chapter5 saturn:compositionandchemistry

Chapter 5Saturn: Composition and Chemistry

Thierry Fouchet, Julianne I. Moses, and Barney J. Conrath

Abstract The chapter reviews our current knowledge ofthe molecular, elemental, and isotopic composition andatmospheric chemistry in Saturn’s shallow atmosphere, i.e.,between the cloud levels and the homopause. We do notrestrict the review to Cassini’s results, as past and currentground-based or Earth-based observations are still funda-mental to draw a complete picture of the planet. We addressthe global composition and its importance in studying theorigin of the planet, and the meridional and vertical gra-dients in composition, stressing their insights into Saturn’sdynamics. We present the current 1D thermochemical andphotochemical models, how these models fare to reproducethe observed composition, and the first attempts to design 2Dchemical models. We present some directions to improve ourknowledge of Saturn’s composition both from observations,modelling and laboratory experiments.

5.1 Introduction

Atmospheric composition and chemistry directly determineSaturn’s horizontal and vertical structure, dynamics andvisible appearance. Composition affects the thermal struc-ture through the radiative balance between solar energy de-position and thermal infrared emission. Condensation ofvolatiles and photochemistry determine the cloud structure,hence the visible appearance of the planet. Chemistry, ei-ther photochemistry or thermochemistry, strongly shapes themolecular composition, and vertical, meridional and seasonalgradients in composition are observed. In turn, gradients inchemical constituent abundances and latent heat release bycondensibles contribute to thermal and density gradients thatpower atmospheric dynamics, which feeds back to affect

T. FouchetLESIA, Observatoire de Paris, Meudon, France

J.I. MosesLunar and Planetary Institute, Houston, TX, USA

B.J. ConrathDepartment of Astronomy, Cornell University, Ithaca, NY, USA

the composition and thermal structure. Hence, observationsof the atmospheric composition provide constraints on thepresent-day chemistry, dynamics, energy balance, appear-ance and other phenomena, whilst also providing a windowinto the past, to the conditions at the time of formation andevolution of the gas giants. Indeed, the elemental abundancesof carbon, oxygen, nitrogen, and sulfur are key parametersneeded for planetary formation scenarios. In this chapter, weaddress the chemical composition and the chemistry of theatmosphere from the homopause level down to below thecloud base. The composition and the structure of the interiorof the planet are reviewed in Chapter 4, while the composi-tion above the homopause level is covered in Chapter 8.

Without any in situ measurements to probe Saturn’s com-position, we have to rely exclusively on remote sensing, andmore specifically on spectroscopy which provides the mostpowerful way to quantitatively measure gaseous composi-tion. The full electromagnetic spectrum, from the ultravioletto radio wavelengths, is used in order to cover the greatestpossible vertical range. The early spectrometric studiesof Saturn’s atmosphere are reviewed in Chapter 2. How-ever, the impact of Cassini on our knowledge of Saturn’schemical composition is still relatively immature exceptin some specific areas. For this reason, we do not restrictour review to Cassini results, but extend our discussion toground-based and space-based observations up to 20 yearsago, when relevant, in order to present a comprehensive andconsistent picture of Saturn’s composition. Ground-basedobservations concomitant with the Cassini mission can alsoprove very useful. In parallel with observations, modelershave been developing chemical models, involving eitherthermochemistry or photochemistry, in order to interpretand to understand the reasons for the observed composition.Many of these models were put together prior to Cassini’sarrival at Saturn and need refinements in light of the newestCassini and ground-based studies.

The chapter is divided into two large sections. Section 5.2reviews the observed composition, starting with the prob-lem of the global composition in helium (Section 5.2.1.1).Then, we gather the different results on the carbon (Section5.2.1.2), nitrogen and sulfur (Section 5.2.1.3) compositions,

M.K. Dougherty et al. (eds.), Saturn from Cassini-Huygens,DOI 10.1007/978-1-4020-9217-6_5, c� Springer Science+Business Media B.V. 2009

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while the isotopic composition is discussed in Section5.2.1.4. We stress that Saturn’s global oxygen content stillcannot be determined from remote sensing studies at present.Section 5.2.2 reviews our current measurements of speciesthat are not in thermodynamic equilibrium at the cloud level,but are rather rapidly transported from the deep interior. InSection 5.2.3 we discuss how photochemistry affects the ob-served composition. First we address the upper troposphere,then we present the family of detected hydrocarbons in themiddle atmosphere and how their abundances vary horizon-tally and vertically. Section 5.2.4 reviews the oxygen-bearingspecies observed to be present in the stratosphere, which im-plies an external oxygen flux to Saturn. Section 5.3 presentsthe current status of modelling the observed composition,starting with the tropospheric chemistry, either due to ther-mochemical reactions (Section 5.3.1.1) or photochemical re-actions (Section 5.3.1.2). In Section 5.3.2 we discuss thehydrocarbon stratospheric photochemistry. We discuss theimportant chemical reactions and how one-dimensional mod-els fare in terms of reproducing the observed composition.We then describe the one-dimensional seasonal models andthe first attempts to design two-dimensional models and theirdifficulties in fitting the observed meridional gradient in hy-drocarbons abundances. Finally, Section 5.3.4 reviews ourcurrent understanding of the oxygen chemistry induced in thestratosphere by the external flux.

5.2 Observed Composition

5.2.1 Major Gases or Bulk Composition

The enrichment of Saturn in heavy elements relative tothe Sun constitutes an essential constraint for formationscenarios. If our views on Saturn’s composition have beenimproving over recent years and during the Cassini primemission, our knowledge of the solar elemental compositionhas also evolved significantly. In the literature, differentauthors have compared Saturn’s composition with differentsolar values, without explicitly stating their reference,making intercomparisons difficult. In addition, authors havealso used the term mixing ratio both for volume mixing ratioand for the mixing ratio relative to H2, different by about20%. To avoid such a caveat in this Chapter, we quote allthe measurements in Saturn in terms of mole fraction, or theequivalent volume mixing ratio. The mole fractions are thenconverted in terms of enrichment relative to the Sun, usingthe solar composition proposed by Grevesse et al. (2007).Hence, our values for Saturn enrichment may not correspondto the values quoted in the cited references, which used anearlier solar composition.

Note, however, that some caveats on the solar enrichmentvalue still exist because of the necessity of making assump-tions about the partitioning of the elements into differentmolecular species (e.g., some oxygen may be tied up in non-H2O condensates in Saturn’s deep atmosphere so that watermay not represent the full complement of Kronian oxygen,Visscher and Fegley 2005, and other similar assumptions forthe other elements come into play).

5.2.1.1 Helium Abundance

Knowledge of the helium abundance in the giant plan-ets is important for studies of the evolutionary history ofthese bodies. During their formation, hydrogen and heliumwere acquired from the primitive solar nebula. Consequently,the volume mixing ratio of helium to molecular hydrogen[He]/[H2] is believed to have been initially uniform and equalto the protosolar value. During the evolution of Jupiter andSaturn, fractionation processes have modified this distribu-tion. In particular, the immiscibility of helium in metallic hy-drogen with resulting gravitational separation in the interiorsof these planets is expected to have resulted in enhancementof helium in their deep interiors with depletion in the outer,molecular envelope. Measurements of [He]/[H2] in the ob-servable atmosphere can strongly constrain evolutionary the-ories of these bodies.

A combination of Voyager infrared spectrometer (IRIS)and radio occultation (RSS) measurements were used to de-termine the helium abundance in the upper tropospheres ofall four giant planets. Analysis of the RSS data yields a pro-file of T=m, the ratio of the temperature to the mean molecu-lar mass. For an assumed atmospheric composition, the meanmolecular mass and microwave refractivity coefficient canbe calculated, and a profile of temperature versus baromet-ric pressure T .p/ can be obtained. A radiative transfer codeis used with this profile to calculate a theoretical thermalemission spectrum that is compared with measured spectraacquired near the occultation point on the planet. With thisapproach, a helium-to-hydrogen mixing ratio ŒHe=ŒH2 of0:110˙ 0:032, corresponding to a mass fraction Y D0:18˙0:04, was obtained for Jupiter (Gautier et al. 1981; Conrathet al. 1984), representing a modest depletion with respect tothe protosolar value Y D 0:28 (Profitt 1994), while a re-markably low value of 0:034˙0:024 (Y D 0:06˙0:05) wasfound for Saturn (Conrath et al. 1984). Subsequent in situmeasurements of He from the Galileo probe gave a value ofŒHe=ŒH2 D 0:157˙ 0:003 on Jupiter (von Zahn et al. 1998;Niemann et al. 1998). The Voyager Jupiter result can be madeconsistent with the Galileo result only if the nominal radiooccultation profile (Lindal 1992) is made cooler at all atmo-spheric levels by �2 K (Conrath and Gautier 2000). Thissuggests the presence of systematic errors in the Voyager

5 Saturn: Composition and Chemistry 85

measurements for Jupiter and raises the possibility of sim-ilar errors in the helium determination for Saturn.

The detailed shape of the thermal emission spectrum inthe far infrared (� < 600 cm�1) provides an additional con-straint on the helium abundance. The differential spectral de-pendence of the S(0) and S(1) collision-induced absorptionlines and translational continuum of H2 is a function of therelative contribution of H2–H2 and H2–He interactions. Con-rath and Gautier (2000) used this dependence to obtain a newdetermination of the Saturn He abundance using VoyagerIRIS measurements only. In addition to helium, this portionof the spectrum is also sensitive to the vertical thermal struc-ture and the molecular hydrogen ortho/para ratio, and it isnecessary to simultaneously retrieve the temperature profile,and the para H2 profile along with the He abundance. Sep-aration of these parameters is dependent on relatively sub-tle effects of each on the shape of the collision-induced H2

spectrum. As a consequence, the retrieval problem is highly“ill-posed” and requires the use of a priori constraints in theinversion algorithm. These take the form of low-pass filter-ing of the temperature and para H2 profiles. Because of theweak separability of the parameters, the results are stronglydependent on these constraints, and only rather broad lim-its can be set on the He abundance. Using this approach,Conrath and Gautier (2000) obtained values of ŒHe=ŒH2

in the range 0.11–0.16 (corresponding to a helium mass frac-tion range 0.17–0.24), significantly larger than the value ob-tained with the IRIS/RSS approach. The IRIS/RSS method isstrongly sensitive to systematic errors in the RSS and/or theIRIS measurements, while the IRIS-only inversion approachis sensitive to any factors that can affect the differential spec-tral shape such as spectrally dependent tropospheric aerosol

opacities that are poorly constrained. Given these uncertain-ties in the Voyager results, a new determination of the Saturnhelium abundance became a major Cassini science objective.The primary approach used in the Cassini analysis makes useof Composite Infrared Spectrometer (CIRS) measurementsalong with Cassini RSS results in a manner similar to theVoyager IRIS/RSS analysis. The range of latitudes and ob-servational geometries covered by the Cassini radio occul-tations can lead to a better understanding of the limitationsand possible error sources associated with this method. Asan additional constraint, direct inversions of CIRS spectraare also being pursued. The extended spectral range to lowerwavenumbers, along with the large spatial and temporal cov-erage available from Cassini, permits better separation of theparameters affecting the shape of the CIRS spectrum, whichmay lead to better constraints on the helium abundance withthe CIRS-only approach than was possible with IRIS.

During the course of the Cassini prime mission, Saturnatmospheric radio occultations have been acquired over arange of latitudes and occultation geometries, along withnear-simultaneous CIRS spectral measurements. Prelimi-nary results based on eleven low-latitude occultation points,all within Saturn’s equatorial jet, give a mean value ofŒHe=ŒH2 D 0:08, corresponding to a He mass fraction of0.13 or a mole fraction of 0.07 (Gautier et al. 2006). An ex-ample of a spectral fit is shown in Fig. 5.1. In this analysis, itwas assumed that only hydrogen, helium, and methane con-tribute significantly to the mean molecular mass and meanrefractivity coefficient, and a methane-to-hydrogen mixingratio ŒCH4=ŒH2 D 4:86 � 10�3 was used. Initial resultsfrom the CIRS-only approach of direct spectral inversionyield somewhat higher values, consistent with the Voyager

Fig. 5.1 Spectra calculated froman RSS T=m profile at 7.4ıS,illustrating the sensitivity of theCIRS/RSS method to helium.The value of ŒHe=ŒH2 assumedin each case is indicated. Anaverage of 450 CIRS spectraacquired near the occultationpoint is shown for comparison.Only the spectral region between220 and 500 cm�1 is used in theanalysis


IRIS-only results of Conrath and Gautier (2000). However,the apparent discrepancy between the CIRS/RSS results andthe CIRS-only results once again suggests the possibility ofsystematic errors. A detailed error analysis is in progress. Er-ror sources considered include uncertainties in the absolutecalibration of CIRS, gaseous absorption coefficient errors, ef-fects of additional opacity sources such as clouds and hazes,uncertainties in radio frequency refractivity coefficients, anduncertainties in the gravitational potential surfaces used inthe RSS analyses. Of particular concern is the sensitivityof the retrieved radio occultation T=m profiles to perturba-tions in the gravitational potential surfaces associated withthe wind field. In a preliminary study of this sensitivity, twodifferent wind models have been used. In one model, theshape of the potential surfaces is based on the Voyager cloud-tracked winds, assumed to be uniform parallel to the plane-tary rotation axis (barotropic). The second model assumesno winds and yields a temperature profile �2 K warmer for agiven molecular mass, resulting in a value of ŒHe=ŒH2 that is�0:02 smaller than that obtained with the barotropic model(Flasar et al. 2008). Further investigations into the effects ofthe wind field are being carried out using radio occultationsand CIRS spectra acquired at higher latitudes away from theequatorial jet. Although major uncertainties remain to be re-solved, the preliminary values from both the CIRS/RSS andCIRS-only analyses fall within the He mass fraction range0.11–0.25 suggested by evolutionary modeling results (seefor example Hubbard et al. 1999; Guillot 1999), and imply atleast some depletion from the proto solar value.

Some constraints on the helium abundance can also besupplied by Cassini UVIS occultation data. PreliminaryUVIS results are presented in Chapter 8.

5.2.1.2 The Para Fraction of Molecular Hydrogen

Molecular hydrogen comes in two states, the ortho state,corresponding to odd rotational quantum numbers, and thepara state corresponding to the even quantum rotationalnumbers. At deeper atmospheric levels, the ortho-para ra-tio approaches its 3:1 high temperature limit. In the shal-low atmosphere, molecular hydrogen can depart from itsthermodynamic equilibrium ortho-para ratio because of theslow conversion between the ortho and para states. An up-welling air parcel tends to retain its initial para hydrogenfraction (fp) corresponding to the warmer temperatures ofthe deeper levels. As a consequence, its value of fp can besmaller than the equilibrium value (fp e) associated with thecooler temperatures of the upper troposphere. Hence, the hy-drogen para fraction is of considerable interest to trace thedynamics in Saturn’s upper troposphere. Since the ortho-paraconversion rate can be shortened through surface catalyticprocesses, fp can also be influenced by the distribution of

atmospheric aerosols. The para hydrogen fraction can bemeasured by remote sensing using the collision-induced H2

continuum. Conrath et al. (1998) and Fletcher et al. (2007a)both retrieved Saturn’s fp in the upper troposphere, be-tween 400 and 100 mbar, respectively from Voyager/IRISand Cassini/CIRS. The different patterns are not easy to in-terpret as the difference fp e � fp changes sign with altitudeand latitude. Conrath et al. (1998) found a fp minimum near60ıS and a fp maximum near 15ıS, consistent with upwardmotion near 60ıS and downwelling in the tropics. The north-ern hemisphere, just emerging from winter, had higher fp .In contrast, Fletcher et al. (2007a) found the lowest fp at theequator, a summer Southern Hemisphere with fp e � fp > 0

and a winter Northern Hemisphere with fp e � fp < 0.Since the seasons probed by Voyager and Cassini are sim-ilar, closer agreement might be expected. Because of thelow upper tropospheric lapse rate on Saturn, especially inthe summer hemisphere, the spectral information content onfp is limited. As a consequence, the retrievals are stronglydependent on the a priori constraints assumed in the inver-sion algorithms, which may account for these differences, atleast in part. This topic remains to be investigated in detail.As Cassini CIRS data continue to be acquired, hemisphericasymmetries associated with changing seasonal conditionswill be better characterized.

5.2.1.3 Carbon Elemental Composition

The elemental composition of carbon is determined throughthe measurements of the methane mole fraction, sincemethane is well-mixed, does not condense, and is expectedto be the thermodynamically stable form of carbon through-out the atmosphere. Before the review by Prinn et al. (1984),all the methane measurements in Saturn had been obtainedin the solar reflected spectral range. Although all the mea-surements concluded that carbon was enriched with respectto the solar composition, the magnitude of the enrichmentvaried widely from one study to another. Since 1984, thequest to measure Saturn’s C/H ratio in the visible and in thenear-infrared spectral regions has continued. The principleremains the same: one needs to observe simultaneously anH2 and a CH4 absorption of similar strength and, if possible,close to each other in the spectral range. With this technique,the two gaseous absorptions probe similar pressure levels andcan be modeled with the same cloud structure.

Recent studies have taken advantage of the improvedknowledge of methane absorption coefficients, and of newand more efficient methods in multiple scattering numericalmodeling. However, the large dispersion, and the incompat-ibility of the different measurements within their respectiveerror bars, has not disappeared, as shown in Table 5.1. Thislarge dispersion in methane mole fraction inferred from solar


Table 5.1 CH4 volume mixing ratios and C/H enrichments relative tothe solar composition. The C/H enrichments are calculated using thesolar composition of Grevesse et al. (2007) and a H2 mole fraction of

0:92. The measurements in the thermal infrared are the most reliable,the value measured by Fletcher et al. (2009a) being the most accurate

CH4 vmr Enrichment Wavelength Reference

.3:9 ˙ 0:4/ � 10�3 8:6˙ 0:9 0.725–1.01 �m Trafton (1985)

.2:1C0:8�0:2 /� 10�3 4:6

C1:8�0:4 0.6 �m Killen (1988)

.3:0 ˙ 0:6/ � 10�3 6:6˙ 1:3 0.46–0.94 �m Karkoschka and Tomasko (1992)

.2:0˙ 0:5/ � 10�3 4:4˙ 1:1 1.7 �m and 3.3 �m Kerola et al. (1997)

.4:3C2:3�1:3 /� 10�3 9:5

C5:1�2:9 7.7 �m Courtin et al. (1984)

.4:5C1:1�1:3 /� 10�3 10:0

C2:4�2:9 8–11 �m Lellouch et al. (2001)

.4:5˙ 0:9/ � 10�3 10:0 ˙ 2:0 96–136 �m Flasar et al. (2005)

.4:7˙ 0:2/ � 10�3 10:4 ˙ 0:4 96–136 �m Fletcher et al. (2009a)

Fig. 5.2 Four rotational lines ofCH4 observed by CIRS arecompared with synthetic spectracomputed for volume ming ratiosof 3:0� 10�3, 4:5 � 10�3 and8:0� 10�3 . Adapted fromFletcher et al. (2009a)

reflected observations can be attributed to the difficulty inmodeling accurately the complex saturnian cloud structure,in the blending with other molecular absorptions, and also inthe still large uncertainties in methane absorption coefficientsat low temperatures.

In contrast, studies in the thermal infrared range haveclustered their results around a methane mole fraction of4:5 � 10�3. Analysis in this spectral range requires first thedetermination of the vertical temperature profile, then, as-suming this profile, the adjustment of the volume mixingratio until the observed methane thermal emission is repro-duced. Courtin et al. (1984) were the first to carry out such ameasurement. They used the temperature profile determinedfrom the Voyager radio occultation experiment along withthe stratospheric CH4 �4 emission observed by IRIS to in-

fer a volume mixing ratio of .4:3C2:3�1:3 / � 10�3. Fifteen years

later, the Short Wavelength Spectrometer (SWS) aboard theInfrared Space Telescope (ISO) observed the 8–11 �m re-gion. Although, this spectral region is dominated by PH3 ab-sorptions, micro-windows between 10 and 11 �m allowedLellouch et al. (2001) to measure the tropospheric tempera-ture, while the �4 wings in the 8.15–8.5�m range probed theCH4 tropospheric mixing ratio. Now, Cassini/CIRS observesfor the first time the methane rotational lines (Fig. 5.2). Theselines, formed on the H2 collision-induced continuum thatprobes the tropospheric temperature, are well isolated fromother gaseous absorption. Hence, they allow a very precisemeasurement. Fletcher et al. (2009a) obtain the most accu-rate measurement, .4:7˙0:2/�10�3, averaging over a largernumber of CIRS observations.


This mole fraction corresponds to a carbon enrichmentof 10.4 with respect to the solar abundance, assuming thata negligible amount of carbon is tied up in constituents otherthan CH4. Cassini hence definitely demonstrates that Saturnlies in between Jupiter, and Uranus and Neptune, in termsof carbon elemental enrichment. This has important impli-cations for the giant planets formation scenarios reviewed inthe Formation Chapter.

5.2.1.4 Nitrogen, Sulfur and Oxygen

About ten astronomical units from the Sun, Saturn is a coldworld. For this reason, the clouds form at large pressures(about 20 bars for the water cloud, a few bars for the chemi-cal NH4SH cloud, and around the 2-bar level for NH3 cloud).In this situation, it is extremely difficult for a remote ob-server to measure the deep, global abundance of the con-densibles below their associated clouds. Only observationsin the centimeter range, between 6 and 70 cm, are able toprobe molecular species that deep. Unfortunately, the inter-pretation of such observations is difficult for several differentreasons. First, the absolute calibration uncertainties are largein this wavelength range, not better than 20%. Second, thelineshapes of the gaseous absorbers are not very well known,although progress has been made recently. Finally, the vari-ous absorbers, gas, liquids, or solids, have broad, relativelyfeatureless spectra; hence the measurements in the centime-ter range do not contain independent information on bothtemperature and composition.

For all these reasons, the published values must be takenwith caution. The most convincing results have been ob-tained by Briggs and Sackett (1989). Their Very Large Ar-ray (VLA) and Arecibo observations were best fit by a deepammonia volume mixing ratio of .4:8 ˙ 1/ � 10�4, hence4:5 ˙ 1:0 times the solar abundance. Moreover, Briggs andSackett (1989), (see also Killen and Flasar 1996; van der Taket al. 1999), found that the brightness temperature in the 2–6 cm range points toward a low ammonia relative humid-ity between 2 and 4 bars. They interpreted this depletion ofNH3 as an evidence for a large H2S abundance, equal to avolume mixing ratio of 4:1 � 10�4, that served as a sink ofNH3 through the formation of a dense NH4SH cloud. Such anabundance corresponds to 17 times the solar composition. Itis hoped that measurements from the Cassini Radio ScienceSubsystem will improve the absolute calibration of Saturn’sobservation in the 2–14 cm range. Combined with the CIRStemperature profiles, a more accurate determination of theN/H and S/H ratios could be obtained.

Although tropospheric water has been detected by ISO inthe 5-�m band (de Graauw et al. 1997), the inferred abun-dance is highly subsolar: ISO observations probe only pres-sure levels (2–4 bars) where water vapor condenses out.

This situation precludes any measurement of the O/H ratioin Saturn, which constitutes an important missing piece ofinformation for constraining the delivery of volatiles to theplanet. Unfortunately, we cannot expect any progress on thisissue from Cassini and will have to wait for a deep entryprobe.

5.2.1.5 Isotopic Composition

The isotopic composition, especially the D/H ratio, isimportant for constraining the fraction of solids relative togases that were accreted to form Saturn. The majority of D/Hdeterminations in Saturn’s atmosphere have been derivedfrom the comparative abundance of methane and deuteratedmethane (CH3D). Besides the uncertainty on CH4 itself, theinterpretation of the CH3D measurements in terms of thebulk deuterium abundance (i.e., in H2) is complicated by theexistence of an isotopic exchange reaction between H2 andCH4 (HD C CH4 • CH3D C H2) whose thermodynamics,kinetics and coupling with atmospheric dynamics are un-certain. According to different studies (Lecluse et al. 1996;Smith et al. 1996), the fractionation coefficient f :

f D .D=H/CH4

.D=H/H2

lies in the range f D 1:34˙ 0:19.Deuterated methane was first detected by Fink and

Larson (1978) in its �2 band at 4.7 �m. Owen et al. (1986)and de Bergh et al. (1986) were the first to publish an abun-dance of CH3D, using high spectral resolution observationsof the 3�2 band at 1.55�m (see Table 5.2 for the values). An-other determination in the solar reflected range was obtainedby Kim et al. (2006), between 2.87 and 3.10 �m (CH3D�3 C �2 band), with a low abundance of 2:5� 10�7. Noll andLarson (1991) used the 4.7-�m spectral region, that probesdeep in Saturn’s troposphere, to determine a volume mix-ing ratio of .3:3 ˙ 1:5/ � 10�7. This spectral region, diffi-cult to analyse due to some strong PH3 absorption, yieldeda similar result from ISO/SWS observations. CH3D abun-dance can also be measured in the 8.6-�m region using the�6 thermal emission. Three studies focused in this spectralregion with medium resolution observation (between 4.3 and

Table 5.2 D/H ratios in H2

.D=H/H2 Method Reference

.1:6C1:3�1:2 / � 10�5 CH3D at 8 �m Courtin et al. (1985)

.1:7C1:7�0:8 / � 10�5 CH3D at 1.6 �m de Bergh et al. (1986)

.1:1 ˙ 1:3/ � 10�5 CH3D at 4.7 �m Noll and Larson (1991)

.2:3C1:2�0:8 /� 10�5 HD R(1) Griffin et al. (1996)

.1:85C0:85�0:60 /� 10�5 HD R(2) & R(3) Lellouch et al. (2001)

.2:01:4�0:7/� 10�5 CH3D at 8 �m Lellouch et al. (2001)

.1:6 ˙ 0:2/ � 10�5 CH3D at 8 �m Fletcher et al. (2009a)


0.5 cm�1): Courtin et al., 1984 using Voyager/IRIS data,Lellouch et al. (2001) with ISO/SWS data, and Fletcheret al. (2009a) with Cassini/CIRS spectra. Overall, the differ-ent measurements cluster around a value for the D/H ratio inmethane of 1:8� 10�5. Given the above estimate of the frac-tionation coefficient f , this gives a low estimate for the D/Hin H2: about 1:5�10�5. Ground-based, high-resolution spec-troscopic observations that resolved the stratospheric cores ofthe �6 CH3D lines would be of great interest to improve theCassini determination.

The first, and to date only, direct measurement of the D/Hratio in molecular hydrogen was obtained with the ISO tele-scope. Griffin et al. (1996) observed the R(1) rotational lineat 56 �m with the Long Wavelength Spectrometer (LWS)aboard ISO. However, their measurement (Table 5.2) mustbe taken with caution, as the ISO/LWS data were difficult tocalibrate for the very large flux of the giant planets. Lellouchet al. (2001) used ISO/SWS to observe the HD R(2) andR(3) rotational lines. From this, they derive a D/H ratio of.1:85C0:85

�0:60 /�10�5. Combining HD and CH3D measurements,Lellouch et al. (2001) concluded to .D=H/H2 D .1:70C0:75

�0:45 /�10�5. This value is not accurate enough to distinguish Saturnfrom Jupiter (.D=H/H2 D .2:25 ˙ 0:35/ � 10�5) and fromthe local interstellar medium (.D=H/H2 D .1:5 ˙ 0:1/ �10�5). In this respect, Saturn does not seem to obey thetrend of increasing D/H from Jupiter to Neptune. Improve-ments on this determination should come in the near futurefrom the Hershell satellite when it observes the R(0) line at2680 GHz, and from better calibrated Cassini/CIRS R(1) lineobservations.

Very few authors have focused on the 12C=13C ratio inSaturn. Combes et al. (1977) observed 13CH4 and 12CH4

lines of the 3�3 band at 1.1 �m to determined a 12C=13C ra-tio of 89C25

�18 . This ratio was later corrected to 71C25�18 by Brault

et al. (1981), who revised the 13CH4:12CH4 intensity ratio inthe 3�3 band based on laboratory spectra of methane. Sadaet al. (1996) measured recently a 12C=13C ratio of 99C43

�23 inethane. Although C2H6 is not the major carbon reservoir inSaturn, we do not expect significant isotopic fraction for thisspecies.

Hence, before the Cassini arrival, the Kronian 12C=13Cratio was compatible with the terrestrial value (89:9C2:6

�2:4 ),but the measurements were not very constraining. The highquality of the CIRS dataset over the prime Cassini mis-sion has allowed Fletcher et al. (2009a) to obtain a muchmore precise value. They use the �4 band thermal strato-spheric emission to infer a 12C=13C ratio of 91:8C5:5

�5:3 , stillcompatible with the terrestrial and the jovian values, butdifferent from the Titan value (Niemann et al. 2005). Thisdifference shows that methane on Titan has suffered fromisotopic fractionation either at its formation or through itsevolution.

5.2.2 Thermochemical Products

Some chemical species have been detected at shallow at-mospheric levels with abundances that largely exceed theabundances predicted by thermodynamical equilibrium. Asexplained in detail in Section 5.3.1.1, the explanation forthe observed abundances involves rapid convective trans-port from the deep, hot, atmosphere where the equilibriumabundances of these species are relatively large. The ob-served mixing ratios are then representative of quenchinglevels (300–500 bars) where the time constants of the conver-sion reactions become equal to or greater than the timescalefor convective mixing. Below this level, thermochemicalequilibrium prevails, whereas above, chemical destruction isinhibited so that the mole fractions remain constant in an up-lifted air parcel. The distribution of thermochemical productsis an important tracer of dynamical processes in the tropo-sphere, and has been given a lot of attention. Hereafter, wedescribe the measurements of such disequilibrium species:phosphine, germane, and arsine. (The specific case of car-bon monoxide, with two different possible origins, is detailedin Section 5.2.4.) All of these measurements were obtained inthe 5-�m window of Saturn’s spectrum (Fig. 5.3). The lowopacity of the major gases in this spectral region offers theopportunity to probe pressure levels of several bars. This longpath length allows the detection of trace constituents, whileat these pressure levels the measured mixing ratios are un-affected by photochemical destruction, hence revealing theabundances of the observed species at the quench level.

The first spectrum of Saturn in the 5-�m windowwas obtained by Larson et al. (1980) using the Fourier

Fig. 5.3 Observed ISO-SWS spectrum (upper curve) and syntheticspectrum of Saturn (lower curve) in the 5�m region. Spectral ab-sorptions are due to NH3, PH3, AsH3, GeH4, CH3D and H2O. In thelower curve, the narrow line corresponds to a calculation without H2O.Adapted from de Graauw et al. (1997)


Transform Spectrometer on the Kuiper Airborne Observa-tory (KAO/FTS). The absorption features of phosphine wereevident in this moderate spectral resolution spectrum, but amore quantitative analysis had to await higher spectral res-olution observations. Bézard et al. (1989) and Larson andNoll (1991) both demonstrated that the abundance of PH3

in the lower troposphere of Saturn, with a volume mixingratio in the range .4–10/ � 10�6, was larger than the valuein Jupiter. ISO observations confirmed this value, with deGraauw et al. (1997) deriving a global volume mixing ratio of4:4�10�6. Saturn’s PH3 global abundance corresponds to anelemental enrichment of a factor of 10 in comparison with thesolar abundance (assuming all phosphorous is tied up in PH3

on Saturn). It would be interesting to know whether this deepmixing ratio varies with latitude, as it would indicate a merid-ional difference in the strength of convection from the in-terior. From CIRS observations, Fletcher et al. (2007b) areunable to disentangle deep variations from variations abovethe radiative-convective boundary. The Visual and Infrared-Mapping Spectrometer (VIMS) aboard Cassini is in positionto study such a meridional variation in the lower troposphere,but no results have been released yet.

The first evidence for germane in Saturn came from ob-servations near 4.7 �m obtained at the United Kingdom In-frared Telescope (UKIRT). Noll et al. (1988) used these datato determine a GeH4 volume mixing ratio of .4˙2/�10�10.However, the analysis of spectra in the 4.7-�m region is com-plicated by the presence of strong PH3 absorptions and by anequal balance between solar reflection and thermal emission.This situation has led Noll and Larson (1991) to concludethat their 4.7-�m Infrared Telescope Facility (IRTF) obser-vations favored the presence of GeH4 in Saturn, but that theycould not exclude its absence. The confirmation of the pres-ence of germane in Saturn hence came recently, from ISOobservations. Although of moderate spectral resolution, ISOspectra achieved signal-to-noise ratios in the 5-�m regionmuch larger than that of previous observations. Using thesedata, de Graauw et al. (1997) measured a deep germane vol-ume mixing ratio of 2 � 10�9 (corresponding to 0.2 timesthe solar abundance), and found evidence for a decreasingmixing ratio above the 1-bar pressure level, possibly due tophotolysis in the upper troposphere.

Arsine was detected independently by two differentteams: Bézard et al. (1989) used the Fourier Transform Spec-trometer mounted on the Canada-France-Hawaii Telescope(FTS/CFHT), while Noll et al. (1989) used the UKIRT. Nolland Larson (1991) at the IRTF and more recently de Graauwet al. (1997) using ISO data confirmed the detection. TwoAsH3 vibration bands are observed in the 4.7-�m region, the�1 and �3. The two bands allow the authors to probe the ar-sine vertical profile between �4 bars and 0.2 bar. In the deepatmosphere, the published volume mixing ratios clusteredaround .2:5˙1/�10�9, while Bézard et al. (1989) measured

a mixing ratio of .3:9C2:1�1:3 /� 10�10 in the upper troposphere.

The deep mixing ratio corresponds to a global As elemen-tal abundance equal to five times the solar abundance. In theupper troposphere, AsH3 may be subject to photochemicaldestruction as is the case for PH3 and GeH4. VIMS is also inposition to derive a meridional distribution of the deep AsH3

abundance.Not all elements experience enhancements in the upper

troposphere, revealing different chemistries. For example,Teanby et al. (2006) used far infrared spectra (10–600 cm�1)from the Cassini Composite InfraRed Spectrometer (CIRS)to determine the best-to-date upper limits of hydrogenhalides HF, HCl, HBr, and HI. These authors obtained 3-�upper limits on HF, HCl, HBr, and HI mole fractions of8:0 � 10�12, 6:7 � 10�11, 1:3 � 10�10, and 1:4 � 10�9, re-spectively, at the 500-mbar pressure level. These upper limitsconfirm sub-solar abundances of halide species for HF, HCl,and HBr in Saturn’s upper atmosphere, consistently with pre-dictions from thermochemical models. We note that the up-per limit for HCl derived by Teanby et al. (2006) is 16 timeslower than the tentative detection at 1:1 � 10�9 reported byWeisstein and Serabyn (1996).

5.2.3 Photochemical Products

5.2.3.1 Evidence for Photochemistry in the UpperTroposphere

Several molecules are known to be affected by photoly-sis in the upper troposphere. Weisstein and Serabyn (1994)were the first to demonstrate, from high spectral resolu-tion of the 1–0 rotational line observations, that a cutoff inphosphine abundance exists at a pressure between 13 and140 mbar. Orton et al. (2000, 2001), also using rotationalline observations, showed that the PH3 abundance droppedfrom 7:4�10�6 at 645 mbar down to 4:3�10�7 at 150 mbar.Such a behaviour was also consistent with ISO/SWS obser-vations, as Lellouch et al. (2001) measured a profile withmole fractions of 6 � 10�6 up to the 600-mbar level, de-creasing to 4 � 10�6 at 250 mbar, and 3 � 10�7 at 150mbar. Since phosphine does not condense at the tropopauseof Saturn, such a decrease with altitude can only be explainedby photolysis. However, none of the products of this phos-phine photochemistry has been detected to date. In this con-text, the monitoring of the meridional phosphine gradient isa powerful tracer of differences in vertical mixing, althoughit should be mentioned that aerosol opacity in the ultravio-let also strongly affects the phosphine gradient and cautionshould be used when trying to disentangle the relative effectsof aerosol shielding and vertical mixing. In fact, phosphinephotolysis may itself constitute a source of haze.


90 80 70 60 50 40 30 20 10 0 –10 –20 –30 –40 –50 –60 –70 –80 –90Planetographic Latitude

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Fig. 5.4 Top panel: The phosphine mole fraction as a function of lat-itude and pressure as retrieved from Cassini/CIRS data. Bottom panel:CIRS spectrum of the equatorial region in the range 900–140 cm�1,

compared with synthetic spectra showing the sensitivity the phosphinemole fraction at 500 mbar. Adapted from Fletcher et al. (2009)

Fletcher et al. (2007b, 2008, 2009b) use the Cassini/CIRSspectra (Fig. 5.4, bottom panel) to measure the phosphineabundance as a function of latitude. Baines et al. (2005)also publish preliminary PH3 meridional variations above thecloud top as retrieved from VIMS data. At 150 mbar their re-sults are in line with previous studies, but at 250 mbar theirabundance is lower than that of Lellouch et al. (2001) any-where on the planet. Reasons for this disagreement have notbeen investigated. The Cassini results are summarized as fol-lows (see also Table 5.3 and Fig. 5.4, Top panel).

1. The equatorial region presents the highest PH3 abundancein the upper troposphere, which is consistent with theelevated equatorial haze, the cold temperature and thesub-equilibrium H2 para fraction measured in this region.

2. Tropical latitudes (˙23ı) present the lowest PH3

abundance, consistent with upwelling at the equator anddownwelling in the neighbouring equatorial belts.

3. Mid-Latitudes at ˙42ı presents local maximum followedby a local minimum at ˙57ı.

Table 5.3 PH3 vertical profiles measured from Cassini/CIRS mid-IRspectra, averaged in latitude regions (from Fletcher et al. (2007b)

qPH3 at 250 mbar qPH3 at 150 mbarLatitude (in ppb) (in ppb)

North Polar65–85 ıN 820˙ 380 220˙ 200

North Temperate15–65 ıN 390˙ 100 62˙ 34

Equatorial15ıS–15 ıN 1700 ˙ 200 470˙ 90

South Temperate65–15 ıS 660˙ 80 84˙ 27

South Polar85–65 ıS 990˙ 130 160˙ 40

4. Polar regions are enhanced in phosphine relative totropical and mid-latitudes, but a sharp phosphinedepletion occurs within ˙2-3ı of the poles, suggestive ofsubsidence over the high-temperature polar cyclones.

5. The northern hemisphere shows lower PH3 abundancethan the southern hemisphere. This is in opposition witha simple prediction based on the higher photolysis rate


in the summer hemisphere compared to that in the winterhemisphere, but maybe explained by a enhanced shieldingby aerosols in the southern hemisphere.

In the upper troposphere the ammonia volume mixing ra-tio decreases with altitude due to the combined effect of con-densation and photolysis. The NH3 vertical profile is slightlysubsaturated around the 700-mbar pressure level (Courtinet al. 1984; Burgdorf et al. 2004), and highly subsaturatedabove that, hence showing evidence for photolysis at lowerpressures, reaching an abundance of 10�9–10�8 around 300–400 mbar (Kerola et al. 1997; Kim et al. 2006). In the up-per troposphere, evidence for photolysis of arsine and ger-mane has been found by Bézard et al. (1989) and de Graauwet al. (1997).

5.2.3.2 Stratospheric Products

In the upper stratosphere, methane is photodissociated byultraviolet solar emission to produce CH, CH2, and CH3

radicals.Subsequentchemicalreactionsbetweenthephotolysisproducts and other atmospheric molecules yield severalheavyhydrocarbons: to date, acetylene (C2H2), ethylene (C2H4),ethane (C2H6), propane (C3H8), methylacetylene (CH3C2H),diacetylene (C4H2), and benzene (C6H6) have been detected;the lighter radical CH3 has also been observed.

C2H6 and C2H2 are the two most abundant species and,not surprisingly, were the first to be detected: acetylene in theUV range (Moos and Clarke 1979), and ethane in the ther-mal infrared (Tokunaga et al. 1975). Courtin et al. (1984),using Voyager/IRIS observations, were the first to deter-

mine reliable abundances: .3:0 ˙ 1:1/ � 10�6 from theethane �9 band at 821 cm�1, and .2:0 ˙ 1:4/ � 10�7 fromthe C2H2 �5 band at 729 cm�1. From ground-based ob-servations in the thermal infrared, Noll et al. (1986b) andSada et al. (2005) found slightly larger values (the dif-ferent measurements are summarized in Fig. 5.5). UsingISO/SWS observations, de Graauw et al. (1997) and Moseset al. (2000a) were the first to demonstrate that the C2H2

volume mixing ratio actually increases with altitude, as ex-pected from photochemical models. Indeed, the emissionsfrom the �4 C �5 � �4 hot band detected by ISO probedhigher altitudes than the �5 band. Moses et al. (2000a) in-ferred a mixing ratio of .1:2C0:9

�0:8 / � 10�6 at 0.3 mbar and.2:7˙ 0:8/ � 10�7 at 1.4 mbar. For ethane, as all lines haveapproximately the same strength, vertical profile informationcannot be obtained; from ISO/SWS data, a volume mixingratio at 0.5 mbar alone was determined: .9 ˙ 2:5/ � 10�6.Ethane and acetylene spectral features have also been unam-biguously detected in the reflected infrared around 3 �m byBjoraker et al. (1981) and Kim et al. (2006) (respectively the�3C�9C�11 of ethane and the �3 of acetylene). These studiessuggested a cut-off in the vertical distributions at about 10–15 mbar, but the uncertainties on the band strengths in thisspectral region make the inferred mole fractions less reliablethan from the thermal infrared. Kim et al. (2006) also de-tected ethane emissions in its �7 band originating from �barlevels. However, since collision relaxation parameters are notknown with enough accuracy for this band, the observationscould only be crudely analyzed yielding no reliable estimatesof the ethane abundance.

As products of methane photolysis, ethane and acety-lene abundances might be expected to exhibit meridional

Fig. 5.5 Hydrocarbon molefractions as a function of pressurein Saturn’s upper atmosphere, asderived from the “Model C” 1-Dsteady-state photochemicalmodel of Moses et al. (2005). Thesolid curves represent the modelprofiles for the individualhydrocarbons (as labeled), andthe symbols with associated errorbars represent various infraredand ultraviolet observations


Fig. 5.6 The latitude variation of the volume mixing ratios of C2H6

(left) and C2H2 (right) at Ls D 270ı (southern summer solstice)at different pressure levels, as labeled. The solid lines represent thetheoretical model profiles from the 1-D seasonal model of Mosesand Greathouse (2005). The diamonds represent the IRTF/TEXES

observations of Greathouse et al. (2005), the crosses represent theCassini/CIRS nadir observations of Howett et al. (2007), and thesquares represent the Cassini/CIRS limb observations of Guerletet al. (2009). Note that the model reproduces the meridional behaviorof C2H2 but not C2H6

and seasonal variations. The observations mentioned abovewere unable to access this geographical dimension as theywere either disk-averaged, or targeted to a specific position.The work by Greathouse et al. (2005) hence opened theera of meridional hydrocarbon study. Using Texas EchelonCross Echelle Spectrograph (TEXES) observations in thethermal infrared, they showed that the C2H2 volume mixingratio at 1.16 and 0.12 mbar decreased by a factor of 2.5from the equator towards the south pole (Fig. 5.6). Incontrast, ethane was found to be stable within error bars, with2.3-mbar mixing ratios of .7:5C2:3

�1:7 / � 10�7 at the equatorand .1:0C0:3

�0:2 / � 10�5 at 83ıS. Cassini/CIRS now measuresboth the C2H2 and C2H6 abundance from nadir observa-tions (Howett et al. 2007), and from limb soundings (Fouchetet al. 2008; Guerlet et al. 2009). CIRS also extends the merid-ional coverage towards the northern hemisphere that was hid-den by the rings to Greathouse et al. (2005). Cassini resultsconfirm that the C2H6 mole fraction remains latitudinallyconstant at 1 mbar (although Howett et al. find a suspiciousincrease southward of 50ıS), and that C2H2 decreases to-wards both poles (Fig. 5.6). This behaviour can be attributed

to the different chemical timescales of the two molecules,C2H6 being a long-lived species compared to C2H2. Hence,the former can be horizontally transported and homogenizedwhile the latter reflects the mean meridional solar irradia-tion. However, this interpretation is not validated by chemi-cal models (see Section 5.3.2.4).

The Cassini/CIRS limb soundings also reveal some dy-namical features in the hydrocarbon meridional profiles. At1 mbar, Guerlet et al. (2009) find that the C2H2 profilespresent a sharp and narrow maximum centered at the equator,not shown by C2H6. They interpret this feature as a signatureof a dynamical process, the descent of air between 0.1 and 1mbar associated with the equatorial oscillation. This descenttransports C2H2 more efficiently than C2H6, as the formermolecule shows a stronger vertical gradient than the latter.At lower pressures (p < 0:1 mbar), that can only be probedby limb soundings or occultations, Guerlet et al. (2009) findthat the C2H2 and C2H6 mole fractions are the largest at mid-northern latitudes, and the lowest at mid-southern latitudes.This situation is in complete opposition with photochemi-cal model predictions of an abundance following the solar


irradiance at these pressure levels. The observations thus sug-gest the existence of a strong meridional circulation, trans-porting molecules from the summer hemisphere across theequator towards the winter hemisphere.

In the upper stratosphere, ethane, ethylene, and acetylenehave been detected from spacecraft ultraviolet obser-vations. The Ultraviolet Spectrometer (UVS) on Voy-ager 1 and 2 recorded six solar and stellar occultations(Broadfoot et al. 1981; Sandel et al. 1982; Festou andAtreya 1982; Smith et al. 1983; Vervack and Moses 2009).The Vervack and Moses (2009) study is the only one to an-alyze all six occultations. Vertical profiles for C2H2, C2H4,and C2H6 have been derived from this analysis, and Ver-vack and Moses (2009) confirm that the mixing ratios forall three species have a peak at high altitudes, with a de-creasing mixing ratio with decreasing altitude away fromthis high-altitude peak. The variability of the results fromthe six UVS occultations also demonstrates that the pressurelevel of the peak mixing ratio varies with latitude and/or timeon Saturn, which has interesting implications with respectto atmospheric transport. To date, the Cassini UltravioletImaging Spectrograph (UVIS) has also performed 15 stel-lar occultations and 7 solar occultations (see Shemansky andLiu 2009, and Chapter 8). The results from some of these oc-cultations are presented by Shemansky and Liu (2009), whoderive C2H2 and C2H4 profiles and further confirm the dis-tinct mixing-ratio peak and the meridional variability. Theultraviolet occultation results are discussed in more detail inChapter 8.

The ISO/SWS instrument, due to its unprecedented sen-sitivity in the thermal infrared, has allowed the detection ofseveral complex hydrocarbons. de Graauw et al. (1997) re-ported the detection of CH3C2H and C4H2 in the range 615–640 cm�1. The emissions are optically thin, and only columndensities can be derived: .1:1˙ 0:3/� 1015 molecules.cm�2for CH3C2H, and .1:2 ˙ 0:3/ � 1014 molecules.cm�2 forC4H2 were reported from the ISO/SWS analysis of Moseset al. (2000a). Bézard et al. (2001a) reported the detectionof benzene, from emission at 674 cm�1, with a column den-sity of .4:7C2:1

�1:1 / � 1013 molecules.cm�2. Cassini/CIRS is inposition to derive meridional distributions for these species,but no results have been published in the refereed literatureyet. ISO/SWS also unveiled the �2 emission from CH3 at16.5 �m. Bézard et al. (1998) derived a CH3 column den-sity in the range 1.5–7.5�1013 molecules.cm�2, taking intoaccount uncertainties in the data calibration, the CH3 bandstrength, and the temperature and methyl vertical profiles.Given recent updates in the measured line strengths of theof �2 fundamental of CH3 (Stancu et al. 2005), the Bézardet al. (1998) CH3 column abundance should be increasedby a factor of �2. Similarly, updates in our understandingof Saturn’s thermal structure at the time of the ISO obser-vations (e.g., Lellouch et al. 2001) and of spectral line pa-

rameters (e.g., Vander Auwera et al. 2007; Jacquinet-Hussonet al. 2005) necessitate some updates to the above quotedabundances from Moses et al. (2000a).

Finally, ground-based thermal infrared observations withthe high-resolution TEXES spectrometer have allowedBézard et al. (2001b) and Greathouse et al. (2006) to de-tect ethylene and propane, respectively. The inferred C2H4

column abundance lies between 2–3�1015 molecules.cm�2.For the C3H8 abundance, Greathouse et al. (2006) reported5-mbar volume mixing ratios of .2:7 ˙ 0:8/ � 10�8 at20ıS and .2:5C1:7

�0:8 / � 10�8 at 80ıS latitude, suggesting thatpropane, like ethane, does not present any meridional vari-ations of its abundance. However, from Cassini/CIRS limbsoundings, Guerlet et al. (2009) find that the propane volumemixing ratio does increase from the northern winter hemi-sphere towards the southern summer hemisphere. This con-tradiction remains to be resolved by future ground-based andCassini/CIRS observations.

5.2.4 External Oxygen Flux

An external oxygen influx to Saturn has long been postulated,originating either from micrometeoroid precipitation, largecometary impacts or from Saturn’s rings and satellites. A fluxof oxygen in the reducing atmosphere of Saturn can have aconspicuous effect on the stratospheric chemistry by formingnew molecules, attenuating the UV flux or providing conden-sation nuclei. The first observational basis for such an oxygensource was presented by Winkelstein et al. (1983). Theseauthors had to introduce a 1:6 � 1017 cm�2 column densityof water in the stratosphere in order to fit their IUE spectrumin the 150–300 nm range. Using HST data covering a similarspectral range, Prangé et al. (2006) showed that the large wa-ter abundance inferred by Winkelstein et al. (1983) resultedfrom their assumption of a vertically uniform acetylene pro-file. Using a C2H2 vertical profile compatible with infraredobservations and photochemical models (see Sections 5.2.3.2and 5.3.1.2), Prangé et al. (2006) showed that only upper lim-its on the H2O abundance can be derived from UV spectra.Water was first firmly detected by Feuchtgruber et al. (1997)using ISO observations. Rotational lines of H2O were clearlydetected at 30.90, 35.94, 39.37, 40.34, 43.89, 44.19, and45.11 �m, yielding a stratospheric column density of .1:4˙0:4/�1015 cm�2 (Moses et al. 2000b). ISO observations alsoallowed de Graauw et al. (1997) to detect the stratosphericemission of the CO2 �2 band at 14.98 �m for the first time.This emission is modeled with a CO2 column abundance of.6:3˙ 1:0/ � 1014 cm�2 (Moses et al. 2000b).

Carbon monoxide can also act as a tracer of an externaloxygen flux. Indeed, oxygen-bearing molecules are photo-chemically converted to CO in the stratosphere, and the CO


photochemical lifetime is long compared with a saturnianyear or other hydrocarbon lifetimes. However, CO can alsooriginate from Saturn’s interior as do PH3, GeH4, and AsH3.To discriminate between both possible sources, observersneed to retrieve the CO vertical profile: a stratospheric abun-dance larger than that in the troposphere constitutes thesignature of an external flux. CO was first detected by Nollet al. (1986a) in the (1–0) vibration band near 4.7 �m.Noll and Larson (1991) observations of the 4.5- to 5-�mregion at the IRTF superseded that of Noll et al. (1986a).About 10 CO-lines from the (1-0) band can be clearly iden-tified in the former spectrum. As demonstrated by Moseset al. (2000b), line intensities are mostly sensitive to theCO column abundance between 100 and 400 mbar, yield-ing a tropospheric volume mixing ratio of .1˙ 0:3/ � 10�9,i. e. a column abundance of .0:7–1:5/ � 1017 cm�2. How-ever, the observations could also be accommodated by astratospheric volume mixing ratio of 2:5 � 10�8; i. e. acolumn abundance of �6 � 1017 cm�2. Both distributionsfit equally well the observations, with the exception ofthe P14 line at 2086.3 cm�1, which is best matched by atropospheric distribution. Unfortunately, this line is entan-gled with phosphine absorption and is not well reproducedby the model spectra in any case, hence undermining theconclusion.

Due to their high spectral resolution, millimetric and sub-millimetric heterodyne observations are well suited to dis-criminate between the narrow stratospheric emission andthe broad tropospheric absorption. After several fruitless at-tempts (Rosenqvist et al. 1992; Cavalié et al. 2008), Cav-alié et al. (2009) obtain the first detection of the CO(3-2)line in Saturn using the James Clerk Maxwell Telescope.They find that the CO line is best matched with a strato-spheric mole fraction of 2:5 � 10�8 at pressures smallerthan 15 mbar, and of 10�10–10�9 at higher pressures. Thisprofile favors an external origin for carbon monoxide, dueto a cometary impact about 200–300 years ago. However,the water observed in Saturn’s stratosphere still needs to beprovided by a continuous source, so that both a continuoussource and a sporadic source of oxygen seem to be active inSaturn.

Herschel and the Atacama Large Millimeter Array(ALMA) will observe stronger CO and H2O lines at otherfrequencies, providing further constraints on the verticalprofiles of these species. Unfortunately Cassini can con-tribute very marginally to the observations of oxygenatedspecies. Water rotational lines are difficult to detect at thespectral resolution of CIRS. Hence, many spectra will haveto be averaged, at the expense of meridional resolution. ForCO2, it should be possible to extract a meridional profilefrom CIRS limb observations at high spectral resolution, butonly a few observations were performed, and have not yetbeen analyzed.

5.3 Chemistry

5.3.1 Tropospheric Chemistry

5.3.1.1 Thermochemistry

In the deep troposphere of Saturn, well below the regionsthat can be probed by remote-sensing techniques, temper-atures become high enough (i.e., �>1000 K) that energybarriers to chemical kinetic reactions can be overcome.Chemical reactions in these high-temperature regions there-fore proceed rapidly, and the atmosphere is expected toattain thermochemical equilibrium. The thermochemical-equilibrium composition is strongly dependent on tem-perature and weakly dependent on pressure, as well asbeing dependent on the relative abundance of the differ-ent elements. Fegley and Prinn (1985) presented the firstcomprehensive thermochemical-equilibrium calculations forSaturn. In this model, the large background atmospheric H2

abundance allows CH4 to be the dominant carbon-bearingmolecule throughout Saturn’s atmosphere, with all other car-bon species having abundances much less than CH4. Carbonmonoxide is expected to have an exceedingly low abun-dance in the observable regions of the upper tropospherebut becomes more and more abundant with increasing tem-perature and depth. Similarly, H2O, NH3, and H2S are thedominant forms of oxygen, nitrogen, and sulfur throughoutthe pressure-temperature regimes found in Saturn’s tropo-sphere. Updates to the major-element thermochemical equi-librium calculations for Saturn can be found in Fegley andLodders (1994), Lodders and Fegley (2002), Visscher andFegley (2005), and Visscher et al. (2006), although the qual-itative conclusions of Fegley and Prinn (1985) still hold.

Fegley and Prinn (1985) expect P4O6 vapor (formed fromthe oxidation of PH3 by water) to be the thermodynami-cally stable form of phosphorus in the �400–900 K regionon Saturn, with PH3 becoming dominant only at deeper lev-els for temperatures in excess of �1000K. At temperaturesbelow �400K (i.e., still well below the water cloud), theP4O6 vapor is expected to be converted to a solid NH4H2PO4

condensate, and gas-phase phosphorous-bearing species areexpected to have low abundances in the upper troposphereof Saturn under thermochemical-equilibrium conditions. Thephosphorous results are somewhat uncertain due to uncertainthermodynamic parameters and elemental ratios: Borunovet al. (1995) suggest that PH3 could be the dominant equi-librium form throughout Jupiter’s atmosphere at all temper-atures greater than �500K, at which point a NH4H2PO4

condensate forms; they expect Saturn’s thermochemistry tobe similar. The latest phosphorus equilibrium calculationsfor Saturn (Visscher and Fegley 2005) produce results qual-itatively similar to that of Fegley and Prinn (1985) in terms


of the phosphorus speciation, with some small quantitativedifferences in the temperature levels at which the differentmajor species take over.

Based on thermochemical equilibrium modeling, bothGeH4 and AsH3 are expected to be relatively abundantat depth on Saturn (Fegley and Prinn 1985; Fegley andLodders 1994) but fall to negligible quantities in the up-per troposphere due to condensate formation (e.g., Ge, GeS,GeTe, and As solid phases). Gas-phase HF is expected to bethe dominant form of fluorine until the temperature dropsbelow �300K, at which point NH4F condenses. Similarly,HCl, HBr, and HI are expected to be major gas-phasespecies at temperatures below �1000K, until condensationof NH4Cl, NH4Br, and NH4I occurs in the 350-450 K region(Fegley and Lodders 1994).

The observed abundance of CO, PH3, GeH4, and AsH3

(see Section 5.2) greatly in excess of thermochemical-equilibrium predictions provides clear evidence that ther-mochemical equilibrium cannot be maintained in the colderregions of Saturn’s troposphere. Based on arguments firstpresented by Prinn and Barshay (1977), the observed dis-equilibrium tropospheric composition is likely caused bystrong convective motions in giant-planet tropospheres thatallow gas species to be mixed vertically at a rate more rapidthan the chemical kinetic destruction can keep pace. As agas parcel is transported upwards, the equilibrium composi-tion is “quenched” or “frozen in” at the level at which thevertical mixing time scale drops below the chemical kinetictime scale of conversion between different forms of the ele-ment. The observed upper tropospheric abundance then rep-resents equilibrium conditions at a much deeper level, withthat level being dependent on the strength of vertical mixingand the kinetic rate coefficients. Because the quench levelis not well constrained from theoretical arguments, the rel-ative partitioning between different molecules containing P,Ge, and As at the quench level is uncertain, and the observedabundances of PH3, GeH4, and AsH3 represent lower limitsto the bulk abundances of these elements.

If one assumes the elemental abundances on Saturn arewell known and the kinetics well understood, the observedabundances of these disequilibrium species can be used toback out transport time scales and one-dimensional eddy dif-fusion coefficients in Saturn’s troposphere (e.g., see Fegleyand Prinn 1985; Fegley and Lodders 1994, who derive eddydiffusion coefficients of order 108–109 cm2 s�1 at the tropo-spheric quench levels based on model comparisons with COand PH3 abundances). Conversely, if one makes assumptionsabout the convective time constants from mixing-length the-ory (e.g., Stone 1976; see also Smith 1998) and the chemicaltime constants from the rate-limiting kinetic reactions for theconversion mechanisms of a particular molecule (e.g., Prinnand Barshay 1977; Yung et al. 1988; Bézard et al. 2002),the observed disequilibrium abundances can be used to back

out the deep-atmospheric abundance of the element in ques-tion. Visscher and Fegley (2005; see also the Bézard et al.2002 calculations for Jupiter) attempt to get the deep oxygenabundance from this method, as the deep O/H ratio on Saturncannot be directly measured by any of the Cassini or Voyagerinstruments. Because the bulk elemental abundances haveimportant implications for giant-planet formation scenarios(e.g., Lunine et al. 2004), such calculations are of great inter-est for understanding the origin of the solar system. In prac-tice, however, current uncertainties in the tropospheric COabundance on Saturn and in the kinetics and rate coefficientsof the CO-CH4 interconversion mechanisms are preventingreliable estimates of the deep oxygen abundance on Saturnfrom being obtained using this method (cf. the Jupiter studyof Bézard et al. 2002). That situation could change in thenear future with tighter observational constraints on tropo-spheric CO from high-resolution ground-based observationsand with expanded laboratory or theoretical investigations ofappropriate rate coefficients and thermodynamic parameters.

5.3.1.2 Photochemistry in the Troposphere

Rapid atmospheric mixing is not the only disequilibrium pro-cess that affects the composition of Saturn. Photochemistry,or the chemistry that is initiated when an atmospheric con-stituent absorbs a photon, plays a major role in controllingthe abundances of trace species. For details of troposphericphotochemistry on Saturn and the other giant planets, seeAtreya et al. (1984), Prinn et al. (1984), and Strobel (1975,1983, 2005). Although Rayleigh scattering, molecular ab-sorption, and aerosol and cloud opacity limit the depth towhich solar ultraviolet photons can penetrate in Saturn’satmosphere (e.g., Tomasko et al. 1984; Pérez-Hoyos andSánchez-Lavega 2006; see also Chapter 7 in this volume),photochemical processes can occur in the few-hundred mbarregion and above. In that region, water has already beenremoved through condensation at depth, and NH4SH and am-monia clouds have formed, but the vapor pressure of NH3

may be high enough at the cloud tops (and the overlying hazeopacity sufficiently low) that NH3 may interact with ultravi-olet photons with wavelengths �<220 nm. Ammonia photo-chemistry may therefore occur in Saturn’s upper troposphere(e.g., Strobel 1975, 1983; Atreya et al. 1980), with ammoniabeing photolyzed at the cloud tops to form predominantly Hatoms and NH2 radicals. The NH2 radicals can recombinewith each other to form hydrazine (N2H4) or with H to re-form NH3. The hydrazine will condense to form an aerosol,but some may be photolyzed or react with H to form N2H3

and eventually produce N2.Phosphine does not condense at Saturnian temperatures,

and it will also participate–and likely dominate–troposphericphotochemistry. The upper tropospheric haze is relatively


optically thick on Saturn (see Chapter 7), which helps toshield the ammonia from photolysis in its condensation re-gion. Phosphine, on the other hand, can diffuse upward untilhaze opacity is low enough for PH3 photolysis to occur, andphosphine photochemistry is therefore guaranteed at someatmospheric level, no matter what the haze opacity. The cou-pled photochemistry of phosphine and ammonia on Saturn hasbeen studied by Kaye and Strobel (1983c, 1984). Phosphineis photodissociated by photons with wavelengths less than�235 nm. The dominant photolysis products are PH2 andH. Analogous with NH3 photochemistry, two PH2 radicalscan combine to form P2H4, which can condense at the coldSaturnian temperatures, or the PH2 can combine with H toreform PH3. The ammonia photolysis products NH2 and Hcan also react with PH3 to provide addition mechanisms forPH2 production and PH3 destruction. The yield of N2H4,N2, and other nitrogen-bearing products is therefore reducedwhen PH3 is present. Dominant products of the coupled PH3-NH3 photochemistry are expected to be P2H4, condensed redphosphorous, NH2PH2, N2H4, and N2. Diphosphine (P2H4)is a leading candidate for the upper tropospheric haze. Ap-propriately designed laboratory experiments investigating thephotolysis of PH3 or NH3-PH3 mixtures (e.g., Ferris and Mo-rimoto 1981; Ferris et al. 1984; Ferris and Khwaja 1985)have been valuable in elucidating the nature of the coupledphosphine-ammonia chemistry of the giant planets.

The possibility of chemical coupling between hydrocar-bons and NH3 or PH3 is a more controversial topic. Methaneis photolyzed at high altitudes on Saturn, well removed fromthe ammonia and phosphine photolysis regions. Numerouslaboratory experiments over the years on “simulated” giant-planet atmospheres (e.g., Sagan et al. 1967; Woeller andPonnamperuma 1969; Ferris and Chen 1975; Raulin et al.1979; Ferris and Morimoto 1981; Bossard et al. 1986; Ferrisand Ishikawa 1988; Ferris et al. 1992; Guillemin et al.1995a) have addressed the possible formation of HCN andother nitriles and organo-nitrogen compounds or organo-phosphorus compounds, but the relative gas abundances orother conditions in those experiments have not always beengood analogs for giant-planet tropospheres. Kaye and Strobel(1983a, b) have used a photochemical model to study severalpossible mechanisms for coupled carbon-nitrogen chemistryon Jupiter. One pathway involves CH3 radicals producedfrom the reaction of methane with hot hydrogen atoms thatwere produced from PH3 and NH2 photolysis; the CH3 com-bines with NH2 to form methylamine (CH3NH2), which canphotolyze to form a small amount of HCN. A second path-way involves reaction of NH2 with C2H3 to form aziridine (orother C2H5N isomers), which can also be photolyzed to formHCN and other interesting compounds. In the first scenario,the hot hydrogen atoms can be quenched by H2, effectivelycutting off production of CH3 and nitrogen-bearing organics(see also Raulin et al. 1979; Ferris and Morimoto 1981).

The second, more promising, of these scenarios has beenstudied in more detail by Ferris and Ishikawa (1987, 1988)and Keane et al. (1996), who have used laboratory simula-tions to study the detailed mechanisms and product quan-tum yields of coupled ammonia-acetylene photochemistry.They favor somewhat different pathways and products for thecoupled photochemistry, but the reaction sequence still startswith the NH2 + C2H3 reaction. The relevance both of theseexperiments and of the models Kaye and Strobel (1983a, b)to the real situation on Saturn is not completely clear becausethe tropospheric C2H2 abundance is likely much smallerthan was assumed in those experiments and models (e.g.,Moses et al. 2000a, 2005). Similarly, coupled PH3-C2H2

photochemistry (e.g., Guillemin et al. 1995a), or coupledchemistry of NH3 and/or PH3 with other unsaturated hy-drocarbons (e.g., Ferris et al. 1992; Guillemin et al. 1997)may be inhibited on Saturn due to the likely low tropo-spheric abundance of C2H2 and other unsaturated hydro-carbons. However, if the tropospheric haze opacity is largeenough to allow PH3 to reach the tropopause (cf. the CIRSobservations of Fletcher et al. 2007b), PH3-hydrocarbon cou-pling is more likely to occur. Observations that detect or putupper limits on the HCN and HCP abundance on Saturn (e.g.,Weisstein and Serabyn 1996) could help constrain the cou-pled NH3-C2H2 and PH3-C2H2 photochemistry.

Because differences in the abundances of NH3, PH3, and(in particular) aerosols lead to differences in the shielding ofthe photochemically active molecules on Saturn as comparedwith Jupiter and because NH3 condenses deeper in Saturn’scolder atmosphere, some differences in tropospheric photo-chemistry are expected to exist between the two planets. PH3

photochemistry may be more important, PH3-hydrocarboncoupling is more likely, and NH3-PH3 coupling may be sup-pressed on Saturn. The extent and consequence of these dif-ferences remain to be quantified in up-to-date photochemicalmodels that include accurate aerosol extinction.

Some H2S could be present in and below the putativeNH4SH cloud on Saturn. Because H2S has a substantial pho-toabsorption cross section out to �260 nm (and a weakH-S bond), some sulfur photochemistry could possibly oc-cur on Saturn, but the deep levels to which the UV radi-ation must penetrate suggest that sulfur photochemistry isnot very important on Saturn, except perhaps in localizedareas with reduced cloud cover. The details of the possi-ble H2S photochemistry are highly uncertain (e.g., Lewisand Prinn 1984; Prinn and Owen 1976). Similarly, GeH4 andAsH3 photochemistry is poorly understood (e.g., Fegley andPrinn 1985; Nava et al. 1993; Guillemin et al. 1995b; Mortonand Kaiser 2003), but more likely to be occurring. In all, tro-pospheric photochemistry on Saturn is less well understoodthan stratospheric photochemistry, due to a critical lack ofreaction rate coefficients for the appropriate reactions. It ishoped that new Cassini and Earth-based observations that


have helped derive the altitude profiles of some of the key tro-pospheric species (NH3, PH3, GeH4, AsH3, see Section 5.2)will help generate a resurgence in interest in troposphericphotochemistry on Saturn.

5.3.2 Stratospheric Hydrocarbon Chemistry

Stratospheric hydrocarbon photochemistry on Saturn and theother giant planets has been reviewed recently by Moseset al. (2005, 2004, 2000a), Strobel (2005), and Yung andDeMore (1999), and the interested reader is referred to thoseworks for more details. Because most of the major equi-librium hydride species condense in the cold upper tropo-sphere of Saturn, stratospheric photochemistry is dominatedby photolysis of the relatively volatile molecule methane.Methane is transported up from the deep interior past thetropopause cold trap to the top of the middle atmosphere(the mesopause region), where its abundance eventually fallsoff due to molecular diffusion of the relatively heavy CH4

molecules in the lighter background H2 gas. A common mis-conception is that photolysis limits the CH4 abundance athigh altitudes–it is actually molecular diffusion, rather thanphotochemistry, that is responsible for the sharp drop off inCH4 abundance with altitude that is observed in spacecraftultraviolet occultation data (e.g., Festou and Atreya 1982;Smith et al. 1983; Vervack and Moses 2009; Shemansky andLiu 2009; see also Chapter 12). Methane can be photolyzedin the upper atmosphere by ultraviolet radiation, and the pho-tolysis products react to form the plethora of complex hy-drocarbons that have been observed in Saturn’s stratosphere(see Section 5.2). These complex hydrocarbons diffuse downinto the troposphere, where they eventually encounter hightemperatures and can be thermochemically converted backto CH4, thus completing a “methane cycle”. Strobel (1969)was the first to work out the concept of this methane cyclefor the giant planets.

5.3.2.1 Chemical Reactions

Hydrocarbon photochemistry on Saturn is initiated bymethane photolysis in the upper atmosphere. Because thephotoabsorption cross section of methane is negligible atwavelengths longer than �145 nm, and because the solarLyman alpha line (121.6 nm) provides the largest flux sourceat wavelengths less than 145 nm, Lyman ˛ photodissoci-ation of CH4 controls much of the subsequent hydrocar-bon photochemistry in Saturn’s stratosphere. Although themethane photolysis branching ratios (i.e., the likelihood offorming a particular set of reaction products during photol-ysis) at 121.6 nm are not completely understood, the major

photolysis products are CH3, excited CH2.a1A1/, and CH

(e.g., Cook et al. 2001; Wang et al. 2000; Smith and Raulin1999; Brownsword et al. 1997; Heck et al. 1996; Mordauntet al. 1993). The CH3 radicals can recombine with anotherCH3 radical to form C2H6, or can combine with H to recy-cle methane. The CH2.a

1A1/ radicals can react with H2 toform CH3 (�<90% of the time) or can be quenched to ground-state CH2 (�>10% of the time) and eventually react with H toform CH. The CH radicals can insert into CH4 to form C2H4.Photolysis of both C2H6 and C2H4 produces C2H2. Atomichydrogen is a major product of hydrocarbon chemistry onSaturn, and reaction of atomic H with hydrocarbons helpsdefine the relative abundance of the observable species.

More complex hydrocarbons are produced throughradical-radical combination reactions (e.g., CH3 + C2H3 +M ! C3H6 + M, where M represents any third moleculeor atom, CH3 + C3H5 + M ! C4H8 + M, CH3 + C2H5

+ M ! C3H8 + M, 2 C2H3 + M ! C4H6 + M), throughCH insertion reactions (e.g., CH + C2H6 ! C3H6 + H,CH + C2H2 ! C3H2 + H, CH + C2H4 ! C3H4 + H), andthrough other radical insertion reactions (e.g., C2H + C2H2

= C4H2 + H, CH3 + C2H3 ! C3H5 + H, C2H + C2H4 !C4H4 + H). Hydrocarbons are destroyed through photolysis,reaction with hydrogen atoms, and various other radicaladdition, insertion, and disproportionation reactions (e.g.,C2H3 + C2H3 ! C2H4 + C2H2). Stratospheric hydrocarbonphotochemistry on Saturn is rich and complex. Rather thangoing through the major production and loss mechanismsfor each of the observed stratospheric constituents, wewill direct interested readers to the reviews of Moseset al. (2000a, 2004, 2005), for which the hydrocarbonreactions and pathways thought to be most important onJupiter and Saturn are discussed in gory detail. Note thatthe dominant reactions are expected to be the same on bothJupiter and Saturn, with quantitative differences caused bydifferent stratospheric temperatures, heliocentric distances,atmospheric transport, auroral processes, condensation, andinflux of external material.

Although the production and loss mechanisms for the ma-jor hydrocarbons are qualitatively understood, a full quanti-tative understanding has been hindered by a lack of relevantchemical kinetics data at low temperatures and low pressures.Moses et al. (2005) provide a table (their Table 6) that listssome critical data needed to improve our current understand-ing of hydrocarbon photochemistry. Of particular impor-tance is information on the photochemistry of benzene andC3Hx molecules under conditions relevant to giant-planetstratospheres, details of the photolysis branching ratios forCH4 at Lyman alpha wavelengths (especially the quantumyield of CH formation), and information on the low-pressurelimit and falloff behavior of the rate coefficients for relevanthydrocarbon termolecular reactions at temperatures of 80–170 K (e.g., Huestis et al. 2008).


5.3.2.2 One-Dimensional Models

Several one-dimensional (1-D; in the vertical direction) mod-els for hydrocarbon photochemistry in Saturn’s stratospherehave been developed in the past several decades (e.g., Strobel1975, 1978, 1983; Atreya 1982; Festou and Atreya 1982; Leeet al. 2000; Ollivier et al. 2000; Moses et al. 2000a, b, 2005;Dobrijevic et al. 2003; Cody et al. 2003; Sada et al. 2005). Inthese models, the continuity equation is typically solved topredict the concentration of atmospheric species as a func-tion of pressure. Photochemical production and loss rates forthe hydrocarbons as a function of pressure are calculated af-ter providing such inputs as a chemical reaction list, photoab-sorption and photolysis cross sections, photolysis branchingratios, and temperature-dependent reaction rate coefficients.Transport of the atmospheric constituents is usually achievedby eddy and molecular diffusion. Molecular diffusion coeffi-cients for various hydrocarbons in H2, He, and other hydro-carbon gases have been studied theoretically and in the labo-ratory (e.g., Marrero and Mason 1972), and empirical formu-las that depend on atmospheric temperature and gas densitiesare typically adopted.

Eddy diffusion, on the other hand, is a parameterizationin these 1-D models that is introduced to account for macro-scopic transport processes that act to keep the atmospherewell mixed (i.e., dissipative waves, small-scale and large-scale eddies, diabatic circulation, and other macroscopicmass motions). Eddy diffusion coefficients cannot be calcu-lated from first principles without knowing the full three-dimensional wind fields from diabatic circulation, waves,etc., which are certainly not known for Saturn. The eddydiffusion coefficient Kzz is therefore an important free pa-rameter in the photochemical models. Most modelers as-sume that the same Kzz profile can be used to determinethe vertical transport rates for all constituents in the atmo-sphere, despite the warning of Strobel (1981, 2005) andWest et al. (1986) that the chemical loss rate of a con-stituent can affect its inferred eddy diffusion coefficientKzz.Constituents like C2H6 and CO that are long-lived chemi-cally are typically used as tracers to help constrain Kzz inthe lower stratosphere of the giant planets. Spacecraft ultra-violet occultations of hydrocarbons in the mesopause regionof Saturn (e.g., Festou and Atreya 1982; Smith et al. 1983;Vervack and Moses 2009; Shemansky and Liu 2009) or ul-traviolet emission from He 58.4 nm or H Lyman ˛ airglow(e.g., Sandel et al. 1982; Atreya 1982; Ben-Jaffel et al. 1995;Parkinson et al. 1998) are used to help constrain the locationof the methane homopause–the altitude level at which Kzz

equals the methane molecular diffusion coefficient–and themagnitude of Kzz in the homopause region.

Accurate constraints on the location of the methanehomopause on Saturn are important for the photochemi-cal models because methane is photolyzed just below its

homopause region, and the pressure at which methane isphotolyzed affects the subsequent chemistry through ter-molecular and other pressure-dependent reactions. One in-teresting result that has arisen from the analysis of the fewCassini/UVIS stellar occultations that have been analyzed todate (Shemansky and Liu 2009), the recent analysis of allthe Voyager/UVS solar and stellar occultations (Vervack andMoses 2009), the analysis of the Cassini/VIMS ˛ CMi stel-lar occultation at 55ı N latitude (Nicholson et al. 2006), andanalysis of auroral images and spectra from Cassini/UVIS(e.g., Gérard et al. 2009; Gustin et al. 2009) is that thehomopause pressure level on Saturn appears to vary signif-icantly with latitude and/or time, a fact that was not real-ized during the Voyager era. If so, the appropriateness of1-D models in representing the entire Saturnian atmosphereis called into question. Chapter 8 in this volume has moredetails about the ultraviolet occultations from Cassini.

The Cassini/UVIS stellar occultation at �43ı latitude de-scribed by Shemansky and Liu (2009) implies a homopausepressure level that is nearly two orders of magnitudegreater (i.e., at a lower altitude) than the Voyager 2 solaringress occultation at 29.5ı latitude analyzed by Vervack andMoses (2009). Figure 5.7 illustrates these differences. TheVoyager 2 stellar egress occultation (3.8ı latitude) analyzedby Smith et al. (1983) and Festou and Atreya (1982) suggestsa homopause at very low pressures (high altitudes), similar tothe results of the Voyager 2 solar ingress profile, whereas theVoyager 1 solar egress profile (�27ı latitude) (Vervack andMoses 2009) suggests a high-pressure homopause more sim-ilar to the Shemansky and Liu (2009) Cassini/UVIS �43ılatitude results (see Fig. 5.7). Although differences in anal-ysis techniques and assumptions can play a role in these re-sults, studies that use a consistent technique to analyze multi-ple occultations (i.e., Shemansky and Liu 2009; Vervack andMoses 2009) derive different homopause levels for differentoccultation latitudes, suggesting real variation with locationand/or time. As suggested by Vervack and Moses (2009), thelikely cause of the variable homopause levels is small verti-cal winds that vary with latitude and time. Existing and fu-ture Cassini/UVIS solar and stellar occultations, as well asCassini/VIMS occultations, may help map out the latitudedependence of the homopause level and perhaps allow windsand circulation in the mesopause region to be derived.

Note that we try to put all quantities on a pressure scaleon the giant planets because the altitude or radius scalevaries significantly with latitude on these rapidly rotating,oblate planets, due to variations in the gravitational accel-eration with latitude. However, occultation data are inher-ently a function of planetary radius, and converting to a pres-sure scale introduces a model dependency in the results (thegreatest assumption being the temperature profile), and thereader should keep that fact in mind with the above discus-sion. The simultaneous or near-simultaneous measurement


Fig. 5.7 Results from forward models developed to reproduce the ultra-violet occultation data from Cassini/UVIS (Shemansky and Liu 2009)and Voyager/UVS (Vervack and Moses 2009): model temperatures(top), eddy diffusion coefficients (middle), and methane mole fractionprofiles (bottom). Although occultation data constrain model parame-ters only at altitudes above �10�4 mbar (for the Voyager data) or above0.01 mbar (for the Cassini data), the full profiles are shown becausemodel assumptions affect the results. Note the large derived variationin the methane homopause pressure level with latitude and/or time forSaturn

of atmospheric temperatures from 1 bar on up to �0:01mbar from Cassini/CIRS limb or other measurements at theUVIS occultation latitudes would greatly aid the occulta-tion analyses, as would more accurate determinations ofthe planetary shape (i.e., determinations of the radius lev-els of isobaric surfaces, which are not well represented byoblate spheroids). Cassini/VIMS occultations (e.g., Nichol-son et al. 2006) may be particularly useful in helping placethe homopause location in pressure space.

Photochemical models for Saturn that have beenpublished since the Voyager encounters all assume a high-altitude methane homopause most relevant to 3.8ı latitude or29ı N latitude during the Voyager flybys. Figure 5.5 showsthe results from one such 1-D photochemical model forSaturn (Moses et al. 2005). The eddy diffusion coefficientin the lower stratosphere for this model is constrained fromthe global-average ISO/SWS observations of C2H6 (e.g.,Moses et al. 2000a, de Graauw et al. 1997). The modelis designed to represent global-average conditions, withan assumed temperature profile that was derived from theglobally averaged ISO observations (Lellouch et al. 2001),an assumed solar UV flux that represents low-to-averageconditions within the solar cycle, and fixed vernal equinoxsolar insolation conditions at 30ı latitude. An external influxof H2O, CO, and CO2 is introduced at high altitudes, andthe oxygen photochemistry slightly affects the abundancesof the unsaturated hydrocarbons. Diacetylene, benzene, andwater are found to condense in the lower stratosphere andcontribute to a stratospheric haze layer (C4H2 and C6H6

condense near �10 mbar in this model, whereas watercondenses closer to 1 mbar, but these values depend ontemperature profiles that need to be updated based on theCassini CIRS results, e.g., Guerlet et al. 2009).

Consistent with the infrared and ultraviolet observationsdiscussed in Section 5.2, the Moses et al. (2005) model–and all other photochemical models–predict that ethane is thesecond-most abundant hydrocarbon in Saturn’s stratosphere(behind methane), followed by acetylene, and propane.Ethylene is abundant at high altitudes but its mole fractionfalls off in the middle and lower stratosphere due to reac-tion with atomic H (to eventually form C2H6) and photolysis(to eventually form C2H2). The Moses et al. model ac-curately predicts the global-average abundances of C2H6,C2H2, CH3C2H, C4H2, and CH3 (not shown), but underpre-dicts the column abundance of C2H4 and C3H8, and greatlyoverpredicts the column abundance of C6H6. Moreover,when the same reaction list is applied to Jupiter, Uranus,and Neptune, the model has difficulty in reproducing theobserved C2H2/C2H4/C2H6 ratio on all the giant planets,suggesting systematic problems with the adopted chemicalinputs.

Although some of the model-data mismatch may becaused by the attempt to represent a three-dimensional


atmosphere with a one-dimensional, steady-state model, thechemical reaction list used by Moses et al. (2005) clearlyneeds improvement. Models developed by other groups alsofail to reproduce all available observations (see below), in-dicating that we do not have a complete quantitative un-derstanding of hydrocarbon photochemistry under Saturnianstratospheric conditions. Sensitivity and “uncertainty” stud-ies (e.g., Dobrijevic et al. 2003; Smith and Nash 2006)can help identify the key reactions that affect species abun-dances at different pressures and can help evaluate the over-all robustness of the models. Laboratory measurements andtheoretical calculations are needed to help fill in current un-certainties in the critical reaction schemes (e.g., see Table 6of Moses et al. 2005), and further observations that constrainthe vertical profiles of the observed constituents will provideimportant model constraints.

Other recent 1-D photochemical models that have provenuseful in defining the hydrocarbon photochemistry on Saturninclude those presented by Ollivier et al. (2000), Dobrijevicet al. (2003), Cody et al. (2003), and Sada et al. (2005).The model of Ollivier et al. (2000), like those of Moseset al. (2000a 2005), considers the chemistry of a long listof hydrocarbon and oxygen species and examines the sensi-tivity of the results to variations in several key input param-eters. The model succeeds in reproducing the observed CH4

and C2H2 abundances but greatly underestimates the C2H6

abundance and overestimates the CH3C2H, C4H2, and CH3

abundances. The CH3 problem may partly be remedied bythe updated line strengths provided by Stancu et al. (2005).The C2H6 underestimation appears to have been caused bythe adoption of a rapid reaction between C2H2 and C2H6

to form C2H3 and C2H5. This reaction between acetyleneand ethane would be exceedingly slow at Saturnian tem-peratures; Ollivier et al. (2000) have apparently mistakenthe reaction of vinylidene (H2CC) radicals plus ethane withthe acetylene plus ethane reaction in their model. Despitethis reaction-rate problem, Ollivier et al. (2000) have pro-vided sensitivity studies for such parameters as solar ir-radiance, latitude, H influx from the thermosphere, exter-nal oxygen influx, and absorption only vs. multiple scatter-ing that are useful in understanding model sensitivities andlimitations.

The Ollivier et al. (2000) C2H2 + C2H6 reaction-rate prob-lem has been corrected in a follow-up model by Dobrijevicet al. (2003). The updated Dobrijevic et al. (2003) resultscompare well with the C2H2 and C2H6 observations fromthe ISO satellite (Moses et al. 2000a), but the model tendsto underestimate CH3C2H and overestimates the abundanceof C4H2, although Dobrijevic et al. (2003) emphasize thatthe model results are acceptable given the uncertainties inthe rate coefficients and other model parameters. In fact,the main advance of the Dobrijevic et al. (2003) study isa quantification of uncertainties in product abundances in

photochemical models based on uncertainties in reaction ratecoefficients and other model inputs.

The model of Cody et al. (2003) is designed to specifi-cally study the influence of new experimentally derived ratecoefficients for the CH3 + CH3 self reaction on the pre-dicted abundance of CH3 on Saturn and Neptune. Codyet al. (2003) emphasize the relative importance of the ratio oflow-pressure limiting vs. high-pressure limiting rate coeffi-cient for the termolecular CH3 + CH3 recombination reactionin affecting the methyl radical abundance in photochemicalmodels.

Sada et al. (2005) have developed a photochemical modelfor Saturn in order to better define the vertical profiles ofC2H6 and C2H2 to more accurately retrieve mole fractionsfrom ground-based infrared observations and Voyager IRISdata. The Sada et al. (2005) model simultaneously repro-duces the emission in the observed C2H2 and C2H6 infraredbands, but the model profiles were shifted by some unspec-ified amount in mole-fraction space to obtain this good fit.Interestingly, their vertical profile for C2H6 differs from thatof other photochemical models in the upper atmosphere suchthat their mole fraction continues to increase sharply from�1 to 0.01 mbar. The C2H6 profiles in other models such asMoses et al. (2000a, 2005) and Ollivier et al. (2000) exhibit amore constant C2H6 mole fraction in the upper stratosphere.Limb observations acquired with Cassini/CIRS (e.g., Guerletet al. 2009) and ultraviolet occultations with Cassini/UVIS(Shemansky and Liu 2009) may help constrain the C2H6 ver-tical profiles to help distinguish between models.

5.3.2.3 Seasonal Variation in 1-D Models

Most photochemical models to date have been concernedwith steady-state conditions for either global-average atmo-spheres or for single specific latitudes and seasons. The time-variable, multiple-latitude model of Moses and Greathouse(2005) is an exception in that the effects of seasonally vary-ing insolation, ring shadowing, and the solar cycle on strato-spheric chemistry are examined in a more realistic manner;however, the model still considers transport in the verticaldirection only–horizontal transport is neglected. Moses andGreathouse find that at very high altitudes (i.e., pressures lessthan �0:01mbar), the hydrocarbon abundances respondedquickly to insolation changes, and the mixing ratios of thephotochemical products are largest at those latitudes and sea-sons where the solar insolation is the greatest. At lower alti-tudes, however, the increased vertical diffusion time scalesare found to introduce increasing phase lags in the chemi-cal response of the atmosphere to the changing solar inso-lation. Below the �1 mbar level, the response times of therelatively long-lived species such as C2H2, C2H6, and C3H8

become larger than a Saturnian year, so that their abundances


c

a b

d

Fig. 5.8 Hydrocarbon mole fractions at �36ı planetocentric lati-tude as a function of pressure and season in Saturn’s upper atmo-sphere, as derived from the 1-D seasonal photochemical model ofMoses and Greathouse (2005). The dotted lines represent Ls D94:2ı (just past southern winter solstice), the dashed lines representLs D 177:4ı (just before southern vernal equinox), the dot-dashed lines

represent Ls D 273:1ı (just past southern summer solstice), and thesolid lines represent Ls D 360ı (southern autumnal equinox). Thedata points with associated error bars represent various infrared andultraviolet observations, as labeled (figure modified from Moses andGreathouse 2005). Note the strong seasonal variability at high altitudesand the virtual absence of seasonal variability at low altitudes

reflect annual-average insolation conditions (see Figs. 5.8and 5.9). Because the annual-average solar insolation de-creases toward the poles, Moses and Greathouse (2005) pre-dict that the abundances of these photochemically producedspecies should decrease with increasing latitude at the few-mbar level (and at lower altitudes) at all seasons.

Figure 5.6 shows how the photochemical model of Mosesand Greathouse (2005) compares with the ground-based,thermal-infrared observations of Greathouse et al. (2005),the Cassini/CIRS nadir data of Howett et al. (2007), theCassini/CIRS limb data of Guerlet et al. (2009), and the HSTultraviolet observations of Prangé et al. (2006). The modelroughly reproduces the observed meridional variation ofC2H2 (albeit not as steeply in the northern hemisphere, whichis likely caused by the constant-temperature-with-latitude as-sumption of the model) but clearly fails to reproduce theobservations for the longer-lived C2H6 (especially in the

southern hemisphere); the observations indicate that at the2-mbar level, the C2H6 mixing ratio increases with increas-ing latitude in the southern summer hemisphere, whereas themodel predicts a strong decrease with increasing latitude.Moses and Greathouse suggest that the long photochemicallifetime of C2H6 (i.e., �700 years at 2 mbar at mid-latitudesin the summer) is the root cause of this behavior–C2H6

is sensitive to horizontal transport, which is not includedin the model (see Nixon et al. 2007 for a similar conclu-sion for Jupiter). Based on the failure of the model to re-produce the C2H6 but not the C2H2 meridional gradient,Moses and Greathouse suggest that the meridional transporttime scale at 2 mbar on Saturn is in the �100–700 yearrange (i.e., somewhere between the photochemical lifetimesof C2H2 and C2H6). Although it is possible that Kzz profilesthat vary with latitude might be developed that could repro-duce some of the observed behavior, it is more likely that


Fig. 5.9 The column density of acetylene (C2H2) above different pres-sure levels as a function of planetocentric latitude and season (Ls ) fromthe Moses and Greathouse (2005) model: above 0.001 mbar (top left),above 0.01 mbar (bottom left), above 0.1 mbar (top right), above 1 mbar(bottom right). The contour intervals and overall scale change for each

figure. Note the strong seasonal dependence at low pressures; the lackof seasonal dependence in the column abundance above 1 mbar is dueto large photochemical and vertical transport time scales at pressures

�>1 mbar (figure modified from Moses and Greathouse 2005)

meridional transport is occurring in Saturn’s stratosphere,and multi-dimensional photochemical models that includehorizontal transport will be needed to make sense of theseobservations.

5.3.2.4 Two-Dimensional Models

The observations and modeling discussed above and shownin Figs. 5.5–5.6 make it clear that the abundances of the pho-tochemically produced species change with altitude, latitude,and time on Saturn. Because ethane and acetylene, alongwith methane, are the dominant coolants in giant-planetstratospheres (e.g., Yelle et al. 2001; Bézard and Gautier

1985), variations in the abundances of these species affect theradiative properties, thermal structure, and energy balancein the atmosphere, which in turn affect atmospheric dynam-ics, which in turn redistributes constituents that feed back onthe chemistry and temperatures. A general circulation model(GCM) will be required to fully explore this complex cou-pling between chemical, dynamical, and radiative processes.Unfortunately, GCMs for Saturn’s stratosphere do not yetexist, and little is known about stratospheric circulation onSaturn due to a lack of clouds or other wind tracers. Thetwo-dimensional “diabatic” or “residual mean” circulationcan in principle be derived from modeling the momentumand energy budgets from seasonal radiative forcing, butthe radiative-dynamical models that have been developed to


date (e.g., Conrath et al. 1990; Barnet et al. 1992; see alsothe purely radiative seasonal climate model of Bézard andGautier 1985) do not go high enough in the stratosphere toencompass the photochemical production regions and do nottake variable hydrocarbon abundances into account. The lat-ter variation and its effect on temperatures has been studiedby Strong et al. (2007), who find that radiative time constantsvary significantly with pressure such that high-altitude tem-peratures respond quickly to changes in insolation.

In the absence of direct information on stratospheric cir-culation, the observed meridional distribution of the hydro-carbons or other tracers can be used to learn somethingabout the general nature of the stratospheric transport (see theJupiter modeling of Friedson et al. 1999; Liang et al. 2005;Lellouch et al. 2006). Temperature maps, such as were pro-duced from Cassini CIRS (Flasar et al. 2005; Simon-Milleret al. 2006; Fletcher et al. 2007a; Fouchet et al. 2008;Guerlet et al. 2009), also provide clues. For example, the ele-vated south polar temperatures (Fletcher et al. 2007a; Flasaret al. 2005) and the observed increase in the C2H6 abundancetoward high southern latitudes (e.g., Howett et al. 2007;Greathouse et al. 2005) led Flasar et al. (2005) to suggestsubsidence in the high-latitude southern stratosphere. Com-plex wave-like structure in the low-latitude regions suggestsan effect similar to the Earth’s semi-annual oscillation but ona �15-year period (Fouchet et al. 2008; Orton et al. 2008;see also Chapter 6). This oscillatory feature seems to be in-fluencing the C2H2, C2H6, and C3H8 vertical distributionsin the low-latitude regions (Fouchet et al. 2008; Guerletet al. 2009). Similarly, fine- and broad-scale features in themeridional profiles of temperatures and abundances have ledGuerlet et al. (2009) to suggest vertical winds are influencingbehavior at certain latitudes.

Although no 2-D photochemistry-transport models haveyet been reported in the refereed literature, some prelimi-nary models have been presented by Moses et al. (2007).In these models, the Caltech/JPL two-dimensional chem-istry transport model (2-D GCM, see Morgan et al. 2004;Shia et al. 2006) is used to study the meridional and ver-tical distribution of stratospheric species. Both advectionand/or horizontal and vertical diffusion are considered in thetransport terms. Various ad hoc scenarios involving large-scale circulation cells or latitude- and altitude-dependenteddy diffusivities are examined, and the results are com-pared to the observed meridional distribution of constituents.The key conclusion of this modeling is that the abundancesof C2H6 and C2H2 are highly linked by both photochem-istry and vertical transport on time scales shorter than theestimated meridional transport time scales of Moses andGreathouse (2005), such that the meridional distribution ofC2H2 in the models closely tracks that of C2H6. This modelresult is in conflict with observations (see Figs. 5.6). Moseset al. (2007) came up with some highly contrived scenar-

ios involving latitude or altitude-dependent diffusivities thatcould roughly reproduce the observed C2H2 and C2H6 distri-butions, but the overall conclusion from this modeling is thatthe cause of the observed uncoupled distributions remainsa mystery. Aerosol and gas-constituent shielding, multipleRayleigh scattering, auroral chemistry, and incorrect modelbranching ratios for C2H6 have all been tentatively ruled outas possibilities. Further modeling, including the developmentof GCMs, is needed.

5.3.3 Oxygen Chemistry

The detection of CO2 and H2O that is unambiguously inthe stratosphere of Saturn points to an external supplyof oxygen to the planet (e.g., Feuchtgruber et al. 1997,1999; de Graauw et al. 1997; Bergin et al. 2000; Moseset al. 2000b; Ollivier et al. 2000; Simon-Miller et al.2005; see also the discussion in the Jupiter papers ofBézard et al. 2002; Lellouch et al. 2002, 2006). Water fromthe deep interior would condense in the troposphere andwould not make it up into the stratosphere. Carbon diox-ide from the interior, on the other hand, might not con-dense and some could diffuse up into the stratosphere; how-ever, the observed stratospheric abundance is much largerthan the quenched equilibrium abundance predicted in ther-mochemical models (e.g., Fegley and Prinn 1985; Feg-ley and Lodders 1994; Visscher and Fegley 2005), indicat-ing an external source. Possible sources of the exogenicoxygen-bearing material include comets, micrometeoroids,or ring/satellite debris.

The chemistry that is initiated from this exogenic oxy-gen influx is discussed by Moses et al. (2000b) and Ollivieret al. (2000) and is illustrated in Fig. 5.10. Although wa-ter is readily photodissociated at wavelengths less than 185nm into predominantly OH + H, shielding by hydrocarbonslengthens its photochemical lifetime in Saturn’s stratosphere;moreover, the OH is efficiently recycled back to H2 throughthe reaction OH + H2 ! H2O + H. A small portion of theH2O can be converted to CO through addition reactions ofOH with unsaturated hydrocarbons (Moses et al. 2000b):

H2O C h� ! H C OH

OH C C2H2 C M ! C2H2OH C M

C2H2OH ! CH3CO

CH3CO C H ! HCO C CH3

HCO C H ! CO C H2

Net W H2O C C2H2 C H ! CO C CH3 C H2


O2

OOH

COCH3O

CH3OH

CO2

CH3CO

H2CO

HCOC2H4OH

CH3CHO

H2CCO

O(1D)

H2Ohn

hnhn

hn

hn

hn

hn

hn

hn hn, C

H

hn,

hn

hn

hn

hnhn

H2

H,

H,

H

H

CH3

CH 3

CH3

CH3

CH

OH

CO

3CH

2

3C

H2

C 2H 2

C

H, H2

H

H2,CH4,

C2H6

OH

H,HCO, C 2H 5

,

H

H, HCO

CH

3

CH 3

C 2H 4C2H4

condensation

H, CH3

Fig. 5.10 (top) The important reaction pathways for oxygen photo-chemistry in Saturn’s stratosphere. The symbol h� corresponds to anultraviolet photon. Figure is from Moses et al. (2000b). (bottom) H2O,CO, CO2 mole fraction profiles from Ollivier et al. (2000). These pro-files were obtained with an external flux of water alone (107 molecules

cm�2 s�1) and tropospheric CO (with a mole fraction equal to 10�9).The square and the triangle correspond, respectively, to the water andcarbon dioxide mole fraction found by Feuchtgruber et al. (1997), andthe diamond-shaped point corresponds to distribution CO inferred byNoll and Larson (1991)

and

H2O C h� ! H C OH

OH C C2H2 C M ! C2H2OH C M

C2H2OH ! CH3CO

CH3CO C H ! H2CCO C H2

H2CCO C h� ! 1CH2 C CO

Net W H2O C C2H2 ! CO C 1CH2 C H2:

Carbon monoxide can in turn be converted to CO2 throughthe reaction of CO + OH ! CO2 + H. The CO2 photolyzesback to CO + O(1D) or CO + O. The O(1D) atoms react withH2 to form OH and eventually water, whereas the O can reactwith CH3 or unsaturated hydrocarbons to eventually reformCO. Other hydrocarbons like H2CO, CH3OH, and CH3CHOare formed in the models, but not in currently observablequantities. Water can diffuse down through Saturn’s strato-sphere and eventually condense in the lower stratosphere.The Ollivier et al. (2000) model differs from that of Moses


et al. (2000b) in that the interesting oxygen photochemistryproceeds through reaction of O + CH3 or O + unsaturated hy-drocarbons rather than through addition reactions of OH withunsaturated hydrocarbons. These differences have some im-pact on the final product abundances and the inferred influxrates from the two models.

As discussed in Section 5.2.4, most observations of COto date have not allowed the discrimination between an inter-nal or external source of CO on Saturn. Ollivier et al. (2000)favor an internal source based on the failure of their external-source models to reproduce the CO abundance derived byNoll and Larson (1991). Moses et al. (2000b), on the otherhand, were able to produce the observed CO column abun-dance from external-source models under certain conditions,although they favor a situation in which CO has both andinternal and external source. Both Ollivier et al. (2000) andMoses et al. (2000b) show how the models are sensitive tothe assumed flux of the external oxygen and use model-datacomparisons to constrain the external flux; they also discussimplications regarding the source of the external oxygen (seealso Feuchtgruber et al. 1997, 1999). Ollivier et al. (2000)do not weigh in with a favored source, whereas Moseset al. (2000b) favor interplanetary dust or ring-particle diffu-sion as the source of the external oxygen. However, this con-clusion came into effect before active venting on Enceladuswas discovered by Cassini (e.g., Porco et al. 2006)–Enceladus may be a major supplier of water and oxygenspecies to Saturn–and before the recent 345 HZ observationsof Cavalié et al. (2009) that suggest an external source of COfrom a large cometary impact 200–300 years ago.

5.3.4 Auroral Chemistry

As on Jupiter (e.g., Waite et al. 1983; Perry et al. 1999; Wonget al. 2000, 2003; Friedson et al. 2002), auroral ion chemistryand subsequent neutral chemistry has the potential for af-fecting the global distribution and abundance of stratosphericconstituents on Saturn. Models of auroral chemistry have notyet been presented for Saturn, but the Jupiter studies dis-cussed above, as well as the obvious importance of ion chem-istry in producing C6H6 on Titan (e.g., Waite et al. 2005,2007; Vuitton 2007, 2008; Imanaka and Smith 2007), sug-gest that auroral ion chemistry may be important for form-ing benzene and polycyclic aromatic hydrocarbons (PAHs)on Saturn. Observations such as those presented by Gérardet al. (1995) demonstrate the possible link between the au-rora and polar haze, most likely due to the formation ofcomplex hydrocarbons. The overall effect of auroral chem-istry on other molecules like C2H2 and C2H6 is unknown,although the Jupiter models of Wong et al. (2000, 2003)show an increase in the production rate of both molecules,

which could affect the observed meridional distribution ofC2H2 and C2H6, but which is not likely the culprit in ex-plaining the disparate observed meridional distribution ofthe two species. Given the potential importance of auro-ral chemistry on Saturn, this topic deserves more study,especially given the high-quality observational constraintsthat can likely be supplied by the Cassini/CIRS and UVISinstruments.

5.4 Summary and Conclusions

Our understanding of the composition and chemistry ofSaturn’s atmosphere has improved widely since the Voyagerflybys. The ever-increasing sensitivity and resolution (in thespatial and spectral dimension) of Earth-based observationshave provided a wealth of new information on the Kronianatmosphere. The Cassini spacecraft is now participating inthis ongoing effort, but its results are still in their infancy.

In terms of global composition, Cassini measured the car-bon abundance and the carbon isotopic ratio with a precisionthat will not be challenged for several years. Saturn’s carbonenrichment relative to the solar composition will vary morecertainly in response to changes in the solar composition thanin the Kronian composition. In contrast, the abundance ofhelium is still a subject of continuing analyses. The inver-sion of the collision-induced hydrogen continuum observedby Cassini in the far infrared yields different ŒHe=ŒH2 ratiosdepending on whether the inversion is carried out includingthe radio occultation profiles or whether both the tempera-ture and the composition are inferred from the far-infraredspectrum only. This discrepancy suggests that unknown sys-tematic uncertainties still affect the data analysis. Of partic-ular concern is the sensitivity of the inversion to the windfield. The elemental composition of nitrogen and sulfur hasnot been constrained from Cassini data yet. Our knowledgeof these two elements still relies on ground-based centime-ter observations that are difficult to calibrate and to analyse.However, there is some hope that Cassini radio science canprovide new estimates in the future. Pre-Cassini observationsyielded low D/H ratios in comparison with the Jupiter deu-terium abundance or with the early solar abundance. The firstCassini observations have yielded even smaller values, whichdo not fit easily in the Solar System picture, although the er-ror bars are still large.

Below the ammonia cloud level, at 1–5 bars, severalmolecular species have been measured to tremendouslyexceed their thermodynamic equilibrium abundances. Thesemolecules, phosphine, germane and arsine, which are ther-modynamically stable in the warm interior of the planet,are transported more rapidly to the shallow atmosphere thanthey are destroyed by chemical reactions. Their measurement


gives clues to the vertical mixing timescales and to theelemental composition of the deep interior. Cassini/VIMS isin position to measure the meridional variation in the abun-dance of these elements that would reveal differential verti-cal mixing, a constraint of great importance for dynamicalmodels of Saturn. However, the kinetics and rate coefficientsof the interconversion mechanisms are still preventing reli-able estimates of the deep abundance on Saturn, and/or themixing timescale, from being obtained using this method.Experimental data are greatly needed here. Simultaneousmeasurements of aerosol opacity at ultraviolet wavelengthsand species profiles would also help separate out the effectsdue to mixing versus the effects due to aerosol shielding.

In the upper troposphere, above the cloud tops, Cassini/CIRS has measured for the first time the meridional vari-ation in phosphine abundance. In this atmospheric region,PH3 is photolyzed along with NH3, and any variation inabundance can trace the intensity of vertical and horizontalmixing. This measurement will hence help to constrain thedynamics above the cloud level. Such variations could alsobe linked with variations in the visible cloud colors to under-stand whether PH3 and NH3 photolysis does produce someof the chromophores that determine Saturn’s visible aspect.However, to obtain quantitative constraints on the dynamics,the tropospheric photochemistry on Saturn would need to bebetter understood than it is presently, due to a critical lackof reaction rate coefficients for the appropriate phosphorusand nitrogen reactions under reducing conditions. It is hopedthat new Cassini and Earth-based observations will generatea resurgence in interest in tropospheric photochemistry onSaturn.

In the stratosphere, several hydrocarbons have been de-tected (CH3, C2H2, C2H4, C2H6, CH3C2H, C3H8, C4H2,C6H6) from Earth-based spectroscopy. These species arecritical in controlling the stratospheric temperature. One-dimensional photochemical models are able to reproducethe observed abundance of ethane, acetylene, and severalof the other observed stratospheric constituents, but havemore troubles in predicting the abundance of some of theheavier hydrocarbons. Moreover, models that best repro-duce Saturn’s hydrocarbon photochemistry are often unableto reproduce the observed hydrocarbon abundances on thethree other Giant Planets. The problem lies partly in a lackof appropriate laboratory data at the conditions (tempera-ture, pressures) relevant to Saturn’s stratosphere. Data onphotolysis quantum yields, branching ratios, chemical path-ways and kinetics are greatly needed. It must also be un-derstood how dynamics interplays with the photochemistry.Ground-based and Cassini measurements have started reveal-ing the meridional profiles in hydrocarbon abundance, whileone-dimensional seasonal models and two-dimensional mod-els are being developed. Currently the models do not succeedin reproducing the observed meridional profiles. These mod-

els now need to reproduce more accurately the dynamics,especially the meridional transport and large-scale circula-tion. The models would be better constrained by the mea-surements of the vertical and meridional distributions oflarge variety of hydrocarbon species. Hopefully, the Cassiniequinox and solstice missions will provide insights intothe seasonal variations of the hydrocarbons abundances.Observations that monitor the location of the methane ho-mopause, and its temporal and spatial variations would alsoprovide critical clues to understanding hydrocarbon photo-chemistry. Cassini CIRS limb observations and UVIS andVIMS occultations are still expected to deliver much new in-formation on this problem.

In the upper stratosphere, Saturn is receiving an exter-nal flux of oxygenated species. A recent study supports adual source, both from a cometary impact and from a con-tinuous flux, conceivably from the oxygen-rich bodies inSaturn’s system. The magnitude of both sources should bebetter constrained in the near future by new sub-millimetricobservations.

If great results have been already obtained, the Cassinispacecraft still promises to deliver much more. The unprece-dented spatial resolution and possible duration over almosthalf a Kronian year should provide a wealth of useful infor-mation to constrain the chemistry and its relation with the dy-namics in Saturn’s atmosphere. The supporting ground-basedobservations, with their unchallenged sensitivity and spec-tral resolution, will also contribute to our study of Saturn.Cassini, with its spectral, spatial and temporal coverage, is aunique endeavor to study in depth a Giant Planet.

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