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DOE OSTI2024

ACS Spotlight: Bipolar Membranes for Electrochemical Energy Conversion, Chemical Manufacturing, and Separations

Sustainable energy conversion, chemical manufacturing, and separations are central to addressing the world’s energy and environmental challenges. Electrochemical platforms stand as a cornerstone in addressing these challenges because they are low exergy and can be powered on renewable electrons. In electrochemical systems, bipolar membranes (BPMs) are emerging as a unique class of ion exchange membranes poised to revolutionize various electrochemical processes via pH control of anode and cathode chambers and in situ pH adjustment. In this Spotlight Review, we provide a comprehensive review of electrochemical platforms utilizing BPMs for energy conversion (water electrolyzers for hydrogen production, fuel cells, and flow batteries), chemical manufacturing (electrolyzers that convert carbon dioxide into value-added chemicals and nitrate into ammonia), and separations. The motivation for using BPMs, as well as their performance and durability, in electrochemical platforms are disseminated. We also discuss current challenges that impede BPM electrochemical systems from competing with state-of-the-art electrochemical systems using monopolar ion-exchange membranes (e.g., anion/hydroxide exchange membranes and cation/proton exchange membranes). Here, the review also covers molecular modeling and continuum modeling efforts to understand the basic mechanisms that govern BPM performance.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2024

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Upgrading Biogas through in situ Conversion of Carbon Dioxide to Biomethane in Anaerobic Digesters

Organic waste streams generated by wastewater treatment plants, agricultural operations, and food processing industries represent an important yet underutilized opportunity for renewable energy production in the United States. Through anaerobic digestion, these waste streams can produce biogas, a mixture primarily composed of methane (CH4) and carbon dioxide (CO2), that can be upgraded to pipeline-quality natural gas. However, most existing upgrading technologies remove CO2 from biogas rather than utilizing it, leaving a significant portion of the potential energy unused. This project investigates a novel biological upgrading approach that converts CO2 into additional CH4 by supplying hydrogen (H2) to specialized microorganisms capable of performing hydrogenotrophic methanation. The main challenges associated with biological biogas upgrading are related to hydrogen supply, gas-liquid mass transfer, and process stability. First, due to the high cost of hydrogen gas, it is preferable that H2 be produced on-site using renewable energy sources such as wind or solar power. Second, hydrogen has low solubility in liquids, which limits its availability to microorganisms and requires strategies to improve gas dissolution and transfer within the reactor. Third, process inhibition may occur as a result of increased pH caused by CO2 consumption or elevated H2 partial pressure, both of which can negatively affect methanogenic activity. Although research in these areas has advanced during the course of this project, these challenges have not yet been fully resolved. To date, the biological systems that have achieved the highest methane concentrations are typically ex-situ reactors, where operational conditions can be more easily controlled. For this reason, the findings of the present project remain highly relevant. The project goal was to develop an innovative system that can accomplish biogas upgrading via biological conversion of CO2 to CH4, in a novel hybrid approach that combines the advantages of both in-situ and ex-situ systems. The proposed system employs a three-phase upflow anaerobic bioreactor with H2 delivery through a gas-permeable membrane, enabling efficient hydrogen transfer and microbial conversion. Under optimized operating conditions, the system achieved 99% H2 consumption and 90% CO2 conversion. A subsequent gas cleaning stage was implemented to further improve gas quality and meet target purity standards. The upgraded gas composition reached 97.7% CH4, 2.2% CO2, and 0.97% O2, while H2S concentrations remained below detection limits. In addition, a flue gas-driven inorganic thermoelectric generator (TEG) system was designed and experimentally validated as a potential source of electricity for H2 production. The system consisted of six TEG modules connected in series and achieved an open-circuit voltage of 4.5 V and a maximum power output of 224 mW at a temperature difference of approximately 53.5 °C, demonstrating effective conversion of waste heat into electrical power under simulated flue gas conditions. Finally, a comprehensive techno-economic analysis was completed to evaluate the capital and operating costs associated with the proposed system. The results provide important insights to guide future scale-up, optimization, and potential deployment of integrated biological biogas upgrading technologies.

09 BIOMASS FUELS↗

DOE OSTI2021

Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification

Synthesis and implementation of highly active, stable, and affordable electrocatalysts for the oxygen evolution reaction (OER) is a major challenge in developing energy efficient and economically viable energy conversion devices such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. The current benchmark electrocatalyst for OER is based on iridium oxide (IrO x ) due to its superior performance and excellent stability. However, large scale applications using IrO x are impractical due to its low abundance and high cost. In this work, we report a highly active hafnium-modified iridium oxide (IrHf x O y ) electrocatalyst for OER. The IrHf x O y electrocatalyst demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than a IrO x electrocatalyst. The highest intrinsic mass activity of the IrHf x O y catalyst in acid conditions was calculated as 6950 A gIrO x -1 at an overpotential (η) of 0.3 V. Combined studies utilizing operando surface enhanced Raman spectroscopy (SERS) and DFT calculations revealed that the active sites for OER are the Ir-O species for both IrO x and IrHf x O y catalysts. The presence of Hf sites leads to more negative charge states on nearby O sites, and shortening the bond lengths of Ir-O, and lowering free energies for OER intermediates to accelerate the OER process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Engineering surface charges of nanofiltration membranes to maximize Li + /Mg 2+ separation properties

Polyamide-based nanofiltration (NF) membranes are attractive for Li + /Mg 2+ separation for lithium recovery from salt brine (containing mainly Mg 2+ ). However, Li + and Mg 2+ have similar hydration radii, resulting in a low separation factor (SF Li/Mg ). Herein, we demonstrate that SF Li/Mg can be significantly enhanced by optimizing the membrane surface positive charges. This results in an unexpected maximum SF Li/Mg at a solution pH slightly below its isoelectric point (IEP). Specifically, NF270 membrane was surface-grafted with 2-(methacryloyloxy)ethyltrimethylammonium chloride (META) or polyethylenimine (PEI) using bio-adhesive dopamine, forming a thin, stable, charged layer (20–40 nm) on the surface. The effects of solution pH and surface modification on the surface zeta potential (ZP) and single- and mixed-salt Li + /Mg 2+ separation properties are thoroughly investigated. For example, the META grafting increases the ZP from 9.2 to 16 mV and SF Li/Mg by 130 % from 35 to 80 at pH 4, superior to the state-of-the-art commercial NF membranes. Furthermore, this surface modification occurs at ≈22 °C in aqueous solutions and can be utilized to enhance commercial modules for practical applications.

Li+/Mg2+ separation↗

DOE OSTI2020

Mineral Scale Prevention on Electrically Conducting Membrane Distillation Membranes Using Induced Electrophoretic Mixing

The growth of mineral crystals on surfaces is a challenge across multiple industrial processes. Membrane-based desalination processes, in particular, are plagued by crystal growth (known as scaling), which restricts the flow of water through the membrane, can cause membrane wetting in membrane distillation, and can lead to the physical destruction of the membrane material. Scaling occurs when supersaturated conditions develop along the membrane surface due to the passage of water through the membrane, a process known as concentration polarization. To reduce scaling, concentration polarization is minimized by encouraging turbulent conditions and by reducing the amount of water recovered from the saline feed. In addition, antiscaling chemicals can be used to reduce the availability of cations. Here, we report on an energy-efficient electrophoretic mixing method capable of nearly eliminating CaSO4 and silicate scaling on electrically conducting membrane distillation (ECMD) membranes. The ECMD membrane material is composed of a percolating layer of carbon nanotubes deposited on porous polypropylene support and cross-linked by poly(vinyl alcohol). The application of low alternating potentials (2 Vpp,1Hz) had a dramatic impact on scale formation, with the impact highly dependent on the frequency of the applied signal, and in the case of silicate, on the pH of the solution.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1988

Fuel neutralization by ozone oxidation

The viability of a hazardous waste disposal system based on ozone oxidation of hydrazine fuels at low aqueous concentrations in the presence of ultraviolet light (UV at 2.537 x 10(exp -7) m or 8.324 x 10(exp -7) ft) excitation was investigated. Important parameters investigated include temperature, solution pH, and ultraviolet light power. Statistically relevant experimentation was done to estimate main factor effects on performance. The best available chemical analysis technology was used to evaluate the performance of the system.

Swartz, A. B.↗

NASA NTRS1992

Reduced vertebral bone density in hypercalciuric nephrolithiasis

Dual-energy x-ray absorptiometry and single-photon absorptiometry were used to determine bone density at the lumbar spine and radial shaft in 62 patients with absorptive hypercalciuria, 27 patients with fasting hypercalciuria, and 31 nonhypercalciuric stone formers. Lumbar bone density was significantly lower in patients with absorptive (-10%) as well as in those with fasting hypercalciuria (-12%), with 74 and 92% of patients displaying values below the normal mean, whereas only 48% of the nonhypercalciuric stone formers had bone density values below the normal mean. In contrast, radial bone density was similar in all three groups of renal stone formers investigated. The comparison of urinary chemistry in patients with absorptive hypercalciuria and low normal bone density compared to those with high normal bone density showed a significantly increased 24 h urinary calcium excretion on random diet and a trend toward a higher 24 h urinary uric acid excretion and a higher body mass index in patients with low normal bone density. Moreover, among the patients with absorptive hypercalciuria we found a statistically significant correlation between the spinal bone density and the 24 h sodium and sulfate excretion and the urinary pH. These results gave evidence for an additional role of environmental factors (sodium and animal proteins) in the pathogenesis of bone loss in absorptive hypercalciuria. In conclusion, our data suggest an osteopenia of trabecular-rich bone tissues in patients with fasting and absorptive hypercalciurias.

Non-NASA Center↗

DOE OSTI2025

Surface Charge in Electrical Double Layer as a Kinetic Descriptor of Electrocatalytic Reactions

The successful commercialization of electrochemical energy-conversion systems hinges on a deeper understanding of electrocatalytic reaction kinetics. Despite extensive research, a key descriptor that characterizes electrolyte effects on reaction kinetics remains elusive. Here, surface charge in electrical double layers (EDLs) is introduced as a descriptor for electrolyte-dependent kinetics. The surface charge is calculated with a continuum EDL model parameterized by density-functional theory. The model is validated by reproducing the anomalously low slope of Pt(111) in Parsons-Zobel plots. Strong correlations are observed between calculated surface charge and experimental kinetic currents for hydrogen evolution, oxygen reduction, and CO 2 -reduction reactions across various pH levels and cationic species. These correlations can be either promotional or inhibitory, depending on solute-intermediate interactions. In acidic media, incorporating adsorbate charge captures specific adsorption effects in oxygen reduction reaction. In conclusion, these findings establish surface charge density as a key descriptor for electrolyte-dependent kinetics, which will guide the design of the electrode/electrolyte interface.

Adsorption↗

DOE OSTI2024

Synthesis and Characterization of Silver-Modified Nanoporous Silica Materials for Enhanced Iodine Removal

In aquatic environments, the presence of iodine species, including radioactive isotopes like 129 I and I 2 , poses significant environmental and health concerns. Iodine can enter water resources from various sources, including nuclear accidents, medical procedures, and natural occurrences. To address this issue, the use of natural occurring nanoporous minerals, such as zeolitic materials, for iodine removal will be explored. This study focuses on the adsorption of iodine by silver-modified zeolites (13X-Ag, 5A-Ag, Chabazite-Ag, and Clinoptilolite-Ag) and evaluates their performance under different conditions. All materials were characterized using scanning electron microscopey (SEM), energy-dispersive X-ray spectroscopy (EDS), powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), and nitrogen adsorption studies. The results indicate that Chabazite-Ag exhibited the highest iodine adsorption capacity, with an impressive 769 mg/g, making it a viable option for iodine removal applications. 13X-Ag and 5A-Ag also demonstrated substantial adsorption capacities of 714 mg/g and 556 mg/g, respectively, though their behavior varied according to different models. In contrast, Clinoptilolite-Ag exhibited strong pH-dependent behavior, rendering it less suitable for neutral to slightly acidic conditions. Furthermore, this study explored the impact of ionic strength on iodine adsorption, revealing that Chabazite-Ag is efficient in low-salinity environments with an iodine adsorption capacity of 51.80 mg/g but less effective in saline conditions. 5A-Ag proved to be a versatile option for various water treatments, maintaining its iodine adsorption capacity across different salinity levels. In contrast, Clinoptilolite-Ag exhibited high sensitivity to ionic competition, virtually losing its iodine adsorption ability at a NaCl concentration of 0.1 M. Kinetic studies indicated that the pseudo-second-order model best describes the adsorption process, suggesting chemisorption mechanisms dominate iodine removal. Chabazite-Ag exhibited the highest initial adsorption rate with a k 2 value of 0.002 mg g -1 h -1 , emphasizing its superior adsorption capabilities. Chabazite and Clinoptilolite, naturally occurring minerals, provide eco-friendly solutions for iodine adsorption. Chabazite superior iodine removal highlights its value in critical applications and its potential for addressing pressing environmental challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1978

Polyglutaraldehyde - A new reagent for coupling proteins to microspheres and for labeling cell-surface receptors

Glutaraldehyde polymerized in basic aqueous solutions was found to react with low molecular weight amines, immunoglobulins and hemoglobin. The polyglutaraldehyde was covalently bound to hydrophilic microspheres. The rate of addition of proteins to the polyglutaraldehyde-derivatized microspheres was investigated spectrophotometrically as a function of pH and temperature. The reaction of polyglutaraldehyde was found to be faster than that of the monomer. The findings led to successful labeling of human lymphocyte subpopulations.

Rembaum, A.↗

DOE OSTI2023

Superconductivity in a strange metal

In a gas of charged particles with the density n, mass m, and charge e, the electrical conductivity σ is given by the Drude formula: σ = ne 2 /mΓ, where Γ is the scattering rate. Standard metals are well described by Landau's Fermi Liquid (FL) theory, in which the electric current is carried by quasi-particles, low-energy excitations of the FL that resemble electrons with some effective mass m*. The scattering rate Γ= 1/τ= v F /l, where t is the (momentum) relaxation) time, l is the mean-free path, and v F is the Fermi velocity, can be expressed ("Matthiessen's Rule") as a sum of contributions from various scattering channels: Γ = Γ 0 + Γ el-el + Γ el-ph + …, where Γ 0 describes scattering on lattice imperfections, Γ el-el the electron-electron scattering, Γ el-ph the electron-phonon scattering, etc. Of these, Γ 0 = v F /l 0 , where l 0 is the average distance between the defects, is temperature-independent. Γ el-el should scale as T 2 because of Fermi statistics; for two electrons to scatter on one another, both must come from the "Debye shell" of the width k B T/E F , where k B is the Boltzmann constant and E F is the Fermi energy. Γ el-ph typically grows as T 5 , so we expect this to overwhelm the other channels at a high enough T. However, since l cannot be shorter than the distance between the atoms, the total Γ saturates at Mott-Ioffe-Regel (MIR) limit, roughly v F /a 0 , where v F is the Fermi velocity and a 0 is the lattice constant. The resistivity should also saturate at low T, at ρ 0 = m*v F /ne 2 l 0 T. FL theory also describes other electronic properties; e.g., it predicts that in the magnetic field B, the resistivity of the metal should increase with B 2 , because σ(B) = σ(B=0)/(1 + (ω c /Γ) 2 ), where ω c = eB/m*.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Optimizing dietary rumen-degradable starch to rumen-degradable protein ratio improves lactation performance and nitrogen utilization efficiency in mid-lactating Holstein dairy cows

The dietary rumen-degradable starch (RDS) to rumen-degradable protein (RDP) ratio, denoted as the RDS-to-RDP ratio (SPR), has been proven to enhance in vitro rumen fermentation. However, the effects of dietary SPR in vivo remain largely unexplored. This study was conducted to investigate the effect of dietary SPR on lactation performance, nutrient digestibility, rumen fermentation patterns, blood indicators, and nitrogen (N) partitioning in mid-lactating Holstein cows. Seventy-two Holstein dairy cows were randomly assigned to three groups (24 head/group), balanced for (mean ± standard deviation) days in milk (116 ± 21.5), parity (2.1 ± 0.8), milk production (42 ± 2.1 kg/d), and body weight (705 ± 52.5 kg). The cows were fed diets with low (2.1, control), medium (2.3), or high (2.5) SPR, formulated to be isoenergetic, isonitrogenous, and iso-starch. The study consisted of a one-week adaptation phase followed by an eight-week experimental period. The results indicated that the high SPR group had a lower dry matter intake compared to the other groups ( p < 0.05). A quadratic increase in milk yield and feed efficiency was observed with increasing dietary SPR ( p < 0.05), peaking in the medium SPR group. The medium SPR group exhibited a lower milk somatic cell count and a higher blood total antioxidant capacity compared to other groups ( p < 0.05). With increasing dietary SPR, there was a quadratic improvement ( p < 0.05) in the total tract apparent digestibility of crude protein, ether extract, starch, neutral detergent fiber, and acid detergent fiber. Although no treatment effect was observed in rumen pH, the rumen total volatile fatty acids concentration and microbial crude protein synthesis increased quadratically ( p < 0.05) as dietary SPR increased. The molar proportion of propionate linearly increased ( p = 0.01), while branched-chain volatile fatty acids linearly decreased ( p = 0.01) with increasing dietary SPR. The low SPR group (control) exhibited higher concentration of milk urea N, rumen ammonia N, and blood urea N than other groups ( p < 0.05). Despite a linear decrease ( p < 0.05) in the proportion of urinary N to N intake, increasing dietary SPR led to a quadratic increase ( p = 0.01) in N utilization efficiency and a quadratic decrease ( p < 0.05) in the proportion of fecal N to N intake. In conclusion, optimizing dietary SPR has the potential to enhance lactation performance and N utilization efficiency. Based on our findings, a medium dietary SPR (with SPR = 2.3) is recommended for mid-lactating Holstein dairy cows. Nevertheless, further research on rumen microbial composition and metabolites is warranted to elucidate the underlying mechanisms of the observed effects.

Chen, Panliang↗

DOE OSTI2021

Near-infrared C-term MCD spectroscopy of octahedral uranium (V) complexes

C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d–d and f–f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(V) complexes of Oh symmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study, C-term NIR MCD of the Laporte forbidden f–f transitions of [UCl 6 ] - and [UF 6 ] - are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ 7 → Γ 8 transitions in [UF 6 ] - . The experimental NIR MCD studies were further extended to [U(OC 6 F 5 ) 6 ] - , [U(CH 2 SiMe 3 ) 6 ] - , and [U(NC(tBu)(Ph)) 6 ] - to evaluate the effects of ligand-type on the f–f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f–f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(V) hexahalide complexes, via the inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(V) complexes and identify areas for continued theoretical development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Experimental-based mechanistic study and optimization of hydrothermal liquefaction of anaerobic digestates

Valorization of agricultural and food waste digestates is crucial for sustainable waste management to reduce environmental impacts and improve the economics of commercial farms. Hydrothermal liquefaction (HTL) of anaerobic digestates was evaluated to recover resources by converting them into carbon-dense biocrude oil and a nutrient-rich HTL aqueous phase (HTL-AP) coproduct. The effects of HTL temperature (280–360 °C), reaction time (10–50 min), feedstock pH (2.5–8.5), digestate salt content (1–5 wt%), and digestate cellulose-to-lignin ratio (0.2–1.8) on energy and nutrient recovery were systematically investigated in a set of well-designed experiments following a half-fractional central composite protocol. Response surface analysis combined with HTL product characterization and comparative literature study produced a comprehensive reaction pathway for HTL of anaerobic digestates. Moreover, this analysis revealed the importance of acidic feedstocks (pH 3.00–5.53), high reaction temperatures (337–360 °C), and reaction times <45 or 45–50 min for digestates with Cel/Lig >1 or <1, for maximizing the energy recovered in biocrude (high carbon yield and low heteroatom content) and the amounts of P, NH 3 –N, and Mg distributed in the HTL-AP. Acidic conditions catalyzed biocrude production, inhibited the Maillard reaction (lowering the nitrogen content in biocrude), and partitioned nutrients into the HTL-AP. Higher reaction temperatures coupled with longer reaction times activated hydro-denitrogenation and deoxygenation reactions to improve biocrude quality. Finally, this work provides not only validated methods to achieve targeted resource recovery for specific feedstock compositions using HTL, but also a comprehensive mechanistic understanding of the HTL of biomass waste for controlling target product characteristics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Facile ab initio approach for self-localized polarons from canonical transformations

Electronic states in a crystal can localize due to strong electron-phonon (e-ph) interactions, forming so-called small polarons. Methods to predict the formation and energetics of small polarons are either computationally costly or not geared toward quantitative predictions. Here we show a formalism based on canonical transformations to compute the polaron formation energy and wave function using ab initio e-ph interactions. Comparison of the calculated polaron and band-edge energies allows us to determine whether charge carriers in a material favor a localized small polaron over a delocalized Bloch state. Due to its low computational cost, our approach enables efficient studies of the formation and energetics of small polarons, as we demonstrate by investigating electron and hole polaron formation in alkali halides and metal oxides and peroxides. We outline refinements of our scheme and extensions to compute transport in the polaron hopping regime.

36 MATERIALS SCIENCE↗

NASA NTRS2007

A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars

The two upcoming robotic missions to Mars, Phoenix and MSL, will both have the capability of measuring the carbon isotopic composition of CO2 in the martian atmosphere, as well as possible CO2 trapped in carbonate minerals in the Martian soil. Results from orbital and landed missions now clearly indicate that no large scale deposits of carbonate materials exist at the surface. However, some results from orbital remote sensing have been interpreted to indicate that carbonate minerals are present as fine particles interspersed at low concentrations (approx. 2%) in the martian dust. One likely mechanism for the production of these carbonates is during the freezing of transient water near the surface. Large deposits of near surface ice and photographic evidence for flowing water on the surface suggest that transient melting and refreezing of H2O is an active process on Mars. Any exposure of these fluids to the CO2 rich atmosphere should al-low the production of HCO3- solutions. Carbonates are likely precipitates from these solutions during freezing as extensive CO2 degassing, driven by the fluid s decreasing volume, drives CO2 out. This rapid CO2 degassing increases the pH of the solution and drives carbonate precipitation. It has been shown in previous studies that this rapid CO2 degassing also results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing a large isotope enrichment of C-13 in the precipitated carbonate. This kinetic isotope enrichment may be very common in the current martian environment, and may be a very important factor in understanding the very high deltaC-13 values of carbonates found in the martian meteorites. However, while previous studies have succeeded in generally quantifying the magnitude of this effect, detailed studies of the consistency of this effect, and the freezing rates needed to produce it are needed to understand any carbon isotope analyses from carbonate minerals in the martian soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates.

Niles, P. B.↗

NASA NTRS2004

Influence of nitrogen nutrition management on biomass partitioning and nitrogen use efficiency indices in hydroponically grown potato

The National Aeronautics and Space Administration (NASA) has been conducting controlled environment research with potatoes (Solanum tuberosum L.) in recirculating nutrient film technique (NFT)-hydroponic systems as a human life support component during long-duration spaceflight. Standard nutrient solution management approaches include constant pH regulation with nitric acid (HNO3) and daily adjustment of electrical conductivity (EC) equivalent to half-strength modified Hoagland's solution, where nitrate (NO3-) is the sole nitrogen (N) source. Although tuber yields have been excellent with such an approach, N use efficiency indices are expected to be low relative to tuber biomass production. Furthermore, the high amount of N used in NFT-hydroponics, typically results in high inedible biomass, which conflicts with the need to minimize system mass, volume, and expenditure of resources for long-duration missions. More effective strategies of N fertilization need to be developed to more closely match N supply with demand of the crop. Hence, the primary objective of this study was to identify the optimal N management regime and plant N requirement to achieve high yields and to avoid inefficient use of N and excess inedible biomass production. In separate 84-day cropping experiments, three N management protocols were tested. Treatments which decreased NO3(-)-N supply indirectly through lowering nutrient solution EC (Expt. I), or disabling pH control, and/or supplying NH4(+)-N (Expt. III) did not significantly benefit tuber yield, but did influence N use efficiency indices. When supplied with an external 7.5 mM NO3(-)-N for the first 42 days after planting (DAP), lowered to 1.0 mM NO3(-)-N during the final 42 days (Expt. II), plants were able to achieve yields on par with plants which received constant 7.5 mM NO3(-)-N (control). By abruptly decreasing N supply at tuber initiation in Expt. II, less N was taken up and accumulated by plants compared to those which received high constant N (control). However, proportionately more plant accumulated N was used (N use efficiency) to produce tuber biomass when N supply was abruptly lowered at tuber initiation in Expt. II. Hence, a hydroponic nutrient solution N management system may be modified to elicit greater plant N-use while maintaining overall high tuber yield as opposed to achieving high tuber yields through excess N supply and shoot growth.

NASA Discipline Life Support Systems↗