Four years of ground-based MAX-DOAS observations of HONO and NO<sub>2</sub> in the Beijing area
Tóm tắt
Abstract. Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrous acid (HONO) and its precursor NO2 (nitrogen dioxide) as well as aerosols have been performed daily in Beijing city centre (39.98° N, 116.38° E) from July 2008 to April 2009 and at the suburban site of Xianghe (39.75° N, 116.96° E) located ~60 km east of Beijing from March 2010 to December 2012. This extensive dataset allowed for the first time the investigation of the seasonal cycle of HONO as well as its diurnal variation in and in the vicinity of a megacity. Our study was focused on the HONO and NO2 near-surface concentrations (0–200 m layer) and total vertical column densities (VCDs) and also aerosol optical depths (AODs) and extinction coefficients retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations. Monthly averaged HONO near-surface concentrations at local noon display a strong seasonal cycle with a maximum in late fall/winter (~0.8 and 0.7 ppb at Beijing and Xianghe, respectively) and a minimum in summer (~0.1 ppb at Beijing and 0.03 ppb at Xianghe). The seasonal cycles of HONO and NO2 appear to be highly correlated, with correlation coefficients in the 0.7–0.9 and 0.5–0.8 ranges at Beijing and Xianghe, respectively. The stronger correlation of HONO with NO2 and also with aerosols observed in Beijing suggests possibly larger role of NO2 conversion into HONO in the Beijing city center than at Xianghe. The observed diurnal cycle of HONO near-surface concentration shows a maximum in the early morning (about 1 ppb at both sites) likely resulting from night-time accumulation, followed by a decrease to values of about 0.1–0.4 ppb around local noon. The HONO / NO2 ratio shows a similar pattern with a maximum in the early morning (values up to 0.08) and a decrease to ~0.01–0.02 around local noon. The seasonal and diurnal cycles of the HONO near-surface concentration are found to be similar in shape and in relative amplitude to the corresponding cycles of the HONO total VCD and are therefore likely driven mainly by the balance between HONO sources and the photolytic sink, whereas dilution effects appear to play only a minor role. The estimation of OH radical production from HONO and O3 photolysis based on retrieved HONO near-surface concentrations and calculated photolysis rates indicate that in the 0–200 m altitude range, HONO is by far the largest source of OH radicals in winter as well as in the early morning at all seasons, while the contribution of O3 dominates in summer from mid-morning until mid-afternoon.
Từ khóa
Tài liệu tham khảo
Brion, J., Chakir, A., Charbonnier, J., Daumont, D., Parisse, C., and Malicet, J.: Absorption Spectra Measurements for the Ozone Molecule in the 350–830 nm Region, J. Atmos. Chem., 30, 291–299, https://doi.org/10.1023/A:1006036924364, 2004.
Brinksma, E. J., Pinardi, G., Volten, H., Braak, R., Richter, A., Schönhardt, A., Van Roozendael, M., Fayt, C., Hermans, C., Dirksen, R. J., Vlemmix, T., Berkhout, A. J. C., Swart, D. P. J., Oetjen, H., Wittrock, F., Wagner, T., Ibrahim, O. W., de Leeuw, G., Moerman, M., Curier, R. L., Celarier, E. A., Cede, A., Knap, W. H., Veefkind, J. P., Eskes, H. J., Allaart, M., Rothe, R., Piters, A. J. M., and Levelt, P. F.: The 2005 and 2006 DANDELIONS NO2 and aerosol intercomparison campaigns, J. Geophys. Res., 113, D16S46, https://doi.org/10.1029/2007JD008808, 2008.
Burrows, J. P., Richter, A., Dehn, A., Deters, B., Himmelmann, S., Voigt, S., and Orphal, J.: Atmospheric Remote-sensing reference data from GOME - 2.Temperature-dependent absorption cross-sections of O3 in the 231–794 nm range, J. Quant. Spectrosc. Radiat. Transfer, 61, 509–517, 1999.
Chou, C. C.-K., Tsai, C.-Y., Chang, C.-C., Lin, P.-H., Liu, S. C., and Zhu, T.: Photochemical production of ozone in Beijing during the 2008 Olympic Games, Atmos. Chem. Phys., 11, 9825–9837, https://doi.org/10.5194/acp-11-9825-2011, 2011.
Clémer, K., Van Roozendael, M., Fayt, C., Hendrick, F., Hermans, C., Pinardi, G., Spurr, R., Wang, P., and De Mazière, M.: Multiple wavelength retrieval of tropospheric aerosol optical properties from MAXDOAS measurements in Beijing, Atmos. Meas. Tech., 3, 863–878, https://doi.org/10.5194/amt-3-863-2010, 2010.
Elshorbany, Y. F., Steil, B., Brühl, C., and Lelieveld, J.: Impact of HONO on global atmospheric chemistry calculated with an empirical parameterization in the EMAC model, Atmos. Chem. Phys., 12, 9977–10000, https://doi.org/10.5194/acp-12-9977-2012, 2012.
Fleischmann, O. C., Hartmann, M., Burrows J. P., and Orphal, J.: New ultraviolet absorption cross-sections of BrO at atmospheric temperatures measured by time-windowing Fourier transform spectroscopy, J. Photochem. Photobiol. A, 168, 117–132 , 2004.
Friess, U., Monks, P. S., Remedios, J. J., Rozanov, A., Sinreich, R., Wagner, T., and Platt, U.: MAX-DOAS O4 measurements: A new technique to derive information on atmospheric aerosols: 2. Modeling studies, J. Geophys. Res. 111, D14203, https://doi.org/10.1029/2005JD006618, 2006.
George, C., Strekowski, R. S., Kleffmann, J., Stemmler, K., and Ammann, M.: Photoenhanced uptake of gaseous NO2 on solid organic compounds: a photochemical source of HONO?, Faraday Discuss., 130, 195–210, https://doi.org/10.1039/B417888M, 2005.
Harder, J. W. and Brault, J. W.: Atmospheric measurements of water vapor in the 442-nm region, J. Geophys. Res., 102, 6245–6252, 1997.
Heland, J., Kleffmann, J., Kurtenbach, R., and Wiesen, P.: A new instrument to measure gaseous nitrous acid (HONO) in the atmosphere, Environ. Sci. Technol., 35, 3207–3212, 2001.
Hendrick, F., Barret, B., Van Roozendael, M., Boesch, H., Butz, A., De Mazière, M., Goutail, F., Hermans, C., Lambert, J.-C., Pfeilsticker, K., and Pommereau, J.-P.: Retrieval of nitrogen dioxide stratospheric profiles from ground-based zenith-sky UV-visible observations: validation of the technique through correlative comparisons, Atmos. Chem. Phys., 4, 2091–2106, https://doi.org/10.5194/acp-4-2091-2004, 2004.
Hermans, C., Vandaele, A. C., Fally, S., Carleer, M., Colin, R., Coquart, B., Jenouvrier, A., and Mérienne, M.-F.: Absorption crosssection of the collision-induced bands of oxygen from the UV to the NIR, in: Proceedings of the NATO Advanced Research Workshop, Weakly Interacting Molecular Pairs: Unconventional Absorbers of Radiation in the Atmosphere, Fontevraud, France, 24 April–2 May 2002, edited by: Camy-Peyret, C. and Vigasin, A. A., NATO Science Series IV Earth and Environmental Sciences, vol. 27, Kluwer Academic Publishers, Boston, 193–202, 2003.
Hönninger, G., von Friedeburg, C., and Platt, U.: Multi axis differential optical absorption spectroscopy (MAX-DOAS), Atmos. Chem. Phys., 4, 231–254, https://doi.org/10.5194/acp-4-231-2004, 2004.
Kanaya, Y., Cao, R., Akimoto, H., Fukuda, M., Komazaki, Y., Yokouchi, Y., Koike, M., Tanimoto, H., Takegawa, N., and Kondo, Y.: Urban photochemistry in central Tokyo: 1. Observed and modeled OH and HO2 radical concentrations during the winter and summer of 2004, J. Geophys. Res., 112, D21312, https://doi.org/10.1029/2007jd008670, 2007.
Kleffmann, J., Heland, J., Kurtenbach, R., Lörzer, J., and Wiesen, P.: A new instrument (LOPAP) for the detection of nitrous acid (HONO), Environ. Sci. Pollut. R., 4, 48–54, 2002.
Kleffmann, J., Gavriloaiei, T., Hofzumahaus, A., Holland, F., Koppmann, R., Rupp, L., Schlosser, E., Siese, M., and Wahner, A.: Daytime formation of nitrous acid: A major source of OH radicals in a forest, Geophys. Res. Lett., 32, L05818, https://doi.org/10.1029/2005GL022524, 2005.
Li, Y., An, J., Min, M., Zhang, W., Wang, F., and Xie, P.: Impacts of HONO sources on the air quality in Beijing, Tianjin, and Hebei Province of China, Atmos. Environ., 45, 4735–4744, 2011.
Li, X., Brauers, T., Häseler, R., Bohn, B., Fuchs, H., Hofzumahaus, A., Holland, F., Lou, S., Lu, K. D., Rohrer, F., Hu, M., Zeng, L. M., Zhang, Y. H., Garland, R. M., Su, H., Nowak, A., Wiedensohler, A., Takegawa, N., Shao, M., and Wahner, A.: Exploring the atmospheric chemistry of nitrous acid (HONO) at a rural site in Southern China, Atmos. Chem. Phys., 12, 1497–1513, https://doi.org/10.5194/acp-12-1497-2012, 2012.
Lu, K. D., Hofzumahaus, A., Holland, F., Bohn, B., Brauers, T., Fuchs, H., Hu, M., Häseler, R., Kita, K., Kondo, Y., Li, X., Lou, S. R., Oebel, A., Shao, M., Zeng, L. M., Wahner, A., Zhu, T., Zhang, Y. H., and Rohrer, F.: Missing OH source in a suburban environment near Beijing: observed and modelled OH and HO2 concentrations in summer 2006, Atmos. Chem. Phys., 13, 1057–1080, https://doi.org/10.5194/acp-13-1057-2013, 2013.
Ma, J. Z., Beirle, S., Jin, J. L., Shaiganfar, R., Yan, P., and Wagner, T.: Tropospheric NO2 vertical column densities over Beijing: results of the first three years of ground-based MAX-DOAS measurements (2008–2011) and satellite validation, Atmos. Chem. Phys., 13, 1547–1567, https://doi.org/10.5194/acp-13-1547-2013, 2013.
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, 1–26, 1998.
Meller, R. and Moortgat, G. K.: Temperature dependence of the absorption cross sections of formaldehyde between 223 and 323K in the wavelength range 225–375 nm, J. Geophys. Res., 105, 7089–7101, 2000.
Perner, D. and Platt, U.: Detection of nitrous acid in the atmosphere by differential optical absorption, Geophys. Res. Lett., 6, 917–920, 1979.
Peters, E., Wittrock, F., Großmann, K., Frieß, U., Richter, A., and Burrows, J. P.: Formaldehyde and nitrogen dioxide over the remote western Pacific Ocean: SCIAMACHY and GOME-2 validation using ship-based MAX-DOAS observations, Atmos. Chem. Phys., 12, 11179–11197, https://doi.org/10.5194/acp-12-11179-2012, 2012.
Platt, U. and Stuz, J.: Differential Optical Absorption Spectroscopy (DOAS), Principles and Applications, ISBN 978-3-540-21193-8, Springer, Berlin-Heidelberg, 2008.
Qin, M., Xie, P., Su, H., Gu, J., Peng, F., Li, S., Zeng, L., Liu, J., Liu, W., and Zhang, Y.: An observational study of the HONO-NO2 coupling at an urban site in Guangzhou City, South China, Atmos. Environ., 43, 5731–5742, https://doi.org/10.1016/j.atmosenv.2009.08.017, 2009.
Richter, A., Burrows, J. P., Nüss, H., Granier, C., and Niemeier, U.: Increase in tropospheric nitrogen dioxide over China observed from space, Nature, 437, 129–132, https://doi.org/10.1038/nature04092, 2005.
Rodgers, C. D.: Inverse Methods for Atmospheric Sounding, Theory and Practice. World Scientific Publishing, Singapore-NewJersey-London-Hong Kong, 2000.
Sörgel, M., Trebs, I., Serafimovich, A., Moravek, A., Held, A., and Zetzsch, C.: Simultaneous HONO measurements in and above a forest canopy: influence of turbulent exchange on mixing ratio differences, Atmos. Chem. Phys., 11, 841–855, https://doi.org/10.5194/acp-11-841-2011, 2011a.
Sörgel, M., Regelin, E., Bozem, H., Diesch, J.-M., Drewnick, F., Fischer, H., Harder, H., Held, A., Hosaynali-Beygi, Z., Martinez, M., and Zetzsch, C.: Quantification of the unknown HONO daytime source and its relation to NO2, Atmos. Chem. Phys., 11, 10433–10447, https://doi.org/10.5194/acp-11-10433-2011, 2011b.
Spurr, R., LIDORT and VLIDORT: Linearized pseudo-spherical scalar and vector discrete ordinate radiative transfer models for use in remote sensing retrieval problems, Light Scattering Reviews, Volume 3, edited by: Kokhanovsky, A., Springer, 2008.
Stavrakou, T., Müller, J.-F., Boersma, K. F., van der A, R. J., Kurokawa, J., Ohara, T., and Zhang, Q.: Key chemical NOx sink uncertainties and how they influence top-down emissions of nitrogen oxides, Atmos. Chem. Phys., 13, 9057–9082, https://doi.org/10.5194/acp-13-9057-2013, 2013.
Stemmler, K., Ammann, M., Donders, C., Kleffmann, J., and George, C.: Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid, Nature, 440, 195–198, https://doi.org/10.1038/nature04603, 2006.
Stutz, J., Kim, E. S., Platt, U., Bruno, P., Perrino, C., and Febo, A.: UV-vis Absorption Cross-Section of Nitrous Acid, J. Geophys. Res., 105, 14585–14592, 2000.
Stutz, J., Alicke, B., and Neftel, A.: Nitrous acid formation in the urban atmosphere: Gradient measurements of NO2 and HONO over grass in Milan, Italy, J. Geophys. Res., 107, 8192, https://doi.org/10.1029/2001JD000390, 2002.
Su, H., Cheng, Y., Oswald, R., Behrendt, T., Trebs, I., Meixner, F. X., Andreae, M. O., Cheng, P., Zhang, Y., and Pöschl, U., Soil nitrite as a source of atmospheric HONO and OH radicals, Science, 333, 1616, https://doi.org/10.1126/science.1207687, 2011.
Vandaele, A. C., Hermans, C., Simon, P. C., Carleer, M., Colin, R., Fally, S., Mérienne, M.-F., Jenouvrier, A., and Coquart, B.: Measurements of the NO2 absorption cross section from 42000 cm−1 to 10000 cm−1 (238–1000 nm) at 220 K and 294 K, J. Quant. Spectrosc. Radiat. Transfer, 59, 171–184, 1998.
Villena, G., Kleffmann, J., Kurtenbach, R., Wiesen, P., Lissi, E., Rubio, M., Croxatto, G., and Rappenglück, B.: Vertical gradients of HONO, NOx and O3 in Santiago de Chile, Atmos. Environ., 45, 3867–3873, https://doi.org/10.1016/j.atmosenv.2011.01.073, 2011.
Vlemmix, T., Piters, A. J. M., Berkhout, A. J. C., Gast, L. F. L., Wang, P., and Levelt, P. F.: Ability of the MAX-DOAS method to derive profile information for NO2: can the boundary layer and free troposphere be separated?, Atmos. Meas. Tech., 4, 2659–2684, https://doi.org/10.5194/amt-4-2659-2011, 2011.
Wagner T., Dix, B., von Friedeburg, C., Friess, U., Sanghavi, S., Sinreich, R., and Platt, U.: MAX-DOAS O4 measurements: A new technique to derive information on atmospheric aerosols – Principles and information content, J. Geophys. Res. 109, D22205, https://doi.org/10.1029/2004JD004904, 2004.
Wagner, T., Deutschmann, T., and Platt, U.: Determination of aerosol properties from MAX-DOAS observations of the Ring effect, Atmos. Meas. Tech., 2, 495–512, https://doi.org/10.5194/amt-2-495-2009, 2009.
Wittrock, F., Oetjen, H., Richter, A., Fietkau, S., Medeke, T., Rozanov, A., and Burrows, J. P.: MAX-DOAS measurements of atmospheric trace gases in Ny-Ålesund – Radiative transfer studies and their application, Atmos. Chem. Phys., 4, 955–966, https://doi.org/10.5194/acp-4-955-2004, 2004.
Wang, S., Ackermann, R., and Stutz, J.: Vertical profiles of O3 and NOx chemistry in the polluted nocturnal boundary layer in Phoenix, AZ: I. Field observations by long-path DOAS, Atmos. Chem. Phys., 6, 2671–2693, https://doi.org/10.5194/acp-6-2671-2006, 2006.
Wong, K. W., Tsai, C., Lefer, B., Haman, C., Grossberg, N., Brune, W. H., Ren, X., Luke, W., and Stutz, J.: Daytime HONO vertical gradients during SHARP 2009 in Houston, TX, Atmos. Chem. Phys., 12, 635–652, https://doi.org/10.5194/acp-12-635-2012, 2012.
Wojtal, P., Halla, J. D., and McLaren, R.: Pseudo steady states of HONO measured in the nocturnal marine boundary layer: a conceptual model for HONO formation on aqueous surfaces, Atmos. Chem. Phys., 11, 3243–3261, https://doi.org/10.5194/acp-11-3243-2011, 2011.
Wu, Q. Z., Wang, Z. F., Gbaguidi, A., Gao, C., Li, L. N., and Wang, W.: A numerical study of contributions to air pollution in Beijing during CAREBeijing-2006, Atmos. Chem. Phys., 11, 5997–6011, https://doi.org/10.5194/acp-11-5997-2011, 2011.
Xia, X., Zong, X., and Sun, Li: Exceptionally active agricultural fire season in mid-eastern China in June 2012 and its impact on atmospheric environment, J. Geophys. Res. Atmos., 118, 9889–9900, https://doi.org/10.1002/jgrd.50770, 2013.
Young, C. J., Washenfelder, R. A., Roberts, J. M., Mielke, L. H., Osthoff, H. D., Tsai, C., Pikelnaya, O., Stutz, J., Veres, P. R., Cochran, A. K., VandenBoer, T. C., Flynn, J., Grossberg, N., Haman, C. L., Lefer, B., Stark, H., Graus, M., de Grouw, J., Gilman, J. B., Kuster, W. C., and Brown, S. S.: Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget, Environ. Sci. Technol., 46, 10965–10973, https://doi.org/10.1021/es302206a, 2012.
Yu, X., Zhu, B., and Zhang, M.: Seasonal variability of aerosol optical properties over Beijing, Atmos. Environ., 43, 4095–4101, 2009a.
Yu, Y., Galle, B., Panday, A., Hodson, E., Prinn, R., and Wang, S.: Observations of high rates of NO2-HONO conversion in the nocturnal atmospheric boundary layer in Kathmandu, Nepal, Atmos. Chem. Phys., 9, 6401–6415, https://doi.org/10.5194/acp-9-6401-2009, 2009b.
Zhang, Q., Streets, D. G., He, K., Wang, Y., Richter, A., Burrows, J. P., Uno, I., Jang, C. J., Chen, D., Yao, Z., and Lei, Y.: NOx emission trends for China, 1995-2004: The view from the ground and the view from space, J. Geophys. Res., 112, D22306, https://doi.org/10.1029/2007JD008684, 2007.