Chemistry Commons^™

High Resolution Spectra Of Carbon Monoxide, Propane And Ammonia For Atmospheric Remote Sensing, Christopher Andrew Beale

OES Theses and Dissertations

Spectroscopy is a critical tool for analyzing atmospheric data. Identification of atmospheric parameters such as temperature, pressure and the existence and concentrations of constituent gases via remote sensing techniques are only possible with spectroscopic data. These form the basis of model atmospheres which may be compared to observations to determine such parameters. To this end, this dissertation explores the spectroscopy of three molecules: ammonia, propane and carbon monoxide.

Infrared spectra have been recorded for ammonia in the region 2400-9000 cm^-1. These spectra were recorded at elevated temperatures (from 293-973 K) using a Fourier Transform Spectrometer (FTS). Comparison between …

Depletion Of Ozone And Reservoir Species Of Chlorine And Nitrogen Oxide In The Lower Antarctic Polar Vortex Measured From Aircraft, T. Jurkat, C. Voigt, S. Kaufmann, J.-U. Grooß, H. Ziereis, A. Dörnbrack, P. Hoor, H. Bozem, A. Engel, H. Bönisch, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N₂O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ∼40% …

Do Halogenated Natural Products Bioaccumulate In Narragansett Bay?, Christine Gardiner, Anna Robuck, Rainer Lohmann

Senior Honors Projects

In recent decades, a new family of chemical compounds has begun to garner research attention—halogenated natural products, or HNPs. These chemicals are produced by algae, bacteria, worms, and sponges, and many are structurally similar to harmful manmade compounds, such as polychlorinated diphenyls (PCBs), or brominated flame retardants (PBDEs), which are known to cause cancer, reproduction issues, endocrine disruption, and death. While HNPs are produced naturally, they are still considered pollutants because of their bioaccumulative behavior and apparent toxicity.

Currently, there is limited research on their presence and effects, with a few studies from Europe and the Pacific highlighting their importance …

The Role Of Sulfur Dioxide In Stratospheric Aerosol Formation Evaluated By Using In Situ Measurements In The Tropical Lower Stratosphere, A. W. Rollins, T. D. Thornberry, L. A. Watts, P. Yu, K. H. Rosenlof, M. Mills, E. Baumann, F. R. Giorgetta, T. V. Bui, M. Höpfner, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Stratospheric aerosols (SAs) are a variable component of the Earth's albedo that may be intentionally enhanced in the future to offset greenhouse gases (geoengineering). The role of tropospheric-sourced sulfur dioxide (SO₂) in maintaining background SAs has been debated for decades without in situ measurements of SO₂ at the tropical tropopause to inform this issue. Here we clarify the role of SO₂ in maintaining SAs by using new in situ SO₂ measurements to evaluate climate models and satellite retrievals. We then use the observed tropical tropopause SO₂ mixing ratios to estimate the global flux of …

Oxidation Of Substituted Catechols At The Air-Water Interface: Production Of Carboxylic Acids, Quinones, And Polyphenols, Elizabeth A. Pillar, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic activities contribute benzene, toluene, and anisole to the environment, which in the atmosphere are converted into the respective phenols, cresols, and methoxyphenols by fast gas-phase reaction with hydroxyl radicals (HO(•)). Further processing of the latter species by HO(•) decreases their vapor pressure as a second hydroxyl group is incorporated to accelerate their oxidative aging at interfaces and in aqueous particles. This work shows how catechol, pyrogallol, 3-methylcatechol, 4-methylcatechol, and 3-methoxycatechol (all proxies for oxygenated aromatics derived from benzene, toluene, and anisole) react at the air-water interface with increasing O3(g) during τc ≈ 1 μs contact time and contrasts their …

Reactivity Of Ketyl And Acetyl Radicals From Direct Solar Actinic Photolysis Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The variable composition of secondary organic aerosols (SOA) contributes to the large uncertainty for predicting radiative forcing. A better understanding of the reaction mechanisms leading to aerosol formation such as for the photochemical reaction of aqueous pyruvic acid (PA) at λ ≥ 305 nm can contribute to constrain these uncertainties. Herein, the photochemistry of aqueous PA (5-300 mM) continuously sparged with air is re-examined in the laboratory under comparable irradiance at 38° N at noon on a summer day. Several analytical methods are employed to monitor the time series of the reaction, including (1) the derivatization of carbonyl (C═O) functional …

Nitrate Radicals And Biogenic Volatile Organic Compounds: Oxidation, Mechanisms And Organic Aerosol, Nga Lee Ng, Steven S. Brown, Alexander T. Archibald, Elliot Atlas, Ronald C. Cohen, John N. Crowley, Douglas A. Day, Neil M. Donahue, Juliane L. Fry, Hendrik Fuchs, Robert J. Griffin, Marcelo I. Guzman, Hartmut Hermann, Alma Hodzic, Yoshiteru Iinuma, José L. Jimenez, Astrid Kiendler-Scharr, Ben H. Lee, Deborah J. Luecken, Jingqiu Mao, Robert Mclaren, Anke Mutzel, Hans D. Osthoff, Bin Ouyang, Benedicte Picquet-Varrault, Ulrich Platt, Havala O. T. Pye, Yinon Rudich, Rebecca H. Schwantes, Manabu Shiraiwa, Jochen Stutz, Joel A. Thornton, Andreas Tilgner, Brent J. Williams, Rahul A. Zaveri

Chemistry Faculty Publications

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO₃) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO₃-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number …

Ozone Depletion, A Big Threat To Climate Change: What Can Be Done?, Sumera Aziz Ali, Savera Aziz Ali, Nadir Suhail

Community Health Sciences

Ozone in the stratosphere is very important as it acts as a safeguard for the earth and protects life from harmful ultraviolet radiations coming from the sun. Depletion of stratospheric ozone, resulting from atmospheric pollution has led to increased ultraviolet radiation at the earth’s surface as well as spectral shifts to the more biologically damaging shorter wavelengths. A decrease in the concentration of stratospheric ozone enhances the solar ultraviolet (UV) radiation, which is harmful to the growth of the plant and various other metabolic processes of the organisms and might cause changes in pigment concentrations, nucleic acids, and proteins. Multiple …

Quantification Of Airborne Fungal Spores Comparing Molecular Tracers Via Ion Chromatography And Uv-Lif Methods, Marie Ila Gosselin

Electronic Theses and Dissertations

Fungal spores represent an understudied subcategory of bioaerosols that can impact human health as pathogenic and allergenic particles. Fungal spores also have been shown to act as effective ice nuclei and giant cloud condensation nuclei in some cases. This has implications on the hydrological cycle on local and regional scales by impacting the formation and evolution of clouds and precipitation. The quantification of fungal spores has been limited in the past due to methods that were costly and that suffered from poor time resolution. The most commonly applied methods for airborne fungal spore analysis have traditionally included microscopy and culturing, …

Investigating The Atmospheric Production Of Perchlorate: Inference From Polar Ice Cores, Thomas S. Cox

Electronic Theses and Dissertations

Perchlorate (ClO₄) in the environment is of concern, because of potential health risks to humans, among other reasons. Evidence suggests that the majority of environmental perchlorate is formed in the atmosphere (likely in the stratosphere), in chemical processes involving ozone and stratospheric chlorine. A lack of knowledge in regards to the processes has resulted in a limited understanding of the environmental conditions and variables that influence perchlorate production and consequently perchlorate prevalence and variability in the environment. In this study, perchlorate was measured, using an established ion chromatography-­‐electrospray ionization-­‐tandem mass spectrometry (IC-­‐ESI-­‐ MS/MS) technique, in over 1,600 snowpit …

Phytoplankton Plastid Proteomics: Cracking Open Diatoms To Understand Plastid Biochemistry Under Iron Limitation, Skyler J. Nunn, Phoebe Dreux Chappell, Kristofer Gomes, Anasthasia Bonderenko, Bethany D. Jenkins, Brook L. Nunn

OES Faculty Publications

Diatoms, such as Thalassiosira pseudonana, are important oceanic primary producers, as they sequester carbon dioxide (CO₂) out of the atmosphere, die, and precipitate to the ocean floor. In many areas of the world’s oceans, phytoplankton, such as diatoms, are limited in growth by the availability of iron (Fe). Fe is an essential nutrient for phytoplankton, as it is central in the electron transport chain component of photosynthesis. Through this study, we examined if Fe-limitation makes a significant difference in the proteins expressed within the chloroplast, the power source for diatoms. Here, we utilized a new plastid isolation technique specific …

New And Improved Infra-Red Absorption Cross Sections And Ace-Fts Retrievals Of Carbon Tetrachloride (Ccl4), Jeremy J. Harrison, Christopher D. Boone, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Carbon tetrachloride (CCl₄) is one of the species regulated by the Montreal Protocol on account of its ability to deplete stratospheric ozone. As such, the inconsistency between observations of its abundance and estimated sources and sinks is an important problem requiring urgent attention (Carpenter et al., 2014) [5]. Satellite remote-sensing has a role to play, particularly limb sounders which can provide vertical profiles into the stratosphere and therefore validate stratospheric loss rates in atmospheric models. This work is in two parts. The first describes new and improved high-resolution infra-red absorption cross sections of carbon tetrachloride/dry synthetic air over …

The Hitran2016 Molecular Spectroscopic Database, I. E. Gordon, L. S. Rothman, C. Hill, R. V. Kochanov, Y. Tan, P. F. Bernath, M. Birk, V. Boudon, A. Campargue, K. V. Chance

Chemistry & Biochemistry Faculty Publications

This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional …

Quantifying Carbonyl Sulfide And Other Sulfur-Containing Compounds Over The Santa Barbara Channel, Julia Black

Scripps Senior Theses

Carbonyl sulfide (OCS) is emitted to the atmosphere through the outgassing of ocean surface waters. OCS is also the primary source of sulfur-containing compounds in the stratosphere and contributes to the formation of the stratospheric sulfate layer, an essential controller of the radiative balance of the atmosphere. During the 2016 Student Airborne Research Program (SARP), 15 whole air samples were collected on the NASA DC-8 aircraft over the Santa Barbara Channel. Five additional surface samples were taken at various locations along the Santa Barbara Channel. The samples were analyzed using gas chromatography in the Rowland-Blake lab at UC Irvine, and …

Improved Characterization And Analysis Strategies For Uv-Lif Bioaerosol Instrumentation: Lab And Field Application, Nicole Justine Savage

Electronic Theses and Dissertations

Atmospheric particles of biological origin, also referred to as bioaerosols or primary biological aerosol particles (PBAP), are important to various human health and environmental systems. There has been a recent steep increase in the frequency of published studies utilizing commercial instrumentation based on ultraviolet laser/light-induced fluorescence (UV-LIF), such as the WIBS (wideband integrated bioaerosol sensor), for bioaerosol detection both outdoors and in the built environment. Significant work over several decades supported the development of these technologies, but efforts to systematically characterize the operation of new commercial sensors has remained lacking. Specifically, there are gaps in the understanding of how different …

Ua66 Ogden College Of Science & Engineering Newsletter, Wku Ogden College Of Science & Engineering

Ogden College of Science & Engineering Publications

Newsletter created by and about WKU Ogden College of Science & Engineering.

• Ogden College Hall Taking Shape on TIme & on Budget
• Alumni Focus: Dr. Talia McKinney Collins
• WKU Research Foundation Launches New Website
• French, Jackson. Stemshot Rocketry Competition
• Agriculture
• Architectural & Manufacturing Sciences
• Grants & Publications
• Dr. Noah Ashley Receives NIH Grant
• Biology - News & Notes
• WKU Chemistry Welcomes Dr. Lawrence Hill & Dr. David Wolfgang
• Gary Kwong Receives McNally Award
• Student Teams Compete in National Engineering Contests Over the Summer
• Geology Major Conducts Research in Ethiopia - Deborah Flynn
• Geography & Geology
• WKU Meterology Launches White Squirrel …

Version 1.3 Aim Sofie Measured Methane (Ch4): Validation And Seasonal Climatology, P. P. Rong, J. M. Russell Iii, B. T. Marshall, D. E. Siskind, M. E. Hervig, L. L. Gordley, P. F. Bernath, K. A. Walker

Chemistry & Biochemistry Faculty Publications

The V1.3 methane (CH₄) measured by the Aeronomy of Ice in the Mesosphere (AIM) Solar Occultation for Ice Experiment (SOFIE) instrument is validated in the vertical range of ~25–70 km. The random error for SOFIE CH₄ is ~0.1–1% up to ~50 km and degrades to ~9% at ∼ 70 km. The systematic error remains at ~4% throughout the stratosphere and lower mesosphere. Comparisons with CH₄ data taken by the SCISAT Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) and the Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) show an agreement within ~15% in the altitude range ~30–60 …

Studies Of Arctic Tropospheric Ozone Depletion Events Through Buoy-Borne Observations And Laboratory Studies, John W. Halfacre

Open Access Dissertations

The photochemically-induced destruction of ground-level Arctic ozone in the Arctic occurs at the onset of spring, in concert with polar sunrise. Solar radiation is believed to stimulate a series of reactions that cause the production and release of molecular halogens from frozen, salty surfaces, though this mechanism is not yet well understood. The subsequent photolysis of molecular halogens produces reactive halogen atoms that remove ozone from the atmosphere in these so-called “Ozone Depletion Events” (ODEs). Given that much of the Arctic region is sunlit, meteorologically stable, and covered by saline ice and snow, it is expected that ODEs could be …

The Use Of Stable Isotopes And Particulate Matter In The Investigation Of Local And Regional Atmospheric Chemistry, Tanya Lynn Katzman

Open Access Dissertations

The chemical composition of particulate matter (PM), a known contributor to air pollution, is highly variable, and elemental analysis reveals information about local and regional sources, as well as how air masses and climate influence PM compositions. Seasonal changes in climate, such as temperature, amount of daylight, or meteorological patterns influence source emissions (increased residential heating activities, decreased natural soil emissions) and the relative importance of certain chemical pathways in the atmosphere. Since the magnitude of these seasonal changes are highly dependent on location, each sampling site is unique and the chemical composition of PM provides valuable insight into local …

Multiple New-Particle Growth Pathways Observed At The Us Doe Southern Great Plains Field Site, Anna L. Hodshire, Michael J. Lawler, Jun Zhao, John Ortega, Coty Jen, Taina Yli-Juuti, Jared F. Brewer, Jack K. Kodros, Kelley C. Barsanti, Dave R. Hanson, Peter H. Mcmurry, James N. Smith, Jeffery R. Pierce

Civil and Environmental Engineering Faculty Publications and Presentations

New-particle formation (NPF) is a significant source of aerosol particles into the atmosphere. However, these particles are initially too small to have climatic importance and must grow, primarily through net uptake of low volatility species, from diameters ∼ 1 to 30–100 nm in order to potentially impact climate. There are currently uncertainties in the physical and chemical processes associated with the growth of these freshly formed particles that lead to uncertainties in aerosol-climate modeling. Four main pathways for new-particle growth have been identified: condensation of sulfuric-acid vapor (and associated bases when available), condensation of organic vapors, uptake of organic acids …

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Aqueous Photochemistry Of Glyoxylic Acid, Alexis J. Eugene, Sha-Sha Xia, Marcelo I. Guzman

Chemistry Faculty Publications

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. While the formation of secondary organic aerosols (SOA) from gas phase precursors is relatively well understood, studying aqueous chemical reactions contributing to the total SOA budget is the current focus of major attention. Field measurements have revealed that mono-, di-, and oxo-carboxylic acids are abundant species present in SOA and atmospheric waters. This work explores the fate of one of these 2-oxocarboxylic acids, glyoxylic acid, which can photogenerate reactive species under solar irradiation. Additionally, the dark thermal aging …

Carbon Nanotubes Affect The Toxicity Of Cuo Nanoparticles To Denitrification In Marine Sediments By Altering Cellular Internalization Of Nanoparticle, Xiong Zheng, Yinglong Su, Yinguang Chen, Rui Wan, Mu Li, Haining Huang, Xu Li

Department of Civil and Environmental Engineering: Faculty Publications

Denitrification is an important pathway for nitrate transformation in marine sediments, and this process has been observed to be negatively affected by engineered nanomaterials. However, previous studies only focused on the potential effect of a certain type of nanomaterial on microbial denitrification. Here we show that the toxicity of CuO nanoparticles (NPs) to denitrification in marine sediments is highly affected by the presence of carbon nanotubes (CNTs). It was found that the removal efficiency of total NO_X⁻-N (NO₃⁻-N and NO₂⁻-N) in the presence of CuO NPs was only 62.3%, but it …

The Marine Cyanate Cycle, Brittany Widner

OES Theses and Dissertations

Cyanate (OCN-) is a reduced nitrogen compound with the potential to serve as a nitrogen and carbon source for marine microbes. Evidence from genomes and culture studies indicated that several marine cyanobacterial groups, including representatives of the globally important genera Synechococcus and Prochlorococcus, might be capable of cyanate assimilation. However, prior to this study, the distribution, bioavailability, and production pathways of cyanate were unknown in natural systems due to the absence of a sensitive cyanate assay; and the ability of organisms to assimilate cyanate on relevant timescales was unknown because we lacked a suitable tracer for measuring uptake. I developed …

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Nitrous Oxide In The Atmosphere: First Measurements Of A Lower Thermospheric Source, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Peter F. Bernath, Bernd Funke

Chemistry & Biochemistry Faculty Publications

Nitrous oxide (N₂O) is an important anthropogenic greenhouse gas, as well as one of the most significant anthropogenic ozone-depleting substances in the stratosphere. The satellite-based instrument Atmospheric Chemistry Experiment-Fourier Transform Spectrometer has been observing the Earth's limb since 2004 and derives profiles of N₂O volume mixing ratios in the upper troposphere to the lower thermosphere. The resulting climatology shows that N₂O is continuously produced in the lower thermosphere via energetic particle precipitation and enhanced N₂O is present at all latitudes, during all seasons. The results are consistent with an N₂O …

Source Apportionment Of Atmospheric Particulate Matter In Developing Countries Using Trace Elements And Stable Metal Isotope Ratios, Nitika Dewan

Electronic Theses and Dissertations

The work presented herein details the source apportionment of atmospheric particulate matter in developing countries (Kyrgyzstan in Central Asia, metropolitan cities in Northern India, and Shenzhen in China) using trace elements and stable metal isotope ratios. The first study focused on the development of a novel method for the concomitant separation of rare-earth elements in environmental samples of any geological origin. The separation procedure is based on three extraction chromatographic materials, referred to as Sr.Spec, TRU.Spec, and Ln.Spec. This triple column arrangement enables the simultaneous isolation of pure Sr and Nd fractions in less than one day and with great …

Intercomparison And Evaluation Of Satellite Peroxyacetyl Nitrate Observations In The Upper Troposphere-Lower Stratosphere, Richard J. Pope, Nigel A. D. Richards, Martyn P. Chipperfield, David P. Moore, Sarah A. Monks, Stephen R. Arnold, Norbert Glatthor, Michael Kiefer, Tom J. Breider, Jeremy J. Harrison, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Peroxyacetyl nitrate (PAN) is an important chemical species in the troposphere as it aids the long-range transport of NO_x and subsequent formation of O₃ in relatively clean remote regions. Over the past few decades observations from aircraft campaigns and surface sites have been used to better understand the regional distribution of PAN. However, recent measurements made by satellites allow for a global assessment of PAN in the upper troposphere-lower stratosphere (UTLS). In this study, we investigate global PAN distributions from two independent retrieval methodologies, based on measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, on …

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …