References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-7-4589-2007

Seasonal variation of peroxyacetylnitrate (PAN) in coastal Antarctica measured with a new instrument for the detection of sub-part per trillion mixing ratios of PAN

Mills

G. P.

¹ Sturges

W. T.

¹ Salmon

R. A.

² Bauguitte

S. J.-B.

² Read

K. A.

³ Bandy

B. J.

School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, UK

British Antarctic Survey, Maddingley Road, Cambridge, UK

Department of Chemistry, University of York, Heslington, York YO19 4RR, UK

07 09 2007

7 17 4589 4599

2007

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An automated gas chromatograph with sample pre-concentration for the measurement of peroxyacetylnitrate (PAN) was constructed with a minimum detection limit below 1 pptv. This instrument was deployed at the British Antarctic Survey's Halley Research Station, Antarctica (75.6° S, 26.6° W) as part of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign. Hourly measurements were carried out between July 2004 and February 2005 with observed maximum and minimum mixing ratios of 52.3 and <0.6 pptv, respectively with a mean PAN mixing ratio for the measurement period of 9.2 pptv (standard deviation: 6.2 pptv). The changes in PAN mixing ratios typically occurred over periods of several days to a week and showed a strong similarity to the variation in alkenes. The mixing ratio of PAN at Halley has a possible seasonal cycle with a winter maximum and summer minimum, though the cycle is incomplete and the data are very variable. Calculations indicate that gross local PAN production is approximately 1 pptv d−1 in spring and 0.6 pptv d−1 in summer. Net loss of PAN transported to Halley in the summer is a small gas-phase source of NOx and net production of PAN in the spring is a very small NOx sink.

References 1

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Part 1 – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, 2004

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, 2006

Barker, J. R., Benson, S. W., Mendenhall, G. D., and Goldern, D. M.: Measurement of rate constants of importance in smog, Rep. PB-274530, Natl. Tech. Inf. Serv., Springfield, Va., 1977.

Beine, H. J. and Krognes, T.: The seasonal cycle of peroxyacetyl nitrate (PAN) in the European Arctic, Atmos. Environ., 34, 933–940, 2000.

Bloss, W., Lee, J., Heard, D., Salmon, R., Bauguitte, S., Roscoe, H., and Jones, A.: Observations of OH and HO2 radicals in coastal Antarctica, Atmos. Chem. Phys., 7, 4171–4185, 2007

Bottenheim, J. W. and Gallant, A. J.: PAN over the Arctic; Observations during AGASP-2 in april 1986, J. Atmos. Chem., 9 , 301–316, 1989

Bridier, I., Caralp, F., Loirat, H., Lesclaux, R. Veyret, B., Becker, K. H., Reimer, A., and Zabel,~F.: Kinetic and theoretical studies of the reactions CH3C(O)O2 + NO2 +M = CH3C(O)O2NO2 + M between 248 and 393 K and between 30 and 760 Torr., J. Phys. Chem., 95, 3594, 1991.

Brough, N., Reeves, C. E., Penkett, S. A., Dewey, K., Kent, J., Barjat, H., Monks, P. S., Ziereis, H., Stock, P., Huntrieser, H., and Schlager, H.: Intercomparison of aircraft instruments on board the C-130 and Falcon 20 over southern Germany during EXPORT 2000, Atmos. Chem. Phys., 3, 2127–2138, 2003.

Crutzen, P. J.: The role of NO and NO2 in the chemistry of the troposphere and the stratosphere, Ann. Rev. Earth Planet. Sci., 7, 443–472, 1979.

Dassau, T. M., Shepson, P. B., Bottenheim, J. W., and Ford, K. M.: Peroxyacetyl nitrate photochemistry and interactions with the arctic surface, J. Geophys. Res., 109, D18302, https://doi.org/10.1029/2004JD004562, 2004.

Flocke, F. M., Weinheimer, A. J., Swanson, A. L., Roberts, J. M., Schmitt, R., and Shertz, S.: On the measurement of PANs by Gas Chromatography and Electron Capture Detection., J. Atm. Chem 52, 19–43, 2005.

Gaffney, J. S., Marley, N. A., Cunningham, M. M., and Doskey, P. V.: Measurements of peroxyacyl nitrates (PANS) in Mexico City: Implications for megacity air quality impacts on regional scales, Atmos. Environ., 33(30), 5003–5012, 1999.

Gallagher, M. S., Carsey, T. P., and Farmer, M. L.: Peroxyacetyl nitrate in the North Atlantic marine boundary layer, Global Biogeochem. Cycles, 4(3), 297–308, 1990.

Hudman, R. C., Jacob, D. J., Cooper, O. R., Evans, M. J., Heald, C. L., Park, R. J., Fehsenfeld, F., Flocke, F., Holloway, J., Hubler, G., Kita, K., Koike, M., Kondo, Y., Neuman, A., Nowak, J., Oltmans, S., Parrish, D., Roberts, J. M., and Ryerson, T.: Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California, J. Geophys. Res., 109(23), 1–14, 2004.

Jacobi, H.-W. and Schrems, O.: Peroxyacetyl nitrate (PAN) distribution over the South Atlantic ocean., Phys. Chem. Chem. Phys.1, 5517–5521, 1999.

Jacobi, H.-W., Weller, R., Jones, A. E., Anderson, P. S., and Schrems, O.: Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99), Atmos. Environ., 34, 5235–5247, 2000.

Jones, A. E., Weller, R., Minikin, A., Wolff, E. W., Sturges, W. T., McIntyre, H. P., Leonard, S. R., Schrems, O., and Bauguitte, S.: Oxidized nitrogen chemistry and speciation in the Antarctic troposphere, J. Geophys. Res. D: Atmos., 104(D17), 21 355–21 366, 1999.

King, J. C.: Low-level wind profiles at an Antarctic coastal station, Antarctic Science, 1(2), 169–178, 1985.

Kotchenruther, R. A., Jaffe, D. A., Beine, H. J., Anderson, T. L., Bottenheim, J. W., Harris, J. M., Blake, D. R., and Schmitt, R.: Observations of ozone and related species in the northeast Pacific during the PHOBEA campaigns, 2, Airborne observations, J. Geophys. Res., 106(D17), 20 507–20 508, 2001.

Leighton, P. A.: Photochemistry of Air Pollution, Elsevier, New York, 1961.

Madronich, S. and Flocke,S.: The role of solar radiation in atmospheric chemistry, in: Handbook of Environmental Chemistry, edited by: Boule, P., Springer_Verlag, Heidelberg, pp. 1-26, 1988.

Moortgat, G. K., Veyret, B., and Lesclaux, R.: Kinetics of the reaction of HO$_2 $withCH3C(O)O2 in the temperature range 253–368 K, Chem. Phys. Lett., 160, 443, 1989.

Muller, K. P. and Rudolph, J.: Measurements of peroxyacetylnitrate in the marine boundary layer over the Atlantic, J. Atmos. Chem., 15, 361–367, 1992.

Rappengluck, B., Oyola, P., Olaeta, I., and Fabian, P.: The evolution of photochemical smog in the Metropolitan Area of Santiago de Chile, J. Appl. Meteorol., 39(3), 275–290, 2000.

Read, K. A., Lewis, A. C., Salmon, R. A., Jones, A. E., and Bauguitte, S.: OH and halogen atom influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer, Tellus, 59B, 22–38. 2007.

Renfrew, I. A. and Anderson, P. S.: The surface climatology of an ordinary katabatic wind regime in Coats Land, Antarctica, Tellus, Ser. A: Dyn. Meteorol. Oceanogr., 54(5), 463–484, 2002.

Ridley, B. A., Shetter, J. D., Walega, J. G., Madronich, S., Elsworth, C. M., Grahek, F. E., Fehsenfeld, F. C., Norton, R. B., Parrish, D. D., Huebler, G., Buhr, M., Williams, E. J., Allwine, E. J., and Westberg, H. H.: The behavior of some organic nitrates at Boulder and Niwot Ridge, Colorado, J. Geophys. Res., 95, 13 949–13 961, 1990.

Roberts, J. M.: Atmospheric chemistry of organic nitrates, Atmos. Environ., 24A, 243–287, 1990.

Roberts, J. M. and Bertman, S. B.: The thermal decomposition of peroxyacetic nitric anhydride (PAN) and peroxymetacrylic nitric anhydride (MPAN), Int. J. Chem. Kinet., 24, 297–307, 1992.

Roberts, J. M., Jobson, B. T., Kuster, W., Goldan, P., Murphy, P., Williams, E., Frost, G., Riemer, D., Apel, E., Stroud, C., Wiedinmyer, C., and Fehsenfeld, F.: An examination of the chemistry of peroxycarboxylic nitric anhydrides and related volatile organic compounds during Texas Air Quality Study 2000 using ground-based measurements, J. Geophys. Res., 108(16), ACH 4-1–ACH 4-12, 2003.

Roberts, J. M., Flocke, F., Chen, G., de Gouw, J., Holloway, J. S., Hubler, G., Neuman, J. A., Nicks, D. K., Nowak, J. B., Parrish, D. D., Ryerson, T. B, Sueper, D. T., Warneke, C., Fehsenfeld, F. C.: Measurement of peroxycarboxylic nitric anhydrides (PANs) during the ITCT 2K2 aircraft intensive experiment, J. Geophys. Res., 109, D23S21, https://doi.org/10.1029/2004JD004960, 2004

Rudolph, J., Vierkorn-Rudplph, B., and Meixner, F. X.: Large-scale distribution of peroxyacetylnitrate results from the STRATOZ III flights, J. Geophys. Res., 92, 6653–6661, 1987.

Staudt, A. C., Jacob, D. J., Ravetta, F., Logan, J. A., Bachiochi, D., Sandholm, S., Ridley, B., Singh, H. B., and Talbot, B.: Sources and chemistry of nitrogen oxides over the tropical Pacific., J. Geophys. Res., 108(2),PEM 11-1–PEM 11-17, 2003.

Singh, H. B. and Hanst, P. L.: Peroxyacetyl nitrate (PAN) in the unpolluted atmosphere: an important reservoir for nitrogen oxides, Geophys. Res. Lett., 8, 941–944., 1981.

Sivakumaran, V. and Crowley, J. N.: Reaction between OH and CH3CHO Part 2. Temperature dependent rate coefficients (201–348 K), Phys. Chem. Chem. Phys., 5, 106–111, 2003

Talukdar, R. K., Burkholder, J. B., Schmoltner, A.-M., Roberts, J. M., Wilson, R. R., and Ravishankara, A. R.: Investigation of the loss processes for peroxyacetyl nitrate in the atmosphere:UV photolysis and reaction with OH, J. Geophys. Res., 100(D7), 14 163–14 173, 1995.

Warneck, P. and Zerbach, T.: Synthesis of peroxyacetyl nitrate in air by acetone photolysis, Environ. Sci. Technol. 26, 74–79, 1992.

Villalta, P. W. and Howard, C. J.: Direct kinetic study of the CH3C(O)O$_2 $+ NO reaction using chemical ionisation mass spectrometry, J. Phys. Chem. 100, 13 624–13 628, 1996.