Digital Commons Network^™

Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

With the increased occurrences of wildfires worldwide, there has been an increase in scientific interest surrounding the chemistry of fire-derived "black" carbon (BC). Traditionally, wildfire research has assumed that condensed aromatic carbon (ConAC) is exclusively produced via combustion, and thus, ConAC is equated to BC. However, the lack of correlations between ConAC in soils or rivers and wildfire history suggests that ConAC may be produced non-pyrogenically. Here, we show quantitative evidence that this occurs during the oxidation of biomass with environmentally ubiquitous hydroxyl radicals. Pine wood boards exposed to iron nails and natural weather conditions for 12 years yielded a …

Infrared Spectra Of Small Radicals For Exoplanetary Spectroscopy: Oh, Nh, Cn, And Ch: The State Of Current Knowledge, Svatopluk Civiš, Adam Pastorek, Martin Ferus, Sergei N. Yurchenko, Noor-Ines Boudjema

Chemistry & Biochemistry Faculty Publications

In this study, we present a current state-of-the-art review of middle-to-near IR emission spectra of four simple astrophysically relevant molecular radicals—OH, NH, CN and CH. The spectra of these radicals were measured by means of time-resolved Fourier transform infrared spectroscopy in the 700–7500 cm⁻¹ spectral range and with 0.07–0.02 cm⁻¹ spectral resolution. The radicals were generated in a glow discharge of gaseous mixtures in a specially designed discharge cell. The spectra of short-lived radicals published here are of great importance, especially for the detailed knowledge and study of the composition of exoplanetary atmospheres in selected new planets. Today, …

Utah Wintertime Measurements Of Heavy-Duty Vehicle Nitrogen Oxide Emission Factors, Gary A. Bishop, Molly J. Haugen, Brian C. Mcdonald, Adam M. Boies

Fuel Efficiency Automobile Test Publications

There have only been a few wintertime studies of heavy-duty vehicle (HDV) NO_x emissions in the U.S., and while they have observed increased emissions, fleet characterization to identify the cause has been lacking. We have collected wintertime measurements of NO_x emission factors from 1,591 HDV at a Utah Port of Entry in December 2020 that includes individual vehicle identification. In general, the NO_x emission factors for 2011 & newer chassis model year HDV are significantly higher than 2017 spring measurements from California. The newest chassis model year HDV (2017 - 2021) NO_x emission factors are similar …

On-Road Vehicle Emission Measurements And Their Use In Evaluating Emission Control Effectiveness {Presentation}, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

The Art Of Poetry And Its Place In The History Of The Coordinating Research Councils Real World Emissions Workshop {Poster}, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Indoor Air Quality Through The Lens Of Outdoor Atmospheric Chemistry, Jonathan P.D. Abbatt, Douglas B. Collins

Faculty Contributions to Books

Outdoor atmospheric chemistry and air quality have been the topic of research that intensified in earnest around the mid-20^th century, while indoor air quality research has only been a key focus of chemical researchers over the last 30 years. Examining practices and approaches employed in the outdoor atmospheric chemistry research enterprise provides an additional viewpoint from which we can chart new paths to increase scientific understanding of indoor chemistry. This chapter explores our understanding of primary chemical sources, homogeneous and multiphase reactivity, gas-surface partitioning, and the coupling between the chemistry and dynamics of indoor air through the lens of …

On-Road Nox Emissions Evaluation Of The Repair Effectiveness For Recalled Volkswagen Group Light-Duty Diesel Vehicles In The United States, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

The admission by the Volkswagen Group in the fall of 2015 that they had duped the United States new vehicle emissions certification testing resulted in perhaps the most expensive violation of U.S. environmental vehicle emission regulations in its history. As part of the subsequent recall of more than 500,000 vehicles in the U.S., owners could sell their vehicles back to the companies or have them repaired. We have used a number of large on-road emission measurement data sets that were routinely collected before and after the recall to evaluate the fuel specific NO_x emissions benefit for the vehicles that …

Unintended Consequences Of Air Cleaning Chemistry, Douglas B. Collins, Delphine K. Farmer

Faculty Journal Articles

Amplified interest in maintaining clean indoor air associated with the airborne transmission risks of SARS-CoV-2 have led to an expansion in the market for commercially available air cleaning systems. While the optimal way to mitigate indoor air pollutants or contaminants is to control (remove) the source, air cleaners are a tool for use when absolute source control is not possible. Interventions for indoor air quality management include physical removal of pollutants through ventilation or collection on filters and sorbent materials, along with chemically reactive processes that transform pollutants or seek to deactivate biological entities. This perspective intends to highlight the …

On-Road Remote Sensing Of Automobile Emissions In The Fresno, Ca Area: Spring 2021, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Winter Measurements Of Heavy-Duty Vehicles To Characterize The Cold Temperature Effectiveness Of Selective Catalytic Reductions Catalyst In Controlling Oxide Of Nitrogen Emissions, Gary A. Bishop, Molly J. Haugen, Brian C. Mcdonald

Fuel Efficiency Automobile Test Publications

No abstract provided.

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

Fuel Efficiency Automobile Test Publications

No abstract provided.

Does California’S Emfac2017 Vehicle Emissions Model Under-Predict California Light-Duty Gasoline Vehicle Nox Emissions?, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

On-road remote sensing measurements of light and medium-duty gasoline vehicles collected within California’s South Coast Air Basin since 1999 generally fall within the range of observed summer ambient molar NO_x/CO measurements collected during morning rush hours. Compared with ambient and on-road emissions, the California Air Resources Board EMFAC model under predicts 2018 gasoline vehicle NO_x emission factors by more than a factor of 2.6. Contributing to these differences is that vehicles older than model year 2006 have NO_x emission deterioration rates that are up to 4 time’s higher on-road than predicted by the EMFAC model. A …

Atmospheric Measurements With Unmanned Aerial Systems (Uas), Marcelo I. Guzman

Chemistry Faculty Publications

This Special Issue provides the first literature collection focused on the development and implementation of unmanned aircraft systems (UAS) and their integration with sensors for atmospheric measurements on Earth. The research covered in the Special Issue combines chemical, physical, and meteorological measurements performed in field campaigns as well as conceptual and laboratory work. Useful examples for the development of platforms and autonomous systems for environmental studies are provided, which demonstrate how careful the operation of sensors aboard UAS must be to gather information for remote sensing in the atmosphere. The work serves as a key collection of articles to introduce …

Iron Speciation In Pm2.5 From Urban, Agriculture, And Mixed Environments In Colorado, Usa, Joseph R. Salazar, David J. Pfotenhauer, Frank Leresche, Fernando L. Rosario-Ortiz, Michael P. Hannigan, Sirine C. Fakra, Brian Majestic

Chemistry and Biochemistry: Faculty Scholarship

Atmospheric iron solubility varies depending on whether the particles are collected in rural or urban areas, with urban areas showing increased iron solubility. In this study, we investigate if the iron species present in different environments affects its ultimate solubility. Field data are presented from the Platte River Air Pollution and Photochemistry Experiment (PRAPPE), aimed at understanding the interactions between organic carbon and trace elements in atmospheric particulate matter (PM). 24-hr PM2.5 samples were collected during the summer and winter (2016–2017), at three different sites on the Eastern Colorado plains: an urban, agricultural, and a mixed site. Downtown Denver had …

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.

On-Road Remote Sensing Of Automobile Emissions In The Tulsa Area: Fall 2019, 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 …

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, …

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 …

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

Fuel Efficiency Automobile Test Publications

No abstract provided.

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

Fuel Efficiency Automobile Test Publications

No abstract provided.

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) …

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 …

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 …

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 …

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.