Caroline C Womack

University of Colorado Boulder | CUB · Cooperative Institute for Research in Environmental Sciences (CIRES)

We report aircraft observations of extreme levels of HCl and the dihalogens Cl2, Br2, and BrCl in an industrial plume near the Great Salt Lake, Utah. Complete depletion of O3 was observed concurrently with halogen enhancements as a direct result of photochemically produced halogen radicals. Observed fluxes for Cl2, HCl, and NOx agreed with facility...

We describe the design and performance of a lightweight broadband cavity-enhanced spectrometer for measurement of NO2 on uncrewed aerial vehicles and light aircraft. The instrument uses a light-emitting diode (LED) centered at 457 nm, high-finesse mirrors (reflectivity =0.999963 at 450 nm), and a grating spectrometer to determine optical extinction...

We present a comparison of fast-response instruments installed onboard the NASA DC-8 aircraft that measured nitrogen oxides (NO and NO2), nitrous acid (HONO), total reactive odd nitrogen (measured both as the total (NOy) and from the sum of individually measured species (ΣNOy)), and carbon monoxide (CO) in the troposphere during the 2019 Fire Influ...

We describe the design and performance of a lightweight broadband cavity-enhanced spectrometer for measurement of NO2 on uncrewed aerial vehicles and light aircraft. The instrument uses an LED centered at 457 nm, high-finesse mirrors (reflectivity=0.999963 at 450 nm), and a grating spectrometer to determine optical extinction coefficients between 4...

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties,...

Biomass burning is a major source of light‐absorbing organic aerosol (brown carbon), but its composition, chemical evolution, and lifetime are not well known. We measured water‐soluble brown carbon absorption from 310 to 500 nm on the National Oceanic and Atmospheric Administration Twin Otter aircraft during flights downwind of western United State...

We present a comparison of fast-response instruments installed onboard the NASA DC-8 aircraft that measured nitrogen oxides (NO and NO2), nitrous acid (HONO), total reactive odd nitrogen (measured both as the total (NOy) and from the sum of individually measured species (SNOy)) and carbon monoxide (CO) in the troposphere during the 2019 Fire Influe...

Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical production and loss as a fire plume ages, and it can be an important oxidant precursor. In this study, we disentangle the processes controlling HCHO by examining its evolution in wildfire plumes sampled by the...

Wildfires are a substantial but poorly quantified source of tropospheric ozone (O₃). Here, to investigate the highly variable O₃ chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O₃ production can be predicted as a function of experimentally constrai...

We present a novel method, the Gaussian observational model for edge to center heterogeneity (GOMECH), to quantify the horizontal chemical structure of plumes. GOMECH fits observations of short-lived emissions or products against a long-lived tracer (e.g., CO) to provide relative metrics for the plume width (wi/wCO) and center (bi/wCO). To validate...

Wildfires are increasing in size across the western US, leading to increases in human smoke exposure and associated negative health impacts. The impact of biomass burning (BB) smoke, including wildfires, on regional air quality depends on emissions, transport, and chemistry, including oxidation of emitted BB volatile organic compounds (BBVOCs) by t...

Wintertime episodes of high aerosol concentrations occur frequently in urban and agricultural basins and valleys worldwide. These episodes often arise following development of persistent cold-air pools (PCAPs) that limit mixing and modify chemistry. While field campaigns targeting either basin meteorology or wintertime pollution chemistry have been...

Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical production and loss as a fire plume ages, and it can be an important oxidant precursor. In this study, we disentangle the processes controlling HCHO by examining its evolution in wildfire plumes sampled by the...

Biomass burning aerosol is a major source of PM2.5, and significantly affects Earth's radiative budget. The magnitude of its radiative effect is poorly quantified due to uncertainty in the optical properties of aerosol formed from biomass burning. Using a broadband cavity-enhanced spectrometer with a recently increased spectral range (360–720 nm) c...

Wildfires are increasing in size across the western U.S., leading to increases in human smoke exposure and associated negative health impacts. The impact of biomass burning (BB) smoke, including wildfires, on regional air quality depends on emissions, transport, and chemistry, including oxidation of emitted BB volatile organic compounds (BBVOCs) by...

Biomass burning aerosol is a major source of PM2.5, and significantly affects Earth's radiative budget. The magnitude of its radiative effect is poorly quantified due to uncertainty in the optical properties of aerosol formed from biomass burning. Using a broadband cavity enhanced spectrometer with a recently increased spectral range (360–720 nm) c...

Atmospheric HONO mixing ratios in indoor and outdoor environments span a range of less than a few parts per trillion by volume (pptv) up to tens of parts per billion by volume (ppbv) in combustion plumes. Previous HONO calibration sources have utilized proton transfer acid displacement from nitrite salts or solutions, with output that ranges from t...

Atmospheric HONO mixing ratios in indoor and outdoor environments span a range of less than a few parts per trillion by volume (pptv) up to tens of parts per billion by volume (ppbv) in combustion plumes. Previous HONO calibration sources have utilized proton transfer acid displacement from nitrite salts or solutions, with output that ranges from t...

Ammonium-containing aerosols are a major component of wintertime air pollution in many densely populated regions around the world. Especially in mountain basins, the formation of persistent cold-air pools (PCAPs) can enhance particulate matter with diameters less than 2.5 µm (PM2.5) to levels above air quality standards. Under these conditions, PM2...

Mountain basins in Northern Utah, including the Salt Lake Valley (SLV), suffer from wintertime air pollution events associated with stagnant atmospheric conditions. During these events, fine particulate matter concentrations (PM2.5) can exceed national ambient air quality standards. Previous studies in the SLV have found that PM2.5 is primarily com...

Ammonium-containing aerosols are a major component of winter time air pollution in many densely populated regions around the world. Especially in mountain basins, the formation of persistent cold air pool (PCAP) periods can enhance particulate matter with diameters less than 2.5 μm (PM2.5) to levels above air quality standards. Under these conditio...

Plain Language Summary Particulate matter (PM) is dangerous to human health and impacts visibility and climate. In the United States, Europe, and Asia, PM is severe in urban areas in the winter when ammonium nitrate, NH4NO3, comprises an appreciable fraction of the total PM mass. A key control strategy is to reduce emissions of the limiting reagent...

Biomass combustion produces black carbon (BC) and brown carbon (BrC) aerosols that contribute substantially to warming the Earth’s atmosphere. Accurate knowledge of their emissions and absorption per unit mass (mass absorption cross-section; MAC) can be used to quantify the radiative impact of these combustion products. We isolated particles genera...

Mountain basins in Northern Utah, including Salt Lake Valley (SLV), suffer from wintertime air pollution events associated with stagnant atmospheric conditions. During these events, fine particulate matter concentrations (PM2.5) can exceed national ambient air quality standards. Previous studies in SLV have found PM2.5 is primarily composed of ammo...

Airborne and ground-based measurements of aerosol concentrations, chemical composition, and gas-phase precursors were obtained in three valleys in northern Utah (USA). The measurements were part of the Utah Winter Fine Particulate Study (UWFPS) that took place in January–February 2017. Total aerosol mass concentrations of PM1 were measured from a T...

Airborne and ground-based measurements of aerosol concentrations, chemical composition and gas phase precursors were obtained in three valleys in northern Utah (U.S.A.). The measurements were part of the Utah Winter Fine Particulate Study (UWFPS) that took place in January–February, 2017. Total aerosol mass concentrations of PM1 were measured from...

Particle morphology is an important parameter affecting aerosol optical properties that are relevant to climate and air quality, yet it is poorly constrained due to sparse in situ measurements. Biomass burning is a large source of aerosol that generates particles with different morphologies. Quantifying the optical contributions of non-spherical ae...

Particle morphology is an important parameter affecting aerosol optical properties that are relevant to climate and air quality, yet it is poorly constrained due to sparse in situ measurements. Biomass burning is a large source of aerosol that generates particles with different morphologies. Quantifying the optical contributions of non-spherical ae...

Owing to questions which still persist regarding the length of the O--H and central O--O bond, and large-amplitude torsional motion of \textit{trans} hydridotrioxygen HOOO, a weakly-bound complex between OH and O$_2$, new $^{18}$O isotopic measurements of HOOO and DOOO have been undertaken using Fourier transform microwave and microwave-millimeter-...

The sum of all reactive nitrogen species (NOy) includes NOx (NO2 + NO) and all of its oxidized forms, and the accurate detection of NOy is critical to understanding atmospheric nitrogen chemistry. Thermal dissociation (TD) inlets, which convert NOy to NO2 followed by NO2 detection, are frequently used in conjunction with techniques such as laser-in...

The sum of all reactive nitrogen species (NOy) includes NOx (NO2 + NO) and all of its oxidized forms, and the accurate detection of NOy is critical to understanding atmospheric nitrogen chemistry. Thermal dissociation (TD) inlets, which convert NOy to NO2 followed by NO2 detection, are frequently used in conjunction with techniques such as laser in...

Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been characterized by molecular beam mass spectrometry (MBMS), laser-induced fluorescence (LIF), microwave spectroscopy, a...

Millimeter-wave detected, millimeter-wave optical double resonance (mmODR) spectroscopy is a powerful tool for the analysis of dense, complicated regions in the optical spectra of small molecules. The availability of cavity-free microwave and millimeter wave spectrometers with frequency-agile generation and detection of radiation (required for chir...

Ozonolysis is one of the dominant oxidation pathways for tropospheric alkenes. Although numerous studies have confirmed a 1,3-cycloaddition mechanism that generates a Criegee intermediate (CI) with form R[subscript 1]R[subscript 2]COO, no small CIs have ever been directly observed in the ozonolysis of alkenes because of their high reactivity. We pr...

We investigate the photolytic production of two radical intermediates in the reaction of OH with propene, one from addition of the hydroxyl radical to the terminal carbon and the other from addition to the center carbon. In a collision-free environment, we photodissociate a mixture of 1-bromo-2-propanol and 2-bromo-1-propanol at 193 nm to produce t...

Carbenes are reactive molecules of the form R1C̈R2 that play a role in topics ranging from organic synthesis to gas-phase oxidation chemistry. We report the first experimental structure determination of dihydroxycarbene (HOC̈OH), one of the smallest stable singlet carbenes, using a combination of microwave rotational spectroscopy and high-level cou...

Carbenes are reactive molecules of the form R1C̈R2 that play a role in topics ranging from organic synthesis to gas-phase oxidation chemistry. We report the first experimental structure determination of dihydroxycarbene (HOC̈OH), one of the smallest stable singlet carbenes, using a combination of microwave rotational spectroscopy and high-level cou...

A number of research groups have recently succeeded in producing the simple carbonyl oxides H2COO and CH3CHOO in sufficient quantity to observe them spectroscopically and to probe the kinetics of their reactions with NO2 and SO2. These latter studies provide evidence that the carbonyl oxides play an important role in the atmosphere, likely contribu...

This paper explores the dynamics of a highly rotationally and vibrationally excited radical, CD2CD2OH. The radical is produced from the 193 nm photodissociation of 2-bromoethanol-d4, so it is imparted with high angular momentum and high vibrational energy and subsequently dissociates to several product channels. This paper focuses on characterizing...

We present the results of our product branching studies of the OH + C2D4 reaction, beginning at the CD2CD2OH radical intermediate of the reaction, which is generated by the photodissociation of the precursor molecule BrCD2CD2OH at 193 nm. Using a crossed laser-molecular beam scattering apparatus with tunable photoionization detection, and a velocit...

This work characterizes the internal energy distribution of the CD(2)CD(2)OH radical formed via photodissociation of 2-bromoethanol-d(4). The CD(2)CD(2)OH radical is the first radical adduct in the addition of the hydroxyl radical to C(2)D(4) and the product branching of the OH + C(2)D(4) reaction is dependent on the total internal energy of this a...

We use a combination of crossed laser-molecular beam scattering experiments and velocity map imaging experiments to investigate the dissociative ionization of the CH3C(O)CH2 radical to C2H5+. We form the radical from C–Cl bond fission in the photodissociation of chloroacetone at 193 nm. Upon 10.5 eV VUV photoionization, the radical is not detected...

The dissociation dynamics of methoxysulfinyl radicals generated from the photodissociation of CH(3)OS(O)Cl at 248 nm is investigated using both a crossed laser-molecular beam scattering apparatus and a velocity map imaging apparatus. There is evidence of only a single photodissociation channel of the precursor: S-Cl fission to produce Cl atoms and...

This work uses the photodissociation of acetyl chloride to assess the utility of a recently proposed impulsive model when the dissociation occurs on an excited electronic state that is not repulsive in the Franck-Condon region. The impulsive model explicitly includes an average over the vibrational quantum states of acetyl chloride when it calculat...

This study photolytically generates, from 2-bromoethanol photodissociation, the 2-hydroxyethyl radical intermediate of the OH + ethene reaction and measures the velocity distribution of the stable radicals. We introduce an impulsive model to characterize the partitioning of internal energy in the C(2)H(4)OH fragment. It accounts for zero-point and...