Cell adhesion of <Emphasis Type="Italic">Shewanella oneidensis</Emphasis>to iron oxide minerals: Effect of different single crystal faces

The results of experiments designed to test the hypothesis that near-surface molecular structure of iron oxide minerals influences adhesion of dissimilatory iron reducing bacteria are presented. These experiments involved the measurement, using atomic force microscopy, of interaction forces generated between Shewanella oneidensis MR-1 cells and single crystal growth faces of iron oxide minerals. Significantly different adhesive force was measured between cells and the (001) face of hematite, and the (100) and (111) faces of magnetite. A role for electrostatic interactions is apparent. The trend in relative forces of adhesion generated at the mineral surfaces is in agreement with predicted ferric site densities published previously. These results suggest that near-surface structure does indeed influence initial cell attachment to iron oxide surfaces; whether this is mediated via specific cell surface-mineral surface interactions or by more general interfacial phenomena remains untested.     

Computer simulation of electron transfer at hematite surfaces

Molecular dynamics simulations in combination with ab initio calculations were carried out to determine the rate of electron transfer at room temperature in bulk hematite (α-Fe₂O₃) and at two low-index surfaces, namely the (012) and (001) surfaces. The electron transfer reactions considered here involve the II/III valence interchange between nearest-neighbor iron atoms. Two electron transfer directions were investigated, namely the basal plane and c direction electron transfers. Electron transfer rates obtained in bulk hematite were in good agreement with ab initio electronic structure calculations thus validating the potential model. The surfaces were considered both in vacuum and in contact with an equilibrated aqueous solution. The reorganization energy is found to increase significantly at the first surface layer and this value is little affected by the presence of water. In addition, in the case of the (012) surface, the electronic coupling matrix element for the topmost basal plane transfer was calculated at the Hartree-Fock level and was found to be weak compared to the corresponding electron transfer in the bulk. Therefore, most surfaces show a decrease in the rate of electron transfer at the surface. However, where iron atoms involved in the electron transfer reaction are directly coordinated to water molecules, water lowers the free energy of activation to a great extent and provides a large driving force for electrons to diffuse toward the bulk thus opposing the intrinsic surface effect. The surfaces considered in this work show different electron transfer properties. Hematite has been shown to exhibit anisotropic conductivity and thus different surfaces will show different intra- and inter-layer rates depending on their orientation. Moreover, the calculations of electron transfers at the hydroxyl- and iron-terminated (001) surfaces revealed that surface termination has a significant effect on the electron transfer parameters in the vicinity of the surface. Finally, our findings indicate that undercoordinated terminal iron atoms could act as electron traps at the surface.     

Bioreduction of natural specular hematite under flow conditions

Dissimilatory reduction of Fe(III) by Shewanella oneidensis MR-1 was evaluated using natural specular hematite as sole electron acceptor in an open system under dynamic flow conditions to obtain a better understanding of biologic Fe(III) reduction in the natural environment. During initial exposure to hematite under advective flow conditions, cells exhibited a transient association with the mineral characterized by a rapid rate of attachment followed by a comparable rate of detachment before entering a phase of surface colonization that was slower but steadier than that observed initially. Accumulation of cells on the hematite surface was accompanied by the release of soluble Fe(II) into the aqueous phase when no precautions were taken to remove amorphous Fe(III) from the mineral surface before colonization. During the period of surface colonization following the detachment phase, cell yield was estimated at 1.5-4 × 10⁷ cells/μmol Fe(II) produced, which is similar to that reported in studies conducted in closed systems. This yield does not take into account those cells that detached during this phase or the Fe(II) that remained associated with the hematite surface. Hematite reduction by the bacterium led to localized surface pitting and localized discrete areas where Fe (II) precipitation occurred. The cleavage plane of hematite left behind after bacterial reduction, as revealed by our results, strongly suggests, that heterogeneous energetics of the mineral surface play a strong role in this bioprocess. AQDS, an electron shuttle shown to stimulate bioreduction of Fe(III) in other studies, inhibited reduction of hematite by this bacterium under the dynamic flow conditions employed in the current study.     

Quantitative mineralogical and chemical assessment of the Nkout iron ore deposit,Southern Cameroon

The Nkout deposit is part of an emerging iron ore province in West and Central Africa. The deposit is an oxide facies iron formation comprising fresh magnetite banded iron formation (BIF) at depth, which weathers and oxidises towards the surface forming caps of high grade hematite/martite–goethite ores. The mineral species, compositions, mineral associations, and liberation have been studied using automated mineralogy (QEMSCAN^®) combined with whole rock geochemistry, mineral chemistry and mineralogical techniques. Drill cores (saprolitic, lateritic, BIF), grab and outcrop samples were studied and divided into 4 main groups based on whole rock Fe content and a weathering index. The groups are; enriched material (EM), weathered magnetite itabirite (WMI), transitional magnetite itabirite (TMI) and magnetite itabirite (MI). The main iron minerals are the iron oxides (magnetite, hematite, and goethite) and chamosite. The iron oxides are closely associated in the high grade cap and liberation of them individually is poor. Liberation increases when they are grouped together as iron oxides. Chamosite significantly lowers the liberation of the iron oxides. Automated mineralogy by QEMSCAN^® (or other similar techniques) can distinguish between Fe oxides if set up and calibrated carefully using the backscattered electron signal. Electron beam techniques have the advantage over other quantitative mineralogy techniques of being able to determine mineral chemical variants of ore and gangue minerals, although reflected light optical microscopy remains the most sensitive method of distinguishing closely related iron oxide minerals. Both optical and electron beam automated mineralogical methods have distinct advantages over quantitative XRD in that they can determine mineral associations, liberation, amorphous phases and trace phases.     

Bioreduction of hematite nanoparticles by the dissimilatory iron reducing bacterium Shewanella oneidensis MR-1

We examined the reduction of different size hematite (α-Fe₂O₃) nanoparticles (average diameter of 11, 12, 30, 43, and 99 nm) by the dissimilatory iron reducing bacteria (DIRB), Shewanella oneidensis MR-1, to determine how S. oneidensis MR-1 may utilize these environmentally relevant solid-phase electron acceptors. The surface-area-normalized-bacterial Fe(III) reduction rate for the larger nanoparticles (99 nm) was one order of magnitude higher than the rate observed for the smallest nanoparticles (11 nm). The Fe(III) reduction rates for the 12, 30, and 43 nm nanoparticles fell between these two extremes. Whole-cell TEM images showed that the mode of Fe₂O₃ nanoparticle attachment to bacterial cells was different for the aggregated, pseudo-hexagonal/irregular and platey 11, 12, and 99 nm nanoparticles compared to the non-aggregated 30 and 43 nm rhombohedral nanoparticles. Due to differences in aggregation, the 11, 12, and 99 nm nanoparticles exhibited less cell contact and less cell coverage than did the 30 and 43 nm nanoparticles. We hypothesize that S. oneidensis MR-1 employs both indirect and direct mechanisms of electron transfer to Fe(III)-oxide nanoparticles and that the bioreduction mechanisms employed and Fe(III) reduction rates depend on the nanoparticles’ aggregation state, size, shape and exposed crystal faces.     

Redox-linked conformation change and electron transfer between monoheme c-type cytochromes and oxides

Electron transfer between redox active proteins and mineral oxides is important in a variety of natural as well as technological processes, including electron transfer from dissimilatory metal-reducing bacteria to minerals. One of the pathways that could trigger electron transfer between proteins and minerals is redox-linked conformation change. We present electrochemical evidence that mitochondrial cytochrome c (Mcc) undergoes significant conformation change upon interaction with hematite and indium-tin oxide (ITO) surfaces. The apparent adsorption-induced conformation change causes the protein to become more reducing, which makes it able to transfer electrons to the hematite conduction band. Although Mcc is not a protein thought to be involved in interaction with mineral surfaces, it shares (or can be conformed so as to share) some characteristics with multiheme outer-membrane cytochromes thought to be involved in the transfer of electrons from dissimilatory iron-reducing bacteria to ferric minerals during respiration. We present evidence that a 10.1 kDa monohoeme cytochrome isolated and purified from Acidiphilium cryptum, with properties similar to those of Mcc, also undergoes conformation change as a result of interaction with hematite surfaces.     

Transformation of magnetite to hematite and its influence on the dissolution of iron oxide minerals

Deformed rocks of the Itabira Iron Formation (itabirites) in Brazil show microstructural evidence of pressure solution of quartz and iron oxides; it appears that magnetite was dissolved and hematite precipitated. The dissolution of magnetite seems to be related to its transformation to hematite by oxidation of Fe²⁺ to Fe³⁺. The transformation of magnetite to hematite occurs along {111} planes, and results in the development of hematite domains along {111} that are parallel to the foliation. The difference in volume created by the transformation of magnetite to hematite and the shear stress acting on the interphase boundaries allow fluids to migrate along these planes. The dissolution of magnetite involves the hydrolyzation of the Fe²⁺—O bonds at interphase boundaries of high normal stress. The high fugacity of oxygen in the fluid phase promotes the reaction of Fe²⁺ (in solution) with oxygen. Fe²⁺ ions oxidize to Fe³⁺ and precipitate as hematite platelets with their longest axes oriented parallel to the direction of maximum stretching. The transformation of magnetite to hematite during deformation plays an important role in the fabric evolution of the iron formation rocks. The transformation along {111} creates planes of weakness that facilitate fracturing. The fracturing plus the dissolution result in a reduction of magnetite grain size, and the oriented precipitation results in layers of hematite platelets. These processes produce a new fabric characterized by a penetrative foliation and lineation.     

Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens

The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p_3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.     

Dependence of microbial magnetite formation on humic substance and ferrihydrite concentrations

Iron mineral (trans)formation during microbial Fe(III) reduction is of environmental relevance as it can influence the fate of pollutants such as toxic metal ions or hydrocarbons. Magnetite is an important biomineralization product of microbial iron reduction and influences soil magnetic properties that are used for paleoclimate reconstruction and were suggested to assist in the localization of organic and inorganic pollutants. However, it is not well understood how different concentrations of Fe(III) minerals and humic substances (HS) affect magnetite formation during microbial Fe(III) reduction. We therefore used wet-chemical extractions, magnetic susceptibility measurements and X-ray diffraction analyses to determine systematically how (i) different initial ferrihydrite (FH) concentrations and (ii) different concentrations of HS (i.e. the presence of either only adsorbed HS or adsorbed and dissolved HS) affect magnetite formation during FH reduction by Shewanella oneidensis MR-1. In our experiments magnetite formation did not occur at FH concentrations lower than 5 mM, even though rapid iron reduction took place. At higher FH concentrations a minimum fraction of Fe(II) of 25-30% of the total iron present was necessary to initiate magnetite formation. The Fe(II) fraction at which magnetite formation started decreased with increasing FH concentration, which might be due to aggregation of the FH particles reducing the FH surface area at higher FH concentrations. HS concentrations of 215-393 mg HS/g FH slowed down (at partial FH surface coverage with sorbed HS) or even completely inhibited (at complete FH surface coverage with sorbed HS) magnetite formation due to blocking of surface sites by adsorbed HS. These results indicate the requirement of Fe(II) adsorption to, and subsequent interaction with, the FH surface for the transformation of FH into magnetite. Additionally, we found that the microbially formed magnetite was further reduced by strain MR-1 leading to the formation of either dissolved Fe(II), i.e. Fe²⁺, in HEPES buffered medium or Fe(II) carbonate (siderite) in bicarbonate buffered medium. Besides the different identity of the Fe(II) compound formed at the end of Fe(III) reduction, there was no difference in the maximum rate and extent of microbial iron reduction and magnetite formation during FH reduction in the two buffer systems used. Our findings indicate that microbial magnetite formation during iron reduction depends on the geochemical conditions and can be of minor importance at low FH concentrations or be inhibited by adsorption of HS to the FH surface. Such scenarios could occur in soils with low iron mineral or high organic matter content.     

Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow

Iron (hydr)oxides not only serve as potent sorbents and repositories for nutrients and contaminants but also provide a terminal electron acceptor for microbial respiration. The microbial reduction of Fe (hydr)oxides and the subsequent secondary solid-phase transformations will, therefore, have a profound influence on the biogeochemical cycling of Fe as well as associated metals. Here we elucidate the pathways and mechanisms of secondary mineralization during dissimilatory iron reduction by a common iron-reducing bacterium, Shewanella putrefaciens (strain CN32), of 2-line ferrihydrite under advective flow conditions. Secondary mineralization of ferrihydrite occurs via a coupled, biotic-abiotic pathway primarily resulting in the production of magnetite and goethite with minor amounts of green rust. Operating mineralization pathways are driven by competing abiotic reactions of bacterially generated ferrous iron with the ferrihydrite surface. Subsequent to the initial sorption of ferrous iron on ferrihydrite, goethite (via dissolution/reprecipitation) and/or magnetite (via solid-state conversion) precipitation ensues resulting in the spatial coupling of both goethite and magnetite with the ferrihydrite surface. The distribution of goethite and magnetite within the column is dictated, in large part, by flow-induced ferrous Fe profiles. While goethite precipitation occurs over a large Fe(II) concentration range, magnetite accumulation is only observed at concentrations exceeding 0.3 mmol/L (equivalent to 0.5 mmol Fe[II]/g ferrihydrite) following 16 d of reaction. Consequently, transport-regulated ferrous Fe profiles result in a progression of magnetite levels downgradient within the column. Declining microbial reduction over time results in lower Fe(II) concentrations and a subsequent shift in magnetite precipitation mechanisms from nucleation to crystal growth. While the initial precipitation rate of goethite exceeds that of magnetite, continued growth is inhibited by magnetite formation, potentially a result of lower Fe(III) activity. Conversely, the presence of lower initial Fe(II) concentrations followed by higher concentrations promotes goethite accumulation and inhibits magnetite precipitation even when Fe(II) concentrations later increase, thus revealing the importance of both the rate of Fe(II) generation and flow-induced Fe(II) profiles. As such, the operating secondary mineralization pathways following reductive dissolution of ferrihydrite at a given pH are governed principally by flow-regulated Fe(II) concentration, which drives mineral precipitation kinetics and selection of competing mineral pathways.     

Nonlocal bacterial electron transfer to hematite surfaces

Mechanisms by which dissimilatory iron-reducing bacteria utilize iron and manganese oxide minerals as terminal electron acceptors for respiration are poorly understood. In the absence of exogenous electron shuttle compounds, extracellular electron transfer is generally thought to occur through the interfacial contact area between mineral surfaces and attached cells. Possible alternative reduction pathways have been proposed based on the discovery of a link between an excreted quinone and dissimilatory reduction. In this study, we utilize a novel experimental approach to demonstrate that Shewanella putrefaciens reduces the surface of crystalline iron oxides at spatial locations that are distinct from points of attachment.     

Electrochemical interaction of Shewanella oneidensis MR-1 and its outer membrane cytochromes OmcA and MtrC with hematite electrodes

Bacterial metal reduction is an important biogeochemical process in anaerobic environments. An understanding of electron transfer pathways from dissimilatory metal-reducing bacteria (DMRB) to solid phase metal (hydr)oxides is important for understanding metal redox cycling in soils and sediments, for utilizing DMRB in bioremedation, and for developing technologies such as microbial fuel cells. Here we hypothesize that the outer membrane cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 are the only terminal reductases capable of direct electron transfer to a hematite working electrode. Cyclic voltammetry (CV) was used to study electron transfer between hematite electrodes and protein films, S. oneidensis MR-1 wild-type cell suspensions, and cytochrome deletion mutants. After controlling for hematite electrode dissolution at negative potential, the midpoint potentials of adsorbed OmcA and MtrC were measured (−201 mV and −163 mV vs. Ag/AgCl, respectively). Cell suspensions of wild-type MR-1, deletion mutants deficient in OmcA (ΔomcA), MtrC (ΔmtrC), and both OmcA and MtrC (ΔmtrC–ΔomcA) were also studied; voltammograms for ΔmtrC–ΔomcA were indistinguishable from the control. When the control was subtracted from the single deletion mutant voltammograms, redox peaks were consistent with the present cytochrome (i.e., ΔomcA consistent with MtrC and ΔmtrC consistent with OmcA). The results indicate that OmcA and MtrC are capable of direct electron exchange with hematite electrodes, consistent with a role as terminal reductases in the S. oneidensis MR-1 anaerobic respiratory pathway involving ferric minerals. There was no evidence for other terminal reductases operating under the conditions investigated. A Marcus-based approach to electron transfer kinetics indicated that the rate constant for electron transfer k_et varies from 0.025 s⁻¹ in the absence of a barrier to 63.5 s⁻¹ with a 0.2 eV barrier.     

Trace element composition of magnetite from the Xinqiao Fe–S(–Cu–Au) deposit,Tongling, Eastern China: constraints on fluid evolution and ore genesis

The Xinqiao deposit is one of several polymetallic deposits in the Tongling ore district. There are two types of mineralization in the Xinqiao: skarn-type and stratiform-type. The skarn-type mineralization is characterized by iron oxides such as magnetite and hematite, whereas stratiform-type mineralization is characterized by massive sulfides with small amounts of magnetite and hematite. We defined three types of ores within the stratiform-type mineralization by the mineral assemblages and ore structures. Type I ore is represented by magnetite crosscut by minor calcite veins. Type II is a network ore composed of magnetite and crosscutting pyrite. Type III is a massive ore containing calcite and hematite. Type I magnetite is characterized by highly variable trace element content, whereas Type II magnetite has consistently higher Si, Ti, V, and Nb. Type III magnetite contains more In, Sn, and As than the other two types. Fluid–rock interaction, oxygen fugacity (fO₂), and temperature (T) are the main factors controlling element variation between the different magnetite types. Type I magnetite was formed by more extensive fluid–rock interaction than the other two types at moderate fO₂ and T conditions. Type II magnetite is thought to have formed in relatively low fO₂ and high-T environments, and Type III in relatively high fO₂ and moderate-T environments. Ca?+?Al?+?Mn and Ti?+?V discrimination diagrams show that magnetite in the Xinqiao deposit is hydrothermal in origin and is possibly linked with skarn.     

Weak interfacial water ordering on isostructural hematite and corundum (0 0 1) surfaces

Ordering of interfacial water at the hematite and corundum (0 0 1)-water interfaces has been characterized using in situ high resolution specular X-ray reflectivity measurements. The hematite (0 0 1) surface was prepared through an annealing process to produce a surface isostructural with corundum (0 0 1), facilitating direct comparison. Interfacial water was found to display a similar structure on this pair of isostructural surfaces. A single layer of adsorbed water having a large vibrational amplitude was present on each surface and additional ordering of water extended at least 1 nm into the bulk fluid, with the degree of ordering decreasing with increasing distance from the surfaces. Consistent with prior studies of the (0 1 2) and (1 1 0) surfaces of hematite and corundum, the configuration of water above the (0 0 1) surfaces is primarily controlled by the surface structure, specifically the arrangement of surface functional groups. However, interfacial water at the (0 0 1) surfaces displayed significantly larger vibrational amplitudes throughout the interfacial region than at other isostructural sets of hematite and corundum surfaces, indicating weaker ordering. Comparison of the vibrational amplitudes of adsorbed water on a series of oxide, silicate, and phosphate mineral surfaces suggests that the presence or absence of a substantial interfacial electrostatic field is the primary control on water ordering and not the surface structure itself. On surfaces for which charge originates dominantly through protonation-deprotonation reactions the controlling factor appears to be whether conditions exist where most functional groups are uncharged as opposed to the net surface charge. The doubly coordinated functional groups on hematite and corundum (0 0 1) surfaces are largely uncharged under slightly acidic to circumneutral pH conditions, leading to weak ordering, whereas singly coordinated groups on (0 1 2) and (1 1 0) surfaces of these phases are always charged, even when the net surface charge is zero, and induce strong water ordering. Surfaces lacking structural charge can thus be divided into two distinct classes that induce either strong or weak ordering of interfacial water. Surface functional group coordination is the ultimate control on this division as it determines the charge state of such groups under different protonation configurations. Ion adsorption and electron transfer processes may differ between these classes of surfaces because of the effect of water ordering strength on interfacial capacitances and hydrogen bonding.     

Review of geology, alteration and origin of iron oxide–apatite deposits in the Cretaceous Ningwu basin, Lower Yangtze River Valley, eastern China: Implications for ore genesis and geodynamic setting

In the Cretaceous Ningwu volcano-sedimentary basin in the Yangtze River Valley metallogenic belt, eastern China, there are three areas with a dense distribution of magnetite or hematite deposits: the Meishan deposit in the north; Washan, Nanshan and Taocun deposits in the center; and the Zhongjiu and Gushan deposits in the south. The mineralization in the Ningwu basin is associated mainly with subvolcanic intrusions, consisting of gabbro–diorite porphyry and/or gabbro–diorite. Alteration zoning of these deposits is pronounced, and includes: (1) an upper light colored zone of argillic, kaolinite, silica, carbonate and pyritic alteration (2) a middle dark colored zone of diopside, fluorapatite–magnetite, phlogopite, and garnet with fluorapatite–magnetite; (3) a lower light colored zone of extensive albitic alteration. However, at the Gushan iron deposit, the lower light colored zone and the middle dark colored zone are absent, whereas the principal alteration is represented by silicification, kaolinization, and carbonatization.The iron oxide–apatite deposits in the Ningwu basin are typically magmatic–metasomatic origin and are similar to the Kiruna-type deposits in Scandinavia, particularly with respect to mineral assemblages, fabric and structure of the iron ores, occurrence of the orebodies and wall rock alteration. The iron oxide–apatite deposits of the Ningwu basin contain magnetite and/or hematite, with diopside or actinolite and apatite gangue. They were formed in a rift or extensional environment and the mineralization is associated with alkaline magmatism. The time interval between magmatism and related mineralization is very short.     

Diagenetic and metamorphic history of the Umm Nar BIF,Eastern Desert,Egypt

The Umm Nar BIF was formed in a sedimentary environment. It is confined to an upper stratigraphic zone of pre-Pan-African metamorphosed shelf deposits. During the Pan-African deformational history, the BIF and the host metasediments were tectonically' overlain by ophiolitic melange succession. The metasediments and the mélange were subjected to a major folding phase and then thrust over the “Shaitian” sheared granite, prior to the intrusion of syn- to late- orogenic granitoids. The BIF is divisible into two main types: oxide-bands including magnetite and hematite, and oxide-silicate bands including magnetite, hematite and stilpnomelane. The associated gangues are quartz, calcite, epidote, garnet, plagioclase, graphite and muscovite. Rhythmic banding and lamination, cross-lamination and flaser structure are the most prominent primary features in the IF bands. The iron minerals and the associated gangue show a variety of textural aspects and microscopic interrelationships which indicate successive episodes of mineral accumulation and formation, involving deposition, recrystallization, blastic growths, overgrowths, replacement and deformations, during continuous burial and subsequent tectonic deformations. Editorial handling: DR     

鞍钢弓长岭三矿区三种矿石类型的工艺矿物学研究

１　矿石的物质组成１－１　矿石的化学成分及矿物组成三矿区矿石的化学成分较简单,碱性系数很低,在０－０３％以下;矿石为高硅、贫铁,低ＣａＯ、ＭｇＯ、Ａｌ２Ｏ３,且有害杂质ＳＯ２、Ｐ２Ｏ５含量低于工业允许值（０－５％）的酸性矿石。随着矿石中ＦｅＯ含量的降低,ＣａＯ、ＭｇＯ、Ｋ２Ｏ含量有依次降低的趋势,Ｐ２Ｏ５及ＣＯ２也随ＦｅＯ降低而逐渐降低。矿石的矿物成分以赤铁矿、磁铁矿和石英为主,其它矿物成分很少,矿石类型不同,主要矿物含量也有差异。根据矿石的化学全分析及电子探针分析结果计算的矿石定量组成见表１。…     

The beach placer iron deposit of Portman Bay,Murcia, SE Spain: the result of 33 years of tailings disposal (1957–1990) to the Mediterranean seaside

Between 1957 and 1990, the Peñarroya Mining and Metallurgical Company (SMMPE) disposed about 60 million tonnes of tailings materials directly to the Mediterranean Sea. A substantial part of it (12.5 Mt) was dragged back by the sea currents progressively infilling the Portman Bay (Murcia, SE Spain), thus making the shoreline advance between 500 and 600 m seaward. The Roberto froth flotation plant processed mineral from manto-type deposits belonging to the Sierra de Cartagena-La Unión lead-zinc district. One of the mineral assemblages present in these deposits comprises greenalite, magnetite, sulfides, carbonates, and silica. Despite that magnetite recovery was undertaken by SMMPE between 1959 and 1967, we estimate that magnetite contained in the tailings hosts a substantial resource that could be as large as 2.3 Mt of iron ore. The ore contains magnetite ± hematite ± siderite. Tidal waves and sea currents led to gravimetric classification of the tailings material, with concentration of the dense iron oxides in the sandy fractions, eventually forming a coastal placer iron deposit. A major problem for magnetic separation is the intimate intergrowth between magnetite, hematite, and siderite. Besides, the sands contain large concentrations of Pb (0.27 %), Zn (0.72 %), and As (559 ppm).     

从矿物粉晶表面反应性到矿物晶面反应性——以黄铁矿氧化行为的晶面差异性为例

地球系统中各种矿物相的物理化学反应大多是从矿物表面或界面开始的。要揭示矿物表面反应性的本质,就需要从控制其反应性的表面结构入手。由于实验条件的限制,绝大多数关于矿物表面物理化学性质的研究主要采用粉晶作为研究对象。尽管粉晶方法在研究诸如硅酸盐、碳酸盐溶解和沉淀结晶等过程中被普遍采用,但这种基于矿物粉晶的研究方法还是有一定的不足。因为形成粉晶的破碎研磨过程会导致晶体高能面的出现,高能面所具有的高活性可能会加速其反应过程,应用于地球化学反应的计算结果就可能高估了实际的地球化学反应速率。本研究以黄铁矿表面氧化反应的晶面差异性为例,从晶面结构制约反应性的角度出发,重新审视了黄铁矿氧化的相关问题,弥补了传统"粉晶研究"中对黄铁矿氧化速率和氧化机理认识的缺陷。黄铁矿宽范围的氧化速率实测值很可能是由不同晶面间较大的反应性差异导致;水在黄铁矿的氧化过程中同时扮演着传递电子的催化剂和反应物的角色,也是黄铁矿氧化反应速控步(rate-limiting step)的核心物质。这些认识首次明确了黄铁矿不同晶面反应性差异的重要性,并提示我们应将传统表面矿物学的研究推向更为精确的晶面矿物学水平。这一从晶面角度考察发生在矿物表面的地球化学反应的研究方法可为构建更为精确的地球化学模型提供理论基础。     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.