Direct observation of heterogeneous chemistry in the atmosphere

Science

Volumn 279, Issue 5354, 1998, Pages 1184-1187

  Gard, Eric E ^a   Kleeman, Michael J ^b   Gross, Deborah S ^a   Hughes, Lara S ^b   Allen, Jonathan O ^b   Morrical, Bradley D ^a   Fergenson, David P ^a   Dienes, Tas ^a   Gälli, Markus E ^a   Johnson, Robert J ^b   Cass, Glen R ^b   Prather, Kimberly A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHLORIDE; HYDROCHLORIC ACID; NITRATE; NITRIC ACID; SODIUM CHLORIDE; SODIUM NITRATE;

ATMOSPHERIC CHEMISTRY; CHLORIDE; NITRATE; TROPOSPHERE;

ARTICLE; ATMOSPHERE; CALCULATION; CHEMICAL REACTION; CHEMISTRY; GAS; MASS SPECTROMETRY; PRIORITY JOURNAL;

EID: 7144235823     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.279.5354.1184     Document Type: Article

References (40)

1. R. J. Charlson et al., Science 255, 423 (1992); J. E. Penner ef al., Bull. Am. Meteorol. Soc. 75, 375 (1994).
2. R. J. Charlson et al., Science 255, 423 (1992); J. E. Penner ef al., Bull. Am. Meteorol. Soc. 75, 375 (1994).
3. National Research Council, Protecting Visibility in National Parks and Wilderness Areas (National Academy Press, Washington, DC, 1993).
4. "Air Quality Criteria for Particulate Matter," EPA/600/ P-95/aF-cF (U.S. Environmental Protection Agency, Research Triangle Park, NC, 1996).
5. 2 Oxidation Mechanisms: Atmospheric Considerations, J. G. Calvert, Ed. (Butterworth, Boston, 1984), pp. 1-62.
6. 2 Oxidation Mechanisms: Atmospheric Considerations, J. G. Calvert, Ed. (Butterworth, Boston, 1984), pp. 1-62.
7. D. Grosjean, in Ozone and Other Photochemical Oxidants (National Academy of Sciences, Washington, DC, 1977), pp. 45-125; S. N. Pandis et al., Atmos. Environ. A 26, 2269 (1992); J. R. Odum, T. P. W. Jungkamp, R. H. Griffin, R. C. Flagan, J. H. Seinfeld, Science 276, 96 (1997).
8. D. Grosjean, in Ozone and Other Photochemical Oxidants (National Academy of Sciences, Washington, DC, 1977), pp. 45-125; S. N. Pandis et al., Atmos. Environ. A 26, 2269 (1992); J. R. Odum, T. P. W. Jungkamp, R. H. Griffin, R. C. Flagan, J. H. Seinfeld, Science 276, 96 (1997).
9. D. Grosjean, in Ozone and Other Photochemical Oxidants (National Academy of Sciences, Washington, DC, 1977), pp. 45-125; S. N. Pandis et al., Atmos. Environ. A 26, 2269 (1992); J. R. Odum, T. P. W. Jungkamp, R. H. Griffin, R. C. Flagan, J. H. Seinfeld, Science 276, 96 (1997).
10. B. J. Finlayson-Pitts and J. N. Pitts Jr., Atmospheric Chemistry: Fundamentals and Experimental Techniques (Wiley, New York, 1986).
11. J. H. Seinfeld, Atmospheric Chemistry and Physics of Air Pollution (Wiley, New York, 1986).
12. See, for example, A. R. Ravishankara, Science 276, 1058 (1997); S. Langer, R. S. Pemberton, B. J. Finlayson-Pitts, J. Phys. Chem. A 101, 1277 (1997); R. Vogt, P. J. Crutzen, R. Sander, Mature 383, 327 (1996); A. A. P. Pszenny ef al., Geophys. Res. Lett. 20, 699 (1993); (6).
13. See, for example, A. R. Ravishankara, Science 276, 1058 (1997); S. Langer, R. S. Pemberton, B. J. Finlayson-Pitts, J. Phys. Chem. A 101, 1277 (1997); R. Vogt, P. J. Crutzen, R. Sander, Mature 383, 327 (1996); A. A. P. Pszenny ef al., Geophys. Res. Lett. 20, 699 (1993); (6).
14. See, for example, A. R. Ravishankara, Science 276, 1058 (1997); S. Langer, R. S. Pemberton, B. J. Finlayson-Pitts, J. Phys. Chem. A 101, 1277 (1997); R. Vogt, P. J. Crutzen, R. Sander, Mature 383, 327 (1996); A. A. P. Pszenny ef al., Geophys. Res. Lett. 20, 699 (1993); (6).
15. See, for example, A. R. Ravishankara, Science 276, 1058 (1997); S. Langer, R. S. Pemberton, B. J. Finlayson-Pitts, J. Phys. Chem. A 101, 1277 (1997); R. Vogt, P. J. Crutzen, R. Sander, Mature 383, 327 (1996); A. A. P. Pszenny ef al., Geophys. Res. Lett. 20, 699 (1993); (6).
16. E. E. Gard et al., Anal. Chem. 69, 4083 (1997) and references therein.
17. D. M. Murphy and D. S. Thomson, J. Geophys. Res. 102, 6341 (1997); P. G. Carson, M. V. Johnston, A. S. Wexler, Aerosol Sci. Technol. 26, 291 (1997); M. Weiss, P. J. T. Verheijen, J. C. M. Marijnissen, B. Scarlett, J. Aerosol Sci. 28, 159 (1997); P. Reilly, R. Gieray, M. Yang, W. Whitten, J. M. Ramsey, Anal. Chem. 69, 36 (1997); K. P. Hinz, R. Kaufman, B. Spengler, Aerosol Sci. Technol. 24, 233 (1996).
18. D. M. Murphy and D. S. Thomson, J. Geophys. Res. 102, 6341 (1997); P. G. Carson, M. V. Johnston, A. S. Wexler, Aerosol Sci. Technol. 26, 291 (1997); M. Weiss, P. J. T. Verheijen, J. C. M. Marijnissen, B. Scarlett, J. Aerosol Sci. 28, 159 (1997); P. Reilly, R. Gieray, M. Yang, W. Whitten, J. M. Ramsey, Anal. Chem. 69, 36 (1997); K. P. Hinz, R. Kaufman, B. Spengler, Aerosol Sci. Technol. 24, 233 (1996).
19. D. M. Murphy and D. S. Thomson, J. Geophys. Res. 102, 6341 (1997); P. G. Carson, M. V. Johnston, A. S. Wexler, Aerosol Sci. Technol. 26, 291 (1997); M. Weiss, P. J. T. Verheijen, J. C. M. Marijnissen, B. Scarlett, J. Aerosol Sci. 28, 159 (1997); P. Reilly, R. Gieray, M. Yang, W. Whitten, J. M. Ramsey, Anal. Chem. 69, 36 (1997); K. P. Hinz, R. Kaufman, B. Spengler, Aerosol Sci. Technol. 24, 233 (1996).
20. D. M. Murphy and D. S. Thomson, J. Geophys. Res. 102, 6341 (1997); P. G. Carson, M. V. Johnston, A. S. Wexler, Aerosol Sci. Technol. 26, 291 (1997); M. Weiss, P. J. T. Verheijen, J. C. M. Marijnissen, B. Scarlett, J. Aerosol Sci. 28, 159 (1997); P. Reilly, R. Gieray, M. Yang, W. Whitten, J. M. Ramsey, Anal. Chem. 69, 36 (1997); K. P. Hinz, R. Kaufman, B. Spengler, Aerosol Sci. Technol. 24, 233 (1996).
21. D. M. Murphy and D. S. Thomson, J. Geophys. Res. 102, 6341 (1997); P. G. Carson, M. V. Johnston, A. S. Wexler, Aerosol Sci. Technol. 26, 291 (1997); M. Weiss, P. J. T. Verheijen, J. C. M. Marijnissen, B. Scarlett, J. Aerosol Sci. 28, 159 (1997); P. Reilly, R. Gieray, M. Yang, W. Whitten, J. M. Ramsey, Anal. Chem. 69, 36 (1997); K. P. Hinz, R. Kaufman, B. Spengler, Aerosol Sci. Technol. 24, 233 (1996).
22. M. J. Kleeman et al., J. Geophys. Res. 102, 21355 (1997).
23. L. Hughes et al., in preparation.
24. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
25. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
26. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
27. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
28. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
29. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
30. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
31. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
32. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
33. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
34. See, for example, P. Beichert and B. J. FinlaysonPitts, J. Phys. Chem. 100, 15218 (1996); R. Vogt et al., Atmos. Environ. 30, 1729 (1996); R. Karisson and E. Ljungstrom, J. Aerosol Sci. 26, 39 (1995); M. T. Leu, R. S. Timonen, L. F. Keyser, Y. L. Yung, J. Phys. Chem. 99, 13203 (1995); R. Vogt and B. J. Finlayson-Pitts, Geophys. Res. Left. 21, 2291 (1994); J. M. Laux, J, C. Hemminger, B. J. Finlayson-Pitts, ibid., p. 1623; F. F. Fenter, F. Caloz, M. J. Rossi, J. Phys. Chem. 98, 9801 (1994); W. Behnke, V. Scheer, C. Zetzsch, J. Aerosol Sci. 24, S115 (1993); Y. Mamane and J. Gottlieb, ibid. 21, S225 (1990); B. J. Finlayson-Pitts, M. J. Ezell, J. N. Pitts Jr., Nature 337, 241 (1989); F. Bruynseels and R. Van Grieken, Atmos. Environ. 19, 1969 (1985).
35. + can be compared to that in sea water with use of the empirical relative sensitivity factor (RSF) measured by D. S. Gross, M. E. Gälli, and K. A. Prather (in preparation). Although the sea-salt particles are identified strictly on the basis of composition, they also have a characteristic aerodynamic diameter greater than 1.0 μm, which helps corroborate their source.
36. Previous models of urban aerosol properties as a computational approximation generally treat all atmospheric particles of the same size as having the same chemical composition and thus cannot differentiate sea-salt particles explicitly from other particles of similar size. See (10) for a discussion of the representation of particle size and composition in modeling calculations.
37. W. R. Goodin et al., J. Appl. Meteorol. 18, 761 (1979).
38. Within the model, the air parcels begin over the ocean with regional background aerosol as measured during the Southern California Air Quality Survey (SCAQS) experiments conducted in Los Angeles in 1987, and they pick up sea-salt aerosol at the concentrations measured during SCAQS as they cross the surf zone at the coastline (10). As the air parcels pass over land, emissions from the urban sources in Los Angeles are inserted into the model on the basis of the 1996 emissions inventory maintained by the South Coast Air Quality Management District, modified according to the procedures of A. Eldering and G. R. Cass [J. Geophys. Res. 101, 19343 (1996)]. The same initial conditions for sea salt are used for each trajectory even though there must be hour-to-hour variations; for that reason, we do not expect exact agreement between predictions and observations at Long Beach.
39. The upper limit of 2.5 μm for particle diameter was chosen as the best match between the size bins used to track particles in the model calculation and the inherent transmission efficiency of the ATOFMS inlet nozzle, which transmits particles below ∼3 μm with high efficiency.
40. We thank R. A. Carlin, D.-Y. Liu, C. A. Noble, P. J. Silva, and S. H. Wood for assistance with ATOFMS data acquisition. In addition, we are grateful to R. Williams and M. Berg at California State University at Long Beach and B. Gill at California State University at Fullerton for use of their facilities. Funding (University of California at Riverside) was provided by the California Air Resources Board (ARB contract 95-305). Funding (California Institute of Technology) was provided by grants from the U.S. Environmental Protection Agency (EPA grant R824970-01-0) and from the California Institute of Technology Center for Air Quality Analysis.