Environmental Chemistry Commons^™

High Altitude Ballooning As A Platform For Measuring Ozone Uptake Over Agricultural Landscapes, Thomas Sykora, Mark Potosnak

DePaul Discoveries

Measuring plant health is a key aspect in maximizing crop outputs. One often overlooked risk to crop fields is damage caused by stomatal ozone uptake; measuring this uptake is an important tool in understanding crop losses. Traditional methods for measuring plant ozone uptake are prohibitively expensive and rely on equipment that cannot easily be moved. Here, we propose high-altitude weather ballooning as a cost-effective alternative for measuring ozone uptake on a regional (~10 km) spatial scale. Ozonesounde data was obtained with weather balloons launched from the National Oceanic and Atmospheric Administration research station in Boulder, Colorado. This data was then …

Fifteen Years Of Hfc-134a Satellite Observations: Comparisons With Slimcat Calculations, Jeremy J. Harrison, Martyn P. Chipperfield, Christopher D. Boone, Sandip S. Dhomse, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

The phase out of anthropogenic ozone-depleting substances such as chlorofluorocarbons under the terms of the Montreal Protocol led to the development and worldwide use of hydrofluorocarbons (HFCs) in refrigeration, air conditioning, and as blowing agents and propellants. Consequently, over recent years, the atmospheric abundances of HFCs have dramatically increased. HFCs are powerful greenhouse gases and are now controlled under the terms of the 2016 Kigali Amendment to the Montreal Protocol. HFC-134a is currently the most abundant HFC in the atmosphere, breaking the 100 ppt barrier in 2018, and can be measured in the Earth's atmosphere by the satellite remote-sensing instrument …

Recent Trends In Stratospheric Chlorine From Very Short‐Lived Substances, Ryan Hossaini, Elliot Atlas, Sandip S. Dhomse, Martyn P. Chipperfield, Peter F. Bernath, Anton M. Fernando, Jens Mühle, Amber A. Leeson, Stephen A. Montzka, Wuhu Feng

Chemistry & Biochemistry Faculty Publications

Very short‐lived substances (VSLS), including dichloromethane (CH₂Cl₂), chloroform (CHCl₃), perchloroethylene (C₂Cl₄), and 1,2‐dichloroethane (C₂H₄Cl₂), are a stratospheric chlorine source and therefore contribute to ozone depletion. We quantify stratospheric chlorine trends from these VSLS (VSLCl_tot) using a chemical transport model and atmospheric measurements, including novel high‐altitude aircraft data from the NASA VIRGAS (2015) and POSIDON (2016) missions. We estimate VSLCl_tot increased from 69 (±14) parts per trillion (ppt) Cl in 2000 to 111 (±22) ppt Cl in 2017, with >80% delivered to …

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 …

An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman

Chemistry Faculty Publications

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric transport. …

Surface Oxygenation Of Biochar Through Ozonization For Dramatically Enhancing Cation Exchange Capacity, Matthew D. Huff, Sarah Marshall, Haitham A. Saeed, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

Background

Biochar cation exchange capacity (CEC) is a key property that is central to biochar environmental applications including the retention of soil nutrients in soil amendment and removal of certain pollutants in water-filtration applications.

Results

This study reports an innovative biochar-ozonization process that dramatically increases the CEC value of biochars by a factor of 2. The ozonized biochars also show great improvement on adsorption of methylene blue by as much as a factor of about 5. In this study, biochar samples treated with and without ozone were analyzed by means of pH and CEC assays, water field capacity measurement, elemental …

The Clean Air Act And Its Impact On Ground Level Ozone Pollution Levels In Los Angeles, California, Rebecca G. Ford

Honors Theses

Ozone (O₃) occurs naturally as a protective, ultraviolet radiation-shielding “Ozone Layer” in the Stratosphere and as a photochemically produced pollutant in the Troposphere. The Clean Air Act (CAA) of 1970 regulates the emission and concentration of O₃ and five other atmospheric pollutants. Since the signing of the CAA, the ongoing question has been whether or not the National Ambient Air Quality Standards (NAAQS) and regulatory policies have had an effect on decreasing O₃ concentration. The Los Angeles metropolitan area is a prime example of how O₃ can be a public health hazard, and taint a …

Mechanisms Of Heterogeneous Oxidations At Model Aerosol Interfaces By Ozone And Hydroxyl Radicals, Elizabeth A. Pillar-Little

Theses and Dissertations--Chemistry

Atmospheric aerosols play an important role in climate by scattering and absorbing radiation and by serving as cloud condensation nuclei. An aerosol’s optical or nucleation properties are driven by its chemical composition. Chemical aging of aerosols by atmospheric oxidants, such as ozone, alters the physiochemical properties of aerosol to become more hygroscopic, light absorbing, and viscous during transport. However the mechanism of these transformations is poorly understood. While ozone is a protective and beneficial atmospheric gas in the stratosphere, it is a potent greenhouse gas in the troposphere that traps heat near the Earth’s surface. It also impacts human heath …

Heterogeneous Oxidation Of Catechol, Elizabeth A. Pillar, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air–solid interface under variable relative humidity (RH = 0–90%). The maximum reactive uptake coefficient of O₃(g) by catechol γ_O3 = (7.49 ± 0.35) × 10^–6 occurs for …

Catechol Oxidation By Ozone And Hydroxyl Radicals At The Air-Water Interface, Elizabeth A. Pillar, Robert C. Camm, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air–water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon …

Modeling Dynamics Of Ozone And Nitrogen Oxides At Summit, Greenland With A 1-D Process-Scale Model, Keenan Anton Murray

Dissertations, Master's Theses and Master's Reports - Open

This work presents a 1-D process scale model used to investigate the chemical dynamics and temporal variability of nitrogen oxides (NO_x) and ozone (O₃) within and above snowpack at Summit, Greenland for March-May 2009 and estimates surface exchange of NO_x between the snowpack and surface layer in April-May 2009. The model assumes the surface of snowflakes have a Liquid Like Layer (LLL) where aqueous chemistry occurs and interacts with the interstitial air of the snowpack. Model parameters and initialization are physically and chemically representative of snowpack at Summit, Greenland and model results are compared to …

Conversion Of Iodide To Hypoiodous Acid And Iodine In Aqueous Microdroplets Exposed To Ozone, Elizabeth A. Pillar, Marcelo I. Guzman, Jose M. Rodriguez

Chemistry Faculty Publications

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O₃) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O₃ and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O₃ at variable iodide (I^–) concentration (0.010–100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates …

Investigation Of Ozone In Urban And Rural Areas Of California, Mia J. Hiles, David Parrish

STAR Program Research Presentations

Ozone is the air pollutant about which we have probably heard the most. Two types of ozone exist: stratospheric and tropospheric. Stratospheric ozone absorbs most of the damaging ultra-violet sunlight and tropospheric ozone comes into direct contact with life-forms and is toxic at high levels. Ozone concentration in California has been studied for over five decades, and there is a long history of control efforts. During 2010, California Air Resources Board (CARB) and National Oceanic and Atmospheric Administration (NOAA) conducted a major climate and air quality study in California called CalNex 2010 (California Research at the Nexus of Air Quality …

Analysis Of Iasi Tropospheric O₃ Data Over The Arctic During Polarcat Campaigns In 2008, M. Pommier, C. Clerbaux, K. S. Law, G. Ancellet, P. Bernath, P.-F. Coheur, J. Hadji-Lazaro, D. Hurtmans, P. Nédélec, J.-D. Paris, F. Ravetta, T. B. Ryerson, H. Schlager, A. J. Weinheimer

Chemistry & Biochemistry Faculty Publications

Ozone data retrieved in the Arctic region from infrared radiance spectra recorded by the Infrared Atmospheric Sounding Interferometer (IASI) on board the MetOp-A European satellite are presented. They are compared with in situ and lidar observations obtained during a series of aircraft measurement campaigns as part of the International Polar Year POLARCAT activities in spring and summer 2008. Different air masses were sampled during the campaigns including clean air, polluted plumes originating from anthropogenic sources, forest fire plumes from the three northern continents, and stratospheric-influenced air masses. The comparison between IASI O₃ [0–8 km], [0–12 km] partial columns and …

Gas-Phase Products And Secondary Aerosol Yields From The Ozonolysis Of Ten Different Terpenes, Anita Lee, Allen H. Goldstein, Melita D. Keywood, Song Gao, Varuntida Varutbangkul, Roya Bahreini, Nga L. Ng, Richard C. Flagan, John H. Seinfeld

Chemistry and Physics Faculty Articles

The ozonolyses of six monoterpenes (α-pinene, β-pinene, 3-carene, terpinolene, α-terpinene, and myrcene), two sesquiterpenes (α-humulene and β-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). …

Maine Acid Rain Study : Reports, Maine Department Of Environmental Protection

Maine Collection

Maine Acid Rain Study : Reports

Maine Department of Environmental Protection, Augusta, Maine (February, 1987).

Contents: Acid Rain Precursor Inventory and Evaluation / Modeled Sulfur Deposition in Maine / High Elevation Lake Monitoring in Maine

Transport Of Ozone Across An Air/Water Interface Coupled With Aqueous Decomposition, Ahmad Ali Mehrabzadeh

Dissertations and Theses

Photoacoustic spectroscopy was used to analyze the transport of ozone through the air/water interface. Experimental results showed that the ozone transport rate is similar to rates measured for other gases of low solubility and low reactivity. The transport rate increases with increasing pH. The decomposition rate of ozone was studied in solutions. The decomposition rate also depends on the pH of the solution, and in high pHs both the deposition velocity and the decomposition rate constant of ozone have larger values. The value of the deposition velocity (Kd) is 3.7 ± .9 x 10^-3 cm/sec and the decomposition rate …