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All sourcesNASA NTRSDOE OSTI
NASA NTRS2020

Mineralogy and Geochemistry of Sedimentary Rocks and Eolian Sediments in Gale Crater, Mars: A Review After Six Earth Years of Exploration with Curiosity

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity was sent to Gale crater to study a sequence of ∼3.5 Ga old sedimentary rocks that, based on orbital visible and near- to short-wave infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence in the lower slopes of Mount Sharp in Gale crater preserves a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate, based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with instruments to examine the sedimentology and identify compositional changes in the stratigraphy. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer. CheMin measures loose sediment samples scooped from the surface and drilled rock powders, and the XRD provides quantitative mineralogy to a detection limit of ∼1 wt.% for crystalline phases. Curiosity has traversed>20 km since landing and has primarily been exploring an ancient lake environment fed by streams and groundwater. Of the 19 drilled rock samples analyzed by CheMin as of sol 2300 (January 2019), 15 are from fluvio-lacustrine deposits that comprise the Bradbury and Murray formations. Most of these samples were drilled from units that did not have a clear mineralogical signature from orbit. Results from CheMin demonstrate an astounding diversity in the mineralogy of these rocks that signifies geochemical variations in source rocks, transportation mechanisms, and depositional and diagenetic fluids. Most detrital igneous minerals are basaltic, but the discovery in a few samples of abundant silicate minerals that usually crystallize from evolved magmas on Earth remains enigmatic. Trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH in lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions in the lake waters themselves and/or in diagenetic fluids. Perhaps one of the biggest mysteries revealed by CheMin is the high abundance of X-ray amorphous materials (15–73 wt.%) in all samples drilled or scooped to date. CheMin has analyzed three modern eolian sands, which have helped constrain sediment transport and mineral segregation across the active Bagnold Dune Field. Ancient eolian sandstones drilled from the Stimson formation differ from modern eolian sands in that they contain abundant magnetite but no olivine, suggesting that diagenetic processes led to the alteration of olivine to release Fe(II) and precipitate magnetite. Fracture-associated halos in the Stimson and the Murray formations are evidence for complex aqueous processes long after the streams and lakes vanished from Gale crater. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

E.B. Rampe↗
DOE OSTI2020

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Sticky roots--implications of widespread, cryptic, viral infection of plants in natural and managed ecosystems for soil carbon processing in the rhizosphere

Plants strongly influence soil properties through rhizodeposition, in which exudates diffuse from roots, additional secretions are actively released, and root cells are sloughed into the soil. This contribution by plants of carbon compounds belowground is at the core of soil health, water holding capacity, and the soil carbon storage that pulls carbon dioxide out of the atmosphere. Once in soil, organic matter can bind with minerals such as iron hydroxides, where it can be protected from microbial attack for millenia, preserving very large terrestrial soil carbon pools. However, those same compounds contributed by roots to soil may also destabilize the long-term protective associations of SOM with minerals, making that soil organic matter (SOM) more vulnerable to microbial attack and decomposition. Plant roots thus influence both the buildup and breakdown of soil carbon pools. DOE’s E3SM Land Model (ELM) includes a representation of soil carbon storage on minerals, but the potential vulnerability of SOM–mineral associations to effects of rhizodeposition is not yet represented in ELM. To begin testing for this effect of rhizodeposition on soil carbon storage and decomposition, we worked to develop a novel approach during this TES Exploratory project DE-SC0019142 – we harnessed the power of plant viral infection. We examined whether plant virus infection can serve as a tool to intensify rhizodeposition at the root surface, and therefore possibly intensify mobilization of SOM from minerals making it visible to our analytical techniques. Viral infection is widespread in terrestrial ecosystems; 25-70% of plants have virus infection, yet the influence of such infection on root traits and terrestrial soil carbon dynamics remains largely unexplored. We used two plant hosts: the annual Avena sativa (oats) and the genetically tractable, model grass Brachypodium distachyon. These grasses were infected with the broad host range virus Barley Yellow Dwarf Virus (BYDV) via aphids (Rhopalosiphum padi). BYDV infects at least 150 grass species in agricultural and natural ecosystems, and in previous experiments, oats infected with BYDV had roots that were very sticky to the touch, strongly suggesting that infection altered rhizodeposition. We developed this new experimental approach mostly in a one virus (Barley Yellow Dwarf Virus)–one plant (Avena sativa) system. (Several effects of infection in a Brachypodium-BYDV system were similar in nature to effects on Avena sativa, but were more variable.) In the BYDV-Avena system, we developed protocols for consistently infecting target plants (and avoiding infection of control plants) using aphid caging on leaves. We measured that infected plants exhibited reduced photosynthesis, plant (including root) biomass, and root:shoot ratio, as well as simplified root system architecture. We established procedures for sampling the organic compounds carried specifically in phloem (vascular tissue) of leaves and roots, using aphid stylectomy. We used FTICR-MS, Orbitrap GC-MS, and LC-MS/MS to analyze organic compounds in phloem, liquid around roots of plants grown hydroponically, and pore water around roots in soil, and found differences in the compounds in solution bathing roots when infected and uninfected plants were grown hydroponically. Finally, we synthesized isotopically-labeled mineral–organic matter (MAOM) associations in the lab and developed assays using them in solution and in soil. Assays quantified the extent and rate of mineralization of labeled MAOM that was mobilized by functionally distinct rhizodeposits and then attacked by microbes. Two mechanisms for MAOM mobilization emerged, with distinct dynamics. During “direct” mobilization, rhizodeposits such as the strong ligand oxalic acid could drive rapid dissolution of minerals, mobilizing MAOM. During “indirect” mobilization, rhizodeposits such as the simple sugar glucose did not attack minerals directly but instead intensified microbial activity, which led to mobilization via changes in e.g. pH, Eh, and microbial metabolite production (Li et al. 2021). Mechanistic understanding derived from these data and our ongoing experiments using these techniques will inform future development of ELM. Plant roots not only contribute newly fixed organic compounds to soils, but also root activities can drive mineralization of the carbon and nutrients mobilized off minerals via “indirect” or “direct” mechanisms. Using viral infection as a new tool, ongoing combined experimentation and modeling will explore the strength and larger-scale significance of the cascade of processes from rhizodeposition to MAOM mobilization for soil carbon storage and nutrient cycling in terrestrial ecosystems. And if viral infection leads quite generally to “sticky roots”, our perception of the potential importance of prevalent virus infection in terrestrial landscapes will be transformed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Microbial communities and biogeochemical functioning across peatlands in the Athabasca Oil Sands region of Canada: Implications for reclamation and management

Abstract Peatlands play an important role in global biogeochemical cycles and are essential for multiple ecosystem functions. Understanding the environmental drivers of microbial functioning and community structure can provide insights to enable effective and evidence‐based management. However, it remains largely unknown how microbial diversity contributes to the functioning of belowground processes. Addressing this gap in knowledge will provide a better understanding of microbial‐mediated processes in peatlands that are undergoing restoration or reclamation. This study assessed the changes in microbial community diversity and structure as well as soil function by measuring microbial respiration on a range of substrates from three natural fen types found in the Athabasca Oil Sands region of Alberta, Canada (a poor fen, a hypersaline fen, and a tree‐rich fen) and a nearby constructed fen undergoing reclamation following open pit mining. Overall, substrate induced respiration was significantly higher in the constructed fen. Alpha diversity of fungi and prokaryotes was highest in the tree‐rich fen, and the composition of microbial communities was significantly different between fens. Both fungal and prokaryotic communities were strongly related to pore water pH and temperature, with plant richness also contributing to the shape of fungal communities. In summary, microbial community structure reflects the underlying differences in soil condition across different fens but plays essential roles in the ecological functions of soil. These findings provide a new outlook for the management of peatlands undergoing post‐mining reclamation. Future research on peatland reclamation should consider the dynamic interaction between communities and ecosystem functionality, for which this study forms a useful baseline.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Seasonal Sulfur Redox Cycling in Two Constructed Wetlands with Insight on How They Age

Long-term metal remediation in wetland treatment systems (WTSs) involves facilitating dissimilatory sulfate reduction to produce sulfide and mineralize metals in deep sediments. We evaluated seasonal sulfur cycling in two constructed wetlands (Maintained WTS constructed in 2007, and the Unmaintained WTS constructed in 2000) on the Savannah River Site in Aiken, South Carolina, USA. Significant interactions in sulfide concentration were observed between sediment depth, season, and wetland (F = 4.64, df = 11, P = 3.28 × 10 − 5). In the Maintained WTS, dissimilatory sulfate reduction dominated the surface sediments during the warm season (0–2 cm depth, t=-2.66, P = 9.70 × 10 − 3), unlike the Unmaintained system. Sulfate concentrations in pore waters increased in the warm season (F = 7.84, df = 1, P = 6.50 × 10 − 3), contrary to expectations. Sulfur limitation in the Unmaintained WTS during the warm season correlated with increased sulfur assimilation in giant bulrush. Lower sulfide concentrations in surface sediments of the Unmaintained WTS illustrated aging effects. The Maintained WTS shows potential for managing erosion, pH reduction, and sulfur limitation observed in the older Unmaintained WTS.

Biogeochemistry↗
DOE OSTI2020

A model for discrete fracture-clay rock interaction incorporating electrostatic effects on transport

Abstract A model based on the code CrunchClay is presented for a fracture-clay matrix system that takes electrostatic effects on transport into account. The electrostatic effects on transport include those associated with the development of a diffusion potential as captured by the Nernst-Planck equation, and the formation of a diffuse layer bordering negatively charged clay particles within which partial anion exclusion occurs. The model is based on a dual continuum formulation that accounts for diffuse layer and bulk water pore space, providing a more flexible framework than is found in the classical mean electrostatic potential models. The diffuse layer model is obtained by volume averaging ion concentrations in the Poisson-Boltzmann equation, but also includes the treatment of longitudinal transport within this continuum. The calculation of transport within the bulk and diffuse layer porosity is based on a new formulation for the Nernst-Planck equation that considers averaging of diffusion coefficients and accumulation factors at grid cell interfaces. Equations for function residuals and the associated Jacobian matrix are presented such that the system of nonlinear differential-algebraic equations can be solved with Newton’s method. As an example, we consider a 2D system with a single discrete fracture within which flow and advective transport occurs that is coupled to diffusion in the clay-rich matrix. The simulation results demonstrate the lack of retardation for anions (e.g., 36 Cl − ) of the contaminant plume within the fracture flow system because they are largely excluded from the charged clay rock, while the migration of cations (e.g., 90 Sr ++ ) is more strongly attenuated. The diffusive loss of divalent cations in particular from the fracture is accentuated by their accumulation in the diffuse layer within the clay-rich matrix.

58 GEOSCIENCES↗
DOE OSTI2021

Preferred orientation of calcium aluminosilicate hydrate compacts: Implications for creep and indentation

Nano/micro-indentation has been extensively used to examine elastic properties and creep of cement-based materials. However, there have been inconsistencies in the measured elastic moduli and debate on the creep mechanism of calcium (alumino) silicate hydrates (C-(A-)S-H). To bring new insights, we examined the deviatoric stress-induced preferred orientation of calcium aluminosilicate hydrate (C-A-S-H), portlandite, and ettringite compacts, using synchrotron-based X-ray diffraction. Intense preferred orientations were observed in C-A-S-H compacts, and the c-axis of unit cells is highly aligned with the compression direction; weaker c-axis related fiber-type texture formed in portlandite and ettringite. Higher humidity, greater compacting pressure, and/or increased duration of the pressure intensified the C-A-S-H preferred orientation, which is facilitated by gel-pore water lubrication. This pressure-induced time-dependent preferential re-orientation of crystallites can contribute to the creep of cement-based materials, and it may cause overrepresentation of the soft c-axis of C-(A-)S-H unit-cell in nanoindentation experiments and underestimation of Young's modulus.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Modelling the development of capillary pressure in freshly 3D-printed concrete elements

3D concrete printing is a promising technology recently developed to automate construction. Since no formwork is used in this technology to support and protect fresh concrete, there are two aspects which considerably accelerate the development of capillary pressure in 3D-printed concrete in comparison to conventionally placed concrete: i) high stiffness of 3D-printed needed to provide sufficient buildability, and ii) very early and fast evaporation of pore water. Accelerated development of capillary pressure may lead to severe plastic shrinkage cracking in 3D-printed elements and, hence, need to be mitigated. This investigation aims at providing a poromechanical model for capillary pressure development in 3D-printed elements. To simulate the development of capillary pressure and plastic shrinkage, environmental factors, material properties, and element geometry need to be considered as a whole. The model inputs – coefficient of permeability, static bulk modulus, air entry pressure and chemical shrinkage rate – were determined experimentally. The model was validated for two fine-grained concretes. Both 3D-printed materials yielded faster capillary pressure increase in comparison to cast concrete, while partial substitution of cement with silica fume further accelerated the capillary pressure development. Furthermore, due to the lower permeability of the mixture containing silica fume, the gradient of capillary pressure between 3D-printed layers increased, as did the gradient of plastic shrinkage.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Sorption and electrokinetic properties of ASR product and C-S-H: A comparative modelling study

Alkali-silica reaction (ASR) is one of the most important concrete durability issues worldwide. ASR products formed at high temperature have a structure similar to the natural mineral shlykovite. Reactive Grand Canonical Simulations were used to investigate sorption of K{sup +}, Cl{sup −} and Ca{sup 2+} on C-S-H and ASR products at different pH (10.0 to 13.0) and pore water chemistry. Divalent ions can overcompensate for the negative surface charge, in particular for C-S-H, which leads to a co-adsorption of negative species such as Cl{sup −}. At high K/Ca in solution, monovalent K{sup +} can desorb calcium from C-S-H and shlykovite surface. The calculated Ca/K partition coefficient shows a higher affinity of ASR product for K{sup +}, while C-S-H favours Ca{sup 2+}. The uptake of K{sup +} by ASR products lowers the alkali concentration in the solution and could thus slow down the rate of ASR.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The large decline in carbonate $\delta^{238}$U from a PETM section at Tingri (South Tibet) was driven by local sea-level changes, not global oceanic anoxia

Uranium isotope compositions (δ 238 ) and Th/U in carbonates are being explored as paleoredox proxies to study global oceanic anoxia. However, the impact of changes to local depositional environments that might cause a decline in δ 238 U and an increase in Th/U has not been thoroughly investigated. Here we report a decline in δ 238 U (from +0.1 to -0.3‰) and an increase in Th/U from shallow-marine carbonates during the Paleocene-Eocene thermal maximum at Tingri (south Tibet). Changes of δ 238 U and Th/U are not fully coupled. The decline in δ 238 U coincided with a local sea-level fall, whereas the increase in Th/U occurred mainly during a sea-level rise. The decline in δ 238 U likely results from changes in redox conditions of pore waters and in primary carbonate mineralogy. The increase in Th/U is ascribed to reduced authigenic U(IV) accumulation. Here our results suggest that changes in local depositional environments can cause behavior of δ 238 U and Th/U resembling that induced by expanded global oceanic anoxia. This finding calls for caution to consider local factors before applying δ 238 U and Th/U as global paleoredox proxies.

58 GEOSCIENCES↗
DOE OSTI2022

Mineralogical, magnetic and geochemical data constrain the pathways and extent of weathering of mineralized sedimentary rocks

The oxidative weathering of sulfidic rock can profoundly impact watersheds through the resulting export of acidity and metals. Weathering leaves a record of mineral transformation, particularly involving minor redox-sensitive phases, that can inform the development of conceptual and quantitative models. In sulfidic sedimentary rocks, however, variations in depositional history, diagenesis and mineralization can change or overprint the distributions of these trace minerals, complicating the interpretation of weathering signatures. Here we show that a combination of bulk mineralogical and geochemical techniques, micrometer-resolution X-ray fluorescence microprobe analysis and rock magnetic measurements, applied to drill core samples and single weathered fractures, can provide data that enable the development of a geochemically consistent weathering model. This work focused on one watershed in the Upper Colorado River Basin sitting within the Mesaverde Formation, a sedimentary sandstone bedrock with disseminated sulfide minerals, including pyrite and sphalerite, that were introduced during diagenesis and subsequent magmatic-hydrothermal mineralization. Combined analytical methods revealed the pathways of iron (Fe), carbonate and silicate mineral weathering and showed how pH controls element retention or release from the actively weathering fractured sandstone. Drill core logging, whole rock X-ray diffraction, and geochemical measurements document the progression from unweathered rock at depth to weathered rock at the surface. X-ray microprobe analyses of a 1-cm size weathering profile along a fracture surface are consistent with the mobilization of Fe(II) and Fe(III) into acidic pore water from the dissolution of primary pyrite, Fe-sphalerite, chlorite, and minor siderite and pyrrhotite. These reactions are followed by the precipitation of secondary minerals such as of goethite and jarosite, a Fe-(oxyhydr)oxide and hydrous Fe(III) sulfate, respectively. Microscale analyses also helped explain the weathering reactions responsible for the mineralogical transformations observed in the top and most weathered section of the drill core. For example, dissolution of feldspar and chlorite neutralizes the acidity generated by Fe and sulfide mineral oxidation, oversaturating the solution in both Fe-oxides. The combination of X-ray spectromicroscopy and magnetic measurements show that the Fe(III) product is goethite, mainly present either as a coating on fracture surfaces in the actively weathering region of the core or more homogeneously contained within the unconsolidated regolith at the top of the core. Low-temperature magnetic data reveal the presence of ferromagnetic Fe-sulfide pyrrhotite that, although it occurs at trace concentrations, could provide a qualitative proxy for unweathered sulfide minerals because the loss of pyrrhotite is associated with the onset of oxidative weathering. Pyrrhotite loss and goethite formation are detectable through room-temperature magnetic coercivity changes, suggesting that rock magnetic measurements can determine weathering intensity in rock samples at many scales. In conclusion, this work contributes evidence that the weathering of sulfidic sedimentary rocks follows a geochemical pattern in which the abundance of sulfide minerals controls the generation of acidity and dissolved elements, and the pH-dependent mobility of these elements controls their export to the ground- and surface-water.

58 GEOSCIENCES↗
DOE OSTI2021

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment

In situ remediation applications of ammonia (NH 3 ) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH 3 treatment. In these batch studies, phyllosilicate minerals (illite and montmorillonite) were exposed to NH 3 gas with subsequent aeration to simulate in situ remediation. Following treatments, solids were characterized using a variety of techniques, including X-ray diffraction, N 2 adsorption-desorption analysis for surface area, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and microscopy methods to investigate physicochemical transformations. The results of this study indicate that, at high pH, the clays are altered as observed by differences in morphology and particle size via microscopy. However, the two clays interact differently with NH 3 . While montmorillonite interlayers collapsed due to intercalation, illite layers were unaffected as confirmed by FTIR analysis. Further, structural changes in silicate ([SiO 4 ] n- ) and aluminol (Al-OH) groups were identified by NMR and FTIR. This research showed that mineral alteration processes occur during and after NH 3 gas treatment which may be used to remove radionuclides from the aqueous phase through sorption, co-precipitation, and coating with secondary phyllosilicate alteration products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Microbiological and geochemical characterization of As-bearing tailings and underlying sediments

Over the past 100 years, extensive oxidation of As-bearing sulfide-rich tailings from the abandoned Long Lake Gold Mine (Canada) has resulted in the formation of acid mine drainage (pH 2.0-3.9) containing high concentrations of dissolved As (similar to 400 mg L -1 ), SO 4 2- , Fe and other metals. Dissolved As is predominantly present as As(III), with increased As(V) near the tailings surface. Pore-gas O 2 is depleted to < 1 vol% in the upper 30-80 cm of the tailings profile. The primary sulfides, pyrite and arsenopyrite, are highly oxidized in the upper portions of the tailings. Elevated proportions of sulfide-oxidizing prokaryotes are present in this zone (mean 32.3% of total reads). The tailings are underlain by sediments rich in organic C. Enrichment in δ 34 S-SO 4 in pore-water samples in the organic C-rich zone is consistent with dissimilatory sulfate reduction. Synchrotron-based spectroscopy indicates an abundance of ferric arsenate phases near the impoundment surface and the presence of secondary arsenic sulfides in the organic-C beneath the tailings. The persistence of elevated As concentrations beneath the tailings indicates precipitation of secondary As sulfides is not sufficient to completely remove dissolved As. The oxidation of sulfides and release of As is expected to continue for decades. The findings will inform future remediation efforts and provide a foundation for the long-term monitoring of the effectiveness of the remediation program.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Comparative uptake, translocation, and plant mediated transport of Tc-99, Cs-133, Np-237, and U-238 in Savannah River Site soil columns for the grass species Andropogon virginicus

Here, this study examines the ability of the grass species Andropogon virginicus to alter the subsurface transport and redistribution of a suite of radionuclides ( 99 Tc, 133 Cs (stable analog for 135 Cs and 137 Cs), 237 Np, 238 U) with varying chemical behaviors in a Savannah River Site soil via the use of vegetated and unvegetated soil columns. After an acclimation period, a small volume of solution containing all radionuclides was introduced into the columns via Rhizon© pore water sampling tubes. Plants were grown for an additional 4 weeks before shoots were harvested, and columns were prepared for sampling. Plant presence led to decreased radionuclide release from the columns, mainly due to radionuclide specific combinations of system hydrology differences resulting from plant transpiration as well as plant uptake. For the most mobile radionuclides, 99 Tc followed by 237 Np, plant presence resulted in significantly different soil concentration profiles between vegetated and unvegetated columns, including notable upward migration for 237 Np in columns with plants. Additionally, plant uptake of 99 Tc was the greatest of all the radionuclides, with plant tissues containing an average of 44 % of the 99 Tc, while plant uptake only accounted for <2 % of 237 Np and <0.5 % of 133 Cs and 238 U in the system. Although overall plant uptake of 133 Cs and 238 U were similar, the majority of 133 Cs taken up by plants was associated with 133 Cs already available in the aqueous phase while 238 U uptake was mainly associated with the solid phase, meaning that plant activity resulted in a fraction of the native 238 U being mobilized and thus, made available for plant uptake. Overall, this study quantified the influence of several plant-mediated physical and biogeochemical factors that have significant influence on radionuclide mobility and transport in this complex system which can be further utilized in future system or site-specific environmental transport and risk assessment models.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Resolving dynamic mineral-organic interactions in the rhizosphere by combining in-situ microsensors with plant-soil reactive transport modeling

Associations between minerals and organic matter represent one of the most important carbon storage mechanisms in soils. Plant roots are major sources of soil carbon, and resolving the dynamics and dominance of microbial consumption versus mineral sorption of root-derived carbon is critical to understanding soil carbon storage. Here we integrate in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the fate of dissolved organic carbon (DOC) in the rhizosphere, particularly its microbial consumption and interaction with Fe oxide minerals. Over several days, a microdialysis probe sampling pore water at the root-soil interface of growing Vicia faba roots in live soil, revealed clear diel patterns of DOC concentration. Daytime DOC spikes coincided with peaks in leaf-level photosynthesis rates and were accompanied by declining redox potential and dissolved oxygen as well as increasing pH in the rhizosphere. Incorporating microsensor data into our modeling framework showed that the measured rapid loss of DOC after each mid-day spike could not be explained by consumption via aerobic respiration, nor via anaerobic respiration dominated by Fe oxide reduction. Rather, in the model, a large fraction of rhizosphere DOC was rapidly immobilized each day by adsorption to Fe oxides. Further, modeled microbial Fe reduction (fueled by DOC) did not mobilize significant organic carbon from Fe oxides during the day. Instead, the model predicted equilibrium desorption of organic carbon from Fe oxides at night. This new mechanistic modeling framework, which couples aboveground plant physiological measurements with non-destructive high-resolution monitoring of rhizosphere processes, has great potential for exploring the dynamics and balance of the various microbial reactions and mineral interactions controlling carbon transformations and storage in soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hydrobiological Mechanism Controlling the Synergistic Effects of Unsaturated Flow and Soil Organic Matter on the Degradation of Emerging Organic Contaminants in Soils

We report hydrology is a key factor influencing microbial degradation of emerging organic contaminants (EOCs) in soils, but the underlying mechanisms are not clear. In this study, biotic and abiotic column experiments were performed to investigate the removal and degradation of five EOCs in soils with different soil organic matter (SOM) contents under saturated and unsaturated flow conditions. In biotic experiments, 54–90% of bisphenol A (BPA) and 9–22% of ibuprofen (IBU) were removed from the aqueous phase of saturated columns due to adsorption and biodegradation. The biodegradation removed 26–65% of BPA and 1–22% of IBU. Decreasing soil pore water saturation from 100 to 80% increased BPA removal to 97–100% and IBU removal to 42–43% due to increased biodegradation (67–81% for BPA and 36–39% for IBU). No significant removal of BPA and IBU was observed in SOM-removed soils under saturated and unsaturated flow conditions. The desaturation did not influence sorptive losses of BPA (< 27%) and IBU (< 7%), suggesting their negligible adsorption at air–water interfaces but increased biodegradation of BPA and IBU sorbed at SOM–water interfaces. The study shows that soil drying and SOM can synergistically degrade BPA and IBU but have no effect on recalcitrant carbamazepine, tetracycline, and ciprofloxacin.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Impact of natural organic matter on plutonium vadose zone migration from an NH4Pu(V)O2CO3(s) source

Large amounts of plutonium produced at the Savannah River Site (SRS) in the latter half of the last century led to the release of plutonium to the subsurface. Low-level waste containing plutonium has also been disposed of in the SRS vadose zone. The mobility and risk posed by these plutonium sources is not well understood, in part, because of unknown interactions of the various mobile plutonium species with natural organic matter (NOM). This study investigated the influence of NOM on the behavior of plutonium(V) in the vadose zone through a combination of field lysimeter and laboratory studies. Well-defined solid sources of NH4PuVO2CO3(s) placed in 5-L lysimeters containing vadose zone soils NOM-amended or unamended were exposed to natural SRS meteorological conditions for three years. These lysimeters were removed from the field and analyzed using wet chemistry methods and X-ray absorption spectroscopy (XAS). Plutonium desorption from soils recovered from the lysimeters and laboratory batch sorption experiments using Pu-free soils both indicated that surface mediated reduction of Pu(V) to Pu(IV) was influencing Pu sorption behavior. For both lysimeters (amended and unamended with NOM), Pu migrated slowly through the lysimeter core, with > 95% of the Pu remaining within 2 cm of the source. However, without the NOM amendments, Pu was transported significantly farther than in the presence of NOM. Thus, the presence of NOM appeared to decrease the mobility. Working hypotheses to explain this behavior are that 1) formation of ternary surface-NOM-Pu complexes enhanced Pu sorption affinity causing less mobility and/or 2) formation of these ternary surface-NOM-Pu complexes prevented reoxidaiton of Pu(IV) to more mobile Pu(V) in the pore water.

plutonium, organic matter↗
DOE OSTI2021

Cutover Peat Limits Methane Production Causing Low Emission at a Restored Peatland

Abstract Peatland degradation due to human activities is contributing to rising atmospheric CO 2 levels. Restoring the carbon (C) sink function in degraded peatlands and preventing further stored C losses is a key climate mitigation strategy, given the global scale of peatland disturbance. Active restoration involving a combination of rewetting and vegetation reestablishment at a post‐extraction peatland in Canada has been shown to successfully re‐establish net CO 2 uptake rates similar to undisturbed peatlands within a decade or two. However, lower than expected CH 4 emissions suggest recovery of belowground C cycling processes may lag behind the recovery of the surface net flux. Using closed chamber measurements over a warm season, we determined that restored Sphagnum , which covers two thirds of the site, was a null source of CH 4 . Emissions from the restored site were primarily attributed to vascular plant substrate inputs, measured as acetate, and plant‐mediated transport. The C isotopic fractionation factor for CH 4 and CO 2 in the pore water from the restored former peat field suggested reduced hydrogenotrophic CH 4 production deeper in the cutover peat profile (0.8 m depth). In contrast, isotopic fractionation in the former drainage ditches showed a balance of acetoclastic and hydrogenotrophic methanogenesis deeper in the profile, indicative of some bulk peat C turnover. This study suggests that the legacy of substrate quality in the cutover peat can reduce the climate warming impact of newly restored peatlands through a reduction in CH 4 production and thus emission.

Nugent, Kelly A.↗