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DOE OSTI2021

Omics-to-Reactive-Transport (ORT): A workflow linking genome-scale metabolic models with reactive transport codes

Motivation: Nutrient and contaminant behavior in the subsurface are governed by multiple coupled hydrobiogeochemical processes which occur across different temporal and spatial scales. Accurate description of macroscopic system behavior requires accounting for the effects of microscopic and especially microbial processes. Microbial processes mediate precipitation and dissolution and change aqueous geochemistry, all of which impacts macroscopic system behavior. As `omics data describing microbial processes is increasingly affordable and available, novel methods for using this data quickly and effectively for improved ecosystem models are needed. Results: We propose a workflow (`Omics to Reactive Transport – ORT) for utilizing metagenomic and environmental data to describe the effect of microbiological processes in macroscopic reactive transport models. This workflow utilizes and couples two open-source software packages: KBase (a software platform for systems biology) and PFLOTRAN (a reactive transport modeling code). We describe the architecture of ORT and demonstrate an implementation using metagenomic and geochemical data from a river system. Our demonstration uses microbiological drivers of nitrification and denitrification to predict nitrogen cycling patterns which agree with those provided with generalized stoichiometries. While our example uses data from a single measurement, our workflow can be applied to spatiotemporal metagenomic datasets to allow for iterative coupling between KBASE and PFLOTRAN. Live, interactive models, which incorporate the results from this narrative into a PFLOTRAN simulation, are available (without login) at https://pflotranmodeling.paf.subsurfaceinsights.com/pflotran-simple-model/.

Rubinstein, Rebecca L↗

NASA NTRS2020

Clay Sediments from Basaltic Terrains: Implications for Sedimentary Processes on Mars

The Mars Science Laboratory (MSL) rover, Curiosity, has been traversing across fluvial, lacustrine, and eolian sedimentary rocks since it touched down in 2012. The CheMin X-ray diffractometer (XRD) on board Curiosity has revealed smectite clay minerals in most fluvio-lacustrine samples and abundant X-ray amorphous materials in all samples analyzed to date. For example, mudstones from the Sheepbed member at the base of the stratigraphic section and the lower part of the Murray formation contain on average ~7 to 20 wt% smectite and ~30 to 46 wt% X-ray amorphous abundances. On Earth, smectite and secondary X-ray amorphous materials are juvenile weathering products that are generated in sedimentary environments and ultimately record the interaction between primary igneous minerals and the hydrosphere, atmosphere, and biosphere. For this study, we investigated glacio-fluvio-eolian sediments generated in basaltic terrains as terrestrial analogs for the mudstones from Gale Crater, Mars. This work focuses on the clay sized sediments (<2 μm) from these deposits as this grain size hosts the most mineralogically and geochemically altered detritus in sedimentary environments. The goal of investigating basaltic sedimentation is to create a terrestrial reference frame that sheds light on the paleoclimate and paleoaqueous conditions responsible for shaping the ancient sedimentary environments of Mars (e.g., Gale Crater and Jezero Crater).

Thorpe, M. T.↗

DOE OSTI2022

Fe Oxidation and Species Distribution at the Rock–Fluid Interface of Marcellus Shale Reacted with Hydraulic Fracturing Fluid

Hydraulic fracturing of shale reservoirs resulted in significant opportunity for increased oil and gas production in the United States. Rock-fluid interactions can cause mineral dissolution and precipitation reactions that lead to permeability changes in the shale matrix, which ultimately may affect transport pathways and hydrocarbon production. Understanding the distribution of secondary precipitates, such as barite and Fe(III) (hydro)oxides, and cation leaching at the rock-fluid interface is an important step to further investigate how these geochemical processes can change permeability and transport pathways. In this study, thin sections of the fracture-matrix interface were made from reacted Marcellus shale cores. The thin sections were characterized using synchrotron X-ray fluorescence imaging and synchrotron X-ray absorption spectroscopy. Fe species with different oxidation states were identified in the maps, together with barite and Ca distribution. The results show that ferrihydrite, as newly formed Fe(III)-bearing precipitates, aligned well with the border of the Ca (e.g., calcite) leaching region in the reaction front. Some Fe-containing clay also dissolved, but the dissolution region for the clay was not as deep as the calcite. Further, the reaction front is about three times deeper in the direction parallel to the shale bedding than that perpendicular to the bedding. The Ca leaching region can be an index for reaction front detection for Marcellus shale. Reactive transport modeling was conducted and the predicted Ca leaching boarder align well with ferrihydrite precipitation, consistent with the experimental observation. The carbonate mineral dissolution can be crucial to promote fluid access into the shale matrix. Together with our previous study on the shale reactive surface, this follow-up study showed similar Ca leaching region and Fe(III) precipitates distribution in the reaction front regardless of barite precipitation on the surface, indicating that the barite coatings on the surface may not pose a significant impact on reactive transport at the shale-fluid interface.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2021

ORT: a workflow linking genome-scale metabolic models with reactive transport codes

Abstract Motivation Nutrient and contaminant behavior in the subsurface are governed by multiple coupled hydrobiogeochemical processes which occur across different temporal and spatial scales. Accurate description of macroscopic system behavior requires accounting for the effects of microscopic and especially microbial processes. Microbial processes mediate precipitation and dissolution and change aqueous geochemistry, all of which impacts macroscopic system behavior. As ‘omics data describing microbial processes is increasingly affordable and available, novel methods for using this data quickly and effectively for improved ecosystem models are needed. Results We propose a workflow (‘Omics to Reactive Transport—ORT) for utilizing metagenomic and environmental data to describe the effect of microbiological processes in macroscopic reactive transport models. This workflow utilizes and couples two open-source software packages: KBase (a software platform for systems biology) and PFLOTRAN (a reactive transport modeling code). We describe the architecture of ORT and demonstrate an implementation using metagenomic and geochemical data from a river system. Our demonstration uses microbiological drivers of nitrification and denitrification to predict nitrogen cycling patterns which agree with those provided with generalized stoichiometries. While our example uses data from a single measurement, our workflow can be applied to spatiotemporal metagenomic datasets to allow for iterative coupling between KBase and PFLOTRAN. Availability and implementation Interactive models available at https://pflotranmodeling.paf.subsurfaceinsights.com/pflotran-simple-model/. Microbiological data available at NCBI via BioProject ID PRJNA576070. ORT Python code available at https://github.com/subsurfaceinsights/ort-kbase-to-pflotran. KBase narrative available at https://narrative.kbase.us/narrative/71260 or static narrative (no login required) at https://kbase.us/n/71260/258. Supplementary information Supplementary data are available at Bioinformatics online.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2018

Phreatic Explosions During Basaltic Fissure Eruptions: Kings Bowl Lava Field, Snake River Plain, USA

Physical and compositional measurements are made at the approx. 7 km-long (approx. 2200 years B.P.) Kings Bowl basaltic fissure system and surrounding lava field in order to further understand the interaction of fissure-fed lavas with phreatic explosive events. These assessments are intended to elucidate the cause and potential for hazards associated with phreatic phases that occur during basaltic fissure eruptions. In the present paper we focus on a general understanding of the geological history of the site. We utilize geospatial analysis of lava surfaces, lithologic and geochemical signatures of lava flows and explosively ejected blocks, and surveys via ground observation and remote sensing.

Phreatic explosions↗

DOE OSTI2023

Verification Testing of OLI Systems Mixed Solvent Electrolyte Model for the Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 ) System to High Ionic Strength at 25°C

This technical report summarizes model verification results and summary statistics for 41 evaporite mineral solubility cases evaluated by Savannah River National Laboratory using OLI Systems’ aqueous electrolyte thermodynamic modeling software. The 41 verification cases containing a total of 60 solubility curves comprise mineral solubility data from low to high ionic strength at 25°C for the eight-component system Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 O as reported by Harvie et al. (1984). Thermodynamic calculations were executed using OLI Systems’ Stream Analyzer computation module within the OLI Studio software platform (Ver. 11.0, Rev. 11.0.1.9). The Mixed Solvent Electrolyte (MSE) thermodynamic framework was chosen for this investigation because of its superiority in modeling high ionic-strength inorganic salt solutions and actinide redox chemistry and solubility, both of which are relevant to the geological repository conditions at the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Mineral solubility data in various inorganic salt solutions were digitized and extracted from figures generated by Harvie et al. (1984). For each of the 60 solubility curves, a case-specific chemistry model and input file were generated in OLI Studio using OLI Stream Analyzer and the MSE (H 3 O + ion) public databank provided by OLI Systems. Model simulation results were exported to Microsoft Excel to calculate summary statistics and to generate graphs comparing the OLI model predictions to the solubility data. Summary statistics include residuals (model – data) and concordance (accuracy × precision, where precision is indicated by the Pearson correlation coefficient and accuracy accounts for bias and scale differential). Private databanks were not developed, and activity coefficient model regressions were not performed to improve OLI model fits to the data. Of the 41 model verification plots, 83% have a mean of the percent residuals less than or equal to 25%. Similarly, 75% display a concordance greater than or equal to 0.75. Only seven of the 41 verification plots fail to show good agreement between the model and data. Of these seven, three are relevant to the WIPP repository because they involve the Mg-OH-Cl-SO 4 -CO 3 aqueous system. The remaining four address salt solubilities at the pH extremes (strong acid and strong base). It should be noted that in two of the three Mg-OH-Cl-SO 4 -CO 3 system cases, the regressed Harvie et al. (1984) solubility curve also deviated from the data. Lack of agreement between the OLI model-predicted solubility curves and the data is attributable to one or more of the following: specific solid species are not included in the OLI MSE databank; there is significant variation among the different solubility datasets chosen by Harvie et al. (1984); the OLI MSE model’s thermodynamic parameters were determined using different solubility datasets; and the activity coefficient parameters for certain relevant ion-ion and ion-molecule pairs have not been optimized via data regression. Two recommendations for future work are to (1) evaluate solubility data for the Mg-OH-Cl-SO 4 -CO 3 system at high ionic strength and, if necessary, develop a private OLI MSE database that includes missing species and, where necessary, regressed standard state properties and interaction parameters; (2) perform similar verification testing of the OLI model for actinide solubility data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1989

Geochemical evolution of Cenozoic-Cretaceous magmatism and its relation to tectonic setting, southwestern Idaho, U.S.A

The relationships between Cretaceous to Neogene magmatism and the tectonic setting of southwestern and central Idaho are evaluated. An overview of the tectonics and geology of the northwestern U.S. is presented. Major element, trace element, and Sr, Pb, and Nd isotopic data for the region are used to place constraints on magma source characteristics, the manner in which the magmatic sources evolved through time, and the nature of interactions among mantle and crustal domains in response to changing tectonic environment.

Norman, Marc D.↗

NASA NTRSDate not supplied

Effect of Pressure and Oxidation State on Pnictogen Metal-Silicate Partitioning

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal- silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa. [1] Righter et al. (2018) GCA 232, 101-123 [2] Righter et al. (2019) MaPS 54, 1379-1394 [3] Steenstra et al. (2020) Icarus, 335, 113391 [4] Righter et al. (2020) Geochem. Persp. Let. 15, 44-49

Kelsey Prissel↗

DOE OSTI2026

Organo-mineral interactions in active layer and permafrost soils along aging Arctic landscapes

Rising temperatures are accelerating permafrost thaw, exposing large soil organic carbon (SOC) stocks to microbial decomposition with implications for global climate. Understanding how permafrost carbon is stored and protected through associations with minerals is critical for predicting its vulnerability to decomposition upon thaw. However, how landscape age, substrate chemistry, and soil depth influence mineral associations remain relatively unexplored. We investigated organo-mineral associations in active layer and permafrost soils across a landscape age and geochemical gradient on Alaska’s North Slope, spanning three glaciated (~11,500–125,000 years) and one unglaciated site. Using selective dissolution extractions, X-ray diffraction, and Mössbauer spectroscopy, we characterized minerals and their relationship with SOC. The three recently deglaciated sites had low soil pH that decreased with age and greater abundances of pyrophosphate- and oxalate-extractable Al and Fe, whereas the oldest unglaciated site exhibited near-neutral pH, greater pyrophosphate-extractable Ca, and distinct mineralogy. Across sites, SOC was positively associated with Al and Fe mineral phases, with stronger relationships in acidic soils. Pyrophosphate-extractable Ca also showed strong relationships with SOC at the acidic sites (up to ~10x greater), suggesting that Ca-mediated protection may operate beyond traditionally recognized high-pH soils. Permafrost soils showed depth-related changes in pH, SOC, and Fe mineralogy, suggesting chemically active, heterogeneous layers may shape mineral dynamics and associated carbon. Our results highlight how landscape age, parent material, and depth create distinct geochemical environments that govern mineral-organic associations. As thaw exposes soil to new conditions, these mineral-mediated protection mechanisms may be altered, potentially affecting the permafrost carbon-climate feedback.

Synthetic Biology↗

NASA NTRS1986

A mid-Archaean ophiolite complex, Barberton Mountain land

New field observations and structurally restored geologic sections through the southern part of 3.5-3.6 Ga Barberton greenstone belt show that its mafic to ultramafic rocks form a pseudostratigraphy comparable to that of Phanerozoic ophiolites; this ancient ophiolite is referred to as the Jamestown ophiolite complex. It consists of an intrusive-extrusive mafic-ultramafic section, underlain by a high-temperature tectono-metamorphic residual peridotitic base, and is capped by a chert-shale sequence which it locally intrudes. Geochemical data support an ophiolitic comparison. Fraction of high temperature melting PGE's 2500 C in the residual rocks suggest a lower mantle origin for the precursors of this crust. An oceanic rather than arc-related crustal section can be inferred from the absence of contemporaneous andesites. The entire simatic section has also been chemically altered during its formation by hyrothermal interaction with the Archean hydrosphere. The most primitive parent liquids, from which the extrusive sequence evolved, may have been picritic in character. Rocks with a komatiitic chemistry may have been derived during crystal accumulation from picrite-crystal mushes (predominantly olivine-clinopyroxene) and/or by metasomatism during one or more subsequent episodes of hydration-dehydration. The Jamestown ophiolite complex provides the oldest record with evidence for the formation of oceanic lithosphere at constructive tectonic boundaries.

Dewit, M. J.↗

DOE OSTI2025

Molecular Insights into Geochemical Reactions of Iron-Bearing Minerals: Implications for Hydrogen Geo-Storage

Here, this study investigates the reaction of hydrogen (H 2 ) with pyrite (FeS 2 ), focusing on how temperature and the presence of water influence the reaction pathways and kinetics. Utilizing computational molecular simulations and kinetic analyses, we explore the impact of these factors on the formation of hydrogen sulfide (H 2 S) and related species. First, grand canonical Monte Carlo/molecular dynamics (GCMC/MD) simulations reveal that physical H 2 adsorption occurs in distinct layers on the pyrite surface. In addition, increased temperatures reduce the absolute adsorption capacities. Reactive MD simulations demonstrate that H 2 interacts differently with pyrite under varying conditions. At 298 K, H 2 reacts with pyrite to form HS – , leading to the formation of HS – through covalent bonding with sulfur of pyrite. However, no H 2 S is produced at this temperature, suggesting that a kinetic barrier (i.e., activation energy) may prevent this reaction. At higher temperatures, H 2 S production significantly increases. The presence of water introduces additional complexity to the reaction mechanism. Unlike dry conditions, water enhances H 2 S generation, even at low temperatures. Water also facilitates the formation of additional products, such as SOH, indicating a more intricate chemical environment on the pyrite surface. Our findings identify the association of HS – ions to form H 2 S as the rate-limiting step, with temperature influencing this process. This finding suggests that while the presence of water can create a more dynamic reaction environment, the overall mechanisms leading to H 2 S formation remain consistent. These outcomes suggest the need for developing targeted strategies to manage and control H 2 S emissions within the context of underground hydrogen storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Energetics of hydroxylbastnäsite solid solutions, La 1-$\chi$ Nd $\chi$ CO 3 OH

Bastnäsites (LnCO 3 (F,OH)) are a group of common rare earth elements (REE)-bearing minerals and are one of the primary global sources of REE. Due to the chemical similarities among REE, bastnӓsites tend to occur as solid solutions instead of end members in REE containing ores. To better understand the processes and the mechanisms of formation of such deposits, it is essential to determine the thermodynamic properties of bastnӓsites, including hydroxylbastnӓsite (LnCO 3 OH) solid solutions. In this work, we performed detailed structural and calorimetric investigations on synthetic hexagonal La–Nd hydroxylbastnӓsite (La 1-$\chi$ NdCO 3 OH, $\chi$ = 0, 0.25, 0.5, 0.75, 1) solid solutions. X-ray diffraction confirms the crystal structure of the solid solution series in the $\ P$6 space group, and pair distribution function (PDF) analysis reveals local bonding environments characterized by three different types of 9-coordinated metal-oxygen polyhedra. Unit cell parameters of La1–xNdxCO3OH exhibit a nearly linear relation with the Nd content x, suggesting a random distribution of La and Nd in the structure. Their standard enthalpies of formation (Δ$\ H$° f ) were determined by high temperature oxide melt drop solution calorimetry, from which the enthalpies of mixing (Δ$\ H$ mix ) were derived. The Δ$\ H$ mix can be fitted by a regular solution model with an interaction parameter of 12.58 ± 0.16 kJ/mol, suggesting enthalpic metastability of La1–xNdxCO3OH relative to the two endmembers. Combining entropy and enthalpy, we further estimated the Gibbs free energies of mixing (Δ$\ G$ mix ) at relevant temperatures, revealing favorable temperatures under which the intermediate La 1-$\chi$ NdCO 3 OH phases can be stabilized. Such entropy-driven stabilization, as is consistent with our geochemical modeling results, may explain the enhancement of thermal stability of the solid solutions in nature. Additionally, the temperature range constrained from this study may be used to estimate the thermal history of REE bastnӓsite deposit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1997

Seventh Annual V. M. Goldschmidt Conference

Topics considered include: Subduction of the Aseismic Cocos Ridge Displaced Magma Sources Beneath the Cordillera de Talamanca, Costa Rica; Topography of Transition Zone Discontinuities: A Measure of 'Olivine' Content and Evidence for Deep Cratonic Roots; Uranium Enrichment in Lithospheric Mantle: Case Studies from French Massif Central; Rare-Earth-Element Anomalies in the Decollement Zone of the nankai Accretionary Prism, Japan: Evidence of Fluid Flow?; Rare Earth Elements in Japanese Mudrocks: The Influence of Provenance; The Evolution of Seawater Strontium Isotopes in the Last Hundred Million Years: Reinterpretation and Consequences for Erosion and Climate Models; From Pat to Tats: The Lead Isotope Legacy in the Studies of the Continental Crust-Upper Mantle System; Geochronology of the Jack Hills Detrital Zircons by Precise Uranium-Lead Isotope-Dilution Analysis of Crystal Fragments; Iridium in the Oceans; The Helium-Heat-Lead Paradox; Control of Distribution Patterns of Heavy Metals in Ganga Plain Around Kanpur Region, India, by Fluvial Geomorphic Domains; Geochemical and Isotopic Features of Ferrar Magmatic Provience (Victoria Land, Antarctica); Rare Earth Elements in Marine Fine-Grained Sediments from the Northwestern Portuguese Shelf (Atlantic); Aspects of Arc Fluxes; General Kinetic Model for Dolomite Precipitation Rate with Application to the Secular History of Seawater Composition; High-Precision Uranium-series Chronology from Speleothems; Trace-Element Modeling of Aqueous Fluid-Peridotite Interaction in the Mantle Wedge of Subduction Zones; Rainfall Variations in Southeastern Australia over the Last 500,000 Years from Speleothem Deposition; The Role of Water in High-Pressure Fluids; The Kinetic Conditions of Metamorphic Minearogenesis: Evidence from Minerals and Assemblages.

Source record↗

DOE OSTI2022

Assessment of chemo-mechanical impacts of CO 2 sequestration on the caprock formation in Farnsworth oil field, Texas

This study evaluates the chemo-mechanical influence of injected CO 2 on the Morrow B sandstone reservoir and the upper Morrow shale caprock utilizing data from the inverted 5-spot pattern centered on Well 13-10A within the Farnsworth unit (FWU). This study also seeks to evaluate the integrity of the caprock and the long-term CO 2 storage capability of the FWU. The inverted 5-spot pattern was extracted from the field-scale model and tuned with the available field observed data before the modeling work. Two coupled numerical simulation models were utilized to continue the study. First, a coupled hydro-geochemical model was constructed to simulate the dissolution and precipitation of formation minerals by modeling three intra-aqueous and six mineral reactions. In addition, a coupled hydro-geomechanical model was constructed and employed to study the effects of stress changes on the caprock’s porosity, permeability, and ground displacement. The Mohr–Coulomb circle and failure envelope were used to determine caprock failure. In this work, the CO 2 -WAG injection is followed by the historical field-observed strategy. During the forecasting period, a Water Alternating Gas (WAG) injection ratio of 1:3 was utilized with a baseline bottom-hole pressure constraint of 5500 psi for 20 years. A post-injection period of 1000 years was simulated to monitor the CO 2 plume and its effects on the CO 2 storage reservoir and caprock integrity. The simulation results indicated that the impacts of the geochemical reactions on the porosity of the caprock were insignificant as it experienced a decrease of about 0.0003% at the end of the 1000-year post-injection monitoring. On the other hand, the maximum stress-induced porosity change was about a 1.4% increase, resulting in about 4% in permeability change. It was estimated that about 3.3% of the sequestered CO 2 in the formation interacted with the caprock. Despite these petrophysical property alterations and CO 2 interactions in the caprock, the caprock still maintained its elastic properties and was determined to be far from its failure.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2020

Conceptual Model Update of Mercury Sources and Flux at Y-12 and Upper East Fork Poplar Creek, Oak Ridge,Tennessee

The interactions between the key processes that control the fate and transport of mercury (Hg) in the sediments, groundwater, and stream water within the Y-12 National Security Complex (Y-12) in Oak Ridge, Tennessee are complex, and many aspects are not well understood. In contaminated environments such as Y-12, conceptual models are frequently developed to aid in visualizing and understanding the dynamic nature of the hydrologic, geochemical, and physical environment. These conceptual models integrate data in an internally consistent manner to understand processes that control the fate and transport of contaminants. Over the past few decades of environmental investigation at Y-12, a number of conceptual models have been developed to identify and define various technical processes at various scales. The main purpose of the activities described in this report is to update the 2011 conceptual model for Upper East Fork Poplar Creek using the most recent Hg concentration and flux data and informed scientific interpretation. Emphasis was placed on improving the previous model by implementing a more detailed spatial and temporal approach to visualize transport pathways in the watershed and trends in flux and concentration over time, and to compare baseflow and stormflow system dynamics. Detailed descriptions of historical and current Hg sources and transport pathways are also provided for the east and west ends of the facility. This conceptual model will allow the US Department of Energy to evaluate past and present remedial activities and provide a strong technical basis for prioritizing and optimizing remedial responses in a cost-effective and efficient manner. Twenty years ago, Hg flux from Outfall (OF) 200 at the headwaters of East Fork Poplar Creek represented approximately 20% of the overall flux leaving Y-12. By the time of the 2011 conceptual model report, that percentage had increased to 70%–80%. Flux estimates compiled for this report using data from 2009 to 2018 show that OF200 accounted for roughly 60% of the flux leaving Y-12. The relative role of the four storm drain conduits to OF200 appeared similar to 2011, with OF163 being the greatest contributor to downstream flux. An increase in Hg concentrations and flux occurred throughout and downstream of west end storm drains in 2011 in response to a storm drain cleanout. Leading up to the 2011 storm drain cleanout, annual baseflow flux was higher at OF200A6 than at Station 17. From 2011 to 2018, the trend reversed with concentrations and flux being higher at Station 17 than at OF200A6. A spike in concentrations occurred in July 2018, potentially due to a one-time influx of Hg that occurred during COLEX decontamination and decommissioning activities at Y-12. This report includes recommendations for improving our conceptual understanding of Hg sources, transport pathways, and flux at Y-12. Important recommendations include further evaluation of transport pathways, concurrent measurement of Hg concentration and flux under baseflow and stormflow conditions at multiple sites, and research to understand the connections among periphyton and methylmercury concentration, bioavailability, and bioaccumulation. Ongoing facility decontamination and decommissioning efforts, site characterization, remedial actions, and research are facilitating the collection of new Hg data at Y-12. The conceptual model update provided herein takes advantage of the extensive recent Hg sampling to provide an updated assessment of Hg mass balance and support a refined understanding of Hg behavior at or near Y-12. This assessment should assist in future environmental management decisions and in mitigating the impacts of Hg on the surrounding environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

A genetic metasomatic link between eclogitic and peridotitic diamond inclusions

Diamond inclusions sample the otherwise inaccessible archive of Earth’s deep interior. The geochemical and petrological diversity of diamond inclusions reflects either pre-metasomatic upper mantle heterogeneity or metasomatism coeval with diamond formation. We focus on the origin of lithospheric garnet and clinopyroxene inclusions by simulating metasomatic reactions between eclogitic fluids and mantle peridotites at 5 GPa, 1000 °C, and across a range of redox conditions (logƒO 2 = -1 to -6 ΔFMQ). Our results demonstrate that fluid-rock interaction can result in the formation of eclogitic, websteritic, and peridotitic silicates from a single fluid during a single diamond-forming metasomatic event. Ergo, the petrogenesis of diamond and their inclusions can be syngenetic, and the petrological diversity of diamond inclusions can reflect metasomatism coeval with diamond formation. Furthermore, during the metasomatism, refractory peridotite can be converted to fertile websterite which could become a pyroxenitic mantle source for oceanic basalts.

58 GEOSCIENCES↗

DOE OSTI2022

Stability of mineral-organic matter associations under varying biogeochemical conditions

It is well-recognized and documented in the literature that a considerable fraction of the soil organic matter (SOM) is associated with Fe-oxide minerals. Recent studies have also showed that the persistence of various classes of SOM may depend on soil Fe mineralogy. Other laboratory studies with model mineral-associated organic matter (MAOM) moieties, which were primarily focused on ferrihydrite, either coated or coprecipitated with natural organic matter (NOM), have suggested that the mineral phase transformation and adsorption-desorption of SOM is rather complex but appears to be largely controlled by the C/Fe ratio of the MAOM moiety and geochemical conditions. It is also clear from multiple recent studies that the nature or type of SOM (microbial vs. plant-derived) adsorbed on mineral surfaces and the rate and extent of SOM biodegradation depend on the type of mineral, and/or metal ions, that are associated with the SOM. Modeling studies that are primarily centered on achieving a better understanding of the effect of mineral type on SOM interactions with minerals and degradation are also reported. These studies have improved the understanding of the nature and stability of MAOM in soils of varying types and under different conditions, positioning researchers to better predict the properties and stabilities of organo-mineral associations in soils.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Understanding Contaminant Migration within a Dynamic River Corridor through Field Experiments and Reactive Transport Modeling

The behavior of a persistent uranium plume within an extended river corridor at the DOE Hanford site is dominantly controlled by river stage fluctuations in the adjacent Columbia River. The plume behavior is further complicated by substantial heterogeneity in physical and geochemical properties of the host aquifer sediments. Multi-scale field and laboratory experiments and reactive transport modeling were integrated to understand the complex plume behavior influenced by highly variable hydrologic and geochemical conditions in time and space. In this paper, we (1) describe multiple data sets from field-scale uranium adsorption and desorption experiments performed at our experimental well-field, (2) develop a reactive transport model that incorporates hydrologic and geochemical heterogeneities characterized from multi-scale and multi-type datasets and a surface complexation reaction network based on laboratory studies, and (3) compare the modeling and observation results to provide insights on how to refine the conceptual model and reduce prediction uncertainties. The experimental results revealed significant spatial variability in uranium adsorption/desorption behavior, while modeling demonstrated that ambient hydrologic and geochemical conditions and heterogeneities in sediment physical and chemical properties both contributed to complex plume behavior and its persistence. This research underscores the great challenges in adequately characterizing this type of site to model the reactive transport processes over scales of 10 m or more. Our analysis provides important insights into the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by dynamic surface water and groundwater interactions.

Chen, Xingyuan↗