Environmental Chemistry Commons^™

The Aging And Impacts Of Atmospheric Soot: Closing The Gap Between Experiments And Models, Ogochukwu Yvonne Enekwizu

Dissertations

The main goal of this dissertation is to generate data and parameterizations to accurately represent soot aerosols in atmospheric models. Soot from incomplete combustion of fossil fuels and biomass burning is a major air pollutant and a significant contributor to climate warming. The environmental impacts of soot are strongly dependent on the particle morphology and mixing state, which evolve continuously during atmospheric transport via a process known as aging. To make predictions of soot impacts on the environment, most atmospheric models adopt simplifications of particle structure and mixing state, which lead to substantial uncertainties. Using an experimentally constrained modeling approach, …

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 …

Long Term Air Quality Analysis In Reference To Thermal Power Plants Using Satellite Data In Singrauli Region, India, H. K. Romana, Ramesh P. Singh, D. P. Shukla

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The exponentially growing population and related anthropogenic activities have led to modifications in local environment. The change in local environment, evolving pattern of land use, concentrations of greenhouse gases and aerosols alter the energy balance of our climate system. This alteration in climate is leading to pre-mature deaths worldwide. This study analyses the air quality of Singrauli region, Madhya Pradesh, India for the past 15 years. Otherwise known as Urjanchal “the energy capital” of India has been declared as critically polluted by CPCB. The study provides an updated list of thermal power plants in the study area and their emission …

Global Atmospheric Budget Of Acetone: Air-Sea Exchange And The Contribution To Hydroxyl Radicals, Siyuan Wang, Eric C. Apel, Rebecca H. Schwantes, Kelvin H. Bates, Daniel J. Jacob, Emily V. Fischer, Rebecca S. Hornbrook, Alan J. Hills, Louisa K. Emmons, Laura L. Pan, Shawn Honomichl, Simone Tilmes, Jean‐François Lamarque, Mingxi Yang, Christa A. Marandino, E. S. Saltzman, Warren J. De Bruyn, Sohiko Kameyama, Hiroshi Tanimoto, Yuko Omori, Samuel R. Hall, Kirk Ullmann, Thomas B. Ryerson, Chelsea R. Thompson, Jeff Peischl, Bruce C. Daube, Róisín Commane, Kathryn Mckain, Colm Sweeney, Alexander B. Thames, David O. Miller, William H. Brune, Glenn S. Diskin, Joshua P. Digangi, Steven C. Wofsy

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both …

Glyoxal’S Impact On Dry Ammonium Salts: Fast And Reversible Surface Aerosol Browning (Raw Data), David O. De Haan Phd, Lelia N. Hawkins Phd, Margaret A. Tolbert Phd, Jean-François Doussin

Chemistry and Biochemistry: Faculty Scholarship

Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in chamber experiments. Under dry conditions (RH < 5%), solid AS, AS/glycine, and methylammonium sulfate aerosol particles brown within minutes upon exposure to GX, while sodium sulfate particles do not. When GX concentrations decline, browning goes away, demonstrating that this dry browning process is reversible. Declines in aerosol albedo are found to be a function of [GX]2, and are consistent between AS and AS/glycine aerosol. Dry methylammonium sulfate aerosol browns 4´ more than dry AS aerosol, but deliquesced AS aerosol browns much less than dry AS aerosol. Optical measurements at 405, 450, and 530 nm provide an estimated Ångstrom absorbance coefficient of -16 ±4. This coefficient and the empirical relationship between GX and albedo are used to estimate an upper limit to global radiative forcing by brown carbon formed by 70 ppt GX reacting with AS (+7.6 ´10-5 W/m2). This quantity is < 1% of the total radiative forcing by secondary brown carbon, but occurs almost entirely in the ultraviolet range.

The zipped data files are in the following formats: Igor experiments (.pxp), Word documents (.docx), Excel spreadsheets (.xlsx), organized by experiment number. “Optical” files contain cavity attenuated phase shift (CAPS) extinction, scattering and albedo data; PILS/waveguide data (experiments 1,2, and 5 only); …

Glyoxal’S Impact On Dry Ammonium Salts: Fast And Reversible Surface Aerosol Browning, David O. De Haan Phd, Lelia N. Hawkins Phd, Kevin Jansen, Hannah G. Welsh, Raunak Pednekar, Alexia De Loera, Natalie G. Jimenez, Margaret A. Tolbert Phd, Mathieu Cazaunau Phd, Aline Gratien, Antonin Bergé, Edouard Pangui, Paola Formenti, Jean-François Doussin

Chemistry and Biochemistry: Faculty Scholarship

Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in chamber experiments. Under dry conditions (RH < 5%), solid AS, AS/glycine, and methylammonium sulfate aerosol particles brown within minutes upon exposure to GX, while sodium sulfate particles do not. When GX concentrations decline, browning goes away, demonstrating that this dry browning process is reversible. Declines in aerosol albedo are found to be a function of [GX]², and are consistent between AS and AS/glycine aerosol. Dry methylammonium sulfate aerosol browns 4´ more than dry AS aerosol, but deliquesced AS aerosol browns much less than dry AS aerosol. Optical measurements at 405, 450, and 530 nm provide an …

Challenges In Quantifying Air‐Water Carbon Dioxide Flux Using Estuarine Water Quality Data: Case Study For Chesapeake Bay, Maria Herrmann, Raymond G. Najjar, Fei Da, Jaclyn R. Friedman, Marjorie A. M. Friedrichs, Sreece Goldberger, Alana Menendez, Elizabeth H. Shadwick, Edward G. Stets, Pierre St-Laurent

Publications and Research

Estuaries play an uncertain but potentially important role in the global carbon cycle via CO₂ outgassing. The uncertainty mainly stems from the paucity of studies that document the full spatial and temporal variability of estuarine surface water partial pressure of carbon dioxide ( pCO₂). Here, we explore the potential of utilizing the abundance of pH data from historical water quality monitoring programs to fill the data void via a case study of the mainstem Chesapeake Bay (eastern United States). We calculate pCO₂ and the air-water CO₂ flux at monthly resolution from 1998 to …

Karena Mckinney: Mapping A Clearer Picture Of Air Pollution's Effects, Christina Nunez

Colby Magazine

"If we want to control air quality and address climate change, the solution won't involve fiddling with nature's emissions-it will be about cleaning up man-made ones." -Karena McKinney, associate professor of atmospheric chemistry

Synergistic Use Of Remote Sensing And Modeling For Estimating Net Primary Productivity In The Red Sea With Vgpm, Eppley-Vgpm, And Cbpm Models Intercomparison, Wenzhao Li, Surya Prakash Tiwari, Hesham El-Askary, Mohamed Ali Qurban, Vassilis Amiridis, K. P. Manikandan, Michael J. Garay, Olga V. Kalashnikova, Thomas C. Piechota, Daniele C. Struppa

Mathematics, Physics, and Computer Science Faculty Articles and Research

Primary productivity (PP) has been recently investigated using remote sensing-based models over quite limited geographical areas of the Red Sea. This work sheds light on how phytoplankton and primary production would react to the effects of global warming in the extreme environment of the Red Sea and, hence, illuminates how similar regions may behave in the context of climate variability. study focuses on using satellite observations to conduct an intercomparison of three net primary production (NPP) models--the vertically generalized production model (VGPM), the Eppley-VGPM, and the carbon-based production model (CbPM)--produced over the Red Sea domain for the 1998-2018 time period. …

Methanethiol, Dimethyl Sulfide And Acetone Over Biologically Productive Waters In The Southwest Pacific Ocean, Sarah J. Lawson, Cliff S. Law, Mike J. Harvey, Thomas G. Bell, Carolyn F. Walker, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Atmospheric methanethiol (MeSH_a), dimethyl sulfide (DMS_a) and acetone (acetone_a) were measured over biologically productive frontal waters in the remote southwest Pacific Ocean in summertime 2012 during the Surface Ocean Aerosol Production (SOAP) voyage. MeSH_a mixing ratios varied from below the detection limit (< 10 ppt) up to 65 ppt and were 3 %–36 % of parallel DMS_a mixing ratios. MeSH_a and DMS_a were correlated over the voyage (R²=0.3, slope = 0.07) with a stronger correlation over a coccolithophore-dominated phytoplankton bloom (R²=0.5, slope 0.13). The diurnal cycle for MeSH_a shows similar behaviour to DMS_a with mixing ratios …

Surface Reservoirs Dominate Dynamic Gas-Surface Partitioning Of Many Indoor Air Constituents, Chen Wang, Douglas B. Collins, Caleb Arata, Allen H. Goldstein, James M. Mattila, Delphine K. Farmer, Laura Ampollini, Peter F. Decarlo, Atila Novoselac, Marina E. Vance, William W. Nazaroff, Jonathan P.D. Abbatt

Faculty Journal Articles

Human health is affected by indoor air quality. One distinctive aspect of the indoor environment is its very large surface area that acts as a poorly characterized sink and source of gas-phase chemicals. In this work, air-surface interactions of 19 common indoor air contaminants with diverse properties and sources were monitored in a house using fast-response, on-line mass spectrometric and spectroscopic methods. Enhanced-ventilation experiments demonstrate that most of the contaminants reside in the surface reservoirs and not, as expected, in the gas phase. They participate in rapid air-surface partitioning that is much faster than air exchange. Phase distribution calculations are …

Air/Sea Transfer Of Highly Soluble Gases Over Coastal Waters, J. G. Porter, Warren J. De Bruyn, S. D. Miller, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The deposition of soluble trace gases to the sea surface is not well studied due to a lack of flux measurements over the ocean. Here we report simultaneous air/sea eddy covariance flux measurements of water vapor, sulfur dioxide (SO₂), and momentum from a coastal North Atlantic pier. Gas transfer velocities were on average about 20% lower for SO₂ than for H₂O. This difference is attributed to the difference in molecular diffusivity between the two molecules (D _{SO 2}/D _{H 2O} = 0.5), in reasonable agreement with bulk parameterizations in air/sea gas …

Volcanic Impact On Stratospheric Chlorine Chemistry And Perchlorate Formation: Evidence From Ice Cores, Joshua Andrew Kennedy

Electronic Theses and Dissertations

Perchlorate, suspected to be chemically formed in both the troposphere and stratosphere, has been recently measured in Arctic snow and ice cores. These comprise both discontinuous snow and ice cores from the Canadian Arctic and a continuous record of perchlorate was compiled from an analysis of Greenland ice cores. While the background perchlorate concentration typically is very low, a few spikes in concentration coinciding with deposition of volcanic sulfate were observed in the Greenland record, suggesting that perchlorate levels in the atmosphere may be impacted by volcanic eruptions. As of yet, no work has been done to investigate the connection …

Nrlmsis 2.0: A Whole-Atmosphere Empirical Model Of Temperature And Neutral Species Densities, J. T. Emmert, D. P. Drob, J. M. Picone, D. E. Siskind, M. Jones Jr., M. G. Mlynczak, Peter F. Bernath, X. Chu, E. Doornbos, B. Funke, L. P. Goncharenko, M. E. Hervig, M. J. Schwartz, P. E. Sheese, F. Vargas, B. P. Williams, T. Yuan

Chemistry & Biochemistry Faculty Publications

NRLMSIS® 2.0 is an empirical atmospheric model that extends from the ground to the exobase and describes the average observed behavior of temperature, eight species densities, and mass density via a parametric analytic formulation. The model inputs are location, day of year, time of day, solar activity, and geomagnetic activity. NRLMSIS 2.0 is a major, reformulated upgrade of the previous version, NRLMSISE-00. The model now couples thermospheric species densities to the entire column, via an effective mass profile that transitions each species from the fully mixed region below ~70 km altitude to the diffusively separated region above ~200 km. Other …

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 …