Abstract
Nitrous acid (HONO) has been observed to build in the atmosphere of cities during the nighttime hours and it is suspected that photolysis of HONO may be a significant source of HO radicals early in the day. The sources of HONO are poorly understood, making it difficult to account for nighttime HONO formation in photochemical modeling studies of urban atmospheres, such as modeling of urban O3 formation. This paper reviews the available information on measurements of HONO in the atmosphere and suggest mechanisms of HONO formation. The most extensive atmospheric measurement databases are used to investigate the relations between HONO and potential precursors. Based on these analyses, the nighttime HONO concentrations are found to correlate best with the product of NO, NO2 and H2O concentrations, or possibly the NO, NO2, H2O, and aerosol concentrations. A new mechanism for nighttime HONO formation is proposed that is consistent with this precursor relationship, namely, reaction of N2O3 with moist aerosols (or other surfaces) to form two HONO molecules. Theoretical considerations of the equilibrium constant for N2O3 formation and the theory of gas-particle reactions show that the proposed reaction is a plausible candidate for HONO formation in urban atmospheres. For photochemical modeling purposes, a relation is derived in terms of gas phase species only (i.e., excluding the aerosol concentration): NO + NO2 + H2O → 2 HONO with a rate constant of 1.68 x 10-17 e6348/T (ppm-2 min-1). This rate constant is based on an analysis of ambient measurements of HONO, NO, NO2 and H2O, with a temperature dependence from the equilibrium constant for formation of N2O3. Photochemical grid modeling is used to investigate the effects of this relation on simulated HONO and O3 concentrations in Los Angeles, and the results are compared to two alternative sources of nighttime HONO that have been used by modelers. Modeling results show that the proposed relation results in HONO concentrations consistent with ambient measurements. Furthermore, the relation represents a conservative modeling approach because HONO production is effectively confined to the model surface layers in the nighttime hours, the time and place for which ambient data exist to show that HONO formation occurs. The empirical relation derived here should provide a useful tool for modelers until such time as knowledge of the HONO forming mechanisms has improved and more quantitative relations can be derived.
Similar content being viewed by others
References
T. Nash, Tellus 26, 175 (1974).
D. Perner and U. Platt, Geophys. Res. Lett. 6, 917 (1979).
W. Platt, D. Pemer, G.W. Harris, A.M. Winer, and J.N. Pitts, Jr., Nature 285, 312 (1980).
G.W. Harris, W.P.L. Carter, A.M. Winer, and J.N. Pitts, Jr., Environ. Sci. Technol. 16, 414 (1982).
J.N. Pitts, Jr., E. Sanhueza, R. Atkinson, W.P.L. Carter, A.M. Winer, G.W. Harris, and C.N. Plum, Int. J. Chem. Kinet. 16, 919 (1984).
A. Sjödin and M. Ferm, Atmos. Environ. 19, 985 (1985).
A. Sjödin, Environ. Sci. Technol. 22, 1086 (1988).
H.W. Biermann, J.N. Pitts, Jr., and A.M. Winer, in Advances in Air Sampling, Lewis Publishers, 1988, Ch. 19, p. 265.
H.W. Biermann, E.C. Tuazon, A.M. Winer, T.J. Wallington, and J.N. Pitts, Jr., Atmos. Environ. 22, 1545 (1988).
M.O. Rodgers and D.D. Davis, Environ. Sci. Technol. 23, 1106 (1989); unpublished additional data from March 16 and March 21–22, 1986, not given in this paper, were available to the author and used in testing mechanisms.
G. Lammel and D. Perner, J. Aerosol Sci. 19, 1199 (1988).
B.R. Appel, A.M. Winer, Y. Tokiwa, and H.W. Biermann, Atmos. Environ. 24A, 611 (1990).
Z. Večera and P.K. Dasgupta, Environ. Sci. Technol. 25, 255 (1991).
J. Notholt, J. Hjorth, and F. Raes, Atmos. Environ. 26A, 211 (1992); Ibid., Ber. Bunsenges Phys. Chem. 92, 290 (1992).
A. Rondon and E. Sanhueza, Tellus 41B, 474 (1989).
Shao-Meng Li, J. Atmos. Chem. submitted for publication, June 28, 1990.
W.R. Stockwell and J.G. Calvert, J. Photochem. 8, 193 (1978).
W.P.L. Carter, R. Atkinson, A.M. Winer, and J.N. Pitts, Jr., Int. J. Chem. Kinet. 13, 735 (1981).
L.G. Wayne and D.M. Yost, J. Chem. Phys. 19, 41 (1951).
R.F. Graham and B.J. Tyler, J. Chem. Soc. Faraday I. 68, 683 (1972).
W.H. Chan, R.J. Nordstrom, J.G. Calvert, and J.H. Shaw, Environ. Sci. Technol. 10, 674 (1976).
R.A. Cox and R.G. Derwent, J. Photochem. 6, 23 (1976/77).
E.W. Kaiser and C.H. Wu, J. Phys. Chem. 81, 187 (1977).
E.W. Kaiser and C.H. Wu, J. Phys. Chem. 81, 1701 (1977).
F. Sakamaki, S. Hatakeyama, and H. Akimoto, Int. J. Chem. Kinet. 15, 1013 (1983).
W.B. DeMore, D.M. Golden, R.F. Hampson, M.J. Kurylo, C.J. Howard, A.R. Ravishankara, C.E. Kolb, and M.J. Molina, Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation No. 10 NASA, Jet Propulson Laboratory, California Institute of Technology, Pasadena, CA (August 15, 1992).
W.R. Stockwell and J.G. Calvert, J. Geophys. Res. 88, 6673 (1983).
C.J. Howard, J. Chem. Phys. 67, 5258 (1977).
J.N. Pitts Jr., H.W. Biermann, R. Atkinson, and W.M. Winer, Geophys. Res. Lett. 11, 557 (1984).
J.P. Killus and G.Z. Whitten, J. Geophys. Res. 90, 2430 (1985).
G.S. Tyndall, J.J. Orlando, and J.G. Calvert, J. Atmos. Chem. (1993) submitted for publication.
J.N. Pitts, Jr., H.W. Biermann, A.M. Winer, and E.C. Tuazon, Atmos. Environ. 18, 847 (1984).
R.A. Gorse, Ford Motor Company World Headquarters, Dearborn, MI, personal communication (1993).
A. Winer and H.W. Biermann, Measurements of nitrous acid, nitrate radicals, formaldehyde, and nitrogen dioxide for the southern California air quality study by differential optical absorption spectroscopy. Final Report, Contract No. A6-146-32, California Air Resources Board, December (1989).
S.E. Schwartz. In: SO 2. NO and NO 2 Oxidation Mechanisms: Atmospheric Considerations, J.G. Calvert (Ed.), Chapter 4, pp. 173–208, Butterworth Publishers, Boston (1984).
H.M. Ten Brink, J.A. Bontje, H. Spoelstra, and J.F. Van de Vate. In: Studies in Environmental Science, Vol. 1, M.M. Benarie (Ed.), pp. 239-244, Elsevier Scientific, Amsterdam.
W.P.L. Carter, R. Atkinson, A.M. Winer, and J.N. Pitts, Jr., Int. J. Chem. Kinet. 14, 1071 (1982).
F. Sakamaki and H. Akimoto, Int. J. Chem. Kinet. 20, 111 (1988).
A.C. Besemer and H. Nieboer, Atmos. Environ. 19, 507 (1985).
R. Svensson, E. Ljungström, and O. Lindqvist, Atmos. Environ. 21, 1529 (1987).
H. Akimoto, H. Takagi, and F. Sakamaki, Int. J. Chem. Kinet. 19, 539 (1987).
M.E. Jenkin, R.A. Cox, and D.J. Williams, Atmos. Environ. 22, 487 (1988).
W. A. Glasson and A.M. Dunker, Environ. Sci. Technol. 23, 970 (1989).
C. Perrino, F. De Santis, and A Febo, Atmos. Environ. 22, 1925 (1988).
J.E. Sickles, II and L.L. Hodson, Atmos. Environ. 23, 2321 (1989).
G.R. Appel. Atmos. Environ. 24A, 717 (1990).
E. Sanhueza, C.N. Plum, and J.N. Pitts, Jr., Atmos. Environ. 18, 1029 (1984).
I. Allegrini, F. De Santis, V. Di Palo, A. Febo, C. Perrino, M. Possanzini, and A. Leberti, Sci. Total Environ. 67, 1 (1987).
J.P. Killus and G.Z. Whitten, Int. J. Chem. Kinet. 22, 547 (1990).
W. Junkermann and T. Ibusuki, Atm. Environ. 26A, 3099 (1992).
B. Finlayson-Pitts, Nature 306, 676 (1983).
F.W. Lurmann, W.P.L. Carter, and L.A. Coyner, A Surrogate Species Chemical Reaction Mechanism for Urban-scale Air Quality Simulation Models, Volume II - Guidelines for Using the Mechanism, Report for EPA Contract No. 68-02-4104 February, 1987.
A. Sjödin and M. Ferm, Authors reply, Atmos. Environ. 20, 409 (1986).
R. Atkinson, W.P.L. Carter, J. N. Pitts, Jr., and A.M. Winer, Atmos. Environ. 20, 408 (1986).
I.W.M. Smith and G. Yarwood, Chem. Phys. Lett. 130, 24 (1986).
M. Mozurkewich and J.G. Calvert, J. Geophys. Res. 93, 15889 (1988).
A. Fried, B.E. Henry, J.G. Calvert, and M. Mozurkewich, J. Geochem. Res. (1993), accepted for publication.
The authors are grateful to Dr. Bart Croes of the California Air Resources Board for providing them with all of the data for the SCAQS study of 1987.
R.E. Morris and T.C. Myers, User’s Guide for the Urban Airshed Model, Volume I: User’s Manual for UAM (CB-IV), U.S. Environmental Protection Agency (EPA-450/4-90-007A), 1990.
M.W. Gery, G.Z. Whitten, J.P. Killus, and M.C. Dodge, J. Geophy. Res. 94(D10), 12,925 (1989).
K.K. Wagner and N.J. Wheeler, In: Tropospheric Ozone and the Environment II, Vol. 20, R.L. Berglund (Ed.), pp. 256–266, Air Waste Management Association, Pittsburgh (1992).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Calvert, J.G., Yarwood, G. & Dunker, A.M. An evaluation of the mechanism of nitrous acid formation in the urban atmosphere. Res Chem Intermed 20, 463–502 (1994). https://doi.org/10.1163/156856794X00423
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1163/156856794X00423