References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-6-5415-2006

Seasonal dependence of peroxy radical concentrations at a Northern hemisphere marine boundary layer site during summer and winter: evidence for radical activity in winter

Fleming

Z. L.

¹ Monks

P. S.

¹ Rickard

A. R.

¹ ³ Bandy

B. J.

² Brough

² Green

T. J.

² Reeves

C. E.

² Penkett

S. A.

Department of Chemistry, University of Leicester, Leicester, UK

School of Environmental Sciences, University of East Anglia, Norwich, UK

now at: Department of Chemistry, University of Leeds, Leeds, UK

05 12 2006

6 12 5415 5433

2006

This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Generic License. To view a copy of this licence, visit https://creativecommons.org/licenses/by-nc-sa/2.5/

This article is available from https://acp.copernicus.org/articles/6/5415/2006/acp-6-5415-2006.html

The full text article is available as a PDF file from https://acp.copernicus.org/articles/6/5415/2006/acp-6-5415-2006.pdf

Peroxy radicals (HO2+Σ RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state.

References 1

Atkinson, R.: Atmospheric chemistry of VOCs and NOx, Atmos. Environ., 34, 2063–2101, 2000.

Bey, I., Aumont, B., and Toupance, G.: A modelling study of the nighttime radical chemistry in the lower continental troposphere 1. Development of a detailed chemical mechanism including nighttime chemistry, J. Geophys. Res., 106, 9959–9990, 2001.

Brönnimann, S.: Early spring ozone episodes: Occurrence and case study, Phys. Chem. Earth Part C, 24, 531–536, 1999

Brough, N., Reeves, C. E., Penkett, S. A., Stewart, D. J., Dewey, K., Kent, J., Barjat, H., Monks, P. S., Ziereis, H., Stock, P., Huntrieser, H., and Schlager, H.: Intercomparisons of aircraft instruments on board the C-130 and Falcon 20 over southern Germany during EXPORT 2000, Atmos. Chem. Phys., 5, 2127–2138, 2003.

Burkert, J., Andrés-Hernández, M. D., Reichert, L., Meyer-Arnek, J., Doddridge, B., Dickerson, R. R., Mühle, J., Zahn, A., Carsey, T., and Burrows, J. P.: Trace gas and radical diurnal behaviour in the marine boundary layer during INDOEX 1999, J. Geophys. Res, 108, 8000, https://doi.org/10.1029/2002JD002790, 2003.

Cantrell, C. A., Stedman, D. H., and Wendel, G. J.,: Measurement of atmospheric peroxy radicals by chemical amplification, Anal. Chem., 56, 1496–1502, 1984.

Cantrell, C. A., Shetter, R. E., and Calvert, J. G.: Dual-inlet Chemical amplifier for atmospheric peroxy radical measurements, Anal. Chem., 58, 4194–4199, 1996.

Cantrell, C. A., Edwards, G. D., Stephens, S., Mauldin, L., Kosciuch, E., Zondlo, M., and Eisele, F.: Peroxy radical observations using chemical ionisation mass spectrometrey during TOPSE, J. Geophys. Res., 108, 8371, https://doi.org/10.1029/2002JD002715, 2003.

Cardenas, L. M., Austin, J. F., Burgess, R. A., Clemitshaw, K. C., Dorling, S., Penkett, S. A., and Harrison, R. M.: Correlation between CO, NOy, O3 and non-methane hydrocarbons and their relationships with meteorology during winter 1993 on the North Norfolk coast, UK, Atmos. Environ., 32, 3339–3351, 1998.

Carpenter, L. J., Clemitshaw K. C., Burgess R. A., Penkett S. A., Cape J. N., and McFadyen G. C.: Investigation and evaluation of the NOx/O3 photochemical steady state, Atmos. Environ., 32, 3353–3365, 1998.

Carslaw, N., Carpenter, L. J., Plane, J. M. C.., Allan, B. J., Burgess, R. A. Clemitshaw, K. C., Coe, H., and Penkett, S. A.: Simultaneous observations of nitrate and peroxy radicals in the marine boundary layer, 1. Model construction and comparison with field measurements, J. Geophys. Res., 102, 18 917–18 933, 1997.

Clemitshaw, K. C. and Penkett, S. A.: TOR station number 7: The Weybourne atmospheric observatory, in: The TOR network. A description of TOR Measurement Stations, edited by: Cvitas, T. and Kley, D., EUROTRAC International Scientific Secretariat Garmisch Partenkirchen, 59–63, 1994.

Clemitshaw, K. C., Carpenter, L. J., Penkett, S. A., and Jenkin, M. E.: A calibrated peroxy radical chemical amplifier (PERCA) for ground-based measurements in the troposphere, J. Geophys. Res., 102, 25 405–25 416, 1997.

Derwent, R. G., Simmonds, P. G., Seuring, S., and Dimmer, C: Observation and interpretation of the seasonal cycles in the surface concentrations of ozone and carbon monoxide at Mace Head, Ireland from 1990 to 1994, Atmos. Env., 32, 145–157, 1998.

Edwards, G. D. and Monks, P. S.: Performance of a single monochromator diode array spectrradiometer for the determination of actinic flux and atmospheric frequencies, J. Geophys. Res., 108, 8546–8558, 2003.

Fleming, Z. L., Monks, P. S., Rickard, A. R., Heard, D. E., Bloss, W. J., Seakins, P. W., Still, T. J., Sommariva, R., Pilling, M. J., Morgan, R., Green, T. J., Brough, N., Penkett, S. A., Lewis, A. C., Lee, J. D., Saiz-Lopez A., and Plane, J. M. C.: Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002, Atmos. Chem. Phys., 6, 2193–2214, 2006.

Geyer, A., Bächmann, K., Hofzumahaus, A., Holland, F., Konrad, S., Klüpfel, T., Pätz, H.-W., Perner, D., Mihelcic, D., Schäfer, H.-J., Volz-Thomas, A., and Platt, U.: Nighttime formation of peroxy and hydroxyl radicals during the BERLIOZ campaign: Observations and modelling studies, J. Geophys. Res., 108, 8249, https://doi.org/10.1029/2001JD000656, 2003.

Green, T. J., Brough, N., Reeves, C. E., Edwards, G. D., Monks, P. S., and Penkett, S. A.: Airborne measurements of peroxy radicals using the PERCA technique, J. Environ. Monitoring, 5, 75–83, 2003.

Green, T. J., Reeves, C. E., Fleming, Z., Brough, N., Rickard, A. R., Bandy, B. J., Monks, P. S., and Penkett, S. A.: An Improved Dual Channel PERCA Instrument for Atmospheric Measurements of Peroxy Radicals, J. Environ. Monitoring, 8, 530–536, 2006.

Heard D. E. and Pilling, M. J.: The hydroxyl radical, Chem. Rev., 103, 5163–5198, 2003.

Heard, D. E., Carpenter, L. J., Creasey D. J., Hopkins, J. R., Lee, J. D., Lewis, A. C., Pilling, M. J., Seakins, P. W., Carslaw, N., and Emmerson, K. M.; High levels of the hydroxyl radical in the winter urban troposphere, Geophys. Res. Lett., 31, L18112, https://doi.org/10.1029/2004GL020544, 2004.

Hernández, M. D. A., Burkert, J., Reichert, L., Stöbener, D., Meyer-Arnek, J., Burrows, J. P., Dickerson, R. R., and Doddridge, B. G.: Marine boundary layer peroxy radical chemistry during the AEROSOLS99 campaign: Measurements and analysis, J. Geophys. Res., 106, 20 833–20 846, https://doi.org/10.1029/2001JD900113, 2001.

Hofzumahaus, A., Lefer, B. L., Monks, P. S., Hall, S. R., Kylling, A., Mayer, B., Shetter, R. E., Junkerman, W., Bais, A., Calvert, J. G., Cantrell, C. A., Madronich, S., Edwards, G. D., Kraus, A., Müller, M., Bohn, B., Schmitt, R., Johnston, P., McKenzie, R., Frost, G. J., Griffioen, E., Krol, M., Martin, T., Pfister, G., Röth E.P., Ruggaber A., Swartz, W. H., Lloyd, S. A., and VanWeele, M.: Photolysis frequency of O3 to O($^1$D): Measurements and modelling during the International Photolysis Frequency Measurement and Modelling Intercomparison (IPMMI), J. Geophys. Res., 109, D08S90, https://doi.org/10.1029/2003JD004333, 2004.

Holland, F., Hofzumahaus, A., Schäfer, J., Kraus, A., and Pätz, H.-W.: Measurements of OH and HO2 radical concentrations and photolysis frequencies during BERLIOZ, J. Geophys. Res., 108, 8246–8267, 2003.

Klonecki, A. A. and Levy II, H.: Tropospheric chemical ozone tendencies in CO-CH4-NOy-H2O system: Their sensitivity to variations in environmental parameters and their application to a global chemistry transport model study, J. Geophys. Res., 102, 21 221–21 237, 1997.

Leighton, P. A.: Photochemistry of air pollution, Academic, San Diego, California, 1961.

Liu, S. C., Kley, D., McFarland, M., Mahlman, M. D., and Levy, H.: On the origin of tropospheric ozone, J. Geophys. Res., 85, 7546–7552, 1980.

Logan, J. A., Prather, M. J., Wofsy, S. C., and McElroy, M. B.: Tropospheric chemistry: A global perspective, J. Geophys. Res., 86, 7210–7254, 1981.

Mannschreck, K., Gilge, S., Plass-Dülmer, C., Fricke, W., and Berresheim, H.: Assessment of the applicability of NO-NO2-O3 photostationary state to long-term measurements at the Hohenpeissenberg GAW station, Germany, Atmos. Chem. Phys., 4, 1265–1277, 2004.

Mihelcic, D., Holland, F., Hofzumahaus, A., Hoppe, L., Konrad, S., Müsgen, P., Pätz, H.-W., Schäfer, H.-J., Schmitz, T., Volz-Thomas, A., Bächmann, K., Schlonski, S., Platt, U., Geyer, A., Alicke, B., and Moorgat, G. K.: Peroxy radicals during BERLIOZ at Pabstthum: Measurements, radical budgets and ozone production, J. Geophys. Res., 108, 8254–8268, 2003.

Mihele, C. M. and Hastie, D. R.: The sensitivity of the amplifier to ambient water vapour, Geophys. Res. Lett., 25, 1911–1913, 1998.

Mihele, C. M., Mozurkewich, M., and Hastie, D. R.: Radical loss in a chain reaction of CO and NO in the presence of water: Implications for the radical amplifier and atmospheric chemistry, Int. J. Chem. Kin., 31, 145–152, 1999.

Monks, P. S., Carpenter, L. J., Penkett, S. A., Ayers, G. P., Gillett, R. W., Galbally, I. E., and Meyer, C. P.: Fundamental ozone photochemistry in the remote boundary layer: The SOAPEX experiment, measurement and theory, Atmos. Environ., 32, 3647–3664, 1998.

Monks, P. S.: A review of the observations and origins of the spring ozone maximum, Atmos. Env., 34, 3545–3561, 2000.

Monks, P. S., Holland, G. Salisbury, G. Penkett, S. A., and Ayers, G. P.: A seasonal comparison of ozone photochemistry in the remote marine boundary layer, Atmos. Env., 34, 2547–2561, 2000.

Monks, P. S.: Chapter 6: Tropospheric photochemistry, "Handbook of Atmospheric science: Principle and Application", edited by: Hewitt, C. N. and Jackson, A. V., Blackwell Publishing, Oxford, 2003.

Monks, P. S., Rickard, A. R., and Hall, S. L.: Attenuation of spectral actinic flux and photolysis frequencies at the surface through homogeneous cloud fields, J. Geophys. Res., 109, D17206, https://doi.org/10.1029/2003JD004076, 2004.

Monks, P. S.: Gas-phase radical chemistry in the troposphere, Chem. Soc. Rev., 34, 376–395, 2005.

Penkett, S. A., Monks, P. S., Carpenter, L. J., and Clemitshaw, K. C.: Relationships between ozone photolysis rates and peroxy radical concentrations in clean air over the Southern Ocean, J. Geophys. Res., 102, 12 805–12 817, 1997.

Penkett, S. A., Clemitshaw, K. C., Savage, N. H., Burgess, R. A., Cardenas, L. M., Carpenter, L. J., McFadyen, G. G., and Cape, J. N.: Studies of oxidant production at the Weybourne Atmospheric Observatory in summer and winter conditions, J. Atmos. Chem., 33, 111–128, 1999.

Reeves, C. E., Penkett, S. A., Bauguitte, S., Law, K. S., Evans, M. J., Bandy, B. J., Monks, P. S., Edwards, G. D., Phillips, G., Barjat, H., Kent, J., Dewey, K., Schmitgen, S., and Kley, D.: Potential for Photochemical Ozone Formation in the Troposphere over the North Atlantic as derived from Aircraft Observations during ACSOE, J. Geophys. Res. (Atmos)., 107, 4707, https://doi.org/10.1029/2002JD002415, 2002.

Ridley, B. A., Madronich, S., Chatfield, R. B., Walega, J. G., Shetter, R. E., Carroll, M. A., and Montzka, D. D.: Measurements and model simulations of the phototstationary state during Mauna Loa Observatory Photochemistry Experiment: Implications for radical concentrations and ozone production and loss rates, J. Geophys. Res., 97, 10 375–10 388, 1992.

Salisbury, G.: Measurement of peroxy radicals in the marine boundary layer, Ph.D. thesis, University of Leicester, 2001.

Salisbury, G., Rickard, A. R., Monks, P. S., Allan, B. J., Bauguitte, S., Penkett, S. A., Carslaw, N., Lewis, A. C., Creasy, D. J., Heard, D. E., Jacobs, P. J., and Lee, J. D.: Production of peroxy radicals at night via reactions of ozone and the nitrate radical in the marine boundary layer, J. Geophys. Res., 106, 12 669–12 687, 2001.

Salisbury, G., Monks, P. S., Bauguitte, S. Bandy, B. J., and Penkett, S. A.: A seasonal comparison of the ozone photochemistry in clean and polluted air masses at Mace Head, Ireland, J. Atmos. Chem., 41, 163–187, 2002.

Seroji, A., Webb, A., Coe, H., Monks, P. S., and Rickard, A. R.: A comparison between the derived photolysis rates of O3, NO2 and CH2O from GUV-541 radiometer with the photolysis rates measured by a spectroradiometer and filter radiometers, J. Geophys. Res., 109, D21307, https://doi.org/10.1029/2003JD004674, 2004.

Shetter, R. E., Junkermann, W., Swartz W. H., Frost, G. J., Crawford, J. H., Lefer, B. L., Barrick, J. D., Hall, S. R., Hofzumahaus, A., Bais, A., Calvert, J. G., Cantrell, C. A., Madronich, S., Müller, M., Kraus, A., Monks, P. S., Edwards, G. D., McKenzie, R. Johnston, P., Schmitt, R., Griffioen, E., Krol, M., Kylling, A., Dickerson, R. R., Lloyd, S. A., Martin, T., Gardiner, B., Mayer, B., Pfister, G., Röth, E.-P., Köpke, P., Ruggaber, A., Schwander, H., and van Weele, M.: Photolysis frequency of NO2: Measurement and modeling during the International Photolysis Frequency Measurement and Modeling Intercomparison (IPMMI), J. Geophys. Res., 108, 8544, https://doi.org/10.1029/2002JD002932, 2003.

Sillman, S. and He, D.: Some theoretical results concerning O3-NOx-VOC chemistry and NOx-VOC indicators, J. Geophys. Res., 107, 4659–4672, 2002.

Solberg, S., Dye, C., Walker, S.-M., and Simpson, D.: Long-term measurements and model calculations of formaldehyde at rural European monitoring sites, Atmos. Environ., 35, 195–207, 2001.

Stroud, C., Madronich, S., Atlas, E., Cantrell, C., Fried, A., Wert, B., Ridley, B., Eisele, F., Mauldin, L., Shetter, R., Lefer, B., Flocke, F., Weinheimer, A., Coffey, M., Heikes, B., Talbot, R., and Blake, D.: Photochemistry in the Arctic Free Troposphere: Ozone Budget and Its Dependence on Nitrogen Oxides and the Production Rate of Free Radicals, J. Atmos. Chem., 47, 107–138, 2004.

Yang, J., Honrath, R. E., Peterson, M. C., Dibb, J. E., Sumner, A. L., Shepson, P. B., Frey, M., Jacobi, H.-W., Swanson, A., and Blake, N.: Impacts of snow pack emissions on deduced levels of OH and peroxy radicals at Summit, Greenland, Atmos. Environ., 36, 2523–2534, 2002.

Yang, J., Honrath, R. E., Peterson, M. C., Parrish, D. D., and Warshawsky, M.: Photostationary state deviation-estimated peroxy radicals and their implications for HO$_x$ and ozone photochemistry at a remote northern Atlantic coastal site, J. Geophys. Res., 109, D02312, https://doi.org/10.1029/2003JD003983, 2004.

Yienger, J. J., Klonecki, A. A., Levy, H., Moxim, W. J., and Carmichael, G. R.: An evaluation of chemistry's role in the winter-spring ozone maximum found in the northern mid-latitude free troposphere, J. Geophys. Res., 104, 3655–3667, 1999.

Volz-Thomas, A., Pätz, H.-W., Houben, N., Konrad, S., Mihelcic, D.,: Inorganic trace gases and peroxy radicals during BERLIOZ at Pabstthum: An investigation of the photostationary state of NOx and O3, J. Geophys. Res., 108, 8248, https://doi.org/10.1029/2001JD001255, 2003.

Zanis, P., Monks, P. S., Green, T. J., Schuepbach, E., Carpenter, L. J., Mills, G. P., Rickard, A. R., Brough, N., and Penkett, S. A.: Seasonal variation of peroxy radicals in the lower free troposphere based on observations from the FREE Tropospheric EXperiments in the Swiss Alps, Geophys. Res. Lett., 30, 1497, https://doi.org/10.1029/2003GL017122, 2003.

Zenker, T., Fischer, H., Nikitas, C., Parchatka, U., Harris, G. W., Mihelcic, D., Müsgen, P., Pätz, H. W., Schultz, M., Volz-Thomas, A., Schmitt, R., Behmann, T., Weissenmayer, M., and Burrows, J. P. :Intercomparison of NO, NO2, NOy, O3 and RO$_x$ measurements during the Oxidising Capacity of the Tropospheric Atmosphere (OCTA) campaign 1993 at Izana, J. Geophys. Res., 103, 13 615–13 634, 1998.