Atmospheric Sciences Commons^™

Production Of Singlet Oxygen (1O2) During The Photochemistry Of Aqueous Pyruvic Acid: The Effects Of Ph And Photon Flux Under Steady-State O2(Aq) Concentration, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The photochemistry of pyruvic acid (PA) in aqueous atmospheric particles contributes to the production of secondary organic aerosols. This work investigates the fate of ketyl and acetyl radicals produced during the photolysis (λ ≥ 305 nm) of 5-100 mM PA under steady state [O₂(aq)] = 260 μM (1.0 ≤ pH ≤ 4.5) for photon fluxes between 1 and 10 suns. The radicals diffuse quickly into the water/air interface of microbubbles and react with dissolved O₂ to produce singlet oxygen (¹O₂^*). Furfuryl alcohol is used to trap and bracket the steady-state production of …

Global Sinusoidal Seasonality In Precipitation Isotopes, Scott T. Allen, Scott Jasechko, Wouter R. Berghuijs, Jeffrey M. Welker, Gregory R. Goldsmith, James W. Kirchner

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Quantifying seasonal variations in precipitation δ²H and δ¹⁸O is important for many stable isotope applications, including inferring plant water sources and streamflow ages. Our objective is to develop a data product that concisely quantifies the seasonality of stable isotope ratios in precipitation. We fit sine curves defined by amplitude, phase, and offset parameters to quantify annual precipitation isotope cycles at 653 meteorological stations on all seven continents. At most of these stations, including in tropical and subtropical regions, sine curves can represent the seasonal cycles in precipitation isotopes. Additionally, the amplitude, phase, and offset parameters of …

Extensive Soot Compaction By Cloud Processing From Laboratory And Field Observations, Janarjan Bhandari, Swarup China, Kamal Kant Chandrakar, Greg Kinney, Will Cantrell, Raymond Shaw, Lynn Mazzoleni, Giulia Girotto, Noopur Sharma, Kyle Gorkowski, Stefania Gilardoni, Stefano Decesari, Maria Cristina Facchini, Nicola Zanca, Giulia Pavese, Francesco Esposito, Manvendra K Dubey, Allison C Aiken, Rajan K Chakrabarty, Hans Moosmüller, Timothy B Onasch, Rahul A Zaveri, Barbara V Scarnato, Paulo Fialho, Claudio Mazzoleni

Michigan Tech Publications, Part 1

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after …

Monitoring Tropospheric Gases With Small Unmanned Aerial Systems (Suas) During The Second Cloudmap Flight Campaign, Travis J. Schuyler, Sean C. C. Bailey, Marcelo I. Guzman

Chemistry Faculty Publications

Small unmanned aerial systems (sUAS) are a promising technology for atmospheric monitoring of trace atmospheric gases. While sUAS can be navigated to provide information with higher spatiotemporal resolution than tethered balloons, they can also bridge the gap between the regions of the atmospheric boundary layer (ABL) sampled by ground stations and manned aircraft. Additionally, sUAS can be effectively employed in the petroleum industry, e.g., to constrain leaking regions of hydrocarbons from long gasoducts. Herein, sUAS are demonstrated to be a valuable technology for studying the concentration of important trace tropospheric gases in the ABL. The successful detection and quantification of …

Intercomparison Of Small Unmanned Aircraft System (Suas) Measurements For Atmospheric Science During The Lapse-Rate Campaign, Lindsay Barbieri, Stephan T. Kral, Sean C. C. Bailey, Amy E. Frazier, Jamey D. Jacob, Joachim Reuder, David Brus, Phillip B. Chilson, Christopher Crick, Carrick Detweiler, Abhiram Doddi, Jack Elston, Hosein Foroutan, Javier González-Rocha, Brian R. Greene, Marcelo I. Guzman, Adam L. Houston, Ashraful Islam, Osku Kemppinen, Dale Lawrence, Elizabeth A. Pillar-Little, Shane D. Ross, Michael P. Sama, David G. Schmale Iii, Travis J. Schuyler, Ajay Shankar, Suzanne W. Smith, Sean Waugh, Cory Dixon, Steve Borenstein, Gijs De Boer

Chemistry Faculty Publications

Small unmanned aircraft systems (sUAS) are rapidly transforming atmospheric research. With the advancement of the development and application of these systems, improving knowledge of best practices for accurate measurement is critical for achieving scientific goals. We present results from an intercomparison of atmospheric measurement data from the Lower Atmospheric Process Studies at Elevation—a Remotely piloted Aircraft Team Experiment (LAPSE-RATE) field campaign. We evaluate a total of 38 individual sUAS with 23 unique sensor and platform configurations using a meteorological tower for reference measurements. We assess precision, bias, and time response of sUAS measurements of temperature, humidity, pressure, wind speed, and …

Using A Balloon-Launched Unmanned Glider To Validate Real-Time Wrf Modeling, Travis J. Schuyler, S. M. Iman Gohari, Gary Pundsack, Donald Berchoff, Marcelo I. Guzman

Chemistry Faculty Publications

The use of small unmanned aerial systems (sUAS) for meteorological measurements has expanded significantly in recent years. SUAS are efficient platforms for collecting data with high resolution in both space and time, providing opportunities for enhanced atmospheric sampling. Furthermore, advances in mesoscale weather research and forecasting (WRF) modeling and graphical processing unit (GPU) computing have enabled high resolution weather modeling. In this manuscript, a balloon-launched unmanned glider, complete with a suite of sensors to measure atmospheric temperature, pressure, and relative humidity, is deployed for validation of real-time weather models. This work demonstrates the usefulness of sUAS for validating and improving …

The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O₂(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O₂(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. …

Characterization Of Ambient Aerosols And Their Evolution Under Various Atmospheric Conditions In The Northeast U.S, Jie Zhang

Legacy Theses & Dissertations (2009 - 2024)

The University at Albany Atmospheric Sciences Research Center (ASRC) mobile laboratory, which includes a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), a Scanning Mobility Particle Sizer (SMPS), and several gas sensors, etc., has been used to characterize atmospheric aerosols and air quality at different locations in the Northeastern US (including urban, forest, and mountain areas) and the aerosol evolutions under a variety of atmospheric conditions (including extreme weather, fog, and cloud, etc.). In this dissertation, I present the findings of the several field measurements using the ASRC mobile lab, focusing on the influences of extreme events (including high O3, heatwave, …

Extreme Molecular Diversity In Biomass Burning Atmospheric Organic Aerosol Observed Through Ultrahigh Resolution Mass Spectrometry, Matthew Brege

Dissertations, Master's Theses and Master's Reports

Ambient atmospheric aerosol is ubiquitous in the atmosphere, originating from a variety of natural and man-made sources. These microscopic particles have profound impacts on the global climate system as well as human health. The organic fraction of atmospheric aerosol is an extremely complex mixture which is not yet fully characterized. These unknown organic aerosol species contribute to the uncertainty in the effect of aerosol on climate and uncertainty in overall ambient aerosol toxicity. Light absorbing organic aerosol can interact with incoming solar radiation and contribute to atmospheric heating; however, the source apportionment and overall fate of these absorbing organic aerosol …

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 …

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, …

Molecular Characterization Of Free Tropospheric Organic Aerosol And The Development Of Computational Tools For Molecular Formula Assignment, Simeon Schum

Dissertations, Master's Theses and Master's Reports

Organic aerosol affects human health and climate. These effects are largely determined by the composition of the organic aerosol, which is a complex mixture of species. Understanding the complexity of organic aerosol is critical to determining its effect on human health and climate. In this study, long range transported organic aerosol collected at the Pico Mountain Observatory was analyzed using ultrahigh resolution mass spectrometry. Organic aerosol transported in the free troposphere had an overall lower extent of oxidation than aerosol transported in the boundary layer. It was hypothesized that the lower oxidation was related to a more viscous phase state …

Eddy Flux Measurements Of Sulfur Dioxide Deposition To The Sea Surface, Jack G. Porter, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Deposition to the sea surface is a major atmospheric loss pathway for many important trace gases, such as sulfur dioxide (SO2). The air–sea transfer of SO2 is controlled entirely on the atmospheric side of the air–sea interface due to high effective solubility and other physical– chemical properties. There have been few direct field measurements of such fluxes due to the challenges associated with making fast-response measurements of highly soluble trace gases at very low ambient levels. In this study, we report direct eddy covariance air–sea flux measurements of SO2, sensible heat, water vapor, and momentum. The measurements were made over …

Molecular And Physical Characteristics Of Aerosol At A Remote Free Troposphere Site: Implications For Atmospheric Aging, Simeon Schum, Bo Zhang, Katja Džepina, Paolo Fialho, Claudio Mazzoleni, Lynn Mazzoleni

Department of Chemistry Publications

Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth's radiative balance. To understand the molecular and physical characteristics of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of …

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. …

Fourier Transform Spectroscopy Of The C³Δ-X³Δ Transition Of Tio In Support Of Exoplanet Spectroscopy, James N. Hodges, Peter Bernath

Chemistry & Biochemistry Faculty Publications

Recent limitations in the TiO line list used in cross-correlation detection schemes have made the detection and quantification of TiO in exoplanetary atmospheres challenging. The quality of the line list appears to degrade at wavelengths shorter than 630 nm. The C³Δ-X³Δ electronic transition has strong rovibronic bands near 500 nm. In an effort to improve the line list, a spectrum of TiO in a furnace at 1950 K is analyzed, and the assigned lines of the C³Δ-X³Δ transition are fit with the N² Hamiltonian in the molecular spectrum fitting software, _{PGOPHER …}

Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman

Chemistry Faculty Publications

Understanding the acid–base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants pK_{a …}

Predicting Spatial Patterns In Precipitation Isotope (Δ2h And Δ18o) Seasonality Using Sinusoidal Isoscapes, Scott T. Allen, James W. Kirchner, Gregory R. Goldsmith

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Understanding how precipitation isotopes vary spatially and temporally is important for tracer applications. We tested how well month‐to‐month variations in precipitation δ18O and δ2H were captured by sinusoidal cycles, and how well spatial variations in these seasonal cycles could be predicted, across Switzerland. Sine functions representing seasonal cycles in precipitation isotopes explained between 47% and 94% of the variance in monthly δ18O and δ2H values at each monitoring site. A significant sinusoidal cycle was also observed in line‐conditioned excess. We interpolated the amplitudes, phases, and offsets of these sine functions across the landscape, using multiple linear …

Ultrahigh Resolution Ft-Icr Ms Data For Biomass Burning Emissions-Influenced Fog And Aerosol From The Po Valley, Matthew Brege, Lynn Mazzoleni

Department of Chemistry Publications

This dataset and the methods used to obtain it were described in "Molecular insights on aging and aqueous phase processing from ambient biomass burning emissions-influenced Po Valley fog and aerosol” submitted to Atmospheric Chemistry and Physics in March of 2018. Briefly, two samples of ambient fog water and two samples of ambient aerosol collected in the Po Valley (Italy) during the 2013 Supersito field campaign were analyzed using negative mode electrospray ionization Fourier transform ion cyclotron mass spectrometry (FT-ICR MS). The extent of “fresh” vs. “aged” biomass burning influence was estimated prior to FT-ICR MS analysis using proton nuclear magnetic …

Ultrahigh Resolution Ft-Icr Ms Data Of Long-Range Transported Free Tropospheric Aerosol Collected At The Pico Mountain Observatory In The Azores, Simeon K. Schum, Lynn Mazzoleni

Department of Chemistry Publications

This dataset and the methods used to obtain it were described in “Molecular and physical characteristics of aerosol at a remote marine free troposphere site: Implications for atmospheric aging” submitted to Atmospheric Chemistry and Physics in February 2018. Briefly, three long-range transported organic aerosol samples were analyzed using negative mode electrospray ionization Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) with a mass resolving power of 400,000 (defined at m/z 400). FLEXPART retroplume simulations indicated that two of the samples (PMO-1 & PMO-3) were influenced by North American wildfire emissions transported in the free troposphere and one (PMO-2) by North …

Field Evaluation Of Portable Air Quality Monitors And Evaluation Of Short-Lived Plume Events Of Atmospheric Pollutants, Joseph Peter Marto

Legacy Theses & Dissertations (2009 - 2024)

Availability of low cost optical sensors has allowed for the supplementation of existing air quality infrastructure with portable, adaptive monitors. While these sensors generally cannot offer the same accuracy and precision as established analysis methods, they can still reliably detect changes in pollutant concentration. This study evaluates the performance of two portable air quality enclosures deployed at collocated research sites to determine their accuracy and usefulness in field deployments. One system deployed collocated sensors for measurement of particulate matter mass concentration (Thermo pDR 1500 and TSI DustTrak DRX for PM2.5) and the second system deployed sensors for measurement of black …

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.

Mls Measurements Of Stratospheric Hydrogen Cyanide During The 2015-2016 El Niño Event, Hugh C. Pumphrey, Norbert Glatthor, Peter F. Bernath, Christopher D. Boone, James W. Hannigan, Ivan Ortega, Nathaniel J. Livesey, William G. Read

Chemistry & Biochemistry Faculty Publications

It is known from ground-based measurements made during the 1982-1983 and 1997-1998 El Niño events that atmospheric hydrogen cyanide (HCN) tends to be higher during such years than at other times. The Microwave Limb Sounder (MLS) on the Aura satellite has been measuring HCN mixing ratios since launch in 2004; the measurements are ongoing at the time of writing. The winter of 2015- 2016 saw the largest El Niño event since 1997-1998. We present MLS measurements of HCN in the lower stratosphere for the Aura mission to date, comparing the 2015- 2016 El Niño period to the rest of the …

Stratospheric Ozone And Hcl Trends (2000-2016): How Significant Is Recent Growth In Chlorinated Very Short-Lived Substances, Ryan Hossaini, Martyn Chipperfield, Peter Bernath, Anton Fernando, Sandip Dhomse, Wuhu Feng

Chemistry & Biochemistry Faculty Publications

[Introduction] Chlorinated very short-lived substances (VSLS), such as dichloromethane (CH₂CL₂), chloroform (CHCl₃₎ and perchloroethylene (C₂Cl₄) constitute a small, but growing source of stratospheric chlorine (e.g. WMO, 2014). High-altitude aircraft observations provide some constraint on the stratospheric source gas injection of chlorine from these compounds, though product gas injection - from VSLS-derived phosgene and HCl produced in the troposphere - is uncertain. Furthermore, in addition to an overall paucity of atmospheric VSLS observations, the impact of VSLS growth on stratospheric composition trends in the recent past (e.g. ozone, HCl) remains poorly constrained.

Analysis Of The Red And Green Optical Absorption Spectrum Of Gas Phase Ammonia, Nikolai F. Zobov, Phillip A. Coles, Roman I. Ovsyannikov, Aleksandra A. Kyuberis, Robert J. Hargreaves, Peter F. Bernath, Jonathan Tennyson, Sergei N. Yurchenko, Oleg L. Polyansky

Chemistry & Biochemistry Faculty Publications

Room temperature NH₃ absorption spectra recorded at the Kitt Peak National Solar Observatory in 1980 are analyzed. The spectra cover two regions in the visible: 15,200 - 15,700 cm^-1 and 17,950 - 18,250 cm^-1. These high overtone rotation-vibration spectra are analyzed using both combination differences and variational line lists. Two variational line lists were computed using the TROVE nuclear motion program: one is based on an ab initio potential energy surface (PES) while the other used a semi-empirical PES. Ab initio dipole moment surfaces are used in both cases. 95 energy levels with J = 1 …

Wildfire Emissions In The Context Of Global Change And The Implications For Mercury Pollution, Aditya Kumar

Dissertations, Master's Theses and Master's Reports

Wildfires are episodic disturbances that exert a significant influence on the Earth system. They emit substantial amounts of atmospheric pollutants, which can impact atmospheric chemistry/composition and the Earth’s climate at the global and regional scales. This work presents a collection of studies aimed at better estimating wildfire emissions of atmospheric pollutants, quantifying their impacts on remote ecosystems and determining the implications of 2000s-2050s global environmental change (land use/land cover, climate) for wildfire emissions following the Intergovernmental Panel on Climate Change (IPCC) A1B socioeconomic scenario.

A global fire emissions model is developed to compile global wildfire emission inventories for major atmospheric …

No Evidence For Trace Metal Limitation On Anaerobic Carbon Mineralization In Three Peatland Soils, Jason K. Keller, Jillian Wade

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Peatlands store roughly one-third of the terrestrial soil carbon and release the potent greenhouse gas methane (CH₄) to the atmosphere, making these wetlands among the most important ecosystems in the global carbon cycle. Despite their importance, the controls of anaerobic decomposition of organic matter to carbon dioxide (CO₂) and CH₄ within peatlands are not well understood. It is known, however, that the enzymes responsible for CH₄ production require cobalt, iron and nickel, and there is a growing appreciation for the potential role of trace metal limitation in anaerobic decomposition. To explore the possibility of …

Unmanned Aerial Systems For Monitoring Trace Tropospheric Gases, Travis J. Schuyler, Marcelo I. Guzman

Chemistry Faculty Publications

The emission of greenhouse gases (GHGs) has changed the composition of the atmosphere during the Anthropocene. Accurately documenting the sources and magnitude of GHGs emission is an important undertaking for discriminating the contributions of different processes to radiative forcing. Currently there is no mobile platform that is able to quantify trace gases at altitudes(UASs) can be deployed on-site in minutes and can support the payloads necessary to quantify trace gases. Therefore, current efforts combine the use of UASs available on the civilian market with inexpensively designed analytical systems for monitoring atmospheric trace gases. In this context, this perspective introduces the …

A Near-Global Atmospheric Distribution Of N2o Isotopologues, Peter F. Bernath, Mahdi Yousefi, Eric Buzan, Chris D. Boone

Chemistry & Biochemistry Faculty Publications

The distributions of the four most abundant isotopologues and isotopomers (N₂O, ¹⁵NNO, N¹⁵NO, and NN¹⁸O of nitrous oxide have been measured in the Earth's stratosphere by infrared remote sensing with the Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer. These satellite observations have provided a near-global picture of N₂O isotopic fractionation. The relative abundances of the heavier species increase with altitude and with latitude in the stratosphere as the air becomes older. The heavy isotopologues are enriched by 20-30% in the upper stratosphere and even more over the poles. These observations are …

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 …