AERONOMICA ACTA

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I N S T I T U T . D ' A G R O N O M I E S P A T I A L E D E ' B E L G I Q U E 3 - Avenue Circulaire

B • 1180 BRUXELLES

A E R O N O M I C A A C T A

A - N° 2 9 5 - 1 9 8 5

Acetonitrile in the e a r t h ' s atmosphere : an upper limit deduced from infrared solar s p e c t r a

by

C. MULLER

B E L G I S C H I N S T I T U U T V O O R R U I M T E - A E R O N O M I E 3 - Ringlaan

B • 1180 BRUSSEL

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FOREWORD

T h i s text will be published in the "Bulletin de la Classe des Sciences de l'Académie Royale de Belgique".

A V A N T - P R O P O S

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VOORWOORD

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VORWORT

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A C E T O N I T R I LE IN T H E E A R T H ' S ATMOSPHERE : AN UPPER LIMIT DEDUCED FROM I N F R A R E D S O L A R S P E C T R A

by

Christian MULLER

Abstract

An upper limit to the atmospheric acetonitrile mixing ratio of 3.2 x

- 1 1

10 is deduced from the high resolution Kitt Peak infrared atlas of the solar spectrum. The survey of the spectral region of CH^CN main absorption shows only stratospheric ozone lines and one water vapor line and does not permit any positive identification of acetonitrile.

Résumé

Une limite supérieure de la fraction molaire du cyanure de méthyle -11

atmosphérique de 3.2 x 10 est déduite de l'atlas infrarouge du spectre solaire à haute résolution de Kitt Peak. L'examen du domaine spectral des absorptions les plus fortes de CH^CN ne montre que des raies de l'ozone stratosphérique et une raie de la vapeur d'eau et ne permet pas l'identification positive du cyanure de méthyle.

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Samenvatting

Een bovenlimiet van de mengverhouding van de atmosferische

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methaancyanide van 3.2 x 10 wordt afgeleid uit de infrarode atlas van het zonnespectrum met hoge resolutie van Kitt Peak. Het onderzoek van het spectraal gebied van de sterkste absorpties van C H ^ C N toont slechts lijnen van stratosferische ozon en één waterdamplijn en laat geen positieve identificatie toe van de methaancyanide.

Zusammenfassung

Ein Oberlimit des M i s c h u n g s v e r h ä l t n i s s e s des atmosphärischen -11

Methanzyanides von 3.2 x 10 wird abgeleitet vom infraroten Atlas des Sonnenspektrumes mit höher Resolution von Kitt Peak. Die F o r s c h u n g des Spektralgebietes der stärksten Absorptionen von C H g C N zeigt nur Linien von stratosphärischem Ozon und einer Wasserdampflinie und erlaubt keine positive Identification des Methanzyanides.

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T h e recent discovery of acetonitrile (CH^CN) in the earth's strato- sphere through positive ion measurements (Arnold et a l . , 1978, A r i j s et a l . , 1983) has led to modelling attempts and to a concern for possible sources ( B r a s s e u r et a l . , 1983). While acetonitrile is not involved in the stratospheric ozone chemistry, it is a plausible source of amino acids in the early atmosphere and might have been one of the precursors of life.

Now, it is thought to originate from biomass burning and industrial processes; moreover, an understanding of the cyanide chemistry is pertinent to the study of the atmosphere of a satellite of S a t u r n : T i t a n , which is marked for future space exploration.

T h e Kitt Peak National Observatory solar atlas (Delbouille et a l . , 1981) is presently the best compilation of ground based spectra avai- lable for solar p h y s i c s . It is a cooperative venture of KPNO, the Astro- physics Institute of the University of Liège and the Belgian Royal Observatory. T h e spectrum used for the present determination was obtained on October 25, 1979 for an air-mass of 1.17. T h e spectral

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domain covered wavenumbers between 2385 and 3770 cm and the achieved spectral resolution was 0.015 cm . T h i s spectral interval is characterized at one edge by the strong 2349 cm C O- 1 ? v.. band and at the other by the water vapor 3652 cm v.. band; between these two,

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lies the intense C H4 Vg, band at 3020 cm . Together with other weaker telluric bands, these leave v e r y few windows through which weak absorbers could be sought. However, between the manifolds of the CH^

band, some clean spectral regions emerge and, by chance, one of them between 3040 and 3041 cm coincides with the most intense CH^CN absorption feature.

T h e resolved structure of the CHgCN spectrum was f i r s t measured by Thompson and Williams (1952) and their analysis was later confirmed by Parker et al. (1957), leaving studies of isotopes and more elaborate spectroscopic properties to later authors (Duncan et a l . , 1978, Kondo and Person, 1974 and references t h e r e i n ) . As only Thompson and Williams (1952) published intensity data for the v^ band, their work will

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be used for the present analysis. Their resolution of 0.3 cm permits - 1

the observation of narrow features; one of the most intense appears at 3040.52 cm and seems to be a single line blended with a weaker one at 3041 cm . The total strength of the main line can be inferred from -1

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the published quantitative data as 2.5 x 10 cm /(molecule cm ) .

As the purpose of the present work was to determine an upper limit, the absorption was assumed to be linear although this is v e r y unlikely at the 60 torr pressure and 60% absorption of the line. T h i s value, if used for determinations of C H ^ C N , will always lead to higher values which could be overestimated by a factor which will only be determined by a high resolution study of the curve of growth of the line.

' The corresponding Kitt Peak spectral interval is shown on figure 1, where many narrow and weak lines appear, the half line width of the

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3040.96 cm line being 0.01 cm ; only the 3040.75 cm line seems to be wider and to exhibit a broad shoulder at 3040.72 cm . The A F G L - 1

line parameter table (Rothman et a l . , 1983) shows O - lines and a single

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H20 line at 3040.728 cm in the 1980 edition, and at 3040.741 cm in the 1982 edition. T h i s feature could be identified with the wide line shoulder. The 1982 edition mentions also a few weak CH^ line which cannot be identified on the observed spectrum.

The quoted S T P line width parameter for all 0_ lines is 0.11 cm - 1

which, converted to the Kitt-Peak altitude, is 0.09 cm . Even on - 1

dividing by 2, to take into account a Curtiss-Godson effect, this is

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much higher than the 0.01 cm observed line width corresponding to a 100 mb level, and indicates that the observed absorption occurs at altitudes of 15 km or above, confirming thus the stratospheric origin of the lines. The analysis of the H„0 shoulder using A F G L water vapor -3 line parameters leads to a water vapor mixing ratio of 1 x 10 which is fully in agreement with the 8.1 mm of water vapor indicated by

Delbouille et al. (1981) for this spectrum.

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WAVENUMBERfcm-

1

)

Fig- 1•" Portion of the Delbouille et al. (1981) atlas indicating the region of expected CH^CN absorption; the width of the lines except for the shoulder marked H^O permits to identify them as stratospheric ozone lines.

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A s it is v e r y unlikely that C H3C N has sources above g r o u n d level ( B r a s s e u r et a l . , 1984) it will be assumed to be already mixed in the troposphere, and a line width of 0.05 cm"1 will be a s s i g n e d in agreement with C H4. . A n absorption of 1 x 1 0- 3 at the location indicated by the arrow on figure 1 should lead in this case to a line of 0.02 c m "1

half line width. T h i s value leads to an equivalent width of 2.0 x 1 0 "5

-1 14 cm , an optical path of 8 x 10 molecules of C H - C N and a

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corresponding mixing ratio of 3.2 x 10 , and it becomes the tentative upper limit of atmospheric C H ^ C N .

T h i s value would need to be refined by quantitative ultra h i g h resolution studies of the C H3C N spectrum; it should be revised to a lower value if the line width should prove narrower than assumed, and to higher if the central absorption were a resolved manifold.

More important, the experimental line s t r e n g t h has been determined by the assumption of linear absorption, which deliberately g i v e s a lower limit. The real value of the line s t r e n g t h could be an order of magni- tude higher, but is only accessible to higher resolution studies. T h i s precise determination would be the main factor in significantly lowering the present upper limit.

Attempts have been made to locate the other strong band v . a b -

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sorption of C H g C N in the 920 cm region but they failed owing to con- tamination of this region by important tropospheric absorptions of C F2C I2 ( L i p p e n s and Muller, 1983).

A s an indication of the results of other techniques, the h i g h 7 x 10 C H g C N mixing ratio value reported b y Becker and lonescu -9 (1982) would have led to a 30% absorption on the figure 1 spectrum which would have swamped the O^ lines. The value of 8.4 x 10 , -11 reported is a maximum by Snider and Dawson, would have appeared as

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a 5 x 10 cm integrated absorption and would have been comparable to the weak O0 line at 3040.04 c m "1.

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In conclusion, this work, does not provide any positive identifica- tion of C H , C N , but the October 25, 1979 spectrum leads to a tentative

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upper limit of 3.2 x 10 C H3C N mixing ratio. A s usual with large polyatomic molecules, laboratory studies are necessary to refine the C H g C N molecular parameters for further quantitative studies.

ACKNOWLEDGMENT

We thank D r . Sauvai, Mr. Nys and Mr. Devos of the Royal Observatory of Belgium for providing us with preliminary copies of the Kitt Peak atlas and D r s . A r i j s , B r a s s e u r and Ingels for access to their unpublished data and for fruitful discussions.

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R O T H M A N , L . S . , G A M A C H E , R . R . , B A R B E , A . , G O L D M A N , A . , G I L L I S J . R . , BROWN, L . R . , T O T H , R . A . , F L A U D , J . M . , and C A M Y - P E Y R E T , C . , A . F . G . L . atmospheric absorption line p a r a - meters compilation : 1982 e d i t i o n , A p p l . O p t . , 22, 2247 ( 1 9 8 3 ) . S N I D E R , J . R . and DAWSON, G . A . , Surface acetonitrile near T u c s o n ,

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