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At least 325 records · Page 18

Study of solid molecular deuterium D 2 growth under gas pressure

The injection of high-speed cryogenic pellets made of frozen hydrogen-isotopes, represents to date the most effective method to fuel magnetically confined thermonuclear fusion plasmas. Additionally, the injection of very large pellets composed of cryogenic solid of some suitable impurity (typically a noble-gas such as H 2 , Ne, or H 2 /Ne, D 2 /Ne mixtures), shattered in relatively small fragments just before entering the plasma, seems to be the most promising method to reduce the damage risks for the plasma-facing components in case of a plasma disruption. This technology, known as "Shattered Pellet Injection" (SPI), allows to spread out the plasma energy and mitigate possible damage to the in-vessel components, as well as to densify the plasma to suppress the formation of runaway electrons, and/or dissipate their energy. Several techniques to produce and launch cryogenic pellets have been investigated in the past decades. "Pipe gun" injectors are reliable and relatively simple devices are still commonly used today. They make use of single- or two-stage pneumatic light-gas guns to accelerate the pellet at high speeds. In these injectors, the cryogenic pellets are formed “ in situ ” (i.e., inside the launching barrel), by de-sublimating them directly from the gas phase, i.e., at temperatures and pressures below those of the triple point. The simplest case is pure deuterium pellets ($\mathcal{T}$ < 18.7 K, $\mathcal{P}$ < 171.3 hPa). The production of good quality solid deuterium, capable of withstanding the mechanical stress during the acceleration of the pellets, is a key issue. To this end the phase transition of deuterium from gas to solid (and vice versa) is modeled with extensive molecular-dynamics (MD) simulations. Furthermore, the solid growth from the gas phase is simulated in an ample range of temperatures and pressures, to find the best compromise between growth velocity and mechanical properties of the resulting solid system.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Ab initio calculations of the carbon and oxygen isotopes: Energies, correlations, and superfluid pairing

We perform ab initio nuclear lattice calculations of the neutron-rich carbon and oxygen isotopes using high-fidelity chiral interactions. We find good agreement with the observed binding energies and compute correlations associated with each two-nucleon interaction channel. For the isospin T = 1 channels, we show that the dependence on T z provides a measure of the correlations among the extra neutrons in the neutron-rich nuclei. For the spin-singlet S-wave channel, we observe that any paired neutron interacts with the nuclear core as well as its neutron pair partner, while any unpaired neutron interacts primarily with only the nuclear core. For the other partial waves, the correlations among the extra neutrons grow more slowly and smoothly with the number of neutrons. These general patterns are observed in both the carbon and oxygen isotopes and may be universal features that appear in many neutron-rich nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effects of surface diffusion in electrocatalytic CO 2 reduction on Cu revealed by kinetic Monte Carlo simulations

We report Kinetic Monte Carlo (KMC) methods are frequently used for mechanistic studies of thermally driven heterogeneous catalysis systems but are underused for electrocatalysis. Here, we develop a lattice KMC approach for electrocatalytic CO 2 reduction. The work is motivated by a prior experimental report that performed electroreduction of a mixed feed of 12 CO 2 and 13 CO on Cu; differences in the 13 C content of C2 products ethylene and ethanol (Δ 13 C) were interpreted as evidence of site selectivity. The lattice KMC model considers the effect of surface diffusion on this system. In the limit of infinitely fast diffusion (mean-field approximation), the key intermediates 12 CO* and 13 CO* would be well mixed on the surface and no evidence of site selectivity could have been observed. Using a simple two-site model and adapting a previously reported microkinetic model, we assess the effects of diffusion on the relative isotope fractions in the products using the estimated surface diffusion rate of CO* from literature reports. We find that the size of the active sites and the total surface adsorbate coverage can have a large influence on the values of Δ 13 C that can be observed. Δ 13 C is less sensitive to the CO* diffusion rate as long as it is within the estimated range. We further offer possible methods to estimate surface distribution of intermediates and to predict intrinsic selectivity of active sites based on experimental observations. This work illustrates the importance of considering surface diffusion in the study of electrochemical CO 2 reduction to multi-carbon products. Our approach is entirely based on a freely available open-source code, so will be readily adaptable to other electrocatalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A dendritic strontium river isoscape for fisheries applications in the Sacramento River basin, California, USA

Objective Understanding the origins and movements of fish is fundamental to effective conservation and fisheries management. Strontium isotope ratios ( 87 Sr/ 86 Sr) in otoliths provide a powerful tracer of natal origin and migratory pathways. However, existing 87 Sr/ 86 Sr isoscapes for the Sacramento River basin, an ecosystem that supports ecologically and economically important salmon populations, rely on discrete classification approaches that overlook unsampled habitats and do not incorporate spatial uncertainty. Our objective was to develop a continuous, network-explicit 87 Sr/ 86 Sr isoscape with quantified uncertainty to fill in data gaps and enable probabilistic assignments of fish origin and movement. Methods We used river water 87 Sr/ 86 Sr data from 106 sites (1997–2021) to develop spatial stream network models that use dendritic connectivity and watershed characteristics (lithology, bedrock age, and land cover) to predict river water 87 Sr/ 86 Sr throughout the basin. Models were fitted using maximum and restricted likelihood and were evaluated via Akaike’s information criterion and leave-one-out cross validation. We produced both historical (pre-dam) and present-day (below-dam) isoscapes, delineated uncertainty-informed isotopic ranges using k -means clustering, and applied a proof-of-concept Bayesian assignment to estimate natal origins and early rearing habitats for two endangered winter-run Chinook Salmon Oncorhynchus tshawytscha. Results Cross validation indicated strong performance of the 87 Sr/ 86 Sr model (leave-one-out cross validation: R 2 = 0.91; root mean square error = 0.0005). Uncertainty-informed clustering identified 19 isotopic “suites” (reaches with indistinguishable 87 Sr/ 86 Sr values) in present-day anadromous habitats and 25 suites in the historical network. Example natal and early rearing assignments included predictions that challenged expectations for juvenile salmon migration based on predicted river 87 Sr/ 86 Sr compositions. Conclusions This study developed a continuous, network-explicit 87 Sr/ 86 Sr isoscape that integrates existing river data to predict 87 Sr/ 86 Sr in unsampled reaches and the likely achievable range and resolution of otolith-based origin and life history inference. The resulting river isoscape provides a valuable tool to predict salmon movements and identify habitats supporting their survival and growth that otherwise might remain undetected. Coupling these predictions with complementary approaches that ground-truth juvenile presence (e.g., targeted fish surveys) represents an important step toward science-informed restoration and management of critical habitats throughout the Sacramento River basin.

Environmental sciences↗

Monte Carlo Analyses of the FOEHN Experiment

The FOEHN critical experiment, which has been carried out at Cadarache (France) in the reactor EOLE in the early 70s, was designed to verify RHF design analyses. This study focuses on the impact of the FOEHN experiment uncertainties on the calculation of the energy deposition. The latter has been obtained by the Monte Carlo codes Serpent and MCNP. In the calculation of the energy deposition, the first code relies on KERMA factors whereas the latter code relies on Q-values. The two Monte Carlo codes share the same geometry and material specifications. In addition to the design and experiment parameters uncertainties, nuclear data also impacts the calculation of the energy deposition. In this study, the MCNP simulations use three different nuclear data library sets: ENDF/B versions VII.0, VII.1, and VIII.0. Finally, the ksens card of MCNP, using perturbation theory, has been used to identify the cross sections and isotopes with largest impact on the effective multiplication factor. By showing that the use of different software and computational methodologies and design parameters uncertainties do not significantly impact the core power distribution, this work demonstrate the appropriateness of the tools and methods employed for the conversion of involute-plate reactors.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effect of microstructure and neutron irradiation defects on deuterium retention in SiC

Retention of hydrogen isotopes is a critical concern for operating fusion reactors as retained tritium both activates components and removes scarce fuel from the fuel cycle. Radiation-induced displacement damage in SiC influences the retention of hydrogen isotopes compared to pristine SiC. Deuterium retention in neutron irradiated high purity SiC has been compared to different microstructures of non-irradiated high purity SiC using thermal desorption spectroscopy after gas charging and low energy ion implantation. Experimental results show lower deuterium retention in single crystal SiC than in polycrystal SiC indicating that grain boundaries are key trapping features in unirradiated SiC. Deuterium is released at lower temperatures in neutron irradiated polycrystal SiC compared to pristine polycrystal SiC, suggesting weaker trapping by radiation-induced defects compared to grain boundary trapping sites in the pristine materials. Low energy ion implantation caused a high deuterium release temperature, highlighting the sensitivity of deuterium release behaviour to radiation defect characteristics. First principles calculations have been conducted to identify energetically favourable trapping sites in SiC at the H ABc V Si and H TSi V C complexes, and migration barriers between interstitial sites. This helps interpret experimental results and derive effective diffusivity of hydrogen isotopes in SiC in the presence of vacancies.

36 MATERIALS SCIENCE↗

DRIFT: Diffusivity Regulation of Isotopes by nanoconFinementT

Spontaneous isotope fractionation has been reported under nanoconfinement conditions in naturally occurring systems, but the origin of this phenomena is currently unknown. Two existing hypotheses have been proposed, one based on changes in the solvation environment of the isotopes that reduces the non-mass dependent hydrodynamics contribution to diffusion. The other is that isotopes have mass-dependent surface adsorption, varying their total diffusion through nanoconfined channels. To investigate these hypotheses, benchtop experiments, nuclear magnetic resonance (NMR) spectroscopy, and molecule scale modeling were applied. Classical molecular dynamics simulations identified that the Na + and Cl - hydration shells across the three different salt solutions ( 22 Na 35 Cl, 23 Na 35 Cl, 24 Na 35 Cl) did not vary as a function of the Na + isotope, but that there was a significant pore size effect, with larger hydration shells at larger pore sizes. Additionally, while total adsorption times did not vary as a function of the Na + isotope or pore size, the free ion concentration, or those adsorbed on the surface for <5% of the simulation time did exhibit isotope dependence. Experimentally, challenges occurred developing a repeatable experiment, but NMR characterization of water diffusion rates through ordered alumina membranes was able to identify the existence of two distinct water environments associated with water inside and outside the pore. Further NMR studies could be used to confirm variation in hydration shells and diffusion rates of dissolved ions in water. Ultimately, mass-dependence adsorption is a primary driver of variations in isotope diffusion rates, rather than variation in hydration shells that occur under nanoconfinement.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Single particle – MC-ICP-MS for isotopic analysis of uranium particles

Single particle – multi-collector – inductively coupled plasma – mass spectrometry (SP-MC-ICP-MS) was employed to measure a suspension of 1 µm U3O8 particles (∼1.3 pg total U/particle) to determine their individual isotopic compositions of 234U/238U, 235U/238U, and 236U/238U. The effects of different detector combinations for 235U and 238U, including secondary electron multipliers (SEM) and Faraday detectors (1011 and 1013 Ω amplifiers), were explored for accuracy and precision optimization on the observed 235U/238U. The minor isotopic ratios (i.e., 234U/238U and 236U/238U) were analyzed such that the 234U and 236U were monitored on SEM detectors and the 238U was monitored on a Faraday (1011 Ω) detector. Various integration times (5, 10, 25, and 50 ms) were investigated in all detector configurations to gain a better understanding of their impact on sensitivity, accuracy, and precision. For 235U/238U ratios of 1 µm U3O8 particles, a dual Faraday detector measurement with 1011 Ω was the optimal choice; measurement of 1021 particles yielded an average 235U/238U ratio of 0.00170 (14), a −1.8% relative difference (% RD) from the reference value. The minor isotopic compositions were determined to be 0.0000070 (14) and 0.0000758 (48) for the 234U/238U and 236U/238U, respectively. These measurements correspond to <8% and <1% RD from their reference value for the 234U/238U and 236U/238U, respectively. SP-MC-ICP-MS was also able to provide insight into measurement sensitivity. In these individual particles, merely 15 and 165 atto-grams (ag) of 234U and 236U were present (calculated). Initial limits of detection for SP-MC-ICP-MS were determined to be ∼1.0 ag (when measured via SEM detectors). This valuable approach is applicable to areas including nuclear forensics, nuclear safeguards, and geochemical analysis, which require high-precision measurements of uranium within micron-sized particles.

Manard, Benjamin [ORNL] (ORCID:0000000207400627)↗

Modeling and simulation of oxygen transport in high burnup LWR fuel

We have developed a formulation for oxygen transport in uranium dioxide nuclear fuel that accounts for the effects of irradiation. The overall simulation combines the evolving isotopic composition, thermochemistry, and oxygen transport in irradiated fuel. The driving forces for oxygen transport are computed from local thermodynamic equilibrium calculations and account for the effects of temperature gradients and composition, including fission products. The proposed method provides a mechanism for including complex thermodynamic models of nuclear fuel in modeling of mass redistribution, and alleviates difficulties associated with the common thermodiffusion formulation. Here, the transport model has been implemented within the nuclear fuel performance code BISON utilizing the thermochemistry code Thermochimica, with burnup calculations provided by the ORIGEN isotopic transmutation code.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Data from Improved Annotation of Untargeted Metabolomics Data through Buffer Modifications That Shift Adduct Mass and Intensity

Annotation of untargeted high-resolution full-scan LC-MS metabolomics data remains challenging due to individual metabolites generating multiple LC-MS peaks arising from isotopes, adducts, and fragments. Adduct annotation is a particular challenge, as the same mass difference between peaks can arise from adduct formation, fragmentation, or different biological species. To address this, here we describe a buffer modification workflow (BMW) in which the same sample is run by LC-MS in both liquid chromatography solvent with 14NH3–acetate buffer and in solvent with the buffer modified with 15NH3–formate. Buffer switching results in characteristic mass and signal intensity changes for adduct peaks, facilitating their annotation. This relatively simple and convenient chromatography modification annotated yeast metabolomics data with similar effectiveness to growing the yeast in isotope-labeled media. Application to mouse liver data annotated both known metabolite and known adduct peaks with 95% accuracy. Overall, it identified 26% of ∼27 000 liver LC-MS features as putative metabolites, of which ∼2600 showed HMDB or KEGG database formula match. This workflow is well suited to biological samples that cannot be readily isotope labeled, including plants, mammalian tissues, and tumors.

Conversion↗

Improved Annotation of Untargeted Metabolomics Data through Buffer Modifications That Shift Adduct Mass and Intensity

Annotation of untargeted high-resolution full-scan LC-MS metabolomics data remains challenging due to individual metabolites generating multiple LC-MS peaks arising from isotopes, adducts and fragments. Adduct annotation is a particular challenge, as the same mass difference between peaks can arise from adduct formation, fragmentation, or different biological species. To address this, here we describe a Buffer Modification Workflow (BMW), in which the same sample is run by LC-MS in both liquid chromatography solvent with 14 NH 3 -acetate buffer, and in solvent with the buffer modified with 15 NH 3 -formate. Buffer switching results in characteristic mass and signal intensity changes for adduct peaks, facilitating their annotation. This relatively simple and convenient chromatography modification annotated yeast metabolomics data with similar effectiveness to growing the yeast in isotope-labeled media. Application to mouse liver data annotated both known metabolite and known adduct peaks with 95% accuracy. Altogether, it identified 26% of ~ 27,000 liver LC-MS features as putative metabolites, of which ~ 2600 showed HMDB or KEGG database formula match. This workflow is well-suited to biological samples that cannot be readily isotope labeled, including plants, mammalian tissues, and tumors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling and design of a separate effects irradiation test targeting fission gas release from Cr-doped UO 2

Fission gas release (FGR) from nuclear fuel during operation can diminish heat transfer properties across the pellet-cladding gap and increase the fuel rod internal pressure, thereby posing a concern to fuel reliability and safety during an accident. Enlarging the fuel grain size, which has been shown to improve fission gas retention, can be achieved by doping the fuel feedstock prior to sintering. In this work, the BISON fuel performance code was used to predict FGR from undoped and chromia-doped UO 2 (referred to as Cr-doped UO 2 ) fuel specimens with different grain sizes and across various temperatures. The BISON models identified the irradiation conditions for which FGR is most significant, and a separate effects irradiation experiment in the High Flux Isotope Reactor (HFIR) was then developed targeting those conditions. Further, the experiment leveraged the MiniFuel irradiation capability at Oak Ridge National Laboratory and consisted of 12 fuel specimens of varying grain size and Cr content. A coupling scheme between BISON FGR results and the ANSYS finite element thermal model used for experiment design was formulated to predict cumulative FGR from each fuel specimen based on expected irradiation temperature histories. The fuel samples were fabricated and characterized as a part of this work, and the fuel compositions modeled in BISON were representative of the specimens used in the experiment. This combined modeling and experimental effort aims to study the effect of fuel grain size and Cr content on FGR and to provide simulated BISON FGR results that can be used for future model validation activities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The role of isotope mass on neutral fueling and density pedestal structure in the DIII-D tokamak

Abstract Experimental measurements on DIII-D of hydrogen neutral penetration lengths ( λ n 0 ) on the high field side (HFS) are longer by a factor of 2 than for deuterium consistent with the thermal velocity ratio for neutrals at the same temperature ( v t h H / v t h D = 2 ) . This ratio is constant for both low and high pedestal electron density. At low pedestal density ( n e ∼ 4 × 10 19 m − 3 ) , the neutral penetration length is greater than the density pedestal width for both isotopes, and the additional 40% increase of neutral penetration in hydrogen widens the pedestal by the same amount. As the density pedestal height increases ( n e ∼ 6 × 10 19 m − 3 ) , the neutral penetration lengths drop below the density pedestal widths for both isotopes, and the increased penetration of hydrogen has no increased effect on the pedestal width compared to deuterium. Extrapolating to future reactor-relevant high electron density pedestals, the isotope-mass change in neutral fueling on the HFS from the deepest neutral penetration of hydrogen, to the shortest neutral penetration of tritium will be negligible (0.2–0.4 cm) in comparison to estimates of the density pedestal width (6–8.5 cm).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Sensitivity analysis of thermal contact conductance modeling to inform MiniFuel irradiation capsule designs

The MiniFuel irradiation platform has been developed by Oak Ridge National Laboratory as a flexible, high-throughput separate effects testing capability within the High Flux Isotope Reactor (HFIR). Finite element thermal models are relied upon to design MiniFuel experiments to achieve a specific time-averaged irradiation temperature for experimental objectives. A previous study identified that uncertainty in the component heat generation rates and thermal contact conductance (TCC) model are the most significant contributors to predicted fuel temperature variance. To address both sources of uncertainty, this work performs sensitivity analysis on the TCC model to identify high-impact, high-uncertainty parameters that contribute to fuel temperature variance. The TCC model is analyzed in increasing detail, first using a standalone Python code, then again after coupling Python to the BISON fuel performance code. Furthermore, the parameters with the largest contributions to fuel temperature variance which can be reduced through design changes are identified as the initial subcapsule gas pressure, contact pressure between the fuel and dish, and the effective surface roughness of the interface. A set of design recommendations for future capsule designs has been established and applied to reduce the previously quantified average fuel temperature uncertainty ranges of ± 40 °C in the HFIR vertical experiment facilities (VXF) and ± 80 °C in the removable beryllium (RB) reflector to approximately ± 32 °C and ± 53 °C, respectively. This equates to a 21 % and 33 % reduction in the uncertainty range of the average fuel temperature for VXF and RB, respectively.

BISON↗

Phoebe: a high-performance framework for solving phonon and electron Boltzmann transport equations

Understanding the electrical and thermal transport properties of materials is critical to the design of electronics, sensors, and energy conversion devices. Computational modeling can accurately predict material properties but, in order to be reliable, requires accurate descriptions of electron and phonon states and their interactions. While first-principles methods are capable of describing the energy spectrum of each carrier, using them to compute transport properties is still a formidable task, both computationally demanding and memory intensive, requiring integration of fine microscopic scattering details for estimation of macroscopic transport properties. To address this challenge, we present Phoebe—a newly developed software package that includes the effects of electron–phonon, phonon–phonon, boundary, and isotope scattering in computations of electrical and thermal transport properties of materials with a variety of available methods and approximations. This open source C++ code combines MPI-OpenMP hybrid parallelization with GPU acceleration and distributed memory structures to manage computational cost, allowing Phoebe to effectively take advantage of contemporary computing infrastructures. We demonstrate that Phoebe accurately and efficiently predicts a wide range of transport properties, opening avenues for accelerated computational analysis of complex crystals.

36 MATERIALS SCIENCE↗

Isotopic and Fuel Lattice Parameter Trends in Extended Enrichment and Higher Burnup LWR Fuel, Volume II: BWR

Commercial light water reactor (LWR) operators and fuel vendors in the United States are pursuing changes to nuclear fuel that include extended enrichment (EE) and accident-tolerant fuel (ATF) designs to further improve reactor safety and plant economics. Extended fuel enrichments above 5% 235 U pin enrichment and up to 10% 235 U are a subset of high assay low-enriched uranium (HALEU) that may be deployed in commercial US LWRs in the near term. ATF features, such as cladding coatings or alternative cladding materials, are designed to improve fuel system performance under accident conditions. One goal of EE is to improve fuel cycle economy by enabling fuel to be depleted to higher burnup than the typical current limits (62 gigawatt-days per metric ton of uranium [GWd/MTU]). Adoption of EE, ATF, and high burnup (HBU) fuels in the US commercial fleet requires a clear understanding of the effects on core physics parameters and used fuel isotopic content, as well as confidence in the accuracy of computer code predictions over an expanded range of materials, enrichment, and burnup. A thorough understanding of the applicability and adequacy of benchmark data (e.g., criticality, decay heat, isotopic content) for computer code validation is necessary to ensure that appropriate safety margins are maintained. As part of the US Nuclear Regulatory Commission (NRC) agreement number 31310019N0008, “SCALE Code Development, Assessment and Maintenance,” the effects of EE, ATF, and HBU are being assessed for selected representative LWR fuel designs. The project is divided into phases, and this report summarizes the findings of the Phase 1 work, which focuses on lattice physics parameter and used fuel isotopic changes for a conventional GE14 10 x 10 boiling water reactor (BWR) design with GNF-2 part length rod patterns to model a modern BWR assembly design.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Machine Learning Prediction of Fracture Toughness in Hydrogen-charged Stainless Steels

Austenitic stainless steels are structural materials utilized in tritium gas pressure boundaries since they are resistant to hydrogen isotope embrittlement [1-3]. However, exposure to tritium over long periods of time leads to tritium uptake which decays to result in helium ingrowth. This helium ingrowth results in further embrittlement effects which are synergistic with that from the hydrogen isotope [4]. Therefore, it is important for tritium facilities to understand the material limitations of stainless steel in this environment. The Savannah River National Laboratory (SRNL) has available a large experimental data set of austenitic stainless steels which have been exposed to tritium environments for various lengths of time. With the availability of this data set, machine learning (ML) algorithms provide an opportunity to model the embrittlement of stainless steel due to the algorithm’s ability to identify patterns in data sets that are difficult and costly to identify in other manners [5]. Ultimately, the amount and quality of the available data is one defining force in the ability of a ML model to accurately predict the desired outputs. The models developed herein will illustrate the ability for the various algorithms to predict the change in fracture toughness in stainless steels due to hydrogen-isotope embrittlement.

Hoar, Eric T.↗

Iron precipitation under controlled oxygen flow: Mineralogical implications for BIF precursors in the Archean ocean

Banded iron formation (BIF) deposition in the Archean ocean is thought to have been initiated by the oxidation of dissolved iron into ferric primary precursor phases that descended through the water column and were deposited on the seafloor. Effective interpretation of the trace element and isotopic composition of BIFs in the geologic record requires an understanding of the identity and longevity of those precursor phases. Temporal and spatial variation in oxidant concentration and ocean chemistry may have driven precursor mineralogy. Furthermore, precursor phases may undergo transitions during descent and burial. This experimental study follows the evolution of iron mineralogy, speciation, and redox state during the precipitation of iron under variable oxygen fluxes and in fluids containing different iron-complexing anions (chloride, sulfate, and phosphate). Additionally, suspensions collected after incomplete oxidation were anoxically aged to simulate changes to precursor mineralogy during descent below the seawater redoxcline. Results from X-ray diffraction, sequential dissolution, colorimetric determination of Fe redox state, and Fe K-edge X-ray absorption fine structure spectroscopy showed that under all experimental conditions, intermediate precipitates collected before complete iron uptake contained mineralized ferrous iron. Purely ferric mineral assemblages were not observed until iron was removed from solution. In low-oxygen experiments, intermediate precipitates contained phases with stoichiometric Fe 2+ , including magnetite, vivianite, and green rust (GR). Chloride green rust (GR1) had more ferric iron than sulfate green rust (GR2) and more readily transitioned to magnetite via disproportionation. GR2 was stable over a broader range of iron uptake; magnetite appeared mainly as an additional oxidation product in sulfate solution. In high oxygen experiments, mineralized ferrous iron occurred in amorphous phases or as a non-stoichiometric component in ferric oxides; final ferric assemblages were less crystalline than in low-oxygen equivalents. Low concentrations of phosphate increased the total iron oxidation rate, but also increased the ferrous content of intermediate precipitates. The incorporation of phosphate stabilized GR2 and facilitated GR2 precipitation over a larger range of iron uptake. In higher concentrations of phosphate, vivianite and poorly crystalline ferric hydroxides formed in place of GR. Here, these findings suggest that over a range of possible ocean chemistries, mixed-valence phases may have been short lived but relevant precursors to BIF. Additionally, anionic chemistry and oxidant concentration are shown to influence the crystallinity and chemical resistivity of final ferric assemblages, affecting their reactivity during later anoxic burial.

58 GEOSCIENCES↗