Fe Isotope Research Articles

Diffusion-driven extreme Mg and Fe isotope fractionation in Panzhihua ilmenite: Implications for the origin of mafic intrusion

To investigate the petrogenesis of Fe-Ti oxide ore deposits, we report Mg and Fe isotopic compositions for coexisting olivine, clinopyroxene and ilmenite in Fe-Ti oxide ores, magnetite-bearing gabbros and gabbros from the Panzhihua Fe-Ti-oxide-bearing layered mafic intrusion, Southwest China. Olivine and clinopyroxene have δ26Mg values ranging from −0.47 to −0.32‰ and −0.40 to −0.18‰, and δ57Fe values from −0.21 to +0.23‰ and −0.16 to +0.20‰, respectively. Most of these mineral pairs display disequilibrium inter-mineral fractionation as they fall off the theoretically predicted equilibrium fractionation lines. Ilmenites from oxide ores and magnetite-bearing gabbros (Group 1) have mantle-like or lower δ26Mg values of −0.80 to −0.13‰ and δ57Fe values of −0.33 to −0.23‰, and those from gabbros (Group 2) display slightly to extremely higher δ26Mg values of +0.48 to +23.10‰ and much lower δ57Fe values of −0.59 to −0.33‰. The δ26Mg negatively correlates with δ57Fe in all ilmenites, which cannot be explained by simple extensive fractional crystallization or Soret diffusion. Instead, the negative correlations between δ26Mg and δ57Fe and between MgO and FeO in ilmenites result from Mg-Fe inter-diffusion among ilmenite, silicate minerals and high-Ti basaltic melts. The extremely large isotopic variations were produced by the large Mg activity gradient between different types of ilmenites and melts, which was enhanced by interstitial liquid immiscibility process. Our study therefore demonstrates that combined Mg-Fe isotopes can be used to trace the genesis of Fe-Ti-oxide-bearing ore.

Rotational behavior of thermally excited 56Fe, 58Fe and 60Fe isotopes

Thermal and rotational behaviors of neutron rich fp-shell isotopes such as [Formula: see text], [Formula: see text] and [Formula: see text] were analyzed microscopically within the framework of statistical theory of hot rotating nuclei (STHRN) for the angular momentum range (0–15)[Formula: see text] at excitation energy above 4[Formula: see text]MeV. Pair-breaking phenomenon and band-crossing phenomenon of Fe isotopes were discussed with and without the inclusion of BCS pairing. The STHRN method with BCS effect was extended to the Fe isotopes to determine the critical temperature [Formula: see text], where the pair-breaking phenomenon takes place and it is found to occur below [Formula: see text][Formula: see text]MeV. The observation of band-crossing phenomenon above the [Formula: see text] was explained without considering the effect of BCS pairing. The single particle energy levels were engendered from triaxially deformed Nilsson Hamiltonian. The outcomes of the present investigation on moment of inertia (MOI), back-bending phenomenon, spin cutoff parameter show a strong evidence of band-crossing phenomenon and it eventually led to a shape transition from spherical to noncollective oblate. Moreover, attention on separation energy of protons and neutrons reveals that the neutron pairs are responsible for band-crossing. STHRN method was able to reproduce results in good agreement with experiments and comparable with other theories such as projected shellmodel (PSM) and shellmodel Monte Carlo (SMMC) method.

A reassessment of the iron isotope composition of the Moon and its implications for the accretion and differentiation of terrestrial planets

The Fe isotope composition of planetary bodies may provide constraints on their accretion modes and/or differentiation processes, but to do so, the Fe isotope systematics of key planetary reservoirs needs to be determined. To investigate this for the Moon, we measured the Fe isotope compositions for a suite of 33 bulk lunar mare basalts and highland rocks. Combined with published data, a compendium of 73 different lunar bulk rocks reveals a statistically significant Fe isotope difference between low-Ti and high-Ti mare basalts, yielding average δ57Fe = 0.127 ± 0.012‰ (2SE; n = 27) and δ57Fe = 0.274 ± 0.020‰ (2 SE; n = 25), respectively, relative to the IRMM-14 isotopic reference material. As lunar basalts are thought to reflect the Fe isotope composition of their respective mantle sources, the estimated relative proportion of the low-Ti and high-Ti source mantle suggests that the lunar upper mantle δ57Fe value should be close to 0.142 ± 0.026‰. Whilst the composition of highland rocks (ferroan anorthosites and Mg-suite rocks) should provide a more global view of the Moon, the calculation of the mean δ57Fe value of 15 available highland rock analyses yields δ57Fe = 0.078 ± 0.124‰. Such a value is not defined precisely enough to be of critical use for comparative planetology. Ferroan anorthosites and Mg-suite rocks also give unresolvable means. It appears that Fe isotope heterogeneity among the lunar highland rocks is caused by non-representatively too small sample aliquots of coarse-grained rocks. It can also be the result of mixed lithologies for some. When the (kinetic) effect of olivine tending towards low δ57Fe and feldspar with predominantly high δ57Fe is cancelled, a more precise δ57Fe value of 0.094 ± 0.035‰ is calculated. It is indistinguishable from the mean δ57Fe of impact melts and is also similar to the upper lunar mantle estimate obtained from mare basalts. Collectively, this newly determined Fe isotope composition of the bulk Moon is indistinguishable from that of the Earth, and heavier than those reported for other planetary bodies. This planetary isotope relationship is only observed for silicon given the currently available mass-dependent stable isotope database. Because both iron and silicon reside in the Earth’s metallic core in significant quantities, this may point to the involvement of metallic cores of the Earth and Moon in the interplanetary Fe and Si isotope fractionation. Rather than via high-pressure metal–silicate fractionation at the core–mantle boundary, this would more likely be achieved by partial vaporization of the liquid outer metallic core in the aftermath of a Moon-forming giant impact.

Iron isotope fractionation during mid-ocean ridge basalt (MORB) evolution: Evidence from lavas on the East Pacific Rise at 10°30′N and its implications

Whether the Earth’s mantle has a chondritic δ56Fe (deviation in 56Fe/54Fe from the IRMM-014 standard in parts per thousand) value or not remains under debate. The current view is that the observed average δ56Fe of mid-ocean ridge basalts (MORB) cannot be explained by partial melting of mantle source with chondritic value alone. Here, we report Fe isotope compositions on 29 MORB glasses sampled along a flowline traverse across the East Pacific Rise (EPR) axis at 10°30′N. These glasses show large MgO variation (1.8–7.4 wt.%) that forms a compositional continuum resulting from varying extent of fractional crystallization, which is accompanied by systematic Fe isotopic variation. Fractional crystallization modeling suggests that early crystallization of olivine, pyroxene and plagioclase gives rise to an iron enrichment trend and an increase in δ56Fe. Once Fe-Ti oxides appear on the liquidus and begin to crystallize, the FeOt and TiO2 contents of the residual melt decrease rapidly, which lead to a slight decrease in δ56Fe. These observations indicate that significant Fe isotope fractionation can indeed take place during MORB melt evolution. Hence, δ56Fe values of variably evolved MORB melts do not represent those of primary MORB melts and thus cannot be used to infer mantle source Fe isotope compositions. Importantly, δ56Fe values of primary MORB melts after correction for the effect of fractional crystallization can be well reproduced by mantle melting. Therefore, our study supports the idea that the Fe isotope composition of the accessible Earth is close to be chondritic. We note that conclusion would assume that the core, which takes up ∼90% of the Earth’s Fe, must have a chondritic Fe isotope composition.

Tracking Fe mobility and Fe speciation in subduction zone fluids at the slab-mantle interface in a subduction channel: A tale of whiteschist from the Western Alps

Fluids released by subducting slabs are important to the geochemical evolution of Earth’s crust-mantle system. However, it is still not well constrained for the mobility of redox sensitive elements (like Fe, C or S) in subduction zone fluids, and its effect on the redox property of the overlying mantle wedge and its derived arc magmas. Iron isotope fractionation is sensitive to the redox state and speciation of Fe in fluids, which can potentially provide clues on the oxygen fugacity (fO2) of slab-derived fluids. Whiteschists at the Dora-Maira Massif in the Western Alps have experienced ultrahigh-pressure metamorphism at subarc depths. They are rich in both SiO2 (mostly >65 wt.%) and MgO (4–10 wt.%), and mainly composed of pyrope, quartz/coesite, talc, phengite and kyanite. They were demonstrated to have a granite protolith, but metasomatized by serpentinite-derived Mg-rich fluids at the slab-mantle interface in a subduction channel. Thus these rocks provide an excellent target to explore the fluid-rock interaction by Fe isotopes. The whiteschists show extremely high δ56Fe values of +0.32 to +1.22‰, being much higher than those of +0.10 to +0.38‰ for the surrounding metagranites. The Fe isotope composition of whiteschists significantly deviates from the igneous differentiation trend defined by rocks with basaltic to rhyolitic compositions. The heavy Fe isotope compositions must be produced by a metasomatic process. The much lower Fe2O3 and FeOt contents and Fe3+/∑Fe ratios but higher δ56Fe values for the whiteschists relative to their protolith suggest the reduction of Fe3+ to Fe2+ and the loss of isotopically light Fe, probably in the form of Fe(II)-Cl and/or Fe(II)-(HS) complexes, through saline fluids and/or HS- bearing fluids. The reduction of Fe3+ to Fe2+ and the possible presence of HS- suggests the occurrence of relatively reduced fluids. Such reduced fluids were probably derived from serpentinite dehydration at the slab-mantle interface in the subduction channel. Therefore, the Fe isotope results demonstrate that the fO2 at the slab-mantle interface can be locally highly heterogeneous, leading to various oxidation states in the mantle wedge and arc magmas.

Modern weathering in outcrop samples versus ancient paleoredox information in drill core samples from a Mesoarchaean marine oxygen oasis in Pongola Supergroup, South Africa

There is growing evidence from Mo and Fe stable isotope tracers that shallow-water sediments of the 2.95 Ga Mozaan Group (Pongola Supergroup) in South Africa were deposited under oxidizing conditions, while mineralogical, elemental and S isotopic evidence favors the contemporaneous atmosphere to have remained reducing. In contrast, the first reported Cr-stable isotope data for White Mfolozi riverbed outcrop samples of the Ijzermijn iron formation (IF), Mozaan Group, and drill core samples of the underlying paleosol of the Nsuze Group were interpreted to require oxidative weathering conditions during the time of deposition. More recent Cr-isotope data of at least the Ijzermijn IF samples of the same White Mfolozi riverbed outcrop, however, suggested that modern weathering effects can superimpose oxidative signatures on paleo-redox proxies.This study compares (234U/238U) activity ratios along with stable Mo and Fe isotope data of corresponding drill core and White Mfolozi riverbed outcrop samples in order (i) to test (234U/238U) disequilibria as a potential tool to identify samples affected by modern weathering and (ii) to further investigate weathering effects on outcrop samples, particularly with regard to the stable Mo and Fe isotope systematics. All drill core samples from the Ijzermijn IF have (234U/238U) activity ratios that are within uncertainties of secular equilibrium (i.e. a value of 1), and thus were not significantly affected by modern weathering-related U gain or loss or other sub-recent rock-water interaction. By contrast, the outcrop IF and shale samples from the White Mfolozi riverbed show very strong deviations from the secular equilibrium (234U/238U) activity ratio. Furthermore, these deviations are accompanied by the observations that (i) outcrop samples have on average heavier δ56/54Fe values (−0.96‰) than drill cores (−1.59‰), and (ii) positive correlations in drill core samples between log[Fe/Mn] and δ98/95Mo or δ56/54Fe are disrupted by inclusion of the outcrop samples, as are negative correlations between log[MnO] and δ98/95Mo. However, δ56/54Fe and δ98/95Mo of our outcrop samples do not correlate with the extent of (234U/238U) disequilibria. As such, (234U/238U) activity ratios fail to act as a direct identification tool for modern weathering effects on stable Fe and Mo isotopes in outcrop samples. Overall, this study confirms the adsorption of isotopically light Mo onto MnO2 particles in oxic surface water conditions in the epicontinental Pongola Sea. Reduction of the Mn-oxides together with microbial Fe reduction in the reduced sediment pile of the Pongola basin led to the formation of Mn- and Fe-carbonates during early diagenesis storing the observed stable Fe and Mo isotopic signatures. We thus extend the so-called MnO2-shuttle first proposed for the Neoarchean 2.46 Ga old Koegas IF to late Mesoarchean shallow-marine depositional settings.

Iron Isotope Fractionation during Bio- and Photodegradation of Organoferric Colloids in Boreal Humic Waters.

Biodegradation and photolysis of dissolved organic matter (DOM) in boreal high-latitude waters are the two main factors controlling not only the aquatic fluxes and residence time of carbon but also metal nutrients associated with DOM such as Fe. The DOM is usually present in the form of organic and organomineral colloids, which also account for the majority of dissolved Fe. Here, we use the stable Fe isotope approach to unravel the processes controlling Fe behavior during bio- and photodegradation of colloids in boreal Fe- and DOM-rich humic waters (a stream and a fen). The adsorption of Fe colloids onto heterotrophic bacteria Pseudomonas aureofaciens produced enrichment in +0.4‰ (δ57Fe) in the heavier isotopes of the cell surface relative to the remaining solution. In contrast, long-term assimilation of Fe by live cells yielded preferential incorporation of lighter isotopes into the cells (-0.7‰ relative to aqueous solution). The sunlight-induced oxidation of Fe(II) in fen water led to the removal of heavier Fe isotopes (+1.5 to +2.5‰) from solution, consistent with Fe(III) hydroxide precipitation from Fe(II)-bearing solution. Altogether, bio- and photodegradation of organoferric colloids, occurring within a few days of exposure time, can produce several per mil isotopic excursions in shallow lentic and lothic inland waters of high-latitude boreal regions. Considerable daily scale variations of Fe isotopic composition should therefore be taken into account during the interpretation of the riverine flux of Fe isotopes to the ocean or tracing weathering processes using Fe isotopes in surface waters at high latitudes.

The Carboniferous Shikebutai Iron Deposit in Western Tianshan, Northwestern China: Petrology, Fe-O-C-Si Isotopes, and Implications for Iron Pathways

Abstract Submarine volcanic-hosted iron deposits are important sources of iron ore in northwestern China. Here we present the petrological characteristics and coupled Fe-O, C, and Si isotope data of iron ores from the Shikebutai submarine volcanic-hosted hematite deposit in the Western Tianshan region. Several stratiform and lenticular hematite-dominated orebodies occur in Carboniferous submarine volcano-sedimentary sequences in this region. The ores are mainly composed of hematite, quartz, and minor siderite with distinct alternating iron-rich and silica-rich bands. The hematite shows δ56Fe and δ18O values in the range of –0.31 to 0.80‰ and 2.2 to 7.0‰, respectively, and the jasper yields δ30Si values of –1.90 to –1.20‰. Iron and Si were both derived from hydrothermal fluids related to submarine magmatism/volcanism. The Fe-bearing minerals in the Shikebutai deposit define distinct formation pathways. Hematite is the primary dehydrated Fe(III) oxyhydroxide, and the Fe isotope data indicate fractionation resulting from the partial oxidation of Fe(II). The O isotope data reflect inheritance from the submarine hydrothermal fluids source. Jasper was produced during coprecipitation of silica adsorbed onto the Fe(III) oxyhydroxides. The siderite-rich iron ore/volcaniclastic rock samples with a high and variable total organic carbon content (0.14–5.57%) show negative δ13C values (–3.0 to –1.1‰) and light δ56Fe values (–1.11 to –0.84‰). Our isotope data, together with the common occurrence of hematite inclusions in siderite, suggest that siderite was mainly produced by microbial dissimilatory iron reduction during diagenesis. The geologic, petrological, and isotopic data suggest that the Carboniferous Shikebutai deposit was precipitated through chemical and biogenic processes.

Iron absorption from supplements is greater with alternate day than with consecutive day dosing in iron-deficient anemic women.

In iron-depleted women without anemia, oral iron supplements induce an increase in serum hepcidin (SHep) that persists for 24 hours, decreasing iron absorption from supplements given later on the same or next day. Consequently, iron absorption from supplements is highest if iron is given on alternate days. Whether this dosing schedule is also beneficial in women with iron-deficiency anemia (IDA) given high-dose iron supplements is uncertain. The primary objective of this study was to assess whether, in women with IDA, alternate-day administration of 100 and 200 mg iron increases iron absorption compared to consecutive-day iron administration. Secondary objectives were to correlate iron absorption with SHep and iron status parameters. We performed a cross-over iron absorption study in women with IDA (n=19; median hemoglobin 11.5 mg/dL; mean serum ferritin 10 mg/L) who received either 100 or 200 mg iron as ferrous sulfate given at 8 AM on days 2, 3 and 5 labeled with stable iron isotopes 57Fe, 58Fe and 54Fe; after a 16-day incorporation period, the other labeled dose was given at 8 AM on days 23, 24 and 26 (days 2, 3 and 5 of the second period). Iron absorption on days 2 and 3 (consecutive) and day 5 (alternate) was assessed by measuring erythrocyte isotope incorporation. For both doses, SHep was higher on day 3 than on day 2 (P<0.001) or day 5 (P<0.01) with no significant difference between days 2 and 5. Similarly, for both doses, fractional iron absorption (FIA) on days 2 and 5 was 40-50% higher than on day 3 (P<0.001), while absorption on day 2 did not differ significantly from day 5. There was no significant difference in the incidence of gastrointestinal side effects comparing the two iron doses (P=0.105). Alternate day dosing of oral iron supplements in anemic women may be preferable because it sharply increases FIA. If needed, to provide the same total amount of iron with alternate day dosing, twice the daily target dose should be given on alternate days, as total iron absorption from a single dose of 200 mg given on alternate days was approximately twice that from 100 mg given on consecutive days (P<0.001). In IDA, even if hepatic hepcidin expression is strongly suppressed by iron deficiency and erythropoietic drive, the intake of oral iron supplements leads to an acute hepcidin increase for 24 hours. The study was funded by ETH Zürich, Switzerland. This study has been registered at www.clinicaltrials.gov as #NCT03623997.

Study of interactions between carboxylated core shell magnetic nanoparticles and polymyxin B by capillary electrophoresis with inductively coupled plasma mass spectrometry

In this work, interactions of carboxylated core shell magnetic nanoparticles with polymyxin B sulfate were studied by connecting capillary electrophoresis with inductively coupled plasma mass spectrometry. The interaction was probed by affinity mode of capillary electrophoresis with 25 mM phosphate buffer at physiological pH. 54Fe, 56Fe, 57Fe, 34S, and 12C isotopes were used to monitor the migration of an electroosmotic flow marker and the interaction of the nanoparticles with polymyxin B. The analysis of interaction data showed two distinct interaction regions, one with low polymyxin B concentration, the second with high polymyxin B concentration. These regions differed in the strength of the interaction, 1.49 × 107 M−1 and 1.60 × 104 M−1, and in the stoichiometry of 0.7 and 3.5, respectively. These differences can be explained by the decrease of electrostatic repulsion between nanoparticles caused by polymyxin B. This is also in agreement with the nanoparticles peak shapes: sharp for low polymyxin B concentrations and broad for high polymyxin B concentrations.

Corrigendum to “The Fe and Zn isotope composition of deep mantle source regions: Insights from Baffin Island picrites” [Geochim. Cosmochim. Acta 238 (2018) 542–562

Corrigendum to “The Fe and Zn isotope composition of deep mantle source regions: Insights from Baffin Island picrites” [Geochim. Cosmochim. Acta 238 (2018) 542–562

Spring flood induced shifts in Fe speciation and fate at increased salinity

Rivers have traditionally been viewed as negligible sources of iron (Fe) to marine waters, as most Fe gets lost during estuarine mixing. However, recent findings demonstrate that Fe from boreal rivers display a higher resistance towards salinity-induced aggregation, presumably due to stabilizing interactions with organic matter. Previous studies have shown that Fe (oxy)hydroxides are selectively removed by aggregation processes, and that organic Fe complexes are less affected by increasing salinity. It has been further proposed that Fe speciation varies in response to seasonal differences in hydrology. In this study X-ray absorption spectroscopy (XAS) was used to determine the temporal variation in Fe speciation and the connection to Fe stability in response to increasing salinity in two boreal rivers (Kalix and Råne River), with the purpose to better understand the fate of riverine Fe export. Sampling was done from winter pre-flood, over the spring flood, to post-flood conditions (early April until mid June). In addition, parallel analyses for Fe speciation and isotope composition (δ56Fe relative to IRMM-14) were made on river samples, as well as salinity-induced aggregates and the fraction remaining in suspension, with the main objective to test if δ56Fe reflect the speciation of Fe.The contribution of organically complexed Fe increased during spring flood compared to the pre- and post-flood, as did Fe transport capacity. However, since Fe (oxy)hydroxides were dominating throughout the sampling period, the seasonal variability was small. Interestingly, salinity-induced aggregation experiments revealed that Fe (oxy)hydroxides, which dominated aggregates, displayed lower δ56Fe than in the river samples Fe, while organic Fe complexes in suspension had higher δ56Fe values. The seasonal variability in Fe isotope signature could not be simply linked to Fe speciation, but was probably also influenced by variation in source areas of Fe and processes along the flow-path that alter both Fe speciation and isotopic composition.

Iron isotope fractionation during sulfide liquid segregation and crystallization at the Lengshuiqing Ni-Cu magmatic sulfide deposit, SW China

Abstract We report the first measurements of Fe isotope fractionation between coexisting pyrrhotite and chalcopyrite from the Lengshuiqing Ni-Cu magmatic sulfide deposit, Southwest China. The δ56Fe values of chalcopyrite (Cp) range from 0.24‰ to 1.25‰, much higher than those in the coexisting pyrrhotite (Po, −1.25‰ to −0.13‰). The δ56Fe values of pyroxene separates from the Lengshuiqing intrusions are in a range from −0.03‰ to 0.18‰. Pyrrhotite in sulfide-mineralized rocks with greater than ∼2 wt.% S has δ56Fe values of −0.3 ± 0.2‰, indicating Δ56FePo-sil (pyrrhotite – silicate melt) in the range of −0.4 ± 0.2‰ with parental silicate magma δ56Fe of 0.1‰ as calculated from the least evolved pyroxene δ56Fe value. This fractionation is similar to that experimentally determined by Schuessler et al. (2007) for pyrrhotite and a rhyolitic melt, suggesting that Δ56FePo-sil of approximately −0.4‰ represents a near-equilibrium value for sulfide-rich mineralization in the Lengshuiqing intrusions. Pyrrhotite-dominated sulfide separates in samples with less than ∼2 wt.% S show δ56Fe values as low as −1.25‰. The low δ56Fe values can be modeled by a non-equilibrium process, where the fractionation between immiscible sulfide liquid and silicate magma decreases from −0.4 to −1.4‰ as the R-factor (mass ratio of silicate melt to coexisting sulfide liquid) increases from 1 to 1000. We suggest that the relative proportion of externally introduced Fe from sulfidic sedimentary country rocks may be higher in low-S samples, controlling the low δ56Fe values of the sulfide assemblage in the mineralized rocks. The trend of Fe isotope enrichment at Lengshuiqing is consistent with Fe-S bond strengths, but the difference between coexisting pyrrhotite and chalcopyrite is not consistent with equilibration at high temperatures. The Δ56FeCp-Po values at Lengshuiqing (1.06–1.77‰) are similar to those measured for samples from the Voisey’s Bay and Eagle Ni-Cu deposits, and suggest that in a cooling sulfide liquid Fe isotope equilibration may continue to temperatures less than 200 °C.

Combined mass-dependent and nucleosynthetic isotope variations in refractory inclusions and their mineral separates to determine their original Fe isotope compositions.

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials that provide crucial information about the isotopic reservoirs present in the early Solar System. For a variety of elements, CAIs have isotope compositions that are uniform yet distinct from later formed solid material. However, despite being the most abundant metal in the Solar System, the isotopic composition of Fe in CAIs is not well constrained. In an attempt to determine the Fe isotopic compositions of CAIs, we combine extensive work from a previously studied CAI sample set with new isotopic work characterizing mass-dependent and mass-independent (nucleosynthetic) signatures in Mg, Ca, and Fe. This investigation includes work on three mineral separates of the Allende CAI Egg 2. For all isotope systems investigated, we find that in general, fine-grained CAIs exhibit light mass-dependent isotopic signatures relative to terrestrial standards, whereas igneous CAIs have heavier isotopic compositions relative to the fine-grained CAIs. Importantly, the mass-dependent Fe isotope signatures of bulk CAIs show a range of both light (fine-grained CAIs) and heavy (igneous CAIs) isotopic signatures relative to bulk chondrites, suggesting that Fe isotope signatures in CAIs largely derive from mass fractionation events such as condensation and evaporation occurring in the nebula. Such signatures show that a significant portion of the secondary alteration experienced by CAIs, particularly prevalent in fine-grained inclusions, occurred in the nebula prior to accretion into their respective parent bodies. Regarding nucleosynthetic Fe isotope signatures, we do not observe any variation outside of analytical uncertainty in bulk CAIs compared to terrestrial standards. In contrast, all three Egg 2 mineral separates display resolved mass-independent excesses in 56Fe compared to terrestrial standards. Furthermore, we find that the combined mass-dependent and nucleosynthetic Fe isotopic compositions of the Egg 2 mineral separates are well correlated, likely indicating that Fe indigenous to the CAI is mixed with less anomalous Fe, presumably from the solar nebula. Thus, these reported nucleosynthetic anomalies may point in the direction of the original Fe isotope composition of the CAI-forming region, but they likely only provide a minimum isotopic difference between the original mass-independent Fe isotopic composition of CAIs and that of later formed solids.

Mineral Defects Enhance Bioavailability of Goethite toward Microbial Fe(III) Reduction.

Surface defects have been shown to facilitate electron transfer between Fe(II) and goethite (α-FeOOH) in abiotic systems. It is unclear, however, whether defects also facilitate microbial goethite reduction in anoxic environments where electron transfer between cells and Fe(III) minerals is the limiting factor. Here, we used stable Fe isotopes to differentiate microbial reduction of goethite synthesized by hydrolysis from reduction of goethite that was further hydrothermally treated to remove surface defects. The goethites were reduced by Geobacter sulfurreducens in the presence of an external electron shuttle, and we used ICP-MS to distinguish Fe(II) produced from the reduction of the two types of goethite. When reduced separately, goethite with more defects has an initial rate of Fe(III) reduction about 2-fold higher than goethite containing fewer defects. However, when reduced together, the initial rate of reduction is 6-fold higher for goethite with more defects. Our results suggest that there is a suppression of the reduction of goethite with fewer defects in favor of the reduction of minerals with more defects. In the environment, minerals are likely to contain defects and our data demonstrates that even small changes at the surface of iron minerals may change their bioavailability and determine which minerals will be reduced.

Shelf-to-basin iron shuttle in the Guaymas Basin, Gulf of California

Enrichments of highly reactive iron (Fe) (sum of Fe (oxyhydr)oxide, carbonate and sulfide minerals) in marine sediments and sedimentary rocks are commonly interpreted as an indication of anoxic conditions in the bottom water at the time of deposition. The model system for this proxy rationale is the semi-restricted Black Sea, where sediments underneath the anoxic and sulfidic (i.e., euxinic) deep-water are enriched in reactive Fe, which was mobilized from the surrounding shelf areas. To test whether such a shelf-to-basin Fe shuttle can operate in semi-restricted basins without euxinic deep water, we investigated sedimentary Fe speciation and Fe isotope compositions in sediments of the Guaymas Basin, Gulf of California. Sediments on the slope underneath the eastern equatorial Pacific oxygen minimum zone and sediments within the oxic deep basin are both enriched in reactive Fe, with reactive Fe making up 45 ± 11% of the total Fe pool. The following mechanisms may contribute to these Fe enrichments: (1) Release of dissolved Fe from anoxic shelf and slope sediments followed by lateral transport of dissolved and/or particulate Fe in the water column; (2) preferential transport of fine-grained, terrigenous particles with a high reactive Fe content into the basin; (3) microbially mediated conversion of non-reactive silicate minerals to reactive Fe minerals during transport; (4) hydrothermal venting and lateral Fe transport within the deep water. The first process can explain reactive Fe enrichments in slope sediments, whereas all processes may contribute to sedimentary Fe enrichments in the deeper basin. The δ 56 Fe value of sediments increases from shelf to slope and decreases from the slope into the basin. This lateral pattern of δ 56 Fe, as well as the pattern of Fe enrichment, is similar to that observed in other marine systems with a Fe shuttle. However, the size of the Fe enrichment, and the range in δ 56 Fe (−0.06 to +0.16‰) is smaller. This difference is due to higher terrigenous sedimentation rates in the Guaymas Basin and, therefore, more intense dilution of shuttle-derived reactive Fe. We argue that, depending on the extent of bathymetric restriction and terrigenous background sedimentation, reactive Fe enrichments can form under a broad range of redox conditions and in diverse sedimentary environments. The concepts applied in this study can be used to identify those circumstances in the paleo-record.

Fe isotopic composition of the Quaternary Red Clay in subtropical Southeast China: Redoxic Fe mobility and its paleoenvironmental implications

To probe Fe isotopic signatures of the Quaternary Red Clay (QRC) in subtropical southeastern China, two QRC profiles located in southern Anhui Province, Southeast China, were studied. The whole profiles were generally in a narrow range in δ56Fe of −0.040 ± 0.061‰—0.117 ± 0.048‰. The Yellow-brown Earth (YBE) and Uniform Red Clay (URC) of the upper profiles were similar in δ56Fe to the Xiashu Loess along the Yangtze River, Southeast China, and the loess, paleosols and Tertiary red clay in the Chinese Loess Plateaus, Northwest China, as well as the baseline of terrestrial igneous rocks. The slight variation of δ56Fe from the YBE to the URC suggests that the chemical weathering and rubification on the aerobic surface did not fractionate Fe isotopes significantly. The Reticulate Red Clay (RRC) underlying the YBE and URC fluctuated in δ56Fe to some extent. The white veins separated from the lower RRC were depleted of Fe oxides and heavier in Fe isotopes, and the red veins, on the contrary, were isotopically lighter in Fe. δ56Fe of the white veins, 0.345 ± 0.053‰ on average, was significantly higher than the bulk samples, 0.033 ± 0.044‰ on average, and the red veins, −0.021 ± 0.046‰ on average. This suggests that the reticulate textures of the RRC were formed by the reductive removal/re-precipitation of Fe due to the cyclical changes of redoxic conditions. Fe isotopic composition of the QRC was dominantly controlled by the redoxic mobility of Fe, rather than the degree of weathering. δ56Fe of the profiles was not correlated with the paleoclimatic events, and thus cannot be used as a paleoclimatic proxy. The fractionation of Fe isotopes in the lower RRC, however, indicated the occurrence of over-humid paleoclimate with alternations between drought and wetness in Southern China during the Pleistocene.

Isotopic fingerprints indicate distinct strategies of Fe uptake in rice

Plants typically take up Fe through either strategy I or strategy II, whereas rice uses both. Stable Fe isotopes potentially reveal pathways of Fe uptake in rice plants. In this study we measured Fe isotopic compositions of rice grown under different conditions, i.e. paddy soil with deficient Fe supply and Fe3+-EDTA aqueous solution with sufficient Fe supply, to investigate whether Fe isotope fractionation is distinct under Fe-deficient and Fe-sufficient conditions as well as their possible controlling mechanisms. Our results show that rice grown in the Fe3+-EDTA aqueous solutions with sufficient Fe supply preferentially takes up light Fe isotopes (Δ56Febulk plant-nutrient = −1.36‰) and accumulates Fe in different parts of plant (roots, stems, leaves, husks, and grains) with large Fe isotope fractionation. Under such a growing condition, rice takes up Fe through strategy I and the reduction of Fe3+ to Fe2+ results in plants enriching isotopically light Fe. Within the plant, the transportation of Fe is accompanied with changes in redox state, which thus causes significant Fe isotope fractionation among different plant tissues. In contrast, rice plants grown in soils with deficient Fe supply are slightly enriched in heavy Fe isotopes (Δ56Febulk plant-soil solution = 0.27‰) and accumulate Fe in different plant tissues with little isotope fractionation. Under this growing condition, the rice plant takes up Fe through strategy II. Plants take up Fe from soils as Fe3+-phytosiderophores (Fe3+-PS) complex and transport Fe as Fe3+-nicotianamine (Fe3+-NA) complex throughout the plant, which does not involve changes in redox state and thus results in very limited isotope fractionation. The observed difference in Fe isotope fractionation indicates two distinct Fe uptake and translocation strategies for rice grown under the two different conditions: strategy I under Fe-sufficient conditions, and strategy II under Fe-deficient conditions. Our results demonstrate that Fe isotope ratios may be used to distinguish Fe-sufficient versus Fe-deficient conditions and to elucidate Fe biogeochemical processes during rice growth.

Reconciling petrological and isotopic mixing mechanisms in the Pitcairn mantle plume using stable Fe isotopes

Ocean-island basalts (OIB) are the products of intra-plate mantle melting above mantle plumes. These hot, buoyant upwellings rise from the deep mantle, possibly the core-mantle boundary, to the Earth's surface. Radiogenic isotope signatures of trace elements in OIB are consistent with a variety of crustally-derived recycled components in their source that are suggested to reside in the plume as eclogite or their pyroxenitic melt-reaction products. The global OIB compositional spectrum exhibits a continuum of radiogenic isotope characteristics (Sr-Nd-Pb-Hf) that indicate mixing of these plume components. However, the petrological mechanisms underpinning this mixing remain elusive. Here, we report stable Fe isotope data for plume-derived lavas of Pitcairn Island from the southwest Pacific. Iron isotope compositions, corrected for olivine fractionation, show a strong co-variation with radiogenic Nd-Sr-Pb isotopes. At Pitcairn, two isotopically distinct components have been identified, one being an enriched-mantle 1 (EM-1) component and the other being a more primitive component, which plots in multiple radiogenic isotope space in the so-called focal zone (FOZO), tentatively identified here as the plume matrix. We suggest a two-stage scenario in which Fe isotopes are first fractionated towards heavier values during formation of a reaction-zone pyroxenite. Partial silicate melt derived from a recycled crustal eclogite, assumed here to be of a subducted sediment origin, reacts with ambient peridotite to form an isotopically heavier Fe isotope pyroxenite with memory of its precursor in radiogenic isotopes. Subsequently, both, isolated and enriched reaction zone pyroxenites and ambient plume matrix reach their solidus and mixing of their partial melts to variable proportions create the spread in radiogenic and stable isotope systematics. This mixing of components is coherent with the widely observed disparity in trajectories between plume matrix and enriched components in long-lived (Sr-Nd-Pb-Hf) and extinct (W) radiogenic and stable (Fe-Mg) isotope systematics and marks a fundamental process for chemical diversity in OIB. It supports a model of isolated plume components in a primitive mantle matrix. Enriched components in the plume that contribute to this mixing appear to be solely pyroxenitic with no or very little direct contribution from the original eclogite. Timing and loci of pyroxenite formation remain to be elucidated.

Tracing and constraining anthropogenic aerosol iron fluxes to the North Atlantic Ocean using iron isotopes

Atmospheric dust is an important source of the micronutrient Fe to the oceans. Although relatively insoluble mineral Fe is assumed to be the most important component of dust, a relatively small yet highly soluble anthropogenic component may also be significant. However, quantifying the importance of anthropogenic Fe to the global oceans requires a tracer which can be used to identify and constrain anthropogenic aerosols in situ. Here, we present Fe isotope (δ56Fe) data from North Atlantic aerosol samples from the GEOTRACES GA03 section. While soluble aerosol samples collected near the Sahara have near-crustal δ56Fe, soluble aerosols from near North America and Europe instead have remarkably fractionated δ56Fe values (as light as −1.6‰). Here, we use these observations to fingerprint anthropogenic combustion sources, and to refine aerosol deposition modeling. We show that soluble anthropogenic aerosol Fe flux to the global surface oceans is highly likely to be underestimated, even in the dusty North Atlantic.