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At least 847 records · Page 47

Transposon tagging and the study of root development in Arabidopsis

The maize Ac-Ds transposable element family has been used as the basis of transposon mutagenesis systems that function in a variety of plants, including Arabidopsis. We have developed modified transposons and methods which simplify the detection, cloning and analysis of insertion mutations. We have identified and are analyzing two plant lines in which genes expressed either in the root cap cells or in the quiescent cells, cortex/endodermal initial cells and columella cells of the root cap have been tagged with a transposon carrying a reporter gene. A gene expressed in root cap cells tagged with an enhancer-trap Ds was isolated and its corresponding EST cDNA was identified. Nucleotide and deduced amino acid sequences of the gene show no significant similarity to other genes in the database. Genetic ablation experiments have been done by fusing a root cap-specific promoter to the diphtheria toxin A-chain gene and introducing the fusion construct into Arabidopsis plants. We find that in addition to eliminating gravitropism, root cap ablation inhibits elongation of roots by lowering root meristematic activities.

NASA Discipline Plant Biology↗

Multiple internal seal right micro-electro-mechanical system vacuum package

A Multiple Internal Seal Ring (MISR) Micro-Electro-Mechanical System (MEMS) vacuum package that hermetically seals MEMS devices using MISR. The method bonds a capping plate having metal seal rings to a base plate having metal seal rings by wafer bonding the capping plate wafer to the base plate wafer. Bulk electrodes may be used to provide conductive paths between the seal rings on the base plate and the capping plate. All seals are made using only metal-to-metal seal rings deposited on the polished surfaces of the base plate and capping plate wafers. However, multiple electrical feed-through metal traces are provided by fabricating via holes through the capping plate for electrical connection from the outside of the package through the via-holes to the inside of the package. Each metal seal ring serves the dual purposes of hermetic sealing and providing the electrical feed-through metal trace.

Hayworth, Ken J.↗

Structural Design and Analysis of the Upper Pressure Shell Section of a Composite Crew Module

This paper presents the results of the structural design and analysis of the upper pressure shell section of a carbon composite demonstration structure for the Composite Crew Module (CCM) Project. The project is managed by the NASA Engineering and Safety Center with participants from eight NASA Centers, the Air Force Research Laboratory, and multiple aerospace contractors including ATK/Swales, Northrop Grumman, Lockheed Martin, Collier Research Corporation, Genesis Engineering, and Janicki Industries. The paper discusses details of the upper pressure shell section design of the CCM and presents the structural analysis results using the HyperSizer structural sizing software and the MSC Nastran finite element analysis software. The HyperSizer results showed that the controlling load case driving most of the sizing in the upper pressure shell section was the internal pressure load case. The regions around the cutouts were controlled by internal pressure and the main parachute load cases. The global finite element analysis results showed that the majority of the elements of the CCM had a positive margin of safety with the exception of a few hot spots around the cutouts. These hot spots are currently being investigated with a more detailed analysis. Local finite element models of the Low Impact Docking System (LIDS) interface ring and the forward bay gussets with greater mesh fidelity were created for local sizing and analysis. The sizing of the LIDS interface ring was driven by the drogue parachute loads, Trans-Lunar Insertion (TLI) loads, and internal pressure. The drogue parachute loads controlled the sizing of the gusset cap on the drogue gusset and TLI loads controlled the sizing of the other five gusset caps. The main parachute loads controlled the sizing of the lower ends of the gusset caps on the main parachute fittings. The results showed that the gusset web/pressure shell and gusset web/gusset cap interfaces bonded using Pi-preform joints had local hot spots in the Pi-preform termination regions. These regions require a detailed three-dimensional analysis, which is currently being performed, to accurately address the load distribution near the Pi-preform termination in the upper and lower gusset caps.

Sleight, David W.↗

Multiple internal seal ring micro-electro-mechanical system vacuum packaging method

A Multiple Internal Seal Ring (MISR) Micro-Electro-Mechanical System (MEMS) vacuum packaging method that hermetically seals MEMS devices using MISR. The method bonds a capping plate having metal seal rings to a base plate having metal seal rings by wafer bonding the capping plate wafer to the base plate wafer. Bulk electrodes may be used to provide conductive paths between the seal rings on the base plate and the capping plate. All seals are made using only metal-to-metal seal rings deposited on the polished surfaces of the base plate and capping plate wafers. However, multiple electrical feed-through metal traces are provided by fabricating via holes through the capping plate for electrical connection from the outside of the package through the via-holes to the inside of the package. Each metal seal ring serves the dual purposes of hermetic sealing and providing the electrical feed-through metal trace.

Hayworth, Ken J.↗

Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

Dingemans, Theodorus J.↗

Gamma-Ray Pulsar Light Curves in Vacuum and Force-Free Geometry

Recent studies have shown that gamma-ray pulsar light curves are very sensitive to the geometry of the pulsar magnetic field. Pulsar magnetic field geometries, such as the retarded vacuum dipole and force-free magnetospheres have distorted polar caps that are offset from the magnetic axis in the direction opposite to rotation. Since this effect is due to the sweepback of field lines near the light cylinder, offset polar caps are a generic property of pulsar magnetospheres and their effects should be included in gamma-ray pulsar light curve modeling. In slot gap models (having two-pole caustic geometry), the offset polar caps cause a strong azimuthal asymmetry of the particle acceleration around the magnetic axis. We have studied the effect of the offset polar caps in both retarded vacuum dipole and force-free geometry on the model high-energy pulse profiles. We find that, compared to the profiles derived from symmetric caps, the flux in the pulse peaks, which are caustics formed along the trailing magnetic field lines, increases significantly relative to the off-peak emission, formed along leading field lines. The enhanced contrast produces improved slot gap model fits to Fermi pulsar light curves like Vela, with vacuum dipole fits being more favorable.

Harding, Alice K.↗

Self-Sealing Wet Chemistry Cell for Field Analysis

In most analytical investigations, there is a need to process complex field samples for the unique detection of analytes, especially when detecting low concentration organic molecules that may identify extraterrestrial life. Wet chemistry based instruments are the techniques of choice for most laboratory- based analysis of organic molecules due to several factors including less fragmentation of fragile biomarkers, and ability to concentrate target species resulting in much lower limits of detection. Development of an automated wet chemistry preparation system that can operate autonomously on Earth and is also designed to operate under Martian ambient conditions will demonstrate the technical feasibility of including wet chemistry on future missions. An Automated Sample Processing System (ASPS) has recently been developed that receives fines, extracts organics through solvent extraction, processes the extract by removing non-organic soluble species, and delivers sample to multiple instruments for analysis (including for non-organic soluble species). The key to this system is a sample cell that can autonomously function under field conditions. As a result, a self-sealing sample cell was developed that can autonomously hermetically seal fines and powder into a container, regardless of orientation of the apparatus. The cap is designed with a beveled edge, which allows the cap to be self-righted as the capping motor engages. Each cap consists of a C-clip lock ring below a crucible O-ring that is placed into a groove cut into the sample cap.

Beegle, Luther W.↗

Large Plant Growth Chambers: Flying Soon on a Space Station near You!

The International Space Station (ISS) now has platforms for conducting research on horticultural plant species, and those capabilities continue to grow. The Veggie vegetable production system will be deployed to the ISS in Spring of 2014 to act as an applied research platform with goals of studying food production in space, providing the crew with a source of fresh food, allowing behavioral health and plant microbiology experimentation, and being a source of recreation and enjoyment for the crew. Veggie was conceived, designed, and constructed by Orbital Technologies Corporation (ORBITEC, Madison, WI). Veggie is the largest plant growth chamber that NASA has flown to date, and is capable of growing a wide array of horticultural crops. It was designed for low energy usage, low launch mass and stowage volume, and minimal crew time requirements. The Veggie flight hardware consists of a light cap containing red (630 nanometers), blue, (455 nanometers) and green (530 nanometers) light emitting diodes. Interfacing with the light cap is an extendable bellows baseplate secured to the light cap via magnetic closures and stabilized with extensible flexible arms. The baseplate contains vents allowing air from the ISS cabin to be pulled through the plant growth area by a fan in the light cap. The baseplate holds a Veggie root mat reservoir that will supply water to plant pillows attached via elastic cords. Plant pillows are packages of growth media and seeds that will be sent to ISS dry and installed and hydrated on orbit. Pillows can be constructed in various sizes for different plant types. Watering will be via passive wicking from the root mat to the pillows. Science procedures will include photography or videography, plant thinning, pollination, harvesting, microbial sampling, water sampling, etcetera. Veggie is one of the ISS flight options currently available for research investigations on plants. The Plant Habitat (PH) is being designed and constructed through a NASA-ORBITEC collaboration, and is scheduled to fly on ISS around 2016. This large plant chamber will control light quality, level, and timing, temperature, CO2, relative humidity, and irrigation, while scrubbing ethylene. Additional monitoring capabilities include leaf temperature sensing and root zone moisture and oxygen sensing. The PH light cap will have red (630 nanometers), blue (450 nanometers), green (525 nanometers), far red (730 nanometers) and broad spectrum white light emitting diodes. There will be several internal cameras to monitor and record plant growth and operations.

Space Biology↗

Physical and Biological Properties of Cobalt- and Copper-Doped Calcium Phosphates as Bone Substitute Materials

Arthritis, osteoporosis, and other bone diseases and defects are common medical issues worldwide. By utilizing ceramic biomaterials as bone substitutes to treat these diseases, bone regeneration can be promoted and toxicity from the substitute material can be limited. Calcium phosphate (CaP) ceramics have become popular as bone substitutes due to their biocompatibility and similarity in composition to natural bone. The purpose of this research was to investigate the physical properties and biological responses of CaP-based bone substitutes, doped with metal ions. Some metal ions are present in natural bone in small amounts, and recent studies show they affect the biological responses of CaPs significantly. Dopants such as magnesium (Mg), strontium (Sr), silicon (Si) and iron (Fe) alter the phase composition, mechanical properties, osteogenesis and angiogenesis properties of CaPs, depending on their concentration and method of addition. In the present study, the effects of cobalt (Co) and copper (Cu) on the physical and biological properties of two main CaP materials, brushite cement (BrC) and tricalcium phosphate (TCP), have been investigated. Different concentrations of dopants in forms of oxide and/or chloride were selected and their effect on phase composition, sintering behavior, density, setting time, compressive strength and in vitro interaction with osteosarcoma and osteoblast cells were studied. Different techniques of sample preparation, challenges during cement preparation and compact sample pressing, sintering, and methods of dopant addition are discussed. The presence of Cu in tricalcium phosphate was found to increase thermal stability of the material and decrease the impact of sintering temperature on porosity. In addition, Cu caused a reduction in expression of inflammatory gene markers by human osteoblast cells and an increased expression at early time points due of osteoinductive markers.The addition of Cu and Co to brushite cement caused an increase in thermal stability of the material, and the addition of Cu caused significant increase in setting time. Small dopant amounts of Co caused decrease in setting time, but higher amounts caused an increase. In addition, Cu dopant in small amounts resulted in an increase of compressive strength. Both Cu and Co led to a decrease in expression of inflammatory gene markers by osteoblast and osteosarcoma cells respectively, and Cu also caused an increase in osteoinductive marker expression. Thus, these results indicate that Cu and Co have a positive impact on the physical, mechanical and biological properties of calcium phosphate biomaterials.

Cummings, Haley V.↗

Changes in the Magnetic Field Topology and the Dayside/Nightside Reconnection Rates in Response to a Solar Wind Dynamic Pressure Front A Case Study

One of the most significant observations associated with a sharp enhancement in solar wind dynamic pressure, SWP, is the poleward expansion of the auroral oval and the closing of the polar cap. The polar cap shrinking over a wide range of magnetic local times (MLTs), in connection with an observed increase in ionospheric convection and the transpolar potential, led to the conclusion that the nightside reconnection rate is significantly enhanced after a pressure front impact. However, this enhanced tail reconnection has never been directly measured. We demonstrate the effect of a solar wind dynamic pressure front on the polar cap closure, and for the first time, measure the enhanced reconnection rate in the magnetotail, for a case occurring during southward background Interplanetary Magnetic Field (IMF) conditions. We use Polar Ultra-Violet Imager (UVI) measurements to detect the location of the open-closed field line boundary, and combine them with Assimilative Mapping of Ionospheric Electrodynamics (AMIE) potentials to calculate the ionospheric electric field along the polar cap boundary, and thus evaluate the variation of the dayside/nightside reconnection rates. We find a strong response of the polar cap boundary at all available MLTs, exhibiting a significant reduction of the open flux content. We also observe an immediate response of the dayside reconnection rate, plus a phased response, delayed by 15–20min, of the nightside reconnection rate. Finally, we provide comparison of the observations with the results of the Open Geospace General Circulation Model (OpenGGCM), elucidating significant agreements and disagreements

A Boudouridis↗

Martian B Storm Genesis and Evolution: Initial Analysis of Thermal Datasets.

Introduction: Dust lifting on Mars likely occurs primarily as a result of the exchange of momentum between the atmosphere and the surface via saltation. During saltation, sand-sized particles are mobilized but do not enter into suspension. When these larger particles fall back to the surface, kinetic energy is transferred to smaller dust particles which are then lofted into suspension in the atmosphere. Depending on the altitude to which dust is lofted, it can have a significant effect on atmospheric temperatures. As a strong absorber and emitter in the infrared, dust can influence atmospheric heating and modify the global circulation and weather on Mars [1,2]. Although dust is present in Mars’ atmosphere throughout the year, the atmosphere is generally dustier during the second half of the year when Mars is near perihelion. Observations reveal that episodic global-scale dust storms and fairly regular regional-scale dust storms are superimposed on a well-defined and highly repeatable seasonal cycle of dust opacity and associated mid-level atmospheric temperature responses. Kass et al. (2016) used 50 Pa temperature observations from MRO/MCS to identify three highly repeatable time periods during which regional dust storms occur, and designated them the “A”, “B” and “C” storms. While “A” and “C” storms have been studied a fair amount to-date, “B” storms have not yet been investigated in detail. This study explores the generation and evolution of the annually recurring regional dust storm known as the “B” storm, which was identified and categorized by Kass et al. (2016) based on 25 km (50 Pa) temperature observations. The B storm is a southern-hemisphere (SH) phenomenon that originates at the cap edge just after perihelion and which reaches peak intensity during the SH summer solstice, Ls 270. It may originate from the cap edge storms that spawn near the edge of the seasonal CO2 cap during retreat, but the mechanisms for B storm genesis have yet to be determined definitively [1]. Methods: We will use observational data sets and a global climate model (GCM) to investigate “B” regional storms. The data analysis component will include the analysis of imagery from MGS/MOC and MRO/MARCI, and spectroscopic data sets of dust and temperatures from MGS/TES and MRO/MCS with the goal of fully characterizing the behavior of these storms. Both MGS and TES provide data well-suited for temperature analysis at 25 km. MCS measures atmospheric temperature, dust extinction, and water ice extinction at 5 km intervals from the surface to about 80 km. TES measured atmospheric temperatures, column dust and water ice opacities, and column water vapor abundances. Measurements made by TES extended from the surface to about 40 km [1]. At the 50 Pa (25 km) level, local dust events usually confined to shallower depths are effectively filtered out of the analysis leaving the regional dust events identifiable by their temperature signatures [1]. Our preliminary analysis makes use of the fact that the brightness temperature at 15 microns (T15 temperature) is a close approximation to observed temperature at 25 km. We first reproduce the zonal mean 50 Pa level temperature plots for MY 29-32 to establish a baseline for our procedures moving forward [1]. Expanding on Kass et al. (2016), we include recent MCS data from MY 33 and 34 as well. Preliminary Analysis: The daytime (3PM) T15 temperatures in Figure 1 indicate: in MY 29, a strong A storm at Ls 240, a B storm at high southern latitudes just after Ls 270, and a C storm at Ls 320; in MY 30, a B storm at Ls 270; in MY 31 & MY 32, a B storm just before Ls 270; in MY 33, a B storm at Ls 270; and in MY 34, a strong A storm in the northern hemisphere at Ls 210, and a B storm around Ls 270 although there is a data gap. For the B storms, each is indicative of lofted dust and resultant warming. The daytime temperature structure illustrates that the B storm occurs annually around Ls 270 and is confined to high southern latitudes. It reaches its peak intensity around SH summer solstice, Ls 270, consistently for all six MY assessed. Since direct solar heating is absent overnight, the nighttime T15 temperatures (Figure 2) are often useful for differentiating the heat signature of direct solar heating from the dynamical response to that heating. However, in the southern polar latitudes at perihelion the sun does not set and direct solar heating remains present throughout the night. Importantly for our study, dust lofted in the B storm experiences this direct heating day and night for the entirety of its lifetime. The B storm expands as far north as -60 latitude and decays in latitudinal extent more gradually than it grows. This feature is less obvious in the nighttime (3AM) T15 temperatures (Figure 2). The temperature signal is stronger at night for MY 30-33. The warm pool is larger in area relative to the background at night in these four cases. This more uniform warming masks the “tail” feature somewhat, such that it is barely noticeable during these years. Unfortunately, gaps in MCS data in MY 29 and 34 prevent confirmation of the tail feature during those years, however, the B storm temperature signature follows a very different pattern than that described for MY 30-33. MY 29 and 34 appear to show smaller centers of warming at night and larger centers of warming during the day. This is in opposition to that previously described for MY 30-33. Conclusions and Future Work: We will continue investigating the heat signatures of B storms by looking at the total column heating as recorded by TES. We will also look at lower altitudes for patterns that may describe the relationship between B storms and the cap edge storms that develop while the seasonal cap is retreating. In the future, we will use GCM simulations to determine the atmospheric and thermo-dynamic conditions associated with these storms.

Courtney Marylou Batterson↗

Implementation of a High-Fidelity Interface Resolving Method in Nek5000

The development and utilization of computational fluid dynamics (CFD) models for large, high-temperature electric melters in the Waste Treatment and Immobilization Plant (WTP) in eastern Washington State have proven to be valuable for various purposes. These models allow for a better understanding of the physio-chemical processes occurring within the melter vessels and can contribute to improving operational efficiency, throughput, and addressing operational issues related to vitrification. The CFD models employed for these melter vessels incorporate multiphase fluid flow and heat transfer simulations in different regions, including the plenum, cold cap, and molten glass regions. As the tank waste and glass formers are introduced into the melter, a reacting batch layer known as the cold cap forms on top of the molten glass. To enhance the melt rate, forced convection bubblers located at the bottom of the melters generate convection currents that help homogenize the molten glass and provide heat to the cold cap. As the bubbles rise through the highly viscous glass, they adopt a spherical-cap shape [1]. Meanwhile, the conversion of the batch to glass generates significant amounts of gases (such as water vapor, carbon dioxide, sulfur dioxide, and NOx) due to thermal decomposition [2]. These gases become trapped between the cold cap and molten glass, forming a foam layer [3]. For modeling multiphase flow in CFD and heat transfer simulations of waste glass melters at different scales, efforts are underway to augment the capabilities of the Nek5000 [4] and NekRS [5] open-source codes [6]. Nek5000/NekRS is a scalable and efficient spectral element code that has been successfully applied to a wide range of fluid dynamics problems. By leveraging the Nek5000/NekRS software, it becomes possible to model the melter systems more affordably and with lower computational requirements compared to currently utilized commercial CFD software. The specific objectives of this ongoing effort include: 1. Implementation of a level set method in Nek5000/NekRS: The level set method is a numerical technique commonly employed in CFD simulations to track and represent the interface between different phases or materials accurately. By incorporating this method into Nek5000/NekRS, the ability to simulate multiphase flows in waste glass melters at a high level of fidelity can be achieved. 2. Demonstration of capability for air bubbling through molten glass: As part of the development process, a specific case of air bubbling through molten glass will be simulated using the augmented Nek5000/NekRS code. This demonstration aims to showcase the ability of the software to accurately capture and analyze the complex phenomena involved in the multiphase flow within waste glass melters. By achieving these objectives, the improved Nek5000/NekRS code will offer a powerful computational tool for simulating and analyzing waste glass melter systems, enabling better understanding, optimization, and troubleshooting of these vitrification processes. The ability to accurately model and simulate multiphase flows has broad relevance across many industries and scientific domains, and the improved functionality can contribute to advancements in various fields beyond waste glass melter simulations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Economic competitiveness of pultruded fiber composites for wind turbine applications

Pultrusion manufacturing of fiber reinforced polymers has been shown to yield some of the highest mechanical properties for unidirectional composites, having a high degree of fiber alignment with consistent performance. Pultrusions offer a low-cost manufacturing approach for producing unidirectional composites with a constant cross-section and are used in many applications, including spar caps of wind turbine blades. However, as an intermediate processing step for wind blades, the additional cost of manufacturing pultrusions must be accompanied by sufficient increases in mechanical performance and system benefits. Wind turbine blades are manufactured using vacuum-assisted resin transfer molding with infused unidirectional fiberglass or carbon pultrusions for the spar cap. Infused fiberglass composites are among the most cost-effective structural materials available and replacing this material in the cost-driven wind industry has proven challenging, where infused fiberglass spar caps are still the predominant material system in use. To evaluate alternative material systems in a pultruded composite form, it is necessary to understand the costs for this additional manufacturing step which are shown to add 33%–55% on top of the material costs. A pultrusion cost model has been developed and used to quantify cost sensitivities to various processing parameters. The mechanical performance for pultruded composites is improved versus resin-infusion manufacturing with a 17% increase in design strength at a constant fiber volume fraction, but also enables higher achievable fiber volume fractions. The cost-specific mechanical performance is compared as a function of processing parameters for pultruded composites to identify the opportunities for alternative material and manufacturing approaches for wind turbine spar caps. Finally, four materials are compared in a representative wind turbine blade model to assess the performance of pultruded carbon fiber systems and pultruded fiberglass relative to infused fiberglass, where the pultruded systems produce lower weight blades with various cost distinctions.

42 ENGINEERING↗

Carbonated apatite lattice parameter variation across incremental growth lines in teeth

Here, results of microbeam mapping (x-ray excited x-ray fluorescence and transmission x-ray diffraction) of Beluga whale cementum and of beaver dentin reveal growth bands are defined by variation in mineral content (carbonated hydroxyapatite, cAp), by variation in Zn content and by variation in cAp lattice parameter a. For both tissues, diffraction and fluorescence data show that Zn signal and a are anti-correlated, that is high Zn signal is co-located with low a, and vice versa. In cementum and bone, treatment with acid removes Ca, Zn and cAp. The data are strong evidence that Zn is incorporated into the cAp lattice in these tissues and that the amount of Zn incorporated varies across two very different types of growth bands, annual bands in Beluga cementum and daily incremental bands in beaver dentin. To the best of the authors’ knowledge, this is the first observation of spatial variation of lattice parameter within growth bands.

36 MATERIALS SCIENCE↗

Molecular Insights into Novel Struvite–Hydrogel Composites for Simultaneous Ammonia and Phosphate Removal

Struvite (NH 4 MgPO 4 ·6H 2 O) mineralization is an effective technique for removing ammonium and phosphate species from wastewater. However, its wider use faces obstacles because of the copresence of various pollutants in wastewater and the additional requirement for magnesium to achieve proper supersaturation conditions. To address these challenges, this study developed novel mineral–hydrogel composites that can remove ammonium and phosphate simultaneously via heterogeneous struvite and calcium phosphate (CaP) mineralization in hydrogel matrices. The composites include in situ formed struvite and CaP mineral seeds, decreasing the nucleation energy barrier of struvite and CaP formation and promoting their heterogeneous nucleation kinetics even under undersaturation conditions in bulk solution. The dual struvite and CaP seeded composites can simultaneously reduce the ammonium and total phosphate concentrations up to 60% (26.3 mg of N/g) and 91% (9.54 mg of P/g), respectively. Furthermore, the average particle sizes in composites were increased from 6.12 to 14.8 nm after wastewater treatment. Moreover, various ions commonly existing in wastewater did not significantly interfere with the removal of ammonium and phosphate. Thus, these new mineral–hydrogel composites can provide an innovative way to lower nutrient levels before discharge to streams. Moreover, encapsulating ammonium and phosphate in mineral-hydrogel composites enables their upcycling in agricultural or biorefinery applications.

Cations↗

Life Cycle Emissions and Health Cost Impacts of Producing Ethanol and Electricity from Willow and Switchgrass in the Riparian Buffers of Mid-Atlantic United States

The United States (US Mid-Atlantic Region (MAR) has the potential to grow a variety of perennial feedstocks such as switchgrass and shrub willow to increase domestic energy production. These cellulosic feedstocks have also shown improved ecosystem services, such as soil carbon sequestration, nitrate leaching reduction, and flood mitigation along rivers and streams as partially harvested riparian buffers. To examine the effects on greenhouse gases (GHGs) and criteria air pollutants (CAPs) from using these feedstocks to produce ethanol or electricity, we conducted a comprehensive life cycle assessment (LCA) and estimated the impact on human health costs when land use is changed from corn production for ethanol. Results indicate up to 54% reduced GHG per hectare from using willow and switchgrass feedstock sources to produce ethanol instead of corn. However, there was a trade-off in terms of CAP emission, as grass-based energy emitted more NO x and SO x compared to the corn ethanol pathway, except for SO X emissions from willow-based electricity. Electricity from cellulosic biomass had higher particulate matter (PM) emission compared to that from corn ethanol. Estimates for health cost to society ranged from $2498 ha –1 for electricity from switchgrass to a net benefit of $448 ha –1 for ethanol production from willow, depending on varying biomass yield under different market scenarios. Although using cellulosic feedstocks to produce bioenergy has great potential to reduce GHG emissions, CAP control measures are needed to manage CAP-induced health costs.

Bioenergy↗

Metal-to-Ligand Charge-Transfer Spectrum of a Ru-Bipyridine-Sensitized TiO 2 Cluster from Embedded Multiconfigurational Excited-State Theory

Understanding optical properties of the dye molecule in dye-sensitized solar cells (DSSCs) from first-principles quantum mechanics can contribute to improving the efficiency of such devices. While density functional theory (DFT) and time-dependent DFT have been pivotal in simulating optoelectronic properties of photoanodes used in DSSCs at the atomic scale, questions remain regarding DFT’s adequacy and accuracy to furnish critical information needed to understand the various excited-state processes involved. In this work, we simulate the absorption spectra of a dye-sensitized solar cell analogue, comprised of a Ru-bipyridine (Ru-bpy) dye molecule and a small TiO2 cluster via DFT and via an accurate embedded correlated wavefunction (CW) theory. We generated CW spectra for the adsorbed Ru-bpy dye via a recently introduced capped density functional embedding theory or capped-DFET (to generate the embedding potential that accounts for the interaction of the molecule and the TiO 2 cluster). We then combined capped-DFET with the accurate but expensive multiconfigurational complete active space second-order perturbation theory (CASPT2)—embedded CASPT2. Because the CW theory is conducted on only a portion of the total system in the presence of an embedding potential that describes that portion’s interaction with its environment, we efficiently obtain CW-quality predictions that reflect local properties of the entire system. Specifically, for example, with capped-DFET and embedded CW theory, we can simulate accurately a plethora of metal-to-ligand charge-transfer excited properties at a manageable computational cost. Here, we predict detailed electronic spectra within the visible region, featuring the lowest three singlet and triplet excited states, along with predictions of the singlets’ lifetimes. We illustrated these results using a Jablonski diagram that show the relative energy position of the singlet and longer-lived triplet excited states and analyzed and proposed relaxation paths for the excited state corresponding to the most intense but short-lived absorption (interconversion, intersystem crossing, fluorescence, and phosphorescence) that may lead to longer-lived excited states necessary for efficient charge separation required to generate current in solar cells.

14 SOLAR ENERGY↗

Feasibility of Metal Oxide Glasses and Polymer Membranes as Sorbents for Gaseous Oxidized Mercury

Mass spectrometry methods are currently under development by the atmospheric mercury (Hg) research community to elucidate the identity of atmospheric oxidized mercury (Hg II ) compounds. Due to high instrument detection limits, materials that can quantitatively preconcentrate atmospheric Hg II without facilitating compound-altering chemical reactions are needed to support these methods. Cation exchange membranes (CEM) and nylon membranes are currently used to preconcentrate ambient Hg II for concentration measurements and Hg II compound estimation, respectively. However, CEM and nylon membranes are poor candidates for observations by mass spectrometry methods due to release of interfering compounds upon heating; glasses do not have this problem. Here, three metal oxide glasses were explored as potential alternatives for Hg II preconcentration for future use with mass spectrometry methods: calcium phosphate (CaP), iron phosphate (FeP), and calcium aluminate (CaAl). The glasses demonstrated quantitative selective capture of HgBr 2 without capture of Hg 0 . Under ambient conditions, the CaP, FeP, and CaAl sorbed 36.4 ± 12.6% of the total HgII as the CEM. However, when Hg concentrations were normalized to surface area, CaP, FeP, and CaAl sorbed more HgBr 2 in the laboratory and ambient HgII compared to CEM. The CEM and CaP retained similar concentrations of HgBr 2 when preloaded samples were deployed in the field. Additionally, a permeation tube-based calibrator was used to load sorbents with HgBr 2 for investigation of HgII retention on CEM and thermal desorption profile changes on nylon membranes during active sampling. Nylon membranes were purchased from three vendors and used to compare HgBr 2 retention; a different HgBr 2 thermal desorption profile was achieved for each vendor’s nylon membrane.

Amides↗