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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 bo

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 bo

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.

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.

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.

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 l

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 av

Incipient warming of peatlands at high latitudes is expected to modify soil drainage and hence the redox conditions, which has implications for Fe export from soils. This study uses Fe isotopes to assess the processes controlling Fe export in a range of Icelandic soils including peat soils derived from the same parent basalt, where Fe isotope variations principally reflect differences in weathering and drainage. In poorly weathered, well-drained soils (non-peat soils), the limited Fe isotope fractionation in soil solutions relative to the bulk soil (D57Fesolution-soil = 0.11 ± 0.12‰) is attributed to proton-promoted mineral dissolution. In the more weathered poorly drained soils (peat soils), the soil solutions are usually lighter than the bulk soil (D57Fesolution-soil = 0.41 ± 0.32‰), which indicates that Fe has been mobilised by reductive mineral dissolution and/or ligand-controlled dissolution. The results highlight the presence of Fe-organic complexes in solution in anoxic conditions. An additional constraint on soil weathering is provided by Si isotopes. The Si isotope composition of the soil solutions relative to the soil (D30Sisolution-soil = 0.92 ± 0.26‰) generally reflects the incorporation of light Si isotopes in secondary aluminosilicates. Under anoxic conditions in peat soils, the largest Si isotope fractionation in soil solutions relative to the bulk soil is observed (D30Sisolution-soil = 1.63 ± 0.40‰) and attributed to the cumulative contribution of secondary clay minerals and amorphous silica precipitation. Si supersaturation in solution with respect to amorphous silica is reached upon freezing when Al availability to form aluminosilicates is limited by the affinity of Al for metal–organic complexes. Therefore, the precipitation of amorphous silica in peat soils indirectly supports the formation of metal–organic complexes in poorly drained soils. These observations highlight that in a scenario of decreasing soil drainage with warming high latitude pea

Recent sediments from the Gotland Deep display enrichments in reactive Fe, associated with elevated Fe/Al ratios and light Fe isotopic signatures of the bulk sediments that are indicative of euxinic (anoxic and sulfidic) conditions. These enrichments can be explained by the Fe shuttle model where benthic Fe is transported from the shelf to the euxinic basin and transferred to the sediments by pyrite precipitation in the sulfidic water. The data provide evidence that the Fe shuttle at present results in accumulations of Fe that are larger compared to Fe enrichments during the Litorina Sea stage in the Gotland Deep probably caused by an increase of the benthic Fe flux from the shelf to the basin. The derived Fe enrichments are also larger compared to those in recent Black Sea sediments, which likely reflects the larger shelf to basin ratio of the Gotland Deep compare to the Black Sea. The Fe isotope data show no correlation with the organic C content of the samples indicating that the negative Fe isotope signatures are not associated with organic materials, as was suggested as an alternative explanation for the origin of the isotopically light Fe in sediments from the Litorina Sea stage. Conversely, pyrites carry the negative Fe isotopic signature of the sediments, which supports the Fe shuttle model. Variations in the abundance and Fe isotopic signature of reactive Fe and pyrite with depth suggest that syngenetically formed pyrite in the sulfidic water column has a less negative Fe isotopic composition compared to diagenetically produced pyrite., authorCount :5

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

The recognition of iron microbial mats in terrestrial environments is of great relevance for the search for extraterrestrial life, especially on mars where significant iron minerals were identified in the subsurface. Most researches focused on very ancient microbial mats (e.g. BIFs) since they formed on Earth at a time where similar conditions are supposed to have prevailed on Mars too. However, environmental proxies are often difficult to use for these deposits on Earth which, in addition, may be heavily transformed due to diagenesis or even metamorphism. Here we present modern and phanerozoic iron microbial mats occurrences illustrating the wide variety of environments in which they form, including many marine settings, ponds, creeks, caves, volcanoes, etc. Contrarily to their Precambrian counterparts, Modern and Phanerozoic deposits are usually less affected by diagenesis and the environmental conditions likely to be better constrained. Therefore, their investigation may help for the search for morphological and geochemical biosignatures (e.g. iron isotopes) in ancient iron microbial occurrences on Earth but also on other Planets. In particular, many of the case studies presented here show that microstromatolithe-like morphologies may be valuable targets for screening potential biosignatures in various rock types., SCOPUS: cp.p, Colloque :Instruments, Methods, and Missions for Astrobiology XI. RB Hoover, GV Levin, AY Rozanov, PCW Davies Eds., info:eu-repo/semantics/published

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

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.

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.

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.