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Nocturnal loss and daytime source of nitrous acid through reactive uptake and displacement

Abstract

The nature of daytime sources and night-time sinks of nitrous acid is a key uncertainty in understanding atmospheric oxidation and radical cycling. The accumulation of nitrous acid in the air has been observed to slow down during the night, implying the presence of a night-time sink. In addition, there may be a photochemical source of nitrous acid during the daytime. We used flow tube experiments, measurements of acid displacement efficiencies, and field monitoring of nitrous acid and nitrite concentrations to study the exchange of nitrous acid with soils. Here we show that nitrous acid can react with carbonates or soil at night and subsequently be displaced from soils during the day by air-to-soil transfer of hydrogen chloride and nitric acid, which are generated in the atmosphere photochemically. These processes provide a critical link between the sink of nitrous acid at night and its emission the following day. We conclude that the acid displacement process could contribute a substantial fraction of daytime nitrous acid emissions in numerous environments, including agricultural, urban and vegetated regions, and in any location subject to deposition of soil-derived mineral dust.

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Figure 1: Schematic of HONO(g) deposition and release from a surface reservoir.
Figure 2: Uptake of HONO(g) on soil proxies and soil with increasing relative humidity.
Figure 3: Displacement of HONO(g) from reactive substrates by common atmospheric acids.
Figure 4: AIM-IC observations during CalNex 2010 at Bakersfield, California.

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Acknowledgements

The authors thank N. L. Wagner for experimental assistance and participants of the CalNex and NACHTT field campaigns for support, particularly X. Ren for the measured HONO(g) flux data. T.C.V. and C.J.Y. acknowledge fellowships from the Natural Science and Engineering Research Council of Canada.

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T.C.V. designed and performed the flow tube experiments with contributions from C.J.Y. and R.K.T. T.C.V. and M.Z.M. collected the HONO and particle nitrite observations at CalNex under the guidance of J.G.M. T.C.V. and C.J.Y. prepared this manuscript under the guidance of J.M.R., S.S.B. and J.G.M.

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Correspondence to Jennifer G. Murphy.

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The authors declare no competing financial interests.

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VandenBoer, T., Young, C., Talukdar, R. et al. Nocturnal loss and daytime source of nitrous acid through reactive uptake and displacement. Nature Geosci 8, 55–60 (2015). https://doi.org/10.1038/ngeo2298

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