Iron Isotope Fractionation Research Articles

Zn, Fe and S isotope fractionation in a large hydrothermal system

The genesis of hydrothermal ore deposits is of crucial economic importance. This study investigates the extent, causes and consequences of zinc and iron isotope fractionation in a large hydrothermal system at the world-class Navan Zn–Pb orebody, Ireland. Large variations in Zn, Fe and S isotope compositions have been measured in microdrilled sphalerite (ZnS) at the millimetre scale. δ66Zn and δ56Fe display a well-defined positive correlation and both also correlate with δ34S. These relationships represent the combined effects of kinetic Zn and Fe isotope fractionation during sphalerite precipitation, and S isotope variation through mixing of hot, metal-rich hydrothermal fluids and cool, bacteriogenic sulfide-bearing brines. Combined with S isotope data, δ56Fe and δ66Zn data on mine concentrates confirm that hydrothermal sulfide is a minor component of the overall deposit signature. Our data suggest that incoming pulses of metal-rich hydrothermal fluid triggered sulfide mineralisation, and that rapid precipitation of sphalerite from hydrothermal fluids will lead to strong kinetic fractionation of Zn and Fe isotopes at very short time and length scales, thereby limiting the use of Fe and Zn isotopes as exploration tools within deposits, but revealing the possibility of detecting new deposits from isotopically heavy Zn–Fe geochemical halos.

Communities of neutrophilic iron-oxidizing microorganisms of ferruginous springs of various types and their involvement in fractionation of stable iron isotopes

Abundance and structure of the communities of neutrophilic lithotrophic iron-oxidizing bacteria (FeOB) inhabiting four low-mineralized ferruginous springs of the Marcial Waters Resort (South Karelia, Russia) and the brackish chalybeate spring of the Staraya Russa Resort (Novgorod region, Russia), were investigated, as well as the physicochemical conditions of these environments. In fresh iron-containing precipitates collected near the spring outlets and within the spring-discharge areas, as well as along the spring watercourses, the numbers of unicellular FeOB enumerated on nutrient media ranged from 105 to 107 cells per 1 mL of sediments irrespective of the initial Fe(II) concentration (11–126 mg L−1). In the spring waters and along the spring watercourses inhabited by iron-oxidizing bacteria, the concentration of dissolved oxygen did not exceed 0.05–0.1 mg L−1. Unicellular FeOB were predominant in three springs, while in the springs with relatively low Fe(II) concentrations (11–22 mg L−1), various morphological forms of Gallionella and uncultured forms of the iron-oxidizing bacterium Toxothrix trichogenes prevailed. In the model experiments with the water samples collected in the ferruginous springs and bogs under controlled conditions, the fractionation of stable iron isotopes and the rate of iron oxidation were found to depend on the oxygen regime and, to a lesser extent, on the initial Fe(II) concentration. The maximum enrichment of the iron oxides formed during the simulation experiments with the light 54Fe isotope was observed during bacterial oxidation under microaerobic conditions at O2 concentrations of 0.1–0.3 mg L−1 and in the cultures of iron-oxidizing bacteria. During the abiogenic oxidation of Fe(II), the extent of stable isotope fractionation was 1.5–2 times lower. Enrichment of Fe(III) oxides with the light 54Fe isotope (3- to 5-fold) was considerably lower at high rates of both the biogenic and abiogenic processes of iron oxidation under aerobic conditions; however, it was more intense during the bacterial processes. Comparison of the rates of enrichment of Fe(III) oxides with the light isotope during the model experiments with pure and enrichment cultures of iron-oxidizing bacteria from the sediments of ferruginous springs and bogs revealed that the biogenic factor plays a key role in the oxidation processes of the iron cycle, as well as in the differentiation of the composition of stable iron isotopes in the studied ecosystems.

Iron isotope fractionation in a sulfide-bearing subterranean estuary and its potential influence on oceanic Fe isotope flux

We trace pathways of Fe reactions in the Indian River Lagoon (Florida, USA) subterranean estuary using Fe isotopes to provide new constraints on Fe-isotopic fractionation in a sulfide-bearing subterranean estuary. Porewater δ56Fe values increase from −1.16‰ at 115cm depth to +0.2‰ at 7cm depth due to isotope fractionation in three distinct lithostratigraphic zones. The deepest zone contains orange sands with elevated Fe-oxide contents (0.2wt.%) that dissolve through diagenetic Fe-oxide reduction and elevate Fe concentrations in porewaters (100 to 300μM/l). This reaction causes porewater δ56Fe values to be ~1‰ lighter than the sediment δ56Fe values. An intermediate zone contains white Fe-poor sands, with Fe-oxide contents <0.1wt.% and dissolved Fe concentrations <20μM/l. This zone is a sink for dissolved Fe through adsorption of isotopically heavy dissolved Fe(II) onto mineral surfaces. This adsorption results in porewater δ56Fe values that are as much as 1.8‰ lighter than sediment δ56Fe values. The uppermost zone contains organic carbon and Fe-sulfide rich black sediments with low dissolved Fe (<1μM/l) and elevated porewater sulfide (up to 600μM/l) concentrations. Precipitation of isotopically light Fe-sulfides increases the porewater δ56Fe values as much as 0.68‰ more than corresponding sediment δ56Fe values. The near-surface Fe-sulfide precipitation delivers to the lagoon dissolved Fe with slightly positive δ56Fe values, averaging about +0.24‰, via submarine groundwater discharge (SGD). Iron-sulfide precipitation in sulfide-containing subterranean estuaries thus may result in a previously unidentified source of isotopically heavy Fe to the coastal oceans.

Stable iron isotope fractionation between aqueous Fe(II) and model Archean ocean Fe–Si coprecipitates and implications for iron isotope variations in the ancient rock record

Iron isotope fractionation between aqueous Fe(II) (Fe(II)aq) and two amorphous Fe(III) oxide–Si coprecipitates was investigated in an aqueous medium that simulated Archean marine conditions, including saturated amorphous silica, low sulfate, and zero dissolved oxygen. The equilibrium isotope fractionation (in 56Fe/54Fe) between Fe(II)aq and Fe(III)-Si coprecipitates at circum-neutral pH, as inferred by the three-isotope method, was −3.51±0.20 (2σ)‰ and −3.99±0.17 (2σ)‰ for coprecipitates that had Fe:Si molar ratios of 1:2 and 1:3, respectively. These results, when combined with earlier work, indicate that the equilibrium isotope fractionation factor between Fe(II)aq and Fe(III)–Si coprecipitates changes as a function of Fe:Si ratio of the solid. Isotopic fractionation was least negative when Fe:Si=1:1 and most negative when Fe:Si=1:3. This change corresponds with changes in the local structure of iron, as revealed by prior spectroscopic studies. The kinetics of isotopic exchange was controlled by movement of Fe(II) and Si, where sorption of Fe(II) from aqueous to solid phase facilitated atom exchange, but sorption of Si hindered isotopic exchange through blockage of reactive surface sites. Although Fe(II)–Fe(III) isotopic exchange rates were a function of solid and solution compositions in the current study, in all cases they were much higher than that determined in previous studies of aqueous Fe(III) and ferrihydrite interaction, highlighting the importance of electron exchange in promoting Fe atom exchange. When compared to analogous microbial reduction experiments of overlapping Fe(II) to Fe(III) ratios, isotopic exchange rates were faster in the biological experiments, likely due to promotion of atom exchange by the solid-phase Fe(II) produced in the biological experiments. These results provide constraints for interpreting the relatively large range of Fe isotope compositions in Precambrian marine sedimentary rocks, and highlight important differences between modern and ancient marine environments due to the absence or presence of dissolved silica. Evidence can be found in the Fe isotope compositions of the ancient rock record for both abiologic and biologic processes, distinction of which becomes apparent when sedimentological and diagenetic processes are fully explored, as well as Fe mass balance.

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ56Fewr=0.06–0.17‰ and δ7Lima=2.5–5.2‰, assuming δ7Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ56Feol=−0.24 to 0.14‰ and δ7Liol=−10.5 to +6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ56Feol between −0.7 and +0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ7Licpx=−17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg#>0.89 and Ni>3000μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ7Liol-melt=−13; Δ56Feol-melt=−0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ7Liol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Liol/Limelt), indicating Li isotope fractionation due to preferential (faster) diffusion of 6Li into olivine during fractional crystallization. Olivine with low Δ7Liol-melt, also have low Δ56Feol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ56Feol-melt (−0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ56Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe3+/Fe2+ of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.

Effect of Aqueous Fe(II) on Arsenate Sorption on Goethite and Hematite

Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10⁻³ M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.

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 (Psat) to 600bar. Precipitation experiments at 200°C and Psat from aqueous solution, in which Fe aqueous speciation is dominated by ferric iron (FeIII) chloride complexes, show no detectable Fe isotope fractionation between hematite and fluid, Δ57Fefluid–hematite=δ57Fefluid−δ57Fehematite=0.01±0.08‰ (2×standard error, 2SE). In contrast, experiments at 300°C and Psat, where ferrous iron chloride species (FeCl2 and FeCl+) dominate in the fluid, yield significant fluid enrichment in the light isotope, with identical values of Δ57Fefluid–hematite=−0.54±0.15‰ (2SE) both for dissolution and precipitation runs. Hematite dissolution experiments at 450°C and 600bar, in which Fe speciation is also dominated by ferrous chloride species, yield Δ57Fefluid–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 FeII and FeIII fractions, and Fe isotope ratios in solution, and identical Δ57Fe values from dissolution and precipitation runs. Our measured equilibrium Δ57Fefluid–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.

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ 56Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ 56Fe. For all soils the lightest isotopic composition was observed in a 1 M NH 2OH–HCl–25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.

Iron isotope fractionation during microbial dissimilatory iron oxide reduction in simulated Archaean seawater

The largest Fe isotope excursion yet measured in marine sedimentary rocks occurs in shales, carbonates, and banded iron formations of Neoarchaean and Paleoproterozoic age. The results of field and laboratory studies suggest a potential role for microbial dissimilatory iron reduction (DIR) in producing this excursion. However, most experimental studies of Fe isotope fractionation during DIR have been conducted in simple geochemical systems, using pure Fe(III) oxide substrates that are not direct analogues to phases likely to have been present in Precambrian marine environments. In this study, Fe isotope fractionation was investigated during microbial reduction of an amorphous Fe(III) oxide-silica coprecipitate in anoxic, high-silica, low-sulphate artificial Archaean seawater at 30 °C to determine if such conditions alter the extent of reduction or isotopic fractionations relative to those observed in simple systems. The Fe(III)-Si coprecipitate was highly reducible (c. 80% reduction) in the presence of excess acetate. The coprecipitate did not undergo phase conversion (e.g. to green rust, magnetite or siderite) during reduction. Iron isotope fractionations suggest that rapid and near-complete isotope exchange took place among all Fe(II) and Fe(III) components, in contrast to previous work on goethite and hematite, where exchange was limited to the outer few atom layers of the substrate. Large quantities of low-δ(56)Fe Fe(II) (aqueous and solid phase) were produced during reduction of the Fe(III)-Si coprecipitate. These findings shed new light on DIR as a mechanism for producing Fe isotope variations observed in Neoarchaean and Paleoproterozoic marine sedimentary rocks.

New data on equilibrium iron isotope fractionation among sulfides: Constraints on mechanisms of sulfide formation in hydrothermal and igneous systems

Fe, S, and Cu reduced partition function ratios (β-factors) allow calculation of equilibrium isotope fractionation factors. β-Factors for chalcopyrite are calculated from experimental and theoretical partial phonon densities of state states ( Kobayashi et al., 2007). The Fe β-factors for mackinawite are calculated from Mössbauer spectroscopy data ( Bertaut et al., 1965). Excellent agreement exists between Fe β-factors for chalcopyrite calculated from the experimental and theoretical 57Fe phonon densities of states, supporting the reliability of the Fe β-factors for chalcopyrite. The 34S β-factor for chalcopyrite is consistent with experimental data on equilibrium sulfur isotope fractionation factors among sulfides and theoretical 34S β-factors, except those recently calculated by a DFT approach. Up-to-date experimental isotope-exchange data on equilibrium Fe isotope fractionation factors between minerals and aqueous Fe were critically reevaluated in conjunction with Fe β-factors for minerals, and the following expressions for β-factors for aqueous Fe 2+ and Fe 3+ were obtained: 10 3 ln β Fe aq 3 + = 1.0063 10 6 T 2 ; T > 273 K 10 3 ln β Fe aq 2 + = 0.6537 10 6 T 2 ; T > 273 K. .Application of these new β-factors to Fe and S isotope fractionation at seafloor hydrothermal conditions shows that chalcopyrite may precipitate in equilibrium with Fe in hydrothermal fluids. In contrast, Fe and S isotope compositions of pyrite are may not be controlled by isotope equilibration with Fe in the hydrothermal fluid. Previously reported data on Fe isotope fractionation between pyrite and chalcopyrite in intrusions in the Grasberg Igneous Complex seem to be reasonable, and are in general agreement with previous “non-isotopic” estimates. Fe isotope fractionation between pyrite and chalcopyrite appear to reflect equilibrium in the intrusions of the Grasberg Igneous Complex, and Fe isotopes may therefore be considered as a potential geothermometer. The pyrite–chalcopyrite Fe isotope geothermometer, however, cannot be applied to the skarn facies of the Grasberg complex, where the initial Fe isotope compositions may have been disturbed by subsequent processes related to skarn formation.

Iron isotope fractionation during skarn-type metallogeny: A case study of Xinqiao Cu–S–Fe–Au deposit in the Middle–Lower Yangtze valley

Fe isotope compositions of mineral separates and bulk samples from Xinqiao Cu–S–Fe–Au skarn type deposit were investigated. An overall variation in δ 57Fe values from − 1.22‰ to + 0.73‰ has been observed, which shows some regularity. The δ 57Fe values of endoskarn and the earliest formed Fe-mineral phase magnetite are ca.1.2‰ and ca. 0.3‰ lower, respectively, relative to the quartz–monzodiorite stock, indicating that fluid exsolved from the stock is enriched in light Fe isotopes. Moreover, spatial and temporal variations in δ 57Fe values are observed, which suggest iron isotope fractionation during fluid evolution. Precipitation of Fe-bearing minerals results in the Fe isotope composition of residual fluids evolving with time. Precipitation of Fe (III) minerals incorporating heavy iron isotopes preferentially leaves the remaining fluid enriched in light isotopes, while precipitation of Fe (II) minerals preferentially taking-up light iron isotopes, and makes the Fe isotopic composition of the fluid progressively heavier. The regularity of Fe isotope variations occurred during fluid exsolution and evolution indicates that the dominant Fe source of Xinqiao deposit is magmatic. Overall, this study demonstrates that Fe isotope composition has great potential in unraveling ore-forming processes, as well as constraining the metal sources of ore deposits.

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries, Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ 56Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from −1.36‰ to −0.10‰ in summer and from −0.30‰ to −0.07‰ in winter, while river samples vary from −0.88‰ to 0.07‰ in summer and from −0.35‰ to −0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ 56Fe value: the δ 56Fe values of SPM in summer were lower than in winter. The seasonal variation in δ 56Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ 56Fe values for SPM in lake. During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ 56Fe values for SPM reach the minima, −0.88‰ for DB station and −1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ 56Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ 56Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.

Fractionation of iron species and iron isotopes in the Baltic Sea euphotic zone

Abstract. To indentify sources and transport mechanisms of iron in a coastal marine environment, we conducted measurements of the physiochemical speciation of Fe in the euphotic zone at three different locations in the Baltic Sea. In addition to sampling across a salinity gradient, we conducted this study over the spring and summer season. Moving from the riverine input characterized low salinity Bothnian Sea, via the Landsort Deep near Stockholm, towards the Gotland Deep in the Baltic Proper, total Fe concentrations averaged 114, 44, and 15 nM, respectively. At all three locations, a decrease in total Fe of 80–90% from early spring to summer was observed. Particulate Fe (PFe) was the dominating phase at all stations and accounted for 75–85% of the total Fe pool on average. The Fe isotope composition (δ 56Fe) of the PFe showed constant positive values in the Bothnian Sea surface waters (+0.08 to +0.20‰). Enrichment of heavy Fe in the Bothnian Sea PFe is possibly associated to input of aggregated land derived Fe-oxyhydroxides and oxidation of dissolved Fe(II). At the Landsort Deep the isotopic fractionation of PFe changed between −0.08‰ to +0.28‰ over the sampling period. The negative values in early spring indicate transport of PFe from the oxic-anoxic boundary at ∼80 m depth. The average colloidal iron fraction (CFe) showed decreasing concentrations along the salinity gradient; Bothnian Sea 15 nM; Landsort Deep 1 nM, and Gotland Deep 0.5 nM. Field Flow Fractionation data indicate that the main colloidal carrier phase for Fe in the Baltic Sea is a carbon-rich fulvic acid associated compound, likely of riverine origin. A strong positive correlation between PFe and chl-a indicates that cycling of suspended Fe is at least partially controlled by primary production. However, this relationship may not be dominated by active uptake of Fe into phytoplankton, but instead may reflect scavenging and removal of PFe during phytoplankton sedimentation.

Iron Isotope Fractionation during Fe Uptake and Translocation in Alpine Plants

The potential of stable Fe isotopes as a tracer for the biogeochemical Fe cycle depends on the understanding and quantification of the fractionation processes involved. Iron uptake and cycling by plants may influence Fe speciation in soils. Here, we determined the Fe isotopic composition of different plant parts including the complete root system of three alpine plant species (Oxyria digyna, Rumex scutatus, Agrostis gigantea) in a granitic glacier forefield, which allowed us, for the first time, to distinguish between uptake and in-plant fractionation processes. The overall range of fractionation was 4.5 per thousand in delta(56)Fe. Mass balance calculations demonstrated that fractionation toward lighter Fe isotopic composition occurred in two steps during uptake: (1) before active uptake, probably during mineral dissolution and (2) during selective uptake of Fe at the plasma membrane with an enrichment factor of -1.0 to -1.7 per thousand for all three species. Iron isotopes were further fractionated during remobilization from old into new plant tissue, which changed the isotopic composition of leaves and flowers over the season. This study demonstrates the potential of Fe isotopes as a new tool in plant nutrition studies but also reveals challenges for the future application of Fe isotope signatures in soil-plant environments.

Iron isotope fractionation between aqueous ferrous iron and goethite

The equilibrium Fe isotope fractionation factor between aqueous Fe(II) and goethite has been experimentally measured to be −1.05±0.08‰ in 56Fe/54Fe (2σ) at 22°C, using the three-isotope method. Experiments were done using two sizes of goethite (81×11nm and 590×42nm), and the experimental products were subjected to serial extraction using acid partial dissolution techniques to determine if surface Fe(III) atoms have different isotopic properties than the bulk goethite. These experiments indicate that the interaction of Fe(II)aq and goethite is dynamic and results in complete or near-complete Fe isotope exchange over 30days, involving at least four components: Fe(II)aq, goethite, sorbed Fe(II), and Fe(III)surface. The equilibrium fractionation factor between Fe(II)aq and Fe(II)sorb is the same for both sizes of goethite, at Δ56FeFe(II)aq–Fe(II)sorb=−1.24±0.14‰; this fractionation factor is significantly different than the results of previous studies on Fe(II) sorption to goethite. The proportion of the Fe(III)surface component is greatest in the experiments that used the smallest goethite, and the Fe(III)surface–Fe(II)aq fractionation is estimated to be at least +2.1‰. The high Fe(III)surface–Fe(II)aq fractionation may exert a significant influence on the Fe isotope compositions of aqueous Fe(II) in natural systems that contain nanoparticulate goethite, including those involving bacterial iron reduction. These results demonstrate that the isotopic properties of nano-scale minerals may be distinct from micron-scale or larger minerals, as is the case for other thermodynamic properties of nanoparticles.

Iron isotope fractionation during proton- and ligand-promoted dissolution of primary phyllosilicates

We studied stable iron isotope fractionation during dissolution of a biotite and chlorite enriched mineral fraction from granite by HCl and 5 mM oxalic acid in a pH range of 4–5.9. Batch experiments covered a time period from 2 h to 100 days and were performed at initial potassium concentrations of 0, 0.5, and 5 mM to induce different levels of biotite exfoliation. All experiments were kept anoxic to investigate solely the dissolution step without the influence of oxidation and precipitation of secondary Fe oxyhydroxides. Oxalic acid increased the release of Fe by a factor of ∼15 compared with the HCl experiments. Addition of 0.5 mM K to initial solutions in proton-promoted dissolution decreased the release of Fe by 30–65% depending on the dissolution stage. In ligand-controlled dissolution, K reduced the Fe release only to a minor extent. All solutions of the early dissolution stages were enriched in light Fe isotopes by up to −1.4‰ in δ56Fe compared with the isotopic composition of biotite and chlorite mineral separates, which we explained by a kinetic isotope effect. In proton-promoted dissolution, early released fractions of K-enriched experiments were significantly lighter (−0.7‰ to −0.9‰) than in the initially K-free experiments. The evolution of Fe isotope ratios in solution was modeled by a linear combination of kinetic isotope effects during two independent dissolution processes attacking different crystallographic sites. In ligand-controlled dissolution, K did not influence the kinetic isotope effect and the Fe isotope composition in solution in the late dissolution stages remained slightly lighter than the bulk composition of the biotite/chlorite enriched mineral fraction. This study demonstrates that the initial Fe weathering flux should be enriched in light Fe isotopes and that Fe isotope data in combination with dissolution kinetics and stoichiometry provide new insights into dissolution mechanisms.

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 (56)Fe/(54)Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ(56)Fe(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.

Electrochemically controlled iron isotope fractionation

Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

Iron isotopes may reveal the redox conditions of mantle melting from Archean to Present

High-precision Fe isotopic data for 104 samples, including modern and ancient (≥ 3.7 Ga) subduction-related magmas and mantle peridotites, are presented. These data demonstrate that mid-ocean ridge and oceanic-island basalts (MORBs and OIBs) have on average small, but distinctly (~+ 0.06‰) higher 56Fe/ 54Fe ratios than both modern and Eoarchean boninites and many island arc basalts (IABs) that are interpreted to form by large degrees of flux melting of depleted mantle sources. Additionally boninites and many IABs have iron isotopic compositions similar to chondrites, fertile mantle peridotites, Eoarchean mantle peridotites, and basalts from Mars and Vesta. The observed variations are best explained by the bulk silicate Earth having a near-chondritic iron isotopic composition, with ~ + 0.3‰ equilibrium isotope fractionation between Fe 3+ and Fe 2+ and preferential extraction of isotopically heavier, incompatible Fe 3+ during mantle melting to form oceanic crust (as represented by MORBs and OIBs). A quantitative model that relates the iron isotopic composition of basaltic magmas to the degree of partial melting, Fe 3+/Fe 2+ ratio, and buffering capacity of the mantle is presented. The concept that redox conditions may influence iron isotopic fractionation during melting provides a new approach for understanding the redox conditions of magma genesis on early Earth and Mars. Experimental and theoretical work is required to establish iron isotopic fractionation as an oxybarometer of mantle melting.

Prediction of Iron-Isotope Fractionation Between Hematite (α-Fe2O3) and Ferric and Ferrous Iron in Aqueous Solution from Density Functional Theory

Density functional theory electronic structure calculations are used to compute equilibrium constants for iron-isotope exchange among Fe2+(aq), Fe3+(aq), and hematite (alpha-Fe2O3). The hematite is represented in both bulk and surface environments. The iron-isotope fractionation between Fe2+(aq) and Fe3+(aq), determined using a range of exchange-correlation functionals and basis sets, is in good agreement with experimental measurements. The calculated reduced partition function ratio for bulk hematite is very close to previous estimates based on Mossbauer and inelastic nuclear resonance X-ray spectroscopy. However, the calculated fractionation between hematite bulk and the aqueous species Fe3+(aq) and Fe2+(aq) differs from experimental measurements carried out at the aqueous-hematite interface. We find a heavy iron enrichment trend in the order Fe2+(aq) < hematite bulk approximately hematite surface < Fe3+(aq). In contrast to experimental studies, we find a significant positive fractionation (heavy enrichment) for Fe(3+)(aq) relative to hematite, regardless of whether the hematite is represented by a bulk or a surface model. Our calculations indicate that it is unlikely that the aqueous interfacial structure of hematite is a simple termination of the bulk structure.