References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-9781-2010

Night-time chemistry above London: measurements of NO3 and N2O5 from the BT Tower

Benton

A. K.

¹ ⁵ Langridge

J. M.

¹ ⁶ Ball

S. M.

² Bloss

W. J.

³ Dall'Osto

³ ⁷ Nemitz

⁴ Harrison

R. M.

³ Jones

R. L.

Centre for Atmospheric Science, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK

Department of Chemistry, University of Leicester, University Road, Leicester, LE1 7RH, UK

National Centre for Atmospheric Science, School of Geography, Earth & Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, UK

Centre for Ecology and Hydrology (Edinburgh), Bush Estate, EH26 0QB, Penicuik, UK

now at: British Antarctic Survey, Natural Environment Research Council, High Cross, Madingley Road, Cambridge, CB3 0ET, UK

now at: Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado at Boulder, and NOAA Earth System Research Laboratory (ESRL), Boulder, Colorado, USA

now at: Instituto de Diagnóstico Ambiental y Estudios del Agua (IDAEA), Consejo Superior de Investigaciones Científicas (CSIC), C/ LLuis Solé i Sabarís s/n; 08028, Barcelona, Spain

19 10 2010

10 20 9781 9795

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.

This article is available from http://www.atmos-chem-phys.net/10/9781/2010/acp-10-9781-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/9781/2010/acp-10-9781-2010.pdf

Broadband cavity enhanced absorption spectroscopy (BBCEAS) has been used to measure the sum of concentrations of NO3 and N2O5 from the BT (telecommunications) Tower 160 m above street level in central London during the REPARTEE II campaign in October and November 2007. Substantial variability was observed in these night-time nitrogen compounds: peak NO3+N2O5 mixing ratios reached 800 pptv, whereas the mean night-time NO3+N2O5 was approximately 30 pptv. Additionally, [NO3+N2O5] showed negative correlations with [NO] and [NO2] and a positive correlation with [O3]. Co-measurements of temperature and NO2 from the BT Tower were used to calculate the equilibrium partitioning between NO3 and N2O5 which was always found to strongly favour N2O5 (NO3/N2O5=0.01 to 0.04). Two methods are used to calculate the lifetimes for NO3 and N2O5, the results being compared and discussed in terms of the implications for the night-time oxidation of nitrogen oxides and the night-time sinks for NOy.

References 1

% vor jede Referenz Aliwell, S. R. and Jones, R. L.: Measurements of tropospheric NO3 at midlatitude, J. Geophys. Res.-Atmos., 103, 5719–5727, 1998.

Allan, B. J., McFiggans, G., Plane, J. M. C., Coe, H., and McFadyen, G. G.: The nitrate radical in the remote marine boundary layer, J. Geophys. Res.-Atmos., 105, 24191–24204, 2000.

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

Ball, S. and Jones, R.: Broadband cavity ring-down spectroscopy, in: Cavity ring-down spectroscopy : techniques and applications, edited by: Berden, G. and Engeln, R., Wiley-Blackwell, Oxford, xix, 57–87, 2009.

Ball, S. M., Langridge, J. M., and Jones, R. L.: Broadband cavity enhanced absorption spectroscopy using light emitting diodes, Chem. Phys. Lett., 398, 68–74, 2004.

Barlow, J. F., Dobre, A., Smalley, R. J., Arnold, S. J., Tomlin, A. S., and Belcher, S. E.: Referencing of street-level flows measured during the DAPPLE 2004 campaign, Atmos. Environ., 43, 5536–5544, doi:10.1016/j.atmosenv.2009.05.021, 2009.

Barlow, J. F., Dunbar, T. M., Nemitz, E. G., Wood, C. R., Gallagher, M. W., Davies, F., O'Connor, E., and Harrison, R. M.: Boundary layer dynamics over London, UK, as observed using Doppler lidar, Atmos. Chem. Phys. Discuss., 10, 19901–19938, doi:10.5194/acpd-10-19901-2010, 2010.

Bertram, T. H. and Thornton, J. A.: Toward a general parameterization of N2O$_5$ reactivity on aqueous particles: the competing effects of particle liquid water, nitrate and chloride, Atmos. Chem. Phys., 9, 8351–8363, doi:10.5194/acp-9-8351-2009, 2009.

Bitter, M., Ball, S. M., Povey, I. M., and Jones, R. L.: A broadband cavity ringdown spectrometer for in-situ measurements of atmospheric trace gases, Atmos. Chem. Phys., 5, 2547–2560, doi:10.5194/acp-5-2547-2005, 2005.

Brown, S. S.: Absorption spectroscopy in high-finesse cavities for atmospheric studies, Chem. Rev., 103, 5219–5238, doi:10.1021/cr020645c, 2003.

Brown, S. S., Stark, H., and Ravishankara, A. R.: Applicability of the steady state approximation to the interpretation of atmospheric observations of NO3 and N2O$_5$, J. Geophys. Res.-Atmos., 108(D17), 4539, doi:10.1029/2003JD003407, 2003a.

Brown, S. S., Stark, H., Ryerson, T. B., Williams, E. J., Nicks, D. K., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nitrogen oxides in the nocturnal boundary layer: Simultaneous in situ measurements of NO3, N2O$_5$, NO2, NO, and O3, J. Geophys. Res.-Atmos., 108(D9), 4299, doi:10.1029/2002JD002917, 2003b.

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. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Nighttime removal of NOx in the summer marine boundary layer, Geophys. Res. Lett., 31(7), L07108, doi:10.1029/2004GL019412, 2004.

Brown, S. S., Osthoff, H. D., Stark, H., Dube, W. P., Ryerson, T. B., Warneke, C., de Gouw, J. A., Wollny, A. G., Parrish, D. D., Fehsenfeld, F. C., and Ravishankara, A. R.: Aircraft observations of daytime NO3 and N2O$_5$ and their implications for tropospheric chemistry, J. Photochem. Photobiol. a-Chem., 176, 270–278, 2005.

Brown, S. S., Dubé, W. P., Osthoff, H. D., Stutz, J., Ryerson, T. B., Wollny, A. G., Brock, C. A., Warneke, C., De Gouw, J. A., Atlas, E., Neuman, J. A., Holloway, J. S., Lerner, B. M., Williams, E. J., Kuster, W. C., Goldan, P. D., Angevine, W. M., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Vertical profiles in NO3 and N2O$_5$ measured from an aircraft: Results from the NOAA P-3 and surface platforms during the New England Air Quality Study 2004, J. Geophys. Res.-Atmos., 112(D22), D22304, doi:10.1029/2007jd008883, 2007a.

Brown, S. S., Dubé, W. P., Osthoff, H. D., Wolfe, D. E., Angevine, W. M., and Ravishankara, A. R.: High resolution vertical distributions of NO3 and N$-2$O$_5$ through the nocturnal boundary layer, Atmos. Chem. Phys., 7, 139–149, doi:10.5194/acp-7-139-2007, 2007b.

Crowley, J. N., Schuster, G., Pouvesle, N., Parchatka, U., Fischer, H., Bonn, B., Bingemer, H., and Lelieveld, J.: Nocturnal nitrogen oxides at a rural mountain-site in south-western Germany, Atmos. Chem. Phys., 10, 2795–2812, doi:10.5194/acp-10-2795-2010, 2010.

Dall'Osto, M., Harrison, R. M., Coe, H., Williams, P. I., and Allan, J. D.: Real time chemical characterization of local and regional nitrate aerosols, Atmos. Chem. Phys., 9, 3709–3720, doi:10.5194/acp-9-3709-2009, 2009.

Dentener, F. J. and Crutzen, P. J.: Reaction of N2O$_5$ on Tropospheric Aerosols – Impact on the Global Distributions of NOx, O3, and OH, J. Geophys. Res.-Atmos., 98, 7149–7163, 1993.

Dube, W. P., Brown, S. S., Osthoff, H. D., Nunley, M. R., Ciciora, S. J., Paris, M. W., McLaughlin, R. J., and Ravishankara, A. R.: Aircraft instrument for simultaneous, in situ measurement of NO3 and N2O$_5$ via pulsed cavity ring-down spectroscopy, Rev. Sci. Instrum., 77, , 034101–11, doi:10.1063/1.2176058, 2006.

Fiedler, S. E., Hese, A., and Ruth, A. A.: Incoherent broad-band cavity-enhanced absorption spectroscopy, Chem. Phys. Lett., 371, 284–294, 2003.

Fish, D. J., Shallcross, D. E., and Jones, R. L.: The vertical distribution of NO3 in the atmospheric boundary layer, Atmos. Environ., 33, 687–691, 1999.

Fuchs, H., Dube, W. P., Cicioira, S. J., and Brown, S. S.: Determination of inlet transmission and conversion efficiencies for in situ measurements of the nocturnal nitrogen oxides, NO3, N2O$_5$ and NO2, via pulsed cavity ring-down spectroscopy, Anal. Chem., 80, 6010–6017, 2008.

Geyer, A., Alicke, B., Konrad, S., Schmitz, T., Stutz, J., and Platt, U.: Chemistry and oxidation capacity of the nitrate radical in the continental boundary layer near Berlin, J. Geophys. Res.-Atmos., 106, 8013–8025, 2001.

Geyer, A. and Stutz, J.: Vertical profiles of NO3, N2O$_5$, O3, and NOx in the nocturnal boundary layer: 2. Model studies on the altitude dependence of composition and chemistry, J. Geophys. Res.-Atmos., 109(D16), D16399, doi:10.1029/2004jd005217, 2004.

Hallquist, M., Stewart, D. J., Baker, J., and Cox, R. A.: Hydrolysis of N2O$_5$ on submicron sulfuric acid aerosols, J. Phys. Chem. A, 104, 3984–3990, 2000.

Hammer, P. D., Dlugokencky, E. J., and Howard, C. J.: Kinetics of the Gas-Phase Reaction NO + NO$_3\to $2NO2, J. Phys. Chem., 90, 2491–2496, 1986.

Higbie, J.: Uncertainty in a Least-Squares Fit, Am. J. Phys., 46, 945–945, 1978.

Jones, R. L., Ball, S. M., and Shallcross, D. E.: Small scale structure in the atmosphere: implications for chemical composition and observational methods, Faraday Discuss., 130, 165–179, doi:10.1039/b502633b, 2005.

Langridge, J. M., Ball, S. M., and Jones, R. L.: A compact broadband cavity enhanced absorption spectrometer for detection of atmospheric NO2 using light emitting diodes, Analyst, 131, 916–922, 2006.

Langridge, J. M.: Development and atmospheric applications of a novel broadband cavity enhanced absorption spectrometer, Dept. of Chem., Univ. of Cambridge, Cambridge, 2008.

Langridge, J. M., Ball, S. M., Shillings, A. J. L., and Jones, R. L.: A broadband absorption spectrometer using light emitting diodes for ultrasensitive, in situ trace gas detection, Rev. Sci. Instrum., 79(12), 165–179, doi:10.1063/1.3046282, 2008a.

Langridge, J. M., Laurila, T., Watt, R. S., Jones, R. L., Kaminski, C. F., and Hult, J.: Cavity enhanced absorption spectroscopy of multiple trace gas species using a supercontinuum radiation source, Opt. Express, 16, 10178–10188, 2008b.

Langridge, J. M., Gustafsson, R. J., Griffiths, P. T., Cox, R. A., Lambert, R. M., and Jones, R. L.: Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?, Atmos. Environ., 43, 5128–5131, doi:10.1016/j.atmosenv.2009.06.046, 2009.

Lee, J. D., McFiggans, G., Allan, J. D., Baker, A. R., Ball, S. M., Benton, A. K., Carpenter, L. J., Commane, R., Finley, B. D., Evans, M., Fuentes, E., Furneaux, K., Goddard, A., Good, N., Hamilton, J. F., Heard, D. E., Herrmann, H., Hollingsworth, A., Hopkins, J. R., Ingham, T., Irwin, M., Jones, C. E., Jones, R. L., Keene, W. C., Lawler, M. J., Lehmann, S., Lewis, A. C., Long, M. S., Mahajan, A., Methven, J., Moller, S. J., Müller, K., Müller, T., Niedermeier, N., O'Doherty, S., Oetjen, H., Plane, J. M. C., Pszenny, A. A. P., Read, K. A., Saiz-Lopez, A., Saltzman, E. S., Sander, R., von Glasow, R., Whalley, L., Wiedensohler, A., and Young, D.: Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments, Atmos. Chem. Phys., 10, 1031–1055, doi:10.5194/acp-10-1031-2010, 2010.

Matsumoto, J., Imai, H., Kosugi, N., and Kaji, Y.: In situ measurement of N2O$_5$ in the urban atmosphere by thermal decomposition/laser-induced fluorescence technique, Atmos. Environ., 39, 6802–6811, 2005a.

Matsumoto, J., Kosugi, N., Imai, H., and Kajii, Y.: Development of a measurement system for nitrate radical and dinitrogen pentoxide using a thermal conversion/laser-induced fluorescence technique, Rev. Sci. Instrum., 76, 064101–11, doi:10.1063/1.1927098, 2005b.

McFiggans, G., Bale, C. S. E., Ball, S. M., Beames, J. M., Bloss, W. J., Carpenter, L. J., Dorsey, J., Dunk, R., Flynn, M. J., Furneaux, K. L., Gallagher, M. W., Heard, D. E., Hollingsworth, A. M., Hornsby, K., Ingham, T., Jones, C. E., Jones, R. L., Kramer, L. J., Langridge, J. M., Leblanc, C., LeCrane, J.-P., Lee, J. D., Leigh, R. J., Longley, I., Mahajan, A. S., Monks, P. S., Oetjen, H., Orr-Ewing, A. J., Plane, J. M. C., Potin, P., Shillings, A. J. L., Thomas, F., von Glasow, R., Wada, R., Whalley, L. K., and Whitehead, J. D.: Iodine-mediated coastal particle formation: an overview of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) Roscoff coastal study, Atmos. Chem. Phys., 10, 2975–2999, doi:10.5194/acp-10-2975-2010, 2010.

McLaren, R., Salmon, R. A., Liggio, J., Hayden, K. L., Anlauf, K. G., and Leaitch, W. R.: Nighttime chemistry at a rural site in the Lower Fraser Valley, Atmos. Environ., 38, 5837–5848, doi:10.1016/j.atmosenv.2004.03.074, 2004.

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, doi:10.5194/acp-10-4187-2010, 2010.

Mentel, T. F., Bleilebens, D., and Wahner, A.: A study of nighttime nitrogen oxide oxidation in a large reaction chamber – The fate of NO2, N2O$_5$, HNO3, and O3 at different humidities, Atmos. Environ., 30, 4007–4020, 1996.

Nemitz, E., Phillips, G. J., Di Marco, C. F., Allan, J., Barlow, J. F., Coe, H., Thorpe, A., Dall'Osto, M., Harrison, R. M., and Williams, P. I.: Concentrations, gradients and fluxes of inorganic reactive gases and aerosol components above London, in preparation, 2010.

Orphal, J., Fellows, C. E., and Flaud, P. M.: The visible absorption spectrum of NO3 measured by high-resolution Fourier transform spectroscopy, J. Geophys. Res.-Atmos., 108(11), 4077, doi:10.1029/2002jd002489, 2003.

Penkett, S. A., Burgess, R. A., Coe, H., Coll, I., Hov, O., Lindskog, A., Schmidbauer, N., Solberg, S., Roemer, M., Thijsse, T., Beck, J., and Reeves, C. E.: Evidence for large average concentrations of the nitrate radical (NO$_3)$ in Western Europe from the HANSA hydrocarbon database, Atmos. Environ., 41, 3465–3478, 2007.

Platt, U., Perner, D., Winer, A. M., Harris, G. W., and Pitts, J. N.: Detection of NO3 in the Polluted Troposphere by Differential Optical-Absorption, Geophys. Res. Lett., 7, 89–92, 1980a.

Platt, U. and Stutz, J.: Differential Optical Absorption Spectroscopy, 1 ed., Physics of Earth and Space Environments, Springer, Verlag, 2008.

Platt, U., Meinen, J., Pöhler, D., and Leisner, T.: Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) – applicability and corrections, Atmos. Meas. Tech., 2, 713–723, doi:10.5194/amt-2-713-2009, 2009.

Povey, I. M., South, A. M., de Roodenbeke, A. T., Hill, C., Freshwater, R. A., and Jones, R. L.: A broadband lidar for the measurement of tropospheric constituent profiles from the ground, J. Geophys. Res.-Atmos., 103, 3369–3380, 1998.

Riemer, N., Vogel, H., Vogel, B., Schell, B., Ackermann, I., Kessler, C., and Hass, H.: Impact of the heterogeneous hydrolysis of N2O$_5$ on chemistry and nitrate aerosol formation in the lower troposphere under photosmog conditions, J. Geophys. Res.-Atmos., 108(D4), 4144, doi:10.1029/2002JD002436, 2003.

Ruth, A. A., Orphal, J., and Fiedler, S. E.: Fourier-transform cavity-enhanced absorption spectroscopy using an incoherent broadband light source, Appl. Optics, 46, 3611–3616, 2007.

Shen, S., Jaques, P. A., Zhu, Y. F., Geller, M. D., and Sioutas, C.: Evaluation of the SMPS-APS system as a continuous monitor for measuring PM$_2.5$, PM$_10$ and coarse (PM$_2.5-10)$ concentrations, Atmos. Environ., 36, 3939–3950, 2002.

Slusher, D. L., Huey, L. G., Tanner, D. J., Flocke, F. M., and Roberts, J. M.: A thermal dissociation-chemical ionization mass spectrometry (TD-CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide, J. Geophys. Res., 109, D19315, doi:10.1029/2004jd004670, 2004.

Smith, N., Plane, J. M. C., Nien, C. F., and Solomon, P. A.: Nighttime Radical Chemistry in the San-Joaquin Valley, Atmos. Environ., 29, 2887–2897, 1995.

Stark, H., Lerner, B. M., Schmitt, R., Jakoubek, R., Williams, E. J., Ryerson, T. B., Sueper, D. T., Parrish, D. D., and Fehsenfeld, F. C.: Atmospheric in situ measurement of nitrate radical (NO$_3)$ and other photolysis rates using spectroradiometry and filter radiometry, J. Geophys. Res.-Atmos., 112(D10), D10S04, doi:10.1029/2006JD007578, 2007.

Stutz, J., Alicke, B., Ackermann, R., Geyer, A., White, A., and Williams, E.: Vertical profiles of NO3, N2O$_5$, O3, and NOx in the nocturnal boundary layer: 1. Observations during the Texas Air Quality Study 2000, J. Geophys. Res.-Atmos., 109(D16), D16398, doi:10.1029/2004jd005216, 2004.

Wangberg, I., Etzkorn, T., Barnes, I., Platt, U., and Becker, K. H.: Absolute Determination of the Temperature Behavior of the NO2 + NO3 +(M) ? N2O$_5$ + (M) Equilibrium, J. Phys. Chem. A, 101, 9694–9698, 1997.

Washenfelder, R. A., Langford, A. O., Fuchs, H., and Brown, S. S.: Measurement of glyoxal using an incoherent broadband cavity enhanced absorption spectrometer, Atmos. Chem. Phys., 8, 7779–7793, doi:10.5194/acp-8-7779-2008, 2008.

Wood, C. R., Lacser, A., Barlow, J. F., Belcher, S. E., Nemitz, E., Helfter, C., Famulari, D., and Grimmond, C. S. B.: Turbulent Flow at 190 m Height Above London During 2006–2008: A Climatology and the Applicability of Similarity Theory, Bound.-Lay. Meteorol., 137, 77–96, doi:10.1007/s10546-010-9516-x, 2010.

Wood, E. C., Bertram, T. H., Wooldridge, P. J., and Cohen, R. C.: Measurements of N2O$_5$, NO2, and O3 east of the San Francisco Bay, Atmos. Chem. Phys., 5, 483–491, doi:10.5194/acp-5-483-2005, 2005.