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At least 577 records · Page 32

Phase Transformation Mechanism of Amorphous Calcium Phosphate to Hydroxyapatite Investigated by Liquid-Cell Transmission Electron Microscopy

Crystallization via phase transformation of a metastable precursor is a ubiquitous and effective strategy used by living systems to direct the growth of crystalline nanomaterials with remarkable functional properties. However, determining the exact process by which transformation occurs at the nanoscale is a difficult challenge. In this work, the recrystallization process of amorphous calcium phosphate (ACP) to hydroxyapatite (HAP) is explored by liquid-cell transmission electron microscopy. The effect of confinement in the liquid-cell is found to increase the size of ACP nanoparticles. In the presence of Mg 2+ , these large ACP nanoparticles transform to HAP by first dissolving from the interior to create a hollow structure, after which HAP forms preferentially on the surface and then subsequently in the bulk solution. We propose that the preferential dissolution within ACP particles is due to a change in the structure and/or chemistry of the ACP surface, likely associated with dehydration before crystallization of HAP. These results imply an important role of the confined environment of the liquid-cell in regulating the size of ACP particles, which then affects the surface structure and the detailed dissolution–recrystallization pathway. Moreover, we stress the key role of Mg 2+ in controlling HAP formation by stabilizing ACP via reduction in ACP solubility. This work provides a better understanding of the roles of additives and confinement during the phase transformation of ACP to HAP through dissolution and recrystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimizing CO 2 -Loaded Aqueous Amine Solutions for Higher Electrocatalytic CO 2 Reduction Activity

The activity of aqueous-based carbon dioxide reduction (CO 2 R) reactions is often limited by the solubility of CO 2 . The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO 2 from dilute streams. Here, in this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO 2 R to CO activity of a molecular Ni(cyclam)Cl 2 catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor–liquid equilibrium modeling (VLE), 13 C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO 2 R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO 2 R activity and selectivity and describe amine properties that lead to these higher performance metrics.

Amines↗

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host–guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru 2 nitride intermediate confined within the interstices of a Ru2-based metal–organic framework (MOF), Ru 3 (btc) 2 X 3 (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C–H functionalization of benzylic C–H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., k H /k D ) of C–H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru 2 nitride to the C–H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C–H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C–H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adaptive Laboratory Evolution for Enhanced Performance of Cupriavidus Necator on Formic Acid

The threat of global warming, driven by rising carbon emissions, highlights the need to decarbonize our economy. This requires innovative solutions for managing carbon waste and its effective utilization. One promising method for CO2 capture and sequestration is the electrochemical reduction of CO2 to formic acid, a soluble C1 molecule that can be used to store carbon and energy, and as a feedstock for biological conversion. Cupriavidus necator H16, a soil bacterium capable of consuming and growing on formic acid as its sole carbon and energy source, is well positioned to upgrade CO2-derived formic acid into platform chemicals and fuel precursors. To improve the performance of C. necator on formic acid, adaptive laboratory evolution (ALE), a proven tool for improving microbial fitness, has been conducted using continuous pH-stat bioreactors. The system works on the basis that consumption of formic acid raises the pH and triggers the addition of more formic acid to maintain the pH (in this case 6.7), such that formic acid is provided at the same rate as it is consumed. This system has been coupled with level control to achieve continuous fermentation where cells acquiring mutations that improve growth on formic acid become more abundant in the population, from which they can be isolated and characterized. During developmental experiments it was discovered that formic acid accumulated to inhibitory levels. It was determined that the nitrogen source, ammonium hydroxide, must be tailored to the carbon consumption to avoid formic acid accumulation. The ALE ran in three lineages for approximately 3000 hours and more than 500 generations. Evolved isolates obtained from each lineage demonstrated an increase in growth rate in conjunction with improve formate utilization compared to the parental strain when evaluated in pH-stat bioreactors. The isolates with improved performance were then subjected to whole genome sequencing to identify potentially causative mutations. Mutations in several key genes across different lineages have been found and will be evaluated individually and in combination to identify those that improve growth on formic acid. Incorporating these mutations into production strains has the potential to greatly improve formic acid conversion and further industrial decarbonization.

adaptive laboratory evolution↗

Determination of Molecular Structure and Dynamics of Molten Salts by Advanced Neutron and X-ray Scattering Measurements and Computer Modeling

The design and development of fully functional Molten-Salt Reactors (MSR) require detailed knowledge of the molten salt properties in order to understand and predict the salt’s behavior. Fundamental properties of interest include molecular structure, speciation, and dynamics (such as diffusion coefficients) of salt components and dissolved corrosion and fission products. Computer modeling is necessary to predict changes in physical and chemical properties due to irradiation, burning of dissolved fuel, and corrosion. The modeling requires experimental data, and advanced neutron and x-ray scattering and spectroscopy provide the most reliable and direct determination of the structure (Pair-Distribution Functions, PDF), and dynamics of ions in the melt. This project dealt with both fluoride and chloride salts. The PDFs have been measured by a combination of neutron and x-ray diffraction. We utilized the techniques of isotope substitutions, a very powerful tool available for neutron-scattering, to extract the details of the liquid structure. Although similar measurements have been done before, modern advanced neutron and x-ray-scattering techniques allow collecting the data at much higher resolution and in a wider range of temperatures. Importantly, we were among the first to study fluoride salts by neutron scattering. The importance of impurities and their effects on salt properties have become apparent recently and so new methods of salt purification were developed. We took advantage of these developments to produce reliable data, which have been used for computer simulations of both clean salts and those with added fission and corrosion products most relevant for MSRs. Ab initio molecular dynamics simulations have been performed to understand the multi-component liquid solution, in particular solubility of impurities and thermodynamic interactions in relation to the ionic-cluster structure of the fluid. We applied machine learning to regress from the simulation and experimental data in order to develop a fast-acting model that can handle molten salt with an arbitrary (≥ 10) number of chemical elements and be able to predict chemical potential as a function of composition and temperature. This project resulted in a number of experimental and computer-simulation publications, a patent application, and numerous conference presentations (American Physical Society, American Chemical Society, and The Electrochemical Society among others). Multiple students and postdocs participated and collaborated on aspects of this project. This project seeded new collaborations between MIT and other institutions, such as the University of Massachusetts Lowell, the University of Illinois Urbana-Champaign, the University of California Berkeley, and Oak Ridge and Los Alamos National Labs. As such, this project has had a broad and lasting impact beyond its original scientific scope.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Comparison of Four Strong Acids on the Precipitation Potential of Gypsum in Brines During Distillation of Pretreated, Augmented Urine

In this study, three different mineral acids were substituted for sulfuric acid (H2SO4) in the urine stabilizer solution to eliminate the excess of sulfate ions in pretreated urine and assess the impact on maximum water recovery to avoid precipitation of minerals during distillation. The study evaluated replacing 98% sulfuric acid with 85% phosphoric acid (H3PO4), 37% hydrochloric acid (HCl), or 70% nitric acid (HNO3). The effect of lowering the oxidizer concentration in the pretreatment formulation also was studied. This paper summarizes the test results, defines candidate formulations for further study, and specifies the injection masses required to stabilize urine and minimize the risk of mineral precipitation during distillation. In the first test with a brine ersatz acidified with different acids, the solubility of calcium in gypsum saturated solutions was measured. The solubility of gypsum was doubled in the brines acidified with the alternative acids compared to sulfuric acid. In a second series of tests, the alternative acid pretreatment concentrations were effective at preventing precipitation of gypsum and other minerals up to 85% water recovery from 95th-percentile pretreated, augmented urine. Based on test results, phosphoric acid is recommended as the safest alternative to sulfuric acid. It also is recommended that the injected mass concentration of chromium trioxide solution be reduced by 75% to minimize liquid resupply mass by about 50%, reduce toxicity of brines, and reduce the concentration of organic acids in distillate. The new stabilizer solution formulations and required doses to stabilize urine and prevent precipitation of minerals up to 85% water recovery are given. The formulations in this study were tested on a limited number of artificially augmented urine batches collected from employees at the Johnson Space Center (JSC). This study successfully demonstrated that the desired physical and chemical stability of pretreated urine and brines can be achieved using alternate pretreatment formulations under laboratory conditions. Additional testing and hazard assessments will be required to determine the feasibility of utilizing the proposed urine pretreatment formulations on ISS.

Muirhead, Dean↗

Understanding Fission Gas Bubble Distribution and Zirconium Redistribution in Neutron-irradiated U-Zr Metallic Fuel Using Machine Learning

U-10wt.% Zr (U-10Zr) based metallic fuel is the leading candidate for next-generation sodium cooled fast reactor in United States. Currently, Idaho National Laboratory (INL) has been the leading national laboratory for research, development, and demonstration (RD&D) on metallic fuel. Advanced post-irradiation characterization will help to understand fuel microstructure and property change during irradiation, benefiting fuel qualification for commercial application. Characterization capabilities ranging from sub-nanometer to micrometer, such as scanning electron microscopy (SEM), focused ion beam (FIB) sampling, transmission electron microscopy (TEM) characterization, and local thermal conductivity microscopy (TCM), have been utilized recently on irradiated U-10Zr fuel samples to gain a better understanding of nuclear fuel microstructure and property evolution inside a reactor. The FIB/SEM coupled with energy dispersive X-ray spectroscopy (EDS) can capture the essential information to achieve better understanding of fuel behaviors. Inside a nuclear reactor, the phase and microstructure of U-10Zr is constantly changing under neutron bombardment. For example, the gaseous fission product atoms have a limited solubility inside fuel matrix and tend to precipitate out in bubble form, which not only contribute to fuel thermal conductivity degradation but also provide a shortcut for movement of fission products, i.e. lanthanides. The resultant deposition of lanthanides at the cladding inner surface will potentially trigger a chemical reaction/interaction between nuclear fuel and cladding at reactor operational conditions, threatening fuel integrity and safety. FIB/SEM coupled with EDS can provide the fission bubble information as well as probe into phase separation or Zr redistribution, which is fundamental to predict the fuel performance. With high velocity image data generating method, such as FIB/SEM, an automatic way to extract the microstructural information quantitively can better serve the needs from post irradiation characterization. A trained machine learning model, named Decision Tree, is employed to generate a bubble classifier and to categorize bubbles into three categories: isolated bubble, connected without lanthanides, and connected with lanthanides bubbles[3]. This work presents a showcase of this approach on six regions of a fuel cross-section along the radial temperature gradient. We obtained distributions of bubble categories and porosity rates along the six regions. Moreover, a secondary phase U-Zr2 was determined and found on regions 5 and 6. The secondary phase fraction was increasing from 15.61% in region 5 to 34.79% in region 6 based on this approach . This quantitative data offers insights into the lanthanide migration and potentially thermal conductivity degradation. This information from machine learning will be fed into fuel design code for better prediction of fuel performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Determination of a suitable molar absorption coefficient (ε) for lignin analysis of fibrous plants using the CASA method

In this study, the benchmarking and applicability of the CASA method for the analysis of fibrous plants, such as flax, hemp, and jute, is evaluated. Lignin is a phenolic biopolymer present in plant cell walls and is composed of three primary monomeric units, designated G, S, and H. Various factors, such as the genetic variability, influence the relative proportions of these units in plant samples. Recently, the cysteine-assisted sulfuric acid (CASA) method has been introduced as a rapid method for the quantification of lignin in wood samples. The aim of this study is to establish a suitable molar absorption coefficient (ε, L·g –1 ·cm –1 ) to adapt the CASA method for use with annual plant fibers. This investigation was motivated by the technical advantages of the CASA method, including higher throughput, lower reaction temperatures, and ecological benefits due to the absence of carcinogenic, mutagenic, or reprotoxic (CMR) substances and the need for minimal sample quantities. In this method, lignin solubilization is facilitated by cysteine, which is an amino acid that enhances the reaction kinetics, using a one-hour incubation period. However, as with any spectrophotometric technique, the CASA method depends on a molar absorption coefficient (ε) that varies according to the ratio of the aromatic units within the polymer. To evaluate the suitability of CASA for quantifying lignin in economically significant plant fibers, we investigate the impact of the unit ratios on the accuracy of ε. The results are compared with those of two widely recognized lignin analytical methods: the Klason method, which is a gravimetric reference method, and the acetyl bromide soluble lignin method, which is the most commonly used spectrophotometric approach. The final ε obtained in this study reveals a relative difference in lignin content ranging from –8 % to +9 % based on a comparison between the CASA and Klason methods across different industrial hemp varieties. As a result, using known G:S ratios in annual fibrous plants, ε can be estimated from our results.

59 BASIC BIOLOGICAL SCIENCES↗

Integration of Biorelevant Pediatric Dissolution Methodology into PBPK Modeling to Predict In Vivo Performance and Bioequivalence of Generic Drugs in Pediatric Populations: a Carbamazepine Case Study

This study investigated the impact of gastro-intestinal fluid volume and bile salt (BS) concentration on the dissolution of carbamazepine (CBZ) immediate release (IR) 100 mg tablets and to integrate these in vitro biorelevant dissolution profiles into physiologically based pharmacokinetic modelling (PBPK) in pediatric and adult populations to determine the biopredictive dissolution profile. Dissolution profiles of CBZ IR tablets (100 mg) were generated in 50–900 mL biorelevant adult fasted state simulated gastric and intestinal fluid (Ad-FaSSGF and Ad-FaSSIF), also in three alternative compositions of biorelevant pediatric FaSSGF and FaSSIF medias at 200 mL. This study found that CBZ dissolution was poorly sensitive to changes in the composition of the biorelevant media, where dissimilar dissolution (F2 = 46.2) was only observed when the BS concentration was changed from 3000 to 89 μM (Ad-FaSSIF vs Ped-FaSSIF 50% 14 BS). PBPK modeling demonstrated the most predictive dissolution volume and media composition to forecast the PK was 500 mL of Ad-FaSSGF/Ad-FaSSIF media for adults and 200 mL Ped-FaSSGF/FaSSIF media for pediatrics. A virtual bioequivalence simulation was conducted by using Ad-FaSSGF and/or Ad-FaSSIF 500 mL or Ped-FaSSGF and/or Ped-FaSSIF 200 mL dissolution data for CBZ 100 mg (reference and generic test) IR product. The CBZ PBPK models showed bioequivalence of the product. This study demonstrates that the integration of biorelevant dissolution data can predict the PK profile of a poorly soluble drug in both populations. Further work using more pediatric drug products is needed to verify biorelevant dissolution data to predict the in vivo performance in pediatrics.

60 APPLIED LIFE SCIENCES↗

Towards an Enhanced Droplet Activation Scheme for Multi-Moment Bulk Microphysics Schemes

Initial droplet spectra produced upon activation impact the ensuing chain of microphysical processes andtherefore play a crucial role in cloud evolution. This work re-examines dependencies of newly formed clouddroplet size distribution (CDSD) characteristics on environmental and aerosol properties via parcel model simulationsthat serve as the basis for a multi-moment bulk microphysics droplet activation scheme suitable for acloud-resolving model (CRM). It is found that applying a fixed size threshold to define activated droplets versusemploying physical considerations can lead to erroneous activation and overly broad CDSDs for high aerosolconcentration and weak updraft conditions. Aerosol distributions characterized by larger median sizes and/orincreased solubility can result in greater activated droplet numbers, whereas impacts of these parameters onCDSD spectral width depend on both aerosol number concentration and updraft velocity. An expansion of theactivation scheme to include CDSD spectral width is proposed to aid efforts to extend high-order momentprediction to cloud droplet categories in CRMs as well as better represent variability in the activation process onthe cloud scale.simulations to investigate the regime dependence of the relative dispersion(d)1 of newly activated CDSDs, where d is the ratio of dropletradius standard deviation (σ) to the mean radius (r ). C16 demonstratedthat increasing Na resulted in increasing (decreasing) d values via reducedcondensational narrowing (spectral broadening) rates within theAL (UL) regime, with d values peaking in the TR regime. Their findingssuggest a similar regime dependence for d as R09 noted for Nc and helpexplain reportedly conflicting relationships between Na and CDSDspectral characteristics (cf. Hudson and Noble, 2014; Liu et al., 2014),although the applicability of these results within bulk microphysicalschemes was not addressed.Simulating aerosol-cloud interactions with CRMs employing bulkmicrophysics requires that the scheme minimally predict two CDSDparameters, namely mass and number concentrations, and represent thedroplet activation process. Various activation schemes aim to determineNc from aerosol and environmental properties and include analyticalexpressions (e.g., Abdul-Razzak et al., 1998; Morrison et al., 2005) aswell as lookup tables (LUTs) based on detailed parcel model calculations(e.g., Saleeby and Cotton, 2004, hereafter SC04; Segal and Khain,2006; Thompson and Eidhammer, 2014). Expressions to diagnose CDSDspectral width from Nc (Grabowski, 1998; Liu et al., 2006; Morrison andGrabowski, 2007) or cloud water content (Geoffroy et al., 2010) havealso been developed, although more robust methods to obtain CDSDspectral width upon activation are presently lacking. This latter point isrelevant for triple-moment (3 M) bulk microphysics that aim to predictdistribution spectral width alongside number and mass concentrations(e.g., Loftus et al., 2014; Milbrandt and Yau, 2005).The current work extends the findings of C16 to the current LUTbasedaerosol activation scheme used in the Regional AtmosphericModeling System (RAMS) (Cotton et al., 2003; SC04; Saleeby and vanden Heever, 2013, hereafter SvdH13) and additionally examinesaerosol size and solubility impacts on newly activated CDSD properties.Because early cloud development processes such as condensationalgrowth, evaporation, and droplet self-collection depend on and impactCDSD spectral width (Hudson and Yum, 1997; Seifert and Beheng 2001;Lu and Seinfeld, 2006; Igel and van den Heever, 2017), an expansion ofthe activation LUTs to include CDSD spectral width is proposed as apreliminary step for extending 3M prediction to CDSDs in CRMs forimproved simulations of aerosol-cloud interactions.2. MethodologyThe current RAMS two-moment microphysics module determinesthe fractional number of aerosol particles that activate to cloud dropletsfrom five-dimensional LUTs based on model predicted air temperature(T), w, Na, and the geometric median radius (rg) and soluble fraction (ε)of the aerosol size distribution (SvdH13). These LUTs are created offlineusing a one-dimensional Lagrangian adiabatic parcel model (Feingoldand Heymsfield, 1992; Heymsfield and Sabin, 1989; SC04) to simulateexplicit droplet activation and initial CDSD growth for a range of ambientatmospheric conditions [T, w] and binned lognormal aerosol sizedistributions given by= ⎡⎣ ⎢− ⎤⎦ ⎥N r Nr π σr rσ( )2 lnexp[ln( / )]2(ln )aggg22 (1)where r is the dry aerosol particle bin radius and σg is the geometricstandard deviation of the distribution. As the parcel model simulationsfocus on the activation process, other processes such as coalescence,sedimentation, and mixing are not considered. Details of the parcelmodel can be found in SC04 and SvdH13, and only a brief description isprovided here. At the onset of parcel model calculations, the initiallydry aerosol particles in all bins first deliquesce and reach theirequilibrium diameters in a sub-saturated environment based on theKöhler equation for solution droplets. The parcel is then lifted at a fixedupward velocity w, and particle growth by vapor diffusion, along withconcurrent changes in the ambient environment, are iteratively computedusing the Variable-coefficient Ordinary Differential Equation(VODE) solver (Brown et al., 1989). The time resolution of these calculationsis determined within the VODE solver, and the frequency atwhich the solver is called is controlled by a longer model time stepbased on fixed upward parcel displacement increments (Δz) at thespecified w (Δt=Δz/w). Model calculations proceed until the parcelreaches a height 50m beyond the level of maximum saturation ratio(Smax) or total parcel displacement exceeds 2 km. Upon model termination,Smax and the fractional number of aerosols (factv) resulting innewly formed cloud droplets, defined as particles having diameters of atleast 2 μm, are cataloged in the LUTs according to the specified T, w, Na,rg, and ε parameter values.A critical point regarding the creation of these LUTs is the use of afixed minimum diameter (Dmin) to define cloud droplets in the parcelmodel, which can produce erroneous CDSD characteristics, particularlywithin the UL regime. For aerosol distributions with large rg valuesunder low SS conditions, for example, deliquesced aerosols within thelarge tail of the distribution can exceed 2 μm in diameter yet remainunactivated as ‘haze’ particles (Levin and Cotton, 2009; McFigganset al., 2006). For this study, aerosol particles activate to cloud dropletsbased on the critical diameter Dcrit as a function of parcel supersaturationratio (Sr) as in R09:D = σ MS RTρ83 ln( ) critsol wr w (2)where σsol is the surface tension of a solution droplet, Mw and ρw are themolar mass and density of liquid water, respectively, and R is theuniversal gas constant. Additionally, at relatively large w values withinthe AL regime, Nc stabilizes shortly after reaching supersaturation.However, parcel ascent and condensational growth continue beyondthe level of Smax, potentially causing additional narrowing of the CDSD.In the current work, model calculations terminate upon reaching Smaxas changes in Nc are negligible with continued ascent (Peng et al., 2007;R09).Parcel model simulations are performed to examine the sensitivitiesof CDSD characteristics to w, Na, rg, and ε, with the ranges for theseparameters listed in Table 1. Aerosols are assumed to be a mix of solubleand insoluble material of equal density, specified by ε, where fullysoluble aerosols correspond to ammonium sulfate with hygroscopicityparameter κ=0.61 (Petters and Kreidenweis, 2007). FollowingSvdH13, aerosol geometric standard deviation is fixed at σg=1.8, andaerosol distributions (Eq. 1) are partitioned into 100 logarithmicallyspacedbins spanning a size range specific to each rg value. For all simulations,Δz=1 m, and initial values of relative humidity, air temperatureand pressure are set to RH=0.99, T=10 °C and p=900 hPa,respectively.

Loftus, Adrian M.↗

Wastewater Recycling Using a Hygroscopic Cooling System

This project by the Energy & Environmental Research Center (EERC), Baltimore Aircoil Company (BAC), and Great River Energy (GRE) evaluated the concept of recycling wastewater at a coal-fired power plant using a hygroscopic cooling system, which is an evaporative cooling technology analogous to conventional cooling towers, except that sparingly soluble dissolved solids are precipitated and removed as waste solids instead of purging them with a liquid blowdown stream. This technology can maximize the use of plant makeup water by obtaining useful evaporative cooling from wastewater while minimizing the volume of wastes needing disposal. Experimental activities were conducted in two phases, a laboratory-based evaluation of the properties of wastewater from the host site, GRE’s Coal Creek Station near Underwood, North Dakota, and a field test of a small pilot hygroscopic cooling system at the host site power plant. Findings from the laboratory study informed the design of the pilot system and the system’s field test performance served as the basis for a techno-economic analysis (TEA) of the hygroscopic recycling concept. At the preferred operating conditions identified during the TEA, the wet-bulb approach temperature of the tower was 7.3°C (13°F) and the volume of blowdown produced by the plant was reduced to 5.4% of its incoming volume. Waste solids produced during field testing were classified as nonhazardous waste based on the measured hazardous element content and evaluation of their leaching potential. However, to qualify as a solid for landfill disposal i.e., as determined by the U.S. Environmental Protection Agency’s paint filter test, it appears that a dewatering step beyond hydrocyclone separation is needed. The baseline levelized cost of wastewater disposal (LCWD) for hygroscopic wastewater recycling was estimated to be $\$ $3.69–$\$ $3.72 per m3 of plant blowdown. Capital cost was estimated to contribute over 54% to the LCWD, and parameters that impact capital cost such as the heat exchange coil material of construction and the tower’s wet-bulb approach temperature were identified as having the greatest impact on overall LCWD. A LCWD estimate prepared for the same application but using thermomechanical brine evaporation was almost 40% higher than that calculated for hygroscopic cooling, despite recovering distilled-quality water for reuse, while the LCWD for disposal-only, deep well injection was estimated to be 30% lower compared to hygroscopic wastewater recycling.

01 COAL, LIGNITE, AND PEAT↗

Spacecraft Adhesive Residue On-Composite Analysis

Tapes are used on space vehicles for numerous reasons. They are used for taping close ports, labeling, and even temporarily attaching something to the spacecraft. This project stemmed from the need to determine which tapes are most effective for our customer's space vehicle during its ground processing stage. During ground processing, there are multiple stages of building where workers need to use tape to temporarily stabilize or close something for a matter of seconds, days, weeks, or even a few months. After peeling these tapes off the flight hardware, the residue left behind by the tape poses potential risks that can lead to incidents, which may not be easily noticeable to the engineers. It is important to identify these issues since nothing can be done once it is in space. The purpose of this project is to assist in research to create an accessible reference for which tapes are preferred on common flight hardware surfaces. Five different substrates and eight tapes were selected for evaluation. The selected substrates were chosen because they comprise the most surface area on the vehicle. The tapes selected were either heritage or new contenders. The adhesive studies were performed for multiple dwell times to study the tendency of different tapes to leave residue behind on various substrates and quantifying that residue. Many other tests were performed to supplement the main objective of the project. These tests included adhesive solubility, peel adhesion, and SEM analyses.

McFadden, Saleah J.↗

Adaptive Laboratory Evolution for Enhanced Performance of Cupriavidus necator on Formic Acid

The need to decarbonize our economy is becoming ever more pressing. CO2, can be electrochemically reduced to formic acid, a soluble C1 molecule that can be used to store carbon and energy. Cupriavidus necator H16, a soil bacterium, capable of consuming and growing on formic acid as its sole carbon source, is well positioned to upgrade CO2-derived formic acid into value added chemicals such as sustainable aviation fuel. To improve the performance of C. necator on formic acid adaptive laboratory evolution (ALE), a proven tool for improving microbial fitness, has been conducted using continuous pH-stat bioreactors. The system works on the basis that consumption of formic acid raises the pH and triggers the addition of more formic acid to maintain the pH at 6.7, such that formic acid is provided at the same rate as it is consumed. This system has been coupled with level control to achieve continuous fermentation where cells acquiring mutations that improve growth on formic acid become more abundant in the population, from which they can be isolate and characterized. This configuration where the dilution rate is controlled by pH-stat has been found to seek out a dilution rate that matches the exponential growth rate of the organism. During developmental experiments it was discovered that formic acid accumulated to inhibitory levels. It was determined that the nitrogen source, ammonium hydroxide, must be tailored to the carbon consumption to avoid formic acid accumulation. ALE has run in three lineages for 2000+ hours and 300+ generations. Growth of evolved isolates derived from all lineages will be evaluated on formic acid and those with improved growth rates or biomass yield will be subjected to whole genome sequencing to identify potentially causative mutations. These mutations will be evaluated individually and in combination to identify those that improve growth on formic acid.

adaptive laboratory evolution↗

Molecular structure models of amorphous bismuth and cerium carboxylate catalyst precursors

As our societal need for materials and energy has grown, so has our need for catalyst processes in hydrogen production. A major function in these applications, for both homogenous and heterogeneous catalysis processes, is the synthesis of an active metal catalyst. It must first be soluble to control the physical properties of the metal being used. Recent work in metal precursors has begun to turn toward these metal carboxylate types of material. Here, structural models are proposed for bismuth 2-ethylhexanoate and 2,2-dimethyloctanoate and cerium 2-ethylhexanoate. The bismuth compounds have been characterized at different ratios of bismuth to carboxylate as solutions of the free acids. Their structures are most consistent with a Bi 4 (RCO 2 ) 12 motif where the Bi ions are arranged in a flattened tetrahedron with Bi – Bi distances of about 4.3 Å. There is evidence for Bi – O – Bi linkages at low free acid concentrations. The cerium compound is most consistent with a linear tetracerium molecule where the Ce – Ce distances repeat at about 4.3 Å out to 16.4 Å. The models were generated by analogy with known crystal structures and compared to high-energy x-ray scattering data. To further evaluate the models, DFT calculations were made, and the equilibrium geometries were compared. The vibrational spectra calculated from those geometries are presented and compared to the experimental results. Magnetization vs. temperature data was collected on the cerium compound, and its behavior was consistent with the proposed model. A geometrical approach to determining the dimensionality and relative positions of the metal ions in these structures is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel perspective on a conventional technique: Impact of ultra-low temperature on bacterial viability and protein extraction

Ultra-low temperature (ULT) storage of microbial biomass is routinely practiced in biological laboratories. However, there is very little insight regarding the effects of biomass storage at ULT and the structure of the cell envelope, on cell viability. Eventually, these aspects influence bacterial cell lysis which is one of the critical steps for biomolecular extraction, especially protein extraction. Therefore, we studied the effects of ULT-storage (-80°C) on three different bacterial platforms: Escherichia coli , Bacillus subtilis and the cyanobacterium Synechocystis sp. PCC 6803. By using a propidium iodide assay and a modified MTT assay we determined the impact of ULT storage on cellular viability. Subsequently, the protein extraction efficiency was determined by analyzing the amount of protein released following the storage. The results successfully established that longer the ULT-storage time lower is the cell viability and larger is the protein extraction efficiency. Interestingly, E . coli and B . subtilis exhibited significant reduction in cell viability over Synechocystis 6803. This indicates that the cell membrane structure and composition may play a major role on cell viability in ULT storage. Interestingly, E . coli exhibited concomitant increase in cell lysis efficiency resulting in a 4.5-fold increase (from 109 μg/ml of protein on day 0 to 464 μg/ml of protein on day 2) in the extracted protein titer following ULT storage. Furthermore, our investigations confirmed that the protein function, tested through the extraction of fluorescent proteins from cells stored at ULT, remained unaltered. These results established the plausibility of using ULT storage to improve protein extraction efficiency. Towards this, the impact of shorter ULT storage time was investigated to make the strategy more time efficient to be adopted into protocols. Interestingly, E . coli transformants expressing mCherry yielded 2.7-fold increase (93 μg/mL to 254 μg/mL) after 10 mins, while 4-fold increase (380 μg/mL) after 120 mins of ULT storage in the extracted soluble protein. We thereby substantiate that: (1) the storage time of bacterial cells in -80°C affect cell viability and can alter protein extraction efficiency; and (2) exercising a simple ULT-storage prior to bacterial cell lysis can improve the desired protein yield without impacting its function.

59 BASIC BIOLOGICAL SCIENCES↗

Altering the cellular mechanical force balance results in integrated changes in cell, cytoskeletal and nuclear shape

Studies were carried out with capillary endothelial cells cultured on fibronectin (FN)-coated dishes in order to analyze the mechanism of cell and nuclear shape control by extracellular matrix (ECM). To examine the role of the cytoskeleton in shape determination independent of changes in transmembrane osmotic pressure, membranes of adherent cells were permeabilized with saponin (25 micrograms/ml) using a buffer that maintains the functional integrity of contractile microfilaments. Real-time videomicroscopic studies revealed that addition of 250 microM ATP resulted in time-dependent retraction and rounding of permeabilized cells and nuclei in a manner similar to that observed in intact living cells following detachment using trypsin-EDTA. Computerized image analysis confirmed that permeabilized cells remained essentially rigid in the absence of ATP and that retraction was stimulated in a dose-dependent manner as the concentration of ATP was raised from 10 to 250 microM. Maximal rounding occurred by 30 min with projected cell and nuclear areas being reduced by 69 and 41%, respectively. ATP-induced rounding was also accompanied by a redistribution of microfilaments resulting in formation of a dense net of F-actin surrounding retracted nuclei. Importantly, ATP-stimulated changes in cell, cytoskeletal, and nuclear form were prevented in permeabilized cells using a synthetic myosin peptide (IRICRKG) that has been previously shown to inhibit actomyosin filament sliding in muscle. In contrast, both the rate and extent of cell and nuclear rounding were increased in permeabilized cells exposed to ATP when the soluble FN peptide, GRGDSP, was used to dislodge immobilized FN from cell surface integrin receptors.(ABSTRACT TRUNCATED AT 250 WORDS).

Non-NASA Center↗

Exploring the impact of multivalent substitution on high-temperature electrical conductivity in doped lanthanum chromite perovskites: An experimental and ab-initio study

Doped LaCrO 3 perovskites hold promise as robust materials for electrical interconnects and sensor applications in harsh environments. In this work, we investigated the high-temperature behavior of La 1–x Sr x CrO 3 , La 1–x Ca x CrO 3 and La 0.8 Sr 0.2 Cr 1-x Mn x O3 (0.1 ≤ x ≤ 0.4) through a combination of computational modeling and physical characterization up to 1500 °C. Crystalline structural properties were determined and compared with ab-initio calculations, which demonstrated excellent agreement with experimental findings. High-temperature electrical conductivity measurements were performed under different atmospheres. Calcium and strontium/manganese co-doped lanthanum chromites exhibited typical semiconductor exponential trends and conductivity showed proportional correlation with substitutions levels up to 30 %. The DFT modelling was completed up to 1500 °C, including low and high temperature chromite phases and oxygen vacancies insertion. Calculations were correlated with experimental electrical properties. This work expands the understanding of doped lanthanum chromites and paves the way for the development of materials suitable for demanding high-temperature applications.

20 FOSSIL-FUELED POWER PLANTS↗

First-principles analysis of the Al-rich corner of Al-Li-Cu phase diagram

The phase diagram of Al-Li-Cu system in the Al-rich region was determined by means of first-principles calculations and statistical mechanics. The mixing enthalpies of many configurations for different lattices in the whole Al-Li-Cu system were determined by density functional theory simulations to find the stable phases in the convex hull. They were fitted with a cluster expansion to calculate the free energy of the configurations with different compositions as a function of temperature in the Al-rich region (Al content > 40 at.%) by means of Monte Carlo simulations. It was found that the ground state phases in the Al-rich part of the Al-Li-Cu phase diagram were α-Al, θ' (Al 2 Cu), $δ$' (Al 3 Li), $δ$ (AlLi) and T 1 (Al 6 Cu 4 Li 3 ), while θ'' (Al 3 Cu), T 1' (Al 2 CuLi) and Al 3 Cu 2 Li were found on the lowest mixing enthalpy surfaces of their lattices and were metastable. α-Al, $δ$ and T 1 are stable phases in the whole temperature range while $δ$' becomes metastable at very low temperature and θ (Al 2 Cu) replaces θ' as the stable phase at approximately 550 K due to the vibrational entropic contribution. In addition, the phase diagram in the Al-rich region was built and it was shown in isothermal sections from 100 to 900 K. They were in good agreement with the limited experimental data in the literature and provided new information regarding the stability, solubility and stoichiometry of the different phases. This information is important to understand the precipitation mechanisms during high temperature aging.

36 MATERIALS SCIENCE↗