Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction

Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced ⁵⁶Fe/⁵⁴Fe ratios for Fe(II)_aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)_aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)_aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO₃) and ca. +0.9‰ for Ca-substituted siderite (Ca_0.15Fe_0.85CO₃) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have ⁵⁶Fe/⁵⁴Fe ratios that are up to 1‰ lower than Fe(II)_aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)_aq.The relative order of δ⁵⁶Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)_aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ⁵⁶Fe >0‰, the calculated δ⁵⁶Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ⁵⁶Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ⁵⁶Fe values. Based on this experimental study, formation of low-δ⁵⁶Fe Fe(II)_aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.     

Experimental evidence for rapid biotic and abiotic reduction of Fe (III) at low temperatures in salt marsh sediments: a possible mechanism for formation of modern sedimentary siderite concretions

Fe (III) reduction is a key component of the global iron cycle, and an important control on carbon mineralization. However, little is known about the relative roles and rates of microbial (biotic) iron reduction, which utilizes organic matter, versus abiotic iron reduction, which occurs without carbon mineralization. This paper reports on the capacity for salt marsh sediments, which typically are rich in iron, to support abiotic reduction of mineral Fe (III) driven by oxidation of sulphide. Sediment was reacted with amorphous FeS under strictly anaerobic conditions at a range of temperatures in biotic and abiotic microcosm experiments. Fe (III) reduction driven by sulphide oxidation occurs abiotically at all temperatures, leading to Fe (II) and elemental sulphur production in all abiotic experiments. In biotic experiments elemental sulphur is also the oxidized sulphur product but higher bicarbonate production leads to FeCO₃ precipitation. Abiotic reduction of Fe (III) occurs at rates that are significant compared with microbial Fe (III) reduction in salt marsh sediments. The solid phases produced by coupled abiotic and biotic reactions, namely elemental sulphur and FeCO₃, are comparable to those seen in nature at Warham, Norfolk, UK. Furthermore, the rates of these processes measured in the microcosm experiments are sufficient to generate siderite concretions on the rapid time scales observed in the field. This work highlights the importance of abiotic Fe (III) reduction alongside heterotrophic reduction, which has implications for iron cycling and carbon mineralization in modern and ancient sediments.     

Model for the formation of arsenic contamination in groundwater. 1. Datong Basin,China

Mineral equilibria were analyzed in the system As-bearing rock-meteoric water. It was shown that carbonate rocks are the most probable source of As and Sr in the waters of the Datong Basin (People's Republic of China). The reason for groundwater enrichment in As is the shift of the equilibrium FeCO₃ (siderite) + H₂O = FeOOH(goethite) + CO₂(g) + H₂(g) to the left (toward siderite formation) owing to organic matter oxidation by atmospheric oxygen and an increase in the equilibrium partial pressure of CO₂, while the Eh of the system remains below ?0.30 ± 0.06 V.     

Geochemistry of carbonate cements in the Sag River and Shublik Formations (Triassic/Jurassic), North Slope, Alaska: implications for the geochemical evolution of formation waters

Carbonate cements (calcite, siderite, dolomite, and ankerite) formed throughout the diagenetic history of the Sag River and Shublik Formations. The trace element and isotopic geochemistry of these cements varies as a function of the timing of precipitation. Earliest calcites, formed prior to significant compaction of the sediment, are relatively enriched in Mg (up to 4·4 mol%), and have ⁸⁷Sr/⁸⁶Sr values (mean = 0·707898) compatible with the original marine pore waters. Later calcites are relatively Fe-rich (up to 5·0 mol%) and are characterized by increasing ⁸⁷Sr/⁸⁶Sr values (up to 0·712823) and Sr content with decreasing age. The Fe content of zoned siderite and dolomite/ankerite rhombs increases towards the outside of the rhombs (i.e. increasing Fe content with decreasing age). These geochemical variations appear principally to result from changes in pore-water chemistry during diagenesis. The increase in ⁸⁷Sr/⁸⁶ Sr and Sr content of the cements is most likely due to interaction between pore waters and ⁸⁷ Sr-rich clay and possibly feldspar in Ellesmerian mudrocks (whole rock ⁸⁷Sr/⁸⁶ Sr signatures for the mudrocks are > 0·716). Pore-water Fe²⁺ concentration was probably controlled by diagenetic alterations involving Fe-bearing minerals (e.g. pyrite precipitation). A reconnaissance examination of carbonate cements in the overlying Kingak Shale indicates that similar alterations occurred in the Kingak. The low δ¹⁸ O value of some calcite cements (-11·96% PDB) suggests that an influx of meteoric water may have occurred in the mid-Neocomian, though the low value could also result from an abnormally high geothermal gradient associated with mid-Neocomian rifting.     

The solubility of rhodochrosite (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments

Natural groundwaters are often reported to be highly supersaturated with the carbonate minerals siderite (FeCO₃) and rhodochrosite (MnCO₃). The kinetics of precipitation and dissolution were determined in the light of new determinations of the solubility products of siderite and rhodochrosite. Laboratory experiments showed that the precipitation kinetics of siderite and rhodochrosite were much slower than that of calcite, and also much slower than their dissolution kinetics. Experiments with supersaturated solutions failed to reach steady state within 474 days in the case of siderite, whereas steady state for rhodochrosite was reached after 140 days. Suspensions of siderite and rhodochrosite crystals reached steady state after 10 and 80 days, respectively. The solubility product of siderite (−log K_S0(FeCO₃)) was 11.03 ± 0.10 for dried crystals and 10.43 ± 0.15 for wet crystals. For rhodochrosite the solubility product (−log K_S0(MnCO₃)) was 11.39 ± 0.14 for dried crystals and 12.51 ± 0.07 for wet crystals. The solubility product determined from supersaturated solutions was −log K_S0(MnCO₃)=11.65 ± 0.14. The observed slow precipitation kinetics of siderite and rhodochrosite might explain the apparent supersaturation that is often reported for anaerobic aquatic environments.     

Siderite mineralization of the Gemericum superunit (Western Carpathians, Slovakia): review and a revised genetic model

The Gemericum is a segment of the Variscan orogen subsequently deformed by the Alpine–Carpathian orogeny. The unit contains abundant siderite–sulphide and quartz–antimony veins together with stratabound siderite replacement deposits in limestones and stratiform sulphide mineralization in volcano-sedimentary sequences. The siderite–sulphide veins and siderite replacement deposits of the Gemericum represent one of the largest accumulations of siderite in the world, with about 160 million tonnes of mineable FeCO₃. More than 1200 steeply dipping hydrothermal veins are arranged in a regional tectonic and compositional pattern, reflecting the distribution of regional metamorphic zones. Siderite–sulphide veins are typically contained in low-grade (chlorite zone) sedimentary, volcano-sedimentary or volcanic Lower and Upper Paleozoic rocks. Quartz–antimony veins are hosted by higher-grade units (biotite zone). Siderite–sulphide veins are dominated by early siderite followed by a complex set of stages, including quartz–sulphide (chalcopyrite, tetrahedrite), barite, tourmaline–quartz, and sulphide-remobilization stages. The temporal evolution of these stages is difficult to study because of the widespread and repeated tectonic processes, within-vein replacement and recrystallization. Siderite–sulphide veins show considerable vertical (up to 1200 m) and lateral (up to 15 km) extent, and a thickness typically reaching several metres. Carbonate-replacement siderite deposits of the Gemericum are hosted by a Silurian limestone belt and are similar to stratabound siderite deposits of the Eastern Alps (e.g., Erzberg, Austria).Based on a review of geological, petrological and geochronological data for the Gemericum, and extensive stable and radiogenic isotope data and fluid inclusion data on hydrothermal minerals, the siderite–sulphide veins and siderite replacement deposits are classified as metamorphogenic in a broad sense. The deposits were formed during several stages of regional crustal-scale fluid flow. Isotope (S, C, Sr, Pb) fingerprinting identifies the metamorphosed rock complexes of the Gemericum as a source of most components of hydrothermal fluids. Fluid inclusion and stable isotope data evidence the participation of several contrasting fluid types, and the existence of contrasting P–T conditions during vein evolution. A high-δ¹⁸O, medium- to high-salinity, H₂O-type fluid is the most important component during siderite deposition, whereas H₂O–CO₂-type fluid inclusion containing dense liquid CO₂ and corresponding to minimal pressures between 1 and 3 kbar were found in a younger tourmaline–quartz stage. Younger quartz–ankerite(±siderite)–sulphide stages are characterized by high-salinity (17 to 35 wt.% NaCl equivalent) and low-temperature (T_h=90 to 180 °C) H₂O-type fluids.The vein deposits are interpreted as a result of multistage hydrothermal circulation, with Variscan and Alpine mineralization phases. Based on available indirect data, the most important mineralization phase was related to regional fluid flow during the uplift of a Variscan metamorphic core complex, producing siderite–sulphide (±barite) mineralization, while tourmaline–quartz stage and sulphide remobilization stages are related to Alpine processes. Two phases of vein evolution are evident from two groups of ⁸⁷Sr/⁸⁶Sr isotope ratios of Sr-rich, Rb-poor hydrothermal minerals: 0.71042–0.71541 in older barite and 0.7190–0.7220 in late-stage celestine and strontianite.     

Lithogeochemical halos and geochemical vectors to stratiform sediment hosted Zn–Pb–Ag deposits, 1. Lady Loretta Deposit, Queensland

Stratiform sediment hosted Zn–Pb–Ag deposits, often referred to as SEDEX deposits, represent an economically important class of ore, that have received relatively little attention in terms of defining lithochemical halos and geochemical vectors useful to exploration. This study concentrates on the Lady Loretta deposit which is a typical example of the class of Proterozoic SEDEX deposits in northern Australia. We examined the major and trace element chemistry of carbonate-bearing sediments surrounding the deposit and defined a series of halos which extend for several hundred metres across strike and up to 1.5 km along strike. The stratiform ore lens is surrounded by an inner sideritic halo [Carr, G.R., 1984. Primary geochemical and mineralogical dispersion in the vicinity of the Lady Loretta Zn–Pb–Ag deposit, North Queensland. J. Geochem. Expl. 22, 217–238], followed by an outer ankerite/ferroan dolomite halo which merges with low iron dolomitic sediments representative of the regional background compositions. Carbonate within the inner siderite halo varies in composition from siderite to pistomesite (Fe_0.6Mg_0.4CO₃), whereas carbonate in the outer ankerite halo varies from ferroan dolomite to ankerite (Ca_0.5Mg_0.3Fe_0.2CO₃). Element dispersion around the stratiform ore lens is variable with Pb, Cu, Ba and Sr showing very little dispersion (<50 m across strike), Zn and Fe showing moderate dispersion (<100 m) and Mn and Tl showing broad dispersion (<200 m). Within the siderite halo Cu, Mg and Na show marked depletion compared to the surrounding sediments. The magnitude of element dispersion and change in carbonate chemistry around the Lady Loretta orebody has enabled the development of three geochemical vectors applicable to exploration. Whole rock analyses are used to calculate the three vector quantities as follows: (1) SEDEX metal index = Zn + 100Pb + 100Tl; (2) SEDEX alteration index = (FeO + 10MnO)100/(FeO + 10MnO + MgO); (3) manganese content of dolomite: MnO_d = (MnO × 30.41)/CaO. All three vectors increase to ore both across strike and along strike. The manganese content of dolomite (MnO_d) exhibits the most systematic pattern increasing from background values of about 0.2 wt% to a maximum of around 0.6 wt% at the boundary between the ankerite and siderite halos. Siderite within the inner halo contains considerably more Mn with MnO values of 0.4 to 4.0 wt%. It is suggested here that the basket of indices defined at Lady Loretta (Zn, Tl, metal index, alteration index, MnO_d and MnO_s) is applicable in the exploration for stratiform Zn–Pb–Ag deposits in dolomite-rich sedimentary basins generally. The indices defined can firstly assist in the identification of sedimentary units favourable for SEDEX mineralisation, and secondly provide vectors along these units to ore. The alteration index and MnO_d, however, should only be used for exploration dolomitic sequences; they are not recommended for exploration in clastic sequences devoid of carbonates.     

Reductive transformation of iron and sulfur in schwertmannite-rich accumulations associated with acidified coastal lowlands

We examined the transformations of Fe and S associated with schwertmannite (Fe₈O₈(OH)₆SO₄) reduction in acidified coastal lowlands. This was achieved by conducting a 91 day diffusive-flux column experiment, which involved waterlogging of natural schwertmannite- and organic-rich soil material. This experiment was complemented by short-term batch experiments utilizing synthetic schwertmannite. Waterlogging readily induced bacterial reduction of schwertmannite-derived Fe(III), producing abundant pore-water Fe^II, SO₄ and alkalinity. Production of alkalinity increased pH from pH 3.4 to pH ∼6.5 within the initial 14 days, facilitating the precipitation of siderite (FeCO₃). Interactions between schwertmannite and Fe^II at pH ∼6.5 were found, for the first time, to catalyse the transformation of schwertmannite to goethite (αFeOOH). Thermodynamic calculations indicate that this Fe^II-catalysed transformation shifted the biogeochemical regime from an initial dominance of Fe(III)-reduction to a subsequent co-occurrence of both Fe(III)- and SO₄-reduction. This lead firstly to the formation of elemental S via H₂S oxidation by goethite, and later also to formation of nanoparticulate mackinawite (FeS) via H₂S precipitation with Fe^II. Pyrite (FeS₂) was a quantitatively insignificant product of reductive Fe and S mineralization. This study provides important new insights into Fe and S geochemistry in settings where schwertmannite is subjected to reducing conditions.     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

Die Kluftankerite des Steirischen Erzberges und ihre mögliche Verwendung als Geothermometer

Conclusions concerning the minimum formation temperatures can be drawn from the chemical compositions of the 15 fissure ankerite crystals from the Steirische Erzberg which were studied. The observed FeCO₃-content of 33 mol% in several of the crystals lies, according to Rosenberg (1967), near the upper limit of the Fe-content possible for the ankerite phase and requires a formation temperature of at least 450°C (at 2 – 3 kbar pressure). Of particular interest is the occurrence of zonal concentration gradients in the individual ankerite crystals.     

The influence on Fe content on Raman spectra and unit cell parameters of magnesite–siderite solid solutions

Characterization of a set of iron–magnesium carbonate mineral samples was done by Raman spectroscopy, X-ray diffraction and electron microprobe. The evolution of unit cell parameters and of the Raman peak positions of the three vibrations modes T, L and 2ν₂ are reported as a function of the Fe content. Fourteen samples spanning the compositional range from FeCO₃ siderite to MgCO₃ magnesite were used for this calibration. Such a calibration provides a non-destructive and rapid method for extracting mineral chemistry, suitable for samples that cannot be moved and need immediate analysis or for samples that cannot be destructed or that are in small quantities.     

Glass-iron-clay interactions in a radioactive waste geological disposal: An integrated laboratory-scale experiment

Glass-iron-clay setups were reacted at 90 °C for 6-18 months to investigate the coupled interactions between glass alteration, Fe corrosion and clay transformation. The reacted interfaces were probed at the microscopic level using complementary characterization methods (scanning electron microscopy coupled with energy-dispersive X-ray analysis, micro-Raman spectroscopy, micro X-ray diffraction, micro X-ray fluorescence spectroscopy, and micro X-ray absorption near-edge structure spectroscopy). The 10-μm thick Fe foil was fully corroded within 10 months, exposing glass to the pore solution. Iron corrosion led to the formation of a layer containing mostly magnetite, siderite and Fe-rich phyllosilicates with one tetrahedral and one octahedral sheet (TO) or two tetrahedral and one octahedral (TOT) sheet per layer. The clay in contact with this corrosion layer was enriched in siderite (FeCO₃). Glass alteration resulted in the formation of a gel layer whose thickness increased with reaction time (from 20 μm after 6 months to 80 μm after 18 months) and a thin layer of secondary precipitates that concentrated lanthanides, P, and Mo. Assuming conservative behavior of Zr, the Si molar concentration in the gel is about 57% that in the glass. Glass dissolution remained at a rate close to the initial dissolution rate r₀. The data are consistent with glass dissolution sustained by the uptake of dissolved Si and charge-compensating cations on secondary (corrosion) products, thus maintaining the gel porosity open and facilitating the leaching of easily soluble elements.     

Strontium isotopic evidence for the origin of siderite,ankerite and magnesite mineralizations in the Eastern Alps

Metasomatic magnesite, siderite and ankerite mineralizations within Paleozoic sediments of the Northern Greywacke zone and its metamorphic counterpart in the crystalline basement (Upper Austroalpine unit) were investigated with respect to their strontium isotopic composition. The results support a sedimentary (s.l.) model for the magnesites within Viséan platform carbonates of the Veitsch nappe and an epigenetic hydrothermal model for the siderites and ankerites in Devonian platform carbonates of the Noric nappe and from Hüttenberg. The Fe transporting fluids can be characterized either as magmatogene or, more probably, as metamorphogene. By increasing the stage of recrystallization and/or remobilization due to at least two later metamorphic overprints, Sr in the various ore minerals beame ± enriched in radiogenic ⁸⁷Sr.     

Ferric iron in sediments as a novel CO2 mineral trap: CO2–SO2 reaction with hematite

Thermodynamic simulations of reactions among SO₂-bearing CO₂-dominated gas, water and mineral phases predict that Fe^III in sediments should be converted almost entirely to dissolved Fe^II and siderite (FeCO₃), and that SO₂ should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150 °C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO₂ in quantity sufficient to reduce much of the iron, and excess CO₂. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ∼17 h, and nucleation of siderite at ∼600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ∼1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that Fe^III can be used to trap CO₂ in siderite if partly oxidized S, as SO₂, is present to reduce the Fe with CO₂ in the gas phase.     

Significance of the chemistry and morphology of diagenetic siderite in clastic rocks of the Mesozoic Scotian Basin

Siderite (FeCO₃) is a widespread minor diagenetic mineral in clastic sedimentary basins. Although eodiagenetic authigenesis of siderite is well-known, siderite formed during burial diagenesis shows habits and chemical compositions that are poorly understood. This study tests the hypothesis that diagenetic siderite cements in sandstones in the Scotian Basin, offshore eastern Canada, show systematic variability in chemistry and habit that is a response to recrystallization and changing composition of basinal fluids. Mineral textures were determined from backscattered electron images, and chemistry mostly from electron microprobe analyses. Five chemical types of siderite are identified using k-means cluster analysis, based on the amount of substitution of Ca, Mg and Mn for Fe. Eodiagenetic microcrystalline coated grains, concretions and intraclasts in sandstones are principally Fe-rich siderite and locally have recrystallised to blocky equant crystals. Mesodiagenetic Mg-rich siderite partly replaced these equant crystals and also framework mica and K-feldspar grains, showing textural evidence for coupled dissolution–reprecipitation. Slender Mg-rich siderite rhombs (lozenges, bladed or wheat-seed siderite) have precipitated before and after the formation of quartz overgrowths in geochemical microenvironments. Magnesium substitution reflects Mg-rich formation waters resulting from smectite to illite conversion. Equivalent Ca-rich siderite occurs where sandstones overlie a Jurassic carbonate bank. Late Mn-rich siderite has complex textures resembling those of Mississippi-Valley type ores, with spheroidal rims, a honeycomb-like mesh and concentric infill around secondary pores. It also occurs in veins or replacing intraclasts, post-dating late ferroan-calcite cements in sandstones that show strong dissolution by hot basinal brines. The Ca, Mg and Mn content of diagenetic siderite, coupled with textural evidence for recrystallization, can thus be used to track changes in ambient formation fluids. Siderite habits and chemistry described from the Scotian Basin are found in many clastic basins, suggesting that the observed recrystallization textures and variation in chemical type are of broad application.     

Cation exchanged Fe(II) and Sr compared to other divalent cations (Ca, Mg) in the bure Callovian–Oxfordian formation: Implications for porewater composition modelling

Iron and Sr bearing phases were thoroughly investigated by means of spectrometric and microscopic techniques in Callovian–Oxfordian (COX) samples originating from the ANDRA Underground Research Laboratory (URL) in Bure (France). Strontium was found to be essentially associated with celestite, whereas Fe was found to be distributed over a wide range of mineral phases. Iron was mainly present as Fe(II) in the studied samples (∼93% from Mössbauer results). Most of the Fe(II) was found to be in pyrite, sideroplesite/ankerite and clay minerals. Iron(III), if present, was associated with clay minerals (probably illite, illite-smectite mixed layer minerals and chlorite). No Fe(III) oxy(hydro)xide could be detected in the samples. Strontianite was not observed either. Based on these observations, it is likely that the COX porewater is in equilibrium with the following carbonate minerals, calcite, dolomite and ankerite/sideroplesite, but not with strontianite. It is shown that this equilibrium information can be combined with clay cation exchange composition information in order to give direct estimates or constraints on the solubility products of the carbonate minerals dolomite, siderite and strontianite. As a consequence, an experimental method was developed to retrieve the cation exchanged Fe(II) in very well preserved COX samples.     

The geochemistry of wall rock alteration in turbidite-hosted gold vein deposits, central Victoria, Australia

Gold deposits hosted in Ordovician to Devonian turbidites in central Victoria, Australia, consist of steeply dipping quartz vein systems hosted mainly by reverse faults. Wall rock alteration of the host metasandstones, metasiltstones and shales (or slates) extends at least 20 m from the veins in the Bendigo-Ballarat zone (BBZ) and 10 m in the Melbourne zone (MZ) deposits. Alteration minerals include carbonates (ankerite, siderite and dolomite) chlorite, seriate, arsenopyrite, pyrite, chalcopyrite and sphalerite, with less common barite, albite and biotite in the BBZ and carbonates (siderite, ankerite, dolomite and ferromagnesite), sericite, chlorite, arsenopyrite, pyrite, and stibnite with less common chalcostibite in the MZ. SiO₂, Na₂O, MgO and Sr with P₂O₅ commonly decreasing during alteration while CO₂, S, As, Sb, Au, V, Al₂O₃, Ga, K₂O and Rb with Ni and Cr commonly increase. TiO₂, FeO, Fe₂O₃, MnO, Th, U, Nb, La, Ce, and Sc showed little change. Concentrations of Zn, Cu, Pb, and Ca are variable.The relatively large decrease of SiO₂ could account for most, if not all, quartz present in the ore veins. The Na₂O and MgO could have crystallized in the veins in the very minor albite and chlorite present. The addition of V in all and Ni and Cr in most deposits probably reflects a source enriched in these elements such as underlying greenstones. The source of both the volatile (S, As, Sb) and lithophile (K₂O and Rb) elements as well as Au is unknown, but they could have been derived from a magmatic source or from the metamorphism of Cambrian greenstones. CO₂, present as carbonate, was derived mainly by the reaction of graphite, originally present in the sediments, with the ore solutions. Al₂O₃, the only other major element after SiO₂, probably increased mainly due to the decrease of the latter.     

Metal corrosion and argillite transformation at the water-saturated,high-temperature iron–clay interface: A microscopic-scale study

In this study, microscopic and spectroscopic techniques (scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman microspectroscopy, micro X-ray fluorescence spectroscopy, micro X-ray fine structure adsorption spectroscopy, and micro laser-induced breakdown spectroscopy) were combined to decipher the chemical and mineralogical properties of a saturated Fe–clay interface reacted at 90 °C and 50 bar for 8 months. The results collectively confirm the presence of a corrosion layer and a clay transformation layer. The corrosion layer is made of a magnetite-containing internal sublayer and a Fe-phyllosilicate external sublayer enriched in Na, with traces of goethite presumably resulting from sample reaction with air. The clay transformation layer is made of predominantly Ca-rich siderite (FeCO₃). It is depleted in Al and K, suggesting dissolution of rock-forming minerals. The corroded thickness determined from the amount of Fe in corrosion and transformation layers and assuming zero porosity equals 19 ± 9 μm. These data indicate that the interfacial clay was transformed by dissolution of calcite and clay minerals and precipitation of siderite close to the original surface. Silica released upon clay dissolution diffused into the corrosion layer and coprecipitated with oxidized Fe to form Fe-phyllosilicate.     

Covariance of C- and O-isotopes with magnetic susceptibility as a result of burial diagenesis of sandstones and carbonates: an example from the Lower Devonian La Vid Group,Cantabrian Zone,NW Spain

The burial diagenesis of sandstones, limestones, and dolostones of the Lower Devonian La Vid Group in the Cantabrian Zone (NW Spain) reveal a covariance of carbon and oxygen isotope values with magnetic susceptibility. Also, strontium isotopes, and to a minor degree Fe, follow this trend. The main carriers of the magnetic susceptibility appear to be diagenetic Fe-carbonates, i.e., siderite, ferroan dolomite, and ankerite, which occur as cements in primary and secondary voids, as well as in fractures. In some layers, especially at the top of the succession there occurs additionally secondary Fe-chlorite and pyrite. The Fe-carbonates were formed during upward migration of a reducing, iron-bearing, petroliferous fluid that was depleted in ¹³C and carried radiogenic Sr. Similar geochemical covariance and/or correlations can be expected in other sedimentary successions affected by the migration of petroliferous formation fluids.     

Carbonate-sulfide equilibria and “stratabound” disseminated epigenetic gold mineralization: a proposal based on examples from Alleghany,California, U.S.A.

“Stratabound” disseminated pyritic Au ore bodies were produced by reactions between wall rocks and through-flowing fluids in Mesozoic epigenetic Au quartz vein systems in the Sierra Nevada metamorphic belt. Equilibrium relations among Fe-bearing carbonate and sulfide minerals were critical in determining which rock types were likely to host disseminated mineralization along portions of discordant veins. The compositions of metasomatic carbonates in hydrothermally altered wall rocks at Alleghany, California, U.S.A., were larely predetermined by the relative proportions of Fe, Mg and Ca in the unaltered wall rocks. Thus, coexisting solid solutions in the magnesite-siderite and dolomite-ankerite series from a variety of different wall rocks yield an empirical phase diagram for a large part of the Ca CO₃MgCO₃FeCO₃ system at the temperature of metasomatism (325 ± 50°C). Because Fe,Mg-silicates were unstable in alteration zones adjacent to the veins, wall rock Fe was partitioned between carbonates and sulfides. Pyritization and disseminated Au mineralization occur in a variety of igneous and metasedimentary wall rocks in which the initial molar Fe/(Fe + Mg) ≧ 0.5. In altered wall rocks with initial molar Fe/(Fe + Mg) ≦ 0.5, Fe was incorporated almost entirely within Mg-rich carbonates (X_FeCO3 ≦ 0.6 in magnesite-siderite solutions). It is proposed that the CO₂-rich vein fluid responsible for the alteration and mineralization was partially buffered with respect to H₂S/CO₂/H₂ ratios by equilibrium between pyrite and Mg_0.4Fe_0.6CO₃ (+graphite?) as it traversed and altered intermediate volcanic and sedimentary rocks. This fluid then locally reacted with lower Fe/(Fe + Mg) rocks to form Fe-bearing dolomite + magnesite assemblages, and reacted with higher Fe/(Fe + Mg) rocks to form ankerite + pyrite assemblages. Gold precipitated from saturated solutions of bisulfide complexes partly in response to fluid desulfidation and reduction caused by the pyritization reactions. In terranes dominated by intermediate metavolcanic and metasedimentary rocks, favorable host rocks for this type of mineralization need not have high Fe contents, but do require high Fe/(Fe + Mg) ratios. They may include felsic volcanic and plutonic rocks, Fe-rich tholeiitic differentiates, banded Fe formations, and a variety of siliceous and argillaceous sedimentary rocks. Rocks which tend not to be heavily sulfidized because they have low initial Fe/(Fe + Mg) ratios include ultramafic and mafic igneous rocks, and some argillaceous sedimentary rocks. Exploration guidelines based on these principles may be useful elsewhere in the Sierra Nevada and in other comparable heterogeneous metamorphic terranes, if modified to reflect the dominant buffering rock types in a given fluid flow path. Carbonate-sulfide equilibria are capable of approximately buffering the carbonate-sulfide ratios of CO₂-rich vein fluids (f_CO2≧ 10^2.8 at 325°C, 200MPa or 2000 bar). The Alleghany fluid (f_CO2 ≈ 10^3.2, or ∼ 10 mol % CO₂) had a molar CO₂/H₂S ratio of approximately 10³, assuming graphite saturation. At lower CO₂ fugacities, Fe-bearing silicates entered the buffering assemblages. Carbonatization reactions could potentially de-sulfidize some wall rocks, releasing S (and associated metals?) to the fluid. This would be most likely to occur in pyrite-bearing mafic and ultramafic rocks and some argillites.