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Articles 1 - 8 of 8
Full-Text Articles in Analytical Chemistry
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
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. …
Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman
Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman
Chemistry Faculty Publications
Aerosols of variable composition, size, and shape are associated with public health concerns as well as with light-particle interactions that play a role in the energy balance of the atmosphere. Photochemical reactions of 2-oxocarboxylic acids in the aqueous phase are now known to contribute to the total secondary organic aerosol (SOA) budget. This work explores the cross reaction of glyoxylic acid (GA) and pyruvic acid (PA) in water, the two most abundant 2-oxocarboxylic acids in the atmosphere, under solar irradiation and dark thermal aging steps. During irradiation, PA and GA are excited and initiate proton-coupled electron transfer or hydrogen abstraction …
Unmanned Aerial Systems For Monitoring Trace Tropospheric Gases, Travis J. Schuyler, Marcelo I. Guzman
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 …
Oxidation Of Substituted Catechols At The Air-Water Interface: Production Of Carboxylic Acids, Quinones, And Polyphenols, Elizabeth A. Pillar, Marcelo I. Guzman
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 …
Aqueous Photochemistry Of Glyoxylic Acid, Alexis J. Eugene, Sha-Sha Xia, Marcelo I. Guzman
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 …
Heterogeneous Oxidation Of Catechol, Elizabeth A. Pillar, Ruixin Zhou, Marcelo I. Guzman
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 γO3 = (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
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 …
Concentration Effects And Ion Properties Controlling The Fractionation Of Halides During Aerosol Formation, Marcelo I. Guzman, Richa R. Athalye, Jose M. Rodriguez
Concentration Effects And Ion Properties Controlling The Fractionation Of Halides During Aerosol Formation, Marcelo I. Guzman, Richa R. Athalye, Jose M. Rodriguez
Chemistry Faculty Publications
During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of …