Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

Silicon and iron isotope compositions of different physically separated components of enstatite chondrites (EC) were determined in this study to understand the role of nebular and planetary scale events in fractionating Si and Fe isotopes of the terrestrial planet-forming region. We found that the metal–sulfide nodules of EC are strongly enriched in light Si isotopes (δ30Si ≥ −5.61 ± 0.12‰, 2SD), whereas the δ30Si values of angular metal grains, magnetic, slightly magnetic, and non-magnetic fractions become progressively heavier, correlating with their Mg# (Mg/(Mg+Fe)). White mineral phases, composed primarily of SiO2 polymorphs, display the heaviest δ30Si of up to +0.23 ± 0.10‰. The data indicate a key role of metal–silicate partitioning on the Si isotope composition of EC. The overall lighter δ30Si of bulk EC compared to other planetary materials can be explained by the enrichment of light Si isotopes in EC metals along with the loss of isotopically heavier forsterite-rich silicates from the EC-forming region. In contrast to the large Si isotope heterogeneity, the average Fe isotope composition (δ56Fe) of EC components was found to vary from −0.30 ± 0.08‰ to +0.20 ± 0.04‰. A positive correlation between δ56Fe and Ni/S in the components suggests that the metals are enriched in heavy Fe isotopes whereas sulfides are the principal hosts of light Fe isotopes in the non-magnetic fractions of EC. Our combined Si and Fe isotope data in different EC components reflect an inverse correlation between δ30Si and δ56Fe, which illustrates that partitioning of Si and Fe among metal, silicate, and sulfidic phases has significantly fractionated Si and Fe isotopes under reduced conditions. Such isotope partitioning must have occurred before the diverse components were mixed to form the EC parent body. Evaluation of diffusion coefficients of Si and Fe in the metal and non-metallic phases suggests that the Si isotope compositions of the silicate fractions of EC largely preserve information of their nebular processing. On the other hand, the Fe isotopes might have undergone partial or complete re-equilibration during parent body metamorphism. The relatively uniform δ56Fe among different types of bulk chondrites and the Earth, despite Fe isotope differences among their components, demonstrates that the chondrite parent bodies were not formed by random mixing of chondritic components from different locations in the disk. Instead, the chondrite components mostly originated in the same nebular reservoir and Si and Fe isotopes were fractionated either due to gas–solid interactions and associated changes in physicochemical environment of the nebular reservoir and/or during parent body processing. The heavier Si isotope composition of the bulk silicate Earth may require accretion of chondritic and/or isotopically heavier EC silicates along with cumulation of refractory forsterite-rich heavier silicates lost from the EC-forming region to form the silicate reservoir of the Earth

HELGES: Helmholtz Laboratory for the Geochemistry of the Earth Surface

New developments in Geochemistry during the last two decades have revolutionized our understanding of the processes that shape Earth's surface. Here, complex interactions occur between the tectonic forces acting from within the Earth and the exogenic forces like climate that are strongly modulated by biota and, increasingly today, by human activity. Within the Helmholtz Laboratory for the Geochemistry of the Earth Surface (HELGES) of the Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, it is our goal to quantify the rates and fluxes of these processes in detail and to develop new techniques to fingerprint them over various temporal and spatial scales. We use mass spectrometry facilities to analyze metal stable isotopes, element concentrations and cosmogenic nuclides to fingerprint and quantify geomorphological changes driven by erosion and weathering processes. We use these novel geochemical tools, to quantify, for example, the recycling of metals in plants after their release during weathering of rocks and soils, soil formation and its erosion rates, and mechanisms and speed of sediment transport through drainage basins. Our research is thus dedicated towards understanding material turnover rates at the Earth's surface by using geochemical fingerprints

Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

Silicon and iron isotope compositions of different physically separated components of enstatite chondrites (EC) were determined in this study to understand the role of nebular and planetary scale events in fractionating Si and Fe isotopes of the terrestrial planet‐forming region. We found that the metal–sulfide nodules of EC are strongly enriched in light Si isotopes (δ30Si ≥ −5.61 ± 0.12‰, 2SD), whereas the δ30Si values of angular metal grains, magnetic, slightly magnetic, and non‐magnetic fractions become progressively heavier, correlating with their Mg# (Mg/(Mg+Fe)). White mineral phases, composed primarily of SiO2 polymorphs, display the heaviest δ30Si of up to +0.23 ± 0.10‰. The data indicate a key role of metal–silicate partitioning on the Si isotope composition of EC. The overall lighter δ30Si of bulk EC compared to other planetary materials can be explained by the enrichment of light Si isotopes in EC metals along with the loss of isotopically heavier forsterite‐rich silicates from the EC‐forming region. In contrast to the large Si isotope heterogeneity, the average Fe isotope composition (δ56Fe) of EC components was found to vary from −0.30 ± 0.08‰ to +0.20 ± 0.04‰. A positive correlation between δ56Fe and Ni/S in the components suggests that the metals are enriched in heavy Fe isotopes whereas sulfides are the principal hosts of light Fe isotopes in the non‐magnetic fractions of EC. Our combined Si and Fe isotope data in different EC components reflect an inverse correlation between δ30Si and δ56Fe, which illustrates that partitioning of Si and Fe among metal, silicate, and sulfidic phases has significantly fractionated Si and Fe isotopes under reduced conditions. Such isotope partitioning must have occurred before the diverse components were mixed to form the EC parent body. Evaluation of diffusion coefficients of Si and Fe in the metal and non‐metallic phases suggests that the Si isotope compositions of the silicate fractions of EC largely preserve information of their nebular processing. On the other hand, the Fe isotopes might have undergone partial or complete re‐equilibration during parent body metamorphism. The relatively uniform δ56Fe among different types of bulk chondrites and the Earth, despite Fe isotope differences among their components, demonstrates that the chondrite parent bodies were not formed by random mixing of chondritic components from different locations in the disk. Instead, the chondrite components mostly originated in the same nebular reservoir and Si and Fe isotopes were fractionated either due to gas–solid interactions and associated changes in physicochemical environment of the nebular reservoir and/or during parent body processing. The heavier Si isotope composition of the bulk silicate Earth may require accretion of chondritic and/or isotopically heavier EC silicates along with cumulation of refractory forsterite‐rich heavier silicates lost from the EC‐forming region to form the silicate reservoir of the Earth.DFG, German Research Foundatio

Replication Data for: Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

- Silicon and iron isotope compositions were analyzed in various components of enstatite chondrites (EC) to understand isotopic fractionation during planet formation. - Metal–sulfide nodules in EC showed significant enrichment in light silicon isotopes. - Silicon isotopic values in different fractions of EC varied, becoming progressively heavier with increasing Mg#. - White mineral phases, primarily SiO2 polymorphs, exhibited the heaviest silicon isotopic values. - Metal–silicate partitioning played a crucial role in determining the silicon isotopic composition of EC. - The overall lighter silicon isotopic composition of bulk EC compared to other planetary materials was attributed to the enrichment of light silicon isotopes in EC metals and loss of heavier silicates. - Iron isotope composition (δ56Fe) in EC components varied, with metals enriched in heavy isotopes and sulfides in light isotopes. - Combined silicon and iron isotope data showed an inverse correlation, indicating significant fractionation under reduced conditions. - Silicon isotopic compositions of silicate fractions largely retained information from nebular processing, while iron isotopes might have undergone re-equilibration during metamorphism. - Uniform δ56Fe among different chondrites and Earth suggests common origin and fractionation processes in nebular reservoirs during planet formation

Secondary Minerals Drive Extreme Lithium Isotope Fractionation During Tropical Weathering

Lithium isotopes are used to trace weathering intensity, but little is known about the processes that fractionate them in highly weathered settings, where secondary minerals play a dominant role in weathering reactions. To help fill this gap in our knowledge of Li isotope systematics, we investigated Li isotope fractionation at an andesitic catchment in Puerto Rico, where the highest rates of silicate weathering on Earth have been documented. We found the lowest δ7Li values published to date for porewater (−27‰) and bulk regolith (−38‰), representing apparent fractionations relative to parent rock of −31‰ and −42‰, respectively. We also found δ7Li values that are lower in the exchangeable fraction than in the bulk regolith or porewater, the opposite than expected from secondary mineral precipitation. We interpret these large isotopic offsets and the unusual relationships between Li pools as resulting from two distinct weathering processes at different depths in the regolith. At the bedrock‐regolith transition (9.3–8.5 m depth), secondary mineral precipitation preferentially retains the lighter 6Li isotope. These minerals then dissolve further up the profile, leaching 6Li from the bulk solid, with a total variation of about +50‰ within the profile, attributable primarily to clay dissolution. Importantly, streamwater δ7Li (about +35‰) is divorced entirely from these regolith weathering processes, instead reflecting deeper weathering reactions (>9.3 m). Our work thus shows that the δ7Li of waters draining highly weathered catchments may reflect bedrock mineralogy and hydrology, rather than weathering intensity in the regolith covering the catchment.Plain Language Summary: Weathering is the process by which rocks are altered at the Earth's surface, transforming fresh minerals into clays with some loss of chemical elements to rivers and eventually oceans. Understanding how intense weathering is now, and has been in the past, is important because it supplies nutrients for ecosystems and is part of the Earth's long‐term carbon cycle (and thus, climate regulation). To do this, geochemists have developed tracers of weathering intensity, of which Li isotopes (expressed as δ7Li) are considered to be the best. However, we know little about the behavior of Li isotopes in the tropics, where weathering is the most intense. To help make δ7Li a more robust tracer, we sampled a 10 m deep soil profile at a tropical catchment in Puerto Rico where rocks are dissolving very fast. We found that weathering here is so intense that clays are continuously dissolving, producing the lowest δ7Li values ever recorded on Earth, but that the stream water draining the catchment does not reflect these values. Our work thus expands the range of known values of this tracer and warns geochemists that δ7Li in rivers might not be directly related to weathering intensity in tropical catchments.Key Points: Lowest δ7Li values reported to date in nature (porewater = −27‰; bulk regolith = −38‰; exchangeable Lithium (Li) = −50‰). Large isotopic differences driven by clay precipitation, dissolution, and re‐precipitation processes. Li isotopes may not be appropriate tracers of weathering intensity for very highly weathered catchments.National Science Foundation (NSF) http://dx.doi.org/10.13039/100000001Alexander von Humboldt‐Stiftung (Humboldt‐Stiftung) http://dx.doi.org/10.13039/100005156https://doi.org/10.4211/hs.28acde53dc5549f4a6e5d820364dd21

In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations