Rapid cycling of reactive nitrogen in the marine boundary layer

Ye, Chunxiang; Zhou, Xianliang; Pu, Dennis; Stutz, J.; Festa, James; Spolaor, Max; Tsai, Catalina; Cantrell, C. A.; Mauldin, R. L.; Campos, T.; Weinheimer, A. J.; Hornbrook, R. S.; Apel, E. C.; Guenther, Alex; Kaser, L.; Yuan, Bin; Karl, T.; Haggerty, Julie; Hall, Samuel R.; Ullmann, Kirk; Smith, James N.; Ortega, John; Knote, Christoph

doi:10.1038/nature17195

Cited by 200 publications

(359 citation statements)

References 44 publications

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“…We find HONO is most important near urban areas close to the surface (<100‐m altitude) over land, contributing <8% to the projected daily radical budget within the MBL, which was typically well mixed from the surface to ~1 km. Our measurements show some support for slower daytime production of HONO from pNO 3 − photolysis than reported by Ye et al () and more broadly consistent with that presented in Romer et al (). We thus conclude that daytime HONO production and contribution to primary radicals remain uncertain, but is likely smaller than previous estimates would have suggested.…”

Section: Discussionsupporting

confidence: 92%

Anthropogenic Control Over Wintertime Oxidation of Atmospheric Pollutants

Haskins

Lopez‐Hilfiker

Lee

et al. 2019

Geophysical Research Letters

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During winter in the midlatitudes, photochemical oxidation is significantly slower than in summer and the main radical oxidants driving formation of secondary pollutants, such as fine particulate matter and ozone, remain uncertain, owing to a lack of observations in this season. Using airborne observations, we quantify the contribution of various oxidants on a regional basis during winter, enabling improved chemical descriptions of wintertime air pollution transformations. We show that 25-60% of NO x is converted to N 2 O 5 via multiphase reactions between gas-phase nitrogen oxide reservoirs and aerosol particles, with~93% reacting in the marine boundary layer to form >2.5 ppbv ClNO 2 . This results in >70% of the oxidizing capacity of polluted air during winter being controlled by multiphase reactions and emissions of volatile organic compounds, such as HCHO, rather than reaction with OH. These findings highlight the control local anthropogenic emissions have on the oxidizing capacity of the polluted wintertime atmosphere.Plain Language Summary During summer, rapid transformations of primary pollutants, those emitted directly into the atmosphere, into secondary pollutants, such as particulate matter and ozone, are driven by reactions with the hydroxyl radical, formed in the atmosphere when sunlight strikes ozone in the presence of water vapor. During winter, when there is less sunlight and water vapor, production of this radical is lower. Yet the conversion of primary pollutants into secondary pollutants still occurs rapidly, pointing to a misunderstanding in the chemical processes that drive this conversion during winter. Using aircraft data collected across the northeast United States during the winter of 2015, we show that reactions with radicals arising from atypical precursors, such as nitryl chloride, account for more than 70% of the reactions that directly emitted pollutants undergo. We show that during winter, the formation of these radicals is tied to human activities. Our data provide critical constraints for improving the descriptions of chemical processes in air quality models, which will help guide improved air quality policy. Other regions of the world, such as China, Europe, and northern India, also experience this seasonal chemical shift in the atmosphere. Our findings, therefore, have global scale implications for understanding wintertime pollution transformations and transport.

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Section: Discussionsupporting

confidence: 92%

Anthropogenic Control Over Wintertime Oxidation of Atmospheric Pollutants

Haskins

Lopez‐Hilfiker

Lee

et al. 2019

Geophysical Research Letters

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“…The linear relationship between HONO production rate and the product of particulate nitrates and its photolysis was recently confirmed by Ye et al (2016b) in the marine boundary layer, where this mechanism plays an important role in recycling NO x . While there is still some debate about the absorption cross section of surface-adsorbed HNO 3 / nitrate, Ye et al (2016a) report that the photolysis of HNO 3 / nitrate is 1 to 3 orders of magnitude faster than that of gas-phase HNO 3 , confirming that this process is a significant source of HONO in many environments.…”

Section: Introductionmentioning

confidence: 81%

“…HONO chemistry can also play a significant role in the recycling of NO x , as recently demonstrated by Ye et al (2016b).…”

Section: Introductionmentioning

confidence: 87%

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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“…the DLR Falcon, Geophysica, NASA Global Hawk, NSF/NCAR C-130) and high-flying balloon (LPMA/DOAS and MIPAS/TELIS/mini-DOAS payload) observations (Ferlemann et al, 2000;Weidner et al, 2005;Kritten et al, 2010;Prados-Roman et al, 2011;Kreycy et al, 2013;Gratz et al, 2015;Ye et al, 2016;Stutz et al, 2017;Werner et al, 2017). The major design criteria for airborne measurements are a small weight (several to tens of kilograms), a small power consumption (200 W), multiple channels of moderate spectral resolution (i.e.…”

Section: Instrument Descriptionmentioning

confidence: 99%

“…The airborne limb measurements of scattered skylight continued with the aircraft studies of Prados-Roman et al (2011) made from aboard the DLR Falcon and more recently from the American High-performance Instrumented Airborne Platform for Environmental Research (HIAPER) aircraft , the NSF/NCAR C-130 (Gratz et al, 2015;Ye et al, 2016), the NASA Global Hawk Werner et al, 2017), and those reported here from HALO, an aircraft based on a Gulfstream G550 jet (http://www.halo.dlr.de/). For first results from measurement campaigns involving the HALO mini-DOAS instrument, the reader is referred to e.g.…”

Section: Introductionmentioning

confidence: 99%

The novel HALO mini-DOAS instrument: inferring trace gas concentrations from airborne UV/visible limb spectroscopy under all skies using the scaling method

et al. 2017

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Abstract. We report on a novel six-channel optical spectrometer (further on called mini-DOAS instrument) for airborne nadir and limb measurements of atmospheric trace gases, liquid and solid water, and spectral radiances in the UV/vis and NIR spectral ranges. The spectrometer was developed for measurements from aboard the German High-Altitude and Long-Range (HALO) research aircraft during dedicated research missions. Here we report on the relevant instrumental details and the novel scaling method used to infer the mixing ratios of UV/vis absorbing trace gases from their absorption measured in limb geometry. The uncertainties of the scaling method are assessed in more detail than before for sample measurements of NO 2 and BrO. Some first results are reported along with complementary measurements and comparisons with model predictions for a selected HALO research flight from Cape Town to Antarctica, which was performed during the research mission ESMVal on 13 September 2012.

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Rapid cycling of reactive nitrogen in the marine boundary layer

Cited by 200 publications

References 44 publications

Anthropogenic Control Over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic Control Over Wintertime Oxidation of Atmospheric Pollutants

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

The novel HALO mini-DOAS instrument: inferring trace gas concentrations from airborne UV/visible limb spectroscopy under all skies using the scaling method

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