作用—以广西湖润锰矿为例

以广西靖西县湖润锰矿床为研究基础，考查了矿床的基本地质特征，简要分析了矿床的成因。为了了解近地表氧化锰矿的形成机理，利用从该矿矿坑水中分离出的两种锰的氧化细菌（Metallogenium Symbioticum和Hyphomicrobium Vulgare)进行了一些锰的氧化实验。实验结果表明这两种细菌对锰具有明显的氧化作用，结合矿床的其他方面特征，认为自然界中微生物在锰的氧化富集过程中起着积极的作用，作用表现在两个方面：一方面微生物可以直接对锰进行氧化，使原生碳酸锰矿转变为氧化锰矿；另一方面微生物又可以改变环境的pH值，促进锰的化学氧化。     

内蒙古额仁陶勒盖银矿床锰矿物的矿物学初步研究

额仁陶勒盖银矿床出现的锰矿物主要为软锰矿、水锰矿、六方锰矿、锰铅矿、锰钾矿、菱锰矿、铁菱锰矿及锰方解石。解主要以独立矿物和离子吸附状态的形式赋存于地表锰铅矿和锰钾矿中；而软锰矿、六方锰矿、锰铅矿、锰钾矿等锰的氧化物和锰的氢氧化物是原生锰碳酸盐矿物的氧化分解而形成的，而水锰矿可能为热液形成；菱锰矿等原生锰的碳酸盐类矿物形成于后期热液阶段。     

鄂东北鹰咀山锰矿床的矿物学与地球化学：对矿床成因的指示

鄂东北地区红安群地层里广泛发育锰矿床（如鹰咀山、四方山-团山沟和孙冲等锰矿床）,目前对该类锰矿床的成因研究相对较为薄弱。本文以鄂东北地区鹰咀山锰矿床为研究对象,在详细论述其矿床地质特征基础上,对其进行矿物学及地球化学研究,认为鹰咀山锰矿床属于沉积变质型锰矿床。其形成后经抬升剥蚀至地表,遭受了表生氧化作用。锰成矿过程可分为3个期次：第1期为沉积成岩成矿期,锰矿物由菱锰矿、锰方解石及锰白云石组成;第2期为变质改造期,锰矿物主要由重结晶菱锰矿、黑锰矿及锰铝榴石等矿物组成;第3期为表生氧化期,锰矿物则主要由硬锰矿、软锰矿及锰钡矿等矿物组成。鹰咀山锰成矿物质来源应主要来自火山喷发和海底热液喷流作用。     

鄂东北鹰咀山锰矿床的矿物学与地球化学：对矿床成因的指示

鄂东北地区红安群地层里广泛发育锰矿床（如鹰咀山、四方山-团山沟和孙冲等锰矿床）,目前对该类锰矿床的成因研究相对较为薄弱。本文以鄂东北地区鹰咀山锰矿床为研究对象,在详细论述其矿床地质特征基础上,对其进行矿物学及地球化学研究,认为鹰咀山锰矿床属于沉积变质型锰矿床。其形成后经抬升剥蚀至地表,遭受了表生氧化作用。锰成矿过程可分为3个期次：第1期为沉积成岩成矿期,锰矿物由菱锰矿、锰方解石及锰白云石组成;第2期为变质改造期,锰矿物主要由重结晶菱锰矿、黑锰矿及锰铝榴石等矿物组成;第3期为表生氧化期,锰矿物则主要由硬锰矿、软锰矿及锰钡矿等矿物组成。鹰咀山锰成矿物质来源应主要来自火山喷发和海底热液喷流作用。     

陕西镇巴—重庆城口锰成矿带矿物特征及成因意义

系统采集陕西镇巴—重庆城口锰成矿带典型矿床各类矿石样品,运用显微镜鉴定、扫描电镜分析和X粉晶衍射分析方法,研究锰矿床中的矿物组分。结果表明,城口锰矿区主要锰矿物为菱锰矿,伴生有黄铁矿、镍黄铁矿、磷酸钙、闪锌矿和重晶石等矿物,镇巴锰矿区富锰矿物有蜡硅锰矿、褐锰矿、方锰矿、菱锰矿和硬锰矿,伴生有重晶石、钠长石、白云石和斜绿泥石等矿物。两锰矿区矿物成分存在显著差异,反映其成矿条件不同。从镇巴锰矿区至城口锰矿区,成矿环境具有从氧化条件逐渐向还原条件转变的趋势。     

湖南湘潭锰矿的地球化学特征及成矿机制

湘潭锰矿床的锰矿层赋存于新元古代南华系(成冰系)大塘坡组底部含锰黑色页岩中,含锰矿物主要为菱锰矿。湘潭锰矿的Fe/Mn值低,Th/U、V/(V+Ni)和V/Cr值等地球化学指标显示其发育在氧化-次氧化的沉积环境中,暗示菱锰矿并不是由Mn~(2+)和CO_3~(2-)直接沉淀形成的。湘潭锰矿稀土元素含量高,稀土元素配分模式存在轻微的中稀土元素富集,具有明显的Ce正异常,这些特征指示湘潭锰矿含锰矿物是以锰氧化物或氢氧化物的形式沉淀的。同时,锰矿的碳同位素富集碳的轻同位素,说明有机物参与了菱锰矿的形成过程。综合分析表明,湘潭锰矿成矿过程可以分为沉淀和转化两个阶段:在氧化性的水体中,Mn以氧化物或氢氧化物的形式沉淀;在缺氧且富含有机物质的成岩环境中,Mn氧化物或氢氧化物被有机物还原而转化生成菱锰矿。这与华南地区其他几个典型的大塘坡式锰矿的成矿机制一致。     

新疆西昆仑奥尔托喀讷什锰矿地质、地球化学及成因

近年来,西昆仑玛尔坎苏地区富锰矿找矿取得重大突破,新发现奥尔托喀纳什等大型锰矿床。该矿床层位稳定,厚度较大,Mn平均品位达35%以上,为中国最富的碳酸锰矿床,属于典型的海相沉积型锰矿床。锰矿体主要赋存于晚石炭世喀拉阿特河组地层中,该组岩性为一套浅海碳酸盐岩台地相沉积建造组合,可划分为台内浅滩、潮坪、开阔台地、局限台地等4个相类型。成矿分为三个期次,第一期为沉积成岩成矿期,矿石矿物由菱锰矿、锰方解石、硼锰矿组成;第二期为热液改造期,形成锰镁绿泥石、红锰矿、硫锰矿、锰方解石(脉)、重结晶菱锰矿、蔷薇辉石及滑石、石膏等;第三期为表生氧化期,发育少量软锰矿、水锰矿、硬锰矿等。锰矿石具有较低的Fe/Mn比值、V/(V+Ni)比值和强烈的Ce正异常,表明Mn是在氧化环境下,以氧化物或氢氧化物的形式沉积富集。含锰岩系顶、底板岩石中含较多成熟度较差的中酸性火山岩岩屑,以及具有较低Al/(Al+Fe+Mn)、Y/Ho、Co/Ni比值的锰矿石,说明其成矿物质来源于海底热水活动。奥尔托喀纳什锰矿具有"内源外生"的特点,锰矿石及菱锰矿具有负的δ~(13)C值(-23.3‰～-13.2‰),表明锰矿经历了先成锰氧化物或氢氧化物、再被还原转化成菱锰矿的过程。此外,有机质所导致的更为强烈的还原作用是本矿床富锰矿形成的重要机制。后期构造叠加致使矿体发生变形,矿体形态受褶皱控制。矿石受到强烈改造,形成锰镁绿泥石、红锰矿、蔷薇辉石等,晚期经历氧化淋滤作用形成软锰矿、水锰矿等。     

贵州铜仁地区南华系大塘坡组黑色页岩型菱锰矿碳、氧同位素特征及锰矿成矿作用

黔湘渝毗邻区是中国南华纪黑色页岩型锰矿的集中产区,近年来在该区域的找矿勘探取得重大进展。但是,该区域内黑色页岩型锰矿的成矿物质来源、成矿机制以及沉积盆地的氧化还原环境及其与成矿的关系尚存争议。文章对贵州高地锰矿的菱锰矿开展了详细的碳、氧同位素研究,样品采自钻孔岩芯,测试结果表明其δ13CV-PDB值和δ18OV-PDB值全部为负值,变化范围分别在-11.5‰~-6.8‰和-15‰~-3.9‰之间。结合前人研究成果,认为黔湘渝毗邻区南华系形成时古海洋处于氧化还原的分层状态,含锰的陆源碎屑物质通过海水的分解作用首先形成氧化锰和氢氧化锰,在浅水滞留盆地环境下古海水由弱氧化状态转变为还原状态,并在有机质降解作用的促使下使锰的氧化物和氢氧化物转化成菱锰矿,并富集沉积形成大塘坡组黑色页岩型菱锰矿矿床。     

浅海Mg~(2+)和SO_4~(2-)对微生物诱导形成锰碳酸盐的影响

为了模拟浅海环境下锰氧化物微生物还原作用诱导碳酸盐沉淀的过程,选取最常见的锰氧化物-水钠锰矿(K_(0.33)Mn_7O_(14)·7H_2O)为研究对象,在不同种类与浓度盐离子(Mg~(2+)、SO_4~(2-))存在条件下开展异化锰还原菌Dietzia cercidiphylli 45-1b好氧还原水钠锰矿的实验研究.通过测试体系蛋白、Mn~(2+)等离子浓度变化,利用X射线衍射(XRD)和X射线吸收谱(XAS)表征反应前后矿物结构变化,来探讨不同初始Mg~(2+)和SO_4~(2-)浓度对于菌株45-1b还原水钠锰矿及诱导碳酸盐矿物沉淀的影响.结果显示体系pH值在4天内从7.0迅速上升至9.3,Mn~(2+)浓度在2天内迅速上升至166μmol/L,随后迅速下降至8μmol/L(第4天),其好氧还原产物为菱锰矿(MnCO3),且其产生量随Mg~(2+)浓度的升高而降低,随SO_4~(2-)浓度的升高而升高.上述实验结果表明好氧环境下菌株45-1b能够利用乙酸为电子供体,水钠锰矿为电子受体还原水钠锰矿释放Mn~(2+),最终转化有机碳为无机碳酸盐矿物菱锰矿.Mg~(2+)通过影响微生物生长和菱锰矿成核对水钠锰矿的还原及菱锰矿沉淀产生抑制作用,而SO_4~(2-)可以缓解Mg~(2+)的抑制作用并促进水钠锰矿的还原及菱锰矿沉淀.     

桃江锰矿锰帽形成的地球化学过程

桃江锰矿区发育有较完整的表生氧化剖面,根据不同深度矿石的结构构造,矿物组合及化学成分特征,将表生氧化剖面分成三个带：氧化矿石带,地渡矿石带和原生矿石带。桃江锰矿原生矿石矿物主要为含锰碳酸盐,表生富集作用包括两上地球化学过程;可溶杂质的溶解淋失作用和锰质的氧化残留作用。在过渡矿石带中,可溶性杂质发生大规模溶解迁移,锰质发生相对富集;氧化矿石带中,碳酸锰氧化成难溶的高价锰的氧化物,使锰质残留下来,形成     

Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms

Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts.     

Effect of exopolymers on oxidative dissolution of natural rhodochrosite by Pseudomonas putida strain MnB1: An electrochemical study

Oxidative dissolution of natural rhodochrosite by the Mn(II) oxidizing bacterium Pseudomonas putida strain MnB1 was investigated based on batch and electrochemical experiments using natural rhodochrosite as the working electrode. Tafel curves and batch experiments revealed that bacterial exopolymers (EPS) significantly increased dissolution of natural rhodochrosite. The corrosion current significantly increased with reaction time for EPS treatment. However, the corrosion process was blocked in the presence of cells plus extra EPS due to formation of the passivation layer. Moreover, the scanning electron microscopy and the energy dispersive spectroscopy (SEM–EDS) results showed that the surface of the natural rhodochrosite was notably changed in the presence of EPS alone or/and bacterial cells. This study is helpful for understanding the role of EPS in bacterially oxidation of Mn(II). It also indicates that the Mn(II) oxidizing bacteria may exert their effects on Mn(II) cycle and other biological and biogeochemical processes much beyond their local ambient environment because of the catalytically dissolution of solid Mn(II) by EPS and the possible long distance transport of the detached EPS.     

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。     

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。     

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite

Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO₂ and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).     

Migration and transformation of manganese during the artificial recharging of a deep confined aquifer

Field tests and laboratory experiments were performed, using an artificial groundwater recharging site in Southeast China as an example, to investigate the migration and transformation of manganese during the artificial recharging of a deep confined aquifer. The migration and transformation of total manganese and divalent manganese (Mn(II)) were influenced by mixing, oxidation reactions, and the dissolution of minerals containing manganese, and increasing the dissolved oxygen (DO) concentration was found to promote the dissolution of minerals containing manganese. The laboratory experiments showed that the retardation factors were higher upstream than downstream of the recharging hole. The amount of dissolution that occurred decreased, and the amount of mixing that occurred increased as the distance from the recharging hole increased. The DO concentration decreased as the amount of dissolution of minerals containing manganese that occurred decreased. A high temperature, a high DO concentration, and the presence of microorganisms were found to promote the dissolution of minerals containing manganese, which caused the total manganese and Mn(II) concentrations to increase.     

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.     

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.     

Quantitative charge state analysis of manganese biominerals in aqueous suspension using scanning transmission X-ray microscopy (STXM)

We have applied Scanning Transmission Soft X-ray Microscopy (STXM) to investigate the charge state distribution of Mn in two kinds of Mn-biominerals, Mn nodules collected from Lake Michigan sediments and Mn precipitates formed by spores of a marine bacillus SG-1 under transport limited reaction conditions. A data analysis technique was developed, which allows for extraction of spatially resolved 2-d charge state maps of manganese on a submicron level. We find that the charge state of Mn dominates the spectral shape of L-edge spectra of environmentally important single oxidation state Mn minerals and that spectra of mixed oxidation state oxides can be modelled by a combination of appropriate single oxidation state reference spectra. Two-dimensional maps of charge state distributions clearly reveal domains of different oxidation states within single particles of Mn-micronodules. Spots of preferred accumulation of Mn(II) were found, which indicates biogenic precipitation of Mn(II)-species as a first step of nodule formation. The presence of Mn(III) in the studied sediment samples suggests the involvement of one-electron oxidation processes and reaction conditions which inhibit or slow down the disproportionation of Mn(III)-products. Under transport limited conditions, Mn oxidation products formed by spores of the marine bacillus SG-1 can vary from cell to cell. The presence of significant amounts of Mn(III) containing species points to the involvement of one-electron oxidation reactions as in the case of the micro-nodules. Our technique and the results obtained form a new basis for the mechanistic understanding of the formation of Mn biominerals in the environment.     

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。