scholarly journals Supplementary material to "Development of a Laser-Photofragmentation Laser-Induced Fluorescence instrument for the detection of nitrous acid and hydroxyl radicals in the atmosphere"

Author(s):  
Brandon Bottorff ◽  
Emily Reidy ◽  
Levi Mielke ◽  
Sebastien Dusanter ◽  
Philip Stevens
2021 ◽  
Author(s):  
Brandon Bottorff ◽  
Emily Reidy ◽  
Levi Mielke ◽  
Sebastien Dusanter ◽  
Philip Stevens

Abstract. A new instrument for the measurement of atmospheric nitrous acid (HONO) and hydroxyl radicals (OH) has been developed using laser photofragmentation (LP) of HONO at 355 nm after expansion into a low-pressure cell, followed by resonant laser-induced fluorescence (LIF) of the resulting OH radical fragment at 308 nm similar to the fluorescence assay by gas expansion technique (FAGE). The LP/LIF instrument is calibrated by determining the photo-fragmentation efficiency of HONO. In this method, a known concentration of OH from the photo-dissociation of water vapor is titrated with nitric oxide to produce a known concentration of HONO. Measurement of the concentration of the OH radical fragment relative to the concentration of HONO provides a measurement of the photo-fragmentation efficiency. The LP/LIF instrument has demonstrated a 1σ detection limit of 9 ppt for a 10-min integration time. Ambient measurements of HONO and OH from a forested environment and an urban setting are presented along with indoor measurements to demonstrate the performance of the instrument.


2021 ◽  
Vol 14 (9) ◽  
pp. 6039-6056
Author(s):  
Brandon Bottorff ◽  
Emily Reidy ◽  
Levi Mielke ◽  
Sebastien Dusanter ◽  
Philip S. Stevens

Abstract. A new instrument for the measurement of atmospheric nitrous acid (HONO) and hydroxyl radicals (OH) has been developed using laser photofragmentation (LP) of HONO at 355 nm after expansion into a low-pressure cell, followed by resonant laser-induced fluorescence (LIF) of the resulting OH radical fragment at 308 nm similar to the fluorescence assay by gas expansion technique (FAGE). The LP/LIF instrument is calibrated by determining the photofragmentation efficiency of HONO and calibrating the instrument sensitivity for detection of the OH fragment. In this method, a known concentration of OH from the photo-dissociation of water vapor is titrated with nitric oxide to produce a known concentration of HONO. Measurement of the concentration of the OH radical fragment relative to the concentration of HONO provides a measurement of the photofragmentation efficiency. The LP/LIF instrument has demonstrated a 1σ detection limit for HONO of 9 ppt for a 10 min integration time. Ambient measurements of HONO and OH from a forested environment and an urban setting are presented along with indoor measurements to demonstrate the performance of the instrument.


2021 ◽  
Author(s):  
Fengxia Bao ◽  
Hang Su ◽  
Uwe Kuhn ◽  
Yafang Cheng

<p>Nitrous acid (HONO) is an important component of the nitrogen cycle. HONO can also be rapidly photolyzed by actinic radiation to form hydroxyl radicals (OH) and exerts a primary influence on the oxidative capacity of the atmosphere. The sources and sinks of HONO, however, are not fully understood. Soil nitrite, produced via nitrification or denitrification, is an important source for the atmospheric HONO production. [HONO]*, the equilibrium gas phase HONO concentration over the soil, has been suggested as key to understanding the environmental effects of soil fluxes of HONO (Su et al., 2011). But if and how [HONO]* may exist and vary remains an open question. In this project, a measurement method using a dynamic chamber has been developed to derive [HONO]* and the atmospheric soil fluxes of HONO can accordingly be quantified. We demonstrate the existence of [HONO]* and determine its variation in the course of soil drying processes. We show that when [HONO]* is higher than the atmospheric HONO concentration, HONO will be released from soil; otherwise, HONO will be deposited on soil. This work advances the understanding of soil HONO emissions, and the evaluation of its impact on the atmospheric oxidizing capacity and the nitrogen cycling.</p>


2006 ◽  
Vol 3 (1) ◽  
pp. 31 ◽  
Author(s):  
Kevin C. Clemitshaw

Environmental Context.Nitrous acid (HONO) is formed in the troposphere in urban, rural and remote environments via several uncertain heterogeneous and photochemical processes that involve nitric acid (HNO3). A recently recognised process is initiated by the deposition and migration of HNO3 within snow-pack surfaces to form nitrate anions (NO3−). Photo-reduction of NO3− followed by acidification of the nitrite (NO2−) photo-product leads to emissions of gas-phase HONO. Seasonal observations at Halley, Antarctica are consistent with the formation of HONO via this process, which is potentially of global significance because much of the Earth’s land (and sea) surface is covered with snow and is sunlit for much of the year. Both HONO and HNO3 significantly influence the production of ozone (O3), which acts as a greenhouse gas in the troposphere, via their respective roles as a source of hydroxyl radicals (OH•) and as a sink for OH• and nitrogen dioxide (NO2). Abstract.The tropospheric photochemistry of nitrous acid (HONO) and its coupling with that of nitric acid (HNO3) in urban, rural and remote atmospheres are highlighted in terms of established and uncertain homogeneous and heterogeneous sources and sinks, together with known and potential effects and impacts. Observations made at Halley, Antarctica, via optical detection of an azo dye derivative of HONO are consistent with snow-pack photochemical production of HONO, which has potential significance for the production of hydroxyl radicals (OH•) and ozone (O3) on regional and global scales. Recent developments in measurement methods for HONO and HNO3 are also highlighted. It is now timely to conduct a formal intercomparison of the methods in order to evaluate and enhance their capabilities, and to validate the growing body of HONO and HNO3 data obtained in urban, rural and remote locations.


2019 ◽  
Author(s):  
Leigh R. Crilley ◽  
Louisa J. Kramer ◽  
Bin Ouyang ◽  
Jun Duan ◽  
Wenqian Zhang ◽  
...  

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