References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-4669-2011

Trends of HCl, ClONO2, and HF column abundances from ground-based FTIR measurements in Kiruna (Sweden) in comparison with KASIMA model calculations

Kohlhepp

¹ Barthlott

¹ Blumenstock

¹ Hase

¹ Kaiser

¹ Raffalski

² Ruhnke

Karlsruhe Institute of Technology (KIT), Institute for Meteorology and Climate Research (IMK), Karlsruhe, Germany

Swedish Institute of Space Physics (IRF), Kiruna, Sweden

18 05 2011

11 10 4669 4677

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/11/4669/2011/acp-11-4669-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/4669/2011/acp-11-4669-2011.pdf

Trends of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) total column abundances above Kiruna (Northern Sweden, 67.84° N, 20.41° E) derived from nearly 14 years (1996–2009) of measurement and model data are presented. The measurements have been performed with a Bruker 120 HR (later Bruker 125 HR) Fourier transform infrared (FTIR) spectrometer and the chemistry-transport model (CTM) used was KASIMA (KArlsruhe SImulation model of the Middle Atmosphere). The total column abundances of ClONO2 and HF calculated by KASIMA agree quite well with the FTIR measurements while KASIMA tends to underestimate the HCl columns. To calculate the long-term trends, a linear function combined with an annual cycle was fitted to the data using a least squares method. The precision of the resulting trends was estimated with the bootstrap resampling method. For HF, both model and measurements show a positive trend that seems to decrease in the last few years. This suggests a stabilisation of the HF total column abundance. Between 1996 and 2009, KASIMA simulates an increase of (+1.51±0.07) %/yr which exceeds the FTIR result of (+0.65±0.25) %/yr. The trends determined for HCl and ClONO2 are significantly negative over the time period considered here. This is expected because the emission of their precursors (chlorofluorocarbons and hydrochlorofluorocarbons) has been restricted in the Montreal Protocol in 1987 and its amendments and adjustments. The trend for ClONO2 from the FTIR measurements amounts to (−3.28±0.56) %/yr and the one for HCl to (−0.81±0.23) %/yr. KASIMA simulates a weaker decrease: For ClONO2, the result is (−0.90±0.10) %/yr and for HCl (−0.17±0.06) %/yr. Part of the difference between measurement and model data can be explained by sampling and the stronger annual cycle indicated by the measurements. There is a factor of about four between the trends of HCl and ClONO2 above Kiruna for both measurement and model data.

References 1

Barret, B., Hurtmans, D., Carleer, M R., de~Mazière, M., Mahieu, E., and Coheur, P.-F.: Line narrowing effect on the retrieval of HF and HCl vertical profiles from ground-based FTIR measurements, J. Quant. Spectrosc. Radiat. Transfer, 95, 499–519, 2005.

Bian, H. and Prather, M J.: Fast-J2: Accurate simulation of stratospheric photolysis in global chemical models, J. Atmos. Chem., 41, 281–296, 2002.

Chipperfield, M P., Burton, M., Bell, W., Paton-Walsh, C., Blumenstock, T., Coffey, M T., Hannigan, J W., Mankin, W G., Galle, B., Mellqvist, J., Mahieu, E., Zander, R., Notholt, J., Sen, B., and Toon, G C.: On the use of HF as a reference for the comparison of stratospheric observations and models, J. Geophys. Res., 102, 12901–12919, 1997.

Duchatelet, P., Demoulin, P., Hase, F., Ruhnke, R., Feng, W., Chipperfield, M P., Bernath, P F., Boone, C D., Walker, K A., and Mahieu, E.: Hydrogen fluoride total and partial column time series above the Jungfraujoch from long-term FTIR measurements: Impact of the line-shape model, characterization of the error budget and seasonal cycle, and comparison with satellite and model data, J. Geophys. Res., 115, D22306, http://dx.doi.org/10.1029/2010JD014677doi:10.1029/2010JD014677, 2010.

Efron, B.: Bootstrap Methods: Another look at the Jackknife, The Annals of Statistics, 7(1), 1–26, 1979.

Efron, B. and Tibshirani, R.: An Introduction to the Bootstrap, Mg. Stat. Pro., 57, 456~pp., 1993.

Froidevaux, L., Livesey, N J., Read, W G., Salawitch, R J., Waters, J W., Drouin, B., MacKenzie, I A., Pumphrey, H C., Bernath, P., Boone, C., Nassar, R., Montzka, S., Elkins, J., Cunnold, D., and Waugh, D.: Temporal decrease in upper atmospheric chlorine, Geophys. Res. Lett., 33, L23812, http://dx.doi.org/10.1029/2006GL027600doi:10.1029/2006GL027600, 2006.

Gardiner, T., Forbes, A., de Maziére, M., Vigouroux, C., Mahieu, E., Demoulin, P., Velazco, V., Notholt, J., Blumenstock, T., Hase, F., Kramer, I., Sussmann, R., Stremme, W., Mellqvist, J., Strandberg, A., Ellingsen, K., and Gauss, M.: Trend analysis of greenhouse gases over Europe measured by a network of ground-based remote FTIR instruments, Atmos. Chem. Phys., 8, 6719–6727, http://dx.doi.org/10.5194/acp-8-6719-2008doi:10.5194/acp-8-6719-2008, 2008.

Hamann, K.: Untersuchung des Trends halogenhaltiger Verbindungen in der Stratosphäre, Diploma thesis at the Institute for Meteorology and Climate Research (IMK-ASF), University of Karlsruhe, 2007.

Hase, F.: Inversion von Spurengasprofilen aus hochaufgelösten bodengebundenen FTIR-Messungen in Absorption, Wissenschaftliche Berichte, FZKA-Report No. 6512, Forschungszentrum Karlsruhe, Germany, 2000.

Hase, F., Blumenstock, T., and Paton-Walsh, C.: Analysis of the instrumental line shape of high-resolution Fourier transform IR spectrometers with gas cell measurements and new retrieval software, Appl. Optics, 38, 3417–3422, 1999.

Hase, F., Hannigan, J W., Coffey, M T., Goldman, A., Höpfner, M., Jones, N B., Rinsland, C P., and Wood, S W.: Intercomparison of retrieval codes used for the analysis of high-resolution, ground-based FTIR measurements, J. Quant. Spectrosc. Radiat. Transfer, 87, 25–52, 2004.

Kohlhepp, R., Ruhnke, R., Chipperfield, M P., de~Mazière, M., Notholt, J., Barthlott, S., Batchelor, R L., Blatherwick, R D., Blumenstock, T., Coffey, M T., Duchatelet, P., Fast, H., Feng, W., Goldman, A., Griffith, D. W T., Hamann, K., Hannigan, J W., Hase, F., Jones, N B., Kagawa, A., Kaiser, I., Kasai, Y., Kirner, O., Kouker, W., Lindenmaier, R., Mahieu, E., Mittermeier, R L., Monge-Sanz, B., Murata, I., Nakajima, H., Morino, I., Palm, M., Paton-Walsh, C., Reddmann, T., Rettinger, M., Rinsland, C P., Rozanov, E., Schneider, M., Senten, C., Sinnhuber, B.-M., Smale, D., Strong, K., Sussmann, R., Taylor, J R., Vanhaelewyn, G., Warneke, T., Whaley, C., Wiehle, M., and Wood, S W.: Observed and simulated time evolution of HCl, ClONO2, and HF total columns, Atmos. Chem. Phys. Discuss., in preparation, 2011.

Kouker, W., Langbein, I., Reddmann, T., and Ruhnke, R.: The Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA), Wissenschaftliche Berichte, FZKA-Report No. 6278, Forschungszentrum Karlsruhe, Germany, 1999.

Mahieu, E., Rinsland, C P., Gardiner, T., Zander, R., Demoulin, P., Chipperfield, M P., Ruhnke, R., Chiou, L S., de~Mazière, M., Duchatelet, P., Lejeune, B., Roland, G., and Servais, C.: Recent trends of inorganic chlorine and halogenated source gases above the Jungfraujoch and Kitt Peak stations derived from high-resolution FTIR solar observations, EGU General Assembly 2010, held 2–7 May, 2010 in Vienna, Austria, p 2420, 2010.

Mikuteit, S.: Trendbestimmung stratosphärischer Spurengase mit Hilfe bodengebundener FTIR-Messungen, Wissenschaftliche Berichte, FZKA-Report No. 7385, Forschungszentrum Karlsruhe, Germany, 2008.

Molina, M J. and Rowland, F S.: Stratospheric sink for chlorofluoromethanes: chlorine atom – catalysed destruction of ozone, Nature, 249, 810–812, 1974.

Reddmann, T., Ruhnke, R., and Kouker, W.: Three-dimensional model simulations of SF$_6$ with mesospheric chemistry, J. Geophys. Res., 106, 14525–14537, 2001.

Rinsland, C P., Levine, J S., Goldman, A., Sze, N D., Ko, M. K W., and Johnson, D W.: Infrared measurements of HF and HCl total column abundances above Kitt Peak, 1997–1990: Seasonal cycles, long-term increases, and comparisons with model calculations, J. Geophys. Res., 96, 15523–15540, 1991.

Rinsland, C P., Zander, R., Mahieu, E., Chiou, L S., Goldman, A., and Jones, N B.: Stratospheric HF column abundances above Kitt Peak (31.9° N latitude): trends from 1977 to 2001 and correlations with stratospheric HCl columns, J. Quant. Spectrosc. Radiat. Transfer, 74, 205–216, 2002.

Rodgers, C D.: Inverse Methods for Atmospheric Sounding: Theory and Praxis, World Scientific Publishing Co., Singapore, 2000.

Rothman, L S., Jacquemart, D., Barbe, A., Benner, D C., Birk, M., Brown, L R., Carleer, M R., Chackerian, C J., Chance, K., Coudert, L H., Dana, V., Devi, V M., Flaud, J.-M., Gamache, R R., Goldman, A., Hartmann, J.-M., Jucks, K W., Maki, A G., Mandin, J.-Y., Massie, S T., Orphal, J., Perrin, A., Rinsland, C P., Smith, M. A H., Tennyson, J., Tolchenov, R N., Toth, R A., Auwera, J V., Varanasi, P., and Wagner, G.: The HITRAN 2004 molecular spectroscopic database, J. Quant. Spectrosc. Radiat. Transfer, 96, 139–204, 2005.

Ruhnke, R., Kouker, W., and Reddmann, T.: The influence of the OH + NO2 + M reaction on the NOy partitioning in the late Arctic winter 1992/1993 as studied with KASIMA, J. Geophys. Res., 104, 3755–3772, 1999.

Stiller, G. P., von Clarmann, T., Höpfner, M., Glatthor, N., Grabowski, U., Kellmann, S., Kleinert, A., Linden, A., Milz, M., Reddmann, T., Steck, T., Fischer, H., Funke, B., López-Puertas, M., and Engel, A.: Global distribution of mean age of stratospheric air from MIPAS SF$_6$ measurements, Atmos. Chem. Phys., 8, 677–695, http://dx.doi.org/10.5194/acp-8-677-2008doi:10.5194/acp-8-677-2008, 2008.

Vigouroux, C., De Maziére, M., Demoulin, P., Servais, C., Hase, F., Blumenstock, T., Kramer, I., Schneider, M., Mellqvist, J., Strandberg, A., Velazco, V., Notholt, J., Sussmann, R., Stremme, W., Rockmann, A., Gardiner, T., Coleman, M., and Woods, P.: Evaluation of tropospheric and stratospheric ozone trends over Western Europe from ground-based FTIR network observations, Atmos. Chem. Phys., 8, 6865–6886, http://dx.doi.org/10.5194/acp-8-6865-2008doi:10.5194/acp-8-6865-2008, 2008.

Wagner, G. and Birk, M.: New infrared spectroscopic database for chlorine nitrate, J. Quant. Spectrosc. Radiat. Transfer, 82, 443–460, 2003.

Weatherhead, E C., Reinsel, G C., Tiao, G C., Meng, X.-L., Choi, D., Cheang, W.-K., Keller, T., DeLuisi, J., Wuebbles, D J., Kerr, J B., Miller, A J., Oltmans, S J., and Frederick, J E.: Factors affecting the detection of trends: Statistical considerations and applications to environmental data, J. Geophys. Res., 103, 17149–17161, 1998.

WMO: Scientific assessment of ozone depletion: 2002, Global ozone research and monitoring project – report no. 47, Geneva, Switzerland, 2003.

WMO: Scientific assessment of ozone depletion: 2006, Global ozone research and monitoring project – report no. 50, Geneva, Switzerland, 2007.

Zander, R., Mahieu, E., Demoulin, P., Duchatelet, P., Roland, G., Servais, C., De Mazière, M., Reimann, S., and Rinsland, C. P.: Our changing atmosphere: Evidence based on long-term infrared solar observations at the Jungfraujoch since 1950, Sci. Total Environ., 391, 184–195, 2008.