Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “HISTORY OF”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Timing the r -process Enrichment of the Ultra-faint Dwarf Galaxy Reticulum II

The ultra-faint dwarf galaxy Reticulum II (Ret II) exhibits a unique chemical evolution history, with ${72}_{-12}^{+10}$% of its stars strongly enhanced in r-process elements. We present deep Hubble Space Telescope photometry of Ret II and analyze its star formation history. As in other ultra-faint dwarfs, the color–magnitude diagram is best fit by a model consisting of two bursts of star formation. If we assume that the bursts were instantaneous, then the older burst occurred around the epoch of reionization, forming ~80% of the stars in the galaxy, while the remainder of the stars formed ~3 Gyr later. When the bursts are allowed to have nonzero durations, we obtain slightly better fits. The best-fitting model in this case consists of two bursts beginning before reionization, with approximately half the stars formed in a short (100 Myr) burst and the other half in a more extended period lasting 2.6 Gyr. Considering the full set of viable star formation history models, we find that 28% of the stars formed within 500 ± 200 Myr of the onset of star formation. The combination of the star formation history and the prevalence of r-process-enhanced stars demonstrates that the r-process elements in Ret II must have been synthesized early in its initial star-forming phase. We therefore constrain the delay time between the formation of the first stars in Ret II and the r-process nucleosynthesis to be less than 500 Myr. This measurement rules out an r-process source with a delay time of several Gyr or more, such as GW170817.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Discrete ordinates analysis of the forced-flight variance reduction technique in Monte Carlo neutral particle transport simulations

This paper presents mathematical formulations and methods to predict the effect of forced-flight variance reduction on Monte Carlo tally variance and calculation time. This includes deducing biasing operators that are then used to construct a history-score probability density function (HSPDF), which represents all possible Monte Carlo random walks and gives the probability of a Monte Carlo history scoring in a tally from a particular phase-space position. The history-score moment equations (HSMEs), the statistical moments of the HSPDF, are then derived to calculate the statistical behavior of the Monte Carlo tally when forced-flight variance reduction is applied. In addition, the future-time equation (FTE) is derived to predict the Monte Carlo computational time as a result of applying forced-flight variance reduction. The solutions of the HSMEs and FTE can be used to predict Monte Carlo computational cost. Furthermore, this work also describes a discrete ordinates method to solve the forced-flight HSMEs and FTE. Several 1-D and 2-D test problems verify that the derivations are performed and implemented correctly.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Agricultural Management Legacy Effects on Switchgrass Growth and Soil Carbon Gains

Switchgrass ( Panicum virgatum L.) is a native North American grass currently considered a high-potential bioenergy feedstock crop. However, previous reports questioned its effectiveness in generating soil organic carbon (SOC) gains, with resultant uncertainty regarding the monoculture switchgrass's impact on the environmental sustainability of bioenergy agriculture. We hypothesize that the inconsistencies in past SOC accrual results might be due, in part, to differences in prior land management among the systems subsequently planted to switchgrass. To test this hypothesis, we measured SOC and other soil properties, root biomass, and switchgrass growth in an experimental site with a 30-year history of contrasting tillage and N-fertilization treatments, 7 years after switchgrass establishment. We determined switchgrass' monthly gross primary production (GPP) for six consecutive years and conducted deep soil sampling. Nitrogen fertilization expectedly stimulated switchgrass growth; however, a tendency for better plant growth was also observed under unfertilized settings in the former no-till soil. In topsoil, SOC significantly increased from 2007 to 2023 in fertilized treatments of both tillage histories, with the greatest increase observed in fertilized no-till. Fertilized no-till also had the highest particulate organic matter content in the topsoil, with no differences among the treatments observed in deeper soil layers. However, regardless of fertilization, the tillage history had a strong effect on stratification with depth of SOC, total N, and microbial biomass C. Results suggested that historic and ongoing N fertilization had a substantial impact on switchgrass growth and soil characteristics, while tillage legacy had a much weaker, but still discernible, effect.

bioenergy crop production system↗
DOE OSTI2020

Hidden sector monopole dark matter with matter domination

The thermal freeze-out mechanism for relic dark matter heavier than O (10 – 100 TeV) requires cross-sections that violate perturbative unitarity. Yet the existence of dark matter heavier than these scales is certainly plausible from a particle physics perspective, pointing to the need for a non-thermal cosmological history for such theories. Topological dark matter is a well-motivated scenario of this kind. Here the hidden-sector dark matter can be produced in abundance through the Kibble-Zurek mechanism describing the non-equilibrium dynamics of defects produced in a second order phase transition. We revisit the original topological dark matter scenario, focusing on hidden-sector magnetic monopoles, and consider more general cosmological histories. We find that a monopole mass of order (1–10 5 ) PeV is generic for the thermal histories considered here, if monopoles are to entirely reproduce the current abundance of dark matter. In particular, in a scenario involving an early era of matter domination, the monopole number density is always less than or equal to that in a pure radiation dominated equivalent provided a certain condition on critical exponents is satisfied. This results in a larger monopole mass needed to account for a fixed relic abundance in such cosmologies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Formation and interior evolution of Mars

The formation and earliest evolution of Mars involved core formation followed by magma ocean solidification and primordial crust formation. Here, in this study, we review the formation and early interior evolution of Mars as understood through meteorite studies. Martian meteorites exhibit ages that span the entire history of the Solar System, but most derive from compositionally distinct sources that formed early in the history of Mars. Geochemical and isotopic studies of Martian meteorites have provided critical information on Mars’ building blocks, bulk composition, and its differentiation into a core, mantle and crust. Radiogenic isotope systems provide vital insights into the petrogenesis of Martian meteorite source regions and into the nature and timescales of primordial differentiation on Mars. Application of short-lived isotope chronometers to Martian meteorites indicates that the Martian core formed early within <10 million years (Ma), while magma ocean differentiation and crust formation occurred soon thereafter, within the first tens of Ma of Solar System history. Bulk silicate Mars is variably depleted in moderately volatile elements relative to chondrites, but to a lesser extent than the Earth. The nature and evolution of more volatile elements and volatile species on Mars (e.g., H 2 O, C, S, halogens) remains an active area of investigation, but overall suggest that Mars is more enriched in volatile elements than the Moon but less than the Earth. While geochemical exploration of Mars coupled with new discoveries of Martian meteorites has provided a wealth of information, the compositional and lithologic diversity on Mars significantly exceeds that seen in the suites of Martian meteorites currently studied. This implies that our current perspective on the planet's evolution is very likely biased, highlighting the need for future sample return missions to Mars.

Kruijer, Thomas S.↗
DOE OSTI2023

Robust deep learning framework for constitutive relations modeling

Modeling the full-range deformation behaviors of materials under complex loading and materials conditions is a significant challenge for constitutive relations (CRs) modeling. Here, we propose a general encoder-decoder deep learning framework that can model high-dimensional stress-strain data and complex loading histories with robustness and universal capability. The framework employs an encoder to project high-dimensional input information (e.g., loading history, loading conditions, and materials information) to a lower-dimensional hidden space and a decoder to map the hidden representation to the stress of interest. We evaluated various encoder architectures, including gated recurrent unit (GRU), GRU with attention, temporal convolutional network (TCN), and the Transformer encoder, on two complex stress-strain datasets that were designed to include a wide range of complex loading histories and loading conditions. All architectures achieved excellent test results with an root-mean-square error (RMSE) below 1 MPa. Additionally, we analyzed the capability of the different architectures to make predictions on out-of-domain applications, with an uncertainty estimation based on deep ensembles. The proposed approach provides a robust alternative to empirical/semi-empirical models for CRs modeling, offering the potential for more accurate and efficient materials design and optimization.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Predicting defects in laser powder bed fusion using in-situ thermal imaging data and machine learning

Variation in the local thermal history during the Laser Powder Bed Fusion (LPBF) process in Additive Manufacturing (AM) can cause micropore defects, which add to the uncertainty of the mechanical properties (e.g., fatigue life, tensile strength) of the built materials. In-situ sensing has been proposed for monitoring the AM process to minimize defects, but successful minimization requires establishing a quantitative relationship between the sensing data and the porosity, which is particularly challenging with a large number of variables (e.g., laser speed, power, scan path, powder property). Physics-based modeling can simulate such an in-situ sensing-porosity relationship, but it is computationally costly. In this work, we develop Machine Learning (ML) models that can use in-situ thermographic data to predict the micropore of LPBF stainless steel materials. This work considers two identified key features from the thermal histories: the time above the apparent melting threshold ($\tau$) and the maximum radiance ( T max ). These features are computed, stored for each voxel in the built material, and then used as inputs. The binary state of each voxel, either defective or normal, is the output. Different ML models are trained and tested for the binary classification task. In addition to using the thermal features of each voxel to predict its own state, the thermal features of neighboring voxels are also included as inputs. This is shown to improve the prediction accuracy, which is consistent with thermal transport physics around each voxel contributing to its final state. Among the models trained, the F1 scores on test sets reach above 0.96 for Random Forests. Feature importance analysis based on the ML models shows that T max is more important to the voxel state than $\tau$ . The analysis also finds that the thermal history of the voxels above the present voxel is more influential than those beneath it. Our study significantly extends the capability of using in-situ thermographic data to predict porosity in LPBF materials. Finally, since ML models are fast, they may play integral roles in the optimization and control of such AM technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Geometric learning for computational mechanics Part II: Graph embedding for interpretable multiscale plasticity

The history-dependent behaviors of classical plasticity models are often driven by internal variables evolved according to phenomenological laws. The difficulty to interpret how these internal variables represent a history of deformation, the lack of direct measurement of these internal variables for calibration and validation, and the weak physical underpinning of those phenomenological laws have long been criticized as barriers to creating realistic models. In this work, geometric machine learning on graph data (e.g. finite element solutions) is used as a means to establish a connection between nonlinear dimensional reduction techniques and plasticity models. Geometric learning-based encoding on graphs allows the embedding of rich time-history data onto a low-dimensional Euclidean space such that the evolution of plastic deformation can be predicted in the embedded feature space. Finally, a corresponding decoder can then convert these low-dimensional internal variables back into a weighted graph such that the dominating topological features of plastic deformation can be observed and analyzed.

42 ENGINEERING↗
DOE OSTI2023

Noble gas insights into early impact delivery and volcanic outgassing to Earth's atmosphere: A limited role for the continental crust

Earth's atmosphere, crust and mantle have evolved together through continuous geochemical exchange throughout Earth's history. Constraints on the transport of volatile elements and compounds between these reservoirs are crucial for understanding how Earth could have stayed habitable for extended periods of time. In this work, we present a new forward model of He, Ne and Ar in the mantle, crust and atmosphere. We explore concentrations of noble gases at the end of accretion, bulk silicate Earth K/U ratios, crustal growth scenarios, and upper mantle processing rates throughout Earth's history. We search for parameter combinations that simultaneously satisfy observational constraints on present-day mantle 4 He/ 3 He and 40 Ar/ 36 Ar (sensitive to mantle outgassing and continental crust growth, which depletes the mantle of U, Th and K), atmospheric 20 Ne/ 22 Ne (which tracks the mix of outgassed vs. delivered Ne in the atmosphere), and atmospheric 40 Ar/ 36 Ar in the past and today (sensitive to volatile delivery, mantle outgassing and crustal growth). Leveraging this intertwined set of noble gas abundances and isotopic compositions yields new constraints on initial noble gas abundances in the mantle and on the proportions of atmospheric volatiles originating from delivery by impact degassing, mantle outgassing, and degassing of the continental crust. We find that atmospheric Ar isotopic evolution is primarily sensitive to the mantle processing rate history; the atmospheric Ar isotopic record should therefore not be used to reconstruct continental crust growth, but instead provides valuable insights into mantle processing rates. Our model predicts a measurably low 20 Ne/ 22 Ne ratio of ~9.7 in Archean atmospheric samples. Most of atmospheric primordial 36 Ar was directly delivered by chondritic bodies and not transferred to the atmosphere during an intense early episode of mantle outgassing. Nitrogen delivered by impact degassing could account for the present-day atmospheric nitrogen inventory.

58 GEOSCIENCES↗
DOE OSTI2025

Probing Cretaceous-Paleogene crustal thickness in southern Tibet using quartz-zircon chronobarometry

Knowledge of the crustal thickness history of southern Tibet during the India-Asia collision is key to understanding what deformation mechanisms accommodated northward propagating crustal shortening. Thermoisotopic models suggest that a relatively thin margin of southern Asia persisted from ca. 200 to 45 Ma whereas trace element paleodepth proxies are interpreted to indicate a thinning phase from ca. 100 to 65 Ma when the crust reached ∼30 km-thickness. As neither of these methods directly measures crustal thickness, resolution of this conflict awaits development of a method that can. Here, in this study, we place bounds on the thickening history of southern Tibet using coupled quartz-zircon thermobarometry and U-Pb geochronology of granitoid plutons in the Gangdese batholith. We find that crustal thicknesses were as high (or higher) as 60–75 km at 65 Ma, or 10–15 Ma prior to the onset of hard continental collision. Magmatic inflation in the lower crust likely contributed to crustal thickening and thermal weakening of the lower crust, suggesting that pure shear in the lower crust was likely the primary accommodation mechanism for N-S shortening during collision. These data are in partial agreement with results of thermoisotopic models of crustal thickness but contradict thickness histories derived from empirical trace element proxies.

Chronobarometry↗
DOE OSTI2023

Chronology of alkali anorthosite 14304 clast “b” records basin forming impact at ~3.95 Ga

Alkali-suite rocks constitute one of three major suites of lunar crustal rocks. As such, constraining their formation timescales and petrogenesis is important for understanding the earliest magmatic history of the Moon. However, the magmatic history of alkali-suite rocks is partly obscured by superimposed effects of major basin-forming impact events on the lunar nearside. Consequently, unambiguous crystallization ages of samples from this suite of rocks have not been determined. Here, the aim of this study is to better understand the petrogenetic history of the alkali-suite and the potential superimposed effects of impact metamorphism by determining Sm-Nd, Rb-Sr, and 40 Ar/ 39 Ar ages for an alkali anorthosite clast from Apollo 14 lithic breccia 14304 termed clast “b”. The new chronologic measurements of clast “b” yield concordant Sm-Nd, Rb-Sr, and 40 Ar/ 39 Ar ages of 3947 ± 13 Ma, 3975 ± 34 Ma, and 3937 ± 37 Ma respectively, resulting in a weighted mean age of 3949 ± 11 Ma. This age is not interpreted to date an igneous event related to production of the lunar highlands crust and instead the chronology and petrography of clast “b” are most readily explained by an impact event at ~3.95 Ga that caused near-complete isotopic re-equilibration of the Sm-Nd, Rb-Sr, and 40 Ar/ 39 Ar chronometers. The weighted mean age of 3949 ± 11 Ma of clast “b” is several hundred Ma younger than 4.3–4.4 Ga ages typically determined for samples of other crustal rock suites but in very good agreement with independent estimates for the formation of Imbrium basin ejecta and other marginally older impact events which are thought to have been sampled at the Apollo 14 landing site. Thus, although petrologic and geochemical examination suggest that clast “b” is a pristine igneous clast, its age likely records an impact event at the Apollo 14 landing site. Whereas the various determined ages of clast “b” do not reflect the timescales of alkali-suite magmatism, the relatively low initial Sr and Nd isotopic compositions of clast “b” indicate that its protolith evolved with very low 147 Sm/ 144 Nd and 87 Rb/ 86 Sr that are distinct from estimates for urKREEP but similar to that of lunar plagioclase. This implies that the igneous protolith of clast “b” derived from a plagioclase-dominated KREEP-rich source that must have formed after the formation of the urKREEP source at ~4.35 Ga but well before the impact event recorded by clast “b” at ~3.95 Ga.

58 GEOSCIENCES↗
DOE OSTI2023

Microscale spatiotemporal patterns of water, soil organic carbon, and enzymes in plant litter detritusphere

Understanding biophysical and biochemical processes in detritusphere is critical to quantifying and modeling plant residue decomposition dynamics and subsequent soil organic carbon (C) accrual. The objectives of the study were to explore (i) micro-environmental conditions within the detritusphere formed around decomposing corn and soybean leaves, and (ii) the relationships between moisture distribution, enzyme activity, and C dynamics during decomposition. We assessed spatial and temporal dynamics of moisture distribution using X-ray and neutron computed tomography, and activities of β-glucosidase and chitinase, two enzymes involved in soil C and N processing, using zymography. We used 13 C labeled residue to track residue contribution to atmospheric CO 2 and soil organic C. Moisture redistribution pattern varied depending on the residue type. While the water was immediately absorbed by the corn leaves and maintained afterward, switchgrass leaves absorbed water more slowly and created water-deficient zones within ~1mm from the residue. This initial moisture depletion led to lower chitinase activity and residue-derived CO 2 emissions in switchgrass. In contrast to chitinase, β-glucosidase activity was influenced by a combination of vegetation history and residue type, and it was higher when the origin of the residue matched the vegetation history of the soil. Pore size had an opposite impact on the studied enzymes, supporting the notion that contrasting soil pore architecture can stimulate activities of different enzymes through a selection of dominant enzyme producers. We concluded that the decomposition dynamics of plant residues is not only a simple function of residue chemistry, but rather a combined effect of the vegetation history, in part through its effect on microbial community composition, the plant residue chemical and likely physical characteristics, and the soil pore structure in the detritusphere. Together, they create temporally dynamic micro-environmental conditions influencing decomposition. Specifically, our study demonstrated that the initial micro-environment formulated in detritusphere can play an important role in enzyme activities and consequent C dynamics.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Impact of temperature variations on BISON predictions of Ag release in AGR-1 and AGR-2 experiments

Understanding and quantifying the release of fission products like silver (Ag) from TRistructural ISOtropic (TRISO) fuel particles is important to assess the safe operation of advanced high temperature reactors. Although the silicon carbide (SiC) layer of TRISO particles is effective as the main fission product barrier, Ag can be released from intact TRISO particles. A mechanistic model for the effective Ag diffusivity, D eff , was previously developed as a function of temperature and microstructure variables informed by atomistic modeling of Ag diffusivity on the mesoscale. Here in this study, we use this model to explore how experimental temperature uncertainties impact the overall predicted Ag release. This analysis shows that temperature uncertainties have a significant impact on the overall Ag release predictions. Furthermore, we show that the time average volume average temperature (TAVA) temperature is not an appropriate proxy for temperature histories to predict fission product release. We attribute this to the Arrhenius dependence of Ag diffusivity with respect to temperature. The detailed temperature histories, therefore, provide the most accurate results are are of most importance for modeling efforts. Overall, this work shows the importance of considering the experimental uncertainty of the temperature on computational predictions of fission product transport and release and the need for more accurate temperature histories from future experiments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Validation of electron backscattering in the MCNP6.3 code

A new electron backscattering validation suite has been developed for the MCNP® code. The calculations in this suite cover both condensed history and single-event transport methods, seven different elemental materials ranging from beryllium to uranium, and incident electron energies from 200 eV to 14.1 MeV. In general, the accuracy of the MCNP code for electron backscattering calculations is energy-dependent. For incident electron energies below 2 keV, the condensed history method is not applied while the single-event method shows poor agreement with experimental measurements due to poor accuracy of the underlying atomic data. For incident energies between 2 keV and 256 keV, the single-event method typically shows better agreement with experiments, while for incident energies above 256 keV the condensed history method gives better accuracy. Additionally, agreement with experimental data is generally worse for low- Z materials such as beryllium and carbon, which may reflect deficiencies in the data or physics underlying electron transport through light elements in the MCNP code. The new electron backscattering validation suite, along with the previously introduced electron stopping power and Lockwood energy deposition validation suites, provide MCNP users with a quantified understanding of the uncertainties in electron transport calculations. Future improvements to electron transport in the MCNP code are necessary for low energies (≤ 2 keV) and for low- Z materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Review of the Lawrence Livermore Nuclear Accident Dosimeter 1980s-present

A Nuclear Accident Dosimetry program is a federal requirement for all facilities that have the potential to have a criticality accident. Personnel Nuclear Accident Dosimeter (PNAD) theory and analytical procedures are driven by various scientific needs and interacting regulations. A brief history of the status of USA Department of Energy (DOE) nuclear accident dosimetry regulations, recommendations, and performance testing criteria are given. Then, the history of the Lawrence Livermore National Laboratory (LLNL) PNAD is explored, including changes in the physical dosimeter and adjustments of the analysis method through the last four decades. Finally, the performance of LLNL’s PNAD at criticality accident intercomparison training exercises since 2009 is explored. In general, reported neutron doses have been within or close to DOE-STD-1098 performance criteria while reported gamma doses have been outside of DOE-STD-1098 performance criteria. Reported total absorbed doses have varied in meeting ANSI/HPS N13.3 and ANSI/HPS N13.3 (R2019) performance criteria. Dosimetry staff retirement and turnover have left historical knowledge gaps, yet provided opportunities within the NAD program at LLNL. This review paper serves as an overview of the history and status of the NAD program. Brief technical, procedural and programmatic recommendations to improve LLNL’s NAD program are given. Technical recommendations include investigating orientation factors through modeling or empirical experimentation, investigating gamma dosimetry methods for high-dose scenarios, and exploring other dosimetric methods for simpler, quicker NAD analysis. Procedural recommendations include better documentation of conversion factor (activity-to-fluence and fluence-to-dose) derivations and spectrum uses, and updated analysis spreadsheets or simple Graphic User Interfaces for dose calculations. In conclusion, programmatic recommendations include formalized training for NAD analysts, and having multiple SMEs trained on the NAD program.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

A universal velocity transformation for boundary layers with pressure gradients

The logarithmic law of the wall does not capture the mean flow when a boundary layer is subjected to a strong pressure gradient. In such a boundary layer, the mean flow is affected by the spatio-temporal history of the imposed pressure gradient; and accounting for history effects remains a challenge. This work aims to develop a universal mean flow scaling for boundary layers subjected to arbitrary adverse or/and favourable pressure gradients. Here, we derive from the Navier–Stokes equation a velocity transformation that accounts for the history effects and maps the mean flow to the canonical law of the wall. The transformation is tested against channel flows with a suddenly imposed adverse or favourable pressure gradient, boundary layer flows subjected to an adverse pressure gradient, and Couette–Poiseuille flows with a streamwise pressure gradient. It is found that the transformed velocity profiles follow closely the equilibrium law of the wall.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Dependence of Uranium Oxide Polymorphism on Plasma Synthesis Conditions

Here, we synthesized uranium oxide nanoparticles using a plasma flow reactor (PFR) and studied the effects of three different experimental parameters on the resulting morphologies and speciation of the particles: (1) collection duration, (2) collection substrate temperature, and (3) radial collection position due to radial temperature gradients in the PFR. We also induced three distinct temperature histories along the axis of the plasma flow reactor by varying the gas flow rates downstream of the plasma torch. Transmission electron microscopy (TEM) analyses of collected particles showed two phases of uranium oxides (fcc-UO 2 and α-UO 3 ). The chemical compositions of the resulting uranium oxide particles were not altered by the three parameters investigated in this work but varied based on the temperature history induced. Preheating of the collection substrate led to deposition of fewer particles, which is attributed to a reduction in thermophoretic force caused by the reduced temperature gradient for preheated substrates. The relative amounts of UO 2 to UO 3 and particle size varied depending on the cooling history employed during synthesis.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe 3+ /ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. Furthermore, these experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history.

58 GEOSCIENCES↗