New Stream Mitigation Requirements in Coastal South Carolina: Providing Mitigation in an Atmosphere of Dynamic Policy and Emerging Science

2010 S.C. Water Resources Conference - Science and Policy Challenges for a Sustainable Futur

Predictive chemical kinetics : enabling automatic mechanism generation and evaluation

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2013.Cataloged from PDF version of thesis.Includes bibliographical references.The use of petroleum-based fuels for transportation accounted for more than 25% of the total energy consumed in 2012, both in the United States and throughout the world. The finite nature of world oil reserves and the effects of burning petroleum-based fuels on the world's climate have motivated efforts to develop alternative, renewable fuels. A major category of alternative fuels is biofuels, which potentially include a wide variety of hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, etc. To select the best species for use as fuel, we need to know if it burns cleanly, controllably, and efficiently. This is especially important when considering novel engine technologies, which are often very sensitive to fuel chemistry. The large number of candidate fuels and the high expense of experimental engine tests motivates the use of predictive theoretical methods to help quickly identify the most promising candidates. This thesis presents several contributions in the areas of predictive chemical kinetics and automatic mechanism generation, particularly in the area of reaction kinetics. First, the accuracy of several methods of automatic, high-throughput estimation of reaction rates are evaluated by comparison to a test set obtained from the NIST Chemical Kinetics Database. The methods considered, including the classic Evans-Polanyi correlation, the "rate rules" method currently used in the RMG software, and a new method based on group contribution theory, are shown to not yet obtain the order-of-magnitude accuracy desired for automatic mechanism generation. Second, a method of very accurate computation of bimolecular reaction rates using ring polymer molecular dynamics (RPMD) is presented. RPMD rate theory enables the incorporation of quantum effects (zero-point energy and tunneling) in reaction kinetics using classical molecular dynamics trajectories in an extended phase space. A general-purpose software package named RPMD-rate was developed for conducting such calculations, and the accuracy of this method was demonstrated by investigating the kinetics and kinetic isotope effect of the reaction OH + CH4 --> CH3 + H2O. Third, a general framework for incorporating pressure dependence in thermal unimolecular reactions, which require an inert third body to provide or remove the energy needed for reaction via bimolecular collisions, was developed. Within this framework, several methods of reducing the full, master equation-based model to a set of phenomenological rate coefficients k(T, P) are compared using the chemically-activated reaction of acetyl radical with oxygen as a case study, and recommendations are made as to when each method should be used. This also resulted in a general-purpose code for calculating pressure-dependent kinetics, which was applied to developing an ab initio model of the reaction of the Criegee biradical CH 200 with small carbonyls that reproduces recent experimental results. Finally, the ideas and techniques of estimating reaction kinetics are brought together for the development of a detailed kinetics model of the oxidation of diisopropyl ketone (DIPK), a candidate biofuel representative of species produced from cellulosic biomass conversion using endophytic fungi. The model is evaluated against three experiments covering a range of temperatures, pressures, and oxygen concentrations to show its strengths and weaknesses. Our ability to automatically generate this model and systematically improve its parameters without fitting to the experimental results demonstrates the validity and usefulness of the predictive chemical kinetics paradigm. These contributions are available as part of the Reaction Mechanism Generator (RMG) software package.by Joshua W. Allen.Ph.D

Effect of Agricultural Activity on River Water Quality: A Case Study for the Lower Colorado River Basin

This case study investigates the effect of a change in cropping pattern involving expanded acres of crops for biofuel feedstock, on the discharge of nutrients to rivers. Annual data from 1968-2008 on stream flow, cropped acres, and precipitation for Wharton County, Texas are used. A positive impact of increased corn acreage over this period on river discharge is identified.Biofuels, Stream Flow, Discharge, Production Economics, Resource /Energy Economics and Policy,

RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett–Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH4, OH+CH4 and H+C2H6 reactions.United States. Dept. of Energy (Office of Basic Energy Sciences under the Energy Frontier Research Center for Combustion Science (Grant No. DE-SC0001198))United States. Dept. of Energy (Energy Frontier Research Center for Combustion Science, Combustion Energy Research Fellowship)King Abdullah University of Science and Technology (Award No. KUS-I1-010-01

14C-Cobalamin Absorption from Endogenously Labeled Chicken Eggs Assessed in Humans Using Accelerator Mass Spectrometry.

Traditionally, the bioavailability of vitamin B-12 (B12) from in vivo labeled foods was determined by labeling the vitamin with radiocobalt (57Co, 58Co or 60Co). This required use of penetrating radioactivity and sometimes used higher doses of B12 than the physiological limit of B12 absorption. The aim of this study was to determine the bioavailability and absorbed B12 from chicken eggs endogenously labeled with 14C-B12 using accelerator mass spectrometry (AMS). 14C-B12 was injected intramuscularly into hens to produce eggs enriched in vivo with the 14C labeled vitamin. The eggs, which provided 1.4 to 2.6 μg of B12 (~1.1 kBq) per serving, were scrambled, cooked and fed to 10 human volunteers. Baseline and post-ingestion blood, urine and stool samples were collected over a one-week period and assessed for 14C-B12 content using AMS. Bioavailability ranged from 13.2 to 57.7% (mean 30.2 ± 16.4%). Difference among subjects was explained by dose of B12, with percent bioavailability from 2.6 μg only half that from 1.4 μg. The total amount of B12 absorbed was limited to 0.5-0.8 μg (mean 0.55 ± 0.19 μg B12) and was relatively unaffected by the amount consumed. The use of 14C-B12 offers the only currently available method for quantifying B12 absorption in humans, including food cobalamin absorption. An egg is confirmed as a good source of B12, supplying approximately 20% of the average adult daily requirement (RDA for adults = 2.4 μg/day)

Seawater Desalination for Municipal Water Production

This paper examines the optimal allocation of several inputs in the context of seawater desalination by reverse osmosis (RO) as a source of municipal (or commercial or industrial) water. A cost-minimization model is developed, a production function is estimated, and sensitivity analyses are conducted using the optimization model to investigate the effect of environmental conditions and economic factors on the optimal input portfolio and the cost of operating a modeled seawater desalination facility. The objectives of this paper are to better understand the effect on the seawater desalination facility’s costs and input portfolio from changes in water quality, membrane lifespan, daily operations schedule, and energy prices. Findings include that lower total facility costs are associated with warm-weather water quality parameters, longer membrane life, and mid-range daily operations schedule (14.265 hours/day). Under most conditions, an interruptible power supply regime reduces facility costs. Exceptions include when the interruptible power supply regime implies significant reductions in operating hours and the associated reduction in energy price is very small.water, production, seawater desalination, Resource /Energy Economics and Policy,

Maximizing precision in saturation-limited absorption measurements

Quantum fluctuations in the intensity of an optical probe is noise which limits measurement precision in absorption spectroscopy. Increased probe power can offer greater precision, however, this strategy is often constrained by sample saturation. Here, we analyse measurement precision for a generalised absorption model in which we account for saturation and explore its effect on both classical and quantum probe performance. We present a classical probe-sample optimisation strategy to maximise precision and find that optimal probe powers always fall within the saturation regime. We apply our optimisation strategy to two examples, high-precision Doppler broadened thermometry and an absorption spectroscopy measurement of Chlorophyll A. We derive a limit on the maximum precision gained from using a non-classical probe and find a strategy capable of saturating this bound. We evaluate amplitude-squeezed light as a viable experimental probe state and find it capable of providing precision that reaches to within > 85% of the ultimate quantum limit with currently available technology.Comment: 12 pages and 5 figure

Photodetector Focal Plane Arrays Integrated with Silicon Micropyramidal Structures in MWIR

Light-concentrating truncated Si micropyramidal arrays with 54.7 degree sidewall angles were successfully integrated with PtSi Schottky barrier photodetectors. Four different devices consisting of 10 x 10 photodetectors with 60 um pitch combined in parallel were tested, where significant enhancement capability was demonstrated by the Si micropyramids. The device consisting of one hundred 22 um square detectors monolithically integrated with the light-concentrating micropyramidal array displayed signal enhancement of up to 4 times compared to the same size 22 um square photodetector device without the light concentrators.Comment: 4 pages, 2 figures, GOMACTech 202