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NASA NTRS1999

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗
DOE OSTI2020

Investigating Secondary Aerosol Processes in the Amazon through Molecular-level Characterization of Semi-Volatile Organics

In areas where biogenic emissions are oxidized in the presence of anthropogenic pollutants, it has become increasingly apparent that secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs) is substantially enhanced. The Amazon forest is the dominant source of BVOCs globally, and the forest is rapidly being converted to urban and agricultural uses. We participated in a collaborative field study located in the Amazon region around Manaus, Brazil, in 2014 (Green Ocean Amazon; GoAmazon). This study was designed to comprehensively examine how BVOC emissions (specifically, the most highly emitted non-methane hydrocarbon, isoprene, and lesser studied sesquiterpenes) and their interaction with anthropogenic pollution (i.e., nitrogen oxides, sulfur dioxide, and black carbon) alter the atmosphere’s oxidative capacity, influence secondary aerosol formation, atmospheric composition and, ultimately, affect the earth’s radiation balance and climate. We provide the first hourly, in-situ measurement of 30 sesquiterpenes and 4 diterpenes, roughly estimating that sesquiterpene oxidation contributes to 10-14% of ozone reactive loss by terpenes and at least 0.4–5% (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. We also provide new perspectives on sulfate, NO x , and particle acidity influencing isoprene-derived SOA, comparing the central Amazon environment with Southeastern U.S.A. summer, representing clean to polluted conditions, respectively. We find that summed concentrations of isoprene-derived SOA tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 μg m -3 reduction in sulfate corresponds with at least ~0.5 μg m -3 reduction in isoprene-derived SOA. We also find that SOA mass derived from isoprene oxidation in the presence of NO x is primarily comprised of aerosol sulfate bound with isoprene oxidation products (i.e. organosulfates), ~97% in the Amazon and ~55% in the Southeastern U.S. We infer under natural conditions in high isoprene emission regions, preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought as representative of anthropogenic influence. We further report the first field observations showing that particle acidity impacts the distribution of isoprene oxidation tracers in the gas and particle phases, providing physicochemical insight into isoprene SOA formation chemistry. Coupled with other co-located measurements by the DOE Atmospheric Radiation Measurement (ARM) team and collaborating PIs at our measurement site (called T3), on the G1 aircraft, and at additional field sites (T0, T1, T2) this data set has been used to understand emission, oxidation, and particle formation pathways at the molecular level, to elucidate how these pathways change when influenced by anthropogenic sources, and to evaluate their importance for the atmospheric budget of aerosols and the earth’s radiation balance on regional scales. Recommendations: Further constraint of the role of sesquiterpenes on ozone (O 3 ) reactivity and SOA formation is limited by the availability of authentic standards and synthesized compounds of sesquiterpenes and their oxidation products. Future research efforts should focus on making such standards available via custom synthesis to allow for accurate quantification and focused oxidation experiments that will fully elucidate the chemistry of these compounds in the atmosphere. Further, reductions in aerosol sulfate (via SO 2 emissions control) continues to be one of the most effective methods to reduce SOA formation from isoprene, but the concerted role of ammonia (NH 3 ) gas emissions from (agricultural) industry and other sources requires more investigation to better understand the role of aerosol acidity in SOA formation and potential controls. As GoAmazon particles can be more acidic compared to areas with greater anthropogenic NH 3 emissions, this promotes relatively greater organosulfate (OS) formation from isoprene even in the presence of NO x . Because OS and inorganic sulfate differ in water uptake properties, this implies preindustrial aerosol sulfate (albeit less abundant) may have been less reflective than current earth system models assume. Further research should investigate the radiative impacts of organic vs inorganic sulfate in aerosols to improve model representation. Finally, future work (currently underway) should include constraint of the contributions of monoterpene (C 10 H 16 ) BVOCs and biomass burning VOCs as precursors to SOA formation in the region as well as their impacts on radiative forcing in the climate system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Methane dissociation on Pt(111): Searching for a specific reaction parameter density functional

The theoretical description of methane dissociating on metal surfaces is a current frontier in the field of gas-surface dynamics. Dynamical models that aim at achieving a highly accurate description of this reaction rely on potential energy surfaces based on density functional theory calculations at the generalized gradient approximation. We focus here on the effect that the exchange-correlation functional has on the reactivity of methane on a metal surface, using CHD{sub 3} + Pt(111) as a test case. We present new ab initio molecular dynamics calculations performed with various density functionals, looking also at functionals that account for the van der Waals (vdW) interaction. While searching for a semi-empirical specific reaction parameter density functional for this system, we find that the use of a weighted average of the PBE and the RPBE exchange functionals together with a vdW-corrected correlation functional leads to an improved agreement with quantum state-resolved experimental data for the sticking probability, compared to previous PBE calculations. With this semi-empirical density functional, we have also investigated the surface temperature dependence of the methane dissociation reaction and the influence of the rotational alignment on the reactivity, and compared our results with experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

Soot and Sulfuric Acid from Aircraft: Is There Enough to Cause Detrimental Environmental E-kCTSs?

Aerosol from aircraft can affect the environment in three ways: First, soot aerosol has been implicated to cause Icing-tern ozone depletion at mid-latitudes in the lower stratosphere at a rate of approx. 5% per decade. This effect is in addition and unrelated to the polar ozone holes which are strongly influenced by heterogeneous chemistry on polar stratospheric clouds. Second, the most obvious effect of jet aircraft is the formation of visible contrails in the upper troposphere. The Salt Lake City region experienced an 8% increase in cirrus cloud cover over a 15-year period which covariates with an increase in regional commercial air traffic. If soot particles act as freezing nuclei to cause contrail formation heterogeneously, they would be linked to a secondary effect to cloud modification that very likely is climatologically important. Third, a buildup of soot aerosol could reduce the single scatter albedo of stratospheric aerosol from 0.993+0.004 to 0.98, a critical value that has been postulated to separate stratospheric cooling from warming. Thus arises an important question: Do aircraft emit sufficient amounts of soot to have detrimental effects and warrant emission controls? During the 1996 SUCCESS field campaign, we sampled aerosols in the exhaust wake of a Boeing 757 aircraft and determined emission indices for sulfuric acid (EI(sub H2SO4) = 9.0E-2 and 5.0E-1 g/kg (sub FUEL) for 75 and 675 ppm fuel-sulfur, respectively) and soot aerosol (2.2E-3 less than EI(sub SOOT) = l.lE-2 g/kg (sub FUEL)). The soot particle analysis accounted for their fractal nature, determined electron-microscopically, which enhanced the surface area by a factor of 26 and the volume 11-fold over equivalent-volume spheres. The corresponding fuel-sulfur to H2SO4 conversion efficiency was 10% (for 675 ppmm fuel-S) and 37% (for 75 ppmm fuel-S). Applying the H2SO4 emission index to the 1990 fuel use by the worlds commercial fleets of 1.3E11 kg, a conversion efficiency of 30% of 500 ppmm fuel-S would have led to an annual contribution to the atmospheric sulfur budget by aircraft of 2.E7 kg H2SO4. This is about one part in 1.E4 of anthropogenic sulfate from other sources. The soot emission index given above yielded a 1990 injection of soot aerosol by aircraft of 1.E6 kg. Thus, soot amounts to only five percent of the aerosol generated by aircraft. Its reactivity with ozone would have to be 20 times that of sulfuric acid particles to make it chemically significant. Nevertheless, the findings, of stratospheric soot loadings commensurate with aircraft fuel consumption, based on the emission index given above and the assumption of stratospheric residence times of the order of one year implicate aircraft as stratospheric polluters. A trend similar to soot of H2SO4 aerosol loading could not be deciphered, neither from in situ measurements nor SAGE II satellite extinction, against the "noise" due to volcanic eruptions. Observation of soot particles at 20 km altitude which, if emitted by aircraft were generated at 10-12 km altitude, suggests a displacement of those particles against gravity. Because eddy mixing is virtually absent in the lower stratosphere and isentropic mixing explains lofting to only about 15 km, radiometric forces acting on morphologically and chemically asymmetric soot particles must be considered a possibility. The consequence could be an extended residence time of soot against that of sulfuric acid aerosol that would lower the single scatter albedo with time.

Pueschel, R. F.↗
DOE OSTI2022

Microporous water with high gas solubilities

Liquids with permanent microporosity can absorb larger quantities of gas molecules than conventional solvents , providing new opportunities for liquid-phase gas storage, transport, and reactivity. Current approaches to designing porous liquids rely on sterically bulky solvent molecules or surface ligands and thus are not amenable to many important solvents, including water. Here, we report a generalizable thermodynamic strategy to preserve permanent microporosity and impart high gas solubilities to liquid water. Specifically, we show how the external and internal surface chemistry of microporous zeolite and metal–organic framework nanocrystals can be tailored to promote the formation of stable dispersions in water while maintaining dry networks of micropores that are accessible to gas molecules. As a result of their permanent microporosity, these aqueous fluids can concentrate gases, including oxygen (O 2 ) and carbon dioxide (CO 2 ), to much higher densities than are found in typical aqueous environments. Furthermore, when these fluids are oxygenated, record-high capacities of O 2 can be delivered to hypoxic red blood cells, highlighting one potential application of this new class of microporous liquids for physiological gas transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Diversity in Photoprotection and Energy Balancing in Terrestrial and Aquatic Phototrophs

The evolution of oxygenic photosynthesis enabled organisms to use sunlight as an energy source, allowing them to colonize new niches. At the same time, life (as we know it) places severe constraints on photosynthesis. For example, the initial reactions of photosynthesis involve highly energetic intermediates that, if not controlled, can generate highly toxic side products (especially reactive oxygen species, ROS), that can damage other essential components of the organisms it powers. Photosynthesis must therefore be tightly regulated to balance the need for efficient energy conversion with the necessity of avoiding photodamage (Gust D, Kramer D, Moore A, Moore T, Vermaas W, Mater Res Bull 33:383–389, 2008). A related constraint on photosynthesis is the need to precisely balance how much energy is stored in ATP and NADPH to precisely meet biochemical demands. If this balancing does not occur, the system will fail, leading to photodamage (Kramer DM, Evans JR, Plant Physiol 155:70–78, 2011). Consideration of these requirements is essential for efforts to improve the efficiency of photosynthesis by introducing CO 2 concentrating mechanisms, altering metabolism or biosynthetic pathways to shunt energy to alternative products (Kramer DM, Evans JR, Plant Physiol 155:70–78, 2011). These balancing processes must be extremely robust to contend with the rapid and unpredictable fluctuations in environmental conditions and metabolic demands that occur in nature. A large body of work has come from model systems, especially terrestrial higher plants and the green alga Chlamydomonas reinhardtii, leading to a model for the regulation of light reactions that involves 1) sensing of the pH gradient component of the thylakoid proton motive force (pmf), and 2) the redox state of the plastoquinone- and stromal pools. Over the short term, these sensors trigger regulation of light capture by altering the activity of ATP synthase leading to adjustments in lumen pH, which fine tunes light capture through nonphotochemical quenching (NPQ) and control of electron flow by adjusting the rate of PQH 2 oxidation at the b 6 f complex. Simultaneously, this system controls the balance of ATP/NADPH by adjusting electron flux to linear and cyclic electron flow pathways to balance ATP/NADPH. This integrated “pmf paradigm” model explains much of the existing data on plants and green algae, but may not extend to other diverse organisms. This review considers how advances in our understanding of photosynthesis over the past 7–8 years, particularly in the discoveries of diverse biochemical/biophysical mechanisms in aquatic photosynthetic species, affects the view of energy balance, including the shunting of electrons to O 2 through the flavodiiron proteins (FLV), the plastid terminal oxidase, the dissipation of electric field by ion movements, and the activation of alternative electron sinks. Furthermore, we will introduce the basic model that has been developed for higher plant chloroplasts, then contrast these with selected aquatic systems, focusing on how the differences impact the needs to re-balance both energy input and its partitioning into energy currencies.

Kanazawa, Atsuko↗
DOE OSTI2019

Enhancement of EM Pump Performance through Modeling and Testing

Liquid sodium has seen development as a nuclear reactor coolant in the United States for over 50 years. While sodium has many desirable characteristics as a heat transfer fluid, its reactivity poses numerous engineering challenges for even the most basic plant components like pumps. Despite the challenges, mechanical pumps have seen success in sodium service albeit at the expense of simplicity and flexibility. In fact, significant failures of these pumps have been recorded which can be attributed to their complexity. Notwithstanding the complexity, mechanical pumps are still widely proposed for the main circuit pump of sodium cooled reactors. However, an alternative to mechanical pumps are Electromagnetic Induction Pumps (EMIPs) which use the principle of the Lorentz Force. EMIPs avoid mechanically moving parts in contact with sodium which simplifies the design by avoiding mechanical wear and seals. Therefore, these pumps are generally safer and more reliable than their mechanical counterparts. That being said, EMIPs suffer from relatively low efficiencies that range from 5% to 45%. Some of the inefficiencies are inherent to the EMIPs pumps; namely, inefficiencies arise in the form of resistive heating losses in the fluid itself. However, other inefficiencies arise from Edge Effects which include Finite Length and Finite Width effects. Due to the significant safety advantages EMIPs have compared to mechanical pumps, there is a strong motivation to integrate these technologies into the design of Generation IV liquid-metal-cooled nuclear power plants. However, EMIPs have low efficiencies partly attributed to Edge Effects. Much of the literature focusing on Edge Effects is dated or simply does not exist in the public domain. More recently, numerical models of EMIPs have shown promising results. However, these models are often custom solvers or use complex software suits which limit their application. This report describes the work completed to understand Edge Effects in two EMIPs designs. These designs are the Annular Linear Induction Pump (ALIP) and Permanent Magnet Induction Pump (PMIP) also known as a Moving Magnet Pump (MMP). The methodology developed during this project aim at measuring key performance parameters (pressure-flowrate and efficiency-slip performance) using high temperature liquid-sodium. Baseline experimental measurements were then used to verify the accuracy of numerical models developed in the software suit ANSYS/FLUENT. On the experimental side, instrumentation was developed to characterize the pressure-flowrate and efficiency-slip performance of both the ALIP and PMIP in high-temperature liquid-sodium. Additionally, instrumentation was developed to measure potential output pressure pulsations and the magnetic field distributions. Moreover, a specialized ALIP was constructed to study the impacts magnetic field tapering, also known as coil grading, on the Finite Length Effect. Lastly, experimental performance curves of the PMIP were collected at 300 oC and 600 oC and compared to analytical theory which accounted for Finite Width Effects. These results showed that the Finite Width Effect and non-uniform magnetic field in a PMIP impact the performance. On the numerical side, models were developed using the software suit FLUENT/ANSYS. These methods were initially compared against a simple MHD flow in a Permanent Magnet Electromagnet Flowmeter (PMEMFM). The results were significant in that they showed agreeance between the numerical model and demonstrated that PMEMFM’s could be calibrated numerically. These modeling methods were then applied to a prototypic PMIP. Results showed that this simple model provided reasonably accurate results of the PMIP p-Q performance.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2018

The Physics and Chemistry of Cluster-based Catalyst Systems

In this project we used first principles calculations to investigate the physical and chemical properties of atomic clusters, small clumps of matter containing up to a few hundred atoms. The calculations are based on density functional theory, the most efficient and accurate method available for computing and thereby predicting the properties of molecules, clusters, and solids. An initial focus of our work involved studying the reactivity of small Pd clusters. We demonstrated that H2 molecules readily dissociate on Pd clusters and that multiple dissociations can occur on clusters larger than a few Pd atoms. For example, up to eight H2 molecules will dissociate on Pd13 at room temperature. A second focus of the project was to study the evolution of the electrical behavior of clusters, in particular, the evolution of metallic behavior in clusters of metal atoms. We developed a technique for using the electric dipole polarizability of the clusters – the response of the cluster to an applied electric field -- as a probe of this behavior. By decomposing the polarizability into so-called charge transfer (or metallic) and local (or insulating) contributions, we obtained the remarkable result that the per atom charge transfer contributions in sodium clusters attain the same value as occurs in bulk sodium metal for clusters containing as few as 10 atoms. Our calculated total polarizabilities matched experimentally measured trends essentially perfectly, validating the reliability of the calculations and supporting our conclusion that tiny clusters already display bulk-like metallic character. Similar results were obtained for other metal atom clusters, including potassium, aluminum, and zinc. We discovered that the evolution toward bulk metallic behavior for each of these cluster species is essentially identical, when judged using these polarizability-based descriptors. This suggests a universality in the approach of metal clusters to bulk-like metallicity. This discovery is a major outcome of our project. We also used our polarizability-based metrics to investigate the evolution of the properties of Si and NaCl clusters. These systems are non-metallic in the bulk limit. For Si, we find the behavior of small clusters to be metal-like and we attribute this to bonding arrangements in the clusters that are very different from the open structure of crystalline silicon. As the clusters get larger, the bonding in the cluster interior becomes more and more like that of the bulk material. We expect a transition from metal-like to insulator-like behavior to accompany this change is structure. Our results point to a transition at sizes beyond 146 atoms, the largest size treated in our study. We hope to study this transition further in the future. A third thrust of our project involved work on a new approach to eliminating unphysical electron self-interaction from density functional theory calculations. Two electrons exert repulsive forces on each other, but a single electron should not interact with itself. Because of approximations made in density functional theory, individual electrons effectively interact with themselves. The effect of this self-interaction is often small, especially when atoms are near their equilibrium positions in molecules. But the effects can be pronounced when bonds are stretched and also in some situations involving transition metals even when the atoms are near equilibrium. Our research involved the further development of a method for removing self-interaction called the Fermi-Löwdin orbital self-interaction correction or FLO-SIC. We conducted the first systematic FLO-SIC calculations for the individual atoms ranging from Li – Kr. We also carried out a critical comparison of the results of FLO-SIC with an older method known as the Perdew-Zunger self-interaction correction (PZ-SIC). FLO-SIC can be thought of as a modified approach to PZ-SIC that is expected to be computationally more efficient. We demonstrated that the two methods are distinct, but give essentially the same results for quantities such as molecular binding energies or electron removal energies. We are continuing to develop the FLO-SIC methodology with a goal of creating a computationally efficient method that is free of self-interaction effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The response of soil carbon storage and microbially mediated carbon turnover to simulated climatic disturbance in a northern peatland forest. Revisiting the concept of soil organic matter recalcitrance

The goal of this project was to investigate changes in the structure of dissolved and solid phase organic matter, the production of CO 2 and CH 4 , and the composition of decomposer microbial communities in response to the climatic forcing of environmental processes that determine the balance between carbon gas production versus storage and sequestration in peatlands. Cutting-edge analytical chemistry and next generation sequencing of microbial genes were been applied to habitats at the Marcell Experimental Forest (MEF), where the US DOE’s Oak Ridge National Laboratory and the USDA Forest Service are constructing a large-scale ecosystem study entitled, “Spruce and Peatland Responses Under Climatic and Environmental Change”(SPRUCE). Our study represented a comprehensive characterization of the sources, transformation, and decomposition of organic matter in the S1 bog at MEF. Multiple lines of evidence point to distinct, vertical zones of organic matter transformation: 1) the acrotelm consisting of living mosses, root material, and newly formed litter (0-30 cm), 2) the mesotelm, a mid-depth transition zone (30-75 cm) characterized by labile organic C compounds and intense decomposition, and 3) the underlying catotelm (below 75cm) characterized by refractory organic compounds as well as relatively low decomposition rates. These zones are in part defined by physical changes in hydraulic conductivity and water table depth. O-alkyl-C, which represents the carbohydrate fraction in the peat, was shown to be an excellent proxy for soil decomposition rates. The carbon cycle in deep peat was shown to be fueled by modern carbon sources further indicating that hydrology and surface vegetation play a role in belowground carbon cycling. We provide the first metagenomic study of an ombrotrophic peat bog, with novel insights into microbial specialization and functions in this unique terrestrial ecosystem. Vertical structuring of microbial communities closely paralleled the chemical evolution of peat, with large shifts in microbial populations occurring in the biogeochemical hotspot, the mesotelm, where the highest rates of decomposition were detected. Stable isotope geochemistry and potential rates of methane production paralleled vertical changes in methanogen community composition to indicate a predominance of acetoclastic methanogenesis mediated by the Methanosarcinales in the mesotelm, while hydrogen-utilizing methanogens dominated in the deeper catotelm. Evidence pointed to the availability of phosphorus as well as nitrogen limiting the microbially-mediated turnover of organic carbon at MEF. Prior to initiation of the experimental treatments, our study provided key baseline data for the SPRUCE site on the vertical stratification of peat decomposition, key enzymatic pathways, and microbial taxa containing these pathways. The sensitivity of soil carbon turnover to climate change is strongly linked to recalcitrant carbon stocks and the temperature sensitivity of decomposition is thought to increase with increasing molecular complexity of carbon substrates. This project delivered results on how climate change perturbations impact the microbially-mediated turnover of recalcitrant organic matter in peatland forest soils, both under controlled conditions in the laboratory and at the ecosystem-scale in the field. This project revisited the concept of “recalcitrance” in the regulation of soil carbon turnover using a combination of natural abundance radiocarbon and optical spectroscopic measurements on bulk DOM, and high resolution molecular characterization of DOM. The project elucidated how organic matter reactivity and decomposition will respond to climate change in a both a qualitative (organic matter lability) and quantitiative (increased rates) manner. An Aromaticity Index was developed to represent a more direct and accurate parameter for modeling of DOM reactivity in peatlands. The abundance and community composition of soil microorganisms that mediate C cycling were interrogated with depth in the peat, with season, and in manipulated climate enclosures at unprecedented resolution. Therefore this project delivered strategic new insights on the functioning of peatland ecosystems that collectively store approximately one-third of the world's soil carbon. Furthermore, results from the detailed characterization of DOM lability and microbial community structure/ function will be employed to further develop biogeochemical models to include microbial respiration pathways as well as to track carbon flow with a term that incorporates relative reactivity based on aromaticity index. As it stands now, detailed soil organic matter structure and microbial parameters are not included in Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Collaborative Research: Natural Organic Matter and Microbial Controls on Mobilization/Immobilization of I and Pu in Soils and Waters Affected by Radionuclide Releases in USA and Japan

In this project, the relationship between natural organic matter (NOM) and two radioactive elements that are relevant to nuclear waste disposal were studied: Plutonium (Pu) and Iodine. The human and environmental risks associated with Pu stem mainly from the very long half-lives of several of its isotopes ( 238 Pu, 88 yr; 239 Pu, 24,100 yr; 240 Pu, 6560 yr) and its radiotoxicity. Understanding Pu biogeochemical behavior in both near-field (>10-11M) and far-field scales (<10-11M) is imperative to the development of approaches for reprocessing Pu, remediation of Pu contamination and accurate assessment of risks posed by disposal practices for Pu-bearing wastes. The environmental mobility of Pu can be affected by redox potential, pH, adsorption, precipitation, complexation, colloid formation, and microbial activity, of which the first characteristic has the most profound influence. Numerous studies have shown high affinity of Pu towards NOM, as well as to mineral phases. NOM is ubiquitous in the environment, e.g., both fulvic and humic acids are able to reduce Pu(V,VI) to Pu(IV) and the redox potential of NOM is positively related to the abundance of phenolic/acidic OH groups. NOM can either facilitate or limit actinide migration, depending on specific biogeochemical conditions including pH, mineral and organic matter characteristics, etc. The other radionuclide of interest is radioiodine ( 129 I). 129I is a major by-product of nuclear fission and of serious concern to the Department of Energy (DOE) as it is among the top risk drivers at existing and potential radiowaste-contaminated sites. The risk of 129 I stems largely from its high bioconcentration factor (90% of the body’s iodine is accumulated in the thyroid), a high inventory at source terms, a very long-half life (16M years), and rapid mobility in the subsurface environment. As a consequence, 129 I has the lowest drinking water standard (1 pCi/L) among all radionuclides in the Federal Register. With a novel and sensitive gas chromatography-mass spectrometry (GC-MS) method developed in our lab, it is possible to quickly and simultaneously determine the distribution of 129 I and stable 127 I forms in environments, as low as 2 pCi/L for 129 I. This method was subsequently validated using accelerator mass spectroscopy, AMS. IO 3 - and organo-I were determined as major species in the groundwater of SRS and the Hanford Site, contrary to thermodynamic predictions that I- should be the dominant species at these sites. Mobility of 129 I was also demonstrated to depend greatly on the I species and its concentration, sediment pH, and redox state, with times to achieve equilibrium taking up to 12 weeks. Along the groundwater pathway in the F-Area of SRS, 129 I- supplied from the seepage basins was transformed to 129 IO 3 - and organo- 129 I with increasing iodine sediment sorption, causing the lower total 127 I and 129 I concentrations along the gradient transect of the waste plume. By contrast, groundwater 129 I concentrations in the wetlands (as high as 1617.3 pCi/L) were greatly elevated with respect to the source term (159.3 pCi/L). While the NOM promoted the uptake of 129 I to the wetland sediment, it also promoted the formation of soluble organic fraction. A small fraction of NOM that is bound to iodine can behave as a mobile organo-I source. Iodide was enzymatically incorporated into NOM, whereas both iodide and iodate were abiotically bound to NOM, under certain conditions. Iodate removal from the mobile aqueous phase can also occur through incorporation into carbonate (e.g., at the Hanford Site, USA). Thus immobilization and re-mobilization of iodine species were influenced by pH, Eh and the presence of NOM and metal oxides, which adds to the complexity of site remediation action. A ground-breaking result was to elucidate the products (i.e. organo-iodine moieties formed via enzymatic and non-enzymatic processes) at the molecular level by nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). We found that iodine-NOM interactions may be influenced by NOM hydrophobic aliphatic moieties. From the perspective of ESI-FTICRMS, organo-iodine formulas were ascribed to the groups of unsaturated hydrocarbons, lignins and proteins. Iodate is likely abiotically reduced to reactive iodine species by lignin- and tannin-like compounds or carboxylic-rich alicyclic molecules (CRAM). We also investigated microbial mechanisms in iodine incorporation into NOM. We established that soil bacteria isolated from F-Area of SRS did not accumulate significant amounts of I- (0.2-2%). Intracellular uptake of I- decreases with increasing pH when pH ranged from 4 to 6. In contrast, 44 out of 84 strains isolated from the F-Area of SRS can transform I- to IO 3 - and organo-iodine. In some cases, oxidation was facilitated in the presence of H 2 O 2 . Microbes can also excrete organic acids that enhance I- oxidation by lowering the ambient pH and reacting with H 2 O 2 to form peroxy carboxylic acids. At lower pH values (≤5), H 2 O 2 hydrolysis was the driving force for iodide-oxidation; whereas, at pH ≥ 6, spontaneous decomposition of peroxy carboxylic acids, originating from H 2 O 2 and organic acids were the primary cause of iodide oxidation. Lastly, it was determined that microbial processes involved in Mn (II) are capable of directly oxidizing I- via enzymatic catalysis (i.e., multicopper oxidases), or indirectly through the formation of reactive oxygen species (ROS) and/or biogenic manganese oxides. ROS-mediated oxidation of I- was found to predominate at pH >5, whereas the enzymatic and Mn oxide pathways were more active at pH < 5. Together, this project has resulted in 9 publications in high-impact journals, and the training of 1 Ph.D and 4 undergraduate students.

54 ENVIRONMENTAL SCIENCES↗