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Rapid cycling of reactive nitrogen in the marine boundary layer

Abstract

Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere1. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides1. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed2,3. A ‘renoxification’ process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies2,3,4, but the mechanisms responsible for this process remain uncertain5,6,7,8,9. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism10,11 suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth’s surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.

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Figure 1: Vertical profiles of HONO, NOx and pNO3 in marine air off the coast of North and South Carolina on 5 July 2013 (RF 14) and 8 July 2013 (RF 16).
Figure 2: Correlation between the required in situ HONO source and the product of the pNO3 concentration and the photolysis frequency of gaseous HNO3.
Figure 3: Simulated diurnal profiles of mixing ratios and budgets for HONO, NOx and total nitrate in the MBL.

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Acknowledgements

This research is funded by National Science Foundation (NSF) grants (AGS-1216166, AGS-1215712, and AGS-1216743). We would like to acknowledge operational, technical and scientific support provided by NCAR’s Earth Observing Laboratory, sponsored by the National Science Foundation. Any opinions, findings, conclusions or recommendations expressed in this paper are those of the authors and do not necessarily reflect the views of NSF.

Author information

Authors and Affiliations

Authors

Contributions

Ye, C. and Zhou, X. designed and performed the field and laboratory studies, interpreted the data and write the manuscript with inputs from all the co-authors; Cantrell, C. and Ye, C. performed model simulations.

Corresponding author

Correspondence to Xianliang Zhou.

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The authors declare no competing financial interests.

Additional information

The data are available in our project data archive (http://data.eol.ucar.edu/master_list/?project=SAS).

Extended data figures and tables

Extended Data Figure 1 Typical back-trajectories of air masses in the MBL.

a, 5 July 2013; b, 8 July 2013. The air mass circulated within the North Atlantic Ocean under a Bermuda high-pressure system for several days before reaching the measurement locations. On 8 July 2013, the air mass near the coast was also occasionally affected slightly by fresh emissions from the southeast coast of the USA. See ref. 44 for definition of the cluster centroid. The C-130 flight tracks are shown in upper panels by the lines from 33° 39′ N, 77° 42′ W to 32° 11′ N, 77° 41′ W over the North Atlantic Ocean. The altitudes of cluster centroids in the lower panels are in metres above ground level (AGL).

Extended Data Figure 2 Typical diurnal HONO and NOx budgets in the clean MBL calculated by the MCM v3.2.

a, HONO budget; b, NOx budget. ‘HONO photolysis’ and ‘HONO+OH’ represent HONO sinks contributed by HONO photolysis and the gas-phase reactions of HONO with the OH radicals. ‘Nitrate photolysis’, ‘NO+OH’, ‘Excited NO2’, ‘HO2·H2O+NO2’ and ‘NO2 heterogeneous’ represent HONO sources contributed by pNO3 photolysis, the gas-phase reactions of NO with OH, of excited NO2 with H2O and of HO2·H2O with NO2, and the heterogeneous reactions of NO2 on sea-salt aerosol particles, respectively. ‘HOx+NOx’ is the NOx sink contributed by gas-phase reactions of NO2 with OH and of NO with HO2 with a branching ratio of 0.5% (ref. 46). ‘Halogen nitrate’ is the NOx sink contributed by gas-phase reactions of NO2 with primarily BrO and IO (ref. 29). ‘Organic nitrate’ is the NOx sink contributed by reactions of RO2 radicals with NO with an effective branching ratio of 7% (refs 30 and 51). ‘Other sinks’ represents other minor NOx sinks, such as hydrolysis of N2O5. ‘Nitrate photolysis’ is the NOx source contributed by pNO3 photolysis and ‘Other sources’ represents other minor NOx sources, such as photolysis of gaseous HNO3.

Extended Data Figure 3 HONO observation comparison between the UCLA Mini-DOAS instrument and the LPAP instrument within two plumes during the research flight on 20 June 2013.

The Mini-DOAS instrument is a limb-scanning Max-DOAS instrument, and the analysis incorporates the DOAS approach36. The differential slant column densities of HONO were scaled to the differential slant column density analysis of HCHO, which were retrieved in the same spectral interval and multiplied by the in situ HCHO measurements, provided by the TOGA instrument40 to derive HONO mixing ratios. The Mini-DOAS data was obtained along various elevation viewing angles from +45° to −10°. Because of the position of the aircraft relative to the plumes, the plume geometry, and the HCHO scaling, the derived HONO mixing ratios do not depend on elevation viewing angle and this information was therefore omitted from the figure. Error bars (±1 s.d.) accompany each DOAS measurement. DOAS measurements influenced by clouds or aircraft manoeuvres have been removed from the figure. For better visibility negative DOAS values, which were statistically indistinguishable from zero, were set to 0 p.p.t.v. and the error bar was removed. Red error bars show a 20% uncertainty (±1 s.d.) for LPAP HONO results.

Source data

Extended Data Figure 4 Comparison of the xenon arc lamp light spectrum with the solar actinic spectrum.

The xenon light source was filtered by a 4-mm 7740 Pyrex filter, and the solar actinic flux was the 10-min measurement data at 360 m above sea level from 18:55 to 19:05 utc during RF14.

Source data

Extended Data Figure 5 Typical diurnal profiles of HO2+RO2 and OH radicals in the clean MBL as observed and calculated by the MCM v3.2.

a, HO2+RO2 radicals; b, OH radicals. The calculated (Model) and measured (Obs) ratio of HO2 radicals to RO2 radicals (CH3O2 plus higher RO2) is about 1. The error bars represent ±1 s.d. of the model calculations and observations.

Extended Data Table 1 Measurements from the NOMADSS study used in this analysis

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Ye, C., Zhou, X., Pu, D. et al. Rapid cycling of reactive nitrogen in the marine boundary layer. Nature 532, 489–491 (2016). https://doi.org/10.1038/nature17195

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