O. D. Edwards, Arnold O. Morgan, Decker S. Womack and Dean Gano to Gov. Ross Barnett, 28 September 1962

Senders state that for every border patrolman sent to carry out Bobby\u27s order they will send another Texan to face him. Message was forwarded to Jackson, MS.https://egrove.olemiss.edu/west_union_gov/1065/thumbnail.jp

Nighttime and daytime dark oxidation chemistry in wildfire plumes: an observation and model analysis of FIREX-AQ aircraft data

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 the hydroxyl radical (OH), nitrate radical (NO3), and ozone (O3). During the daytime, when light penetrates the plumes, BBVOCs are oxidized mainly by O3 and OH. In contrast, at night or in optically dense plumes, BBVOCs are oxidized mainly by O3 and NO3. This work focuses on the transition between daytime and nighttime oxidation, which has significant implications for the formation of secondary pollutants and loss of nitrogen oxides () and has been understudied. We present wildfire plume observations made during FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality), a field campaign involving multiple aircraft, ground, satellite, and mobile platforms that took place in the United States in the summer of 2019 to study both wildfire and agricultural burning emissions and atmospheric chemistry. We use observations from two research aircraft, the NASA DC-8 and the NOAA Twin Otter, with a detailed chemical box model, including updated phenolic mechanisms, to analyze smoke sampled during midday, sunset, and nighttime. Aircraft observations suggest a range of NO3 production rates (0.1&ndash;1.5&thinsp;ppbv&thinsp;h&minus;1) in plumes transported during both midday and after dark. Modeled initial instantaneous reactivity toward BBVOCs for NO3, OH, and O3 is 80.1&thinsp;%, 87.7&thinsp;%, and 99.6&thinsp;%, respectively. Initial NO3 reactivity is 10&ndash;104 times greater than typical values in forested or urban environments, and reactions with BBVOCs account for &gt;97&thinsp;% of NO3 loss in sunlit plumes (jNO2 up to ), while conventional photochemical NO3 loss through reaction with NO and photolysis are minor pathways. Alkenes and furans are mostly oxidized by OH and O3 (11&thinsp;%&ndash;43&thinsp;%, 54&thinsp;%&ndash;88&thinsp;% for alkenes; 18&thinsp;%&ndash;55&thinsp;%, 39&thinsp;%&ndash;76&thinsp;%, for furans, respectively), but phenolic oxidation is split between NO3, O3, and OH (26&thinsp;%&ndash;52&thinsp;%, 22&thinsp;%&ndash;43&thinsp;%, 16&thinsp;%&ndash;33&thinsp;%, respectively). Nitrate radical oxidation accounts for 26&thinsp;%&ndash;52&thinsp;% of phenolic chemical loss in sunset plumes and in an optically thick plume. Nitrocatechol yields varied between 33&thinsp;% and 45&thinsp;%, and NO3 chemistry in BB plumes emitted late in the day is responsible for 72&thinsp;%&ndash;92&thinsp;% (84&thinsp;% in an optically thick midday plume) of nitrocatechol formation and controls nitrophenolic formation overall. As a result, overnight nitrophenolic formation pathways account for 56&thinsp;%&plusmn;2&thinsp;% of NOx loss by sunrise the following day. In all but one overnight plume we modeled, there was remaining NOx (13&thinsp;%&ndash;57&thinsp;%) and BBVOCs (8&thinsp;%&ndash;72&thinsp;%) at sunrise. &nbsp;</p

Evaluation of the accuracy of thermal dissociation CRDS and LIF techniques for atmospheric measurement of reactive nitrogen species

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-induced fluorescence (LIF) and cavity ring-down spectroscopy (CRDS) to measure total NOy when set at &gt; 600 °C or speciated NOy when set at intermediate temperatures. We report the conversion efficiency of known amounts of several representative NOy species to NO2 in our TD-CRDS instrument, under a variety of experimental conditions. We find that the conversion efficiency of HNO3 is highly sensitive to the flow rate and the residence time through the TD inlet as well as the presence of other species that may be present during ambient sampling, such as ozone (O3). Conversion of HNO3 at 400 °C, nominally the set point used to selectively convert organic nitrates, can range from 2 to 6 % and may represent an interference in measurement of organic nitrates under some conditions. The conversion efficiency is strongly dependent on the operating characteristics of individual quartz ovens and should be well calibrated prior to use in field sampling. We demonstrate quantitative conversion of both gas-phase N2O5 and particulate ammonium nitrate in the TD inlet at 650 °C, which is the temperature normally used for conversion of HNO3. N2O5 has two thermal dissociation steps, one at low temperature representing dissociation to NO2 and NO3 and one at high temperature representing dissociation of NO3, which produces exclusively NO2 and not NO. We also find a significant interference from partial conversion (5–10 %) of NH3 to NO at 650 °C in the presence of representative (50 ppbv) levels of O3 in dry zero air. Although this interference appears to be suppressed when sampling ambient air, we nevertheless recommend regular characterization of this interference using standard additions of NH3 to TD instruments that convert reactive nitrogen to NO or NO2

Evaluation of the accuracy of thermal dissociation CRDS and LIF techniques for atmospheric measurement of reactive nitrogen species

Abstract. 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 induced fluorescence (LIF) and cavity ringdown spectroscopy (CRDS) to measure total NOy when set at &gt; 600 °C, or speciated NOy when set at intermediate temperatures. We report the conversion efficiency of known amounts of several representative NOy species to NO2 in our TD-CRDS instrument, under a variety of experimental conditions. We find that the conversion efficiency of HNO3 is highly sensitive to the flow rate and the residence time through the TD inlet, as well as the presence of other species that may be present during ambient sampling, such as ozone (O3). Conversion of HNO3 at 400 °C, nominally the set point used to selectively convert organic nitrates, can range from 2–6 % and may represent an interference in measurement of organic nitrates under some conditions. The conversion efficiency is strongly dependent on the operating characteristics of individual quartz ovens, and should be well calibrated prior to use in field sampling. We demonstrate quantitative conversion of both gas phase N2O5 and particulate ammonium nitrate in the TD inlet at 650 °C, the temperature normally used for conversion of HNO3. N2O5 has two thermal dissociation steps, one at low temperature representing dissociation to NO2 and NO3, and one at high temperature representing dissociation of NO3, which produces exclusively NO2 and not NO. We also find a significant interference from partial conversion (5–10 %) of NH3 to NO at 650 °C in the presence of representative (50 ppbv) levels of O3 in dry zero air. Although this interference appears to be suppressed when sampling ambient air, we nevertheless recommend regular characterization of this interference using standard additions of NH3 to TD instruments that convert reactive nitrogen to NO or NO2. </jats:p

Nighttime and daytime dark oxidation chemistry in wildfire plumes: an observation and model analysis of FIREX-AQ aircraft data

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 the hydroxyl radical (OH), nitrate radical (NO3), and ozone (O3). During the daytime, when light penetrates the plumes, BBVOCs are oxidized mainly by O3 and OH. In contrast, at night or in optically dense plumes, BBVOCs are oxidized mainly by O3 and NO3. This work focuses on the transition between daytime and nighttime oxidation, which has significant implications for the formation of secondary pollutants and loss of nitrogen oxides (NOx=NO+NO2) and has been understudied. We present wildfire plume observations made during FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality), a field campaign involving multiple aircraft, ground, satellite, and mobile platforms that took place in the United States in the summer of 2019 to study both wildfire and agricultural burning emissions and atmospheric chemistry. We use observations from two research aircraft, the NASA DC-8 and the NOAA Twin Otter, with a detailed chemical box model, including updated phenolic mechanisms, to analyze smoke sampled during midday, sunset, and nighttime. Aircraft observations suggest a range of NO3 production rates (0.1–1.5 ppbv h−1) in plumes transported during both midday and after dark. Modeled initial instantaneous reactivity toward BBVOCs for NO3, OH, and O3 is 80.1 %, 87.7 %, and 99.6 %, respectively. Initial NO3 reactivity is 10–104 times greater than typical values in forested or urban environments, and reactions with BBVOCs account for >97 % of NO3 loss in sunlit plumes (jNO2 up to 4×10−3s−1), while conventional photochemical NO3 loss through reaction with NO and photolysis are minor pathways. Alkenes and furans are mostly oxidized by OH and O3 (11 %–43 %, 54 %–88 % for alkenes; 18 %–55 %, 39 %–76 %, for furans, respectively), but phenolic oxidation is split between NO3, O3, and OH (26 %–52 %, 22 %–43 %, 16 %–33 %, respectively). Nitrate radical oxidation accounts for 26 %–52 % of phenolic chemical loss in sunset plumes and in an optically thick plume. Nitrocatechol yields varied between 33 % and 45 %, and NO3 chemistry in BB plumes emitted late in the day is responsible for 72 %–92 % (84 % in an optically thick midday plume) of nitrocatechol formation and controls nitrophenolic formation overall. As a result, overnight nitrophenolic formation pathways account for 56 %±2 % of NOx loss by sunrise the following day. In all but one overnight plume we modeled, there was remaining NOx (13 %–57 %) and BBVOCs (8 %–72 %) at sunrise