Chemistry Commons^™

Computation Of Atmospheric Concentrations Of Molecular Clusters From Ab Initio Thermochemistry, Tuguldur T. Odbadrakh, Ariel G. Gale, Benjamin T. Ball, Berhane Temelso, George C. Shields

Chemistry Publications

The computational study of the formation and growth of atmospheric aerosols requires an accurate Gibbs free energy surface, which can be obtained from gas phase electronic structure and vibrational frequency calculations. These quantities are valid for those atmospheric clusters whose geometries correspond to a minimum on their potential energy surfaces. The Gibbs free energy of the minimum energy structure can be used to predict atmospheric concentrations of the cluster under a variety of conditions such as temperature and pressure. We present a computationally inexpensive procedure built on a genetic algorithm-based configurational sampling followed by a series of increasingly accurate screening …

Water-Mediated Peptide Bond Formation In The Gas Phase: A Model Prebiotic Reaction, George C. Shields, Ariel Gale, Tuguldur T. Odbadrakh, Tyler Ball

Chemistry Publications

The emergence of life on the prebiotic Earth must have involved the formation of polypeptides, yet the polymerization of amino acids is thermodynamically unfavorable under biologically relevant aqueous conditions because amino acids are zwitterions in solution and because of the production of a water molecule through a condensation reaction. Many mechanisms for overcoming this thermodynamic unfavorability have been proposed, but the role of gas phase water clusters has not been investigated. We present the thermodynamics of the water-mediated gas phase dimerization reaction of glycine as a model for the atmospheric polymerization of amino acids prior to the emergence of biological …

On-Road Remote Sensing Of Automobile Emissions In The Denver Area: Winter 2020, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Are Electric Vehicles A Panacea For Reducing Ozone Precursor Emissions?, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Vehicle Exhaust Remote Sensing Device Method To Screen Vehicles For Evaporative Running Loss Emissions, Gary A. Bishop, Timothy H. Defries, James A. Sidebottom, James M. Kemper

Fuel Efficiency Automobile Test Publications

Vehicle hydrocarbon (HC) emissions can be emitted from either tailpipe or non-tailpipe locations and understanding their fleet apportionment is important for successful air pollution policy. Vehicles initially misidentified as having elevated tailpipe HC emissions first indicated that roadside exhaust sensors could detect the presence of evaporative HC emissions as increased noise in the HC/carbon dioxide (CO₂) correlation measurement. The 90^th percentile of the largest residual of the HC/CO₂ correlation is defined as a running loss index (RLI) for each measurement. An RLI that is three standard deviations or greater above the instruments noise indicates possible evaporative …

On-Road Remote Sensing Of Automobile Emissions In The Tulsa Area: Fall 2019, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Inspection And Maintenance Evaluation Using Historical U.S. Remote Sensing Measurements, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

An Annual Time Series Of Weekly Size-Resolved Aerosol Properties In The Megacity Of Metro Manila, Philippines, Connor Stahl, Melliza Templonuevo Cruz, Paola Angela Bañaga, Grace Betito, Rachel A. Braun, Mojtaba Azadi Aghdam, Maria Obiminda L. Cambaliza, Genevieve Rose Lorenzo, Alexander B. Macdonald, Preciosa Corazon Pabroa, John Robin Yee, James Bernard Simpas, Armin Sorooshian

Physics Faculty Publications

Size-resolved aerosol samples were collected in Metro Manila between July 2018 and October 2019. Two Micro-Orifice Uniform Deposit Impactors (MOUDI) were deployed at Manila Observatory in Quezon City, Metro Manila with samples collected on a weekly basis for water-soluble speciation and mass quantification. Additional sets were collected for gravimetric and black carbon analysis, including during special events such as holidays. The unique aspect of the presented data is a year-long record with weekly frequency of size-resolved aerosol composition in a highly populated megacity where there is a lack of measurements. The data are suitable for research to understand the sources, …

Ozone And Reactive Oxidized Nitrogen Chemistry In The Northeast U.S, Matthew Ninneman

Legacy Theses & Dissertations (2009 - 2024)

Ongoing reductions in oxides of nitrogen concentrations ([NOx] = nitric oxide ([NO]) + nitrogen dioxide ([NO2])) throughout the continental United States (U.S.) have important implications for tropospheric ozone (O3) and reactive oxidized nitrogen chemistry (NOy ≈ NOx + nitric acid (HNO3) + particle nitrate (pNO3) + peroxy nitrates (PNs) + alkyl nitrates (ANs)). Specifically, decreasing [NOx] concentrations have likely (1) increased the sensitivity of O3 to the [NOx] level, and (2) affected NOy speciation and partitioning. An understanding of the impacts of continued [NOx] reductions is needed to inform current and future air pollution control strategies, especially since the National …

Applications Of Drones In Atmospheric Chemistry, Travis J. Schuyler

Theses and Dissertations--Chemistry

The emission of greenhouse gases (GHGs) has changed the composition of the atmosphere during the Anthropocene. A major technical and scientific challenge is quantifying the resulting fugitive trace gas fluxes under variable meteorological conditions. Accurately documenting the sources and magnitude of GHGs emission is an important undertaking for discriminating contributions of different processes to radiative forcing. Therefore, the adverse environmental and health effects of undetected gas leaks motivates new methods of detecting, characterizing, and quantifying plumes of fugitive trace gases. Currently, there is no mobile platform able to quantify trace gases at altitudes(UASs), or drones, can be deployed on-site in …

Laser Spectroscopic Investigations Of Organic Alkoxy And Peroxy Radicals., Md Asmaul Reza

Electronic Theses and Dissertations

Understanding the mechanism of combustion reactions is key for advancing internal combustion engine design, improving the efficiency of ignition chemical reactions, and reducing pollutant formation. In order to model the extremely complicated chemical kinetics of combustion processes, it is critical to detect and identify transient reactive chemical intermediates, particularly free radicals. Hence, it needs to be fully understood the gas-phase chemistry of organic compounds in the lower atmosphere. Over the past fifty years, parallel advancement in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role of organic compounds in the atmosphere. Combustion chemistry …

Viscosities, Diffusion Coefficients, And Mixing Times Of Intrinsic Fluorescent Organic Molecules In Brown Limonene Secondary Organic Aerosol And Tests Of The Stokes–Einstein Equation, Dagny A. Ullmann, Mallory L. Hinks, Adrian M. Maclean, Christopher Butenhoff, James W. Grayson, Kelley Barsanti, Jose L. Jimenez, Sergey A. Nizkorodov, Saeid Kamal, Allan K. Bertram

Physics Faculty Publications and Presentations

Viscosities and diffusion rates of organics within secondary organic aerosol (SOA) remain uncertain. Using the bead-mobility technique, we measured viscosities as a function of water activity (a_w) of SOA generated by the ozonolysis of limonene followed by browning by exposure to NH₃ (referred to as brown limonene SOA or brown LSOA). These measurements together with viscosity measurements reported in the literature show that the viscosity of brown LSOA increases by 3–5 orders of magnitude as the aw decreases from 0.9 to approximately 0.05. In addition, we measured diffusion coefficients of intrinsic fluorescent organic molecules within brown …

Three Decades Of On-Road Mobile Source Emissions Reductions In South Los Angeles, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

In May of 2018, the University of Denver repeated on-road optical remote sensing measurements at two locations in Lynwood, CA. Lynwood area vehicle tailpipe emissions were first surveyed in 1989 and 1991 because the area suffered with a large number of carbon monoxide (CO) air quality violations. These new measurements allow for the estimation of fuel specific CO and total hydrocarbon (HC) emissions reductions, changes in the longevity of emission-control components, and the prevalence of high emitters in the current fleet.

Since 1989 CO emissions decreased approximately factors of 10 (120 ± 8 to 12.3 ± 0.2 gCO/kg of fuel) …

Measuring Emissions From The On-Road Vehicle Fleet In West Los Angeles, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Remote Sensing Of Automobile Emissions In The Chicago Area: Fall 2018, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Phosgene In The Upper Troposphere And Lower Stratosphere: A Marker For Product Gas Injection Due To Chlorine-Containing Very Short Lived Substances, Jeremy J. Harrison, Martyn P. Chipperfield, Ryan Hossaini, Christopher D. Boone, Sandip Dhomse, Wuhu Feng, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Abstract: Phosgene in the atmosphere is produced via the degradation of carbon tetrachloride, methyl chloroform, and a number of chlorine‐containing very short lived substances (VSLS). These VSLS are not regulated by the Montreal Protocol even though they contribute to stratospheric ozone depletion. While observations of VSLS can quantify direct stratospheric source gas injection, observations of phosgene in the upper troposphere/lower stratosphere can be used as a marker of product gas injection of chlorine‐containing VSLS. In this work we report upper troposphere/lower stratosphere measurements of phosgene made by the ACE‐FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) instrument and compare with results …

Developing X-Ray Spectromicroscopic Techniques To Quantitatively Determine Population Statistics And Individual Particle Composition Of Complex Mixed Aerosols, Matthew Fraund

University of the Pacific Theses and Dissertations

Aerosols are a major source of uncertainty in estimates of anthropogenic effects on global radiative forcing and can pose serious health concerns. While many instrumental techniques capable of analyzing aerosol samples are available, individual-particle spectromicroscopic techniques like the ones presented here are the only ones to offer morphological and compositional measurements together. Studying the composition and mixing state of aerosol populations allowed for important aspects to be uncovered, such as: aerosol source, formation mechanism, hygroscopicity, optical properties, level of aging, and inhalation dangers. Ambient aerosols from the Amazon, both biogenic and anthropogenic, were apportioned based on their individual composition. Recently …

Effect Of Carbonaceous Nanoparticles On Naturally Occurring Iron Reduction By Carboxylates, Ashleen Reddy

All Master's Theses

The emission of ambient particulate matter (PM) is regulated by many institutions due to the detrimental effects on health, environment and climate; yet many underlying mechanisms of PM reactivity are still not well understood. In the current study, the effect of carbonaceous nanoparticles (CNPs), contained within ultrafine PM (particle diameter ≤ 100 nm), is investigated on naturally occurring processes that increase the abundance of bioavailable iron. Enhancing iron bioavailability (i) increases primary productivity of iron-limited microorganisms, affecting the carbon cycle and global climate, and (ii) increase toxicity of inhaled particles through the associated production of reactive oxygen species (ROS). Specifically, …

Atmospheric Chemistry Of Ch3Cho: The Hydrolysis Of Ch3Cho Catalyzed By H2So4, Ellen Mitchell, Xing-Feng Tan, Bo Long, Wei-Jun Zhang, Zheng-Wen Long

Chemistry Faculty Scholarship

Elucidating atmospheric oxidation mechanisms and the reaction kinetics of atmospheric compounds is of great importance and necessary for atmospheric modeling and the understanding of the formation of atmospheric organic aerosols. While the hydrolysis of aldehydes has been detected in the presence of sulfuric acid, the reaction mechanism and kinetics remain unclear. Herein, we use electronic structure methods with CCSD(T)/CBS accuracy and canonical variational transition state theory combined with small-curvature tunneling to study the reaction mechanism and kinetics of the hydrolysis of CH3CHO. The calculated results show that the hydrolysis of CH3CHO needs to overcome an energy barrier of 37.21 kcal …

Revisit Lynwood, Ca: On-Road Remote Sensing Of Automobile Emissions In The Lynwood, Ca: 2018, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Remote Sensing Of Heavy And Medium-Duty Trucks At The Peralta Weigh Station In The South Coast Air Basin: Spring 2017, Molly J. Haugen, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Physical Chemistry Of Gas-Liquid Interfaces: Foreword, Jennifer Faust

All Faculty Articles

Physical Chemistry of Gas-Liquid Interfaces, the first volume in the Developments in Physical & Theoretical Chemistry series, addresses the physical chemistry of gas transport and reactions across liquid surfaces. Gas-liquid interfaces are all around us, especially within atmospheric systems such as sea spray aerosols, cloud droplets, and the surface of the ocean. Because the reaction environment at liquid surfaces is completely unlike bulk gas or bulk liquid, chemists must readjust their conceptual framework when entering this field. This book provides the necessary background in thermodynamics and computational and experimental techniques for scientists to obtain a thorough understanding of the …

On-Road Remote Sensing Of Automobile Emissions In The Denver Area: Winter 2017, Gary A. Bishop, Molly J. Haugen

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Remote Sensing Of Automobile Emissions In The Tulsa Area: Fall 2017, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Investigate The Durability Of Diesel Engine Emission Controls, Gary A. Bishop, Molly J. Haugen

Fuel Efficiency Automobile Test Publications

No abstract provided.

Evaluation Of Emissions Benefits Of Federal Reformulated Gasoline Versus Conventional Gasoline, Gary A. Bishop, S. Kent Hoekman, Amber Broch

Fuel Efficiency Automobile Test Publications

No abstract provided.

The Story Of Ever Diminishing Vehicle Tailpipe Emissions As Observed In The Chicago, Il Area, Gary A. Bishop, Molly J. Haugen

Fuel Efficiency Automobile Test Publications

The University of Denver has collected on-road fuel specific vehicle emissions measurements in the Chicago area since 1989. This nearly 30 year record illustrates the large reductions in light-duty vehicle tailpipe emissions and the remarkable improvements in emissions control durability to maintain low emissions over increasing periods of time. Since 1989 fuel specific carbon monoxide (CO) emissions have been reduced by an order of magnitude and hydrocarbon (HC) emissions by more than a factor of 20. Nitric oxide (NO) emissions have only been collected since 1997 but have seen reductions of 79%. This has increased the skewness of the emissions …

Long-Term Fuel-Specific Nox And Particle Emission Trends For In-Use Heavy-Duty Vehicles In California, Molly J. Haugen, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

Two California heavy-duty fleets have been measured in 2013, 2015 and 2017 using the On-road Heavy-duty Measurement System. The Port of Los Angeles drayage fleet has increased in age by 3.3 model years (4.2 to 7.5 years old) since 2013, with little fleet turnover. Large increases in fuel specific particle emissions (PM) observed in 2015 were reversed in 2017, returning to near 2013 levels, suggesting repairs and or removal of high emitting vehicles. Fuel specific oxides of nitrogen (NO_x) emissions of this fleet have increased and NO_x after-treatment systems do not appear to perform ideally in this …

Evaluation Of Heavy- And Medium-Duty On-Road Vehicle Emissions In California's South Coast Air Basin, Molly J. Haugen, Gary A. Bishop, Arvind Thiruvengadam, Daniel K. Carder

Fuel Efficiency Automobile Test Publications

Emission measurements were collected from heavy-duty (HDVs) and medium-duty vehicles (MDVs) at the Peralta weigh station long-term measurement site near Anaheim, CA in 2017. Two Fuel Efficiency Automobile Test units sampled elevated and ground-level exhaust vehicles totaling 2,315 measurements. HDVs (1844 measurements) exhibited historical reductions in fuel specific oxides of nitrogen (NO_x) from the 2008 measurements (55%) with increased use of exhaust gas recirculation and selective catalytic reduction systems. However, as these technologies have aged, the in-use benefits have declined. Infrared %opacity measurements of tailpipe soot decreased 14% since 2012 with increased diesel particulate filter (DPF) use, DPF …

Polar Ozone Depletion: Mario J. Molina, Kirsten Oberg

Natural Sciences Student Research Presentations

This poster for the Natural Sciences Poster Session at Parkland College features the contribution of Mario J. Molina to the field of atmospheric chemistry, especially in regards to the formation and decomposition aspects of the ozone layer.