Si Isotope Composition Research Articles

Reduced partition function ratios of iron, magnesium, oxygen, and silicon isotopes in olivine: A GGA and GGA + U study

Olivine, typically occurring as a forsterite-fayalite solid solution, is a major rock-forming mineral in mafic and ultramafic igneous rocks, and it is important for understanding the genesis, evolution, and alteration of its host rocks. In this study, both GGA and GGA + U methods were employed to calculate the reduced partition function ratios of Fe, Mg, O, and Si isotopes for the forsterite-fayalite solid solution, aiming to elucidate the impacts of Fe content and Hubbard U correction on the isotope fractionation signatures of Fe, Mg, O, and Si in olivine. On the whole, the βFe-factor, βMg-factor, βO-factor, and βSi-factor decrease with increasing Fe content. The linear correlations between β-factors and bond lengths obtained from GGA + U are better compared to those from GGA. The Hubbard U correction can increase the βFe-factor. When Fe/(Fe + Mg) ≤ 1/8, ≤ 1/2, and ≤ 1/2, the effect of Hubbard U correction on βMg-factor, βO-factor, and βSi-factor can be considered negligible, respectively, suggesting that the βMg-factor, βO-factor, and βSi-factor of Fe-bearing olivine calculated using GGA + U and those of Fe-free minerals calculated using GGA can be combined to derive 103lnα and trace geological processes. Furthermore, equilibrium fractionation of Fe, Mg, O, and Si isotopes between olivine and other minerals, including troilite, clinopyroxene, and garnet, were also calculated. Our results are helpful in interpreting the observed data regarding Fe, Mg, O, and Si isotopic compositions of olivine, leading to a comprehensive understanding of relevant geological processes.

Oxygen and silicon isotopic compositions of Archean silicified lava and cherts of the Onverwacht Group: Implication for seafloor hydrothermalism and the nature of recycled components in the source of granitoids

Cherts are commonly used as proxies for Archean environmental conditions such as oceanic temperature. However, because cherts encompass a wide variety of silica-rich rocks, including post-depositional silicified of clastic sediments or chemical precipitates from seawater, reconstructions of the Archean environment based on their O and Si isotopic compositions remain controversial. In this study, we present triple O isotope analyses associated with SIMS O and Si isotope measurements of Palaeoarchean pervasively silicified lavas and clastic sediments, which have been less studied than the associated cherts within the Onverwacht Group (Barberton Greenstone Belt, South Africa). We also provide triple O isotopic compositions of seawater-precipitated cherts. The O and Si isotope composition of silicified clastic sediments and lavas is not considerably variable through the Onverwacht succession. These lithologies display relatively low δ18O (11.3–14.9 ‰) and high Δ’17O values (−0.05 to - 0.07 ‰) attributed to precipitation of silica from hydrothermal fluids at lower temperatures than 200 °C. Using these results, we reconstruct the approximate O isotope composition of the hydrothermal fluids. Water-rock interaction models suggest that this fluid composition is consistent with the existence of low δ18O oceans, but the exact δ18O value of the Palaeoarchean ocean remains elusive. Seawater-precipitated cherts show a mixture of hydrothermal and seawater-like triple O isotope signatures, confirming that cherts are not a straightforward proxy for constraining Archean seawater composition or temperature. The average δ30Si value of the pervasively silicified lavas and clastic sediments is positive (> +0.19 ‰) and compositionally similar to published values of the seawater-precipitated cherts. This suggests comparable δ30Si values between Archean hydrothermal fluids and seawater. A gradual increase of δ18O values of silicified lavas and cherts from 10 to 13 ‰ to 15–20 ‰ observed along the Onverwacht succession is ascribed to local lithospheric cooling occurring between 3.47 Ga and 3.3 Ga, while Si isotope compositions remained mostly unchanged in the silica-rich rocks. As silicified lavas are likely part of materials that melted to generate Palaeoarchean granitoids, the evolutional difference between O and Si isotopes may have characterised the silicified rocks that were recycled in different generations of granitoid sources. This may explain the variation in O isotopic compositions measured in different granitoid generations in the Barberton area.

Clay minerals control silicon isotope variations of fine-grained river sediments: Implication for the trade-off between physical erosion and chemical weathering

Stable silicon (Si) isotopes in fluvial sediments can provide insights into understanding silicate weathering processes on the Earth's surface. However, a lack of comprehensive studies has hindered full understanding of the factors influencing Si isotope fractionation during continental weathering. In this study, through the analysis of Si isotopes in fine-grained sediments from 13 rivers surrounding the South China Sea, significant variation of Si isotopes in bulk detrital sediments (<63 μm) was observed, with δ30Si values ranging from −0.17‰ to −1.09‰. At basin scale, the δ30Si values are influenced by multiple controlling factors such as climatic conditions, lithology, and tectonic settings, which have a close relationship with the content of clay minerals. The characteristics of weathering types and intensities are ultimately reflected in the weathering products, specifically clay minerals. Compiling data across multiple grain sizes from major rivers globally, robust correlations based on clay mineral classification between δ30Si and Al/Si ratio have been observed, which are unaffected by regional and grain-size variations. As the dominant clay mineral group transitions from illite/chlorite to smectite and kaolinite, the degree of Si isotope fractionation increases progressively. This sequence indicates a shift from stronger physical erosion to more intensive chemical weathering, suggesting a transition in the weathering regime from weathering-limited to transport-limited. This study reveals the intrinsic link between Si isotopic compositions and clay mineral assemblages, providing implications for similar stable isotope research and offering a potential indicator for understanding continental weathering processes and their contributions to the global carbon cycle.

Determination of silicon isotopic composition in soil using gas-source isotope ratio mass spectrometry by thermal decomposition of barium hexafluorosilicate

Determining the Si isotopic compositions of samples of the Earth’s surface is crucial to understanding the implications of the biogeochemistry cycling of Si. This study established an alternative method for high-precision Si isotopic measurement in soil samples using gas-source isotope ratio mass spectrometry, which involved the conversion of Si in the samples into SiF4 gas, which was purified cryogenically and collected for isotopic analysis. The proposed method was applied to determine the Si isotopic composition of two reference materials (GBW04421 and GBW04422), and the results were found to be in good agreement with the certified values. Moreover, the proposed method exhibited a long-term measurement precision of 0.05 ‰–0.08 ‰ (2 s) for the δ30Si values. The δ30Si values obtained from ten soil reference materials ranged from −1.84 ‰ to −0.17 ‰, which were within the range of the values reported in the literature (−1.82 ‰ to −0.15 ‰). The sample preparation and analysis method in this study provided an easy and effective approach to determining the Si isotopic composition of solid samples and offers to the promise of being applicable to biogeochemical analyses of the Earth’s surface processes.

Determination of the Nanoscale Silica Mass Fraction by AF4/ICP-MS with Isotope Dilution Analysis Using 29Si-Enriched Silica Nanoparticles.

A methodology based on the use of asymmetrical flow field-flow fractionation (AF4) coupled to ICP-MS with size fraction-targeted isotope dilution analysis (IDA) has been developed, validated, and applied for the first time to determine the mass fraction of nanoscale silica (SiO2). For this purpose, 29Si-enriched SiO2 nanoparticles, to be used as an IDA spike/internal standard, were synthesized and characterized in-house. Double IDA was used to quantify an aqueous suspension of Stöber silica particles of similar characteristics to those of the 29SiO2 nanoparticle (NP) spike using a representative test material of natural Si isotopic composition as the calibrant. For fumed SiO2 NP in a highly complex food matrix, a methodology based on single IDA with AF4/ICP-MS using the same 29SiO2 NP spike was developed and validated. Relative expanded measurement uncertainties (k = 2) of 4% (double IDA) and 8% (single IDA) were achieved for nanoscale silica mass fractions of 5143 and 107 mg kg-1 in water suspension and food matrix, respectively. To assess the accuracy of AF4/ICP-IDMS for the characterization of SiO2 NP in a food matrix, standard addition measurements on samples spiked with Aerosil AF200, also in-house characterized for Si mass fraction, were undertaken, with an average recovery of 95.6 ± 4.1% (RSD, n = 3) obtained. The particle-specific IDA data obtained for both SiO2 NP-containing samples were also compared with that of post-AF4 channel external calibration using inorganic Si standards. The mass fractions obtained by IDA agreed well with those obtained by external calibration within their associated measurement uncertainties.

Silicon isotopes in an Archaean migmatite confirm seawater silicification of TTG sources

Unraveling ancient melting processes is key to understanding how the earliest, tonalite-trondhjemite-granodiorite (TTG)-dominated continental crust formed from partial melting of amphibolite. Application of silicon isotope analysis to ancient crust reveals that Archaean TTGs exhibit consistently high Si isotope values (δ30Si) compared to modern granitoids, attributed to seawater-derived silica introduced by either (a) partial melting of variably silicified basalts or (b) assimilation of authigenic silica-rich marine lithologies in the melt source. However, both mechanisms can introduce highly variable δ30Si, conflicting with the strikingly consistent δ30Si compositions of Archaean TTGs. This study investigates an alternative model, whereby the distinct mineralogy and chemistry of TTG melt sources impart a distinct silicon isotope composition to the melt, compared with “modern” granitoids. We measured δ30Si in component parts (melanosome and leucosome) of an Archaean (2.7 Ga) mafic migmatite and coeval amphibolites and mafic granulites from the Kapuskasing uplift, Canada, to explore how Si isotopes fractionate during incipient TTG melt formation. Our data reveal leucosome (i.e., melt) exhibits consistently high δ30Si values compared to a relatively isotopically lighter melanosome (i.e., residuum). We also derive inter-mineral silicon isotope fractionation factors for mineral separates that agree well with those of ab initio estimates for the same minerals and show that the magnitude of equilibrium fractionation between TTG source rock and melt replicates that in Phanerozoic granitoids. We conclude the effects of magmatic differentiation on δ30Si have remained consistent throughout Earth history, meaning that Archaean TTGs must require a source isotopically heavier than unaltered basalt, as reflected by our amphibolites and mafic migmatite components. The consistently heavy δ30Si of seawater through Earth history, and the high SiO2 content of amphibolites relative to coeval leucosome-free granulites in our study area, imply seawater silicification is the source of the observed high δ30Si. Thus, the consistently heavy Si isotope compositions measured in Archaean melt products define a unique aspect of ancient crust formation: that of the silicification of TTG source rock, implying the intrinsic involvement of a primeval hydrosphere.

Fluid metasomatism of subducted continental crust: Insights from Si isotope compositions of metasomatic rocks from the Western and Eastern Alps

Serpentinite-derived fluids play a crucial role in mass exchange between the Earth's crust and mantle. However, there is currently a limited understanding of how serpentinite-derived fluids influence the Si isotope composition of mantle and subducted crustal materials. Whiteschists in the Dora-Maira Massif of the Western Alps and leucophyllites in Austria of the Eastern Alps were formed through serpentinite-derived fluid metasomatism of metagranite protoliths. Thus, they can provide valuable insights into the geochemical diversity of such rocks resulting from fluid–rock interactions. A special focus is on Si isotope compositions, which were analyzed in whiteschists, leucophyllites, and their corresponding country rocks. The aim of this paper is to investigate the impact of serpentinite-derived metasomatic fluids on the Si isotope compositions of subducted continental crust. With the exception of one whiteschist sample, which contains high amounts of pyrope, and one pyrope megablast, all other whiteschists and leucophyllites exhibit Si isotope compositions similar to those of their country rocks. This observation suggests that the Si isotopes of whiteschists and leucophyllites were inherited from their respective country rocks; fluid metasomatism did not significantly modify the Si isotope compositions of whiteschists and leucophyllites. Because pyrope has much lower δ30Si values than quartz and phengite as further major mineral constituents of the studied whiteschists, the samples with high pyrope contents reveal lighter Si isotopes than those containing lower amounts of pyrope. Interestingly, the metagranites and the majority of whiteschists and leucophyllites exhibit Si isotope compositions below the igneous array, implying that their protoliths are S-type granites. These granites commonly contain sedimentary components derived from their sources. Our results document that Si behaves immobile during serpentinite-derived fluid metasomatism of the subducted continental crust. Combined with previous results, we were able to show that slab derived fluids, including serpentinite-derived fluids, produce only a minimal influence on the Si isotope composition of the overlying mantle wedge and its derived magmas. Thus, the Si isotope compositions of rocks, even if highly affected by metasomatizing fluids, can be used as significant fingerprints that refer to their unaltered precursors.

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

AbstractSilicon 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.

Seawater silica cycling and chert formation at the Neoproterozoic–Cambrian transition: Insights from δ30Si and Ge/Si systematics of hydrothermal cherts from the Bohemian Massif

The genesis of cherts, rocks with >90 wt% SiO2, is suggested to be linked with dissolved seawater silica and its elevated precipitation in the Phanerozoic due to massive biological activity in the Earth's oceans compared to the Precambrian where hydrothermal fluids played a more dominant role. Because cherts may record a history of global seawater Si cycle, their Si isotope systematics may serve as a proxy for their origin and depositional environment. In this study, Si isotope compositions, combined with Ge/Si ratios, were determined for a suite of shallow-water, deep-water and stromatolitic cherts from the Blovice accretionary complex (Bohemian Massif, Czech Republic), representative of deep marine and subduction settings, to establish the nature of cherts and processes of their formation, identify the sources of Si and Ge, and discuss the possible effect of the Neoproterozoic–Cambrian transition. The predominantly high δ30Si values > +0.23‰, associated with low Ge/Si, in deep-water cherts suggest their precipitation from seawater-derived low-temperature fluids at the seawater–sediment interface with subordinate admixture of terrigenous material. Moreover, the tight relationship between δ30Si and organic matter contents in these deep-water cherts is indicative of either equilibrium precipitation of isotopically lighter Si as the organic content of the medium increases or global decrease of δ30Si values of seawater during the Meso–Neoproterozoic related to coupled Si and C cycles. On the other hand, a δ30Si variation of ∼2.5‰ (−0.94‰ to +1.60‰) in shallow-water cherts argues for precipitation from seawater interacting with hydrothermal fluids of variable temperature. Organic matter, Fe-(oxy)-hydroxides and clays represent important sinks for Ge (and Si in case of organic matter) and thus play a determining role in global marine Si−Ge cycling. This, together with the presence of abundant cherts at the Neoproterozoic–Cambrian transition, appears to be associated with redox-controlled Fe cycle which itself is related to microbial reduction and the increasing presence of organic matter towards the Phanerozoic.

The formation and aqueous alteration of CM2 chondrites and their relationship to CO3 chondrites: A fresh isotopic (O, Cd, Cr, Si, Te, Ti, and Zn) perspective from the Winchcombe CM2 fall

AbstractAs part of an integrated consortium study, we have undertaken O, Cd, Cr, Si, Te, Ti, and Zn whole rock isotopic measurements of the Winchcombe CM2 meteorite. δ66Zn values determined for two Winchcombe aliquots are +0.29 ± 0.05‰ (2SD) and +0.45 ± 0.05‰ (2SD). The difference between these analyses likely reflects sample heterogeneity. Zn isotope compositions for Winchcombe show excellent agreement with published CM2 data. δ114Cd for a single Winchcombe aliquot is +0.29 ± 0.04‰ (2SD), which is close to a previous result for Murchison. δ130Te values for three aliquots gave indistinguishable results, with a mean value of +0.62 ± 0.01‰ (2SD) and are essentially identical to published values for CM2s. ε53Cr and ε54Cr for Winchcombe are 0.319 ± 0.029 (2SE) and 0.775 ± 0.067 (2SE), respectively. Based on its Cr isotopic composition, Winchcombe plots close to other CM2 chondrites. ε50Ti and ε46Ti values for Winchcombe are 3.21 ± 0.09 (2SE) and 0.46 ± 0.08 (2SE), respectively, and are in line with recently published data for CM2s. The δ30Si composition of Winchcombe is −0.50 ± 0.06‰ (2SD, n = 11) and is essentially indistinguishable from measurements obtained on other CM2 chondrites. In conformity with petrographic observations, oxygen isotope analyses of both bulk and micromilled fractions from Winchcombe clearly demonstrate that its parent body experienced extensive aqueous alteration. The style of alteration exhibited by Winchcombe is consistent with relatively closed system processes. Analysis of different fractions within Winchcombe broadly support the view that, while different lithologies within an individual CM2 meteorite can be highly variable, each meteorite is characterized by a predominant alteration type. Mixing of different lithologies within a regolith environment to form cataclastic matrix is supported by oxygen isotope analysis of micromilled fractions from Winchcombe. Previously unpublished bulk oxygen isotope data for 12 CM2 chondrites, when combined with published data, define a well‐constrained regression line with a slope of 0.77. Winchcombe analyses define a more limited linear trend at the isotopically heavy, more aqueously altered, end of the slope 0.77 CM2 array. The CM2 slope 0.77 array intersects the oxygen isotope field of CO3 falls, indicating that the unaltered precursor material to the CMs was essentially identical in oxygen isotope composition to the CO3 falls. Our data are consistent with earlier suggestions that the main differences between the CO3s and CM2s reflect differing amounts of water ice that co‐accreted into their respective parent bodies, being high in the case of CM2s and low in the case of CO3s. The small difference in Si isotope compositions between the CM and CO meteorites can be explained by different proportions of matrix versus refractory silicates. CMs and COs may also be indistinguishable with respect to Ti and Cr isotopes; however, further analysis is required to test this possibility. The close relationship between CO3 and CM2 chondrites revealed by our data supports the emerging view that the snow line within protoplanetary disks marks an important zone of planetesimal accretion.

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.

New Constraints for Supernova Models from Presolar Silicon Carbide X Grains with Very High 26Al/27Al Ratios

We report C, N, Mg-Al, Si, and S isotope data of six 1–3 μm-sized SiC grains of Type X from the Murchison CM2 chondrite, believed to have formed in the ejecta of core-collapse supernova (CCSN) explosions. Their C, N, and Si isotopic compositions are fully compatible with previously studied X grains. Magnesium is essentially monoisotopic 26Mg which gives clear evidence for the decay of radioactive 26Al. Inferred initial 26Al/27Al ratios are between 0.6 and 0.78 which is at the upper end of previously observed ratios of X grains. Contamination with terrestrial or solar system Al apparently is low or absent, which makes the X grains from this study particularly interesting and useful for a quantitative comparison of Al isotope data with predictions from supernova models. The consistently high 26Al/27Al ratios observed here may suggest that the lower 26Al/27Al ratios of many X grains from the literature are the result of significant Al contamination and in part also of an improper quantification of 26Al. The real dispersion of 26Al/27Al ratios in X grains needs to be explored by future studies. The high observed 26Al/27Al ratios in this work provide a crucial constraint for the production of 26Al in CCSN models. We explored different CCSN models, including both “classical” and H ingestion CCSN models. It is found that the classical models cannot account for the high 26Al/27Al ratios observed here; in contrast, H ingestion models are able to reproduce the 26Al/27Al ratios along with C, N, and Si isotopic ratios reasonably well.

Silicon isotopic compositions of dissolved silicic acid in pre- and post-diatom oceans

Silicon (Si) isotopic compositions of marine authigenic and biogenic silica deposits are valuable proxies for reconstructing Si cycling in the Earth’s oceans. Recent studies predict that pre-diatom-controlled oceans would have Si isotopic compositions of dissolved silicic acid (δ30SiDSi) that were enriched in heavier isotopes, ranging from +1.9‰ to +4.6‰, relative to NBS28 silica. This predicted range is based on calculations that assume a fractionation factor between sponges and silicic acid (Δ30Sis) in ancient (or modern) ocean waters of −3.8‰. Recently published data on sponge silicon isotopic compositions (δ30Si) and Δ30Sis, indicate that a Δ30Sis value for ancient sponges is more accurately calculated by applying corrections based on Michaelis–Menten enzyme kinetics. Predicted Δ30Sis values for pre-diatom sponges using the Michaelis–Menten enzyme kinetics corrections are −4.6 ± 0.1‰, roughly 0.9‰ lower than previous predictions. The new Δ30Sis value, applied to silicon isotopic compositions of silicified mid-Paleozoic and mid-Cenozoic coral fossils, allows for the calculation of δ30SiDSi between +2.0‰ and +2.3‰ for a Paleozoic open shelf environment. Applying the model to silicified mid-Cenozoic coral fossils, using Δ30Si values based on diatoms (−1.1‰) and sponges (−3.0 to −3.5, corresponding to DSi of 10 to 20 µM), resulted in an estimation of ocean’s δ30SiDSi of +0.8 to +2.9‰. The mid-Cenozoic samples highlight the strong control of Δ30Si on the calculated values for δ30SiDSi. The results show the promise of these approaches in understanding the ocean water δ30SiDSi from Si isotope abundances measured in abiotic precipitates where DSi and Δ30Si are accurately known.

Presolar silicon carbide grains of types Y and Z: their strontium and barium isotopic compositions and stellar origins

We report the Sr and Ba isotopic compositions of 18 presolar SiC grains of types Y (11) and Z (7), rare types commonly argued to have formed in lower-than-solar metallicity asymptotic giant branch (AGB) stars. We find that the Y and Z grains show higher 88Sr/87Sr and more variable 138Ba/136Ba ratios than mainstream (MS) grains. According to FRANEC Torino AGB models, the Si, Sr, and Ba isotopic compositions of our Y and Z grains can be consistently explained if the grains came from low mass AGB stars with 0.15 Zsun <= Z < 1.00 Zsun, in which the 13C neutron exposure for the slow neutron-capture process is greatly reduced with respect to that required by MS grains for a 1.0 Z8 AGB star. This scenario is in line with the previous finding based on Ti isotopes, but it fails to explain the indistinguishable Mo isotopic compositions of MS, Y, and Z grains.

Active Silica Diagenesis in the Deepest Hadal Trench Sediments

AbstractPorewater dissolved silicic acid (DSi) concentrations and stable Si isotope compositions (δ30Si) together with biogenic silica (bSiO2) contents of sediments in five sediment cores collected from the southern Mariana Trench are presented. These data suggest the occurrence of bSiO2 dissolution and concomitant authigenic clay formation in three bSiO2‐bearing cores. A reaction‐transport model constrained by the measured geochemical data was applied to quantify the rates of Si turnover. Model results predicted the greatest rates of both bSiO2 dissolution and authigenic clay formation at the trench axis core that displayed low bSiO2 contents and abundant detrital materials, suggesting that detrital materials may be a limiting factor for bSiO2 diagenesis. Model results further predicted that ∼40%–70% of DSi generated by bSiO2 dissolution is consumed by authigenic clay formation. This is the first study that demonstrates active silica diagenesis in the hadal realm and has implications for understanding benthic Si cycling in deep‐sea settings.

Benthic silicon cycling in the Arctic Barents Sea: a reaction–transport model study

Abstract. Over recent decades the highest rates of water column warming and sea ice loss across the Arctic Ocean have been observed in the Barents Sea. These physical changes have resulted in rapid ecosystem adjustments, manifesting as a northward migration of temperate phytoplankton species at the expense of silica-based diatoms. These changes will potentially alter the composition of phytodetritus deposited at the seafloor, which acts as a biogeochemical reactor and is pivotal in the recycling of key nutrients, such as silicon (Si). To appreciate the sensitivity of the Barents Sea benthic system to the observed changes in surface primary production, there is a need to better understand this benthic–pelagic coupling. Stable Si isotopic compositions of sediment pore waters and the solid phase from three stations in the Barents Sea reveal a coupling of the iron (Fe) and Si cycles, the contemporaneous dissolution of lithogenic silicate minerals (LSi) alongside biogenic silica (BSi), and the potential for the reprecipitation of dissolved silicic acid (DSi) as authigenic clay minerals (AuSi). However, as reaction rates cannot be quantified from observational data alone, a mechanistic understanding of which factors control these processes is missing. Here, we employ reaction–transport modelling together with observational data to disentangle the reaction pathways controlling the cycling of Si within the seafloor. Processes such as the dissolution of BSi are active on multiple timescales, ranging from weeks to hundreds of years, which we are able to examine through steady state and transient model runs. Steady state simulations show that 60 % to 98 % of the sediment pore water DSi pool may be sourced from the dissolution of LSi, while the isotopic composition is also strongly influenced by the desorption of Si from metal oxides, most likely Fe (oxyhydr)oxides (FeSi), as they reductively dissolve. Further, our model simulations indicate that between 2.9 % and 37 % of the DSi released into sediment pore waters is subsequently removed by a process that has a fractionation factor of approximately −2 ‰, most likely representing reprecipitation as AuSi. These observations are significant as the dissolution of LSi represents a source of new Si to the ocean DSi pool and precipitation of AuSi an additional sink, which could address imbalances in the current regional ocean Si budget. Lastly, transient modelling suggests that at least one-third of the total annual benthic DSi flux could be sourced from the dissolution of more reactive, diatom-derived BSi deposited after the surface water bloom at the marginal ice zone. This benthic–pelagic coupling will be subject to change with the continued northward migration of Atlantic phytoplankton species, the northward retreat of the marginal ice zone and the observed decline in the DSi inventory of the subpolar North Atlantic Ocean over the last 3 decades.

Homogenising the upper continental crust: The Si isotope evolution of the crust recorded by ancient glacial diamictites

Twenty-four composite samples of the fine-grained matrix of glacial diamictites deposited from the Mesoarchaean to Palaeozoic have been analysed for their silicon isotope composition and used to establish, for the first time, the long-term secular Si isotope record of the compositional evolution of upper continental crust (UCC). Diamictites with Archaean and Palaeoproterozoic Nd model ages show greater silicon isotope heterogeneity than those with younger model ages (irrespective of depositional age). We attribute the anomalously light Si isotope compositions of some diamictites with Archaean model ages to the presence of glacially milled banded iron formation (BIF), substantiated by the high iron content and Ge/Si in these samples. We infer that relatively heavy Si isotope signatures in some Palaeoproterozoic diamictites (all of which have Archaean Nd model ages) are due to contribution from tonalite-trondhjemite-granodiorites (TTGs), evidenced by the abundance of TTG clasts. By the Neoproterozoic (with model ages ranging from 2.3 to 1.8 Ga), diamictite Si isotope compositions exhibit a range comparable to modern UCC. This reduced variability through time is interpreted as reflecting the decreasing importance of BIF and TTG in post-Archaean continental crust. The secular evolution of Si isotopes in the diamictites offers an independent test of models for the emergence of stable cratons and the onset of horizontal mobile-lid tectonism. The early Archaean UCC was heterogeneous and incorporated significant amounts of isotopically light BIF, but following the late Archaean stabilisation of cratons, coupled with the oxygenation of the atmosphere that led to the reduced neoformation of BIF and diminishing quantities of TTGs, the UCC became increasingly homogeneous. This homogenisation likely occurred via reworking of preexisting crust, as evidenced by Archaean Nd model ages recorded in younger diamictites.

Origin of Carnian Ma’antang cherts, northwestern Sichuan Basin, South China: Field, petrographic, and geochemical perspectives

Abundant Carnian bedded and nodular cherts occur in the Sichuan foreland basin, South China. These cherts faithfully record the Carnian Pluvial Episode and the earliest evolution of the Sichuan foreland basin. However, importantly, the formation mechanisms of the cherts and the source of silica remain controversial. To understand the origin of these cherts, we performed a multitracer study by combining field logging, petrological analyses, Si and O isotope analysis, and major and trace element analysis of chert samples from two stratigraphically correlated sections. The Ma'antang cherts have low Ge/Si ratios (∼0.02 μmol/mol) and display flat seawater-like rare earth element plus Y (REY) distributions with (Pr/Yb)PAAS < 1 and superchondritic Y/Ho ratios (Y/Ho ≥ 27). In addition, siliceous sponge body fossils and spicules appear both in the field and in thin sections, implying a biogenic origin. Insignificant negative Ce anomalies (0.83–1.54; average 1.06) indicate REY contributions to anoxic ferruginous seawater. The heterogeneous distribution and high values of stable Si isotope compositions (δ30Si = 0.5‰-1.2‰) and the very low Ge/Si molar ratio for microcrystalline matrix quartz clearly reveal biogenic (e.g., sponge-derived) silica as the Si source, excluding hydrothermal silica. The chert precipitation occurred under the temperatures of ∼29 to 33 °C, as determined using an oxygen isotope thermometer. Quantitative simulation based on isotopic and REY data suggest that Ma’antang cherts were frequently affected by freshwater influx into marine water. We propose that the biogenic extraction and precipitation of silica from upwelling seawater was the source of silica for cherts in Upper Triassic oceans.

New Quartz And Zircon Si Isotopic Reference Materials For Precise And Accurate SIMS Isotopic Microanalysis

Here we report the Si isotope compositions of four potential reference materials, including one fused quartz glass (Glass-Qtz), one natural quartz (Qinghu-Qtz), and two natural zircons (Qinghu-Zir and Penglai-Zir), suitable for in-situ Si isotopic microanalysis. Repeated SIMS (Secondary Ion Mass Spectrometry) analyses demonstrate that these materials are more homogeneous in Si isotopes (with the spot-to-spot uncertainty of 0.090-0.102‰), compared with the widely used NIST RM 8546 (previously NBS-28) quartz standard (with the spot-to-spot uncertainty poorer than 0.16‰). Based on the solution-MC-ICP-MS determination, the recommended 𝛿30Si values are −0.10 ± 0.04 ‰ (2SD), −0.03 ± 0.05 ‰ (2SD), −0.45 ± 0.06 ‰ (2SD), and −0.34 ± 0.06 ‰ (2SD), for Glass-Qtz, Qinghu-Qtz, Qinghu-Zir, and Penglai-Zir, respectively. Our results reveal no detectable matrix effect on SIMS Si isotopic microanalysis between the fused quartz glass (Glass-Qtz) and natural quartz (Qinghu-Qtz) standards. Therefore, we propose that this synthetic quartz glass may be used as an alternative, more homogenous standard for SIMS Si isotopic microanalysis of natural quartz samples.

The origin of early continental crust: New clues from coupling Ge/Si ratios with silicon isotopes

The recent discovery of heavy Si isotopic compositions in both high-Na Tonalite-Trondhjemite-Granodiorite (TTG) and High-K Granite-Monzonite-Syenite (GMS) suites of early continental crust requires that a notable seawater-derived silica-rich component had been added to their respective protoliths prior to melting. Here we use the Ge/Si ratio as a complementary tracer to δ30Si in order to delineate the exact role of modal quartz and silicified basalts from the Archean seafloor among the primary controls of the early appearance of felsic melts on Earth. We have approached the question by (1) specifying the Ge/Si signatures of various Archean and post-Archean rock types by compiling the Ge-SiO2 data stored within the GEOROC database; (2) coupling Ge/Si investigation to silicon isotopes on a large selection of silicified and unsilicified altered mafic and ultramafic greenstones, felsic volcanics, TTG and GMS granitoids and mineral separates from TTGs of the Barberton Greenstone Belt (BGB) of South Africa. The GEOROC compilation demonstrates that Archean TTGs and granites display much lower Ge/Si (1.15±0.10 and 1.13±0.11 μmol/mol, respectively) than post-Archean adakites, granites, tonalites and granodiorites (with average Ge/Si in the range of 1.64 to 1.85 μmol/mol). This result is corroborated by the Ge/Si ratios we report from BGB rocks that formed prior to Kaapvaal craton stabilisation, including 3.5 Ga Theespruit Formation felsic volcanic rocks, 3.5-3.2 Ga TTGs and 3.2-3.1 Ga GMSs, all of which exhibit low ratios (0.68±0.23; 0.92±0.17; 1.05±0.19 μmol/mol, respectively). Based on their low TTG-like Ge/Si, pre-cratonic GMSs are dismissed as being derived from melting of both TTG and metasedimentary sources. Instead, TTGs and GMSs originated from similar Ge-depleted sources. Low Ge/Si ratios, coupled to heavy Si isotopic signatures (−0.14‰<δ30Si<+0.27‰) are also a characteristic feature of mafic and ultramafic BGB greenstones subjected to low-temperature hydrothermal seafloor alteration, especially at the interface between silicified (0.2<Ge/Si<1.2 μmol/mol) and unsilicified (1.8<Ge/Si<3.1 μmol/mol) portions of the altered Archean seafloor. We infer that both Na-rich and K-rich Archean felsic melts are derived from a unique class of protoliths: Ge-depleted metabasalts containing a significant modal proportion of supracrustal quartz generated by the silicification of the Eo-Paleoarchean basaltic seafloors. The transition from Na-rich to K-rich felsic melts in the BGB is assumed to be connected to a gradual increase of potassium as a key element associated with seafloor silicification. In contrast, younger (3.07-2.69 Ga), post-cratonic BGB granites have higher Ge/Si (1.93±0.23 μmol/mol) and were generated through the reworking of a TTG-like basement, by incongruent melting of biotite and hornblende (1.79<Ge/Si<2.97 μmol/mol) leaving an oligoclase-rich (0.64<Ge/Si<0.72) residue. The Earth changed from a prevalent Ge-depleted felsic crust in early-middle Archean times to a widespread Ge-enriched post-Archean crust, which emphasizes the importance of late Archean changes in the Earth dynamics. In particular, our data suggest the likelihood of generating primitive felsic continents by rather shallow melting processes, without the need for inducing high pressures by subduction, as long as Archean ocean floors were silicified.