References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-3243-2011

Pseudo steady states of HONO measured in the nocturnal marine boundary layer: a conceptual model for HONO formation on aqueous surfaces

Wojtal

¹ Halla

J. D.

¹ McLaren

Centre for Atmospheric Chemistry, York University, Toronto, ON, Canada

05 04 2011

11 7 3243 3261

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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A complete understanding of the formation mechanism of nitrous acid (HONO) in the ambient atmosphere is complicated by a lack of understanding of processes occurring when aqueous water is present. We report nocturnal measurements of HONO, SO2 and NO2 by differential optical absorption spectroscopy over the ocean surface in a polluted marine environment. In this aqueous environment, we observed reproducible pseudo steady states (PSS) of HONO every night, that are fully formed shortly after sunset, much faster than seen in urban environments. During the PSS period, HONO is constant with time, independent of air mass source and independent of the concentration of NO2. The independence of HONO on the concentration of NO2 implies a 0° order formation process, likely on a saturated surface, with reversible partitioning of HONO to the gas phase, through vaporization and deposition to the surface. We observed median HONO/NO2 ratios starting at 0.13 at the beginning of the PSS period (with an apparent lower bound of 0.03), rising to median levels of ~0.30 at the end of the PSS period (with an upper bound >1.0). The implication of these numbers is that they suggest a common surface mechanism of HONO formation on terrestrial and aqueous surfaces, with an increase in the HONO/NO2 ratio with the amount of water available at the surface. The levels of HONO during the nocturnal PSS period are positively correlated with temperature, consistent with a partitioning of HONO from the surface to the gas phase with an apparent enthalpy of vaporization of ΔHSNL (HONO)=55.5±5.4 kJ mol−1. The formation mechanism on aqueous surfaces is independent of relative humidity (RH), despite observation of a negative HONO-RH correlation. A conceptual model for HONO formation on ambient aqueous surfaces is presented, with the main elements being the presence of a surface nanolayer (SNL), highly acidic and saturated with N(IV) precursors, production of HNO3, that diffuses to underlying water layers, and HONO, which partitions reversibly between the SNL and the gas phase. Implications of the conceptual model are discussed.

References 1

Acker,~K., Wieprecht,~W., Auel,~R., Kalass,~D., and Möller,~D.: Evidence for heterogeneous formation of nitrous acid on cloud droplets, J Aerosol Sci., 31(1), S352–S353, 2000.

Acker,~K., Spindler,~G., and Brüggemann,~E.: Nitrous and nitric acid measurements during the INTERCOMP2000 campaign in Melpitz, Atmos. Environ., 38, 6497–6505, 2004.

Alicke,~B., Platt,~U., and Stutz,~J.: Impact of nitrous acid photolysis on the total hydroxyl radical budget during the limitation of oxidant production/Pianura Padana Produzione di Ozono study in Milan, J Geophys. Res., 107(D22), 8196, http://dx.doi.org/10.1029/2000JD000075doi:10.1029/2000JD000075, 2002.

Alicke,~B., Geyer,~A., Hofzumahaus,~A., Holland,~F., Konrad,~S., Pätz,~H W., Schäfer,~J., Stutz,~J., Volz-Thomas,~A., and Platt,~U.: OH formation by HONO photolysis during the BERLIOZ experiment, J Geophys. Res., 108, 8247, http://dx.doi.org/10.1029/2001JD000579doi:10.1029/2001JD000579, 2003.

Aubin,~D G. and Abbatt,~J P D.: Interaction of \chemNO_2 with hydrocarbon soot: focus on HONO yield, surface modification, and mechanism, J Phys. Chem. A, 111, 6263–6273, 2007.

Becker,~K H., Kleffmann,~J., Kurtenbach,~R., and Wiesen,~P.: Solubility of nitrous acid (HONO) in sulfuric acid solutions, J Phys. Chem., 100, 14984–14990, 1996.

Bongartz,~A., Kames,~J., Welter,~F., and Schurath,~U.: Near-UV absorption cross sections and trans/cis equilibrium of nitrous acid, J Phys. Chem., 95, 1076–1082, 1991.

Bongartz,~A., Kames,~J., Schurath,~U., George,~Ch., Mirabel,~Ph., and Ponche,~J L.: Experimental determination of HONO mass accommodation coefficients using two different techniques, J Atmos. Chem., 18, 149–169, 1994.

Brown,~S S., Dibb,~J E., Stark,~H., Aldener,~M., Vozella,~M., Whitlow,~S., Williams,~E J., Lerner,~B M., Jakoubek,~R., Middlebrook,~A M., DeGouw,~J A., Warneke,~C., Goldan,~P D., Kuster,~W C., Angevine,~W M., Sueper,~D T., Quinn,~P K., Bates,~T S., Meagher,~J., Fehsenfeld,~F C., and Ravishankara,~A R.: Nighttime removal of NOx in the summer marine boundary layer, Geophys. Res. Lett., 32, L07108, http://dx.doi.org/10.1029/2004GL019412doi:10.1029/2004GL019412, 2004.

Chameides,~W L. and Stelson,~A W.: Aqueous-phase chemical processes in deliquescent seasalt aerosols, Ber. Bunsenges. Phys. Chem., 96, 461–470, 1992.

Cheung,~J L., Li,~Y Q., Boniface,~J., Shi,~Q., Davidovits,~P., Worsnop,~D R., Jayne,~J T., and Kolb,~C E.: Heterogeneous interactions of \chemNO_2 with aqueous surfaces, J Phys. Chem. A, 104, 2655–2662, 2000.

Dentener,~F J. and Crutzen,~P J.: Reaction of N2O$_5$ on tropospheric aerosols: impact on the global distributions of \chemNO_x, O3, and OH, J Geophys. Res., 98, 7149–7163, 1993.

Environment Canada, National Climate Data and Information Archive, available at: http://www.climate.weatheroffice.ec.gc.ca/welcome_e.html, 2008.

Finlayson-Pitts,~B J., Ezell,~M J., and Pitts Jr.,~J N.: Formation of chemically active chlorine compounds by reactions of atmospheric NaCl particles with gaseous N2O$_5$ and \chemClONO_2, Nature, 337, 241–244, 1989.

Finlayson-Pitts,~B J., Wingen,~L M., Sumner,~A L., Syomin,~D., and Ramazan,~K A.: 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.

Freely,~R A., Sabine,~C L., Hernandez-Ayon,~J M., and Ianson Debby,~H B.: Evidence for upwelling of corrosive \qutacidified water onto the continental shelf, Science, 320, 1490–1492, 2008.

George,~C., Strekowski,~R S., Kleffmann,~J., Stemmler,~K. and Ammann,~M.: Photoenhanced uptake of gaseous NO2 on solid organic compounds: A photochemical source of HONO, Faraday Discuss., 130, 195-210, 2005.

Grasshoff,~K.: Hydrochemistry of landlocked basins and fjords, in: Chemical Oceanography, Vol. 2, edited by: Riley,~J P. and Skirrow,~G., Academic Press, New York, USA, 456–598, 1975.

Hardy,~J T.: The sea surface microlayer: biology, chemistry and anthropogenic enrichment, Progress Oceanogr., 11, 307–328, 1982.

Harris,~G W., Carter,~W P L., Winer,~A M., Abbas,~A A., Pitts Jr.,~J N. Platt,~U., and Perner,~D.: Observations of nitrous acid in the Los Angeles atmosphere and implications for predictions of ozone-precursor relationships, Environ. Sci. Technol., 16, 414–419, 1982.

Harrison,~R M. and Kitto,~A M N.: Evidence for a surface source of atmospheric nitrous acid, Atmos. Environ., 28, 1089–1094, 1994.

Harrison,~R M., Peak,~J D., and Collins,~G.: Tropospheric cycle of nitrous acid, J Geophys. Res., 101, 14429–14439, 1996.

He,~Y., Zhou,~X., Hou,~J., Gao,~H., Bertman,~S.: Importance of dew in controlling the air-surface exchange of HONO in rural forested environments, Geophys. Res. Lett., 33, L02813, http://dx.doi.org/10.1029/2005GL024348doi:10.1029/2005GL024348, 2006.

Hermans,~C., Vandaele,~A C., Carleer,~M., Fally,~S., Colin,~R., Jenouvrier,~A., Coquart,~B., and Mérienne,~M.-F.: Absorption cross-sections of atmospheric constituents: \chemNO_2, \chemO_2, and \chemH_2O, Environ. Sci. Poll. Res., 6, 151–158, 1999.

Jenkin,~M E., Cox,~R A., and Williams,~D J.: Laboratory studies of the kinetics of formation of nitrous acid from the thermal reaction of nitrogen dioxide and water vapour, Atmos. Environ., 22, 487–498, 1988.

Junkermann,~W. and Ibusuki,~T.: FTIR spectroscopic measurements of surface bond products of nitrogen oxides on aerosol surfaces – implications for heterogeneous \chemHNO_2 production, Atmos. Environ., 26A, 3099–3103, 1992.

Kitto,~A M N. and Harrison,~R M.: Nitrous and nitric acid measurements at sites in South-East England, Atmos. Environ., 26A, 235–241, 1992.

Kleffmann,~J., Kurtenbach,~R., Lo�rzer,~J C., Wiesen,~P., Kalthoff,~N., Vogel,~B. and Vogel,~H.: Measured and simulated vertical profiles of nitrous acid, part I: Field measurements, Atmos. Environ., 37, 2949-2955, 2003.

Kraus,~S G.: DOASIS: a framework design for DOAS, Thesis, Universität Mannheim, Germany, 2006.

Kurtenbach,~R., Becker,~K H., Gomes,~J A G., Kleffmann,~J., Lörzer,~J C., Spittler,~M., Wiesen,~P., Ackermann,~R., Geyer,~A., and Platt,~U.: Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel, Atmos. Environ., 35, 3385–3394, 2001.

Lammel,~G.: Formation of nitrous acid: parameterisation and comparison with observations. Rep. 286, Max-Planck-Institut für Meteorologie, 1999.

Lammel,~G. and Cape,~J N.: Nitrous acid and nitrite in the atmosphere, Chem. Soc. Rev., 25, 361–369, 1996.

McLaren,~R., Wojtal,~P., Majonis,~D., McCourt,~J., Halla,~J D., and Brook,~J.: NO3 radical measurements in a polluted marine environment: links to ozone formation, Atmos. Chem. Phys., 10, 4187–4206, http://dx.doi.org/10.5194/acp-10-4187-2010doi:10.5194/acp-10-4187-2010, 2010.

Mertes,~S. and Wahner,~A.: Uptake of nitrogen dioxide and nitrous acid on aqueous surfaces, J Phys. Chem., 99, 14000–14006, 1995.

Osthoff,~H D., Roberts,~J M., Ravishankara,~A R., Williams,~E J., Lerner,~B M., Sommariva,~R., Bates,~T S., Coffman,~D., Quinn,~P K., Dibb,~J E., Stark,~H., Burkholder,~J B., Talukdar,~R K., Meagher,~J., Fehsenfeld,~F C., and Brown,~S S.: High levels of nitryl chloride in the polluted subtropical marine boundary layer, Nature Geosci., 1, 324–328, http://dx.doi.org/10.1038/ngeo177doi:10.1038/ngeo177, 2008.

Park,~J.-Y. and Lee,~Y.-N.: Solubility and decomposition kinetics of nitrous acid in aqueous solution, J Phys. Chem., 92, 6294–6302, 1988.

Platt,~U., Perner,~D., Harris,~G W., Winer,~A M., and Pitts Jr.,~J N.: Observations of nitrous acid in an urban atmosphere by differential optical absorption, Nature, 285, 312–314, 1980.

Ponche,~J L., George,~Ch., and Mirabel,~Ph.: Mass transfer at the air/water interface: mass accomodation coefficients of \chemSO_2, HNO3, \chemNO_2 and NH3, J Atmos. Chem., 16, 1–21, 1993.

Roberts,~J M., Osthoff,~H D., Brown,~S S., and Ravishankara,~A R.: N2O$_5$ oxidizes chloride to Cl2 in acidic atmospheric aerosol, Science, 321, 1059–1100, 2008.

Stutz,~J., Alicke,~B., and Neftel,~A.: Nitrous acid formation in the urban atmosphere: gradient measurements of \chemNO_2 and HONO over grass in Milan, Italy, J Geophys. Res., 107, 8192, http://dx.doi.org/10.1029/2001JD00390doi:10.1029/2001JD00390, 2002.

Stutz,~J., Alicke,~B., Ackermann,~R., Geyer,~A., Wang,~S., White,~A B., Williams,~E J., Spicer,~C W., and Fast,~J D.: Relative humidity dependence of HONO chemistry in urban areas, J Geophys. Res., 109, D03307, http://dx.doi.org/10.1029/2003JD004135doi:10.1029/2003JD004135, 2004.

Stutz,~J. and Platt,~U.: Improving long-path differential optical absorption spectroscopy with a quartz-fiber mode mixer, Appl. Opt., 36, 1105–1115, 1997.

Tang,~I N., Tridico,~A C., and Fung,~K H.: Thermodynamic and optical properties of sea salt aerosols, J Geophys. Res., 102, 23269–23275, 1997.

Vandaele,~A C., Simon,~P C., Guilmot,~J M., Carleer,~M., and Colin,~R.: SO2 absorption cross section measurement in the UV using a Fourier transform spectrometer, J Geophys. Res., 99(D12), 25599–25605, 1994.

Vandaele,~A C., Hermans,~C., Simon,~P C., Carleer,~M., Colin,~R., Fally,~S., Mérienne,~M.-F., Jenouvrier,~A., and Coquart,~B.: Measurements of the \chemNO_2 absorption cross-section from 42 000 cm−1 to 10 000 \unitcm−1 (238–1000 \unitnm) at 220 \unitK and 294 \unitK, J Quant. Spectrosc. Rad., 59, 171–184, 1998.

Veče\vra,~Z., Mikuska,~P., Smolik,~J., Eleftheriadis,~K., Bryant,~C., Colbeck,~I., and Lazaridis,~M.: Shipboard measurements of nitrogen dioxide, nitrous acid, nitric acid and ozone in the Eastern Mediterranean Sea, Water Air Soil Pollut. Focus, 8, 117–125, 2008.

Wang,~S., Ackermann,~R., and Stutz,~J.: Vertical profiles of O3 and NO$_x$ chemistry in the polluted nocturnal boundary layer in Phoenix, AZ: I Field observations by long-path DOAS, Atmos. Chem. Phys., 6, 2671–2693, http://dx.doi.org/10.5194/acp-6-2671-2006doi:10.5194/acp-6-2671-2006, 2006.

Yu,~Y., Galle,~B., Panday,~A., Hodson,~E., Prinn,~R., and Wang,~S.: Observations of high rates of NO2-HONO conversion in the nocturnal atmospheric boundary layer in Kathmandu, Nepal, Atmos. Chem. Phys., 9, 6401–6415, http://dx.doi.org/10.5194/acp-9-6401-2009doi:10.5194/acp-9-6401-2009, 2009.

Zafiriou,~O C. and True,~M B.: Nitrite photolysis in seawater by sunlight, Marine Chem., 8, 9–32, 1979.

Zhang,~Z., Liu,~L., Wu,~Z., Li,~J., and Ding,~H.: Physicochemical studies of the sea surface microlayer: I Thickness of the sea surface microlayer and its experimental determination, J Coll. Interf. Sci., 204, 294–299, 1998.

Zhang,~Z B., Pan,~M X., Wang,~Z D., Zhao,~W., Huang,~H H., Wei,~G F., Gao,~H L., Peng,~Y H., Zhu,~Z H., and Li,~L.: Biological and chemical studies of sea surface microlayer (SML) in Daya Bay, China, Chin. J. Oceanol. Limnol., 19, 272–281, 2001.

Zhang,~Z B., Liu,~C., and Liu,~L.: Physicochemical studies of the sea-surface microlayer, Front. Chem. China, 1, 1–14, http://dx.doi.org/10.1007/s11458-005-0003-8doi:10.1007/s11458-005-0003-8, 2006.

Zhou,~X., Civerolo,~K., Dai,~H., Huang,~G., Schwab,~J J., and Demerjian,~K L., Summertime nitrous acid chemistry in the atmospheric boundary layer at a rural site in New York State, J. Geophys. Res., 107(D21), 4590, http://dx.doi.org/10.1029/2001JD001539doi:10.1029/2001JD001539, 2002.