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

Nature Geoscience volume 8, pages 5560 (2015) | Download Citation

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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References

  1. 1.

    & Detection of nitrous acid in the atmosphere by differential optical absorption. Geophys. Res. Lett. 6, 917–920 (1979).

  2. 2.

    et al. Investigations of emission and heterogeneous formation of HONO in a road traffic tunnel. Atmos. Environ. 35, 3385–3394 (2001).

  3. 3.

    & Interaction of NO2 with hydrocarbon soot: Focus on HONO yield, surface modification and mechanism. J. Phys. Chem. A 111, 6263–6273 (2007).

  4. 4.

    , , , & The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism. Phys. Chem. Chem. Phys. 5, 223–242 (2003).

  5. 5.

    , & Nitrous acid formation in the urban atmosphere: Gradient measurements of NO2 and HONO over grass in Milan, Italy. J. Geophys. Res. 107, 8192 (2002).

  6. 6.

    , , & Impact of HONO on global atmospheric chemistry calculated with an empirical parameterization in the EMAC model. Atmos. Chem. Phys. 12, 9977–10000 (2012).

  7. 7.

    et al. Amplified trace gas removal in the troposphere. Science 324, 1702–1704 (2009).

  8. 8.

    et al. Daytime HONO vertical gradients during SHARP 2009 in Houston, TX. Atmos. Chem. Phys. 12, 635–652 (2012).

  9. 9.

    et al. Nitric acid photolysis on forest canopy surface as a source for tropospheric nitrous acid. Nature Geosci. 4, 440–443 (2011).

  10. 10.

    , , , & Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid. Nature 440, 195–198 (2006).

  11. 11.

    et al. Heterogeneous production of nitrous acid on soot in polluted air masses. Nature 395, 157–160 (1998).

  12. 12.

    et al. Effect of humidity on nitric acid uptake to mineral dust aerosol particles. Atmos. Chem. Phys. 6, 2147–2160 (2006).

  13. 13.

    et al. Mineral dust is a sink for chlorine in the marine boundary layer. Atmos. Environ. 41, 7166–7179 (2007).

  14. 14.

    , , & Heterogeneous uptake and reactivity of formic acid on calcium carbonate particles: A Knudsen cell reactor, FTIR and SEM study. Phys. Chem. Chem. Phys. 7, 3587–3595 (2005).

  15. 15.

    , , & Reactive uptake of acetic acid on calcite and nitric acid reacted calcite aerosol in an environmental reaction chamber. Phys. Chem. Chem. Phys. 10, 142–152 (2008).

  16. 16.

    Introduction to Soil Chemistry: Analysis and Instrumentation 71–90 (Wiley, 2005).

  17. 17.

    et al. HONO emissions from soil bacteria as a major source of atmospheric reactive nitrogen. Science 341, 1233–1235 (2013).

  18. 18.

    et al. Nitrogen, Aerosol Composition and Halogens on a Tall Tower (NACHTT): Overview of a wintertime air chemistry field study in the front range urban corridor of Colorado. J. Geophys. Res. 118, 8067–8085 (2013).

  19. 19.

    , , & Atmospheric gas-aerosol equilibrium: IV. Thermodynamics of carbonates. Aerosol Sci. Technol. 23, 131–154 (1995).

  20. 20.

    et al. Soil nitrite as a source of atmospheric HONO and OH radicals. Science 333, 1616–1618 (2011).

  21. 21.

    & Continuous generation system for low-concentration gaseous nitrous acid. Anal. Chem. 62, 630–633 (1990).

  22. 22.

    , , & Evaluation of a high-purity and high-stability continuous generation system for nitrous acid. Environ. Sci. Technol. 29, 2390–2395 (1995).

  23. 23.

    et al. Understanding the role of the ground surface in HONO vertical structure: High resolution vertical profiles during NACHTT-11. J. Geophys. Res. 118, 10155–10171 (2013).

  24. 24.

    et al. Evidence for a nitrous acid (HONO) reservoir at the ground surface in Bakersfield, CA during CalNex 2010. J. Geophys. Res. Atmos. 119, 9093–9106 (2014).

  25. 25.

    et al. A relaxed eddy accumulation system for measuring vertical fluxes of nitrous acid. Atmos. Meas. Tech. 4, 2093–2103 (2011).

  26. 26.

    et al. Quantification of the unknown HONO daytime source and its relation to NO2. Atmos. Chem. Phys. 11, 10433–10447 (2011).

  27. 27.

    et al. Aircraft measurement of HONO vertical profiles over a forested region. Geophys. Res. Lett. 36, L15820 (2009).

  28. 28.

    , , , & Vertical profiles of nitrous acid in the nocturnal urban atmosphere of Houston, TX. Atmos. Chem. Phys. 11, 3595–3609 (2011).

  29. 29.

    , , , & Importance of dew in controlling the air-surface exchange of HONO in rural forested environments. Geophys. Res. Lett. 33, L02813 (2006).

  30. 30.

    , & Uptake of gas phase nitrous acid onto boundary layer soil surfaces. Environ. Sci. Technol. 48, 375–383 (2014).

  31. 31.

    & Reactive uptake of HONO to TiO2 surface: “Dark” reaction. J. Phys. Chem. A 116, 3665–3672 (2012).

  32. 32.

    , & Reactive uptake of HONO on aluminium oxide surface. J. Photochem. Photobiol. A 250, 50–57 (2012).

  33. 33.

    , & Kinetics and products of heterogeneous reaction of HONO with Fe2O3 and Arizona Test Dust. Environ. Sci. Technol. 47, 6325–6331 (2013).

  34. 34.

    et al. Light changes the atmospheric reactivity of soot. Proc. Natl Acad. Sci. USA 107, 6605–6609 (2010).

  35. 35.

    et al. Light induced conversion of nitrogen dioxide into nitrous acid on submicron humic acid aerosol. Atmos. Chem. Phys. 7, 4237–4248 (2007).

  36. 36.

    , , & Photoenhanced NO2 loss on simulated urban grime. ChemPhysChem 11, 3956–3961 (2010).

  37. 37.

    et al. HONO emissions from snow surfaces. Environ. Res. Lett. 045005 (2008).

  38. 38.

    , , , & Photoenhanced uptake of NO2 by pyrene solid films. J. Phys. Chem. A 112, 9503–9508 (2008).

  39. 39.

    , , , & Photoenhanced uptake of gaseous NO2 on solid organic compounds: A photochemical source of HONO? Faraday Discuss. 130, 195–210 (2005).

  40. 40.

    et al. Photoenhanced uptake of NO2 on mineral dust: Laboratory experiments and model simulations. Geophys. Res. Lett. 35, L05812 (2008).

  41. 41.

    et al. Measurements of ambient HONO concentrations and vertical HONO flux above a northern Michigan forest canopy. Atmos. Chem. Phys. 12, 8285–8296 (2012).

  42. 42.

    et al. Reactive nitrogen distribution and partitioning in the North American troposphere and lowermost stratosphere. J. Geophys. Res. 112, D12S04 (2007).

  43. 43.

    et al. Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): Application to biomass burning emissions. Atmos. Meas. Tech. 3, 981–990 (2010).

  44. 44.

    et al. Diode laser-based cavity ring-down instrument for NO3, N2O5, NO, NO2 and O3 from aircraft. Atmos. Meas. Tech. 4, 1227–1240 (2011).

  45. 45.

    , & Characterization and optimization of an online system for the simultaneous measurement of atmospheric water-soluble constituents in the gas and particle phases. J. Environ. Monit. 14, 1872–1884 (2012).

  46. 46.

    et al. Evidence of rapid production of organic acids in an urban air mass. Geophys. Res. Lett. 38, L17807 (2011).

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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.

Author information

Author notes

    • Trevor C. VandenBoer

    Present address: Department of Earth Science, Memorial University, St John’s, Newfoundland A1B 3X5, Canada

    • Cora J. Young

    Present address: Department of Chemistry, Memorial University, St John’s, Newfoundland A1B 3X7, Canada

    • Milos Z. Markovic

    Present address: Air Quality Research Division, Environment Canada, Toronto, Ontario M3H 5T4, Canada

Affiliations

  1. Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada

    • Trevor C. VandenBoer
    • , Milos Z. Markovic
    •  & Jennifer G. Murphy
  2. Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309, USA

    • Cora J. Young
    •  & Ranajit K. Talukdar
  3. Chemical Sciences Division, National Oceanic and Atmospheric Administration, Boulder, Colorado 80305, USA

    • Cora J. Young
    • , Ranajit K. Talukdar
    • , Steven S. Brown
    •  & James M. Roberts

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Contributions

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.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jennifer G. Murphy.

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DOI

https://doi.org/10.1038/ngeo2298

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