Recovery of Rare Earth Elements from Coal Fly Ash Using Ionic Liquids

Rare earth elements (REEs), the 15 lanthanides and Sc and Y, have played an invaluable role in the progress of clean energy technology and high-tech manufacturing in past decades. Their high demand and global scarcity have led to disruptions in supply, exacerbated by the fact that there are no adequate replacements. Thus, it is crucial to develop alternative sources to secure a steady supply of REEs. Coal fly ash (CFA), a byproduct of burning coal for electricity, may be one such source. Conventional REE-CFA recovery methods are energy and material intensive and leach elements indiscriminately, generating impure mixtures of REEs. Ionic liquids (ILs) may be one solution, but to date, they have not been applied to CFA. This dissertation focuses on the IL betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) for preferential extraction of REEs from different CFAs. Efficient extraction relies on [Hbet][Tf2N]’s thermomorphic behavior with water: upon heating, water and the IL form a single liquid phase, and REEs are leached from CFA via a proton-exchange mechanism. Upon cooling, the water and IL separate, and leached elements partition between the IL and aqueous (AQ) phases. REEs were preferentially extracted over bulk elements from CFAs into the IL phase then recovered in a subsequent mild acid stripping step, regenerating the IL. Two optimizations, alkaline pretreatment and adding supplement betaine, significantly improved REE leaching efficiency and separation between REEs and bulk elements. Significantly, this method consistently exhibits a particularly high extraction efficiency for scandium. The IL extraction process yields a mildly acidic REE-rich solution contaminated with Fe. To address this, three strategies for limiting Fe coextraction into the IL phase were investigated: magnetic separation, alternative salts, and ascorbic acid reduction. The latter two methods proved successful and should be used to generate an REE-rich acidic solution with very low concentrations of Fe. To gain a better understanding of CFA leaching behavior with [Hbet][Tf2N], eighteen additional elements were studied (29 total). It was found that in the IL phase, bulk elements were found in low concentrations, trace elements were not found, and of the actinides, Th was extracted into the IL phase and U was not leached at all. Other important optimizations were also studied, including pH, temperature, and duration of leaching. The process is also compared to several published CFA solid extraction methods and CFA leacheate separation methods to place this dissertation in context with existing literature. Finally, a number of process sustainability improvements are recommended, including the use of microwave heating, water and IL recovery strategies, and beneficial uses of residual solids. Finally, two other ILs were studied along with [Hbet][Tf2N] to investigate the effect of IL’s cation functional group modifications. The two ILs possess the same anion [Tf2N], but one with a less acidic cation having an alcohol group, choline [Chol], and one with a more acidic cation having an alkyl sulfonic acid group, trimethylammoniumethane hydrogen sulfate ([N111C2OSO3H]), in comparison with [Hbet], which has a carboxyl group. [Chol][Tf2N] was broadly unsuccessful at leaching almost all elements from all CFA samples tested. [N111C2OSO3H][Tf2N] was more successful, achieving greater or comparable leaching efficiencies but was not able to separate REEs from bulk and trace constituents. Overall, the research outcome of this dissertation filled several knowledge gaps in REE recovery. The method presented is novel and is among the first to demonstrate direct application of an IL to solid CFA for efficient recovery of REEs. The recyclability of IL and mild extraction conditions offer significant advantages for environmental sustainability. Altogether, this thesis builds a foundation for new IL-based strategies for future extractions from CFA and other REE-rich wastes.Ph.D

Biotic interactions and biogeochemical processes in the soil environment

Soils play a key role in the terrestrial carbon (C) cycle by storing and emitting large quantities of C. The impact of abiotic conditions (mainly soil temperature and moisture) on soil C turnover is well documented, but unravelling the influence of these drivers across temporal and spatial scales remains an important challenge. Biotic factors, such as microbial abundance and diversity, macro-faunal food webs and below-ground plant (i.e. root) biomass and diversity, play an important role in controlling soil C storage and emission, but remain under-investigated. To better understand the soil processes underlying terrestrial C cycling, the interactions between plants (autotrophs) and soil organisms (heterotrophs) need to be addressed more explicitly and integrated with short- and long-term effects of abiotic drivers. This special issue presents recent advances in field, laboratory, and modelling studies on soil C dynamics, with a particular emphasis on those aiming to resolve abiotic and biotic influences. The manuscripts highlight three areas of investigation that we suggest are central to current and future progress in ecosystem C dynamic research: (1) novel interpretations of abiotic controls on soil CO2 efflux, (2) legacy effects of abiotic drivers of soil C dynamics, and (3) the interaction between plant C dynamics and soil biological processes

The Primordial Helium Abundance: Towards Understanding and Removing the Cosmic Scatter in the dY/dZ Relation

We present results from photoionization models of low-metallicity HII regions. These nebulae form the basis for measuring the primordial helium abundance. Our models show that the helium ionization correction factor (ICF) can be non-negligible for nebulae excited by stars with effective temperatures larger than 40,000 K. Furthermore, we find that when the effective temperature rises to above 45,000 K, the ICF can be significantly negative. This result is independent of the choice of stellar atmosphere. However, if an HII region has an [O III] 5007/[O I] 6300 ratio greater than 300, then our models show that, regardless of its metallicity, it will have a negligibly small ICF. A similar, but metallicity dependent, result was found using the [O III] 5007/H$\beta$ ratio. These two results can be used as selection criteria to remove nebulae with potentially non-negligible ICFs. Using our metallicity independent criterion on the data of Izotov & Thuan (1998) results in a 20% reduction of the rms scatter about the best fit $Y-Z$ line. A fit to the selected data results in a slight increase of the value of the primordial helium abundance.Comment: 10 pages, 5 figures, accepted by the Ap

An Approach to the Bio-Inspired Control of Self-reconfigurable Robots

Self-reconfigurable robots are robots built by modules which can move in relationship to each other. This ability of changing its physical form provides the robots a high level of adaptability and robustness. Given an initial configuration and a goal configuration of the robot, the problem of self-regulation consists on finding a sequence of module moves that will reconfigure the robot from the initial configuration to the goal configuration. In this paper, we use a bio-inspired method for studying this problem which combines a cluster-flow locomotion based on cellular automata together with a decentralized local representation of the spatial geometry based on membrane computing ideas. A promising 3D software simulation and a 2D hardware experiment are also presented.National Natural Science Foundation of China No. 6167313

On the Biological Importance of the 3-hydroxyanthranilic Acid: Anthranilic Acid Ratio

Of the major components of the kynurenine pathway for the oxidative metabolism of tryptophan, most attention has focussed on the N-methyl-D-aspartate (NMDA) receptor agonist quinolinic acid, and the glutamate receptor blocker kynurenic acid. However, there is increasing evidence that the redox-active compound 3-hydroxyanthranilic acid may also have potent actions on cell function in the nervous and immune systems, and recent clinical data show marked changes in the levels of this compound, associated with changes in anthranilic acid levels, in patients with a range of neurological and other disorders including osteoporosis, chronic brain injury, Huntington’s disease, coronary heart disease, thoracic disease, stroke and depression. In most cases, there is a decrease in 3-hydroxyanthranilic acid levels and an increase in anthranilic acid levels. In this paper, we summarise the range of data obtained to date, and hypothesise that the levels of 3-hydroxyanthranilic acid or the ratio of 3-hydroxyanthranilic acid to anthranilic acid levels, may contribute to disorders with an inflammatory component, and may represent a novel marker for the assessment of inflammation and its progression. Data are presented which suggest that the ratio between these two compounds is not a simple determinant of neuronal viability. Finally, a hypothesis is presented to account for the development of the observed changes in 3-hydroxyanthranilic acid and anthranilate levels in inflammation and it is suggested that the change of the 3HAA:AA ratio, particularly in the brain, could possibly be a protective response to limit primary and secondary damage

The Low- and Intermediate-Mass Stellar Population in the Small Magellanic Cloud: The Central Stars of Planetary Nebulae

We present a study on the central stars (CSs) of Planetary Nebulae (PNe) observed in the Small Magellanic Cloud (SMC) with the Space Telescope Imaging Spectrograph instrument on-board the HST. The stellar magnitudes have been measured using broad-band photometry, and Zanstra analysis of the nebulae provided the stellar temperatures. From the location of the CSs on the HR diagram, and by comparing the observed CSs with current models of stellar evolution, we infer the CSs masses. We examine closely the possibility of light contamination in the bandpass from an unrecognized stellar companion, and we establish strong constraints on the existence and nature of any binary companion. We find an average mass of 0.63 Msun, which is similar to the mass obtained for a sample of CSs in the LMC (0.65 Msun). However, the SMC and LMC CS mass distributions differ slightly, the SMC sample lacking an intermediate-mass stellar population (0.65 to 0.75 Msun). We discuss the significance and possible reasons for the difference between the two mass distributions. In particular, we consider the differences in the star formation history between the clouds and the mass-loss rate dependence on metallicity.Comment: 30 pages, 6 figures, 5 tables. To be published in ApJ (October 20

Drought supersedes warming in determining volatile and tissue defenses of piñon pine (Pinus edulis)

Trees are suffering mortality across the globe as a result of drought, warming, and biotic attacks. The combined effects of warming and drought on in situ tree chemical defenses against herbivory have not been studied to date. To address this, we transplanted mature pinon pine trees-a well-studied species that has undergone extensive drought and herbivore-related mortality-within their native woodland habitat and also to a hotter-drier habitat and measured monoterpene emissions and concentrations across the growing season. We hypothesized that greater needle temperatures in the hotter-drier site would increase monoterpene emission rates and consequently lower needle monoterpene concentrations, and that this temperature effect would dominate the seasonal pattern of monoterpene concentrations regardless of drought. In support of our hypothesis, needle monoterpene concentrations were lower across all seasons in trees transplanted to the hotter-drier site. Contrary to our hypothesis, basal emission rates (emission rates normalized to 30 degrees C and a radiative flux of 1000 mu mol m(-2) s(-1)) did not differ between sites. This is because an increase in emissions at the hotter-drier site from a 1.5 degrees C average temperature increase was offset by decreased emissions from greater plant water stress. High emission rates were frequently observed during June, which were not related to plant physiological or environmental factors but did not occur below pre-dawn leaf water potentials of -2 MPa, the approximate zero carbon assimilation point in pinon pine. Emission rates were also not under environmental or plant physiological control when pre-dawn leaf water potential was less than -2 MPa. Our results suggest that drought may override the effects of temperature on monoterpene emissions and tissue concentrations, and that the influence of drought may occur through metabolic processes sensitive to the overall needle carbon balance.National Science Foundation, Division of Atmospheric and Geospace Sciences [0919189]; USDA National Institute of Food and Agriculture Hatch project [MONB00389, 228396]; National Science Foundation, Division of Integrative Organismal Systems [1755346]; National Science Foundation Division of Environmental Biology [1552976]; Department of the Energy National Institute for Climate Change Research (Western Region) [DE-FCO2-O6ER64159]; National Science Foundation Macrosystems Biology [EF-1340624, EF-1550756]; Critical Zone Observatories [EAR-1331408]; DIRENet [DEB-0443526]; Biosphere 2 through the Philecology Foundation (Fort Worth, TX); US Environmental Protection Agency (STAR Fellowship Assistance Agreement) [FP-91717801-0]Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Modelling the Pan-Spectral Energy Distribution of Starburst Galaxies: III. Emission Line Diagnostics of Ensembles of Evolving HII Regions

We build, as far as theory will permit, self consistent model HII regions around central clusters of aging stars. These produce strong emission line diagnostics applicable to either individual HII regions in galaxies, or to the integrated emission line spectra of disk or starburst galaxies. The models assume that the expansion and internal pressure of individual HII regions is driven by the net input of mechanical energy from the central cluster, be it through winds or supernova events. This eliminates the ionization parameter as a free variable, replacing it with a parameter which depends on the ratio of the cluster mass to the pressure in the surrounding interstellar medium. These models explain why HII regions with low abundances have high excitation, and demonstrate that at least part of the warm ionized medium is the result of overlapping faint, old, large, and low pressure HII regions. We present line ratios (at both optical and IR wavelengths) which provide reliable abundance diagnostics for both single HII regions or for integrated galaxy spectra, and we find a number that can be used to estimate the mean age of the cluster stars exciting individual HII regions.Comment: 22 pages. 18 figures. Accepted for publication in Astrophysical journal Supplements. Electronic tabular material is available on request to [email protected]