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The microscopic mechanisms of high temperature oxidation of Haynes 282

Nickel-based superalloy finds widespread applications in aerospace and extreme environments. They are known for their high temperature oxidation resistance under extended periods. However, the oxide formation and evolution which sets the stages for the later parabolic oxidation kinetics is not fully understood. This paper aims to provide new insights into the transient stage oxidation mechanism and kinetics of a typical Ni-based superalloy (Haynes 282). While tracking the chemical and microstructural evolution under micrometer scale at 800°C, we show that the oxide scale and its grain boundary species change significantly during the initial stages of oxidation and can have a profound impact on the oxidation kinetics. Cr 2 O 3 forms initially at the grain boundary along with minor amount of Al 2 O 3 . Then, the grain boundary region is enriched with copious amounts TiO 2 while Cr migrates away from the grain boundary. A noticeable change in the isothermal oxidation kinetics observed likely results from a mechanistic change from uniform surface oxidation to preferential outward diffusion of Ti 4+ ions through the grain boundary. Through first-principles calculations combined with energy dispersive spectroscopy, we confirmed the preferential outward diffusion of Ti 4+ ions as the diffusion barrier is lower for Ti than Cr along the grain boundaries. In conclusion, these findings highlight the critical role of early-stage grain boundary oxidation dynamics in dictating the long-term oxidation resistance of Ni-based superalloys and provide a foundation for future strategies to enhance their performance in extreme environments.

DFT↗

Monte-Carlo Simulation of Heavy Ion Track Structure Calculation of Local Dose and 3D Time Evolution of Radiolytic Species

Heavy ions have gained considerable importance in radiotherapy due to their advantageous dose distribution profile and high Relative Biological Effectiveness (RBE). Heavy ions are difficult to produce on Earth, but they are present in space and it is impossible at this moment to completely shield astronauts from them. The risk of these radiations is poorly understood, which is a concern for a 3-years Mars mission. The effects of radiation are mainly due to DNA damage such as DNA double-strand breaks (DSBs), although non-targeted effects are also very important. DNA can be damaged by the direct interaction of radiation and by reactions with chemical species produced by the radiolysis of water. The energy deposition is of crucial importance to understand biological effects of radiation. Therefore, much effort has been done recently to improve models of radiation tracks.

Plante, Ianik↗

Tracking Aerosol Convection Interactions Experiment (TRACER) Field Campaign Report

Convective clouds serve a critical role in the Earth’s energy and water cycles through their transport of heat, moisture, momentum, and chemical species through the troposphere driving the global circulation (e.g., Hartmann et al. 1984, Del Genio et al. 2012, Su et al. 2014). On more local scales, convective clouds impact the atmospheric heating profile through diabatic heating effects, removal of water from the atmospheric column through precipitation, and conditioning of the local environment impacting further development of clouds (e.g., Sullivan and Voigt 2021). These critical roles underscore the importance of realistic representation of convective processes across scales of models from large-eddy simulation (LES), to convection-permitting models (CPM; e.g., Kendon et al. 2020, Marinescu et al. 2021), to numerical weather prediction (NWP) models used for operational weather forecasting, to Earth system models used to predict climate sensitivity (Sanderson et al. 2011, Sherwood et al. 2014, Tomassini et al. 2014, Zhao et al. 2016, Cronin et al. 2017). A key component of improving model representation of convective clouds is better quantification and parameterization of updraft microphysics and dynamics, including their interactions with the surrounding environment and storm organization (Bony et al. 2015, Hagos and Houze 2016, Donner et al. 2016, Morrison et al. 2020). Aerosol is an important environmental factor that could affect convective clouds and precipitation since cloud droplet and ice formation processes are initiated by it. Andrae et al. (2004) hypothesized that aerosols associated with increased biomass burning particles acting as cloud condensation nuclei (CCN) result in smaller and more monodisperse cloud droplets leading to suppression of warm rain formation, ultimately leading to more cloud water being lofted above the freezing level based on observations in the Amazon region. The subsequent increase in latent heat release increases the buoyancy of rising convective parcels invigorating the deep convection. This work was followed by a description of the theoretical basis for this “cold-phase invigoration” by Rosenfeld et al. (2008), who argued that it could have a significant effect for deep convective clouds with warm cloud-bases. Several modeling studies (e.g., Khain et al. 2005, 2009, van den Heever et al. 2006, Fan et al. 2007, 2009, 2012, Lee et al. 2008, Storer et al. 2010, Lebo et al. 2012, Storer and van den Heever 2013, Chen et al. 2020, Dagan et al. 2022) have investigated these aerosol-convection interactions and the environmental factors that influence their relative importance and magnitude. More recently, several studies have indicated that “warm-phase invigoration”, the enhancement of convection through condensational heating, also appears to play a role in enhancing both shallow cumuli (Seiki and Nakajima 2014, Saleeby et al 2015) and deeper tropical convection (Lebo and Seinfeld 2011, Khain et al. 2012, Sheffield et al 2015, Fan et al. 2018, Igel and van den Heever 2021), as well as Houston thunderstorms (Fan et al. 2007, 2020). However, still other studies have provided additional evidence of systematic biases in simulated convective outflow ice size distribution properties, which are consistent with a lack of poorly understood secondary ice production within convective updrafts (e.g., Fridlind et al. 2017). To help address these critical gaps in our understanding of cloud processes, aerosol processes and aerosol-cloud interactions, the Tracking Aerosol Convection Interactions Experiment was designed building upon efforts by the Aerosol, Cloud, Precipitation and Climate (ACPC) Initiative (http://acpcintiative.org/), a joint effort of the International Geosphere-Biosphere Programme (IGBP) and the World Climate Research Program (WCRP) that focused on resolving uncertainties in the interactions between aerosol and clouds towards better understanding the role that these interactions play in the climate system. The TRACER campaign was motivated by recommendations from a number of pilot studies undertaken by ACPC (van den Heever et al. 2017, Fridlind et al. 2019, Hu et al. 2019, Fan et al. 2020, Marinescu et al. 2021, Hernandez-Deckers et al. 2022) that pointed towards the southeastern Texas region as a locale where aerosol-convection interactions could be studied owing to the copious occurrence of isolated convection during the summer months accompanied by diverse and significant sources of aerosols from both anthropogenic and natural sources. The TRACER campaign began on 01 October 2021 and extended through 30 September 2022 with an intensive operational period (IOP) during June-September 2022. Three main sites (Table 1) were managed by the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility.

54 ENVIRONMENTAL SCIENCES↗

NUMERICAL INVESTIGATION OF FUEL PROPERTY EFFECTS ON MIXED-MODE COMBUSTION IN A SPARK-IGNITION ENGINE

In the present study, mixed-mode combustion of an E30 fuel in a direct-injection spark-ignition engine is numerically investigated at a fuel-lean operating condition using multidimensional computational fluid dynamics (CFD). A fuel surrogate matching Research Octane Number (RON) and Motor Octane Number (MON) of E30 is first developed using neural network based non-linear regression model. To enable efficient 3D engine simulations, a 164-species skeletal reaction mechanism incorporating NO, chemistry is reducedfrom a detailed chemical kinetic model. A hybrid approach that incorporates the G-equation model for tracking turbulentflame front, and the multi-zone well-stirred reactor model for predicting auto-ignition in the end gas, is employed to account for turbulent combustion interactions in the engine cylinder. Predicted in-cylinder pressure and heat release rate traces agree well with experimental measurements. The proposed modelling approach also captures moderated cyclic variability. Two different types of combustion cycles, corresponding to purely deflagrative and mixed-mode combustion, are observed. In contrast to the purely deflagrative cycles, mixed-mode combustion cycles feature early flame propagation followed by end-gas auto-ignition, leading to two distinctive peaks in heat release rate traces. The positive correlation between mixed-mode combustion cycles and early flame propagation is well captured by simulations. With the validated numerical setup, effects of NOx chemistry on mixed-mode combustion predictions are investigated. NOx chemistry is found to promote auto-ignition through residual gas recirculation, while the deflagrative flame propagation phase remains largely unaffected. Local sensitivity analysis is then performed to understand effects of physical and chemical properties of the fuel, i.e., heat of evaporation (HoV) and laminar flame speed (S-L). An increased HoV tends to suppress end-gas auto-ignition due to increased vaporization cooling, while the impact of HoV on flame propagation is insignificant. In contrast, an increased SL is found to significantly promote both flame propagation and auto-ignition. The promoting effect of SL on auto-ignition is not a direct chemical effect; it is rather caused by an advancement of the combustion phasing, which increases compression heating of the end gas.

detailed chemical kinetics↗

Initial Engineering Framework for Species Tracking in MSRs Involving Fuel Salt and Structures

This report implements a high-fidelity multiphysics modeling framework using the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program tools to track leaching and plating of materials between the fuel salt and structures in Molten Salt Reactors (MSRs). Specifically, this framework is demonstrated in modeling various processes within MSRs including hot and cold leg corrosion, redox potential driven corrosion, colloid precipitation and deposition, and noble metal plating and decay heat modeling. The model integrates neutronics, thermal-hydraulics, depletion, and thermochemistry to simulate the evolving chemical behavior of the fuel salt in interactions with structural materials. Initial findings suggest that hot-cold leg corrosion in MSR systems may become significant if the redox potential of the fuel salt is not sufficiently controlled. Additionally, the impact of noble metal decay heat deposition in large power reactors is explored. The resulting engineering framework for species tracking will be applied in the future toward specific validation work with ongoing experimental efforts focusing on both chloride and fluoride salt loop experiments with in-situ corrosion and redox control instrumentation.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Reduced-order condensed-phase kinetic models for polyethylene, polypropylene and polystyrene thermochemical recycling

Thermochemical recycling of plastic waste (PW) into chemicals and energy vectors requires coupling particle and reactor-scale simulations to accurate condensed phase pyrolysis mechanisms for each constituent. This work proposes a methodology to derive reduced-order condensed-phase kinetic models from validated semi-detailed kinetic mechanisms. Two types of kinetic models are obtained for polyethylene (PE), polypropylene (PP) and polystyrene (PS): reduced semi-detailed models and multi-step fully lumped ones. These families offer different compromises between accuracy and computational cost. The former employ 50–100 gas + liquid species and describe both the radical degradation and the detailed carbon distribution of the products. Conversely, the latter involves 5–10 species per polymer tracking only the main petroleum cuts. The kinetic mechanisms are complemented by the definition of thermochemical properties of gas, liquid, and solid-phase species, accounting for phase-transitions through pseudo-chemical reactions. Model validations are performed by comparison with experimental data and the original semi-detailed mechanisms in terms of mass loss, heat fluxes and product distribution profiles. The resulting CHEMKIN-like condensed-phase models are attached as Supplementary Material and as a GitHub repository. Extending the proposed approach to other polymers and coupling it with existing subsets in the CRECK kinetic framework (e.g., biomass, PVC, PET) offers a powerful tool to model thermochemical recycling of PW and biomass/PW mixtures.

kinetics↗

Organic Evaporation, Oxidation, and Hydrolysis Testing in Support of Hanford Sample-and-Send

The Hanford site has approximately 54 to 56 million gallons of radioactive mixed waste stored in 156 unretrieved underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste, which are regulated on a concentration based standard in the final waste form. Hence, if the quantity of organics in LAW is high enough, they must be destroyed or removed to make a waste form compatible with disposal in a mixed low level waste landfill. This work evaluates potential avenues for treatment of LDR organics to eliminate the impediment and permit possible use of a cementitious waste form. Vacuum evaporation testing to remove LDR organics consisted of preparing a non-radioactive LAW simulant, spiking that simulant with organic chemicals, and evaporating the mixture via differential distillation. The apparatus was a laboratory-scale vacuum evaporator operated at 60 ±5 torr absolute (vacuum evaporation). The LAW simulant represented the liquid expected to be retrieved from the Hanford tank farms at approximately 4.0 M [Na+] total sodium ion concentration. The concentration of the organic chemicals added was significantly higher than typically found in the tank waste samples since the higher levels were necessary to assist in analytical measurement and tracking of the spiked species.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transient Pulse-Response Time-of-Flight Mass Spectrometry for Complex, Deactivating Heterogeneous Catalytic Systems: Application to Ethane Dehydroaromatization

The study of complex, multistep bond-forming and -breaking reactions in heterogeneous catalytic systems often encounters challenges associated with the involvement of large numbers of intermediates among branching pathways. Kinetic information obtained from traditional steady-state measurements can be complemented with that from time-resolved methods to uncover details of the underlying chemistry. Herein, we describe an approach for tracking the complete time-resolved chemical composition (ca. 4–200 u) of a reactor effluent in response to a reactant pulse. We use a six-port rotary valve with a metered sampling loop to pulse reactants at ambient pressure into a flow reactor packed with a catalyst bed within the isothermal region of a heated furnace. The temporal evolution of effluent species is tracked using time-resolved molecular-beam time-of-flight mass spectrometry. We highlight the possibilities that this method has to offer by studying the complex bifunctional mechanism of ethane dehydroaromatization over an HZSM-5-supported platinum catalyst. We demonstrate that energy-tunable ionization sources, which facilitate isomer resolution, enable the measurement of the full mass spectral time-dependent system response. This includes the evolution of major products and mechanistically relevant reactive intermediates such as 1,3-butadiene and cyclopentadiene; these species have not previously been observed from this reaction. In additional studies, we also assess the role of platinum in the catalyst by examining temporal responses to ethane and ethylene feeds. Results show that two temporally distinct formation pathways exist for methane and benzene, and that their importance depends on both catalyst composition and reactant identity. Additionally, characteristics of catalyst deactivation are uniquely observable in the time-resolved mass spectral response, including the selective deactivation of a benzene formation pathway. The combination of time-of-flight mass spectrometry with tunable ionization enables the simultaneous observation of all effluents in a complex mixture of intermediates with isomer/isobar differentiation capabilities that can be applied to any complex reaction system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiphase Reacting Flow Simulations and Optimization of Commercial-Scale Aerobic Bioreactors

Aerobic bioreactors are widely used in the synthesis of value-added products in pharmaceutical and biotechnology industries, wherein microbial bioreactions aid in the conversion of sugars to macromolecules. These reactors are also being actively investigated as a cost-effective pathway for the production of low-value commodities such as biofuels and animal feed. Reactor scale-up is one of the important challenges when designing these systems. Gas and liquid phase transport, mass-transfer, and mixing physics at large length scales can significantly affect microbial conversion rates, particularly when the microbial reaction requires a narrow set of conditions. These phenomena are difficult to study in small-scale bench-top reactors that are typically well-mixed. Predictive computational fluid dynamics (CFD) based simulations can therefore aid in the design and optimization of these reactors. This work presents multiphase Euler-Euler CFD simulations of commercial-scale (~ 500 m3) aerobic bioreactors. Our mathematical model treats the gas and liquid as interpenetrating phases. This approach reduces the computational complexity of tracking individual gas bubbles that are several orders of magnitude smaller than reactor dimensions. We solve the Reynolds averaged Navier-Stokes (RANS) multiphase equations that account for phase and chemical species transport, interphase mass and momentum transfer and uses a phenomenological model for oxygen uptake by microbes. We use a customized solver derived from open-source CFD toolbox, OpenFOAM, to perform these simulations, which has been validated against small-scale reactors in our previous work. This work examines the performance of three different reactor designs, viz. bubble column reactor, airlift reactor with an internal draft tube, and a stirred-tank reactor with Rushton impellers. Reactor oxygen mass-transfer coefficient, gas hold-up, and oxygen distribution are critically analyzed among reactors, and sensitivity studies pertaining to gas flow rates and reactor geometry will be presented.

09 BIOMASS FUELS↗

Gas-Liquid Flow Modeling for Renewable Fuels Production

Aerobic/anaerobic and gas fermentation pathways have emerged as promising new technologies for the generation of renewable fuels/chemicals from biomass derived sugars, and mixtures of greenhouse/energy rich gas streams (CO2/CH4/H2/CO) via microbial action. Example pathways include sugars-to-ethanol conversion, biomethanation (CO2/H2 to CH4), biogas upgrading, CO fermentation and wet-waste conversion. Gas and liquid phase transport, mass-transfer, and mixing physics at large length scales can significantly affect microbial conversion rates, particularly when the microbial reaction requires a narrow set of conditions. These phenomena are difficult to study in small-scale bench-top reactors that are typically well-mixed. Predictive computational fluid dynamics (CFD) based simulations can therefore aid in the scale-up, design and optimization of these reactors. This work presents multiphase Euler-Euler CFD simulations of at-scale (~500 m3) bioreactors. Our mathematical model treats the gas and liquid as interpenetrating phases. This approach reduces the computational complexity of tracking individual gas bubbles that are several orders of magnitude smaller than reactor dimensions. We solve the Reynolds averaged Navier-Stokes (RANS) multiphase equations that account for phase and chemical species transport, interphase mass and momentum transfer and uses a phenomenological model for gas uptake by microbes. We use a customized solver derived from open-source CFD toolbox, OpenFOAM [1], to perform these simulations, which has been validated against small-scale reactors in our previous work [2]. There is currently a knowledge-gap regarding bubble-size distributions when using gas mixtures with vastly different properties, which can have a significant impact overall mass-transfer. For example, hydrogen bubbles are more buoyant compared to other relatively heavier gases (CO2/CH4/CO), resulting in a large distribution of residence times and bubble sizes. This work therefore develops a deeper understanding of bubble dynamics and interphase mass transfer in such heterogenous gas mixtures through well-resolved computational models. We use a population balance model (PBM) for bubble-size-distribution modeling that is validated against small-scale experiments in our solver with an uncertainty quantification study for bubble coalescence and break-up model parameters. Results pertaining to multiple simulations of gas-fermentation reactors are presented where gas mixtures with varying compositions of CO2/CH4/CO/H2 are imposed at the sparger boundaries. The spatio-temporal variations in bubble-size distribution and mass transfer coefficient are analyzed for varying superficial velocities and gas-compositions for varying sizes of bubble-column and airlift reactors. This work will also examine the performance of different reactor designs, viz. bubble column reactor, airlift reactor with an internal draft tube, and a stirred-tank reactor with Rushton impellers. Reactor mass-transfer coefficient, gas hold-up, and dissolved gas distribution are critically analyzed among reactors, and sensitivity studies pertaining to gas flow rates and reactor geometry will be presented. [1] Weller, H., Tabor, G., Jasak, H. and Fureby, C., A tensorial approach to computational continuum mechanics using object-oriented techniques, Computers in physics, 12, 6, 620--631, 1998. [2] Rahimi, M., Sitaraman, H., Humbird, D. and Stickel, J., Computational fluid dynamics study of full-scale aerobic bioreactors: Evaluation of gas-liquid mass transfer, oxygen uptake, and dynamic oxygen distribution, Chemical Engineering Research and Design, 139: 283-295.

BIOMASS FUELS↗

A Radiation Chemistry Code Based on the Green's Function of the Diffusion Equation

Stochastic radiation track structure codes are of great interest for space radiation studies and hadron therapy in medicine. These codes are used for a many purposes, notably for microdosimetry and DNA damage studies. In the last two decades, they were also used with the Independent Reaction Times (IRT) method in the simulation of chemical reactions, to calculate the yield of various radiolytic species produced during the radiolysis of water and in chemical dosimeters. Recently, we have developed a Green's function based code to simulate reversible chemical reactions with an intermediate state, which yielded results in excellent agreement with those obtained by using the IRT method. This code was also used to simulate and the interaction of particles with membrane receptors. We are in the process of including this program for use with the Monte‐Carlo track structure code Relativistic Ion Tracks (RITRACKS). This recent addition should greatly expand the capabilities of RITRACKS, notably to simulate DNA damage by both the direct and indirect effect.

Plante, Ianik↗

Lidar Technology at the Goddard Laser and Electro-Optics Branch

The Laser and Electro-Optics Branch at Goddard Space flight Center was established about three years ago to provide a focused center of engineering support and technology development in these disciplines with an emphasis on spaced based instruments for Earth and Space Science. The Branch has approximately 15 engineers and technicians with backgrounds in physics, optics, and electrical engineering. Members of the Branch are currently supporting a number of space based lidar efforts as well as several technology efforts aimed at enabling future missions. The largest effort within the Branch is support of the Ice, Cloud, and land Elevation Satellite (ICESAT) carrying the Geoscience Laser Altimeter System (GLAS) instrument. The ICESAT/GLAS primary science objectives are: 1) To determine the mass balance of the polar ice sheets and their contributions to global sea level change; and 2) To obtain essential data for prediction of future changes in ice volume and sea-level. The secondary science objectives are: 1) To measure cloud heights and the vertical structure of clouds and aerosols in the atmosphere; 2) To map the topography of land surfaces; and 3) To measure roughness, reflectivity, vegetation heights, snow-cover, and sea-ice surface characteristics. Our efforts have concentrated on the GLAS receiver component development, the Laser Reference Sensor for the Stellar Reference System, the GLAS fiber optics subsystems, and the prelaunch calibration facilities. We will report on our efforts in the development of the space qualified interference filter [Allan], etalon filter, photon counting detectors, etalor/laser tracking system, and instrument fiber optics, as well as specification and selection of the star tracker and development of the calibration test bed. We are also engaged in development work on lidar sounders for chemical species. We are developing new lidar technology to enable a new class of miniature lidar instruments that are compatible with small Discovery-class orbiters now in the NASA planetary program. The purpose of the lidar is to continuously profile the water vapor and dust in the Mars atmosphere from orbit in order to quantify its dynamics, their relationship in the diurnal cycles, and to infer water vapor exchange with the Mars surface. To remotely measure the water-vapor height profiles, we will use the differential absorption lidar (DIAL) technique. We are also developing a laser sensor for measuring the total column content of CO2 in the atmosphere of the earth. CO2 is the principal greenhouse gas and has increased by roughly 80 ppm in the last century and a half. We will report our efforts in the development of the laser transmitter and photon counting detector components for a Mars Orbiting DIAL system and for the CO2 sounder.

Heaps, William S.↗

Standoff Detection of Chemical Plumes Using Swept-ECQCL Remote Detection Technology: Results from EMRTC Complex Terrain Dual Tracer Experiment

As part of the Complex Terrain Dual Tracer Experiments performed in support of the LYNM program, a swept-wavelength external cavity quantum cascade laser (swept-ECQCL) remote detection system was deployed to measure chemical plume propagation with high temporal resolution. The swept-ECQCL remote detection technology was initially developed at PNNL, and is now under further development at Opticslah, LLC under SBIR funding from DOE (DOE SBIR Phase I Project DE-SC0019855, Remote Detection Technologies, Program Manager Chris Ramos). The swept-ECQCL technology provides a single-frequency infrared laser source which is rapidly scanned over a large wavelength range to measure the infrared absorption of gases, liquids, or solids. Analysis of the measured infrared absorption spectrum is used to detect, identify, and quantify the chemical species which are present. While most previous laser-based techniques used small wavelength tuning ranges to measure only a few isolated spectral lines of a few species, the swept-ECQCL provides the large tuning range needed to measure multiple species simultaneously, and to detect broad absorption features from large molecules or condensed phase materials. In addition, the swept-ECQCL systems have high enough spectral resolution and sensitivity to measure narrow lines of small molecules and determine isotope ratios. The remote detection system for gas plumes is based on the swept-ECQCL technology, and consists of a swept-ECQCL source, infrared detector, control electronics, and beam transmitting and alignment optics. The remote detection system directs the infrared output of the swept-ECQCL to a target retro reflector typically located at ~10-10,000 m distance. The swept-ECQCL wavelength is varied continuously over a large wavelength range (>1000 nm) at rates up to 1000 Hz. The swept ECQCL light reflected from the remote target is collected and focused onto an infrared photodetector. By measuring the detector signal continuously as the swept-ECQCL wavelength is varied, a time-series of absorption spectra are measured for the gases along the beam line of-sight. Based on analysis and fitting of the measured absorption spectra, the time-dependent chemical concentrations of species are determined. Multiple species and mixtures can be detected simultaneously, for all species with absorption features above the sensor noise floor. The sensor output is thus a continuous, high-speed record of identified chemicals along with their concentrations and isotope ratios of interest. The high-speed operation enables low-noise operation in conditions of atmospheric turbulence and allows tracking of fluctuating concentrations in transient chemical plumes as needed for reliable remote detection applications. All components operate with minimal cooling requirements and no cryogens are needed. In addition, the output infrared light is invisible with an intensity below the maximum permissible exposure (MPE) threshold of 100 mW/cm2 for these infrared wavelengths and thus eye safe. The measurement concept for plume detection using the swept-ECQCL remote detection system is as follows. The ECQCL beam is directed toward a remote retro-reflector, which reflects the beam back to the ECQCL system where it is focused onto an infrared photodetector. The line-of-sight from the ECQCL system to the retro-reflector defines the measurement path. The detected infrared signal is recorded continuously and detects the absorption of molecular species along the measurement path. Before a plume release, the system measures absorption from atmospheric constituents, which in this LWIR band consist primarily of lines from H 2 O and CO 2 , with additional weaker absorption from N 2 O, NH 3 , and O 3 possibly contributing. The system then measures any changes in absorption due to the tracer compounds when they enter the measurement path. The shape of absorption features is used to distinguish and identify the different tracer compounds, and the strength of the absorption is used to determine the path-integrated concentration – also called the column density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The active titration method for measuring local hydroxyl radical concentration

We are developing a method for measuring ambient OH by monitoring its rate of reaction with a chemical species. Our technique involves the local, instantaneous release of a mixture of saturated cyclic hydrocarbons (titrants) and perfluorocarbons (dispersants). These species must not normally be present in ambient air above the part per trillion concentration. We then track the mixture downwind using a real-time portable ECD tracer instrument. We collect air samples in canisters every few minutes for roughly one hour. We then return to the laboratory and analyze our air samples to determine the ratios of the titrant to dispersant concentrations. The trends in these ratios give us the ambient OH concentration from the relation: dlnR/dt = -k(OH). A successful measurement of OH requires that the trends in these ratios be measureable. We must not perturb ambient OH concentrations. The titrant to dispersant ratio must be spatially invariant. Finally, heterogeneous reactions of our titrant and dispersant species must be negligible relative to the titrant reaction with OH. We have conducted laboratory studies of our ability to measure the titrant to dispersant ratios as a function of concentration down to the few part per trillion concentration. We have subsequently used these results in a gaussian puff model to estimate our expected uncertainty in a field measurement of OH. Our results indicate that under a range of atmospheric conditions we expect to be able to measure OH with a sensitivity of 3x10(exp 5) cm(exp -3). In our most optimistic scenarios, we obtain a sensitivity of 1x10(exp 5) cm(exp -3). These sensitivity values reflect our anticipated ability to measure the ratio trends. However, because we are also using a rate constant to obtain our (OH) from this ratio trend, our accuracy cannot be better than that of the rate constant, which we expect to be about 20 percent.

Sprengnether, Michele↗

Low soil phosphorus availability triggers maize growth stage specific rhizosphere processes leading to mineralization of organic P

Phosphorus (P) is one of the essential nutrients for all living organisms. High-quality mineral P fertilizer is a finite resource with only an estimated 80-100 years of reserves remaining globally. Both plants and microbes have developed several mechanisms such as secretion of organic acids, acidification of the rhizosphere, and production of extracellular enzymes to enhance the acquisition of P from soils. Increased activity of phosphatase occurs in response to P deficiency as part of P starvation responses which catalyze the hydrolysis of P o from soil organic matter (SOM) and release inorganic P (P i ). However, the specific interactions between plants and microbial communities in the rhizosphere soil triggered by P deficiency are largely unknown. In a greenhouse study we grew maize plants in low and high P containing soils and examined the role of rhizosphere processes on mineralization of organic P (P o ) in soils with low and high P availability and different P speciation 23 (Po dominated versus P i dominated) and determine its effect on plant growth. Plant biomass was determined and rhizosphere soils, and soil samples from pots with and without plants were collected at key vegetative growth stages (VGS). A variety of biogeochemical parameters (e.g. microbial biomass C and P, potential phosphatase activities, plant biomass P, soil P species etc.) were determined using both conventional (sequential chemical extraction) and advanced (e.g. high resolution mass spectrometry (FTICR-MS) and 3129 P solution NMR) techniques. Here, we used phospholipid fatty acid (PLFA) and DNA based microbial community analysis to track changes in microbial community structure and diversity. Low P availability induced changes in biogeochemical processes and microbial community composition in the rhizosphere soils of plants grown in low P containing soil. At early VGS, the plants in low P soil were visually struggling which correlated with greater rhizosphere potential acid phosphatase activity and a reduction in P o fractions. At late VGS, the plants appeared to recover which correlated with a decrease in Meh (III) extractable P, an increase in microbial biomass C and P and greater total P in the plant biomass (roots, shoots and leaves). In high P containing soil, on the other hand, greater P availability masked these rhizosphere processes. Our results confirmed the degradation of SOM and Po mineralization in rhizosphere soils driven by microbe and plant need for P. P deficiency may have favored the abundance of fungi which utilized easily degradable root exudates for the production of extracellular enzymes responsible for the mineralize of SOM P o . This study highlights the intertwined mechanisms involved, and emphasizes the importance of, P o sources for plant nutrition and survival in marginal soils.

59 BASIC BIOLOGICAL SCIENCES↗

Prototype Demonstration of an Integration of a Gibbs Energy Minimizer with TRANSFORM for Molten Salt Reactor Mass Accountancy Studies

Mass accountancy in a molten salt reactor (MSR) system is the ability to track and quantify the radioactive species throughout all portions of the reactor, not just the core. This is critical for the design, analysis, and regulation of these novel reactors. This report discusses a chemistry-based approach for understanding the chemical state, physical characteristics, and time-dependent location of a species throughout an MSR system. This report does not represent a completed capability; rather, it indicates that specific activities are needed (i.e., chemistry coupling and benchmark creation) and require sustained support to enable MSR development and deployment.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Electron–Ion Covariance Reveals Geometry-Resolved Inner-Shell Spectra in CS 2 Photodissociation

The chemical shifts of inner-shell atomic orbitals are highly sensitive to chemical bonding and molecular structure. In evolving systems, however, the spectra of distinct molecular species and geometries overlap, obscuring the underlying chemical dynamics. Here we demonstrate the use of electron–ion covariance analysis to combine the structural sensitivity of Coulomb explosion imaging with inner-shell spectroscopy, yielding geometry-specific spectra of transient and product species. We apply this approach to the excited state dynamics of CS 2 probed by ionization above the S 2p edge. Electron–ion covariance with time- and momentum-selected S + and S 2+ ions isolates distinct S 2p photoelectron spectra for ground-state CS 2 , bent photoexcited CS 2 , the CS photoproduct, and bare atomic sulfur ─ species whose spectra overlap strongly in the channel-averaged measurement. Clear chemical shifts are observed in the covariance photoelectron spectrum for each of these species, all of which are consistent with high-level calculations. Here, by extracting the atomic S contribution to the photoelectron spectrum in a finely time-resolved manner we can disentangle this contribution to the overall time-resolved photoelectron spectrum as the photodissociation proceeds. These results demonstrate the promise of electron–ion covariance as a general approach to geometry-resolved inner-shell spectroscopy, opening a route to tracking structural evolution through chemical shifts in complex photoexcited molecules.

Ionization↗

Interactions between microbial diversity and substrate chemistry determine the fate of carbon in soil.

Microbial decomposition drives the transformation of plant-derived substrates into microbial products that form stable soil organic matter (SOM). Recent theories have posited that decomposition depends on an interaction between SOM chemistry with microbial diversity and resulting function. Here, we explicitly test these theories by coupling quantitative stable isotope probing and metabolomics to track the fate of 13C enriched substrates that vary in chemical composition as they are assimilated by microbes and transformed into new metabolic products in soil. We found that mycorrhizal-driven differences in forest nutrient economies (e.g., nutrient cycling, microbial competition) led to arbuscular mycorrhizal (AM) soils harboring greater micro8ial diversity than ectomycorrhizal (ECM) soils. When incubated with 13C enriched substrates, substrate type drove shifts in the identity of active decomposers and their metabolic products in the highly diverse AM soils. The decomposition pathways were more static in the less diverse, ECM soil. Importantly, the majority of these shifts were driven by taxa only present in the AM soil suggesting a strong link between microbial identity and specialized function. Collectively, these results highlight an important interaction between ecosystem-level processes and microbial diversity; whereby the identity and function of active decomposers impacts the composition of decomposition products that can form stable SOM.

Raczka, Nanette↗