A two-channel thermal dissociation cavity ring-down spectrometer for the detection of ambient NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, RO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and RONO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;

Thieser, J.; Schuster, G.; Schuladen, Jan; Phillips, G. J.; Reiffs, Andreas; Parchatka, Uwe; Pöhler, Denis; Lelieveld, Jos; Crowley, John N.

doi:10.5194/amt-9-553-2016

Cited by 54 publications

(73 citation statements)

References 88 publications

(135 reference statements)

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“…The shape of the dissociation curve did not match that calculated using the dissociation rate, and the authors speculated that reactions on the heated fused silica surface may have an impact. Thieser et al (2016), who also used a higher gas flow rate than that used by TD-LIF, observed ClNO 2 and RONO 2 s were fully dissociated by 450°C. The TD-LIF temperature set points for WINTER were chosen based on experiments with n-propyl nitrate and HNO 3 directly prior to the campaign to determine the best temperature set point to avoid species overlap.…”

Section: Clnomentioning

confidence: 99%

“…In addition to the primary detection of species indicated above, many of these techniques have been coupled to strategies for converting all or selected fractions of NO y to lower oxides (e.g., NO 3 , NO 2 , or NO) that can be readily measured. Examples include photolytic conversion of NO 2 to NO (Walega et al, 1991), catalytic conversion of NO y to NO (Walega et al, 1991), and thermal conversion of classes of NO z to NO 3 , NO 2 , or NO (Day et al, 2002;Paul et al, 2009;Thieser et al, 2016;Wagner et al, 2011;Wild et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

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Comparison of Airborne Reactive Nitrogen Measurements During WINTER

et al. 2019

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We present a comparison of instruments measuring nitrogen oxide species from an aircraft during the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign over the northeast United States. Instrument techniques compared here include chemiluminescence (CL), thermal dissociation laser‐induced fluorescence (TD‐LIF), cavity ring‐down spectroscopy (CRDS), high‐resolution time of flight, iodide‐adduct chemical ionization mass spectrometry (I‐CIMS), and aerosol mass spectrometry. Species investigated include NO2, NO, total nitrogen oxides (NOy), N2O5, ClNO2, and HNO3. Particulate‐phase nitrate is also included for comparisons of HNO3 and NOy. Instruments generally agreed within reported uncertainties, with individual flights sometimes showing much better agreement than the data set taken as a whole, due to flight‐to‐flight slope changes. NO measured by CRDS and CL showed an average relative slope of 1.16 ± 0.01 across all flights, which is outside of combined uncertainties. The source of the error was not identified. For NO2 measured by CRDS and TD‐LIF the average was 1.02 ± 0.00; for NOy measured by CRDS and CL the average was 1.01 ± 0.00; and for N2O5 measured by CRDS and I‐CIMS the average was 0.89 ± 0.01. NOy budget closure to within 20% is demonstrated. We observe nonlinearity in NO2 and NOy correlations at concentrations above ~30 ppbv that may be related to the NO discrepancy noted above. For ClNO2 there were significant differences between I‐CIMS and TD‐LIF, potentially due in part to the temperature used for thermal dissociation. Although the fraction of particulate nitrate measured by the TD‐LIF is not well characterized, it improves comparisons to include particulate measurements.

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Section: Clnomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Comparison of Airborne Reactive Nitrogen Measurements During WINTER

et al. 2019

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“…x , sulfur-containing radical anions, or Cl − 2 ) is generally of minor importance and the presence of NO 3 in aqueous particles is largely a result of transfer from the gas phase Tilgner et al, 2013). Concentrations of NO 3 in tropospheric aqueous solutions cannot be measured in situ, and literature values are based on multiphase model predictions (Herrmann et al, 2010).…”

Section: Aqueous-phase Reactionsmentioning

confidence: 99%

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Brown¹

2016

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Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO 3 ) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO 3 -BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO 3 -BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO 3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO 3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models.This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO 3 -BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO 3 -BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models. Isoprene Monoterpenes O 3 •NO 3 NO x Nitrates Aerosol Biogenic VOCs NO, NO 2 Air quality Climate Atmos.

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“…Techniques that detect the major individual components of NO y include detection of NO and NO 2 by chemiluminescence (Ridley and Howlett, 1974;Kley and McFarland, 1980), cavity ring-down spectroscopy (CRDS; Fuchs et al, 2009), or laser-induced fluorescence (LIF; Thornton et al, 2000), as well as detection of HNO 3 by chemical ionization mass spectrometry (CIMS; Fehsenfeld et al, 1998;Huey et al, 1998;Neuman et al, 2002;Huey, 2007) or mist chamber sampling (Talbot et al, 1990). Additionally, speciated peroxyacyl nitrates (PANs) have been detected by gaschromatography electron capture detection (Darley et al, 1963;Flocke et al, 2005) and CIMS (Slusher et al, 2004), while N 2 O 5 and ClNO 2 have been detected by CRDS (Dubé et al, 2006;Thaler et al, 2011) and CIMS (Kercher et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

Author response to Reviewer 2

Womack¹

2017

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The sum of all reactive nitrogen species (NO y ) includes NO x (NO 2 + NO) and all of its oxidized forms, and the accurate detection of NO y is critical to understanding atmospheric nitrogen chemistry. Thermal dissociation (TD) inlets, which convert NO y to NO 2 followed by NO 2 detection, are frequently used in conjunction with techniques such as laser-induced fluorescence (LIF) and cavity ring-down spectroscopy (CRDS) to measure total NO y when set at > 600 • C or speciated NO y when set at intermediate temperatures. We report the conversion efficiency of known amounts of several representative NO y species to NO 2 in our TD-CRDS instrument, under a variety of experimental conditions. We find that the conversion efficiency of HNO 3 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 (O 3 ). Conversion of HNO 3 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 N 2 O 5 and particulate ammonium nitrate in the TD inlet at 650 • C, which is the temperature normally used for conversion of HNO 3 . N 2 O 5 has two thermal dissociation steps, one at low temperature representing dissociation to NO 2 and NO 3 and one at high temperature representing dissociation of NO 3 , which produces exclusively NO 2 and not NO. We also find a significant interference from partial conversion (5-10 %) of NH 3 to NO at 650 • C in the presence of representative (50 ppbv) levels of O 3 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 NH 3 to TD instruments that convert reactive nitrogen to NO or NO 2 .

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A two-channel thermal dissociation cavity ring-down spectrometer for the detection of ambient NO<sub>2</sub>, RO<sub>2</sub>NO<sub>2</sub> and RONO<sub>2</sub>

Cited by 54 publications

References 88 publications

Comparison of Airborne Reactive Nitrogen Measurements During WINTER

Comparison of Airborne Reactive Nitrogen Measurements During WINTER

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Author response to Reviewer 2

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