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The early Cambrian Takab iron ore deposit is situated in the northern part of the Sanandaj-Sirjan zone, western Iran. It consists of banded, nodular and disseminated magnetite hosted in folded micaschists. Trace element and Fe and O isotopic experiments reveal various hydrothermal precipitation environments under reduced to slightly oxidizing conditions. Disseminated magnetite has high Ti (945–1940 ppm) positively correlated with Mg + Al + Si, and heavy Fe (+0.76 to +1.86‰) and O (+1.0 to +4.07‰) isotopic compositions that support a magmatic/high-T hydrothermal origin. Banded magnetite has low Ti (15−200 ppm), V (≤100 ppm), Si and Mg (mostly ≤300 ppm) and variable Al. The ∂56Fe values vary from −0.2‰ to +1.12‰ but most values also support a magmatic/high-T hydrothermal origin. However, variable ∂18O (−2.52 to +1.22‰) values provide evidence of re-equilibration with lower-T fluid at ~200–300 °C. Nodular magnetite shows high Mn (≤1%), and mostly negative ∂56Fe values (average, −0.3‰) indicative of precipitation from an isotopically light hydrothermal fluid. Re-equilibration with carbonated rocks/fluids likely results in a negative Ce anomaly and higher ∂18O (average, +6.30‰). The Takab iron ore deposit has, thus, experienced a complex hydrothermal history.

International audience; The early Cambrian Takab iron ore deposit is situated in the northern part of the Sanandaj-Sirjan zone, western Iran. It consists of banded, nodular and disseminated magnetite hosted in folded micaschists. Trace element and Fe and O isotopic experiments reveal various hydrothermal precipitation environments under reduced to slightly oxidizing conditions. Disseminated magnetite has high Ti (945-1940 ppm) positively correlated with Mg + Al + Si, and heavy Fe (+0.76 to +1.86‰) and O (+1.0 to +4.07‰) isotopic compositions that support a magmatic/high-T hydrothermal origin. Banded magnetite has low Ti (15−200 ppm), V (≤100 ppm), Si and Mg (mostly ≤300 ppm) and variable Al. The ∂ 56 Fe values vary from −0.2‰ to +1.12‰ but most values also support a magmatic/high-T hydrothermal origin. However, variable ∂ 18 O (−2.52 to +1.22‰) values provide evidence of re-equilibration with lower-T fluid at ~200-300 • C. Nodular magnetite shows high Mn (≤1%), and mostly negative ∂ 56 Fe values (average, −0.3‰) indicative of precipitation from an isotopically light hydrothermal fluid. Re-equilibration with carbonated rocks/fluids likely results in a negative Ce anomaly and higher ∂ 18 O (average, +6.30‰). The Takab iron ore deposit has, thus, experienced a complex hydrothermal history.

International audience; Sediments are considered to be refractory materials with limited influences on dissolved iron (dFe) pool in the ocean. However, recent field observations and laboratory experiments suggest that iron released from resuspended sediment particles and transported from continental margins is prone to fertilize large areas of the world ocean. Here we conducted a dissolution experiment to quantify the amount of dFe released from two types of resuspended sediments (silicate and calcite-rich) to open ocean surface seawater under two temperatures (5 and 15 °C). We followed pH, dissolved oxygen (dO2), phosphate, silicate, dissolved Fe and Mn concentrations (dFe and dMn), and bacterial abundance over 250 days. Extremely low and undetectable phosphate concentrations (< 50 pmol kg-1) were measured throughout the duration of the experiment, causing limited bacteria growth and stable pH and dissolved O2 concentrations under all conditions. Silicate and dFe concentrations increased through time and high temperature (15 °C) induced more iron dissolution from the two sediments than low temperature (5 °C). Temperature had no effect on the dissolution of Mn. Our results further show that Fe and Mn are not released concurrently from the sediment source and that their distribution can be very different. Scavenging of Fe likely caused a decrease of dFe observed during the experiment, which was probably linked to the formation of Mn oxides. We also observed elevated dissolved Fe isotope ratios after dissolution, around +0.16 to +0.27 ‰. Isotopically heavy Fe was released from sediments to the dissolved pool during the dissolution but no difference in Fe isotope ratios was observed between the two temperature conditions. The Fe isotope fractionation can likely be attributed to ligand complexation and scavenging of Fe. These two mechanisms can be important factors not only in controlling the amount of Fe released from sediments but also in fractionating Fe isotopes at the sediment-seawater boundary.; Les sédiments sont considérés comme étant des matériaux réfractaires avec une influence limitée sur le pool de fer dissous (dFe) dans l'océan. Cependant, des observations récentes sur le terrain et des expériences en laboratoire suggèrent que le fer libéré par les particules de sédiments remises en suspension et transportées depuis les marges continentales est susceptible de fertiliser de vastes zones de l'océan mondial. Dans cette étude, nous avons monitoré la dissolution de deux types de sédiments en suspension (riches en silicate et en calcite) pour quantifier la quantité de dFe libérée dans l'eau de mer de surface en océan ouvert à deux températures (5 et 15 °C). Nous avons suivi le pH, l'oxygène dissous (dO2), le phosphate, les silicates, les concentrations de Fe et de Mn dissous (dFe et dMn) et l'abondance bactérienne pendant 250 jours. Des concentrations en phosphate extrêmement faibles et indétectables (< 50 pmol kg-1) ont été mesurées pendant toute la durée de l'expérience, entraînant une croissance bactérienne limitée et des concentrations de pH et d'O2 dissous stables dans toutes les conditions. Les concentrations de silicates et de dFe ont augmenté avec le temps et une température élevée (15 °C) a induit une plus grande dissolution du fer dans les deux sédiments qu'une température basse (5 °C). La température n'a pas eu d'effet sur la dissolution du Mn. Nos résultats montrent en outre que le Fe et le Mn ne sont pas libérés simultanément de la source sédimentaire et que leur distribution peut être très différente. Le piégeage du Fe est probablement à l'origine d'une diminution du dFe observée au cours de l'expérience, probablement liée à la formation d'oxydes de Mn. Nous avons également observé des rapports isotopiques élevés du Fe dissous après dissolution, de l'ordre de +0,16 à +0,27 ‰. Le Fe isotopiquement lourd a été libéré des sédiments vers le pool dissous pendant la dissolution, mais aucune différence dans les rapports isotopiques du Fe n'a été observée entre les deux conditions de température. Le fractionnement isotopique du Fe peut probablement être attribué à la complexation du ligand et au piégeage du Fe. Ces deux mécanismes peuvent être des facteurs importants non seulement pour contrôler la quantité de Fe libérée des sédiments, mais aussi pour fractionner les isotopes du Fe à la limite sédiments-eau.

Dissolved iron (Fe) isotopes in river water have a pivotal role in understanding the Fe cycle in the surficial environment. A total of 13 samples of river water were collected from the Mun River to analyze the Fe isotopes and their controlling factors in river water, such as dissolved organic carbon (DOC) and different supply sources. The results showed that dissolved Fe (DFe) concentrations ranged from 21.49 μg/L to 232.34 μg/L in the dry season and ranged from 10.48 μg/L to 135.27 μg/L in the wet season, which might be ascribed to the dilution effect. The δ56Fe of the dry season (−0.34 to 0.57‰, with an average 0.09‰) was lower than that of the wet season (−0.15 to 0.48‰, with an average 0.14‰). Combined with the δ56Fe and DFe/DAl ratios, the end-members of DFe were identified, including rock weathering (high δ56Fe and low DFe/DAl ratio), anthropogenic inputs (high δ56Fe and high DFe/DAl ratio) and groundwater inputs (low δ56Fe and low DFe/DAl ratio). The relationship between δ56Fe and DOC concentrations suggested that the chelation of organic matter with heavy Fe isotopes was one of the important sources of heavy Fe isotopes in river water.

Anoxic seawater may have played an important role in the preservation of volcanogenic massive sulfide (VMS) deposits in the Hokuroku district, northeast Japan, which is the type locality for Kuroko-type VMS deposits. In this study, we investigated the Fe isotopic compositions of sulfide ores and overlying ferruginous sedimentary rocks in these deposits. These data, coupled with petrographic and geochemical data, enable us to investigate the key formation processes and conditions during the formation of large Kuroko-type VMS deposits. Large Fe isotope variations of ca. 4 parts per thousand (delta Fe-56) associated with negative or positive Ce anomalies characterize the ferruginous sedimentary rocks formed in the Kuroko VMS deposits and post-Kuroko hydrothermal activity. This suggests that iron (hydr)oxides were precipitated by the partial oxidation of dissolved Fe2+ derived from hydrothermal fluids in anoxic or suboxic pools in the Hokuroku Basin. Positive Eu anomalies in the ferruginous cherts closely associated with the Kuroko VMS deposits indicate formation from high-temperature hydrothermal fluids. Zincrich black ores in both the Matsumine and Fukazawa deposits have lower delta Fe-56 values, due to rapid precipitation of pyrite triggered by the mixing of hydrothermal fluids with seawater. Positive shifts in delta Fe-56 values in the ferruginous cherts from the Ezuri and Fukazawa deposits may be explained by simultaneous precipitation of ferruginous sedimentary rocks with black ores, which modified the delta Fe-56 values of the hydrothermal fluids to positive values. However, Cu-rich yellow ores show no significant Fe isotope fractionation as compared with the dissolved Fe in the hydrothermal fluids, and were likely formed by slow growth of pyrite that replaced the black ores. The difference in the abundance of sulfide ores between the Matsumine and Fukazawa deposits may reflect the duration of hydrothermal circulation.

Lavas produced at subduction zones represent the integration of both source heterogeneity and an array of crustal processes, such as: differentiation; mixing; homogenisation; assimilation. Therefore, unravelling the relative contribution of the sub-arc mantle source versus these crustal processes is difficult when using the amalgamated end products in isolation. In contrast, plutonic xenoliths provide a complementary record of the deeper roots of the magmatic plumbing system and provide a unique record of the true chemical diversity of arc crust. Here, we present the δ56Fe record from well characterised plutonic xenoliths from two distinct volcanic centres in the Lesser Antilles volcanic arc–the islands of Martinique and Statia. The primary objective of this study is to test if the Fe isotope systematics of arc lavas are controlled by sub-arc mantle inputs or during subsequent differentiation processes during a magma’s journey through volcanic arc crust. The Fe isotopic record, coupled to petrology, trace element chemistry and radiogenic isotopes of plutonic xenoliths from the two islands reveal a hidden crustal reservoir of heavy Fe that previously hasn’t been considered. Iron isotopes are decoupled from radiogenic isotopes, suggesting that crustal and/or sediment assimilation does not control the Fe systematics of arc magmas. In contrast to arc lavas, the cumulates from both islands record MORB-like δ56Fe values. In Statia, δ56Fe decreases with major and trace element indicators of differentiation (SiO2, Na2O + K2O, Eu/Eu*, Dy/Yb), consistent with fractionating mineral assemblages along a line of liquid descent. In Martinique, δ56Fe shows no clear relationship with most indicators of differentiation (apart from Dy/Yb), suggesting that the δ56Fe signature of the plutonic xenoliths has been overprinted by later stage processes, such as percolating reactive melts. Together, these data suggest that magmatic processes within the sub-arc crust overprint any source variation of the sub-arc mantle and that a light Fe source is not a requirement to produce the light Fe isotopic compositions recorded in volcanic arc lavas. Therefore, whenever possible, the complimentary plutonic record should be considered in isotopic studies to understand the relative control of the mantle source versus magmatic processes in the crust.

International audience; Colloids have been recognized as key vectors of pollutants in aqueous environment. Amongst them, those formed by iron (Fe) and organic matter (OM) are of major importance due to their ubiquity in the surface environment and strong affinity for metals. In the recent years, Fe stable isotopes have been increasingly used to elucidate the sources and biogeochemical cycling of Fe in Earth's surface environments. In this study, we aim to elucidate (i) the possible Fe isotopic signature resulting from the Fe/OM colloid formation and (ii) the mechanisms involved in the development of such isotopic signature. For this purpose, Fe-OM associations were synthesized through binding and titration experiments. Various pH levels were used in order to study the isotope behavior of Fe occurring as free species at pH 1, as Fe-OM complexes at pH 2 and as mixed Fe-oxyhydroxide/OM nanoaggregates or particles at pH 6.5. Organic matter-free, Fe-free and OM membrane-deposition experiments were also performed. These suspensions were (ultra)filtered at 0.2 µm, 30 kDa and 5 kDa to evidence the possible Fe isotope fractionation between fractions. This protocol allowed also testing the potential of (ultra)filtration techniques to generate isotope fractionation. The results provided evidence that abiotic Fe precipitation, (ultra)filtration techniques and OM deposition were not able to produce significant Fe isotope fractionation under the experimental conditions. However, at circum-neutral pH, the Fe-OM binding and titration experiments displayed a significant enrichment of heavy Fe isotopes in the < 30 kDa fractions relative to the total Fe pool δ56Fe = 0.35 ± 0.05‰ and 0.26 ± 0.05‰ (95% confidence interval, 2σ and relative to international standard IRMM-14), respectively. Mass balance and error propagation calculation showed Fe isotope fractionation in binding and titration experiments between the > 30 kDa and < 30 kDa fractions for -0.35 ± 0.05‰ and -0.27 ± 0.05‰, respectively. This Fe isotope fractionation could be due to the complexation of Fe by OM in the < 30 kDa fractions. At pH 2, the OM-free experiment, the < 30 kDa fraction showed Fe isotope ratio δ56Fe = 0.75 ± 0.03‰ with an enrichment in heavy Fe isotopes of δ56Fe’ = 0.14 ± 0.04‰ relative the total Fe pool (δ56Fe’ is δ56Fe value which was corrected by δ56Fe of total fraction). This enrichment in heavy Fe isotopes induced an isotopic fractionation factor of -0.87 ± 0.26‰ between the > 30 kDa and < 30 kDa fractions produced by the complexation between the heavy Fe isotopes and OH- ligands in the < 30 kDa fraction. Natural Fe-OM associations were further investigated through oxidation experiments of a reduced wetland soil solution. The oxidized soil solution was (ultra)filtered at 5 µm, 3 µm, 0.2 µm, 30 kDa and 5 kDa. The highest δ56Fe was obtained in the smallest size fraction, i.e. < 5 kDa fraction, yielding a negative isotopic fractionation Δ56Fe >5kDa

International audience; Microbial activity is often invoked as a direct or indirect contributor to the precipitation of ancient chemical sedimentary rocks such as Precambrian iron formations (IFs). Determining a specific metabolic pathway from the geological record remains a challenge, however, due to a lack of constraints on the initial conditions and microbially induced redox reactions involved in the formation of iron oxides. Thus, there is ongoing debate concerning the role of photoferrotrophy, that is the process by which inorganic carbon is fixed into organic matter using light as an energy source and Fe(II) as an electron donor, in the deposition of IFs. Here, we examine ~2.74‐Ga‐old Neoarchean IFs and associated carbonates from the Carajás Mineral Province, Brazil, to reconstruct redox conditions and to infer the oxidizing mechanism that allowed one of the world's largest iron deposits to form. The absence of cerium (Ce) anomalies reveals that conditions were pervasively anoxic during IF deposition, while unprecedented europium (Eu) anomalies imply that Fe was supplied by intense hydrothermal activity. A positive and homogeneous Fe isotopic signal in space and time in these IFs indicates a low degree of partial oxidation of Fe(II), which, combined with the presence of 13C‐depleted organic matter, points to a photoautotrophic metabolic driver. Collectively, our results argue in favor of reducing conditions during IF deposition and suggest anoxygenic photosynthesis as the most plausible mechanism responsible for Fe oxidation in the Carajás Basin.

Fe isotopes have been applied to the petrogenesis of ore deposits. However, the behavior of iron isotopes in the mineralization of porphyry-skarn deposits is still poorly understood. In this study, we report the Fe isotopes of ore mineral separations (magnetite, pyrite, chalcopyrite and pyrrhotite) from two different skarn deposits, i.e., the Tonglvshan Cu-Fe skarn deposit developed in an oxidized hydrothermal system and the Anqing Cu skarn deposit developed in a reduced hydrothermal system. In both deposits, the Fe isotopes of calculated equilibrium fluids are lighter than those of the intrusions responsible for the skarn and porphyry mineralization, corroborating the “light-Fe fluid” hypothesis. Interestingly, chalcopyrite in the oxidized-Tonglvshan skarn deposit has lighter Fe than chalcopyrite in the reduced-Anqing skarn deposit, which is best understood as the result of the prior precipitation of magnetite (heavy Fe) from the ore fluid in the oxidized-Tonglvshan systems and the prior precipitation of pyrrhotite (light Fe) from the ore fluid in the reduced-Anqing system. The δ56Fe for pyrite shows an inverse correlation with δ56Fe of magnetite in the Tonglvshan. In both deposits, the Fe isotope fractionation between chalcopyrite and pyrite is offset from the equilibrium line at 350 °C and lies between the FeS-chalcopyrite equilibrium line and pyrite-chalcopyrite equilibrium line at 350 °C. These observations are consistent with the FeS pathway towards pyrite formation. That is, Fe isotopes fractionation during pyrite formation depends on a path from the initial FeS-fluid equilibrium towards the pyrite-fluid equilibrium due to the increasing extent of Fe isotopic exchange with fluids. This finding, together with the data from other deposits, allows us to propose that the pathway effect of pyrite formation in the Porphyry-skarn deposit mineralization is the dominant mechanism that controls Fe isotope characteristics.

Weathering processes on Ni-rich ultramafic rocks in tropical areas produce laterites that become exploitable for Ni mining. To better understand these processes, samples were collected stratigraphically with water samples from several Ni mines in the Philippines and studied for Ni and Fe isotope compositions. This study found that Ni isotope fractionation takes place during the formation of Ni-enriched minerals (goethite), when light Ni isotopes are preferentially incorporated into new minerals formed, leaving heavy Ni isotopes in groundwater. The Δ60NiLimonite-Bedrock is up to -0.19 ± 0.32‰. Even though Fe is partitioned with redox state change during these reactions, Fe isotope fractionation was not detected within our analytical precision. In complement, iron meteorites were analyzed for their δ57Fe to shed light on the origin of Lovina ataxite. This study supports other reports that Lovina has instead a terrestrial origin.

Iron oxides are one of the most reactive mineral phases in soils. As a consequence, their transformations can considerably affect the dynamics of the adsorbed elements and of the associated soil ecosystem services. Understanding the dynamics of Fe oxides in soils is therefore a key issue for the evolution of soil and associated ecosystem services. A potentially powerful tool to study the transformations of Fe-oxides in soil is stable Fe isotopes. However, there are still important gaps in our knowledge of Fe isotope fractionations. In order to examine the Fe isotope fractionations related to each process occurring in soils, we focused on a drainage-influenced sequence of Retisols, a soil type characterized by clay translocation and subsequent degradation by redox processes inducing a strong spatial Fe segregation in contrasted soil volumes. We combined the isotopic approach at the scale of a bulk horizon and at the scale of the different soil volumes, with mineralogical analyses and mass balance calculations in order to investigate the consequences of the drainage on Fe isotope fractionation. We showed that while there were no Fe isotope fractionations at the profile scale, Fe isotopic signatures varied significantly among soil volumes (delta Fe-56 values from -0.49 +/- 0.05 to 0.29 +/- 0.06 parts per thousand). These variations suggest that redox processes are the main mechanisms responsible for the Fe redistribution among the volumes, and particularly that Fe accumulation during Mn oxide precipitation makes a significant contribution to Fe isotopic fractionation, during these Retisol differentiation. In contrast, drainage-induced eluviation does not result in further Fe isotope fractionations in soil volumes in these Retisols. The isotopic signatures of the different mineral phases present in the volumes were calculated using the mass balance approach and suggest that the iron oxides (goethite, ferrihydrite) have delta Fe-56 values close to 0 parts per thousand, while the clay minerals are enriched in heavy Fe isotopes and the Mn oxides in light Fe isotopes. This study provides insight into the dynamics of Fe minerals in hydromorphic soils and offers a new perspective on stable Fe isotope fractionation in soils.

Chondrules are a major constituent of primitive meteorites. The formation of chondrules is one of the most elusive problems in cosmochemistry. We use Fe isotope compositions of chondrules and bulk chondrites to constrain the conditions of chondrule formation. Iron isotope compositions of bulk chondrules are so far only known from few studies on CV and some ordinary chondrites. We studied 37 chondrules from the CM chondrite Murchison. This is particularly challenging, as CM chondrites contain the smallest chondrules of all chondrite groups, except for CH chondrites. Bulk chondrules have δ 56 Fe between −0.62 and +0.24‰ relative to the IRMM-014 standard. Bulk Murchison has as all chondrites a δ 56 Fe of 0.00‰ within error. The δ 56 Fe distribution of the Murchison chondrule population is continuous and close to normal. The width of the δ 56 Fe distribution is narrower than that of the Allende chondrule population. Opaque modal abundances in Murchison chondrules is in about 67% of the chondrules close to 0 vol.%, and in 33% typically up to 6.5 vol.%. Chondrule Al/Mg and Fe/Mg ratios are sub-chondritic, while bulk Murchison has chondritic ratios. We suggest that the variable bulk chondrule Fe isotope compositions were established during evaporation and recondensation prior to accretion in the Murchison parent body. This range in isotope composition was likely reduced during aqueous alteration on the parent body. Murchison has a chondritic Fe isotope composition and a number of chondritic element ratios. Chondrules, however, have variable Fe isotope compositions and chondrules and matrix have complementary Al/Mg and Fe/Mg ratios. In combination, this supports the idea that chondrules and matrix formed from a single reservoir and were then accreted in the parent body. The formation in a single region also explains the compositional distribution of the chondrule population in Murchison.

The formation processes of the unusually metal-rich CB and CH chondrites are highly debated. Chemically and isotopically zoned metal, unzoned metal, and cryptocrystalline (CC) chondrules from these meteorites are proposed to have formed by condensation. However, it is still unclear if they condensed directly from the solar nebula or from an impact-induced vapor plume, and how metal and chondrule formation are related. This thesis aims at unravelling the formation conditions of CH and CB chondrite constituents by laser ablation analyses of Fe, Ni, and Si isotopes in combination with trace element analyses. Parallel zoning of Fe and Ni isotopes in zoned metal from CH and CBb chondrites confirm a condensation origin of the zoning and exclude exchange diffusion as the formation process. Tungsten in zoned metal grains is depleted relative to other refractory elements which is suggestive for elevated oxygen fugacities in the gas reservoir, and thus, also for an impact event. Combined results of isotope and trace element analyses reveal that zoned metal formed in the fast-cooling shell regions, which favor kinetic fractionation while unzoned metal would have condensed from the slow-cooling interior of the plume under more equilibrium-like conditions. CC chondrules from CH and CBb chondrites were analyzed for Si isotope and trace element compositions to unravel their formation histories. Trace element abundances revealed two different populations of CC chondrules: (1) superchondritic refractory element contents and depletion in volatile elements most likely condensed from an unfractionated reservoir, and (2) with generally subchondritic element contents formed from a reservoir that was fractionated beforehand by an ultrarefractory phase. Tungsten, Mo, and Cr concentrations in metal and chondrules indicate elevated oxygen fugacities, and formation of those constituents from a closed system. Silicon isotope compositions of chondrules are heavier than BSE and the chondritic average. Thus, we propose that light Si isotopes were extracted from the gas reservoir, either due to the impact or by condensation of forsterite or melilite prior to CC chondrule formation. A relationship between CB, CH, and CR chondrites is proposed due to isotopic similarities (Cr, Ti, N, O), high metal contents, and similarities in hydrated clasts from CH and CB chondrites with CR matrix. Iron and Ni isotope results, combined with trace element contents, reveal relatively homogeneous composition of CR chondrite metal. These findings combined with textural differences, lead to the conclusion that metal from CR chondrites did not form in the same event as that of CH and CB chondrites. Bulk isotopic similarities (Cr, Ti, N, O) of the three chondrite groups may reflect (1) formation of precursor material in the same region, (2) accretion in the same region, or (3) inheritance of the isotope signature of a CR impactor by CH and CB chondrites. DFG/SPP 1385/WE 2850/13-1/ ZI 1196/3-1/EU

The stable isotope ratio compositions of Fe, Ni, and Cu (δ56Fe, δ60Ni, and δ65Cu) are reported for the first time in rocks from the Sudbury Igneous Complex (SIC). Massive sulfide ores, Quartz Diorite (QD), Inclusion bearing Quartz Diorite (IQD), and rocks from members of the Main Mass of the SIC were analyzed. The objective was to better understand the origin(s) and source(s) of the Offset Dikes and the associated sulfide mineralization. Based on stable isotope ratios and petrographic observations, two distinct types of sulfide mineralization hosted within the Offset Dikes are identified. Massive sulfide mineralization hosted within the Offset Dikes was identified to be different than the disseminated blebby sulfide mineralization found within the QD and IQD, based on coordinated isotopic and petrographic analyses. Comparisons of the stable isotope ratios of Fe, Ni, and Cu between rock samples from different Offset Dikes established a homogeneity in Fe, Ni, and Cu compositions. Including between the QD and IQD, and their disseminated sulfides. A correlation between δ60Ni, and δ65Cu values, with lighter compositions for the massive sulfides compared to the residual main mass, indicates an early magmatic origin for the massive sulfides compared to the disseminated sulfides contained in the Offset Dikes.

The majority of the Earth’s crust is formed by magmas, and understanding their production and differentiation is important to interpret the geologic rock record. A powerful tool to investigate magmatic processes is the distribution of the stable isotopes of the major redox-sensitive element in magmas, Fe. Fe isotope compositions of magmatic rocks exhibit systematic differences, where the heaviest compositions are found in rhyolites and granites. Understanding of these systematics is complicated by a lack of constraints on Fe isotope fractionation among minerals and liquids under magmatic conditions, and basic knowledge about the complementarity of erupted magmas and crystal loads left behind during the course of magmatic differentiation, as well as, the residues remaining after partial melting within the crust and mantle. This Ph.D. dissertation addresses basic questions about the differentiation of magmas from the perspective of Fe stable isotopes, integrated with petrology, by studying igneous rocks and their constituent phases (minerals and glasses) from the Bushveld Complex, South Africa, Thingmuli, Iceland, Pantelleria, Italy, and the Bishop Tuff, USA. The findings are interpreted in terms of available theory, experiments and forward modeling incorporating petrologic constraints.Mafic cumulate rocks from the Bushveld Complex exhibit resolvable whole rock Fe isotopic variation with modal mineralogy and mineral composition, to a 1st order reflecting partitioning of Fe3+ and Fe2+ between melt and minerals. The isotope composition of mineral phases of Bushveld cumulate rocks is highly variably, and records closure temperatures, modal abundance and inter-mineral textural relations. In contrast, isotope compositions of mafic to intermediate lavas from Thingmuli volcano vary little, while silicic lavas are systematically heavier. Generation of heavy Fe isotope compositions is shown to be strongly affected by the intensive variable governing magmatic differentiation, most importantly, oxygen fugacity, mineral and melt composition and structure governing the distribution of Fe2+ and Fe3+ during differentiation, and strongly favored by low magma Fe contents at the terminal stages of crystallization.I also determine Fe isotope fractionation factors for minerals and melts in rhyolite systems by measuring the isotopic compositions for minerals and quenched liquids (glasses or fine-grained matrices) in volcanic rocks. This work shows that fractionation factors strongly depend on the abundance of Fe3+ in minerals. Fractionation factors also correlate moderately well with Fe3+/Fetot in the melt, but show better correlation with calculated viscosity of the melt at magmatic conditions, reflecting the important influence of melt structure on Fe isotope fractionation. I illustrate these interdependences and provide new constraints of melt force constants of silicic magmas. These results have direct applicability for explaining the enrichment of heavy Fe isotopes during differentiation and for more quantitative model of the magmatic processes producing enigmatic stable isotope compositions of rhyolitic and granite magmas.

Iron is the most abundant multivalent element in planetary reservoirs, meaning its isotope composition (expressed as δ57Fe) may record signatures of processes that occurred during the formation and subsequent differentiation of the terrestrial planets. Chondritic meteorites, putative constituents of the planets and remnants of undifferentiated inner solar system bodies, have δ57Fe ≈ 0‰; an isotopic signature shared with the Martian Shergottite–Nakhlite–Chassignite (SNC) suite of meteorites. The silicate Earth and Moon, as represented by basaltic rocks, are distinctly heavier, δ57Fe≈+0.1‰. However, some authors have recently argued, on the basis of iron isotope measurements of abyssal peridotites, that the composition of the Earth’s mantle is δ57Fe = +0.04 ± 0.04‰, indistinguishable from the mean Martian value. To provide a more robust estimate for Mars, we present new high-precision iron isotope data on 17 SNC meteorites and 5 mineral separates. We find that the iron isotope compositions of Martian meteorites reflect igneous processes, with nakhlites and evolved shergottites displaying heavier δ57Fe(+0.05 ± 0.03‰), whereas MgO-rich rocks are lighter (δ57Fe≈−0.01 ±0.02‰). These systematics are controlled by the fractionation of olivine and pyroxene, attested to by the lighter isotope composition of pyroxene compared to whole rock nakhlites. Extrapolation of the δ57Fe SNC liquid line of descent to a putative Martian mantle yields a δ57Fe value lighter than its terrestrial counterpart, but indistinguishable from chondrites. Iron isotopes in planetary basalts of the inner solar system correlate positively with Fe/Mn and silicon isotopes. While Mars and IV-Vesta are undepleted in iron and accordingly have chondritic δ57Fe, the Earth experienced volatile depletion at low (1300 K) temperatures, likely at an early stage in the solar nebula, whereas additional post-nebular Fe loss is possible for the Moon and angrites.

Multiple sulfur isotope variability in Archean sedimentary rocks provides constraints on the composition of the Earth’s earliest atmosphere. The magnitude and sign of mass-independent anomalies reflect not only atmospheric processes, but also transformations due to the Archean marine sulfur cycle prior to preservation into sedimentary pyrite. The processes affecting the Archean marine sulfur cycle and the role of microbial or abiotic redox reactions during pyrite formation remain unclear. Here we combine iron (Fe) and multiple sulfur (S) isotope data in individual pyrite grains with petrographic information and a one-dimensional reactive transport model, to investigate the sources of Fe and S in pyrite formed in a Paleoarchean sedimentary basin. Pyrites were selected from mudstones, sandstones and chert obtained from a drill core in the ca. 3.2 Ga Mapepe and Mendon Formations of the Fig Tree and Onverwacht Groups, respectively, in the Barberton Greenstone Belt, Kaapvaal Craton, South Africa. Pyrite textures and δ 56 Fe distinguish early-diagenetic pyrite formed with pore-water ferrous iron (disseminated grains with average δ 56 Fe pyrite = 0‰) from late-diagenetic pyrite formed through sulfidation of iron oxide minerals (layered and aggregate forms with average δ 56 Fe pyrite = + 1‰). Mass dependent S isotope variability in pyrite was small (δ 34 S pyrite ranged from − 1.1 to + 3.3‰) with a correspondingly minor spread in Δ 33 S pyrite (ranging from + 0.3 to + 2.1‰) and Δ 36 S pyrite (ranging from − 3.08 to + 0.27‰) that indicates a lack of post-depositional re-working with other distinct sulfur sources. Our combined Fe and S isotope data are most readily explained with pyrite sulfide derived from microbial-reworking of solid elemental S. Iron oxide minerals were necessary to buffer sulfide concentrations and provide favorable conditions for microbial sulfur disproportionation to proceed. The lack of a negative Δ 33 S signal indicates that pyrite from relatively deep marine diagenetic environments only partially records the products of atmospheric photolysis, consistent with low sulfate concentrations in the Paleoarchean ocean.

Concentrically laminated pyrite is a relatively common, although volumetrically minor, component of auriferous conglomerates in the Archaean (ca. 3.0–2.7 Ga) Witwatersrand Basin of South Africa. This type of pyrite contains high amounts (several tens of ppm) of Au, but the origin of the pyrite is debated, and the timing of Au deposition in these grains is not known. In order to constrain the formation of pyrite, we have studied concentrically laminated pyrite and other coexisting types of pyrite (inclusion-rich, massive pyrite) by analysing the contents and distribution of Au and other trace elements by laser ablation ICP-MS, the S and Fe isotope composition by SIMS, and the mineral inclusions by scanning electron microscope and laser Raman spectroscopy. Trace element maps indicate that concentrically laminated pyrite is enriched in Sb, Mn, Au, Ag, Tl, Cu, Mo, Mn, and contains two types of gold: finely dispersed Au (“invisible gold”, with Au/Ag ~ 0.1 and likely of primary origin) and Au inclusions with Au/Ag ~ 10 of secondary origin. The study of mineral inclusions revealed the presence of muscovite, chlorite, fine-grained carbonaceous matter, monazite, Ti-oxides, and quartz. Iron and multiple S isotopes suggest that concentrically laminated pyrite and inclusion-rich pyrite were formed from two separate pools of S and Fe with different isotope characteristics. Sulfur was derived from atmospheric S that had undergone mass-independent isotope fractionation to form SO 4 2− with negative Δ 33 S that constituted concentrically laminated pyrite, and elemental S with positive Δ 33 S that formed inclusion-rich pyrite. Iron pools were derived from partial oxidation of Fe 2 + , so that concentrically laminated pyrite formed from a low-δ 56 Fe residual Fe 2 + (average + 0.2‰) and inclusion-rich pyrite formed from a high-δ 56 Fe Fe 3 + pool (average + 2.7‰). Biological activity may have been involved in the reduction of SO 4 2− , causing a wide spread of δ 34 S values (~ 25‰, S reducing microorganisms), as well as in the partial oxidation of Fe 2 + (anaerobic photosynthetic Fe reducers or photosynthetic O 2 producers), and in the formation of pyrite from Fe 3 + (dissimilatory Fe reducers). We propose that concurrent biogenically-mediated pyrite formation and Au trapping suggest that microbial activity was responsible for the accumulation of Au and other trace elements (e.g. Sb, Mn, Ag, Tl, Cu, Mo, Mn) which are commonly enriched in organic matter-rich sediments.

The source and cycling of Fe in groundwaters from the phreatic aquifer which characterizes a site impacted by metallurgical activity in a coastal area of northern Italy (Adriatic Sea) have been investigated by Fe-isotope analyses, H-O-Sr stable-isotope systematics and major and trace element chemistry. Waters are characterized by circum-neutral to alkaline pH and dissolved O-2 zoning, and range from a low-salinity Ca-Mg-HCO3 type to a brackish Na-Cl type resulting from seawater intrusion. The O-H isotopic data indicate that the Ca-Mg-HCO3 waters originate from meteoric precipitation that infiltrated at elevated altitudes, and that a variable seawater fraction, in some cases exceeding 90%, characterizes the Na-Cl type waters. The Fe content ranges from 0.48 to 9.99 mg/L and from 2.50 to 43.8 mg/L in low-salinity and brackish waters, respectively. The delta Fe-56 value varies over the wide range from +0.87 parts per thousand to -5.29 parts per thousand in low-salinity waters and between +2.15 parts per thousand and -2.34 parts per thousand in brackish waters. The isotopically lighter compositions are interpreted as reflecting isotopic fractionation during repeated cycling of Fe precipitation. Positive delta Fe-56 values might indicate either a higher solubility of oxyhydroxides, which during diagenesis preferentially incorporated the isotopically heavier fraction of Fe, or the leaching of the foundry landfill disposal which characterizes the site.

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. d66Zn and d56Fe display a well-defined positive correlation and both also correlate with d34S. 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, d56Fe and d66Zn 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. Science Foundation Ireland DG 16/10/2012

Neutron capture cross sections are the key nuclear physics input to understand nucleosynthesis of the slow neutron capture process (s process). At the neutron time of flight facility n_TOF at CERN neutron capture cross sections of astrophysical interest are measured over a wide energy range. A measurement campaign to determine the stellar (n ; g ) cross sections of Fe and Ni isotopes is currently being pursued. First results on the stellar cross section of 62Ni(n ; g ) confirm previous experimental results. The cross section of the radioactive s-process branching 63Ni was measured for the first time at stellar energies and is about a factor of 2 higher than theoretical predictions. Future facilities and upgrades will allow to access a number of other radioactive nuclides which are crucial for understanding physical conditions of s-process environments.

ELEMENTAL AND ISOTOPIC STUDY OF DIFFERENTIATED METEORITES AND IMPLICATIONS FOR THE ORIGIN AND EVOLUTION OF THEIR PARENT BODIES Iron meteorites are differentiated meteorites composed largely of Fe-Ni alloys. The metallic phase of many iron meteorites shows a texture called the Widmanstätten pattern, which develops as a two-phase intergrowth of kamacite (α-bcc, ferrite) and taenite (γ-fcc, austenite), and forms by nucleation and growth of kamacite from taenite during slow cooling of the parent body. Selected iron meteorites - octahedrites of different structural and chemical groups (Canyon Diablo, Toluca, Bohumilitz, Horh Uul, Alt Biela, Nelson County, Gibeon and Joe Wright Mountain) were studied with intention to evaluate the scale and extent of Fe isotopic heterogeneities in iron meteorites and to find the possible link between the isotopic variations and thermal histories of the respective meteorite parent bodies. The Fe isotopic compositions of kamacite and taenite in the studied meteorites, obtained by three independent analytical techniques with different spatial resolution capabilities (laser ablation and solution MC ICP-MS and SIMS) show significant variations of up to ~4.5‰ in δ56 Fe. The taenite is isotopically heavier compared to kamacite in all studied meteorites. There is no correlation...

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM-EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO(3)) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08 per thousand

International audience; Iron concentrations and isotopic compositions were measured in spherical hematite and goethite concretions, together with associated red (Fe-oxide coated) and white (bleached) sandstones from the Jurassic Navajo formation, Utah (USA). Earlier studies showed that, in the Navajo Sandstone, reducing fluids (presumably rich in hydrocarbons) mobilized Fe present as Fe-oxide coatings on detrital quartz grains. Dissolved Fe then precipitated as spherical concretions by interaction with oxidizing groundwater. Despite being depleted in Fe by not, vert, similar 50%, the bleached sandstones have Fe isotopic compositions similar to adjacent red sandstones (not, vert, similar 0‰/amu relative to IRMM-014). This shows that dissolution of Fe-oxide did not produce significant isotope fractionation, in agreement with previous experimental studies of abiotic Fe-oxide dissolution. In contrast, the concretions are depleted in the heavy isotopes of iron by − 0.07 to − 0.68‰/amu. This is opposite to the expected fractionation for partial Fe oxidation, which tends to enrich the precipitate in the heavy isotopes. Several scenarios are considered for explaining the measured Fe isotopic compositions. Although diffusion might be an important process in controlling the growth of spherical concretions, the associated isotopic fractionation is negligible compared to the observed variations. Kinetic isotope fractionation during precipitation can be ruled out as well because no isotopic zonation is seen within indurated concretions and Fe isotope evidence supports the occurrence of dissolution–reprecipitation reactions consistent with equilibrium growth conditions. The Fe isotopic compositions of the concretions are best explained by evolution of the fluid composition through precipitation and/or adsorption of isotopically heavy Fe during fluid flow through the sandstone. This scenario is supported by a regional trend in the isotopic composition of Fe, showing that this element was transported in fluids over several kilometres along major tectonic structures. These results demonstrate for the first time the virtue of Fe isotopes for tracing the directions and scales of paleofluid flows in porous media.

International audience; 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 parts per thousand in delta Fe-57 [Poitrasson, F., Halliday, AX, 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 parts per thousand). 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 (> similar to 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 delta Fe-57 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.

Temporal variations in Fe isotope compositions at three locations in the Pacific Ocean over the last 10 Ma are inferred from high-resolution analyses of three hydrogenetic ferromanganese crusts. Iron pathways to the central deep Pacific Ocean appear to have remained constant over the past 10 Ma, reflected by a remarkably constant Fe isotope composition, despite large changes in the Fe delivery rates to the surface ocean via dust. These results suggest that the Fe cycle in the deep ocean is decoupled from that in surface waters. By contrast, one ferromanganese crust from the Izu-Bonin (IB) back-arc/marginal basin of the W. Pacific exhibits large delta Fe-56 variations. In that crust, decreases in delta Fe-56 values correlate with increases in Mn, Mg, Ni, Cu, Zn, Me, and V contents, and consistent with periods of intense hydrothermal input and increased growth rates. A second crust located within 100 km of the first IB sample does not record any of these periods of enhanced hydrothermal input. This probably reflects the isolated pathways by which hydrothermally sourced Fe may have migrated in the back arc, highlighting the high degree of provinciality that Fe isotopes may have in the modem (oxic) oceans. Our results demonstrate that despite efficient removal at the source, hydrothermal Fe injected into the deep ocean could account for a significant fraction of the dissolved Fe pool in the deep ocean, and that hydrothermally sourced Fe fluxes to the open ocean may have lower delta(56) Fe values than those measured so far in situ at hydrothermal vents. Correlation between 656 Fe values and elements enriched in hydrothermal fluids may provide a means for distinguishing hydrothermal Fe from other low-delta Fe-56 sources to the oceans such as dissolved riverine Fe or porewaters in continental shelf sediments. (c) 2006 Elsevier B.V. All rights reserved.

Iron isotopic compositions of olivine, clinopyroxene and titanomagnetite of the Baima Fe–Ti oxide-bearing layered mafic intrusion, SW China, are used to investigate Fe isotopic fractionation during the formation of the Fe–Ti oxide ore bodies and to constrain the origin of silicate minerals and Fe–Ti oxides. The Baima intrusion comprises the Lower Zone of interlayered troctolite, clinopyroxenite and oxide ores and the Upper Zone of gabbros. Significant differences of Fe isotope values between olivine ( δ Fe 56 = − 0.01 to + 0.11 ‰ ), clinopyroxene ( δ Fe 56 = + 0.11 to + 0.22 ‰ ), and titanomagnetite ( δ Fe 56 = + 0.20 to + 0.31 ‰ ) were observed in rocks and ores of the Lower Zone. Iron isotopic fractionation between olivine and clinopyroxene, olivine and titanomagnetite and clinopyroxene and titanomagnetite exhibits large variations of 0.06‰ to 0.22‰, 0.12‰ to 0.27‰, and 0.00‰ to 0.20‰, respectively, suggesting disequilibrium fractionation. This disequilibrium cannot be explained by thermal or chemical gradient-induced kinetic fractionation or by possible subsolidus exsolution of granular ilmenite from titanomagnetite. Instead, it could be attributed to crystallization of silicates and titanomagnetite from two immiscible Si-rich and Fe-rich liquids. Continuous segregation of the Fe-rich liquid changed the Fe isotopic composition of the Si-rich liquid and thus the Fe isotopic compositions of olivine and clinopyroxene crystallized from it, resulting in disequilibrium Fe isotopic fractionation between them. The effect of oxygen fugacity on the crystallization order of titanomagnetite and ilmenite from the Fe-rich melts, on the other hand, gave rise to the disequilibrium Fe isotope fractionation between titanomagnetite and olivine/clinopyroxene.

International audience; High mass resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was assessed for iron isotope measurement of natural samples after matrix separation by anion exchange chromatography. No remaining interferences were observed on the plateaus used for the mass spectrometric measurements. The approach developed and the instrument used permitted analyses in the static mode. Various mass bias corrections using Ni doping were tested, and even the assumption of similar fractionation factors for Fe and Ni did not produce significantly inaccurate data. However, the daily regression method between In Fe-57/(54) Fe and 1n(61)Ni/Ni-60 on the standard reference material IRMM-14 to characterize the instrumental mass bias appeared to give the best precision. The reproducibility observed over four months is about 0.013 parts per thousand/amu, 2 SD, on both delta(57)Fe/Fe-54 and delta(56)Fe/Fe-54 values, provided that each sample is analyzed at least six times. Accuracy, as estimated on interlaboratory comparison of natural samples that included geostandards, lies within this uncertainty. Among the bulk granitic rocks analysed, those with MgO below 0.6 wt.% and SiO2 above 71 wt.% have delta(57) Fe/Fe-54 values significantly heavier than the bulk mafic Earth. This shows that the iron isotope composition of terrestrial igneous rocks is more scattered than previously thought. There are good correlations between the Fe isotope composition and the MgO and SiO2 contents of the granitoids. These correlations are interpreted as reflecting the exsolution of late magmatic aqueous fluids from the granitic melt that preferentially removed the lighter isotopes of iron and enriched the residual magma in the heavier isotopes.

In this thesis, the hypothesis that photoautotrophic Fe(II)-oxidizing bacteria catalyzed the deposition of Banded Iron Formations (BIFs), an enigmatic class of ancient sedimentary rocks is explored. Ecophysiological, geochemical, genetic and biochemical approaches are taken to elucidate the molecular mechanism of photoautotrophic Fe(II) oxidation in an effort to identify molecular biosignatures that are unique to this metabolism and capable of being preserved BIFs. In an ecophysiological approach, we show that Fe(II) oxidation by these phototrophs proceeds at appreciable rates in the presence of high concentrations of H2 when CO2 is abundant. These findings substantiate a role for the involvement of these phototrophs in BIF deposition under the presumed geochemical conditions of the Archean. In a geochemical approach, we find that although phylogenetically distinct phototrophs fractionate Fe isotopes in a way that is consistent with Fe isotopic values found in Precambrian BIFs, it is unlikely that this fractionation can be used as a biosignature for this metabolism given its similarity to fractionations produced by abiotic Fe(II) oxidation reactions. In two distinct genetic approaches, we identify genes involved in Fe(II) oxidation in Rhodopseudomonas palustris TIE-1 and Rhodobacter SW2. Genes identified in TIE-1 encode a predicted integral membrane protein that appears to be part of an ABC transport system and a putative CobS, an enzyme involved in cobalamin (vitamin B12) biosynthesis. Candidate genes on a cloned fragment of the Rhodobacter SW2 genome that confer Fe(II) oxidation activity to a non-oxidizing strain include those predicted to encode permeases and a protein with potential redox capability. Finally, in a preliminary biochemical approach, c-type cytochromes and other proteins that are exclusive or more highly expressed under Fe(II) growth conditions in TIE-1 and SW2 are identified in SDS-PAGE gels. The work described here furthers our search for a biosignature unique to photoautotrophic Fe(II) oxidation by providing mechanistic information on this metabolism.