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Fabrication and testing of U–7Mo monolithic plate fuel with Zircaloy cladding

The Materials Management and Minimization program is developing fuel designs to replace highly enriched fuel with fuels of low enrichment. In the most challenging cases, U–(7–10wt%)Mo monolithic plate fuel are proposed. The chosen design includes aluminum-alloy cladding, which provides some challenges in fabrication and fuel/cladding interaction in service. We investigated zircaloy cladding, specifically Zry–4as an alternative cladding, and development of a fabrication method was performed by researchers with the Comisión Nacionalde Energia Atómica (CNEA) in Argentina, resulting in test fuel plates (Zry–4 clad U–7Mo) which were subsequently tested in the Advanced Test Reactor in Idaho. Because Zry–4 and U–(7–10)Mo have similar high-temperature mechanical properties, fabrication was simplified in that the fuel foil and cladding could be co-rolled and bonded. The challenge was to prevent a thermal-expansion mismatch which could destroy the fuel/cladding bond before complete bonding was achieved; the solution was to prevent the composites from cooling significantly between roll passes. Our final product performed very well in-reactor, showing good bonding, very little fuel/cladding interaction, either from fabrication or in-reactor testing, and little swelling, especially no detectable heterogeneous bubble formation at the fuel/cladding interface tested to a fission density of up to 2.54E+21

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A new method for detecting velocity shifts and distortions between optical spectra

Recent quasar spectroscopy from the Very Large Telescope (VLT) and Keck suggests that fundamental constants may not actually be constant. To better confirm or refute this result, systematic errors between telescopes must be minimized. We present a new method to directly compare spectra of the same object and measure any velocity shifts between them. This method allows for the discovery of wavelength-dependent velocity shifts between spectra, i.e., velocity distortions, that could produce spurious detections of cosmological variations in fundamental constants. This 'direct comparison' method has several advantages over alternative techniques: it is model-independent (cf. line-fitting approaches), blind, in that spectral features do not need to be identified beforehand, and it produces meaningful uncertainty estimates for the velocity shift measurements. In particular, we demonstrate that, when comparing echelle-resolution spectra with unresolved absorption features, the uncertainty estimates are reliable for signal-to-noise ratios ≳7 per pixel. We apply this method to spectra of quasar J2123–0050 observed with Keck and the VLT and find no significant distortions over long wavelength ranges (∼1050 Å) greater than ≈180 m s{sup –1}. We also find no evidence for systematic velocity distortions within echelle orders greater than 500 m s{sup –1}. Moreover, previous constraints on cosmological variations in the proton-electron mass ratio should not have been affected by velocity distortions in these spectra by more than 4.0 ± 4.2 parts per million. This technique may also find application in measuring stellar radial velocities in search of extra-solar planets and attempts to directly observe the expansion history of the universe using quasar absorption spectra.

79 ASTRONOMY AND ASTROPHYSICS↗

Distributed ADMM Using Private Blockchain for Power Flow Optimization in Distribution Network With Coupled and Mixed-Integer Constraints

The optimization problem for scheduling distributed energy resources (DERs) and battery energy storage systems (BESS) integrated with the power grid is important to minimize energy consumption from conventional sources in response to demand. Conventionally this optimization problem is solved in a centralized manner, limiting the size of the problem that can be solved and creating a high communication overhead because all the data is transferred to the central controller. These limitations are addressed by the proposed distributed consensus-based alternating direction method of multiplier (DC-ADMM) optimization algorithm, which decomposes the optimization problem into subproblems with private cost function and constraints. The distribution feeder is partitioned into low coupling subnetworks/regions, which solves the private subproblem locally and exchanges information with the neighboring regions to reach consensus. The relaxation strategy is employed for mixed-integer and coupled constraints introduced in the optimal power flow (OPF) problem by stationary and transportable BESS because DC-ADMM convergence is only guaranteed for strict convex problems. The information exchange and synchronization between subnetworks/regions are vital for distributed optimization. In this work, both of these aspects are addressed by the blockchain. The smart contract deployed on the blockchain network acts as a mediator for secure data exchange and synchronization in distributed computation. The blockchain-based distributed optimization problem’s effectiveness is tested for a 0.5-MW laboratory microgrid for one hour ahead and day-ahead for the IEEE 123-bus and EPRI J1 test feeders, and results are compared with a centralized solution.

25 ENERGY STORAGE↗

Technical and Economic Assessment of Solar Photovoltaic for Groundwater Extraction on the Hanford Site

The overall goal of environmental remediation is to protect human health and the environment. Implementing renewable energy sources such as solar photovoltaic (PV) in groundwater extraction and pump-and-treat (P&T) systems may help minimize the environmental footprint of remediation efforts. The first step in considering solar PV for powering Hanford groundwater extraction is assessing the technical and economic feasibility and identifying potential target locations where implementation would be most successful. Accordingly, a techno-economic assessment of solar PV for Hanford groundwater extraction was completed in FY15. Multiple solar PV alternatives ranging in size from 1.2 to 22.4 kWp DC were evaluated and compared against traditional grid-powered systems. Results indicate that the degree to which solar PV alternatives are feasible is primarily a function of the distance of avoided power cable costs and the inclusion of an energy storage component. Standalone solar PV systems provide an energy source at the well and avoid the costs and logistics associated with running long lengths of expensive power cable to the well-head. When solar PV systems include a battery storage component, groundwater can be pumped continuously day and night in a year-round schedule. However, due to the high cost premium of the energy storage component, a fully solar-powered solution could not provide an economic direct replacement for line-powered pumping systems. As a result, the most ideal target locations for successful implementation of solar PV on the Hanford Site are remote or distant extraction wells where the primary remedial objective is contaminant mass removal (as opposed to hydraulic containment) and three-season (March through October) intermittent pumping is acceptable (e.g. remediation of hexavalent chromium in 200-UP-1).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A cost effective data management subsystem for the LST

The paper outlines the approach used in developing DMS (Data Management Subsystem) alternatives for the LST (Large Space Telescope) and in selecting the concept considered to be the most cost effective means of implementing the LST DMS requirements. Two candidate DMS concepts are discussed: a functionally integrated and a functionally separated one. For the single vehicle LST program, separation of the DMS functions best provides high reliability, operations flexibility, minimal interface complexity, and the least complex software development and verification task. The use of available hardware and NASA standard components is stressed.

Dougherty, J. A.↗

Acoustic transducer apparatus with reduced thermal conduction

A horn is described for transmitting sound from a transducer to a heated chamber containing an object which is levitated by acoustic energy while it is heated to a molten state, which minimizes heat transfer to thereby minimize heating of the transducer, minimize temperature variation in the chamber, and minimize loss of heat from the chamber. The forward portion of the horn, which is the portion closest to the chamber, has holes that reduce its cross-sectional area to minimize the conduction of heat along the length of the horn, with the entire front portion of the horn being rigid and having an even front face to efficiently transfer high frequency acoustic energy to fluid in the chamber. In one arrangement, the horn has numerous rows of holes extending perpendicular to the length of horn, with alternate rows extending perpendicular to one another to form a sinuous path for the conduction of heat along the length of the horn.

Lierke, Ernst G.↗

Water on Mars: Evidence from MER Mission Results

The Viking and the Mars Exploration Rover missions observed that the surface of Mars is encrusted by a thinly cemented layer, or "duricrust". Elemental analyzes at five sites on Mars show that these soils have sulfur content and chlorine content consistent with the presence of sulfates and halides as mineral cements. The soil is highly enriched in the salt-forming elements compared with rock. Analysis of the soil cementation indicates some features which may be evidence of liquid water. At both MER sites, duricrust textures revealed by the Microscopic Imager show features including the presence of fine sand-sized grains, some of which may be aggregates of fine silt and clay, surrounded by a pervasive light colored material that is associated with microtubular structures and networks of microfractures. Stereo views of undisturbed duricrust surfaces reveal rugged microrelief between 2-3 mm and minimal loose material. Comparisons of microscopic images of duricrust soils obtain before and after placement of the Mossbauer spectrometer indicate differing degrees of compaction and cementation. Two models of a transient water hypothesis are offered, a "top down" hypothesis that emphasizes the surface deposition of frost, melting and downward migration of liquid water and a "bottom up" alternative that proposes the presence of interstitial ice/brine, with the upward capillary migration of liquid water. The viability of both of these models ultimately hinges on the availability of seasonally transient liquid water for brief periods.

Landis, Geoffrey A.↗

Materials-of-Construction Radiation Sensitivity for a Fission Surface Power Convertor

A fission reactor combined with a free-piston Stirling convertor is one of many credible approaches for producing electrical power in space applications. This study assumes dual-opposed free-piston Stirling engines/linear alternators that will operate nominally at 825 K hot-end and 425 K cold-end temperatures. The baseline design options, temperature profiles, and materials of construction discussed here are based on historical designs as well as modern convertors operating at lower power levels. This notional design indicates convertors primarily made of metallic components that experience minimal change in mechanical properties for fast neutron fluences less than 10(sup 20) neutrons per square centimeter. However, these radiation effects can impact the magnetic and electrical properties of metals at much lower fluences than are crucial for mechanical property integrity. Moreover, a variety of polymeric materials are also used in common free-piston Stirling designs for bonding, seals, lubrication, insulation and others. Polymers can be affected adversely by radiation doses as low as 10(sup 5) - 10(sup 10) rad. Additionally, the absorbing dose rate, radiation hardness, and the resulting effect (either hardening or softening) varies depending on the nature of the particular polymer. The classes of polymers currently used in convertor fabrication are discussed along possible substitution options. Thus, the materials of construction of prototypic Stirling convertor engines have been considered and the component materials susceptible to damage at the lowest neutron fluences have been identified.

Bowman, Cheryl L.↗

Axial Flow Conditioning Device for Mitigating Instabilities

A flow conditioning device for incrementally stepping down pressure within a piping system is presented. The invention includes an outer annular housing, a center element, and at least one intermediate annular element. The outer annular housing includes an inlet end attachable to an inlet pipe and an outlet end attachable to an outlet pipe. The outer annular housing and the intermediate annular element(s) are concentrically disposed about the center element. The intermediate annular element(s) separates an axial flow within the outer annular housing into at least two axial flow paths. Each axial flow path includes at least two annular extensions that alternately and locally direct the axial flow radially outward and inward or radially inward and outward thereby inducing a pressure loss or a pressure gradient within the axial flow. The pressure within the axial flow paths is lower than the pressure at the inlet end and greater than the vapor pressure for the axial flow. The invention minimizes fluidic instabilities, pressure pulses, vortex formation and shedding, and/or cavitation during pressure step down to yield a stabilized flow within a piping system.

Ahuja, Vineet↗

Study of a Tricarbide Grooved Ring Fuel Element for Nuclear Thermal Propulsion

Deep space exploration, especially that of Mars, is on the horizon as the next big challenge for space exploration. Nuclear propulsion, through which high thrust and efficiency can be achieved, is a promising option for decreasing the cost and logistics of such a mission. Work on nu- clear thermal engines goes back to the days of the NERVA program. Currently, nuclear thermal propulsion is under development again in various forms to provide a superior propulsion system for deep space exploration. The authors have been working to develop a concept nuclear thermal engine that uses a grooved ring fuel element as an alternative to the traditional hexagonal rod design. The authors are also studying the use of carbide fuels. The concept was developed in order to increase surface area and heat transfer to the propellant. The use of carbides would also raise the operating temperature of the reactor. It is hoped that this could lead to a higher thrust to weight nuclear thermal engine. This paper describes the modeling of neutronics, heat transfer, and fluid dynamics of this alternative nuclear fuel element geometry. Fabrication experiments of grooved rings from carbide refractory metals are also presented along with material characterization and interactions with a hot hydrogen environment. Results of experiments and associated analysis are desired densities with some success in material distribution and reaching a solid solution. Future work is needed to improve distribution of material, minimize oxidation during the milling process, and de ne a fabrication process that will serve for constructing grooved ring fuel rods for large system tests.

Taylor, Brian↗

Assessment of Brine Management for Geologic Carbon Sequestration

Geologic carbon sequestration (GCS) is the injection of carbon dioxide (CO 2 ), typically captured from stationary emission sources, into deep geologic formations to prevent its entry into the atmosphere. Active pilot facilities run by regional United States (US) carbon sequestration partnerships inject on the order of one million metric tonnes (mt) CO 2 annually while the US electric power sector emits over 2000 million mt-CO 2 annually. GCS is likely to play an increasing role in US carbon mitigation initiatives, but scaling up GCS poses several challenges. Injecting CO 2 into sedimentary basins raises fluid pressure in the pore space, which is typically already occupied by naturally occurring, or native, brine. The resulting elevated pore pressures increase the likelihood of induced seismicity, of brine or CO 2 escaping into potable groundwater resources, and of CO 2 escaping into the atmosphere. Brine extraction is one method for pressure management, in which brine in the injection formation is brought to the surface through extraction wells. Removal of the brine makes room for the CO 2 and decreases pressurization. Although the technology required for brine extraction is mature, this form of pressure management will only be applicable if there are cost-­effective and sustainable methods of disposing of the extracted brine. Brine extraction, treatment, and disposal may increase the already substantial capital, energy, and water demands of Carbon dioxide Capture and Sequestration (CCS). But, regionally specific brine management strategies may be able to treat the extracted water as a source of revenue, energy, and water to subsidize CCS costs, while minimizing environmental impacts. By this approach, value from the extracted water would be recovered before disposing of any resulting byproducts. Until a price is placed on carbon, we expect that utilities and other CO 2 sources will be reluctant to invest in capital intensive, high risk GCS projects; early technical, economic, and environmental assessments of brine management are extremely valuable for determining the potential role of GCS in the US. We performed a first order feasibility and economic assessment, at three different locations in the US, of twelve GCS extracted-­water management options, including: geothermal energy extraction, desalination, salt and mineral harvesting, rare-­earth element harvesting, aquaculture, algae biodiesel production, road de-­icing, enhanced geothermal system (EGS) recharge, underground reinjection, landfill disposal, ocean disposal, and evaporation pond disposal. Three saline aquifers from different regions of the US were selected as hypothetical GCS project sites to encompass variation in parameters that are relevant to the feasibility and economics of brine disposal. The three aquifers are the southern Mt. Simon Sandstone Formation in the Illinois Basin, IL; the Vedder Formation in the southern San Joaquin Basin, CA; and the Jasper Interval in the eastern Texas Gulf Basin, TX. These aquifers are candidates for GCS due to their physical characteristics and their close proximity to large CO 2 emission sources. Feasibility and impacts were calculated using one mt-­CO 2 injected as the functional unit of brine management. Scenarios were performed for typical 1000MW coal-­fired power plants (CFPP) that incurred an assumed 24 percent carbon capture energy penalty (EP), injected 90 percent of CO 2 emissions (~9 million mt-­ CO 2 injected annually), and treated extracted water onsite. Net present value (NPV), land requirements, laws and regulations, and technological limits were determined for each stage of disposal, and used to estimate feasibility. The boundary of the assessment began once extracted water was brought to the surface, and ended once the water evaporated, was injected underground, or was discharged into surface water bodies. Results of the assessment were generated, stored, and analyzed using Microsoft Excel spreadsheets and ESRI Geographical Information System (GIS) maps. Conclusions about the relative benefits and impacts of alternative brine-­management strategies were highly sensitive to local climate and weather, and aquifer water chemistry. The NPV of certain scenarios ranged from -­$50/mt-­CO 2 (a cost) to +$10/mt-­CO 2 (revenue). The land footprint of the scenarios in this study ranged from <1 km 2 to 100 km 2 . Brine extraction as a pressure management tool for GCS has potential for improving the economics and for minimizing the environmental impacts of CCS. In order to maximize this potential, careful analysis of each saline aquifer and region must be conducted to determine a regionally appropriate brine use sequence (BUS) at the time of site selection. Models that use GIS will be essential tools in determining such sequences for individual CFPP. Future studies that perform risk and life cycle assessments (LCA) of BUS scenarios, incorporate additional impact metrics into the BUS model, and enhance the temporal sensitivity of the model would improve the robustness of this regional assessment method.

54 ENVIRONMENTAL SCIENCES↗

In Situ Decommissioning (ISD) Concepts and Approaches for Excess Nuclear Facilities Decommissioning End State - 13367

The United States Department of Energy (DOE) currently has numerous radiologically contaminated excess nuclear facilities waiting decommissioning throughout the Complex. The traditional decommissioning end state is complete removal. This commonly involves demolishing the facility, often segregating various components and building materials and disposing of the highly contaminated, massive structures containing tons of highly contaminated equipment and piping in a (controlled and approved) landfill, at times hundreds of miles from the facility location. Traditional demolition is costly, and results in significant risks to workers, as well as risks and costs associated with transporting the materials to a disposal site. In situ decommissioning (ISD or entombment) is a viable alternative to demolition, offering comparable and potentially more protective protection of human health and the environment, but at a significantly reduced cost and worker risk. The Savannah River Site (SRS) has completed the initial ISD deployment for radiologically contaminated facilities. Two reactor (P and R Reactors) facilities were decommissioned in 2011 using the ISD approach through the American Recovery and Reinvestment Act. The SRS ISD approach resolved programmatic, regulatory and technical/engineering issues associated with avoiding the potential hazards and cost associated with generating and disposing of an estimated 124,300 metric tons (153,000 m{sup 3}) of contaminated debris per reactor. The DOE Environmental Management Office of Deactivation and Decommissioning and Facility Engineering, through the Savannah River National Laboratory, is currently investigating potential monitoring techniques and strategies to assess ISD effectiveness. As part of SRS's strategic planning, the site is seeking to leverage in situ decommissioning concepts, approaches and facilities to conduct research, design end states, and assist in regulatory interactions in broad national and international government and private industry decommissioning applications. SRS offers critical services based upon the SRS experience in decommissioning and reactor entombment technology (e.g., grout formulations for varying conditions, structural and material sciences). The SRS ISD approach follows a systems engineering framework to achieve a regulatory acceptable end state based on established protocols, attains the final end state with minimal long stewardship requirements, protects industrial workers, and protects groundwater and the environment. The ISD systems engineering framework addresses key areas of the remedial process planning, technology development and deployment, and assessment to attain the ultimate goal of natural resource stewardship and protecting the public. The development and deployment of the SRS ISD approach has established a path for ISD of other large nuclear facilities in the United States and around the globe as an acceptable remedial alternative for decommissioning nuclear facilities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Laboratory Evaporation Testing Of Hanford Waste Treatment Plant Low Activity Waste Off-Gas Condensate Simulant

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream, LAW Off-Gas Condensate, from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable de-coupled operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of canistered glass waste forms. This LAW Off-Gas Condensate stream contains components that are volatile at melter temperatures and are problematic for the glass waste form. Because this stream recycles within WTP, these components accumulate in the Condensate stream, exacerbating their impact on the number of LAW glass containers that must be produced. Approximately 32% of the sodium in Supplemental LAW comes from glass formers used to make the extra glass to dilute the halides to be within acceptable concentration ranges in the LAW glass. Diverting the stream reduces the halides in the recycled Condensate and is a key outcome of this work. Additionally, under possible scenarios where the LAW vitrification facility commences operation prior to the WTP Pretreatment facility, identifying a disposition path becomes vitally important. This task examines the impact of potential future disposition of this stream in the Hanford tank farms, and investigates auxiliary evaporation to enable another disposition path. Unless an auxiliary evaporator is used, returning the stream to the tank farms would require evaporation in the 242-A evaporator. This stream is expected to be unusual because it will be very high in corrosive species that are volatile in the melter (chloride, fluoride, sulfur), will have high ammonia, and will contain carryover particulates of glass-former chemicals. These species have potential to cause corrosion of tanks and equipment, precipitation of solids, release of ammonia gas vapors, and scale in the tank farm evaporator. Routing this stream to the tank farms does not permanently divert it from recycling into the WTP, only temporarily stores it prior to reprocessing. Testing is normally performed to demonstrate acceptable conditions and limits for these compounds in wastes sent to the tank farms. The primary parameter of this phase of the test program was measuring the formation of solids during evaporation in order to assess the compatibility of the stream with the evaporator and transfer and storage equipment. The origin of this LAW Off-Gas Condensate stream will be the liquids from the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP) from the LAW facility melter offgas system. The stream is expected to be a dilute salt solution with near neutral pH, and will likely contain some insoluble solids from melter carryover. The soluble components are expected to be mostly sodium and ammonium salts of nitrate, chloride, and fluoride. This stream has not been generated yet, and, thus, the composition will not be available until the WTP begins operation, but a simulant has been produced based on models, calculations, and comparison with pilot-scale tests. This report discusses results of evaporation testing of the simulant. Two conditions were tested, one with the simulant at near neutral pH, and a second at alkaline pH. The neutral pH test is comparable to the conditions in the Hanford Effluent Treatment Facility (ETF) evaporator, although that evaporator operates at near atmospheric pressure and tests were done under vacuum. For the alkaline test, the target pH was based on the tank farm corrosion control program requirements, and the test protocol and equipment was comparable to that used for routine evaluation of feed compatibility studies for the 242-A evaporator. One of the radionuclides that is volatile in the melter and expected to be in high concentration in this LAW Off-Gas Condensate stream is Technetium-99 (99Tc). Technetium will not be removed from the aqueous waste in the Hanford WTP, and will primarily end up immobilized in the LAW glass by repeated recycle of the off-gas condensate into the LAW melter. Other radionuclides that are also expected to be in appreciable concentrations in the LAW Off-Gas Condensate are 129I, 90Sr, 137Cs, and 241Am. The concentrations of these radionuclides in this stream will be much lower than in the LAW, but they will still be higher than limits for some of the other disposition pathways currently available. At this time, these scoping tests did not evaluate the partitioning of the radionuclides to the evaporator condensate, since ample data are available separately from other experience in the DOE complex. Results from the evaporation testing show that the neutral SBS simulant first forms turbidity at ~7.5X concentration, while the alkaline-adjusted simulant became turbid at ~3X concentration. The major solid in both cases was Kogarkoite, Na3FSO4. Sodium and lithium fluorides were also detected. Minimal solids were formed in the evaporator bottoms until a substantial fraction of liquid was removed, indicating that evaporation could minimize storage volume issues. Achievable concentration factors without significant insoluble solids were 17X at alkaline pH, and 23X at neutral pH. In both runs, significant ammonia carried over and was captured in the condenser with the water condensate. Results also indicate that with low insoluble solids formation in the initial testing at neutral pH, the use of Reverse Osmosis is a potential alternate method for concentrating the solution, although an evaluation is needed to identify equipment that can tolerate insoluble solids. Most of the ammonia remains in the evaporator bottoms during the neutral pH evaporation, but partitions to the condensate during alkaline evaporation. Disposition of both streams needs to consider the management of ammonia vapor and its release. Since this is an initial phase of testing, additional tasks related to evaporation methods are expected to be identified for development. These tasks likely include evaluation and testing of composition variability testing and evaluations, corrosion and erosion testing, slurry storage and immobilization investigations, and evaporator condensate disposition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Alternative hypothesis for the origin of CCF xenon

The relative abundances and origins of the xenon isotopes found in carbonaceous meteorites are discussed. It is proposed that carbonaceous-chondrite-fission (CCF) xenon is not caused by fission, but is the direct result of a modified r-process nucleosynthesis which produces a peak at Z = 54 and N = 82. The xenon produced in this way would have been trapped in dust grains which were subsequently incorporated in the solar system with minimal degassing.

Black, D. C.↗

Alternate routes to acetate tolerance lead to varied isoprenol production from mixed carbon sources in Pseudomonas putida

ABSTRACT Lignocellulose is a renewable resource for the production of a diverse array of platform chemicals, including the biofuel isoprenol. Although this carbon stream provides a rich source of sugars, other organic compounds, such as acetate, can be used by microbial hosts. Here, we examined the growth and isoprenol production in a Pseudomonas putida strain pre-tolerized (“PT”) background where its native isoprenol catabolism pathway is deleted, using glucose and acetate as carbon sources. We found that PT displays impaired growth in minimal medium containing acetate and often fails to grow in glucose-acetate medium. Using a mutant recovery-based approach, we generated tolerized strains that overcame these limitations, achieving fast growth and isoprenol production in the mixed carbon feed. Changes in the glucose and acetate assimilation routes, including an upregulation in PP_0154 (SpcC, succinyl-CoA:acetate CoA-transferase) and differential expression of the gluconate assimilation pathways, were key for higher isoprenol titers in the tolerized strains, whereas a different set of mechanisms were likely enabling tolerance phenotypes in media containing acetate. Among these, a coproporphyrinogen-III oxidase (HemN) was upregulated across all tolerized strains and in one isolate required for acetate tolerance. Utilizing a defined glucose and acetate mixture ratio reflective of lignocellulosic feedstocks for isoprenol production in P. putida allowed us to obtain insights into the dynamics and challenges unique to dual carbon source utilization that are obscured when studied separately. Together, this enabled the development of a P. putida bioconversion chassis able to use a more complex carbon stream to produce isoprenol. IMPORTANCE Acetate is a relatively abundant component of many lignocellulosic carbon streams and has the potential to be used together with sugars, especially in microbes with versatile catabolism such as P. putida . However, the use of mixed carbon streams necessitates additional optimization. Furthermore, the use of P. putida for the production of the biofuel target, isoprenol, requires the use of engineered strains that have additional growth and production constraints when cultivated in acetate and glucose mixtures. In this study, we generate acetate-tolerant P. putida strains that overcome these challenges and examine their ability to produce isoprenol. We show that acetate tolerance and isoprenol production, although independent phenotypes, can both be optimized in a given P. putida strain. Using proteomics and whole genome sequencing, we examine the molecular basis of both phenotypes and show that tolerance to acetate can occur via alternate routes and result in different impacts on isoprenol production.

de Siqueira, Guilherme M. V. (ORCID:00000002364563↗

Vertical and adiabatic excitations in anthracene from quantum Monte Carlo: Constrained energy minimization for structural and electronic excited-state properties in the JAGP ansatz

We study the ionization energy, electron affinity, and the π → π{sup ∗} ({sup 1}L{sub a}) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the {sup 1}L{sub a} excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral {sup 1}L{sub a} excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Downstream Separation of Formic Acid with Anion-Exchange Resin from Electrocatalytic Carbon Dioxide (CO 2 ) Conversion: Adsorption, Kinetics, and Equilibrium Modeling

The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) that produces liquid formic acid (FA) is one potential route to minimize the CO 2 concentration in the atmosphere by utilizing CO 2 as a feedstock. However, one of the main disadvantages of this route is the high energy demand required for purification through conventional distillation. This method of purification has been shown to result in a large carbon footprint in life-cycle analysis (LCA). Therefore, finding an alternative purification technique that can integrate with an electrochemical CO 2 RR process with the potential to lower the carbon footprint would be of great interest. Under the experimental conditions of the CO 2 RR, FA remains in its basic form as the formate anion in the catholyte. Anion exchange resins with their basic properties can separate the formate anion from the catholyte mixture as an alternative to energy intensive distillation. In this work, three anion exchange resins with increasing basicity order: Amberlite IRA-96 < Amberlite IRA-910 < Ambersep 900 are tested to separate FA in the presence of aqueous solution of potassium bicarbonate catholyte with varying levels of resin and FA. Kinetics and equilibrium studies data for the FA adsorption are interpreted using several kinetics and isotherm models. The kinetics data fit well with a pseudo-first-order model at high initial FA concentrations and a pseudo-second-order model at low initial FA concentrations. The experimental data can be best explained with the Freundlich isotherm model. The fitted results show that strongly basic Ambersep 900 is more effective at separating FA, with a maximum adsorption capacity of 336.7 mg/g compared to Amberlite IRA-96 (275.2 mg/g) and Amberlite IRA-910 (209.2 mg/g) in neutral water. However, weakly basic Amberlite IRA-96 (110.8 mg/g) can separate FA more efficiently from potassium bicarbonate catholyte than Amberlite IRA-910 (99.9 mg/g) and Ambersep 900 (40.0 mg/g). As a result, competitive adsorption occurs in the presence of potassium bicarbonate catholyte, but the formic acid adsorption capacity is still sufficient for adequate separation.

20 FOSSIL-FUELED POWER PLANTS↗

Direct Air Capture of CO 2 with Aqueous Amino Acids and Solid Bis-iminoguanidines (BIGs)

We report a bench-scale direct air capture (DAC) process comprising CO 2 absorption with aqueous amino acid salts (i.e., potassium glycinate, potassium sarcosinate), followed by room-temperature regeneration of the amino acids by reaction with solid meta-benzene-bis(iminoguanidine) (m-BBIG), resulting in crystallization of the hydrated m-BBIG carbonate salt, (m-BBIGH 2 )(CO 3 )(H 2 O) n (n = 3–4). The CO 2 is subsequently released by mild heating (60–120 °C) of the carbonate crystals, which regenerates the m-BBIG solid quantitatively. This low-temperature crystallization-based DAC process circumvents the need to heat the aqueous amino acid sorbents, thereby minimizing their loss through thermal and oxidative degradation. The CO 2 cyclic capacity for the sarcosine/m-BBIG system, measured over three consecutive absorption/regeneration cycles, is in the range of 0.12–0.20 mol/mol. The regeneration energy of m-BBIG, comprising the enthalpy of CO 2 and water release, and the sensible heat, is 360 kJ/mol (8.2 GJ/ton CO 2 ). Alternatively, the aqueous amino acids can be regenerated by boiling under reflux, with measured cyclic capacities of up to 0.64 mol/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗