Genesis of variegated redbeds in the fluvial Aztec Siltstone (late devonian), southern victoria land,Antarctica

The Aztec Siltstone (Late Devonian) formed in a meandering fluviatile environment and is a variegated redbed sequence consisting of red or drab overbank mudstones and drab channel sandstones, commonly arranged in fining-upwards cycles. The pigmentation in the red mudstones is caused by euhedral cryptocrystalline haematite which is dispersed throughout the matrix, masking the green colour of the underlying illitic and chloritic clays. Textural, mineralogical and chemical analyses suggest that the pigment formed in situ by dehydration and crystallization of a detrital, amorphous or poorly crystalline, yellow-brown ferric oxide precursor. The hydrated precursor apparently was derived from the weathering of iron silicates in a source area regolith, and transported in suspension with the Aztec alluvium, commonly by attachment onto surfaces of clay platelets. The association of the precursor with the clays is a contributing reason for the absence of red sandstones in the formation.Dehydration and crystallization of the yellow-brown ferric oxide to form the red haematite pigment occurred prior to deep burial of the host sediment. At least part of it occurred before burial, in an oxidising environment in well-drained and well-aerated overbank soils which were exposed for prolonged periods of time (4,000–10,000 years) under a hot and at least seasonally arid climate. Crystallization of the red pigment may have been completed during early diagenesis.Reducing conditions, induced by the presence of organic debris in the sediment and a relatively high water table, affected much of the deposit by removing the “free” hydrated ferric oxide, either partially or completely, from the in-channel sands, the low-lying and poorly drained overbank sediments, and the lacustrine sediments. This reduction was both a syndepositional and an early post-depositional process.Iron analyses indicate that, on average, the red mudstones are enriched in total iron (Fe) and Fe³⁺ by 2%, all of which is attributable to the inherited “free” ferric oxide. There is no other significant difference in whole-rock mineralogy or major-element chemistry between the red and non-red mudstones.     

Origin of red beds in the Ringerike Group (Silurian) of Norway

The Ringerike Group is a meandering fluviatile succession which is about 60% red. Most of the red zones are formed of mudrocks and siltstones and correspond to the fine members of fining-upwards cyclothems. The majority of coarse members are drab coloured.Textural studies of thin and polished sections show that the red colour is caused by finely crystalline hematite as matrix and grain-coatings. This hematite apparently crystallized post-depositionally. Hematite also occurs in other textural sites: within altered phyllosilicates, as detrital grains and as totally pseudomorphed phyllosilicates. This, and the lack of consistency between colour and clay mineralogy, suggests that the red beds have had a long and complex diagenetic history.Iron analyses indicate that the red beds are enriched in Fe³⁺ and total iron (FeO) by about 1%. This is thought to have been derived from the pre-depositional weathering of iron minerals and introduced into the sediments as amorphous iron hydroxide or iron-bearing clays. Crystallization of iron hydroxide under oxidizing conditions and the post-depositional alteration of iron-silicates and oxides is thought to be responsible for the formation of the red beds.     

Determination of bioavailable Fe(III) content in column experiments with the reactive tracer phosphate

Different methods were compared to evaluate the oxidation capacity of ferric iron in column studies. The specific adsorption of the reactive tracer phosphate on the Fe(III) oxide surface was used as an alternative approach to determine the oxidation capacity utilizing the linear correlation between the long-term extent of Fe(III) reduction and the specific surface area of the oxide. Although a low crystalline form of ferric iron (two-line ferrihydrite) was used as electron acceptor and toluene as a carbon source, only 31 and 24% respectively of the total iron was reduced by Geobacter metallireducens in parallel experiments. The results of the phosphate tracer tests were in good agreement with the Fe(III) that was actually reduced and the microbially oxidized toluene. The oxidation capacity of ferric iron is therefore overestimated by the chemical extraction methods, which completely dissolve the ferrihydrite and neglect surface-dependent limitations.     

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.     

Using trace elements of magnetite to constrain the origin of the Pingchuan hydrothermal low-Ti magnetite deposit in the Panxi area,SW China

The Pingchuan iron deposit, located in the Yanyuan region of Sichuan Province, SW China, has an ore reserve of 40 Mt with ~ 60 wt% Fe. Its genesis is still poorly understood. The Pingchuan iron deposit has a paragenetic sequence of an early Fe-oxide–Pyrite stage (I) and a late Fe-oxide–pyrrhotite stage (II). Stage I magnetite grains are generally fragmented, euhedral–subhedral, large-sized crystals accompanying with slightly postdated pyrite. Stage II magnetite grains are mostly unfragmented, anhedral, relatively small-sized grains that co-exist with pyrrhotite. Combined with micro-textural features and previously-obtained geochronological data, we consider that these two stages of iron mineralization in the Pingchuan deposit correspond to the Permian ELIP magmatism and Cenozoic fault activity event. Both the Stage I and II magnetites are characterized with overall lower contents of trace elements (including Cr, Ti, V, and Ni) than the ELIP magmatic magnetite, which suggests a hydrothermal origin for them. “Skarn-like” enrichment in Sn, Mn, and Zn in the Stage I magnetite grains indicate significant material contributions from carbonate wall-rocks due to water–rock interaction in ore-forming processes. Stage II magnetite grains contain higher Mn concentrations than Stage I magnetite grains, which possibly implies more contribution from carbonate rocks. In multiple-element diagrams, the Stage I magnetite shows systematic similarities to Kiruna-type magnetite rather than those from other types of deposits. Combined with geological features and previous studies on oxygen isotopes, we conclude that hydrothermal fluids have played a key role in the generation of the Pingchuan low-Ti iron deposit.

     

Field investigations and laboratory simulation of clogging in Lixi tailings dam of Jinduicheng,China

Clogging is one of the most important factors affecting the stability of the tailings dams. Firstly, this work investigates the clogging materials of Lixi tailings dam using ICP-AES, X-ray powder diffraction (XRD) and SEM analysis methods. The ICP-AES results indicate that Fe is the dominant element in the clogging materials. The iron contents of clogging samples collected from 2# radial-well pipe and the access hole of the starter dam are 54.35 and 40.24%, respectively. XRD spectra show that ferric hydroxide is the main initial component of the clogging materials. Other compounds such as akaganeite, hematite and goethite are products from ferric hydroxide transformation. Therefore, the clogging materials are a mixture of ferric hydroxide and its converted products. The clogging materials commonly exist in an amorphous form with a cluster microstructure when viewed under SEM. Secondly, this work uses a continuous flow column to simulate clogging in the laboratory, and the clogging materials are analyzed with XRD and SEM. The chemical analysis indicates that the iron content of the clogging materials from the experiment is 45.43%. XRD spectra show that hematite is the only compound detected. The clogging materials generated experimentally are also in amorphous cluster microstructure when viewed under SEM.     

Fe isotopic fractionation during mineral dissolution with and without bacteria

Fe released into solution is isotopically lighter (enriched in the lighter isotope) than hornblende starting material when dissolution occurs in the presence of the siderophore desferrioxamine mesylate (DFAM). In contrast, Fe released from goethite dissolving in the presence of DFAM is isotopically unchanged. Furthermore, Δ⁵⁶Fe_{solution-hornblende} for Fe released to solution in the presence of ligands varies with the affinity of the ligand for Fe. The extent of isotopic fractionation of Fe released from hornblende also increases when experiments are agitated continuously. The Fe isotope fractionation observed during hornblende dissolution with organic ligands is attributed predominantly to retention of ⁵⁶Fe in an altered surface layer, while the lack of isotopic fractionation during goethite dissolution in DFAM is consistent with the lack of an altered layer. When a siderophore-producing soil bacterium is added to the system (without added organic ligands), Fe released to solution from both hornblende and goethite differs isotopically from Fe in the bulk mineral: Δ⁵⁶Fe_{solution-starting material} = −0.56 ± 0.19 (hornblende) and −1.44 ± 0.16 (goethite). Increased isotopic fractionation is attributed in this case to the fact that as bacterial respiration depletes the system in oxygen and aqueous Fe is reduced, equilibration between aqueous ferrous and ferric iron creates a pool of isotopically heavy ferric iron that is assimilated by bacterial cells. Adsorption of isotopically heavy ferrous iron (Fe(II) enriched in the heavier isotope) or precipitation of isotopically heavy Fe minerals may also contribute to observed fractionations.To test whether these Fe isotope signatures are recorded in natural systems, we also investigated extractions of samples of soils from which the bacteria were isolated. These extractions show variability in the isotopic signatures of exchangeable Fe and Fe oxyhydroxide fractions from one soil sample to another, but exchangeable Fe is observed to be lighter than Fe in soil Fe oxyhydroxides and hornblende. This observation is consistent with isotopically light Fe-organic complexes in soil pore water derived from the Fe-silicate starting materials in the presence of growing microorganisms, as documented in experiments reported here. The contributions from phenomena including organic ligand-promoted nonstoichiometric dissolution of Fe silicates, uptake of ferric iron by organisms, adsorption of isotopically heavy ferrous iron, and precipitation of iron minerals should create complex isotopic signatures in soils. Better understanding of these processes and the timescales over which they contribute to fractionation is needed.     

Iron isotope fractionation by Fe(II)-oxidizing photoautotrophic bacteria

Photoautotrophic bacteria that oxidize ferrous iron (Fe[II]) under anaerobic conditions are thought to be ancient in origin, and the ferric (hydr)oxide mineral products of their metabolism are likely to be preserved in ancient rocks. Here, two enrichment cultures of Fe(II)-oxidizing photoautotrophs and a culture of the genus Thiodictyon were studied with respect to their ability to fractionate Fe isotopes. Fe isotope fractionations produced by both the enrichment cultures and the Thiodictyon culture were relatively constant at early stages of the reaction progress, where the ⁵⁶Fe/⁵⁴Fe ratios of poorly crystalline hydrous ferric oxide (HFO) metabolic products were enriched in the heavier isotope relative to aqueous ferrous iron (Fe[II]_aq) by ∼1.5 ± 0.2‰. This fractionation appears to be independent of the rate of photoautotrophic Fe(II)-oxidation, and is comparable to that observed for Fe isotope fractionation by dissimilatory Fe(III)-reducing bacteria. Although there remain a number of uncertainties regarding how the overall measured isotopic fractionation is produced, the most likely mechanisms include (1) an equilibrium effect produced by biological ligands, or (2) a kinetic effect produced by precipitation of HFO overlaid upon equilibrium exchange between Fe(II) and Fe(III) species. The fractionation we observe is similar in direction to that measured for abiotic oxidation of Fe(II)_aq by molecular oxygen. This suggests that the use of Fe isotopes to identify phototrophic Fe(II)-oxidation in the rock record may only be possible during time periods in Earth’s history when independent evidence exists for low ambient oxygen contents.     

Experimental Study on Gold Dissolution from Hosting Minerals of the Hadamengou Gold Deposit and the Implications

The Hadamengou gold deposit is located in western part of the northern margin of the North China craton. It is a hydrothermal deposit related to alkaline magmatism. Dissolution of Au, Fe from pyrite and iron oxide （including magnetite and hematite） individual minerals in the three main types of ore shows： in iron oxides （magnetite and hematite）, Au and Fe were dissolved simultaneously and their solubilities are positively correlated, which means Au is mainly chemical-bonded （lattice gold） and/or colloidal-adsorbed in iron oxides; while in pyrite, on the contrary, Au dissolution obviously lags behind Fe and the solubility of Au shows negative relationship with that of Fe, which indicates Au is mainly hosted as grains of elemental gold （or native gold） within pyrite. Previous studies revealed that the Hadamengou gold deposit is characterized by intensive K-feldspathization and holds high content of iron oxides occasionally replaced by sulfides, which was caused by oxidizing K-enriched alkaline fluids under a stretching geodynamic setting. These geological features, together with the high Au-content in iron oxides, comparable with that of the Olympic Dam deposit in South Australia, suggest that this deposit is the first example of iron oxide-type gold deposits in China.     

Iron mineralization in the Garagu Formation of Gara Mountain,Duhok Governorate,Kurdistan, NE Iraq: geochemistry,mineralogy and origin

The iron mineralization is hosted in carbonate beds of the Garagu Formation (Early Cretaceous) at Gara Mountain, Duhok Governorate, Kurdistan Region, NE Iraq. The Garagu Formation is composed of a series of limestone and siltstone beds with iron-rich beds in the middle part. The iron-rich limestones are iron-rich oolitic grainstone and bioclastic wackestone with hematite and goethite minerals. Geochemical results drawn from this study indicate that the percentage of iron in these beds reaches 19.73 %. Moreover, petrographical investigation of thin and polished sections reveals the presence of different types of fossils, indicating an open marine interior platform depositional environment. Different iron minerals, including hematite, goethite, siderite, pyrite and magnetite, were identified in the sections, and their geneses were related to syngenetic and diagenetic processes. The geochemical distribution of major and trace elements, as well as the V/Ni, V/(V+Ni), V/Cr and Sr/Ba ratios, indicates a reducing environment during the precipitation of carbonate sediments and a subsequent oxidizing condition during the concentration of iron minerals via diagenesis.     

Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO₄·2H₂O), ferric arsenates, arseniosiderite (Ca₂Fe₃(AsO₄)₃O₂·3H₂O), Ca-Fe arsenates, pharmacosiderite (KFe₄(AsO₄)₃(OH)₄·6-7H₂O), jarosite (K₂Fe₆(SO₄)₄(OH)₁₂) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%.Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As⁵⁺in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides.The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.     

Reactive iron(III) in sediments: Chemical versus microbial extractions

The availability of particulate Fe(III) to iron reducing microbial communities in sediments and soils is generally inferred indirectly by performing chemical extractions. In this study, the bioavailability of mineral-bound Fe(III) in intertidal sediments of a eutrophic estuary is assessed directly by measuring the kinetics and extent of Fe(III) utilization by the iron reducing microorganism Shewanella putrefaciens, in the presence of excess electron donor. Microbial Fe(III) reduction is compared to chemical dissolution of iron from the same sediments in buffered ascorbate-citrate solution (pH 7.5), ascorbic acid (pH 2), and 1 M HCl. The results confirm that ascorbate at near-neutral pH selectively reduces the reactive Fe(III) pool, while the acid extractants mobilize additional Fe(II) and less reactive Fe(III) mineral phases. Furthermore, the maximum concentrations of Fe(III) reducible by S. putrefaciens correlate linearly with the iron concentrations extracted by buffered ascorbate-citrate solution, but not with those of the acid extractions. However, on average, only 65% of the Fe(III) reduced in buffered ascorbate-citrate solution can be utilized by S. putrefaciens, probably due to physical inaccessibility of the remaining fraction of reactive Fe(III) to the cells. While the microbial and abiotic reaction kinetics further indicate that reduction by ascorbate at near-neutral pH most closely resembles microbial reduction of the sediment Fe(III) pool by S. putrefaciens, the results also highlight fundamental differences between chemical reductive dissolution and microbial utilization of mineral-bound ferric iron.     

Electron microprobe analysis and ore microscopic study of magnetic spherules and grains collected from the Greenland ice

Numerous magnetic spherules and grains collected from the Greenland ice and suspected of being of cosmic origin were studied microscopically and with the microprobe. Seven types of spherules and grams were recognized.Several magnetite spherules contain metallic cores. The metallic cores of three spherules are composed of nearly pure Fe with traces of Ni. The metallic nuclei of two other spherules contain appreciable amounts of Ni; the nucleus of one of these is composed of a Ni-rich NiFe alloy (96.9% Ni), and that of the other contains 3% Ni. This latter spherule is probably of cosmic origin, perhaps formed in the fusion crust of an iron meteorite. Its magnetic shell contains no detectable Ni.The majority of the spherules consist of magnetite, which is more or less transected by martite lamellae [parallel to {111} planes of the magnetite]. One composite grain of titanomagnetite, ilmenite, hematite, and pyroxene was also found. This grain is of terrestrial origin, probably derived from the metamorphic crystalline complex of Greenland. The mineralogy and chemistry of the observed magnetite spherules and grains are discussed in detail.This work was begun at Smithsonian Astrophysical Observatory, Cambridge, Massachusetts, where it was supported in part by Grant GA-855 from the National Science Foundation, and completed at Max-Planck-Institut für Kernphysik, Heidelberg.     

内蒙古哈达门沟金矿床单矿物金浸出实验研究及其地质意义

哈达门沟金矿床产于华北克拉通北缘西段，形成于伸展构造背景中，成矿流体富钾高碱且氧化性强，矿石建造中铁氧化物含量高，并且可见铁氧化物被硫化物交代的现象。文章拟揭示金在铁氧化物中的含量和赋存状态，并探讨金矿床成因。对哈达门沟金矿3种类型矿石中的黄铁矿、铁氧化物(磁铁矿和赤铁矿)单矿物进行金、铁浸取实验，结果表明：铁氧化物含金较高；黄铁矿中的金和铁的浸出曲线不同步，金浸出率与铁浸出率呈负相关，表明黄铁矿中的金主要以颗粒金形式存在；铁氧化物中金、铁同步浸出，浸出率为正相关，表明铁氧化物中的金主要以品格金和(或)胶体吸附金形式存在。哈达门沟金矿床的上述特征均表明其具铁氧化物型金矿床的特点。     

Determination of Fe3+ and Fe2+ concentrations in feldspar by optical absorption and EPR spectroscopy

Ferrous and ferric iron concentrations in feldspars with low total iron content (<0.32 wt% total Fe) were determined from optical and electron paramagnetic resonance (EPR) spectra to better than ±15 percent of the amount present. Optical spectra indicate that Fe²⁺ occupies two distorted M-sites in plagioclases of intermediate structural state. The linear dependence of the Fe²⁺/Fe total ratio on An content demonstrates that Fe²⁺ substitutes for Ca (not Na) so that the number of Ca-sites is a principal factor in iron partitioning in plagioclase. EPR powder spectra show that the number of sites for Fe³⁺ depends on structural state rather than on plagioclase chemistry. The observed linear correspondence of EPR double-integrated intensities with optical peak areas shows that all Fe³⁺ is tetrahedrally coordinated in both plagioclase and disordered potassium feldspar. Microcline perthites show, in addition to tetrahedral Fe³⁺, a signal due to axially coordinated ferric iron, which we associate with formation of hematite inclusions.     

酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义

酸性矿山废水(acid mine drainage,AMD)是一类pH低并含有大量有毒金属元素的废水。AMD及受其影响的环境中次生高铁矿物类型主要包括羟基硫酸高铁矿物(如黄铁矾和施威特曼石等)和一些含水氧化铁矿物(如针铁矿和水铁矿等),而且这些矿物在不同条件下会发生相转变,如施氏矿物向针铁矿或黄铁矾矿物相转化。基于酸性环境中生物成因次生矿物的形成会"自然钝化"或"清除"废水中铁和有毒金属这一现象所获得的启示,提出利用这些矿物作为环境吸附材料去除地下水中砷,不但吸附量大(如施氏矿物对As的吸附可高达120mg/g),而且可直接吸附As(III),还几乎不受地下水中其他元素影响。利用AMD环境中羟基硫酸高铁矿物形成的原理,可将其应用于AMD石灰中和主动处理系统中,构成"强化微生物氧化诱导成矿-石灰中和"的联合主动处理系统,以提高AMD处理效果和降低石灰用量。利用微生物强化氧化与次生矿物晶体不断生长的原理构筑生物渗透性反应墙(PRB)并和石灰石渗透沟渠耦联,形成新型的AMD联合被动处理系统,这将有助于大幅度增加处理系统的寿命和处理效率。此外,文中还探讨了上述生物成因矿物形成在AMD和地下水处理方面应用的优点以及今后需要继续研究的问题。     

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.     

Micro-scale tracing of Fe and Si isotope signatures in banded iron formation using femtosecond laser ablation

We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite–carbonate–chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ⁵⁶Fe values of 0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ⁵⁶Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ⁵⁶Fe end member values are 0.4‰ for siderite and −0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ³⁰Si values that range between −1.0‰ and −2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate–chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite–carbonate–chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF’s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.     

Crystal chemistry of iron in natural grandidierites: an X-ray absorption fine-structure spectroscopy study

 Fe–K edge XAFS spectra (pre-edge, XANES and EXAFS) were collected for eight grandidierites from Madagascar and Zimbabwe, as well as for Fe(II) and Fe(III) model compounds (staurolite, siderite, enstatite, berlinite, yoderite, acmite, and andradite). The pre-edge spectra for these samples are consistent with dominantly 5-coordinated ferrous iron. The analysis of the XANES and EXAFS spectra confirms that Fe(II) substitutes for Mg(II) in grandidierite, with a slight expansion of the local structure around Mg by ∼2%. In addition, ferric iron was also detected in some samples [5–10 mol% of the total Fe or 500–1100 ppm Fe(III)]. Based on theoretical calculations of the EXAFS region, Fe(III) appears to be located in the 5-coordinated sites of Mg(II) or in the most distorted 6-coordinated sites of Al (depending on the sample studied). Special attention is therefore required when using grandidierite as a model for ferrous iron in C_3v geometry, because of the possible presence of an extra contribution related to Fe(III). This additional contribution enhances significantly the Fe–K pre-edge integrated area [+40% for 1000 ppm Fe(III)]. Therefore, only a few grandidierite samples can be used as a robust structural model for the study of the Fe(II) coordination in glasses and melts. Received: 26 June 2000 / Accepted: 19 February 2001     

EARLY DIAGENETIC IRON SULPHIDE IN RECENT SEDIMENTS OF THE WASH (ENGLAND)

Microscopical and chemical examination of intertidal flats of the Wash indicate that phases of iron corresponding to ferric hydroxide and iron monosulphide are involved in the early diagenetic formation of pyrite, the first being an important source of the iron. Sedimentological data are tested against analyses of total iron extractable by hydrochloric acid and concentrated nitric acid, and of the pyritic fraction of this iron; ignition data for residual organic matter are considered. The occurrence of the pyrite as isolated grains and spherules of framboidal texture is recorded, their size ranges given, and iron monosulphide recognised as the precursor of both forms. Ordering in the pyrite framboidal spherules is recorded and internal coalescence confirmed as a feature of primary growth which obscures the ordering.