Influence of pH and dissolved Si on Fe isotope fractionation during dissimilatory microbial reduction of hematite

Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low ⁵⁶Fe/⁵⁴Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ⁵⁶Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ⁵⁶Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.     

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.     

Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria

Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)_aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in ⁵⁶Fe/⁵⁴Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ⁵⁶Fe_{Fe(OH)3-Fe(II)aq} fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)_aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)_aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)_aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)_aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.     

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared ⁵⁶Fe/⁵⁴Fe ratios of coexisting aqueous iron (Fe(II)_aq, Fe(III)_aq) and iron oxyhydroxide precipitates (Fe(III)_ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO₄²⁻ and Cl⁻ salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, ⁵⁶Fe/⁵⁴Fe ratios of residual Fe(II)_aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor α_{Fe(III)aq-Fe(II)aq} ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)_aq and Fe(III)_aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in ⁵⁶Fe/⁵⁴Fe ratios between Fe(III)_aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N₂-atmosphere, and Fe(II)_aq was in most cases and on average close to 2.9‰ (α_{Fe(III)aq-Fe(II)aq} ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)_aq and Fe(III)_aq. The ferric iron precipitation experiments revealed that ⁵⁶Fe/⁵⁴Fe ratios of Fe(III)_aq were generally equal to or greater than those of Fe(III)_ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.     

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.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

Iron isotope fractionation and atom exchange during sorption of ferrous iron to mineral surfaces

The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al₂O₃), goethite (α-FeOOH), quartz (α-SiO₂), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)_aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)_sorb-Fe(II)_aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ^56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)_aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ^56/54Fe(II)_aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)_aq to be affected by sorption.     

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.     

Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(III) and hematite

Application of the Fe isotope system to studies of natural rocks and fluids requires precise knowledge of equilibrium Fe isotope fractionation factors among various aqueous Fe species and minerals. These are difficult to obtain at the low temperatures at which Fe isotope fractionation is expected to be largest and requires careful distinction between kinetic and equilibrium isotope effects. A detailed investigation of Fe isotope fractionation between [Fe^III(H₂O)₆]³⁺ and hematite at 98°C allows the equilibrium ⁵⁶Fe/⁵⁴Fe fractionation to be inferred, which we estimate at 10³lnα_{Fe(III)-hematite} = −0.10 ± 0.20‰. We also infer that the slope of Fe(III)-hematite fractionation is modest relative to 10⁶/T², which would imply that this fractionation remains close to zero at lower temperatures. These results indicate that Fe isotope compositions of hematite may closely approximate those of the fluids from which they precipitated if equilibrium isotopic fractionation is assumed, allowing inference of δ⁵⁶Fe values of ancient fluids from the rock record. The equilibrium Fe(III)-hematite fractionation factor determined in this study is significantly smaller than that obtained from the reduced partition function ratios calculated for [Fe^III(H₂O)₆]³⁺ and hematite based on vibrational frequencies and Mössbauer shifts by [Polyakov 1997] and [Polyakov and Mineev 2000], and Schauble et al. (2001), highlighting the importance of experimental calibration of Fe isotope fractionation factors. In contrast to the long-term (up to 203 d) experiments, short-term experiments indicate that kinetic isotope effects dominate during rapid precipitation of ferric oxides. Precipitation of hematite over ∼12 h produces a kinetic isotope fractionation where 10³lnα_{Fe(III)-hematite} = +1.32 ± 0.12‰. Precipitation under nonequilibrium conditions, however, can be recognized through stepwise dissolution in concentrated acids. As expected, our results demonstrate that dissolution by itself does not measurably fractionate Fe isotopes.     

Redox history of the Three Gorges region during the Ediacaran and Early Cambrian as indicated by the Fe isotope

The Ediacaran-Cambrian transition is characterized by numerous events such as the emergence of large multi-cellular metazoans and surface environmental disturbances.Based on geological evidence,it has been proposed that this transition coincided with the increase in the atmospheric oxygen level that was key to the evolution of life.Even though ancient redox conditions can be inferred from the composition of sedimentary iron mineral species,this method is not necessarily applicable to all rocks.In the Earth system,the cycling of iron is of considerable interest owing to its sensitivity to redox conditions.Information regarding the paleo-oceanic iron cycle is revealed in the iron isotopic composition of ironbearing minerals.Unfortunately,only limited iron isotopic data exists for Ediacaran-to Cambrianperiod oceans.To circumvent this deficiency,we drilled a fossiliferous Ediacaran to Early Cambrian sedimentary succession in the Three Gorges region,South China.We analyzed the iron isotope ratios(δ~(56/54)Fe)of pyrite grains in the drill cores using laser ablation multi collector inductively coupled plasma mass spectrometry.The results demonstrate large variations inδ~(56/54)Fe,from-1.6 to 1.6‰,and positive iron isotope ratios are observed in many successions.The presence of positiveδ~(56/54)Fe in pyrite indicates that the ferrous iron in the seawater was partially oxidized,suggesting that seawater at Three Gorges was ferruginous during the Ediacaran and Early Cambrian periods.However,aggregated pyrite grains in organic carbon-rich black shales at Member 4 of the Doushantuo Formation and the base of the Shuijingtuo Formation yield near-zeroδ~(56/54)Fe values;this suggests that the ocean was transiently dominated by sulfidic conditions during these periods.Notably negativeδ~(56/54)Fe values,lower than-1‰,can be interpreted as a signature of DIR.The DIR also might contribute in part to the re-mineralization of organic matter during the largest negative carbon isotope anomaly in the Ediacaran.     

Deciphering formation processes of banded iron formations from the Transvaal and the Hamersley successions by combined Si and Fe isotope analysis using UV femtosecond laser ablation

To investigate the genesis of BIFs, we have determined the Fe and Si isotope composition of coexisting mineral phases in samples from the ∼2.5 billion year old Kuruman Iron Formation (Transvaal Supergroup, South Africa) and Dales Gorges Member of the Brockman Iron Formation (Hamersley Group, Australia) by UV femtosecond laser ablation coupled to a MC-ICP-MS. Chert yields a total range of δ³⁰Si between −1.3‰ and −0.8‰, but the Si isotope compositions are uniform in each core section examined. This uniformity suggests that Si precipitated from well-mixed seawater far removed from its sources such as hydrothermal vents or continental drainage. The Fe isotope composition of Fe-bearing mineral phases is much more heterogeneous compared to Si with δ⁵⁶Fe values of −2.2‰ to 0‰. This heterogeneity is likely due to variable degrees of partial Fe(II) oxidation in surface waters, precipitation of different mineral phases and post-depositional Fe redistribution. Magnetite exhibits negative δ⁵⁶Fe values, which can be attributed to a variety of diagenetic pathways: the light Fe isotope composition was inherited from the Fe(III) precursor, heavy Fe(II) was lost by abiotic reduction of the Fe(III) precursor or light Fe(II) was gained from external fluids. Micrometer-scale heterogeneities of δ⁵⁶Fe in Fe oxides are attributed to variable degrees of Fe(II) oxidation or to isotope exchange upon Fe(II) adsorption within the water column and to Fe redistribution during diagenesis. Diagenetic Fe(III) reduction caused by oxidation of organic matter and Fe redistribution is supported by the C isotope composition of a carbonate-rich sample containing primary siderite. These carbonates yield δ¹³C values of ∼−10‰, which hints at a mixed carbon source in the seawater of both organic and inorganic carbon. The ancient seawater composition is estimated to have a minimum range in δ⁵⁶Fe of −0.8‰ to 0‰, assuming that hematite and siderite have preserved their primary Fe isotope signature. The long-term near-zero Fe isotope composition of the Hamersley and Transvaal BIFs is in balance with the assumed composition of the Fe sources. The negative Fe isotope composition of the investigated BIF samples, however, indicates either a perturbation of the steady state, or they have to be balanced spatially by deposition of isotopically heavy Fe. In the case of Si, the negative Si isotope signature of these BIFs stands in marked contrast to the assumed source composition. The deviation from potential source composition requires a complementary sink of isotopically heavy Si in order to maintain steady state in the basin. Perturbing the steady state by extraordinary hydrothermal activity or continental weathering in contrast would have led to precipitation of light Si isotopes from seawater. Combining an explanation for both elements, a likely scenario is a steady state ocean basin with two sinks. When all published Fe isotope records including BIFs, microbial carbonates, shales and sedimentary pyrites, are considered, a complementary sink for heavy Fe isotopes must have existed in Precambrian ocean basins. This Fe sink could have been pelagic sediments, which however are not preserved. For Si, such a complementary sink for heavy Si isotopes might have been provided by other chert deposits within the basin.     

Iron isotope fractionation during hydrothermal ore deposition and alteration

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ⁵⁶Fe between −2.3‰ and +1.3‰. Primary hematite (δ⁵⁶Fe: −0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe (δ⁵⁶Fe: −0.5‰) leached from the crystalline basement. Occasional input of CO₂-rich waters resulted in precipitation of isotopically light siderite (δ⁵⁶Fe: −1.4 to −0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.     

First experimental determination of iron isotope fractionation between hematite and aqueous solution at hydrothermal conditions

Although iron isotopes provide a new powerful tool for tracing a variety of geochemical processes, the unambiguous interpretation of iron isotope ratios in natural systems and the development of predictive theoretical models require accurate data on equilibrium isotope fractionation between fluids and minerals. We investigated Fe isotope fractionation between hematite (Fe₂O₃) and aqueous acidic NaCl fluids via hematite dissolution and precipitation experiments at temperatures from 200 to 450 °C and pressures from saturated vapor pressure (P_sat) to 600 bar. Precipitation experiments at 200 °C and P_sat from aqueous solution, in which Fe aqueous speciation is dominated by ferric iron (Fe^III) chloride complexes, show no detectable Fe isotope fractionation between hematite and fluid, Δ⁵⁷Fe_{fluid-hematite} = δ⁵⁷Fe_fluid − δ⁵⁷Fe_hematite = 0.01 ± 0.08‰ (2 × standard error, 2SE). In contrast, experiments at 300 °C and P_sat, where ferrous iron chloride species (FeCl₂ and FeCl⁺) dominate in the fluid, yield significant fluid enrichment in the light isotope, with identical values of Δ⁵⁷Fe_{fluid-hematite} = −0.54 ± 0.15‰ (2SE) both for dissolution and precipitation runs. Hematite dissolution experiments at 450 °C and 600 bar, in which Fe speciation is also dominated by ferrous chloride species, yield Δ⁵⁷Fe_{fluid-hematite} values close to zero within errors, 0.15 ± 0.17‰ (2SE). In most experiments, chemical, redox, and isotopic equilibrium was attained, as shown by constancy over time of total dissolved Fe concentrations, aqueous Fe^II and Fe^III fractions, and Fe isotope ratios in solution, and identical Δ⁵⁷Fe values from dissolution and precipitation runs. Our measured equilibrium Δ⁵⁷Fe_{fluid-hematite} values at different temperatures, fluid compositions and iron redox state are within the range of fractionations in the system fluid-hematite estimated using reported theoretical β-factors for hematite and aqueous Fe species and the distribution of Fe aqueous complexes in solution. These theoretical predictions are however affected by large discrepancies among different studies, typically ±1‰ for the Δ⁵⁷Fe _{Fe(aq)-hematite} value at 200 °C. Our data may thus help to refine theoretical models for β-factors of aqueous iron species. This study provides the first experimental calibration of Fe isotope fractionation in the system hematite-saline aqueous fluid at elevated temperatures; it demonstrates the importance of redox control on Fe isotope fractionation at hydrothermal conditions.     

The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid ⁵⁵Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.     

Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)

Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl⁻) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using ⁵⁷Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60-80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl⁻ (∼10 mM HNO₃) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl⁻ solutions.The average measured equilibrium isotope fractionations, Δ_{Fe(III)-Fe(II)}, in 0, 11, and 111 mM Cl⁻ solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured Δ_{Fe(III)-Fe(II)} fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl⁻ solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: where the isotopic fractionation is independent of Cl⁻ contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl⁻ contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation.     

Iron isotope fractionation between pyrite (FeS2), hematite (Fe2O3) and siderite (FeCO3): A first-principles density functional theory study

In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α⁵⁷Fe/⁵⁴Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III)_aq-hematite and Fe(II)_aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions (β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived β-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined.     

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.     

Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a Fe-Fe double spike

We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a ⁵⁸Fe-⁵⁴Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ⁵⁶Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ⁵⁶Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ⁵⁶Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ⁵⁶Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.     

Fe(II) adsorption on hematite (0 0 0 1)

The surface structure of α-Fe₂O₃(0 0 0 1) was studied using crystal truncation rod (CTR) X-ray diffraction before and after reaction with aqueous Fe(II) at pH 5. The CTR results show the unreacted α-Fe₂O₃(0 0 0 1) surface consists of two chemically distinct structural domains: an O-layer terminated domain and a hydroxylated Fe-layer terminated domain. After exposing the α-Fe₂O₃(0 0 0 1) surface to aqueous Fe(II), the surface structure of both co-existing structural domains was modified due to adsorption of Fe at crystallographic lattice sites of the substrate, resulting in six-coordinated adsorbed Fe at the surface. The average Fe-O bond lengths of the adsorbed Fe are consistent with typical Fe(III)-O bond lengths (in octahedral coordination), providing evidence for the oxidation of Fe(II) to Fe(III) upon adsorption. These results highlight the important role of substrate surface structure in controlling Fe(II) adsorption. Furthermore, the molecular scale structural characterization of adsorbed Fe provides insight into the process of Fe(II) induced structural modification of hematite surfaces, which in turn aids in assessing the effective reactivity of hematite surfaces in Fe(II) rich environments.