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We present bulk-rock and mineral Fe isotope data of ultramafic to mafic xenoliths and basaltic to andesitic lavas from Adagdak Volcano (Adak Island, Central Aleutians) to study the effects of early differentiation on the Fe isotopic evolution of island arc basalts and their crystallization products. The Fe isotope composition of ultramafic cumulate xenoliths increases from dunite (δ56Fe = –0.09 to –0.02 ‰) to clinopyroxenite (δ56Fe = +0.06 to +0.09 ‰), consistent with higher modal proportions of clinopyroxene (δ56Fe = –0.05 to +0.11 ‰) relative to olivine (δ56Fe = –0.10 to +0.06 ‰) in the latter. Mid-crustal cumulate amphibole gabbro and hornblendite cumulates also record heavier Fe isotope compositions (δ56Fe = +0.04 to +0.08 ‰) due to the abundance of isotopically heavy amphibole (δ56Fe = +0.07 to +0.09 ‰) and magnetite (δ56Fe = +0.11 to +0.13 ‰) in these rocks. High inter-mineral fractionations observed in spinel-olivine and spinel-clinopyroxene pairs (Δ56Fe spl-ol = +0.12 to +0.28 and Δ56Fe spl-cpx = +0.06 to +0.19) suggest that spinel is not recording equilibrium crystallization conditions for the ultramafic assemblages, likely due to subsolidus Fe-Mg exchange. Our data also include Fe isotope measurements of one mantle dunite (δ56Fe = +0.03 ± 0.05 ‰). Five Adagdak lavas, spanning from basalts to andesites, yield a narrow range of δ56Fe between +0.03 and +0.06 ‰. Our results highlight the potential of amphibole in driving the Fe isotope depletion trends observed in many erupted arc lavas, as amphibole hosts 28–99 % of the FeO T budget in the amphibole gabbro and hornblendite cumulates. This is also supported by single-crystal synchrotron Mössbauer spectroscopy of two amphibole grains, the first from an amphibole gabbro and the second from a hornblendite, which yield Fe3+/ΣFe ratios of 0.55 ± 0.06 and 0.58 ± 0.02, respectively. Water content and hydrogen isotope compositions determined by secondary-ion mass spectrometry from the same amphibole grains indicate partial dehydrogenation. Using Rayleigh fractionation modeling to account for oxidation during post-crystallization dehydrogenation, we calculate magmatic Fe3+/ΣFe ratios of 0.41 ± 0.04 for the amphibole gabbro and 0.30 ± 0.05 for the hornblendite. These data are then used to estimate an appropriate Fe force constant for Adagdak amphibole and quantitatively evaluate the effects of amphibole fractionation. Through a fractional crystallization model, we show how arc melts may experience periods of increasing δ56Fe during olivine-dominated fractionation, followed by decreasing δ56Fe once magnetite and amphibole saturate as cumulate phases. Notably, this dichotomy between fractionation of isotopically light versus heavy cumulate assemblages and its effects on the Fe isotope evolution of arc magmas is not captured by the Adagdak lava record, highlighting the utility of cumulates in chronicling the early isotopic evolution of magmatic systems. [ABSTRACT FROM AUTHOR]

The Ediacaran age (ca. 570 Ma) Shuram excursion, a ca. $12‰$ depletion in $\delta ^{13}\mathrm{C}_{\mathrm{carb}}$, may record a dramatic oxidation of marine sediments associated with a reorganization of Earth’s carbon cycle closely preceding the rise of large metazoans. However, several geochemical indicators suggest it may instead record secondary processes affecting the sediments such as post-depositional alteration. The stable isotopic composition of iron incorporated within carbonates $(\delta ^{56}\mathrm{Fe}_{\mathrm{carb}})$ reveals an anomalous $^{56}\mathrm{Fe}$-depletion (down to $-1.05‰$) in strata containing the Shuram excursion, while the underlying and overlying strata have crustal $\delta ^{56}\mathrm{Fe}_{\mathrm{carb}}$ values. These depleted $\delta ^{56}\mathrm{Fe}_{\mathrm{carb}}$ data during the Shuram excursion reflect incomplete reduction of iron oxides, limited by low ambient organic carbon contents. This elevated pulse of sedimentary iron oxides would consume the majority of the limited pool of organic carbon and therefore would give rise to very low net organic carbon burial during a time of enhanced detrital delivery of oxidized iron to the sediments. These results imply a syndepositional origin for the Shuram excursion, which represents a shift in the redox composition of Earth’s sedimentary shell toward more oxidizing conditions, perhaps removing a long-lived buffer on atmospheric oxygen.

The Ediacaran age (ca. 570 Ma) Shuram excursion, a ca. 12‰ depletion in δ13Ccarb, may record a dramatic oxidation of marine sediments associated with a reorganization of Earth's carbon cycle closely preceding the rise of large metazoans. However, several geochemical indicators suggest it may instead record secondary processes affecting the sediments such as post-depositional alteration. The stable isotopic composition of iron incorporated within carbonates (δ56Fecarb) reveals an anomalous 56Fe-depletion (down to -1.05‰) in strata containing the Shuram excursion, while the underlying and overlying strata have crustal 56Fe-δ56Fecarb values. These depleted δ56Fecarb data during the Shuram excursion reflect incomplete reduction of iron oxides, limited by low ambient organic carbon contents. This elevated pulse of sedimentary iron oxides would consume the majority of the limited pool of organic carbon and therefore would give rise to very low net organic carbon burial during a time of enhanced detrital delivery of oxidized iron to the sediments. These results imply a syndepositional origin for the Shuram excursion, which represents a shift in the redox composition of Earth's sedimentary shell toward more oxidizing conditions, perhaps removing a long-lived buffer on atmospheric oxygen. [ABSTRACT FROM AUTHOR]

Iron, Cu and Zn stable isotope systems are applied in constraining a variety of geochemical and environmental processes. Secondary reference materials have been developed by the Institute of Geology, Chinese Academy of Geological Sciences (CAGS), in collaboration with other participating laboratories, comprising three solutions (CAGS‐Fe, CAGS‐Cu and CAGS‐Zn) and one basalt (CAGS‐Basalt). These materials exhibit sufficient homogeneity and stability for application in Fe, Cu and Zn isotopic ratio determinations. Reference values were determined by inter‐laboratory analytical comparisons involving up to eight participating laboratories employing MC‐ICP‐MS techniques, based on the unweighted means of submitted results. Isotopic compositions are reported in per mil notation, based on reference materials IRMM‐014 for Fe, NIST SRM 976 for Cu and IRMM‐3702 for Zn. Respective reference values of CAGS‐Fe, CAGS‐Cu and CAGS‐Zn solutions are as follows: δ56Fe = 0.83 ± 0.07 and δ57Fe = 1.20 ± 0.13, δ65Cu = 0.57 ± 0.06, and δ66Zn = −0.79 ± 0.12 and δ68Zn = −1.65 ± 0.24, respectively. Those of CAGS‐Basalt are δ56Fe = 0.15 ± 0.07, δ57Fe = 0.22 ± 0.10, δ65Cu = 0.12 ± 0.08, δ66Zn = 0.17 ± 0.13, and δ68Zn = 0.34 ± 0.26 (2s). Key Points: Three reference solutions (CAGS‐Fe, CAGS‐Cu and CAGS‐Zn) and one basalt reference material (CAGSR) for calibrating Fe, Cu and Zn isotope ratio measurements have been developed.CAGS‐Fe, CAGS‐Cu, CAGS‐Zn and CAGSR show sufficient homogeneity and stability.Recommended reference values were determined by inter‐laboratory comparison of results from participating laboratories. [ABSTRACT FROM AUTHOR]

Recent marine mineral investigations in the South China Sea (SCS) have found increasingly significant abundances of Fe–Mn polymetallic crusts and nodules with variable substrates and nuclei. There is, however, no systematic and complete study of the SCS crusts and nodules. The lack of mineralogical and geochemical studies affects our explicit understanding of the mineralization characteristics and genesis of the crusts and nodules. In this study, we analyzed a set of SCS polymetallic crusts and nodules obtained from ten sites to determine their mineralogy, chemistry, and Fe and Os isotopes. The SCS crusts/nodules are composed predominantly of vernadite (δ–MnO 2 ) and amorphous Fe oxides/hydroxides. The nodules also contain minor todorokite. TEM imaging and electron diffractions show that the Fe–Mn minerals are nano–sized minerals with very poor crystallinity. Nitrogen adsorption/desorption analysis indicates an average specific surface area of 257.128 m 2 /g for the SCS crusts and nodules, and main apertures of 2–10 nm for their nanopores in the Fe–Mn minerals. It is noteworthy that the SCS crusts/nodules contain substantial amount of terrigenous detritus, suggesting that marginal sea–type Fe–Mn deposits are strongly influenced by terrigenous sedimentary input. Furthermore, geochemical analysis indicates that the SCS crusts/nodules have relatively lower Co (1482 ppm), Cu (556.2 ppm), Ni (3132 ppm), Mo (276.2 ppm), and Zn (598.3 ppm) compared to open oceanic crusts/nodules, but relatively high concentrations of REY (1647 ppm), PGE (234.0 ppb), Ba (1056 ppm), Pb (1878 ppm), Sr (995.9 ppm), Te (28.81 ppm), and Tl (67.87 ppm). Iron isotopic compositions suggest that the Fe sources of the SCS crusts/nodules may have been Fe dissolved in terrigenous (fluvial) inputs. Osmium isotopes indicate that the main ore–forming elements came directly from the ambient seawater, which was mainly influenced by terrigenous inputs, although there may have been mixing with minor mantle–derived signatures. Evidence from mineralogy, major element geochemistry, shale–normalized rare earth element (REE) patterns, and the Fe and Os isotopes suggest that the SCS crusts/nodules are mainly hydrogenetic, whilst the formation of some nodules may have been contributed by minor pore waters of their surrounding sediments. The SCS crusts/nodules had probably much higher growth rates (mean 19.20 mm/Ma) than most hydrogenetic Fe–Mn deposits in other open oceans, which are typical of marginal sea Fe–Mn deposits that contain sufficient supply of ore–forming terrigenous detritus. Grades of some critical metals of economic interest (notably Co, Cu, Ni, Mo, and Zn) are slightly lower in the SCS crusts and nodules than in the crust and nodules from Pacific prime mineralization zones. Concentrations of Mn, REY, Pt, Mo, Co, Te, and Bi, however, show relatively high concentrations relative to the continental crust. The SCS crusts and nodules could thus represent a strategic REE, Co and Pt resource, and will likely catalyse additional investigation of seabed resources in the South China Sea. [ABSTRACT FROM AUTHOR]

This study reports elemental and iron isotopic compositions of feldspar and its coexisting minerals from four Dabie I-type granitoids to evaluate the factors that control inter-mineral Fe isotopic fractionation in granitoids. The order of heavy iron isotope enrichment is feldspar > pyrite > magnetite > biotite ≈ hornblende. Feldspar has heavier iron isotopic compositions than its co-existing magnetite (Δ 56 Fe plagioclase–magnetite = +0.376‰ to +1.084‰, Δ 56 Fe alkali-feldspar–magnetite = +0.516‰ to +0.846‰), which can be attributed to its high Fe 3+ /Fe tot ratio and low coordination number (tetrahedrally-coordinated) of Fe 3+ . Δ 56 Fe magnetite–biotite of coexisting magnetite and biotite ranges from 0.090‰ to 0.246‰. Based on homogeneous major and iron isotopic compositions of mineral replicates, the inter-mineral fractionation in this study should reflect equilibrium fractionation. The large variations of inter-mineral fractionation among feldspar, magnetite and biotite cannot be simply explained by temperature variation, but strongly depend on mineral compositions. The Δ 56 Fe plagioclase–magnetite and Δ 56 Fe alkali-feldspar–magnetite are positively correlated with albite mode in plagioclase and orthoclase mode in alkali-feldspar, respectively. This could be explained by different Fe–O bond strength in feldspar due to different Fe 3+ /∑Fe or different crystal parameters. The Δ 56 Fe magnetite–biotite increases with decreasing Fe 3+ /∑Fe biotite and increasing mole (Na + K)/Mg biotite , indicating a decrease of β factor in low Fe 3+ /∑Fe and high (Na + K)/Mg biotite. High-silica leucosomes from Dabie migmatites with a feldspar accumulation petrogenesis have higher δ 56 Fe values (δ 56 Fe = 0.42–0.567‰) than leucosome that represents pristine partial melt (δ 56 Fe = 0.117 ± 0.016‰), indicating that accumulation of feldspar could account for high δ 56 Fe values of these rocks. High δ 56 Fe values are also predicted for other igneous rocks that are mainly composed of cumulate feldspar crystals, e.g., anorthosites. Feldspar accumulation, however, cannot explain high δ 56 Fe values of most high-silica granitoids reported in the literature, based on their low Sr, Ba contents and negative Eu anomalies. [ABSTRACT FROM AUTHOR]

The Rapitan-type banded iron formation (BIF) in the Banda Alta Formation (Fm) of the Neoproterozoic Jacadigo Group in Brazil was deposited in a redox-stratified, marine sub-basin, which was strongly influenced by glacial advance/retraction cycles with temporary influx of continental freshwater and upwelling metal-enriched seawater from deeper anoxic parts. These new finding are based on new stratigraphic, whole-rock geochemical, and stable Fe and C isotope data from the “Santa Cruz” hematite deposit near Corumbá, Mato Grosso do Sul, where a stratigraphy of lower and upper dolomite-rich and intermediate chert-rich BIF facies with up to three intercalated diamictites is revealed. The Ca-Mg-Fe-Mn-carbonate-chert-hematite and chert-hematite BIF (∼30–45 wt% Fe) of the lower dolomite-rich facies shows chemical signatures consistent with well-oxidized seawater, i.e. low (Pr/Yb) PAAS , strong negative Ce PAAS -, and positive Gd PAAS - and Y PAAS -anomalies, as well as negative-δ 13 C carbonate typical for Neoproterozoic glaciogenic carbonates. Sedimentation in a rather shallow water depth during relatively warm interglacial periods was likely influenced by abundant freshwater from fluviatile runoff and melting icebergs. In such conditions abundant microbial activity accommodated CO 2 sequestration in carbonates as spheroids and mats and fractionated δ 57 Fe (−2.6 and −1.2‰) in primary Fe-hydroxides. In contrast, the intermediate chert-rich facies, characterized by chert-hematite BIF (∼35–55 wt% Fe) and isolated hematite chert and hematite mud, recorded trace element signatures of non-oxidized (absence of Ce anomalies and variable Y PAAS -anomalies), more metal-enriched (Fe, Mn, Si, Ni, Zn, Pb, U) seawater, thus deposition was within and below the shallow-level redoxcline during ice cover. Colder water and isolation from sunlight reduced microbial activity, and thus an almost non-fractionated δ 57 Fe (−0.7 to 0.0‰) fluid signature reveals that low-temperature (based on almost absence of Eu anomaly in BIF) hydrothermal (MOR) vents or (sub-) seafloor alteration of mafic or felsic rocks, or shales fertilized seawater with metals. All results lead to the model that the Jacadigo Group formed during one major marine transgression-regression cycle, and BIF facies in the Banda Alta Fm were a response to first- and second-order periodic variations of the depth of the redoxcline, induced by the juxtaposition of glacial advance/retraction cycles, active graben tectonics, and glacial isostatic adjustment or eustatic water level changes. The chert-rich BIF facies marked the maximum of transgression. Age and tectonic setting of the Jacadigo basin remains contentious: it may represent a continental back arc basin of the Brasiliano collision zone (∼590 Ma), in which submarine alteration was possibly related to low-temperature hydrothermal fluids moving through the active graben system (as an alternative to basin-wide benthic pore water flux). This would place the Jacadigo group to the suite of Ediacarian “Gaskier” glaciations, although a relationship to the Marinoan glaciation (660–635 Ma), mainly based on the published sedimentation age-bracket of 706–587 Ma, is also possible. [ABSTRACT FROM AUTHOR]

An ongoing controversy in mantle geochemistry concerns the oxidation state of the sources of island arc lavas (IAL). Three key factors control oxidation–reduction (redox) of IAL sources: (i) metasomatism of the mantle wedge by fluids and/or melts, liberated from the underlying subducted slab; (ii) the oxidation state of the wedge prior to melting and metasomatism; and (iii) the loss of melt from IAL sources. Subsequently, magmatic differentiation by fractional crystallisation, possible crustal contamination and degassing of melts en route to and at the surface can further modify the redox states of IAL. The remote nature of sub-arc processes and the complex interplay between them render direct investigations difficult. However, a possible gauge for redox-controlled, high-temperature pre-eruptive differentiation conditions is variations in stable Fe isotope compositions (expressed here as δ 57 Fe) in erupting IAL because Fe isotopes can preserve a record of sub-surface mass transfer reactions involving the major element Fe. Here we report Fe isotope compositions of bulk IAL along the active Banda arc, Indonesia, which is well known for a prominent subducted sediment input. In conjunction with other arc rocks, δ 57 Fe in erupted Banda IAL indicates that fractional crystallisation and possibly crustal contamination primarily control their Fe isotope signatures. When corrected for fractional crystallisation and filtered for contamination, arc magmas that had variable sediment melt contributions in their sources show no resolvable co-variation of δ 57 Fe with radiogenic isotope tracers. This indicates that crustal recycling in the form of subducted sediment does not alter the Fe isotope character of arc lavas, in agreement with mass balance estimates. Primitive sources of IAL, however, are clearly isotopically lighter than those sourced beneath mid-ocean ridges, indicating either preferential Fe 3+ -depletion in the mantle wedge by prior, δ 57 Fe-heavy melt extraction, and/or addition of an isotopically-light slab-derived agent. Based on our findings and previous models of arc redox conditions, we propose a three-stage process to explain the Fe isotope composition of IAL: (i) prior melt depletion lowers Fe 3+ /ΣFe (Fe 3+ over total Fe) in the residues, leaving refractory, δ 57 Fe-light and possibly reduced mantle wedge protoliths beneath arcs. The oxygen fugacity ( f O 2 ) of these refractory protoliths may be up to −2 log 10 units reduced relative to the fayalite–magnetite–quartz synthetic oxygen buffer (ΔFMQ); (ii) oxidised, slab-derived fluids, Fe-poor but possibly rich in sulphate (i.e., S 6+ ), trigger melting of depleted protoliths with minimal effect on δ 57 Fe. Melts derived from this fluid-modified wedge source have high Fe 3+ /ΣFe, oxidised by the reduction of S 6+ , but importantly retain the light δ 57 Fe from their mantle wedge source; (iii) after melt liberation from the mantle wedge, arc magmas initially become progressively oxidised and isotopically heavier in Fe through fractional crystallisation of ferromagnesian silicates. In summary, reduction consequent to Fe 3+ -rich melt extraction and subsequent oxidation, likely by S 6+ -rich fluids, results in a “redox yo-yo” in IAL sources. Fractional crystallisation will further oxidise and elevate δ 57 Fe in erupting IAL. Iron isotope signatures in IAL record a complex magmatic history with no simple relation between δ 57 Fe and calculated f O 2 in erupted lavas. Records of higher f O 2 in subduction zones compared to MORB sources are inherited from the subduction component. [ABSTRACT FROM AUTHOR]

The first data set of high-precision Fe isotopic compositions of olivine, orthopyroxene and chromite from harzburgites, dunites and chromitites from the Kızıldağ ophiolite, southern Turkey is reported here. The Fe isotopic compositions of the minerals are variable, with δ 56 Fe ranging from 0.005‰ to 0.222‰ in olivine, from − 0.005‰ to 0.024‰ in orthopyroxene and from − 0.214‰ to 0.072‰ in chromite. The forsterite contents and δ 56 Fe values of the olivine in the harzburgites and dunites range from 90.5 to 90.9 and from 0.005‰ to 0.050‰, respectively, similar to the values of abyssal peridotites. The Fe isotope variations of the minerals together with petrological features and major elemental compositions, suggest a residual origin for the harzburgites and an accumulation process associated with the dunite formation. The δ 56 Fe of the chromite correlates positively with Fe 3 + /Fe total ratio and negatively with FeO content, indicative of correlations with mantle oxygen fugacity and fractional crystallization. Comparisons between the results from the Kızıldağ and those from Luobusa ophiolite indicate that these chromitites were most likely formed by the change of oxygen fugacity and magmatic differentiation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Magnetite can be used to trace metal and fluid sources in iron oxide copper gold (IOCG) deposits using O, Fe, and Ti stable isotope geochemistry. • This is the first work to explore Ti isotope geochemistry in a hydrothermal system and in a mineral deposit. • Magnetite from the Ernest Henry IOCG deposit in Queensland, Australia exhibits magmatic O isotope signatures, but non-magmatic Fe isotope signatures, suggesting that much of the Fe in the deposit was sourced from the leaching of crustal rocks by magmatic-hydrothermal fluids. • Ti isotope signatures indicate that Ti was mobilized during the mineralization of the copper ore resulting in Ti isotope compositions that are more fractionated than what has been observed in magmatic systems. Iron oxide copper gold (IOCG) deposits are globally important sources of Cu; however, their origins remain poorly understood with respect to the metal and fluid sources involved in their formation. In this work, we utilize integrated Fe, Ti, and O isotopic data for magnetite to trace major metal and fluid inputs for the Proterozoic-aged Ernest Henry IOCG deposit—the largest known IOCG deposit in the Cloncurry District, Queensland, Australia. Magnetite separates from ore stage and pre-ore biotite-magnetite (bt-mgt) and magnetite-actinolite (mgt-act) alteration assemblages from Ernest Henry were analyzed for their O, Fe, and Ti isotope abundances, reported as δ18O (VSMOW), δ56Fe (IRMM-14), and δ49Ti (OL-Ti). Select magnetite samples were also analyzed for 17O (reported as Δ'17O 0.5305) and range from −0.118 to −0.056 ‰—suggesting evaporitic input. The δ18O values from ore stage (+1.57 to +7.36 ‰), bt-mgt (+0.34 to +5.68 ‰), and mgt-act (+1.68 to +2.10 ‰) samples are consistent with a magmatic-hydrothermal origin for ore and pre-ore mineralizing fluids at Ernest Henry; non-magmatic δ18O values > c. 5 ‰ may be explained through localized carbonate wall rock assimilation. Despite this, δ56Fe values for ore stage (−0.50 to +0.33 ‰), bt-mgt (−0.65 to +0.38 ‰), and mgt-act (−0.26 to +0.30 ‰) magnetite are generally isotopically lighter than the accepted range (c. +0.06 to +0.49 ‰) for igneous and magmatic-hydrothermal magnetite and exhibit a relatively large range of c. 1 ‰, suggesting Fe source mixing within the deposit. Ore stage magnetite δ49Ti (−1.64 to + 3.79 ‰; avg: +1.49 ‰; 2σ = 2.63 ‰) compositions are generally higher and more variable than either the bt-mgt (-0.44 to + 1.49 ‰; avg: +0.62 ‰; 2σ = 1.13 ‰) or mgt-act (+0.27 to + 1.89 ‰; avg: +1.05 ‰; 2σ = 1.56 ‰) and suggest that Ti isotope fractionation occurred due to differential mobility in the fluid. The data are best explained by models invoking both magmatic and non-magmatic metal and fluid input. Fluid flow channeled between the footwall and hanging wall shear zones introduced non-magmatic Fe that may have been leached from local mafic units by magmatic-hydrothermal fluids, resulting in neoformed and regeneratively replaced magnetite with magmatic δ18O, but non-magmatic δ56Fe values during pre-ore alteration. These fluids may have mixed with Fe-poor evaporitic fluids prior to magnetite formation. Later magmatic Fe and O contributions during ore stage mineralization resulted in magnetite with variable δ56Fe and irresolvable δ18O overprinting. Ernest Henry is the first known example of an IOCG deposit with a major leached metal component identified through metal stable isotope geochemistry. [ABSTRACT FROM AUTHOR]

Before the Great Oxidation Event (GOE) 2.4–2.2 billion years ago it has been traditionally thought that oceanic water columns were uniformly anoxic due to a lack of oxygen-producing microorganisms. Recently, however, it has been proposed that transient oxygenation of shallow seawater occurred between 2.8 and 3.0 billion years ago. Here, we present a novel combination of stable Fe and radiogenic U–Th–Pb isotope data that demonstrate significant oxygen contents in the shallow oceans at 3.2 Ga, based on analysis of the Manzimnyama Banded Iron Formation (BIF), Fig Tree Group, South Africa. This unit is exceptional in that proximal, shallow-water and distal, deep-water facies are preserved. When compared to the distal, deep-water facies, the proximal samples show elevated U concentrations and moderately positive δ 56 Fe values, indicating vertical stratification in dissolved oxygen contents. Confirmation of oxidizing conditions using U abundances is robustly constrained using samples that have been closed to U and Pb mobility using U–Th–Pb geochronology. Although redox-sensitive elements have been commonly used in ancient rocks to infer redox conditions, post-depositional element mobility has been rarely tested, and U–Th–Pb geochronology can constrain open- or closed-system behavior. The U abundances and δ 56 Fe values of the Manzimnyama BIF suggest the proximal, shallow-water samples record precipitation under stronger oxidizing conditions compared to the distal deeper-water facies, which in turn indicates the existence of a discrete redox boundary between deep and shallow ocean waters at this time; this work, therefore, documents the oldest known preserved marine redox gradient in the rock record. The relative enrichment of O 2 in the upper water column is likely due to the existence of oxygen-producing microorganisms such as cyanobacteria. These results provide a new approach for identifying free oxygen in Earth's ancient oceans, including confirming the age of redox proxies, and indicate that cyanobacteria evolved prior to 3.2 Ga. [ABSTRACT FROM AUTHOR]

Abstract: Plots such as ε54Cr vs. ε50Ti and ε54Cr vs. Δ17O reveal a fundamental dichotomy among planetary materials. The “carbonaceous” chondrites, by virtue of high ε50Ti and high ε62Ni, as well as, especially for any given Δ17O, high ε54Cr, are separated by a wide margin from all other materials. The significance of the bimodality is further manifested by several types of meteorites with petrological-geochemical characteristics that suggest membership in the opposite category from the true pedigree as revealed by the stable isotopes. Ureilites, for example, despite having diversely low Δ17O and about the same average carbon content as the most C-rich carbonaceous chondrite, have clear stable-isotopic signatures of noncarbonaceous pedigree. The striking bimodality on the ε54Cr vs. ε50Ti and ε54Cr vs. Δ17O diagrams suggests that the highest taxonomic division in meteorite/planetary classification should be between carbonaceous and noncarbonaceous materials. The bimodality may be an extreme manifestation of the effects of episodic accretion of early solids in the protoplanetary nebula. However, an alternative, admittedly speculative, explanation is that the bimodality corresponds to a division between materials that originally accreted in the outer solar system (carbonaceous) and materials that accreted in the inner solar system (noncarbonaceous). In any event, both the Earth and Mars plot squarely within the noncarbonaceous composition-space. Applying the lever rule to putative mixing lines on the ε50Ti vs. ε54Cr and Δ17O vs. ε54Cr diagrams, the carbonaceous/(carbonaceous+noncarbonaceous) mixing ratio C/(C + NC) is most likely close to (very roughly) 24% for Earth and 9% for Mars. Estimated upper limits for C/(C + NC) are 32% for Earth and 18% for Mars. However, the uncertainties are such that isotopic data do not require or even significantly suggest that Earth has higher C/(C + NC) than Mars. Among known chondrite groups, EH yields a relatively close fit to the stable-isotopic composition of Earth. [Copyright &y& Elsevier]

Abstract: Assessing the level of homogeneity of different planetary reservoirs is an essential step to establish a new isotopic tracer. In recent studies, we concluded that most igneous rocks from the continental crust were homogeneous to < ±0.05‰ in δ 57Fe [Poitrasson, F., Halliday, A.N., Lee, D.C., Levasseur, S., Teutsch, N., 2004. Iron isotope differences between Earth, Moon, Mars and Vesta as possible records of contrasted accretion mechanisms. Earth Planet. Sci. Lett., 223, 253-266.; Poitrasson, F., Freydier, R., 2005. Heavy iron isotope composition of granites determined by high resolution MC-ICP-MS. Chem. Geol., 222, 132-147.]. This conclusion was previously reached by Beard et al. [Beard, B.L., Johnson, C.M., Skulan, J.L., Nealson, K.H., Cox, L., Sun, H., 2003. Application of Fe isotopes to tracing the geochemical and biological cycling of Fe. Chem. Geol., 195, 87-117.], though defined by a broader range (±0.08‰). The main purpose of the Beard and Johnson [Beard, B.L., Johnson, C.M., 2006. Comment on “Heavy iron isotope composition of granites determined by high resolution MC-ICP-MS” by F. Poitrasson and R. Freydier, Chemical Geology, volume 222, pages 132-147. Chem. Geol., this issue.] comment is to emphasize again this conclusion reached by the two groups: the degree of the iron isotope variability observed in most bulk rocks from the continental crust is small. However, controversy lies with high silica magmatic rocks (> ∼ 71 wt.% SiO2) that we concluded were significantly heavier than less silicic rocks from the crust on the basis of Fe isotopic analyses of seven bulk rock samples from different geological settings. Beard and Johnson [Beard, B.L., Johnson, C.M., 2006. Comment on “Heavy iron isotope composition of granites determined by high resolution MC-ICP-MS” by F. Poitrasson and R. Freydier, Chemical Geology, volume 222, pages 132-147. Chem. Geol., this issue.] challenge this finding on the basis of previously “published” data. It is shown here that this controversy stems from the confusion between whole-rock and mineral iron isotope analyses, since this isotopic tracer, like many others, is more heterogeneous at the mineral scale than the bulk rock scale. Thus, minerals cannot be used in place of bulk rock Fe isotope compositions. The controversy also arises from different levels of analytical uncertainties. If only the best Fe isotope probes of planetary reservoirs — bulk rocks — are considered, then the conclusion that igneous rocks with SiO2 >71 wt.% are significantly heavier than the mean δ 57Fe of the continental crust [Poitrasson, F., Freydier, R., 2005. Heavy iron isotope composition of granites determined by high resolution MC-ICP-MS. Chem. Geol., 222, 132-147.] remains valid. Nonetheless, given that granites represent only a minor fraction of the continental crust, this finding does not change the bulk igneous Fe isotope composition estimate previously defined for the Earth. [Copyright &y& Elsevier]

Direct fossil evidence for early microbial life on Earth is rare. Microbiological data indicate that sulfate and iron reduction are both among the earliest forms of microbial respiration, and direct evidence for the early origin of sulfate reduction comes from sulfur isotopic anomalies in ancient sediments. Fe isotope geochemistry potentially provides a new way of identifying microbial iron reduction early in Earth's history. We present Fe isotopic data for sedimentary pyrite from the 2.7 Ga Belingwe sedimentary basin in Zimbabwe. Isotopically light Fe and a remarkable covariation between Fe and S isotopes provide strong evidence for coexisting Fe and S reduction. Our results are consistent with an early origin for sulfate reduction and provide direct geochemical evidence for the antiquity of bacterial Fe reduction. The covariation of Fe and S isotopes may provide a useful new tracer of microbial evolution early in Earth history. [ABSTRACT FROM AUTHOR]