Papers by Callum E Flowerday
Enhanced Fluorescence in a Scattering Medium
Applied Spectroscopy, 2021
Often only small amounts of sample are available for spectroscopic analytical determinations. Thi... more Often only small amounts of sample are available for spectroscopic analytical determinations. This work investigates the enhancement of signal in columns packed with silica particles. We propose that silica particles cause the light to scatter through the column, effectively increasing optical path length. Packed columns are shown to be effective with fluorescence spectroscopy, but results were inconclusive with absorbance spectroscopy. Graphical Abstract
Research Square (Research Square), Mar 11, 2024
The Great Salt Lake (GSL) has undergone a reduction in size, from 1046.0 miles 2 on January 1, 20... more The Great Salt Lake (GSL) has undergone a reduction in size, from 1046.0 miles 2 on January 1, 2015, to 940.5 miles 2 on January 1, 2022, exposing 105.5 miles 2 of playa that was once covered. This emerging playa raises concerns regarding the toxicity of the ensuing dust. While considerable efforts have been made to understand aeolian dust in urban areas along the Wasatch Front, located just east of the GSL, there is still a need to consolidate existing research and conduct a compositional analysis of the dust found in these urban areas. In this study, we investigated the dust reaching urban monitoring sites around the GSL, managed by the Utah Division of Air Quality. By analyzing historical data dating back to 1988, we found no evidence to support the idea that the decrease in the GSL's surface area has led to an increase in dust events in urban areas. Backwind trajectories align with prior research, indicating that heightened dust levels in urban areas coincide with winds originating from the south or west, passing over identi ed playas and deserts such as the Milford ats, Sevier Dry Lake, Tule Dry Lake, Great Salt Lake Desert, Dugway Proving Grounds, and the West Desert of Utah. Conducting a compositional analysis of urban dust revealed no concentrations of metals that raise health concerns, with the highest health quotient being four orders of magnitude lower than a level of concern.
OH Radical Detection Using Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS) in an Open-Path Configuration
Twenty-Year Review of Outdoor Air Quality in Utah, USA
Atmosphere, Sep 26, 2023
Air quality is a prevalent concern due to its imposing health risks. The state of Utah, USA, at t... more Air quality is a prevalent concern due to its imposing health risks. The state of Utah, USA, at times over the last 20 years has suffered from some of the worst air quality in the nation. The propensity for the state of Utah to experience elevated concentrations of particulate matter and ozone can in part be attributed to its unique geography that features dry, mountainous topography. Valleys in Utah create ideal environments for extended cold-pool events. In this review, we summarize the research executed in Utah over the past 20 years (2002–2022) by dividing the state into six regions: Utah Valley, Summit County, Southern Utah (regions south of Utah Valley), Cache Valley, Uinta Basin, and Salt Lake Valley. We review the published literature chronologically and provide a summary of each region identifying areas where additional research is warranted. We found that the research effort is weighted towards Uinta Basin and Salt Lake Valley, with the other regions in Utah only adding up to 20% of the research effort. We identified a need for more source apportionment studies, speciated volatile organic compound (VOC) studies, and ozone isopleths. Where ozone isopleths are not able to be created, measurement of glyoxal and formaldehyde concentrations could serve as surrogates for more expensive studies to inform ozone mitigation policies.
Sensors, Sep 6, 2023
Air quality has important climate and health effects. There is a need, therefore, to monitor air ... more Air quality has important climate and health effects. There is a need, therefore, to monitor air quality both indoors and outdoors. Methods of measuring air quality should be cost-effective if they are to be used widely, and one such method is low-cost sensors (LCS). This study reports on the use of LCSs in Ulaanbataar, Mongolia to measure PM2.5 concentrations inside yurts or “gers”. Some of these gers were part of a non-government agency (NGO) initiative to improve insulating properties of these housing structures. The goal of the NGO was to decrease particulate emissions inside the gers; a secondary result was to lower the use of coal and other biomass material. LCSs were installed in gers heated primarily by coal, and interior air quality was measured. Gers that were modified by increasing their insulating capacities showed a 17.5% reduction in PM2.5 concentrations, but this is still higher than recommended by health organizations. Gers that were insulated and used a combination of both coal and electricity showed a 19.1% reduction in PM2.5 concentrations. Insulated gers that used electricity for both heating and cooking showed a 48% reduction in PM2.5 but still had higher concentrations of PM2.5 that were 6.4 times higher than recommended by the World Health Organization (WHO). Nighttime and daytime trends followed similar patterns and trends in PM2.5 concentrations with slight variations. It was found that at nighttime the outside PM2.5 concentrations were generally higher than the inside concentrations of the gers in this study, meaning that PM2.5 would flow into the ger whenever the doors were opened, causing spikes in PM2.5 concentrations.
Journal of Molecular Spectroscopy, 2023
Absorption cross-sections for the 5th (6 ← 0) and 6th (7 ← 0) OH overtones for gas-phase methanol... more Absorption cross-sections for the 5th (6 ← 0) and 6th (7 ← 0) OH overtones for gas-phase methanol, ethanol, and isopropanol were measured using a slow flow cell and Incoherent Broadband Cavity-Enhanced Absorption Spectroscopy (IBBCEAS). Measurements were performed in two wavelength regions, 447–457 nm, and 508–518 nm, using two different instruments. The experimental results are consistent with previous computational predictions of the excitation energies for these transitions. Treating the OH stretch as a local mode allowed for calculation of the fundamental vibrational frequency (ωe), anharmonicity constant (ωexe), and the vertical dissociation energy (VDE) for each alcohol studied. The fundamental vibrational frequency is 3848 ± 18 cm 1, 3807 ± 55 cm 1, and 3813 ± 63 cm 1 for methanol, ethanol, and isopropanol, respectively. The anharmonicity constant was measured to be 84.8 ± 2.1 cm 1, 80.2 ± 5.9 cm 1, and 84.4 ± 6.8 cm 1 for methanol, ethanol, and isopropanol, respectively. The OH vertical dissociation energy was measured to be 499.4 ± 18.4 kJ/mol, 518.0 ± 56.7 kJ/mol, and 492.7 ± 59.9 kJ/mol. The spectroscopically measured values are compared to thermodynamically measured OH bond dissociation energies. The observed differences in previous measurements of the bond dissociation energies compared to the values reported herein can be explained due to the difference between vertical dissociation energies and bond dissociation energies. If the OH overtone stretching mode is excited in methanol to either the 5th or 6th overtone, the bimolecular reaction between methanol and O2 becomes thermodynamically feasible and could contribute to formation of methoxy and HO2 radical under the proper combination of pressure and temperature.
Sensors, 2022
Sulfur dioxide (SO2) is an important precursor for the formation of atmospheric sulfate aerosol a... more Sulfur dioxide (SO2) is an important precursor for the formation of atmospheric sulfate aerosol and acid rain. We present an instrument using Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS) for the measurement of SO2 with a minimum limit of detection of 0.75 ppbv (3-σ) using the spectral range 305.5–312 nm and an averaging time of 5 min. The instrument consists of high-reflectivity mirrors (0.9985 at 310 nm) and a deep UV light source (Light Emitting Diode). The effective absorption path length of the instrument is 610 m with a 0.966 m base length. Published reference absorption cross sections were used to fit and retrieve the SO2 concentrations and were compared to fluorescence standard measurements for SO2. The comparison was well correlated, R2 = 0.9998 with a correlation slope of 1.04. Interferences for fluorescence measurements were tested and the BBCEAS showed no interference, while ambient measurements responded similarly to standard measurement techniques.
Atmosphere
The Wasatch Front in Utah, USA is currently a non-attainment area for ozone according to the Envi... more The Wasatch Front in Utah, USA is currently a non-attainment area for ozone according to the Environmental Protection Agency’s (EPA) National Ambient Air Quality Standards (NAAQS). Nitrogen oxides (NOx = NO2 + NO) and volatile organic compounds (VOCs) in the presence of sunlight lead to ozone formation in the troposphere. When the rate of oxidant production, defined as the sum of O3 and NO2, is faster than the rate of NOx production, a region is said to be NOx-limited and ozone formation will be limited by the concentration of NOx species in the region. The inverse of this situation makes the region VOC-limited. Knowing if a region is NOx-limited or VOC-limited can aid in generating effective mitigation strategies. Understanding the background or regional contributions to ozone in a region, whether it be from the transport of precursors or of ozone, provides information about the lower limit for ozone concentrations that a region can obtain with regulation of local precursors. In th...
Research Article, 2023
Absorption cross-sections for the 5th (6 ← 0) and 6th (7 ← 0) OH overtones for gas-phase methanol... more Absorption cross-sections for the 5th (6 ← 0) and 6th (7 ← 0) OH overtones for gas-phase methanol, ethanol, and isopropanol were measured using a slow flow cell and Incoherent Broadband Cavity-Enhanced Absorption Spectroscopy (IBBCEAS). Measurements were performed in two wavelength regions, 447–457 nm, and 508–518 nm, using two different instruments. The experimental results are consistent with previous computational predictions of the excitation energies for these transitions. Treating the OH stretch as a local mode allowed for calculation of the fundamental vibrational frequency (ωe), anharmonicity constant (ωexe), and the vertical dissociation energy (VDE) for each alcohol studied. The fundamental vibrational frequency is 3848 ± 18 cm 1, 3807 ± 55 cm 1, and 3813 ± 63 cm 1 for methanol, ethanol, and isopropanol, respectively. The anharmonicity constant was measured to be 84.8 ± 2.1 cm 1, 80.2 ± 5.9 cm 1, and 84.4 ± 6.8 cm 1 for methanol, ethanol, and isopropanol, respectively. The OH vertical dissociation energy was measured to be 499.4 ± 18.4 kJ/mol, 518.0 ± 56.7 kJ/mol, and 492.7 ± 59.9 kJ/mol. The spectroscopically measured values are compared to thermodynamically measured OH bond dissociation energies. The observed differences in previous measurements of the bond dissociation energies compared to the values reported herein can be explained due to the difference between vertical dissociation energies and bond dissociation energies. If the OH overtone stretching mode is excited in methanol to either the 5th or 6th overtone, the bimolecular reaction between methanol and O2 becomes thermodynamically feasible and could contribute to formation of methoxy and HO2 radical under the proper combination of pressure and temperature.
Research Article, 2022
Sulfur dioxide (SO2) is an important precursor for the formation of atmospheric sulfate aerosol a... more Sulfur dioxide (SO2) is an important precursor for the formation of atmospheric sulfate aerosol and acid rain. We present an instrument using Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS) for the measurement of SO2 with a minimum limit of detection of 0.75 ppbv (3-s) using the spectral range 305.5–312 nm and an averaging time of 5 min. The instrument consists of high-reflectivity mirrors (0.9985 at 310 nm) and a deep UV light source (Light Emitting Diode). The effective absorption path length of the instrument is 610 m with a 0.966 m base length. Published reference absorption cross sections were used to fit and retrieve the SO2 concentrations and were compared to fluorescence standard measurements for SO2. The comparison was well correlated, R2 = 0.9998 with a correlation slope of 1.04. Interferences for fluorescence measurements were tested and the BBCEAS showed no interference, while ambient measurements responded similarly to standard measurement techniques.
Research Article, 2024
Glyoxal (CHOCHO) is a trace gas in the atmosphere, often used as an indicator of biogenic emissio... more Glyoxal (CHOCHO) is a trace gas in the atmosphere, often used as an indicator of biogenic emissions. It is frequently compared to formaldehyde concentrations, which serve as indicators of anthropogenic emissions, to gain insights into the characteristics of the environmental source. This study employed broadband cavity-enhanced absorption spectroscopy to detect gaseous CHOCHO, methylglyoxal, and NO2. Two different detection methods are compared. Spectrograph and CCD Detection: This approach involves coupling the system to a spectrograph with a charge-coupled device (CCD) detector. It achieved a 1 min 1-σ detection limit of 2.5 × 108 molecules/cm3, or 10 parts per trillion (ppt). Methylglyoxal and NO2 achieved 1 min 1-σ detection limits of 34 ppt and 22 ppt, respectively. Interferometer and PMT Detection: In this method, an interferometer is used in conjunction with a photomultiplier tube (PMT) detector. It resulted in a 2 min 1-σ detection limit of 1.5 × 1010 molecules/cm3, or 600 ppt. The NO2 2 min 1-σ detection limit was determined to be 900 ppt. Concentrations of methylglyoxal were difficult to determine using this method, as they appeared to be below the detection limit of the instrument. This study discusses the advantages and limitations of each of these detection methods.
The Wasatch Front in Utah, USA is currently a non-attainment area for ozone according to the Envi... more The Wasatch Front in Utah, USA is currently a non-attainment area for ozone according to the Environmental Protection Agency's (EPA) National Ambient Air Quality Standards (NAAQS). Nitrogen oxides (NO x = NO 2 + NO) and volatile organic compounds (VOCs) in the presence of sunlight lead to ozone formation in the troposphere. When the rate of oxidant production, defined as the sum of O 3 and NO 2 , is faster than the rate of NO x production, a region is said to be NO x -limited and ozone formation will be limited by the concentration of NOx species in the region. The inverse of this situation makes the region VOC-limited. Knowing if a region is NO x -limited or VOC-limited can aid in generating effective mitigation strategies. Understanding the background or regional contributions to ozone in a region, whether it be from the transport of precursors or of ozone, provides information about the lower limit for ozone concentrations that a region can obtain with regulation of local precursors. In this paper, measured oxidant and NO x concentrations are analyzed from 14 counties in the state of Utah to calculate the regional and local contributions to ozone for each region. This analysis is used to determine the nature of the atmosphere in each county by determining if the region is VOC-or NO x -limited. Furthermore, this analysis is performed for each county for the years 2012 and 2022 to determine if there has been a change in the oxidative nature and quantify the regional and local contributions to ozone over a 10-year period. All studied counties-except for Washington County-in Utah were found to be VOC-limited in 2012. This shifted in 2022 to most counties being either in a transitional state or being NO x -limited. Local contributions to ozone increased in two major counties, Cache and Salt Lake Counties, but decreased in Carbon, Davis, Duchesne, Uinta, Utah, Washington, and Weber Counties. Generally, the regional contributions to oxidant concentrations decreased across the state. A summertime spike in both regional and local contributions to oxidants was seen. Smoke from wildfires was seen to increase the regional contributions to oxidants and shift the local regime to be more NO x -limited.
Research Article, 2023
Air quality is a prevalent concern due to its imposing health risks. The state of Utah, USA, at t... more Air quality is a prevalent concern due to its imposing health risks. The state of Utah, USA, at times over the last 20 years has suffered from some of the worst air quality in the nation. The propensity for the state of Utah to experience elevated concentrations of particulate matter and ozone can in part be attributed to its unique geography that features dry, mountainous topography. Valleys in Utah create ideal environments for extended cold-pool events. In this review, we summarize the research executed in Utah over the past 20 years (2002–2022) by dividing the state into six regions: Utah Valley, Summit County, Southern Utah (regions south of Utah Valley), Cache Valley, Uinta Basin, and Salt Lake Valley. We review the published literature chronologically and provide a summary of each region identifying areas where additional research is warranted. We found that the research effort is weighted towards Uinta Basin and Salt Lake Valley, with the other regions in Utah only adding up to 20% of the research effort. We identified a need for more source apportionment studies, speciated volatile organic compound (VOC) studies, and ozone isopleths. Where ozone isopleths are not able to be created, measurement of glyoxal and formaldehyde concentrations could serve as surrogates for more expensive studies to inform ozone mitigation policies.
Research Article, 2023
Air quality has important climate and health effects. There is a need, therefore, to monitor air ... more Air quality has important climate and health effects. There is a need, therefore, to monitor air quality both indoors and outdoors. Methods of measuring air quality should be cost-effective if they are to be used widely, and one such method is low-cost sensors (LCS). This study reports on
the use of LCSs in Ulaanbataar, Mongolia to measure PM2.5 concentrations inside yurts or “gers”. Some of these gers were part of a non-government agency (NGO) initiative to improve insulating
properties of these housing structures. The goal of the NGO was to decrease particulate emissions inside the gers; a secondary result was to lower the use of coal and other biomass material. LCSs were installed in gers heated primarily by coal, and interior air quality was measured. Gers that were modified by increasing their insulating capacities showed a 17.5% reduction in PM2.5 concentrations, but this is still higher than recommended by health organizations. Gers that were insulated and used a combination of both coal and electricity showed a 19.1% reduction in PM2.5 concentrations. Insulated gers that used electricity for both heating and cooking showed a 48% reduction in PM2.5 but still had higher concentrations of PM2.5 that were 6.4 times higher than recommended by the World Health Organization (WHO). Nighttime and daytime trends followed similar patterns and trends in PM2.5 concentrations with slight variations. It was found that at nighttime the outside PM2.5 concentrations were generally higher than the inside concentrations of the gers in this study, meaning that PM2.5 would flow into the ger whenever the doors were opened, causing spikes in PM2.5 concentrations.
Research Article, 2021
Often only small amounts of sample are available for spectroscopic analytical determinations. Thi... more Often only small amounts of sample are available for spectroscopic analytical determinations. This work investigates the enhancement of signal in columns packed with silica particles. We propose that silica particles cause the light to scatter through the column, effectively increasing optical path length. Packed columns are shown to be effective with fluorescence spectroscopy, but results were inconclusive with absorbance spectroscopy.
Research Article, 2024
The Great Salt Lake (Utah, USA) is reducing in size, which raises several ecological concerns, in... more The Great Salt Lake (Utah, USA) is reducing in size, which raises several ecological concerns, including the effect of an increasing area of dry playa exposed by the retreating lake. This study focuses solely on concerns about the toxicity of metals in the dust blowing off the playa. Although considerable efforts have been made to understand aeolian dust in urban areas along the Wasatch Front, located just east and south of the Great Salt Lake, there is still a need to consolidate existing research and to conduct a compositional analysis of the dust found in these urban areas. We investigated the dust reaching urban monitoring sites around the Great Salt Lake that are managed by the Utah Division of Air Quality. By analyzing historical data, we found that the decrease in the Great Salt Lake’s surface area has not led to a statistically significant increase in dust events in urban areas. Windrose plots align with prior research, indicating that heightened dust levels in urban areas coincide with winds originating from the south or west, passing over identified playas and deserts such as the Milford Flats, Sevier Dry Lake, Tule Dry Lake, Great Salt Lake Desert, Dugway Proving Grounds, and the West Desert of Utah. Metallic compositional analysis of urban dust was used to evaluate potential health risks associated with the dust using the hazard quotient, air regional screening levels, and cancer risk methods. This analysis revealed no significant increase in concentrations of toxic metals. However, this is not to preclude a risk of dust-related health concerns, especially due to pre-existing arsenic and lead levels.
Synopsis: This study provides insights into dust-related health risks and environmental impacts in Utah, analyzing dust exposure from shrinking Great Salt Lake.
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Papers by Callum E Flowerday
the use of LCSs in Ulaanbataar, Mongolia to measure PM2.5 concentrations inside yurts or “gers”. Some of these gers were part of a non-government agency (NGO) initiative to improve insulating
properties of these housing structures. The goal of the NGO was to decrease particulate emissions inside the gers; a secondary result was to lower the use of coal and other biomass material. LCSs were installed in gers heated primarily by coal, and interior air quality was measured. Gers that were modified by increasing their insulating capacities showed a 17.5% reduction in PM2.5 concentrations, but this is still higher than recommended by health organizations. Gers that were insulated and used a combination of both coal and electricity showed a 19.1% reduction in PM2.5 concentrations. Insulated gers that used electricity for both heating and cooking showed a 48% reduction in PM2.5 but still had higher concentrations of PM2.5 that were 6.4 times higher than recommended by the World Health Organization (WHO). Nighttime and daytime trends followed similar patterns and trends in PM2.5 concentrations with slight variations. It was found that at nighttime the outside PM2.5 concentrations were generally higher than the inside concentrations of the gers in this study, meaning that PM2.5 would flow into the ger whenever the doors were opened, causing spikes in PM2.5 concentrations.
Synopsis: This study provides insights into dust-related health risks and environmental impacts in Utah, analyzing dust exposure from shrinking Great Salt Lake.