Silicon Isotope Research Articles

A New Method for Silicon Triple Isotope Analysis With Application to Siliceous Sponge Spicules

AbstractMultiple isotope ratios of elements disclose information on the fractionation mechanism that cannot be obtained from a single isotope ratio alone. We describe a laser fluorination technique in combination with gas source mass spectrometry for the measurement of triple Si isotope ratios with high precision that allows resolving ppm‐level variability in triple silicon isotope ratios (29Si/28Si, 30Si/28Si) Δ‘29Si due to purely mass‐dependent fractionation in Si isotopes. We demonstrate how the triple silicon isotope ratios can be used to characterize different mass‐dependent processes that fractionate silicon isotopes. We report new data on reference materials (NBS‐28 [RM8546], Diatomite, BigBatch) and on siliceous sponges. Our triple silicon isotope data resolve that kinetic fractionation, possibly related to breaking Si(OH)4 molecules, causes the low δ30Si of sponges. The data further suggest that the cause for fractionation may be the same for the groups of Demospongiae, Homoscleromorpha, and Hexactinellida and that triple silicon isotope ratios of sponges have potential as seawater silicon isotope proxy.

The Holocene silicon biogeochemistry of Yellowstone Lake, USA

Silicon (Si) is an essential macronutrient for diatoms, an important component of lacustrine primary productivity that represents a link between the carbon and silicon cycles. Reconstructions of lake silicon cycling thus provide an underexploited window onto lake and catchment biogeochemistry. Silicon isotope geochemistry has potential to provide these reconstructions, given the competing source and process controls can be deconvolved. The silica-rich volcanic and hydrothermal systems in Yellowstone National Park are a great source of dissolved silicon into Yellowstone Lake, a system with high silicon, and thus carbon, export rates and the formation of diatom–rich sediment. Yellowstone Lake sediments should be an archive of past silicon biogeochemistry, although the effect of sublacustrine hydrothermal activity or hydrothermal explosion events is unclear.Here, we analysed lake water, tributaries, and hydrothermal vent fluids from Yellowstone Lake for their dissolved Si concentrations, isotope composition (δ30Si) and Ge/Si ratios to evaluate the sources of variability in the lake's Si cycle. Bulk elemental composition and biogenic SiO2 (bSiO2) content, together with δ30Si and Ge/Si ratios from a single diatom species, Stephanodiscus yellowstonensis, were analysed in two sediment cores spanning the last 9880 cal. yr BP. We investigate these datasets to identify long term Holocene changes in hydrothermal activity and effects of large and short-term events i.e., hydrothermal and a volcanic eruption.Combinations of bSiO2, δ30Si and Ge/Si with XRF and lithology data revealed that Yellowstone Lake has a resilient biogeochemical system: hydrothermal explosions are visible in the lithology but have no identifiable impact on bSiO2 accumulation or on the δ30Si signature. Both cores show similarities that suggest a stable and homogeneous dSi source across the entire lake. A narrow range of δ30Si and Ge/Si values suggests that the productive layer of the lake was well mixed and biogeochemically stable, with consistently high hydrothermal inputs of Si throughout the Holocene to buffer against the disturbance events. Variation in bSiO2 concentration through time is weakly correlated with an increase towards younger sediment in the δ30Si fossil diatom record in both cores. This increase mirrors that seen in ocean records, and follows changes known in summer insolation, summer temperatures and lake water-column mixing since the deglaciation. This suggests that climate forcing, and soil formation ultimately govern the silicon isotope record, which we suggest is via a combination of changes in weathering stoichiometry, diatom production, and relative proportion of dSi sources.

Heavy silicon and oxygen isotope signatures of TTGs formed in distinct tectonic settings

Tonalite–trondhjemite–granodiorite suites (TTGs) are key components of Archean continental crust and are therefore crucial to understanding the evolution of Archean Earth. However, the tectonic settings of their formation remain unresolved. Here we present new in situ zircon Si–O–Hf isotopes and quartz Si–O isotopes from 2.95 to 2.54 Ga TTGs of the Jiaodong terrane in the North China Craton. Through first-principles calculations, the corresponding TTG melt δ30Simelt and δ18Omelt values are determined as –0.03 ‰ to 0.06 ‰ and 7.12 ‰ to 7.60 ‰, respectively, indicating heavier isotope signatures than those of mantle-derived juvenile rocks. The 2.95–2.93 Ga and 2.56–2.54 Ga TTGs have depleted Hf isotopes [εHf(t) = +3.7 to +4.9, and +2.5 to +5.5, respectively] and higher (La/Yb)N ratios compared with the 2.75–2.71 Ga TTGs, which have relatively less depleted Hf isotopes [εHf(t) = +0.9 to +2.0] and lower (La/Yb)N ratios. Although the heavy Si–O isotope compositions indicate the involvement of supracrustal materials in the melting sources of all studied TTGs, the variable zircon Hf isotopes and (La/Yb)N ratios suggest that these rocks formed in distinct tectonic settings. The 2.95–2.93 Ga and 2.56–2.54 Ga TTGs are inferred to have been generated in a subduction setting involving the melting of juvenile oceanic crust under high-pressure conditions, whereas the 2.75–2.71 Ga TTGs are inferred to have been derived from the melting of buried ancient oceanic crust under a mantle-plume-induced lower-pressure environment. We conclude that the heavy Si–O isotope signatures of Archean TTGs may not be directly related to plate-tectonic processes.

Isotope Ratio – Discharge Relationships of Solutes Derived From Weathering Reactions

To date, the vast majority of studies seeking to link discharge to solute concentrations have been based on representations of fluid age distributions in watersheds that are time-invariant. As increasingly detailed spatial and temporal datasets become available for weathering-derived riverine solute concentrations, the capacity to link this mass flux to transient routing of reactive fluids through Critical Zone environments is vital to quantitative interpretation. Relationships between fluid age distributions and the stable isotope ratios of these geogenic solutes are even less developed, yet these signatures are vital to parsing the suite of water-rock-life interactions that create concentration-discharge relationships. Here we offer the first merging of a hydrological model featuring time-variant fluid age distributions with a geochemical model for isotopically fractionating weathering reactions. Using SiO2(aq) and the corresponding silicon isotope ratio δ30Si as an example, we show that the stable isotope signatures of riverine solutes produced by weathering reactions reflect a component of the fluid age distribution that is unique to the corresponding solute concentrations. This distinct sensitivity is the result of a stronger link between isotope ratios and the age distribution parameters describing a given watershed. This novel modeling framework is used to provide a quantitative basis for the interpretation of SiO2(aq) and δ30Si in six low-order streams spread across a diversity of climates, geologies, and ecosystems. To our knowledge, this is the first forward and process-based model to describe the isotopic signatures of solutes derived from weathering reactions in watersheds subject to time-varying discharge.

No evidence of supracrustal recycling in Si-O isotopes of Earth's oldest rocks 4 Ga ago.

Identifying the oldest evidence for the recycling of hydrated crust into magma on Earth is important because it is most effectively achieved by subduction. However, given the sparse geological record of early Earth, the timing of first supracrustal recycling is controversial. Silicon and oxygen isotopes have been used as indicators of crustal evolution on Archean igneous rocks and minerals to trace supracrustal recycling but with variable results. We present Si-O isotopes of Earth's oldest rocks [4.0 billion years ago (Ga)] from the Acasta Gneiss Complex, northwest Canada, obtained using multiple techniques applied to zircon, quartz, and whole rock samples. Undisturbed zircon is considered the most reliable recorder of primary Si signatures. By combining reliable Si isotope data from the Acasta samples with filtered data from Archean rocks globally, we observe that widespread evidence for a heavy Si signature is recorded since 3.8 Ga, marking the earliest record of surface silicon recycling.

Silicon Isotopes Highlight the Role of Glaciated Fjords in Modifying Coastal Waters

AbstractGlaciers and ice sheets are experiencing rapid warming under current climatic change and there is increasing evidence that glacial meltwaters provide key dissolved and dissolvable amorphous nutrients to downstream ecosystems. However, large debate exists around the fate of these nutrients within complex and heterogenous fjord environments, where biogeochemical cycling is still often poorly understood. We combine silicon (Si) concentration data with isotopic compositions to better understand silicon cycling and export in two contrasting fjordic environments in south‐west Greenland. We show that both fjords have isotopically light dissolved silicon (DSi) within surface waters, despite an apparently rapid biological drawdown of DSi with increasing salinity. We hypothesize that such observations cannot be explained by simple water mass mixing processes, and postulate that an isotopically light source of Si, most likely glacially derived amorphous silica (ASi), is responsible for further modifying these coastal waters within the fjords and beyond. Fjord to coastal exchange is likely a relatively slow process (several months), and thus is less impacted by short‐term (<seasonal) changes of glacial meltwater input into the fjord, which has implications when considering the role of glacial meltwaters on nutrient export beyond the shelf break. We highlight the need for isotopic studies combined with dissolved and particulate nutrient concentration analysis to provide a more detailed analysis into the biogeochemical cycles within these highly dynamic fjord environments.

Fluorosilicic acid: secondary raw material and reagent in technological practice and preparative synthesis (a review)

The present review systematizes and summarizes the results of research on utilization processes of fluorosilicic acid solutions as large-tonnage toxic by-products of phosphate fertilizers, phosphoric acid and elemental phosphorus production. Considering the marked decline in the world's fluorspar reserves, fluorosilicic acid is emerging as the main alternative source of fluoride for the chemical industry. The main ways of H2SiF6 processing are highlighted with obtaining of commercially demanded products: hexafluoridosilicates of metals and ammonium, metal fluorides, anhydrous hydrogen fluoride, hydrochloric acid, amorphous silicon dioxide, aluminosilicates and titanosilicates catalysts, and enriched isotopes of silicon. Examples of H2SiF6 use as a main reagent for drinking water fluoridation municipal programs, in processes of surface modification and removal of trialkylsilyl protection in reactions of organic synthesis are also discussed. Known examples of H2SiF6 use as a raw material and reagent in industrial technologies and laboratory tests largely conform to principles of green chemistry.

Prehistoric population expansion in Central Asia promoted by the Altai Holocene Climatic Optimum

How climate change in the middle to late Holocene has influenced the early human migrations in Central Asian Steppe remains poorly understood. To address this issue, we reconstructed a multiproxy-based Holocene climate history from the sediments of Kanas Lake and neighboring Tiewaike Lake in the southern Altai Mountains. The results show an exceptionally warm climate during ~6.5–3.6 kyr is indicated by the silicon isotope composition of diatom silica (δ30Sidiatom) and the biogenic silica (BSi) content. During 4.7-4.3 kyr, a peak in δ30Sidiatom reflects enhanced lake thermal stratification and periodic nutrient limitation as indicated by concomitant decreasing BSi content. Our geochemical results indicate a significantly warm and wet climate in the Altai Mountain region during 6.5–3.6 kyr, corresponding to the Altai Holocene Climatic Optimum (AHCO), which is critical for promoting prehistoric human population expansion and intensified cultural exchanges across the Central Asian steppe during the Bronze Age.

Decoupling of Barium and Silicon at the Congo River‐Dominated Southeast Atlantic Margin: Insights From Combined Barium and Silicon Isotopes

AbstractThe correlation between concentrations of dissolved barium (dBa) and silicon (dSi) in the modern ocean supports the use of Ba as a paleoceanographic proxy. However, the mechanisms behind their linkage and the exact processes controlling oceanic Ba cycling remain enigmatic. To discern the extent to which this association arises from biogeochemical processes versus physical mixing, we examine the behavior of Ba and Si at the Congo River‐dominated Southeast Atlantic margin where active biological processes and large boundary inputs override the large‐scale ocean circulation. Here we present the first combined measurements of dissolved stable Ba (δ138Ba) and Si (δ30Si) isotopes as well as Ba and Si fluxes estimated based on 228Ra from the Congo River mouth to the northern Angola Basin. In the surface waters, river‐borne particle desorption or dissolution and shelf inputs lead to non‐conservative additions of both dBa and dSi to the Congo‐shelf‐zone, with the Ba flux increasing more strongly than that of Si across the shelf. In the epipelagic and mesopelagic layers, Ba and Si are decoupled likely due to different depths of in situ barite precipitation and biogenic silica production. In the deep waters of the northern Angola Basin, we observe large enrichment of dBa, likely originating from high benthic inputs from the Congo deep‐sea fan sediments. Our results reveal different mechanisms controlling the biogeochemical cycling of Ba and Si and highlight a strong margin influence on marine Ba cycling. Their close association across the global ocean must therefore mainly be a consequence of the large‐scale ocean circulation.

Determination of Hyaluronic Acid Dermal Filler Impurities Using SEM/EDS Analysis.

Although hyaluronic acid (HA) filler injections are associated with various non-vascular inflammatory complications, the underlying mode of action remains unclear. The hyaluronic acid filler may not be sufficiently pure, leading to an immune response. The present study attempted to identify any impurities in hyaluronic acid fillers available on the market. Particles were counted after degrading hyaluronic acid filler with hyaluronidase. Particulate matter was subsequently observed using scanning electron microscopy, and the particle components were evaluated using energy-dispersive X-ray spectroscopy. Different quantities of impurity particles (>10 and 25 μm) were detected microscopically. Silicon and aluminum isotopes were also detected. Hyaluronic acid fillers were contaminated with these particles. The degree of contamination varied substantially among the tested filler products. These contaminant particles may evoke reactions in the patient's body. Clinicians should be aware of this source of possible contamination and its effects.

Evidence for late winter biogeochemical connectivity in permafrost soils

The permafrost active layer is a key supplier of soil organic carbon and mineral nutrients to Arctic rivers. In the active layer, sites of soil-water exchange are locations for organic carbon and nutrient mobilization. Previously these sites were considered as connected during summer months and isolated during winter months. Whether soil pore waters in active layer soils are connected during shoulder seasons is poorly understood. In this study, exceptionally heavy silicon isotope compositions in soil pore waters show that during late winter, there is no connection between isolated pockets of soil pore water in soils with a shallow active layer. However, lighter silicon isotope compositions in soil pore waters reveal that soils are biogeochemically connected for longer than previously considered in soils with a deeper active layer. We show that an additional 21% of the 0–1 m soil organic carbon stock is exposed to soil - water exchange. This marks a hot moment during a dormant season, and an engine for organic carbon transport from active layer soils. Our findings mark the starting point to locate earlier pathways for biogeochemical connectivity, which need to be urgently monitored to quantify the seasonal flux of organic carbon released from permafrost soils.

Triple silicon isotope insights into the formation of Precambrian cherts

Cherts are pervasive in the Precambrian and their O and Si isotopic compositions have been used extensively for reconstructing seawater paleo-temperatures. However, these reconstructions are obscured by the fact that cherts exhibit, at a given age, a large isotopic (O and Si) heterogeneity at bulk and micrometer scales. This is understood as reflecting the fact that cherts are an assemblage of silica precursors having different origins, and that diagenesis and metamorphism have modified the isotopic compositions acquired during the last equilibration with seawater. To test the contributions of the different processes that control the Si isotopic composition of cherts, we developed high-precision triple Si isotope measurements by Multicollector-Inductively Coupled-Plasma Mass-Spectrometer (MC-ICP-MS). This approach allows to identify deviations from the equilibrium Si isotopic fractionation at the level of a few ppm. Triple Si isotope data combined with trace elements and O isotope data in Precambrian cherts demonstrate that three different sources of silica were involved in the formation of cherts, and that both equilibrium and kinetic isotopic fractionation took place for Si. Archean seawater is predicted to have a triple Si isotopic composition kinetically fractionated relative to bulk silicate Earth. This requires a large kinetic isotopic fractionation during hydrothermalism of the oceanic crust and appears consistent with warm oceans in the Precambrian. However more work is required on the triple isotope systematics of Si inputs and output to seawater by rivers and authigenic clays formation. Triple Si isotope variations can thus be used as a new tool to unravel the origin of cherts and of their O and Si isotopic compositions. The present evidence of kinetic isotopic fractionations for Si isotopes also implies that Si isotopes should be associated to triple O isotope for paleotemperature reconstructions.

Isotope sample preparation of diatoms for paleoenvironmental research.

Isotopes in diatoms are increasingly used in palaeoenvironmental studies in both lacustrine and marine settings, enabling the reconstruction of a range of variables including temperature, precipitation, salinity, glacial discharge, carbon dynamics and biogeochemical cycling. This protocol details an optimised methodology for extracting diatoms for isotope analysis from sediment samples, using a range of chemical and density separation techniques that minimise sample loss and avoids the need for expensive equipment. Whilst designed for the extraction of diatoms for oxygen, silicon and carbon isotope analysis, additional stages are outlined for the analysis of other isotopes that are of increasing interest to the palaeo community (e.g., boron and zinc). The protocol also includes procedures for assessing sample purity, to ensure that analysed samples produce robust palaeoenvironmental reconstruction. Overall, the method aims to improve the quality of palaeoenvironmental research derived from isotopes in diatoms by maximising sample purity and the efficiency of the extraction process.

Исследование относительной восприимчивости изотопов кремния к потоку тепловых нейтронов

To solve problems related to the study of the possibility of changing the properties of promising semiconductor materials, the mechanisms of interaction of neutron radiation with silicon isotopes are investigated. The study of this semiconductor material is especially relevant because of its widespread use in modern semiconductor technologies for the construction integrated circuits. The types of interactions of neutron radiation with matter, the main mechanisms of formation of crystal lattice defects under the influence of thermal neutrons are investigated. Random processes of interaction of thermal neutron flux with three isotopes of silicon 28Si, 29Si and 30Si are simulated. The isotope 29Si, which is most susceptible to elastic interactions, has been determined. In the case of reactions (n, γ), the isotope 28Si was the most sensitive.

Теплопроводность SiC: расчет изотопического эффекта из первых принципов

The thermal conductivity temperature dependence kappa(T) of a hexagonal 2H-SiC silicon carbide crystal was calculated using the first-principle approach for the orientation of the heat flux in the basal plane and along the hexagonal axis c in the temperature range from 100 to 500 K. The effect of silicon and carbon isotopic disorder on thermal conductivity is considered. It was found that, at a temperature of 300 K, the thermal conductivity of isotopically pure 2H-SiC containing 100% 28Si and 100% 12C is higher by 15.2% and 12.4% for directions along and across the basal plane, respectively, than that of crystals with a natural composition of silicon and carbon isotopes. For crystals with a natural mixture of carbon isotopes natC, the isotope effect for silicon is 14.5% and 11.9% for these directions.

SiC thermal conductivity: calculation of the isotope effect from first principles

The thermal conductivity temperature dependence kappa(T) of a hexagonal 2H-SiC silicon carbide crystal was calculated using the first-principle approach for the orientation of the heat flux in the basal plane and along the hexagonal axis c in the temperature range from 100 to 500 K. The effect of silicon and carbon isotopic disorder on thermal conductivity is considered. It was found that, at a temperature of 300 K, the thermal conductivity of isotopically pure 2H-SiC containing 100% 28Si and 100% 12C is higher by 15.2% and 12.4% for directions along and across the basal plane, respectively, than that of crystals with a natural composition of silicon and carbon isotopes. For crystals with a natural mixture of carbon isotopes textnatC, the isotope effect for silicon is 14.5% and 11.9% for these directions. Keywords: single crystal, thermal conductivity, silicon carbide, first principle calculation.

Tracing the role of Arctic shelf processes in Si and N cycling and export through the Fram Strait: insights from combined silicon and nitrate isotopes

Abstract. Nutrient cycles in the Arctic Ocean are being altered by changing hydrography, increasing riverine inputs, glacial melt and sea-ice loss due to climate change. In this study, combined isotopic measurements of dissolved nitrate (δ15N-NO3 and δ18O-NO3) and silicic acid (δ30Si(OH)4) are used to understand the pathways that major nutrients follow through the Arctic Ocean. Atlantic waters were found to be isotopically lighter (δ30Si(OH)4=+ 1.74 ‰) than their polar counterpart (δ30Si(OH)4=+ 1.85 ‰) owing to partial biological utilisation of dissolved Si (DSi) within the Arctic Ocean. Coupled partial benthic denitrification and nitrification on Eurasian Arctic shelves lead to the enrichment of δ15N-NO3 and lighter δ18O-NO3 in the polar surface waters (δ15N-NO3= 5.44 ‰, δ18O-NO3= 1.22 ‰) relative to Atlantic waters (δ15N-NO3= 5.18 ‰, δ18O-NO3= 2.33 ‰). Using a pan-Arctic DSi isotope dataset, we find that the input of isotopically light δ30Si(OH)4 by Arctic rivers and the subsequent partial biological uptake and biogenic Si burial on Eurasian shelves are the key processes that generate the enriched isotopic signatures of DSi exported through Fram Strait. A similar analysis of δ15N-NO3 highlights the role of N-limitation due to denitrification losses on Arctic shelves in generating the excess dissolved silicon exported through Fram Strait. We estimate that around 40 % of DSi exported in polar surface waters through Fram Strait is of riverine origin. As the Arctic Ocean is broadly N-limited and riverine sources of DSi are increasing faster than nitrogen inputs, a larger silicic acid export through the Fram Strait is expected in the future. Arctic riverine inputs therefore have the potential to modify the North Atlantic DSi budget and are expected to become more important than variable Pacific and glacial DSi sources over the coming decades.

Formation conditions of Ediacaran–Cambrian cherts in South China: Implications for marine redox conditions and paleoecology

The Ediacaran–Cambrian transition period was a critical time interval for the environmental fluctuations and organismal evolution in geological history, popularly known as the “Cambrian Explosion”. The diagenetic mechanism of the widely developed Liuchapo bedded cherts in South China remain unclear and controversial during this critical time interval. To address this, we examined silicon and oxygen isotopes, as well as major and trace elements in the Liuchapo cherts from three wells developed from slope to basin facies in South China. Results reveal that the bedded cherts from the three wells were affected by episodic hydrothermal activity, and the percentage of hydrothermal fluids is highest in the Xc1 well and lowest in the Xb1 well. The paleo-seawater temperature, calculated from chert oxygen isotope values, present a gradual increasing trend from shallow- to deep- areas in South China from 542 to 526 Ma. Redox proxies indicate that the water column of the Xa1 and Xc1 wells were dominated by suboxic condition, while those of the Xb1 well was mainly in oxic conditions. There should exist an oxygen minimum zone (OMZ) during the shelf and slope transition. A suitable temperature and oxic environment are conducive to biological reproduction, which is consistent with higher primary productivity and abundant acritarch fossils in the Xb1 well. Silicon isotope values range from −0.6 ‰ to 1.2 ‰ in the three wells. The diagenetic origin of the Xa1, Xb1, and Xc1 wells was the consequence of the mixture of hydrothermal fluid and seawater, biological activity, and direct hydrothermal precipitation, respectively. Due to the redox condition and seawater temperature variation, silica-secreting organisms should be relatively limited. The episodic hydrothermal fluid, biological activity, and replacement of precursor rock may jointly affect the formation of the Liuchapo bedded cherts during the Ediacaran–Cambrian transition.

Iron and silicon isotope fractionation in silicate melts using first-principles molecular dynamics

The direct determination of silicate melts iron and silicon isotopes signature remains a major challenge of high-temperature isotope geochemistry. For this reason, melts are often approximated by silicate glasses. Calculation of precise equilibrium Si and Fe isotopes fractionation factors between minerals and melt would indeed allow us to distinguish equilibrium fractionation from diffusion-driven kinetic fractionation involved in the iron and silicon isotopes signatures of Earth and other planets. In this study, we use for the first time, first-principles molecular dynamics based on density functional theory to determine iron and silicon isotope compositions of different silicate melts, namely: iron-rich basalt, iron-depleted basalt, basanite, trachyte and phonolite. The 57Fe/54Fe reduced partition function ratios (β-factors) of the different melts span over a 1.1 ‰ range at 1000 Kelvin (K) while 30Si/28Si β-factors are much less influenced by the melt composition with a 0.5 ‰ fractionation range at the same temperature. The main parameter controlling iron isotope fractionation in silicate melts having similar iron oxidation state is, after temperature, the average Fe-O bond length. The chemical environment around iron (e.g. Fe-Fe distances) is suggested to contribute to Fe isotope fractionation as well. Silicon isotopes fractionation seems also affected, but to a lesser extent, by its local chemical composition with decreasing Si-Fe distances leading to slightly higher Si β-factor in the melt. From these melts Fe and Si β-factors, a new set of equilibrium fractionation factors between a variety of minerals and melts has been calculated. These new Δ57Femin-melt and Δ30Simin-melt sets allow us to discuss whether processes such as fractional crystallization, partial melting and diffusion could be responsible for the documented Fe and Si isotopes variations in igneous rocks. Our results suggest that: 1) fractional crystallization may explain at least part of the Fe and Si isotopic evolution during magmatic differentiation, for values up to δ57Fe = 0.65 ‰ and δ30Si = -0.1 ‰, respectively, 2) partial melting of the upper mantle can produce the Mid-Ocean Ridge Basalts (MORB) iron isotopes signature. Finally, we calculated that olivine at equilibrium with a basaltic melt could display an iron isotope composition down to −0.1 ‰ for δ57Fe. Hence, the lower isotopic compositions (δ57Fe < -0.1 ‰) observed in natural olivines are most likely due to diffusion-driven kinetic fractionation.

Early differentiation processes on Mars inferred from silicon isotopes

Accretion of terrestrial planets involved partial or global melting events such as magma oceans or magma ponds. Mars experienced large-scale differentiation very early in its history, as shown by its 146Sm-142Nd and 182Hf-182W record. The broad variations in ε142Nd and ε142W of SNC meteorites highlight the presence of mantle sources that must have remained isolated, at least partly, after the crystallization of a global magma ocean. In this study, we have investigated whether the crystallization of the martian magma ocean could have generated mantle reservoirs characterized by different silicon isotope signatures, as the fractionation of Si isotopes between minerals and melts is known to depend on pressure. Thus, the goal of this study was to investigate whether there were any relationships between magma ocean crystallisation and possible variations in the Si isotope record of SNC meteorites. High resolution silicon isotope measurements were performed on twelve meteorites from the Shergottite, Nakhlite and Chassignite groups using a Neptune Plus MC-ICP-MS in dry plasma mode. The δ30Si values are in good agreement with previous studies but display a narrower range of variations with a mean value at −0.46 ‰ ± 0.07 (2SD). A magma ocean crystallization model shows that the range of δ30Si in SNCs is consistent with that generated by magma ocean crystallisation. In particular, there is a correlation between calculated 147Sm/144Nd for the moderately depleted mantle sources with δ30Si values; this correlation is consistent with the crystallization model if one includes trapped melt in the cumulates. In contrast, enriched shergottites displayed a very homogenous composition in Sm/Nd ratios, despite significant variability in δ30Si. This observation could be related to either fluid-rock interactions or redox effect during magma differentiation. Altogether, silicon isotope compositions of SNC provide new constraints about magma ocean crystallization processes in Mars.