Agns Perrin Improved spectral parameters for HNO 3

Agnès Perrin Improved spectral parameters for HNO 3 : validation of MIPAS satellite measurements Jean-Marie Flaud, Agnés Perrin, Laboratoire Interuniversitaire des Systémes Atmosphériques (LISA), CNRS, Université Paris XII, , France. F. Mencaraglia, G. Bianchini, A. Boscaleri, B. Carli, S. Ceccherini Istituto di Fisica Applicata Carrara, Firenze - Italy G. Brizzi, M. Carlotti, and M. Ridolfi Dipartimento di Chimica Fisica e inorganica, Bologna, Italy Ohio State, June 2006

Agnès Perrin Outlines Ø Improved parameters for HNO 3 in the MIPAS spectral range • Line positions • Line intensities • Line broadening. Ø Validation of the HNO 3 atmospheric measurements of: MIPAS on ENVISAT satellite (Michelson Interferometer for Passive Atmospheric Sounding (@11µm) IBEX (Infrared Balloon EXperiment) in the far infrared (22 cm-1). Ohio State, June 2006

Michelson Interferometer for Passive Atmospheric Sounding Agnès Perrin HNO 3 is measured in « real time » using an « operational code » which MIPAS is an high resolution IR FTS spectrometer onboard(26 km) use « limited » microwindows (11µm for HNO 3) the ENVISAT satellite since march 2002 Futur projects: to use more of the informations included in MIPAS spectra Futur projects: to extend the range of the microwindows 11µm n 5, 2 n 9 8. 3µm. n 8+n 9 7. 6µm n 3, n 4 5. 8µm n 2 —›MIPAS dedicated Database J-M. Flaud, C. Piccolo, B. Carli, A. Perrin, L. Coudert, J. L. Teffo, L. Brown, J. of Atmos. Ocean and Optics, 16, 172 -182 (2003). Ohio State, June 2006

Improved line positions Agnès Perrin 11µm (improved) Cold n 5, 2 n 9 ; Hot n 5+n 9 -n 5 8. 3µm (weak) n 8+n 9 (improved) {n 8+n 9, n 6+n 7} (interactions accounted for #) No change (line positions) 7. 6µm {n 3, n 4} (strong) need to be improved !!!!! 5. 8 µm n 2 (strong) #Perrin, Flaud, Keller, Goldman, Blatherwick, Murcray, & Rinsland, J. Mol. Spectr 194 (1999) 113. Perrin, Orphal, Flaud, Klee, Mellau, Mäder, Walbrodt, Winnewisser, J. Mol. Spect. 228 (2004) 375 Flaud, Piccolo, Carli, Perrin, Coudert, Teffo & Brown , J. Atmospheric and Ocean Optics, 16 (2003), 172. Flaud, Perrin, Orphal, Kou, Durkiewick & Piccolo, J. Q. S. R. T. 77 (2003) 355. Flaud, Brizzi, Carlotti, Perrin, Ridolfi, Atmos. Chem. Phys. Discuss, 6 (2006) 4251 Ohio State, June 2006 #(see paper TG 03 by D. Petkie et al. )

Improved HNO 3 line intensities Ohio State, June 2006 Agnès Perrin

Intensities for the 11 µm bands . decrease of 14% Giver et al. J. Opt. Soc. Am. B 1, 715 (1984) Chackerian, Sharpe & Blake, JQSRT 82, 429 (2003) Toth, Brown & Cohen J. Mol. Spectr 218, 151 (2003) HIT-2 K HIT-04: Ohio State, &June 2006 Rothman et al. JQSRT 82, 5 (2003), 96, 139 (2005) MIPAS: Flaud et al. Atmos Oceanic Opt. 16, 172 (2003) Agnès Perrin

Agnès Perrin Comparison of observed and simulated MIPAS spectra in band A for an altitude of 24 km 2 n 9 Q branch Old database Ohio State, June 2006 New database

Status of the n 3 & n 4 bands (7. 5µm) …still unsatisfactory !!!!! . n 3 Q branch Ohio State, June 2006 Agnès Perrin . n 3 Q branch

Agnès Perrin Improved line broadening parameters for HNO 3 • Numerous excellent line broadening measurements were performed mainly in the millimeter wave spectral range • Strong rotational dependence of the broadenings • Sometime, the n- temperature dependance of the g was also measured. Goyette T. M. , W. L. Ebenstein, F. C. De Lucia and P. Helminger, J. Mol. Spectrosc. 128, (1988) 108. Goyette T. M. , W. Guo, F. C. De Lucia and P. Helminger, J. Q. S. R. T. 46, (1991) 293. Goyette T. M. , E. A. Cohen, and F. De Lucia, J. Q. S. R. T. 60, (1998) 377. Zu L. , P. A. Hamilton and P. B. Davies, J. Q. S. R. T. 73, (2002) 545. Colmont, Bakri, Rohart, Wlodarczak, J. Mol. Spectr. 220 (2003) 52. Cazzoli, Dore, June Puzzarini, Ohio State, 2006 Bakri, Colmont, Rohart and Wlodarczak J. Mol. Spect 229 (2005) 158.

Model for HNO 3 line broadening. Agnès Perrin gair(J)= aair + bair. (J’+J’’) gair (J)= constant Ohio State, June 2006 There is need for a « correct » model for the broadening….

Agnès Perrin Preliminary intercomparison of HNO 3 profiles MIPAS FTS on ENVISAT 11µm 900 cm-1 Line parameters From HITRAN-2 K IBEX FTS on a balloon Far infrared 20 cm-1 Ohio State, June 2006 Parameters from JPL catalog

Comparison MIPAS IBEX Agnès Perrin Because of geographical and time dependence of the atmospheric composition correlative measurements should done over the same air mass; Exact “rendez-vous” satellite balloon. Ohio State, June 2006

Agnès Perrin Concentration profile of HNO 3 MIPAS IBEX These two profiles desagree…. …………. , this may be due to a different geographical or time dependence of HNO 3……. . In our case this required an exact “rendez-vous” between two moving platforms: satellite and balloon. …. or to spectroscopic problems in. State, the. June 11µm… (or/and) in the far infrared Ohio 2006

The pure rotation band for HNO 3 Agnès Perrin . . was updated…in HITRAN-04: was updated using the JPL catalog For the v=0 (ground ground) only Intensities are incorrect for atmospheric uses (in JPL and …. . therefore in HITRAN-04) Ohio State, June 2006

Agnès Perrin JPL catalog: status of the intensities (@300 K) Int(300 K)JPL= (e-E”/k. T-e-E’/k. T)1/ZJPL(T)|<f'|m 0|f">|2 ZJPL rotation partition function ZTot(T) =ZRot(T)*ZVib(T) ZVib(T=300 K) 1. 30 Not accounted for For Int(T) this MIPAS IBEX intercomparison, we JPL= Int. TRUE(T)*ZVib(T=300 K) performed a new calculation of the MW-Far infrared region for. Intensities HNO 3 (ground-ground hot overestimated of+ 30% bands) (i) best line position parameters (ii) corrected line intensities Ohio State, June 2006 Cohen, Delisky, Pearson & Müller, JQSRT; 60, 1998 Picket, Poynter,

Agnès Perrin Final results 11 µm ØNew line positions ØOverall intensities were divided by 1. 14 Far infrared (~22 cm-1) ØNew line positions ØOverall intensities were divided by 1. 30 Ohio State, June 2006

Agnès Perrin MIPAS: 11µm Ohio State, June 2006 IBEX: Far IR

Agnès Perrin Conclusion Ø Improved parameters for HNO 3 in the MIPAS spectral range (line positions, line intensities, line broadening). Ø The 7. 6µm region need to be updated Validation of the HNO 3 atmospheric measurements of MIPAS on ENVISAT satellite (@11µm) IBEX (Infrared Balloon EXperiment) in the far infrared (22 cm-1). Ohio State, June 2006

HITRAN #Molecular line parameters for the Agnès Perrin MASTER database” Ohio. C. Puzzarini, State, June 2006 A. Perrin, J. -M. Colmont, C. Verdes, G. Wlodarczak, G. Cazzoli, S. Buehler, J. -M. Flaud, and J. Demaison (Journal of Atmospheric Chemistry, in press

Agnès Perrin Geographical « rendez-vous » Ohio State, June 2006

The n 5+n 9 -n 9 hot band of HNO 3 Agnès Perrin Comparison between ATMOS measurements and atmospheric simulations obtained using the NEW and the OLD database OLD db NEW db J. -M. FLAUD , C. PICCOLO, B. CARLI, A. PERRIN , L. H. COUDERT , J. -L. TEFFO AND L. R. BROWN, Molecular line parameters for the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) experiment, J. Atmospheric and Ocean Optics, 16, 172 -182 (2003) Ohio State, June 2006

Improvements for MIPAS i. Old parameters i. New parameters Ohio State, June 2006 . X 2 Error From P. Raspollini( Private comm. ) Agnès Perrin

Agnès Perrin 11 mm region ( n 5 & 2 n 9 cold bands, n 5 +n 9 -n 9 hot bands => recent line (positions) improvement (now in MIPAS-PF 3. 2) Perrin, Orphal, Flaud, Klee, Mellau, Mäder, Walbrodt, Winnewisser, J. Mol. Spect. 228 (2004) 375. Ohio State, June 2006