Seawater carbonate chemistry, sample density and Strongylocentrotus purpuratus size, filtering and respiration rate during experiments, 2011

Anthropogenic CO2 emissions are acidifying the world's oceans. A growing body of evidence is showing that ocean acidification impacts growth and developmental rates of marine invertebrates. Here we test the impact of elevated seawater pCO2 (129 Pa, 1271 µatm) on early development, larval metabolic and feeding rates in a marine model organism, the sea urchin Strongylocentrotus purpuratus. Growth and development was assessed by measuring total body length, body rod length, postoral rod length and posterolateral rod length. Comparing these parameters between treatments suggests that larvae suffer from a developmental delay (by ca. 8%) rather than from the previously postulated reductions in size at comparable developmental stages. Further, we found maximum increases in respiration rates of + 100 % under elevated pCO2, while body length corrected feeding rates did not differ between larvae from both treatments. Calculating scope for growth illustrates that larvae raised under high pCO2 spent an average of 39 to 45% of the available energy for somatic growth, while control larvae could allocate between 78 and 80% of the available energy into growth processes. Our results highlight the importance of defining a standard frame of reference when comparing a given parameter between treatments, as observed differences can be easily due to comparison of different larval ages with their specific set of biological characters.

CT Image Electron Density Quantification in Regions with Metal Implants: Implications for Radiotherapy Treatment Planning

In radiotherapy planning, computed tomography (CT) images are used to quantify the electron density of tissues and provide spatial anatomical information. Treatment planning systems use these data to calculate the expected spatial distribution of absorbed dose in a patient. CT imaging is complicated by the presence of metal implants which cause increased image noise, produce artifacts throughout the image and can exceed the available range of CT number values within the implant, perturbing electron density estimates in the image. Furthermore, current dose calculation algorithms do not accurately model radiation transport at metal-tissue interfaces. Combined, these issues adversely affect the accuracy of dose calculations in the vicinity of metal implants. As the number of patients with orthopedic and dental implants grows, so does the need to deliver safe and effective radiotherapy treatments in the presence of implants. The Medical Physics group at the Cancer Centre of Southeastern Ontario and Queen's University has developed a Cobalt-60 CT system that is relatively insensitive to metal artifacts due to the high energy, nearly monoenergetic Cobalt-60 photon beam. Kilovoltage CT (kVCT) images, including images corrected using a commercial metal artifact reduction tool, were compared to Cobalt-60 CT images throughout the treatment planning process, from initial imaging through to dose calculation. An effective metal artifact reduction algorithm was also implemented for the Cobalt-60 CT system. Electron density maps derived from the same kVCT and Cobalt-60 CT images indicated the impact of image artifacts on estimates of photon attenuation for treatment planning applications. Measurements showed that truncation of CT number data in kVCT images produced significant mischaracterization of the electron density of metals. Dose measurements downstream of metal inserts in a water phantom were compared to dose data calculated using CT images from kVCT and Cobalt-60 systems with and without artifact correction. The superior accuracy of electron density data derived from Cobalt-60 images compared to kVCT images produced calculated dose with far better agreement with measured results. These results indicated that dose calculation errors from metal image artifacts are primarily due to misrepresentation of electron density within metals rather than artifacts surrounding the implants.

Energy efficiency in the Chinese provinces: a fixed effects stochastic frontier spatial Durbin error panel analysis

Energy efficiency improvement has been a key objective of China’s long-term energy policy. In this paper, we derive single-factor technical energy efficiency (abbreviated as energy efficiency) in China from multi-factor efficiency estimated by means of a translog production function and a stochastic frontier model on the basis of panel data on 29 Chinese provinces over the period 2003–2011. We find that average energy efficiency has been increasing over the research period and that the provinces with the highest energy efficiency are at the east coast and the ones with the lowest in the west, with an intermediate corridor in between. In the analysis of the determinants of energy efficiency by means of a spatial Durbin error model both factors in the own province and in first-order neighboring provinces are considered. Per capita income in the own province has a positive effect. Furthermore, foreign direct investment and population density in the own province and in neighboring provinces have positive effects, whereas the share of state-owned enterprises in Gross Provincial Product in the own province and in neighboring provinces has negative effects. From the analysis it follows that inflow of foreign direct investment and reform of state-owned enterprises are important policy handles.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

A 3D printed electromagnetic nonlinear vibration energy harvester

A 3D printed electromagnetic vibration energy harvester is presented. The motion of the device is in-plane with the excitation vibrations, and this is enabled through the exploitation of a leaf isosceles trapezoidal flexural pivot topology. This topology is ideally suited for systems requiring restricted out-of-plane motion and benefits from being fabricated monolithically. This is achieved by 3D printing the topology with materials having a low flexural modulus. The presented system has a nonlinear softening spring response, as a result of designed magnetic force interactions. A discussion of fatigue performance is presented and it is suggested that whilst fabricating, the raster of the suspension element is printed perpendicular to the flexural direction and that the experienced stress is as low as possible during operation, to ensure longevity. A demonstrated power of ~25 μW at 0.1 g is achieved and 2.9 mW is demonstrated at 1 g. The corresponding bandwidths reach up-to 4.5 Hz. The system's corresponding power density of ~0.48 mW cm−3 and normalised power integral density of 11.9 kg m−3 (at 1 g) are comparable to other in-plane systems found in the literature.

Estimating Bat and Bird Mortality Occurring at Wind Energy Turbines from Covariates and Carcass Searches Using Mixture Models

Environmental impacts of wind energy facilities increasingly cause concern, a central issue being bats and birds killed by rotor blades. Two approaches have been employed to assess collision rates: carcass searches and surveys of animals prone to collisions. Carcass searches can provide an estimate for the actual number of animals being killed but they offer little information on the relation between collision rates and, for example, weather parameters due to the time of death not being precisely known. In contrast, a density index of animals exposed to collision is sufficient to analyse the parameters influencing the collision rate. However, quantification of the collision rate from animal density indices (e.g. acoustic bat activity or bird migration traffic rates) remains difficult. We combine carcass search data with animal density indices in a mixture model to investigate collision rates. In a simulation study we show that the collision rates estimated by our model were at least as precise as conventional estimates based solely on carcass search data. Furthermore, if certain conditions are met, the model can be used to predict the collision rate from density indices alone, without data from carcass searches. This can reduce the time and effort required to estimate collision rates. We applied the model to bat carcass search data obtained at 30 wind turbines in 15 wind facilities in Germany. We used acoustic bat activity and wind speed as predictors for the collision rate. The model estimates correlated well with conventional estimators. Our model can be used to predict the average collision rate. It enables an analysis of the effect of parameters such as rotor diameter or turbine type on the collision rate. The model can also be used in turbine-specific curtailment algorithms that predict the collision rate and reduce this rate with a minimal loss of energy production.

Urban Retrofit and Resilience: The challenge of Energy Efficiency and Vulnerability

Urban retrofit is becoming increasingly established as one of the most effective solutions to contain the energy consumption of the existing building stock, to reduce vulnerability to natural and man-made risk and generally improve the quality of built space. However, the planning of retrofit interventions at urban scale should take account of the actual feasibility of measures lest they remain only on paper. This contribution supplies an overview of the many issues related to the subject of urban regeneration, proposing a procedure to identify practical interventions to minimize costs and maximize benefits, in terms of energy efficiency, an increase in resilience and improvement in the quality of the building stock. This procedure was applied to a case study of a neighborhood in the city of Naples, a high-density urban area which is particularly vulnerable to volcanic and seismic risk, and to risks due to climate change.

Study of salinity gradients in the Persian Gulf and an experimental model for electric energy extraction from them using nano-membranes

Salinity gradient power (SGP) is the energy that can be obtained from the mixing entropy of two solutions with a different salt concentration. River estuary, as a place for mixing salt water and fresh water, has a huge potential of this renewable energy. In this study, this potential in the estuaries of rivers leading to the Persian Gulf and the factors affecting it are analysis and assessment. Since most of the full water rivers are in the Asia, this continent with the potential power of 338GW is a second major source of energy from the salinity gradient power in the world (Wetsus institute, 2009). Persian Gulf, with the proper salinity gradient in its river estuaries, has Particular importance for extraction of this energy. Considering the total river flow into the Persian Gulf, which is approximately equal to 3486 m3/s, the amount of theoretical extractable power from salinity gradient in this region is 5.2GW. Iran, with its numerous rivers along the coast of the Persian Gulf, has a great share of this energy source. For example, with study calculations done on data from three hydrometery stations located on the Arvand River, Khorramshahr Station with releasing 1.91M/ energy which is obtained by combining 1.26m3 river water with 0.74 m3 sea water, is devoted to itself extracting the maximum amount of extractable energy. Considering the average of annual discharge of Arvand River in Khorramshahr hydrometery station, the amount of theoretical extractable power is 955 MW. Another part of parameters that are studied in this research, are the intrusion length of salt water and its flushing time in the estuary that have a significant influence on the salinity gradient power. According to the calculation done in conditions HWS and the average discharge of rivers, the maximum of salinity intrusion length in to the estuary of the river by 41km is related to Arvand River and the lowest with 8km is for Helle River. Also the highest rate of salt water flushing time in the estuary with 9.8 days is related to the Arvand River and the lowest with 3.3 days is for Helle River. Influence of these two parameters on reduces the amount of extractable energy from salinity gradient power as well as can be seen in the estuaries of the rivers studied. For example, at the estuary of the Arvand River in the interval 8.9 days, salinity gradient power decreases 9.2%. But another part of this research focuses on the design of a suitable system for extracting electrical energy from the salinity gradient. So far, five methods have been proposed to convert this energy to electricity that among them, reverse electro-dialysis (RED) method and pressure-retarded osmosis (PRO) method have special importance in practical terms. In theory both techniques generate the same amount of energy from given volumes of sea and river water with specified salinity; in practice the RED technique seems to be more attractive for power generation using sea water and river water. Because it is less necessity of salinity gradient to PRO method. In addition to this, in RED method, it does not need to use turbine to change energy and the electricity generation is started when two solutions are mixed. In this research, the power density and the efficiency of generated energy was assessment by designing a physical method. The physical designed model is an unicellular reverse electro-dialysis battery with nano heterogenic membrane has 20cmx20cm dimension, which produced power density 0.58 W/m2 by using river water (1 g NaCl/lit) and sea water (30 g NaCl/lit) in laboratorial condition. This value was obtained because of nano method used on the membrane of this system and suitable design of the cell which led to increase the yield of the system efficiency 11% more than non nano ones.

MAGIC observations of the February 2014 flare of 1ES 1011+496 and ensuing constraint of the EBL density

Context. In February-March 2014, the MAGIC telescopes observed the high-frequency peaked BL Lac 1ES 1011+496 (z=0.212) in flaring state at very-high energy (VHE, E>100GeV). The flux reached a level more than 10 times higher than any previously recorded flaring state of the source. Aims. Description of the characteristics of the flare presenting the light curve and the spectral parameters of the night-wise spectra and the average spectrum of the whole period. From these data we aim at detecting the imprint of the Extragalactic Background Light (EBL) in the VHE spectrum of the source, in order to constrain its intensity in the optical band. Methods. We analyzed the gamma-ray data from the MAGIC telescopes using the standard MAGIC software for the production of the light curve and the spectra. For the constraining of the EBL we implement the method developed by the H.E.S.S. collaboration in which the intrinsic energy spectrum of the source is modeled with a simple function (< 4 parameters), and the EBL-induced optical depth is calculated using a template EBL model. The likelihood of the observed spectrum is then maximized, including a normalization factor for the EBL opacity among the free parameters. Results. The collected data allowed us to describe the flux changes night by night and also to produce di_erential energy spectra for all nights of the observed period. The estimated intrinsic spectra of all the nights could be fitted by power-law functions. Evaluating the changes in the fit parameters we conclude that the spectral shape for most of the nights were compatible, regardless of the flux level, which enabled us to produce an average spectrum from which the EBL imprint could be constrained. The likelihood ratio test shows that the model with an EBL density 1:07 (-0.20,+0.24)stat+sys, relative to the one in the tested EBL template (Domínguez et al. 2011), is preferred at the 4:6 σ level to the no-EBL hypothesis, with the assumption that the intrinsic source spectrum can be modeled as a log-parabola. This would translate into a constraint of the EBL density in the wavelength range [0.24 μm,4.25 μm], with a peak value at 1.4 μm of λF_ = 12:27^(+2:75)_ (-2:29) nW m^(-2) sr^(-1), including systematics.

A kinetic energy budget and internal instabilities in the Fine Resolution Antarctic Model

An energy analysis of the Fine Resolution Antarctic Model (FRAM) reveals the instability processes in the model. The main source of time-mean kinetic energy is the wind stress and the main sink is transfer to mean potential energy. The wind forcing thus helps maintain the density structure. Transient motions result from internal instabilities of the Bow rather than seasonal variations of the forcing. Baroclinic instability is found to be an important mechanism in FRAM. The highest values of available potential energy are found in the western boundary regions as well as in the Antarctic Circumpolar Current (ACC) region. All subregions with predominantly zonal flow are found to be baroclinically unstable. The observed deficit of eddy kinetic energy in FRAM occurs as a result of the high lateral friction, which decreases the growth rates of the most unstable waves. This high friction is required for the numerical stability of the model and can only be made smaller by using a finer horizontal resolution. A grid spacing of at least 10-15 km would be required to resolve the most unstable waves in the southern part of the domain. Barotropic instability is also found to be important for the total domain balance. The inverse transfer (that is, transfer from eddy to mean kinetic energy) does not occur anywhere, except in very localized tight jets in the ACC. The open boundary condition at the northern edge of the model domain does not represent a significant source or sink of eddy variability. However, a large exchange between internal and external mode energies is found to occur. It is still unclear how these boundary conditions affect the dynamics of adjacent regions.

OBSERVATIONS AND EMISSIONS OF ENERGY-ASSOCIATED OZONE PRECURSORS IN THE MID-ATLANTIC UNITED STATES

Surface ozone is formed in the presence of NOx (NO + NO2) and volatile organic compounds (VOCs) and is hazardous to human health. A better understanding of these precursors is needed for developing effective policies to improve air quality. To evaluate the year-to-year changes in source contributions to total VOCs, Positive Matrix Factorization (PMF) was used to perform source apportionment using available hourly observations from June through August at a Photochemical Assessment Monitoring Station (PAMS) in Essex, MD for each year from 2007-2015. Results suggest that while gasoline and vehicle exhaust emissions have fallen, the contribution of natural gas sources to total VOCs has risen. To investigate this increasing natural gas influence, ethane measurements from PAMS sites in Essex, MD and Washington, D.C. were examined. Following a period of decline, daytime ethane concentrations have increased significantly after 2009. This trend appears to be linked with the rapid shale gas production in upwind, neighboring states, especially Pennsylvania and West Virginia. Back-trajectory analyses similarly show that ethane concentrations at these monitors were significantly greater if air parcels had passed through counties containing a high density of unconventional natural gas wells. In addition to VOC emissions, the compressors and engines involved with hydraulic fracturing operations also emit NOx and particulate matter (PM). The Community Multi-scale Air Quality (CMAQ) Model was used to simulate air quality for the Eastern U.S. in 2020, including emissions from shale gas operations in the Appalachian Basin. Predicted concentrations of ozone and PM show the largest decreases when these natural gas resources are hypothetically used to convert coal-fired power plants, despite the increased emissions from hydraulic fracturing operations expanded into all possible shale regions in the Appalachian Basin. While not as clean as burning natural gas, emissions of NOx from coal-fired power plants can be reduced by utilizing post-combustion controls. However, even though capital investment has already been made, these controls are not always operated at optimal rates. CMAQ simulations for the Eastern U.S. in 2018 show ozone concentrations decrease by ~5 ppb when controls on coal-fired power plants limit NOx emissions to historically best rates.

Nano-Engineering of Densely Packed Electrochemical Energy Storage Architectures by Atomic Layer Deposition

Nanostructures are highly attractive for future electrical energy storage devices because they enable large surface area and short ion transport time through thin electrode layers for high power devices. Significant enhancement in power density of batteries has been achieved by nano-engineered structures, particularly anode and cathode nanostructures spatially separated far apart by a porous membrane and/or a defined electrolyte region. A self-aligned nanostructured battery fully confined within a single nanopore presents a powerful platform to determine the rate performance and cyclability limits of nanostructured storage devices. Atomic layer deposition (ALD) has enabled us to create and evaluate such structures, comprised of nanotubular electrodes and electrolyte confined within anodic aluminum oxide (AAO) nanopores. The V2O5- V2O5 symmetric nanopore battery displays exceptional power-energy performance and cyclability when tested as a massively parallel device (~2billion/cm2), each with ~1m3 volume (~1fL). Cycled between 0.2V and 1.8V, this full cell has capacity retention of 95% at 5C rate and 46% at 150C, with more than 1000 charge/discharge cycles. These results demonstrate the promise of ultrasmall, self-aligned/regular, densely packed nanobattery structures as a testbed to study ionics and electrodics at the nanoscale with various geometrical modifications and as a building block for high performance energy storage systems[1, 2]. Further increase of full cell output potential is also demonstrated in asymmetric full cell configurations with various low voltage anode materials. The asymmetric full cell nanopore batteries, comprised of V2O5 as cathode and prelithiated SnO2 or anatase phase TiO2 as anode, with integrated nanotubular metal current collectors underneath each nanotubular storage electrode, also enabled by ALD. By controlling the amount of lithium ion prelithiated into SnO2 anode, we can tune full cell output voltage in the range of 0.3V and 3V. This asymmetric nanopore battery array displays exceptional rate performance and cyclability. When cycled between 1V and 3V, it has capacity retention of approximately 73% at 200C rate compared to 1C, with only 2% capacity loss after more than 500 charge/discharge cycles. With increased full cell output potential, the asymmetric V2O5-SnO2 nanopore battery shows significantly improved energy and power density. This configuration presents a more realistic test - through its asymmetric (vs symmetric) configuration – of performance and cyclability in nanoconfined environment. This dissertation covers (1) Ultra small electrochemical storage platform design and fabrication, (2) Electron and ion transport in nanostructured electrodes inside a half cell configuration, (3) Ion transport between anode and cathode in confined nanochannels in symmetric full cells, (4) Scale up energy and power density with geometry optimization and low voltage anode materials in asymmetric full cell configurations. As a supplement, selective growth of ALD to improve graphene conductance will also be discussed[3]. References: 1. Liu, C., et al., (Invited) A Rational Design for Batteries at Nanoscale by Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 23-30. 2. Liu, C.Y., et al., An all-in-one nanopore battery array. Nature Nanotechnology, 2014. 9(12): p. 1031-1039. 3. Liu, C., et al., Improving Graphene Conductivity through Selective Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 133-138.

Modeling and analysis of thermoelectric energy conversion efficiency in nanostructures.

116 p.

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

Computing the structural and vibrational properties of polymorphic organic molecular crystals through van der Waals corrected density functional theory and the electronic properties of organic thin films through microelectrostatic calculations.

The present Thesis reports on the various research projects to which I have contributed during my PhD period, working with several research groups, and whose results have been communicated in a number of scientific publications. The main focus of my research activity was to learn, test, exploit and extend the recently developed vdW-DFT (van der Waals corrected Density Functional Theory) methods for computing the structural, vibrational and electronic properties of ordered molecular crystals from first principles. A secondary, and more recent, research activity has been the analysis with microelectrostatic methods of Molecular Dynamics (MD) simulations of disordered molecular systems. While only very unreliable methods based on empirical models were practically usable until a few years ago, accurate calculations of the crystal energy are now possible, thanks to very fast modern computers and to the excellent performance of the best vdW-DFT methods. Accurate energies are particularly important for describing organic molecular solids, since they often exhibit several alternative crystal structures (polymorphs), with very different packing arrangements but very small energy differences. Standard DFT methods do not describe the long-range electron correlations which give rise to the vdW interactions. Although weak, these interactions are extremely sensitive to the packing arrangement, and neglecting them used to be a problem. The calculations of reliable crystal structures and vibrational frequencies has been made possible only recently, thanks to development of some good representations of the vdW contribution to the energy (known as “vdW corrections”).