Uptake of Gas Phase Nitrous Acid onto Boundary Layer Soil Surfaces

Donaldson, Melissa A.; Berke, Andrew E.; Raff, Jonathan D.

doi:10.1021/es404156a

Cited by 57 publications

(80 citation statements)

References 74 publications

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“…Either process increases with relative humidity, which is a possible explanation for the decrease in NO 2 À (p) /HONO (g) during the warm and dry period after 11 June during the campaign. More recently, Donaldson et al [2014] have demonstrated by flow tube experiments that soil layers will take up HONO (g) efficiently under atmospheric conditions, consistent with the previous findings of VandenBoer et al [2013] during NACHTT-11, leaving nitrite at the surface. The authors suggest uptake by an adsorption mechanism, but HONO (g) was not released back to the gas phase after exposure, indicating an irreversible sink that may also be reactive in nature.…”

Section: 1002/2013jd020971supporting

confidence: 89%

“…The typical diurnal cycle shown in Figure 3 can be explained by photolysis during the day (R1) and accumulation overnight, most likely from heterogeneous conversion of NO 2 on wet surfaces (R3) with increasing relative humidity over the course of a night. [Czader et al, 2012;Wong et al, 2011], but the fate of HONO (g) lost to the surface is uncertain, despite new constraints on surface uptake showing consistency with those derived by models [Donaldson et al, 2014;VandenBoer et al, 2013]. Figure 4 shows that the absolute mass loading of NO 2 À (p) generally scales according to the measured amount of HONO (g) .…”

Section: Intercomparison Of Hono (G) Measurements Between Aim-ic and mentioning

confidence: 76%

“…To date, larger aerosols, such as fog droplets [He et al, 2006;Rubio et al, 2008;Rubio et al, 2009;Sörgel et al, 2011a] and solutions of higher pH [Hirokawa et al, 2008], have been shown to accommodate significant amounts of HONO (g) . The role of the ground surface may also be an important sink for HONO (g) at night to consider, potentially generating a reservoir for emission the following day [Donaldson et al, 2014;VandenBoer et al, 2013].…”

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confidence: 99%

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

et al. 2014

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Measurements of HONO (g) were validated to be free of known interferences for wet chemical instrumentation. The accumulation of nitrite into particulate matter was found to be enhanced when gaseous mixing ratios of HONO (g) were highest. Reactive uptake of HONO (g) on to lofted dust and the ground surface, forming a reservoir, is a potential mechanism to explain these observations. The AIM-IC HONO (g) measurements were parameterized in a chemical model to calculate the ground surface daytime HONO (g) source strength at 4.5 m above the surface, found to be on the order of 1.27 ppb h À1, to determine the relative importance of a surface reservoir. If all deposited nighttime HONO (g) is reemitted the following day, up to 30% of the daytime HONO (g) source at CalNex-SJV may be accounted for. The observations of HONO (g) and NO 2 À (p) in Bakersfield, during CalNex, suggest a surface sink and source of HONO (g) . Extension of currently accepted unknown daytime HONO (g) source reactions to include a potential surface HONO (g) reservoir should therefore be sound, but quantitation of the relative contributions of each surface source toward daytime HONO (g) production remains to be resolved.

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Section: 1002/2013jd020971supporting

confidence: 89%

Section: Intercomparison Of Hono (G) Measurements Between Aim-ic and mentioning

confidence: 76%

mentioning

confidence: 99%

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

et al. 2014

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“…Maljanen et al (2013) measured a maximum HONO flux of about 2 µg m −2 h −1 in terms of N. This would equal a source strength of 7.1 × 10 3 molecules cm −3 s −1 (1 ppt h −1 ) considering a boundary layer height of 1000 m and hence is negligible. The laboratory measurements of soil samples represent potential HONO emission fluxes as HONO can simultaneously be taken up by soil (Donaldson et al, 2014) or deposited to soil and re-emitted as proposed by VandenBoer et al (2013). In addition to emissions from the soil surface, the evaporation of dew can release HONO (He et al, 2006), also enhancing HONO fluxes in the early morning when temperatures increase.…”

Section: Indirect Influence Of J (No 2 ) On P Unknownmentioning

confidence: 99%

A comparison of HONO budgets for two measurement heights at a field station within the boreal forest in Finland

et al. 2015

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Abstract. Atmospheric concentrations of nitrous acid (HONO), one of the major precursors of the hydroxyl radical (OH) in the troposphere, significantly exceed the values predicted by the assumption of a photostationary state (PSS) during daytime. Therefore, additional sources of HONO were intensively investigated in the last decades. This study presents budget calculations of HONO based on simultaneous measurements of all relevant species, including HONO and OH at two different measurement heights, i.e. 1 m above the ground and about 2 to 3 m above the canopy (24 m above the ground), conducted in a boreal forest environment. We observed mean HONO concentrations of about 6.5 × 10 8 molecules cm −3 (26 ppt) during daytime, more than 20 times higher than expected from the PSS of 0.2 × 10 8 molecules cm −3 (1 ppt). To close the budgets at both heights, a strong additional source term during daytime is required. This unidentified source is at its maximum at noon (up to 1.1 × 10 6 molecules cm −3 s −1 , 160 ppt h −1 ) and in general up to 2.3 times stronger above the canopy than close to the ground. The insignificance of known gas phase reactions and other processes like dry deposition or advection compared to the photolytic decomposition of HONO at this measurement site was an ideal prerequisite to study possible correlations of this unknown term to proposed HONO sources. But neither the proposed emissions from soils nor the proposed photolysis of adsorbed HNO 3 contributed substantially to the unknown source. However, the unknown source was found to be perfectly correlated to the unbalanced photolytic loss of HONO.

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“…Nocturnal HONO formation is partly counteracted by HONO uptake on the ground, with reported surface uptake coefficients in the range of 2×10 −5 to 2×10 −4 (VandenBoer et al, 2013;Donaldson et al, 2014;Wong et al, 2012). Uptake on aerosol is also likely, but little information on this process is available.…”

Section: Introductionmentioning

confidence: 99%

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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Uptake of Gas Phase Nitrous Acid onto Boundary Layer Soil Surfaces

Cited by 57 publications

References 74 publications

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

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

A comparison of HONO budgets for two measurement heights at a field station within the boreal forest in Finland

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

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