Evidence for a nitrous acid (HONO) reservoir at the ground surface in Bakersfield, CA, during CalNex 2010

VandenBoer, Trevor C.; Markovic, M. Z.; Sanders, John; Ren, Xinrong; Pusede, Sally E.; Browne, E. C.; Cohen, R. C.; Zhang, L.; Thomas, Jordan; Brune, William H.; Murphy, J. G.

doi:10.1002/2013jd020971

Cited by 71 publications

(69 citation statements)

References 100 publications

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“…However, our results seem to indicate that both photolysis of surface HNO 3 / nitrate and photo-enhanced NO 2 conversion are likely active. Acid displacement of HONO deposited during the night, as proposed by VandenBoer et al (2014), can contribute to the observed HONO flux, but a calculation of the total deposited HONO throughout the night with the integrated daytime flux reveals that this mechanism by itself cannot explain the observed daytime HONO formation. The low temperatures and alkaline soil make the bacterial production of nitrite and its release (Su et al, 2011) likely unimportant.…”

Section: Discussionmentioning

confidence: 97%

Nitrous acid formation in a snow-free wintertime polluted rural area

et al. 2018

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Abstract. Nitrous acid (HONO) photolysis is an important source of hydroxyl radicals (OH) in the lower atmosphere, in particular in winter when other OH sources are less efficient. The nighttime formation of HONO and its photolysis in the early morning have long been recognized as an important contributor to the OH budget in polluted environments. Over the past few decades it has become clear that the formation of HONO during the day is an even larger contributor to the OH budget and additionally provides a pathway to recycle NO x . Despite the recognition of this unidentified HONO daytime source, the precise chemical mechanism remains elusive. A number of mechanisms have been proposed, including gas-phase, aerosol, and ground surface processes, to explain the elevated levels of daytime HONO. To identify the likely HONO formation mechanisms in a wintertime polluted rural environment we present LP-DOAS observations of HONO, NO 2 , and O 3 on three absorption paths that cover altitude intervals from 2 to 31, 45, and 68 m above ground level (a.g.l.) during the UBWOS 2012 experiment in the Uintah Basin, Utah, USA. Daytime HONO mixing ratios in the 2-31 m height interval were, on average, 78 ppt, which is lower than HONO levels measured in most polluted urban environments with similar NO 2 mixing ratios of 1-2 ppb. HONO surface fluxes at 19 m a.g.l., calculated using the HONO gradients from the LP-DOAS and measured eddy diffusivity coefficient, show clear upward fluxes. The hourly average vertical HONO flux during sunny days followed solar irradiance, with a maximum of (4.9 ± 0.2) × 10 10 molec. cm −2 s −1 at noontime. A photostationary state analysis of the HONO budget shows that the surface flux closes the HONO budget, accounting for 63 ± 32 % of the unidentified HONO daytime source throughout the day and 90 ± 30 % near noontime. This is also supported by 1-D chemistry and transport model calculations that include the measured surface flux, thus clearly identifying chemistry at the ground as the missing daytime HONO source in this environment. Comparison between HONO surface flux, solar radiation, NO 2 and HNO 3 mixing ratios, and results from 1-D model runs suggest that, under high NO x conditions, HONO formation mechanisms related to solar radiation and NO 2 mixing ratios, such as photo-enhanced conversion of NO 2 on the ground, are most likely the source of daytime HONO. Under moderate to low NO 2 conditions, photolysis of HNO 3 on the ground seems to be the main source of HONO.

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Section: Discussionmentioning

confidence: 97%

Nitrous acid formation in a snow-free wintertime polluted rural area

et al. 2018

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“…Despite specifying a 'lower-limit' value, this investigation may be effectively considering the high end of contribution of soil bacteria to HONO because "optimum" values of flux are used for both soil types. Source S3 is the re-emission of HONO from a surface nitrite reservoir by displacement from HNO 3 and HCl, as in VandenBoer et al (2014VandenBoer et al ( , 2015 and shown in Eq. (6):…”

Section: Parameterization and Evaluation Of Newly Identified Hono Soumentioning

confidence: 99%

“…, and h is the displacement efficiency, ranging from 1% to 9% to 20% for 'lowerlimit', 'likely', and 'upper-limit' values, respectively (VandenBoer et al, 2014). This parameterization was constrained by the calculation of a 'reservoir' of nitrite from deposited HONO, approximated from a material balance on the ground where the source of nitrite is mechanism L1 and loss is due to displacement from mechanism S3.…”

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confidence: 99%

Evaluation of nitrous acid sources and sinks in urban outflow

Gall

Griffin

Steiner

et al. 2016

Atmospheric Environment

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“…The contributions of O 3 and H 2 CO were 34 and 26 %, respectively. Noontime HONO concentrations during CalNex-SJV were between 30 and 250 ppt (Ren et al, 2011;VandenBoer et al, 2013) making HONO an important daytime radical source (32 %). H 2 O 2 photolysis (1 %) and O 3 + alkene reactions (7 %) are less important to the daytime total.…”

Section: S E Pusede Et Al: Temperature-dependent Impacts Of Emissimentioning

confidence: 99%

On the temperature dependence of organic reactivity, nitrogen oxides, ozone production, and the impact of emission controls in San Joaquin Valley, California

et al. 2014

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Abstract. The San Joaquin Valley (SJV) experiences some of the worst ozone air quality in the US, frequently exceeding the California 8 h standard of 70.4 ppb. To improve our understanding of trends in the number of ozone violations in the SJV, we analyze observed relationships between organic reactivity, nitrogen oxides (NO x ), and daily maximum temperature in the southern SJV using measurements made as part of California at the Nexus of Air Quality and Climate Change in 2010 (CalNex-SJV). We find the daytime speciated organic reactivity with respect to OH during CalNex-SJV has a temperature-independent portion with molecules typically associated with motor vehicles being the major component.Published by Copernicus Publications on behalf of the European Geosciences Union. S. E. Pusede et al.: Temperature-dependent impacts of emission controlsAt high temperatures, characteristic of days with high ozone, the largest portion of the total organic reactivity increases exponentially with temperature and is dominated by small, oxygenated organics and molecules that are unidentified. We use this simple temperature classification to consider changes in organic emissions over the last and next decade. With the CalNex-SJV observations as constraints, we examine the sensitivity of ozone production (P O 3 ) to future NO x and organic reactivity controls. We find that P O 3 is NO x -limited at all temperatures on weekends and on weekdays when daily maximum temperatures are greater than 29 • C. As a consequence, NO x reductions are the most effective control option for reducing the frequency of future ozone violations in the southern SJV.

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Evidence for a nitrous acid (HONO) reservoir at the ground surface in Bakersfield, CA, during CalNex 2010

Cited by 71 publications

References 100 publications

Nitrous acid formation in a snow-free wintertime polluted rural area

Nitrous acid formation in a snow-free wintertime polluted rural area

Evaluation of nitrous acid sources and sinks in urban outflow

On the temperature dependence of organic reactivity, nitrogen oxides, ozone production, and the impact of emission controls in San Joaquin Valley, California

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