1 Citation:

2 Postberg, F., Clark, R.N., Hansen, C.J., Coates, A.J., Dalle Ore, C.M., Scipioni, F., Hedman, M.M., and Waite,
3 J.H. (2018b) Plume and Surface Composition of Enceladus, in Enceladus and the Icy Moons of Saturn,
4 University of Arizona Press (Eds.: Schenk, Clark, Howett, Verbicer, Waite), pp 129-162.
5 Plume and Surface Composition of Enceladus
6
7 Frank Postberg
8 University of Heidelberg, Free University of Berlin
9
10 Roger N. Clark and Candice J. Hansen
11 Planetary Science Institute
12
13 Andrew J. Coates
14 University College London
15
16 Cristina M. Dalle Ore and Francesca Scipioni
17 NASA Ames Research Center
18
19 Matthew M. Hedman
20 University of Idaho
21
22 J. Hunter Waite
23 Southwest Research Institute
24
25 ABSTRACT
26 This chapter provides a comprehensive review of Enceladus’ plume and surface composition
27 as determined by the end of the Cassini mission. The Enceladean plume is composed of three
28 different phases: Gas, solids (dust), and ions. In all three phases, water is by far the most
29 abundant constituent, but other chemical species are also present. In the gas, H2 and NH3 and
30 CO2 are present with volume mixing ratios of at least fractions of a percent. Methane is the
31 most abundant organic compound (≈ 0.2%), but several, yet unspecified, C2 - and probably C3
32 - species are present. The D/H ratio in the plume is much higher than in Saturn’s atmosphere.
33 Macroscopic (r > 0.2 µm) plume ice grains appear to be composed of ice in a primarily
34 crystalline state. The main non-icy compounds in these grains are sodium salts and organic
35 material. These materials are heterogeneously distributed over three compositionally diverse
36 ice grain populations and can reach percent-level abundance in individual grains. Ice grains
37 carrying salts or organics are larger than pure water ice grains and are found at higher
38 frequencies in the plume than in the E ring. Organics in ice grains are more refractory than in
39 plume gas with atomic masses of up to at least 200 u. O- and N-bearing organics are likely
40 present in both gas and ice grains. The plume also hosts at least two kinds of nanograins. One,
41 probably icy, population is dispersed inside the plume. The other is dominated by SiO2 and
42 appears to be embedded in larger ice grains and is only released later in the E ring. The
43 possible origins of the different constituents in Enceladus’ interior are discussed. There are
44 more negatively than positively charged water ions in the plume. Cations have the form HnO+
45 (n = 0 - 3) and respective dimers, anions are dissociated water molecules (OH, H-, O-) or
46 cluster of the form (H2O)nOH- (n = 1 - 3). Saturn’s magnetosphere hosts an abundance of non-
47 water cations that likely originate from plume constituents: NH+ is the most abundant, with a
48 mixing ratio of a few percent, followed by N+, C+ and cations with masses of 28 u.
49
50 Vertical compositional stratification of ice grains in the plume has been clearly documented,
51 but there are also hints of compositional variations in ice grains emerging from different Tiger
52 Stripe fractures. In cones of supersonic gas, heavier molecular species (e.g. CO2) have a
 53 narrower lateral spread than light species (e.g., H2). Other spatial variations in the gas are
54 likely, but could not be observed by Cassini’s instruments. Although the plume shows clear
55 activity variations over time, currently no compositional fluctuation could be linked to these
56 variations.
57
58 Enceladus’ surface is subject to constant resurfacing by deposition of plume ices and exhibits
59 the cleanest water ice surface in the solar system. From infrared observations, CO2 is present
60 in these ices in the south polar terrain (SPT), deposition of aliphatic organics is also indicated
61 there. From disk averaged UV observations, NH3 might be generally present in surface ices.
62 The best candidates for an additional UV absorber are “tholins” or iron rich nanograins.
63 Predictions for plume deposition rates can be reasonably well matched with observations in
64 various wavelengths, and indicate strong variations in grain size, but possibly also
65 compositional variations. From plume composition, the SPT should be enriched in salts but
66 these have not yet been detected with remote sensing. In the SPT, crystalline ice from plume
67 deposits seems to be predominant. It is currently unclear whether amorphous ice exists on
68 Enceladus’ surface.
69
70 1. INTRODUCTION
71
72 The plume of Enceladus can be seen as the defining feature of Enceladus’ uniqueness because
73 no other icy body in the Solar System is currently known to exhibit such continuous and
74 large-scale activity. The composition of the plume immediately became one of the highest
75 priorities of the Cassini mission because it was suspected that compositional information
76 would yield unique insights into interior processes, including (at the time putative) subsurface
77 liquid water. And indeed, the current knowledge of the moon’s interior exceeds that of most
78 other planetary bodies (see chapters by Glein et al. Spencer et al. and Hemingway et al., this
79 volume).
80
81 The diverse and flexible payload of the Cassini-Huygens flagship mission turned out to be a
82 huge advantage because it enabled immediate follow-up investigations of the plume’s
83 composition without designing and launching an entirely new mission. Cassini’s instruments
84 were able to measure the composition of emitted gas, solid material (dust), and charged
85 particles with both in situ and remote sensing techniques. During Cassini’s extended mission
86 (2008 – 2017) multiple close Enceladus flybys were incorporated into Cassini’s tour around
87 Saturn. During these flybys the spacecraft flew directly through the plume in order to allow
88 Cassini’s in situ instruments to investigate fresh samples from the Enceladean subsurface.
89 Other flybys allowed high resolution imaging at ultraviolet, visible, and infrared wavelengths
90 to observe the ice grains from the plume and the surface composition that resulted from the
91 outflowing plume materials. A greater part of the ejected micron-sized and sub-micron-sized
92 ice grains falls back onto the moon (Porco et al., 2006; Kempf et al., 2008; Ingersoll and
93 Ewald, 2011) and Enceladus’ surface is constantly exposed to ice particle deposition from the
94 plume (Kempf et al., 2010, Schenk et al. 2011). Therefore the composition of the moon’s
95 surface is closely linked to the composition of the plume.
96
97 However, material emerging from Enceladus is not only apparent close to the moon: Cassini’s
98 measurements have shown that a greater part of all matter residing in the vast space between
99 the orbits of the main rings and Titan is dominated by compounds that once were part of
100 Enceladus. The most prominent witness to this fact is Saturn’s diffuse E ring, which consists
101 of ice grains that, after ejection into the plume, escape Enceladus’ gravitational domain (see
102 chapter by Kempf et al., this volume). In fact, a substantial part of our current knowledge
103 about the plume’s composition has been inferred by analyzing the material that escaped the
104 moon’s gravity. Neutral gas is ejected at such high velocities that it almost entirely escapes
105 from Enceladus (Hansen et al., 2008). This is also true for charged particles that are quickly
106 coupled to Saturn’s magnetosphere.
107
108 In this chapter the word “jet” is used for individual, collimated sources that emerge from
109 Enceladus’ south polar fractures. “Plume” is used to refer to the entire south polar emission
110 composed of all jets and diffuse sources along the fractures. We first discuss the composition
111 of the plume’s 3 distinct phases: Gas, micron-sized grains, and ionized particles (sections 2 –
112 4). We then try to link the identified compounds to possible subsurface sources (section 5).
113 We review the current state of knowledge regarding Enceladus’ surface composition (section
114 6) and then explore relationships between the compositions of the plume and the surface
115 (section 7). The chapter concludes with an integrated summary and a presentation of major
116 open questions (section 8).
117
118
119 2. COMPOSITION OF THE GAS PHASE
120
121 Two Cassini instruments have measured the gaseous component of Enceladus’ plume: The
122 Ion and Neutral Mass Spectrometer (INMS) and the Ultraviolet Imaging Spectrograph
123 (UVIS). These instruments observe the plume from quite different and complementary
124 perspectives. While INMS is an in situ detector that measures the composition along the flight
125 path of the spacecraft through the plume, UVIS is a remote sensing instrument that observes
126 the plume gas from a large distance, thereby integrating along the line of sight between the
127 spacecraft and the star or Sun that is being occulted.

128 The analytical method of INMS is mass spectrometry. In its “closed source mode” neutral gas
129 is collected in an antechamber, which is subsequently transferred through a tube into an
130 ionization chamber. There, the gas is ionized by electron impact from electron guns. The
131 atomic and molecular masses of the cations that form from this electron bombardment are
132 then inferred by a quadrupole mass spectrometer with integer mass resolution (m / Δm ~
133 unitary). The mass range of the instrument is 2 u – 99 u (u = atomic mass unit). The INMS
134 also provides an open source mode where the neutral gas is ionized ’on the fly’ and directly
135 enters the quadrupole mass selection unit without interaction with the walls of the
136 instrument’s interior. For details about the INMS instrument see Waite et al. (2004).

137 UVIS identifies neutral gases in the plume by absorption of star- or sunlight at ultraviolet
138 wavelengths (110 – 190 nm for stellar occultations, 55 – 110 nm for the solar occultation).
139 Certain absorption features are specific to the molecules in the gas. The spectrum of starlight
140 transmitted through an absorbing gas will be attenuated at different wavelengths in a manner
141 that is diagnostic of the composition of the gas. The extinction due to absorption at a given
142 wavelength for a particular gas is generally given as a cross-section. Then, to estimate the
143 column density, the spectrum of the transmitted signal is compared to the spectral absorption
144 features of a specific gas calculated from these cross-sections as a function of wavelength. For
145 details about the UVIS instrument see Esposito et al. (2004).

146 To fully understand the current view of the plume gas composition it is helpful to review
147 Cassini’s exploration in chronological order. For that reason this section starts with the “early
148 results” (subsection 2.1). Those readers that are just interested in the current state of the art
149 might directly jump to subsection 2.2.

150 2.1 Early Cassini results

151 The first measurements of the gas composition of the plume of Enceladus by INMS and UVIS
152 were both obtained on July 14th, 2005. Since the exact location of the plume was not known at
153 that time, the measurements were serendipitous for both instruments.

154 It turned out that Cassini just touched the fringe of the plume during the July 2005 encounter
155 (E2). Nevertheless, INMS mass spectra identified the main gas components of the plume. The
156 data indicated that the atmospheric plume and coma was dominated by water, with significant
157 amounts of carbon dioxide (~ 3%), an unidentified species with a mass of 28 u (~ 4% at that
158 time reported to be either carbon monoxide (CO) or molecular nitrogen (N2)), and methane
159 (CH4). Ammonia was detected at a level that did not exceed 0.5%. Trace quantities of
160 acetylene and propane were also reported (Waite et al., 2006).

161 The UVIS occultation of gamma Orionis, observed on the same day as the INMS
162 measurement, showed that water is a clear match for all absorption features observed with
163 adequate signal to noise ratio in the spectra. The best fit for the column density was given as
164 1.5 x 1016 H2O molecules / cm2. From that column density a total gaseous water emission rate
165 of 150 - 350 kg/s could be inferred (Hansen et al., 2006). This number varied only slightly
166 through subsequent occultations. The occultations of Zeta Orionis (Oct 2007), the Sun (May
167 2010), epsilon & zeta Orionis (Oct 2011), and epsilon Orionis (March 2016) yielded similar
168 emission rates ranging from 170 kg/s to 250 kg/s, assuming the same typical gas velocities
169 (Hansen et al., 2011, Hansen et al., 2017). Data shown in Figure 1 are from the occultation of
170 zeta Orionis observed in 2007, compared to the theoretical water vapor spectrum calculation
171 (Fig. 1).

172
173 Figure 1. The spectrum from zeta Orionis shows narrow absorption features between 115
174 and 130 nm diagnostic of water vapor and a broad absorption at ~155-175 nm. The smooth
175 curve compares water vapor to the spectrum for the best-fit column density of 1.4 x 1016 cm-2.
176
177 In all individual occultations UVIS does not detect components other than water. However,
178 tight upper limits for a number of constituents could be constrained and will be discussed in
179 section 2.2.
180 The next opportunities to measure the plume of Enceladus in situ were the E3 and E5
181 encounters by Cassini in March and October 2008. As in the case of E2 the trajectories were
182 highly inclined but the relative speed was much higher than at E2, with E5 providing the
183 highest flyby speed of all Enceladus encounters (17.7 km/s compared to 8.2 km/s for E2). The
184 higher flyby speed and the closer distance to the sources of the plume provided a substantial
185 increase in signal-to-noise ratio of E5 compared to E2 and E3.
186
187 The E5 flyby data indicated inferential evidence for a liquid water ocean based on 40Ar and
188 ammonia detection in the plume (Waite et al., 2009). However, 40Ar has not been reproduced
189 in subsequent measurements. The plume composition measurements, shown in Figure 2 &
190 Table 1 (reproduced from Table 1 and Figure 1 of Waite et al., 2009) indicate similar values
191 to those of the earlier E2 flyby with two notable exceptions: 1) the number and concentration
192 of organic compounds, especially above 50 u were significantly enhanced and 2) there was a
193 substantially increased H2 component in the plume. These anomalies were later explained as
194 follows:
195
196 i. Excess organic compounds were fragmentation products: A view from the broader
197 perspective of subsequent flybys (E14, E17, and E18; < 8 km s-1 flyby, see below)
198 suggests that the higher flyby speed of E5 (17.7 km s-1) lead to significant
199 fragmentation of organic compounds with heavy molecular weight, outside the INMS
200 mass range, that are found in the ice grains (Postberg et al., 2018). Ice grains
201 inevitably enter the INMS antechamber during plume traversals. In addition,
202 fragmentation of gaseous molecules that hit the antechamber walls at these high
203 speeds also contribute to the ambiguity of the spectrum. Consequently, most of the
204 abundances depicted in Figure 2 & Table 1 and concentrations given therein, do not
205 reflect the intrinsic gas composition (see caption of Table 1 for details). This is
206 especially true for species with masses greater than 27u.
207 ii. Excess hydrogen: The hydrogen excess was explained by the vaporization of raw
208 titanium from the walls of the titanium antechamber by hyper-velocity impacts of ice
209 grains. Subsequent titanium oxidation reactions (TiO, TiO2), lead to dissociation of
210 H2O vapor, yielding gaseous H2 that was then measured by the mass spectrometer.
211 Verification of this hypothesis using ballistic impact modeling has been published by
212 Walker et al. (2015). Later low levels of native H2 have been detected in the plume
213 (section 2.3).
214
215 The serendipitous occurrence of the dissociation reaction described in ii. allowed the
216 determination of the D/H ratio in H2O from the relatively low mass resolution measurements
217 provided by INMS. The value of 2.9 (+1.5/–0.7) x 10-4 is in the mid range of observed
218 cometary D/H values and very similar to the values measured at Comet Halley (Balsiger et
219 al., 1995), as opposed to the order of magnitude lower values found in the atmosphere of
220 Saturn (Pierel et al., 2017). Based on this finding Waite et al. (2009) hypothesized that
221 Enceladus might not have formed by sub nebula condensation processes during the cooling of
222 the sub nebula but was formed or captured late in the Saturnian sub nebula formation process.
223
224 The E5 flyby could not resolve the determination and quantification of the species at 28 u
225 because CO was abundantly produced by dissociation of larger CO-bearing species by
226 molecular or ice grain hypervelocity impacts on, and reaction with, the walls of the INMS
227 antechamber. Waite et al. (2009), estimated that up to 80% of the signal at mass 28 u was
228 produced this way. The residual (~20%) of the mass 28 signal was attributed to N2 or C2H4
229 (ethylene) or a combination of both with an upper limit of 1.2% (volume mixing ratio) for
230 each substance. A ‘small contribution’ from intrinsic CO was also possible.
231
Group Species E5 Volume Mixing Ratio (%) Fragmentation Class
1 H2O* 90 ± 0.01
H 2* [0.39] II
CO2* 0.053 ± 0.01
CO* [0.044] II
CH4 0.009 ± 0.005 I
NH3 0.0082 ± 0.0002
2 C 2H 2 (3.3 ± 2) x 10-3 II
C 2H 4 < 0.012 I
C 2H 6 < 1.7 x 10-3 I
HCN < 7.4 x 10-3 I
N2 < 0.011 I
H2CO (3.1 ± 1) x 10-3 I
CH3OH (1.5 ± 0.6) x 10-4 I
H 2S (2.1 ± 1) x 10-5 I+
3 (40Ar)** (3.1 ± 0.3) x 10-4 II
C 3H 4 < 1.1 x 10-4 I
C 3H 6 (1.4 ± 0.3) x 10-3 II
C 3H 8 < 1.1 x 10-4 II
C 2H 4O < 7.0 x 10-4 I
C 2H 6O < 3.0 x 10-4 I
4 C 4H 2 (3.7 ± 0.8) x 10-5 I+
C 4H 4 (1.5 ± 0.6) x 10-5 I+
C 4H 6 (5.7 ± 3) x 10-5 I+
C 4H 8 (2.3 ± 0.3) x 10-4 II
C4H10 < 7.2 x 10-4 II
C 5H 6 < 2.7 x 10-6 I+
C5H12 < 6.2 x 10-5 I+
C 6H 6 (8.1 ± 1) x 10-5 I+
232 Figure 2 & Table 1. Volume mixing ratios based on analysis of the E5 data presented in Waite et al.
233 (2009), Figure 2 with permission from Nature. Abundances cover the range of accepted composition
234 models for ionization and fragmentation by INMS’s electron guns that adequately fit the E5 mass
235 spectrum. This table has been augmented to include insights from later flybys. In particular, most
236 values are heavily influenced by molecular fragmentation from high velocity wall impacts, of mostly
237 heavy organics, that are responsible for a greater part of the organic species in the spectrum.
238 Species listed with upper limits (grey color) are present in some INMS ionization models but absent
239 from others and are potentially present rather than definitive detections. Fragmentation Class
240 indicates the apparent contribution from heavy organic fragmentation by high velocity wall impacts
241 upon the listed abundances observed during the fast E5 flyby (~17.7 km/s). It is based upon the
242 increase in abundance compared to “slow” (< 8 km/s) flybys (E14, E17, E18, E21). Fragmentation
243 Class I indicates a species with a substantial contribution from fragmentation (factor of 2 – 20 larger
244 than at “slow” flybys), Class II indicates species that are almost exclusively due to fragmentation (>
245 factor 20 abundance compared to slow flybys). Class “I+” indicates a species that has not been
246 detected on slow flybys and thus Class I is only a lower limit for the degree of contributions from
247 fragmentation. It is very likely that the abundances for these species are primarily or exclusively due
248 to heavy organic fragmentation. Group 1 indicates major species, group 2 represents the “C2 region”
249 of the spectrum (masses 24-34), group 3 the “C3 region” (masses 36-46) and group 4 the “C4+
250 region” (masses 48-80) of the spectrum.
251 * The mixing ratios for H2 in brackets have been included in the mixing ratio for H2O as it is
252 believed the vast majority of H2 is produced from interaction of hyper-velocity ice grains on
253 the INMS antechamber (see item ‘ii’ above). The fragmentation class assigned to H2 is with
254 respect to H2O. The mixing ratio for CO in brackets has likewise been included in the mixing
255 ratio for CO2 due to indications of a similar hyper-velocity-induced dissociation process.
256 However, from the low abundance of CO2 during slow flybys (Table 2) it seems that CO is
257 rather an organic fragmentation product and thus the value for CO2 in Table 1 and Waite et
258 al. (2009) is substantially overestimated by the addition of CO (4.4%) to the E5 CO2 raw
259 signal of just 0.9%.
260 ** 40
Ar abundance was originally based upon the lack of fit at mass channel 40 from other
261 potentially contributing species such as C3H4 and C3H6. However, subsequent analysis of the
262 “slow” Enceladus flybys indicates a large reduction in the abundance of species at mass 40
263 (and neighbors), as can be seen by the fragmentation class of II. 40Ar cannot be a product of
264 heavy organic fragmentation, so it is much more likely that the 40Ar signal originally reported
265 for the E5 flyby is rather due to some mixture of organic fragments not yet fully understood.
266

267 2.2. Refined Cassini Results

268 UVIS plume occultations between 2007 and 2011 helped place strong constraints on the
269 possibilities for the ambiguous species at mass 28 (CO, N2, C2H4). An analysis of deviations
270 from a pure water vapor spectrum during stellar occultations yielded an upper limit of 0.9%
271 for CO (Hansen et al. 2006, 2017). A solar occultation by the plume in 2010 presented the
272 unique opportunity to use UVIS’ extreme ultraviolet channel (55 – 110nm) to constrain the N2
273 abundance in the plume because this wavelength range includes N2 absorption features.
274 Although the solar occultation did not reveal any absorptions by N2, the non-detection of such
275 features set an upper limit of 0.5% N2 in the plume. These upper limits further reduced the
276 options left from the INMS E5 data (Waite et al., 2009). Recently, the UVIS team summed
277 many extremely long UVIS integrations of ultraviolet light reflected by the plume and
278 produced a multiply scattered spectrum with features associated with those of hydrocarbon
279 absorbers, primarily C2H4 (Shemansky et al., 2016). Although this is the first unambiguous
280 detection of a 28 u gas species, a mixing ratio has not been inferred yet.

281 The UVIS data have been tested for the presence of both methanol (CH3OH) and ammonia
282 (NH3). Fits of the spectrum improve when methanol is added to the pure water absorption
283 spectrum, however there are no spectral features with adequate signal to noise ratios to allow
284 unambiguous identification or even an upper limit of methanol as a constituent. As was the
285 case for methanol, adding NH3 to the model plume composition improved the overall fit by
286 increasing absorption at short wavelengths. In the case of NH3 there are definitive spectral
287 features that should show up in the spectrum. However, these features are not detectable at
288 the 0.4 to 1.3% level reported by INMS (Waite et al., 2017; see Table 2). UVIS data are thus
289 consistent with, but cannot be used to independently verify the INMS NH3 estimate.

290 INMS plume spectra obtained from the E14, E17, and E18 flybys in 2011 and 2012 provided
291 a much more consistent picture of the gas composition of the plume than previous INMS data.
292 The flybys all occurred with ~7.5 km/s relative speed horizontally over the south polar region
293 with closest approaches ranging from 75 to 100 km in altitude above the vent surface. This
294 configuration allowed for good signal to noise ratios, but avoided effective molecular breakup
295 from wall impacts (evident by the lack of species above 50u). As can be seen in Figure 3, the
296 mass spectra were remarkably similar allowing a deconvolution analysis of the compositional
297 data (Magee et al., in preparation). This allowed a more confident determination of the major
298 volatiles (Table 2) with the exception of the abundance of native H2 (due to interference with
299 H2 from H2O dissociation, see item ‘ii’ in section 2.1).

300 Therefore, the efforts of E14, E17, and E18 were complemented in October 2015 by the
301 measurements of the E21 flyby, a horizontal south polar flyby with a closest approach of only
302 50 km and a relative speed of 8.5 km/s. Here, the INMS for the first time used its open source
303 mode in the Enceladean plume. Although the open source mode is a factor of 400 less
304 sensitive than the closed source mode and comes with strict pointing requirements, it allows
305 for mitigation of the effects from titanium reactions of the closed source antechamber since
306 the material is ionized without wall interaction. The open source concentrations of major
307 volatiles measured during E21 agree with the numbers inferred during E14, E17, and E18
308 with the exception of mass 28 (see discussion below). The E21 measurements most
309 importantly enabled the detection and quantification of the mixing ratio of H2 in the plume
310 (Waite et al., 2017). All resulting major volatiles are shown in Table 2.

311
312 Figure 3: The mass spectra from flybys E14 (light grey), E17 (black), and E18 (medium grey)
313 show the reproducibility of the gas composition from these lower velocity flybys (~7.5 km s-1).
314 The summed signal amplitude of each spectrum is set relative to the noise floor, such that the
315 minimum value on the y-scale represents unit signal-to-noise ratio.

316 Table 2: Final volume mixing ratios of all confirmed neutral gas compounds in Enceladus’
317 plume from Cassini INMS measurements reproduced from Waite et al., 2017 Table 1 (with
318 permission from Science).

H2 O CO2 CH4 NH3 H2

96 to 99 % 0.3 to 0.8 % 0.1 to 0.3 % 0.4 to 1.3 % 0.4 to 1.4 %
319

320 Surprisingly a species with a mass of 28 u was not seen in the open source data from E21
321 suggesting that the respective signal seen in the closed source is largely due to a
322 fragmentation product (CO or C2H4) from heavier, maybe organic, molecules. The results
323 exclude any 28 u intrinsic species in the plume gas at a mixing ratio of 0.1% (Waite et al.
324 2017). It is currently unclear if this low fraction of a native plume volatile at 28 u is sufficient
325 to be in agreement with the tentative detection of weak C2H4 reflection features by UVIS
326 (Shemansky et al., 2016).

327 Analysis of the organic compounds via mass deconvolution for both organic compounds
328 carrying 2 or 3 carbon atoms (C2 and C3 species) obtained at E14, E17, and E18 leads to a
329 host of ambiguities (Magee et al., in preparation) that can only be resolved with higher mass
330 resolution mass spectrometers on future missions. These compounds with unresolved
331 ambiguities that might be present in the plume are shown in Table 3. Organic molecular
332 species with 3 or more carbon atoms or other species above 50 u were not detected on the low
333 speed flybys. These compounds are not present in the plume gas at mixing ratios accessible to
334 INMS and the concentrations given in Table 3 can be seen as upper limits. The detection of
335 organic species with high molecular masses in detectable concentration on high-speed flybys,
336 at E3 and E5 (Waite et al., 2009) was due to fragmentation of organic molecules (Figure 2 &
337 Table 1) above the mass range of INMS, likely residing in ice grains (Postberg et al., 2018).
338 Also see sections 3.1 and 5.1.

339
340 Table 3. (modified from Magee & Waite, 2017): Ambiguous constituents and their possible
341 concentrations from the deconvolution analysis of INMS spectra obtained at “slow” flybys
342 (E14, E17, E18, and E21). Left panel: Some combination of at least four of the listed species
343 at concentration >100 ppm is required to match the INMS spectra. These species dominate
344 the C2 region of the spectrum (masses 24-34). Right panel: Many possible combinations of
345 the listed species at low concentrations may match the INMS spectra, but at least some of
346 these species are necessary to do so. Isomers are possible in some cases. These species are
347 primarily used to fit the C3 region (masses 36-46).

Minor Species I Minor Species II

Moderate Ambiguity High Ambiguity
> 100 ppm < 0.2% < 100 ppm
Hydrocarbons N-bearing O-bearing NO-bearing Others…
C2H2 (26) C3H4 (40) CH5N (31) O2 (32) C2H7NO (61) H2S (34)
HCN (27) C3H6 (42) C2H3N (41) CH3OH (32) C2H5NO2 (75) PH3 (34)
C2H4 (28) C3H8 (44) C2H7N (45) C2H2O (42) C3H7NO2 (89) Ar (36,40)
CO (28) C4H8 (56) C2H6N2 (58) C2H4O (44) C3H5Cl (76)
N2 (28) C4H10 (58) C4H9N (71) C2H6O (46)
C2H6 (30) C5H10 (70) C4H8N2 (84) C3H6O (58)
CH2O (30) C5H12 (72) C6H12N4 (140) C3H8O (60)
NO (30) C8H18 (114) C2H4O2 (60)
C2H6O2 (62)
C4H10O (74)
C4H6O2 (86)

348

349 2.3. Compositional variation in space and time

350 Horizontal variation of the neutral gas density within the plume is substantial. The gas plume
351 seems to consist of supersonic collimated high velocity components (‘jets’) and emissions
352 from much slower outgassing all along the south polar fractures (Hansen et al. 2008, Teolis et
353 al. 2017). This idea is in agreement with the observed stratified ice grain emission (Postberg
354 et al. 2011a, Porco et al. 2014, Spitale et al. 2015) (see section 3.2). It is currently unclear if a
355 compositional variation is linked to this emission because of the low spatial resolution of the
356 published UVIS and INMS compositional results. However, INMS measurements indicate
357 that in supersonic jets, emissions of heavy molecular species (e.g. CO2, 44u) are subject to a
358 smaller lateral spread than lighter species (e.g., H2, H2O) (Yeoh et al. 2015, Perry et al. 2015).
359 Modeling of these effects shows that the relative abundance of CO2 and H2O at altitude can
360 vary more than 30% from the center to the edge of a jet (Hurley et al. 2015). This scenario is
361 true for individual sources (Figure 4) but probably also generally affects the south polar
362 plume as a whole, which is a superposition of these sources.

363 In contrast to ice grain emission, variations in time of the integrated gas emission rate in the
364 entire south polar plume appear to be mild (Hansen et al. 2011, 2017). However, emission
365 rate variations of individual gas jets are substantial (Hansen et al. 2017, Teolis et al. 2017). It
366 is not known if these variations over time correlate with variation in the composition of the
367 gas phase. Limited compositional variations in the gas of individual jet sources over time are
368 likely but have not yet been identified in the Cassini data although major compositional
369 changes in the overall plume gas composition were not observed (Waite et al. 2017, Magee et
370 al., in preparation).

371
372 Figure 4 (from Perry et al. 2015): Illustration of the mass dependent behavior of high-
373 velocity molecules emitted by the jets. For molecules emitted at the same supersonic velocity
374 and in thermal equilibrium with each other at the time they are emitted, the cone angle or
375 spreading of the molecules depends on the molecular mass. This behavior causes differences
376 in spatial composition that are measured by the INMS. Depending on the temperature, bulk
377 velocity and mass, spreading angles vary from 10 to 45 degrees. Cassini’s closest approach
378 during horizontal south polar flybys typically was between 50 and 100 km.
379
380 3. COMPOSITION OF THE SOLID PHASE
381
382 Three Cassini instruments have assessed the chemical composition of the icy component of
383 Enceladus’ plume: The Cosmic Dust Analyser – CDA (Srama et al. 2004), the Cassini Plasma
384 Spectrometer (CAPS) (Young et al. 2004), and the Visible and Infrared Mapping
385 Spectrometer (VIMS) (Brown et al. 2004). The former two are in situ detectors that measure
386 the particles along the flight path of the spacecraft through the plume. While the CDA’s Time
387 of flight – mass spectrometer (TOF-MS) subsystem is sensitive to ice grains with radii of
388 about 0.2 – 2 µm, CAPS observes much smaller grains with sizes of up to about 0.003 µm.
389 VIMS is a remote sensing instrument that observes the plume ice grains from a large distance
390 at infrared wavelengths (1 – 5 µm), thereby integrating along its line of sight. On a few
391 occasions the observation geometry allowed VIMS to acquire spatially resolved spectra of the
392 plume.

393 It is important to remember that a small fraction of plume particles (about 5 - 10% by mass)
394 are launched fast enough to escape Enceladus' gravity and populate the E ring, while the rest
395 of the icy grains fall back onto the moon's surface (Porco et al., 2006; Kempf et al., 2008,
396 2010; Hedman et al. 2009, Ingersoll and Ewald, 2011). Hence the composition of E ring
397 grains, as well as plume particles can provide information about Enceladus’ interior.

398 We will first discuss implications for the plume composition derived from the CDA’s E ring
399 spectra (3.1) and then the results from plume traversals (3.2). We address the nanodust
400 population in the plume observed by CAPS (3.3) and finally the remote sensing results from
401 VIMS (3.4).

402 3.1 CDA measurements in the E ring.

403 In practice, most of the knowledge of the composition of ice grains emitted by Enceladus
404 comes from the CDA, an impact ionization detector. When dust or ice grains strike the
405 detector’s metal target plate with speeds in excess of 1 km/s, a part of the impactor is ionized.
406 CDA then produces time-of-flight mass spectra of the cations present in each individual
407 impact cloud with a transmission cadence of up to 1 spectrum every 2 seconds. The mass
408 resolution of the instrument is relatively low: m/Δ m increases from ≈ 10 at 1u up to ≈ 50 at
409 the upper end of the CDA mass range at about 200u (Postberg et al., 2006). From 2004 to
410 2017 CDA obtained tens of thousands of mass spectra of individual ice grains. Most of them
411 were recorded in the E ring and only a few hundred directly in the plume. As CDA was not
412 built to operate in a dense dusty environment like the Enceladean plume, the instrument
413 settings needed to be tweaked to allow plume measurements. These instrument settings
414 always compromised the quality of plume spectra. However, in the E ring, CDA could be
415 operated nominally and therefore, the E ring spectra provide both, the highest quality spectra
416 and the better statistics, whereas measurements in the plume provide insights into its spatial
417 compositional structure.

418 The impact ionization process yields different cation abundances of identically composed
419 particles at different impact speeds (Postberg et al., 2008, 2011b). Impact speeds of ice grains
420 during the Cassini mission vary between 3.5 km/s to 20 km/s. It often is a challenge to
421 disentangle speed effects on the spectra from spectral variations that are due to actual
422 compositional variations.

423 CDA measurements obtained during Cassini's first E-ring crossing in October 2004 quickly
424 confirmed that the particles in the E-ring are mostly composed of water ice (Hillier et al.,
425 2007). Over 99% of particles detected in the entire E ring are dominated by water ice.
426 However, CDA also found that there are significant differences in the compositions of these
427 ice grains, and that about 95% of all E ring mass spectra from the CDA can be categorized
428 into three major distinct families (Postberg et al., 2008, 2009a). The abundance of each
429 compositional type given below is based on the evaluation of about 10,000 E ring ice grain
430 spectra. These families are also present in the plume itself, though in different proportions
431 (see section 3.2). Although interplanetary and interstellar dust (Altobelli et al., 2016) has been
432 detected in the E ring, it does not have an E ring origin and therefore is not discussed here.

433
434
435 Figure 5: Panels a and b from Postberg et al. (2009a). Different compositional Types in
436 representative CDA mass spectra of E ring ice grains. (a) Type I spectra show mostly water
437 with only traces of sodium. In contrast, Type III spectra shown in (b) exhibit strong mass lines
438 from different sodium salts. Type II spectra (c) and (d), show a wide variety within their
439 group. Many are very similar to Type I with the addition of subtle mass lines in agreement
440 with molecular organic cations carrying only 1 - 3 carbon atoms (c). A few Type II spectra
441 show abundant organic cations, some of them in excess of 100u (d).

442 • Type I particles: About 65% of all E ring spectra belong to this group, increasing to
443 even higher fractions with decreasing particle size. These grains appear to be
444 composed of nearly pure water ice because their spectra are dominated by mass lines
445 caused by water-cluster cations (H2O)n(H3O)+, (n = 0 - 15, see Figure 5a). Na+ and K+
446 and their respective water cluster ions (H2O)n(Na, K)+ are often present and form the
447 only non-water mass lines. These lines imply mostly very low concentrations of alkali
448 salts in the ice grains with Na/H2O ratios on the order of 10-7 (Postberg et al., 2009a).
449 • Type II particles: Type II particles on average produce higher total ion yields upon
450 impact, implying they are larger on average than Type I particles. Type II spectra
451 represent the second most abundant E ring family (≈ 25%, increasing with increasing
452 grain size) and in most cases show the same characteristic as Type I with an additional
453 distinct feature at mass 27u to 31u and/or 39u to 45u, with each of these mostly
454 organic features representing more than one ion species (Postberg et al., 2008). In
455 some cases additional non-water signatures, indicative of additional organic
456 compounds, appear. The fraction of organics and the composition of the organic
457 species can vary dramatically among the different grains (Figures 4c and d).
458 Furthermore, while organic signatures are the most prominent non-water species,
459 sometimes contributions from silicates and salts may be present. Most Type II spectra
460 are salt-poor, similar to Type I.
461 • Type III particles: This family of about 10% of E ring spectra exhibits a totally
462 different pattern of mass lines (Figure 5b) than the other two. In contrast to Type I and
463 II, the water cluster peaks (H2O)n(H3O)+ are absent or barely recognizable. The
464 characterizing mass lines are of the form (NaOH)n(Na)+ (n = 0 - 4) indicating a
465 Na/H2O mole ratio well above 10-3. Frequent mass lines of NaCl-Na+ and Na2CO3-Na+
466 reveal NaCl and NaHCO3 and/or Na2CO3 as the main sodium bearing compounds.
467 Ground experiments with analogue material indicate an average concentration of 0.5 -
468 2% sodium and potassium salts by mass, with K compounds being less abundant by
469 far (Postberg et al., 2009a, 2009b). Impacts of Type III particles have an average ion
470 yield which is several times higher than of Type I particles, implying a considerably
471 larger size (Postberg et al., 2011a).

472 In a few impact spectra, a combination of spectral features from different Types (e.g., Type II
473 and Type III) are found. While Type I and Type III grains are fairly homogenous within their
474 compositional family, the organic bearing Type II grains are quite compositionally diverse,
475 with the concentrations of organic species varying from traces up to the percent level
476 (Postberg et al., 2018). Most Type II grains show one or two groups of organic mass lines
477 between 26u and 31u and 39u and 45u respectively. These cations are indicative of C2 and C3
478 hydrocarbons respectively but could also contain oxygen and nitrogen bearing species, e.g.
479 CHxO+, x = 1-3 or CH2NH2+ between 29 and 31u or respective C2 species between 41u and
480 45 u. In general these organic species are in agreement with volatile organics observed by
481 INMS (Magee et al., in preparation).

482 However, a small fraction of Type II grains exhibits strong organic mass lines at masses in
483 excess of 70u up to the end of the CDA mass range at 200u (Postberg et al., 2018). These high
484 mass organics cations (HMOC) indicative of concentrations on the percent level might stem
485 from refractory organic inclusions in the ice grains (section 5.1). The HMOC type grains
486 show aromatic and aliphatic constituents with functional groups containing oxygen and likely
487 nitrogen. It is possible that all these constituents originate from cross-linked or polymerized
488 macromolecules (Postberg et al. 2018). These high-mass organics species residing in ice
489 grains might have also been observed by the INMS in the plume during high speed flybys,
490 where the high impact velocity disintegrated large molecules to organic fragments small
491 enough to show up in INMS limited mass range (< 100 u) (Postberg et al., 2018, see section
492 2.1). The observation of unspecified high mass molecular species in the plume by CAPS
493 (Coates et al., 2010a, 2010b) might also be due to large fragment ions from these organic
494 species (see section 4.1).

495 Another dust population observed by the CDA instrument that can provide information about
496 the E ring's composition, and thus Enceladus’ plume, are the so-called `stream particles'.
497 These are high-speed, nanometer-sized dust particles that are not gravitationally bound to the
498 Saturnian system and were seen for the first time well before Cassini reached Saturn (Kempf
499 et al., 2005b; Hsu et al., 2010). These tiny grains of dust, once charged, gain sufficient kinetic
500 energy from Saturn’s magnetic field to be thrown out of orbit into interplanetary space (Grün
501 et al., 1993; Hamilton and Burns, 1993; Horanyi et al., 1993; Kempf et al., 2005b; Hsu et al.,
502 2010, 2011, 2012). Numerical modeling of their trajectories indicates that the majority of
503 Saturn's stream particles were once part of the E ring before they were ejected into the
504 streams. Moreover, from their composition and dynamical modeling these particles are
505 thought to be inclusions released from much larger E ring ice grains by the magnetospheric
506 plasma erosion (Hsu et al., 2011, 2015).
507 CDA can only detect these tiny grains because they hit the detector with extraordinary high
508 speed, acquired by their magnetospheric interaction, typically exceeding 100 km/s (Hsu et al.,
509 2010). Still, only the largest of stream particles (≈ 20%) produce a signal that is strong enough
510 to allow a rough characterization of their composition with CDA (Hsu et al. 2011). These
511 particles provide unique information about the plume’s composition because, unlike E ring
512 grains, many of these largest Saturnian stream particles have silicon as a major constituent
513 and are depleted in water ice (Kempf et al., 2005a; Hsu et al., 2011). Co-adding of the weaker
514 signals shows that at least a part of the grains that show no individual particle signal (≈ 80%)
515 have a similar silicon-rich composition (Hsu et al. 2011). The strongest stream particle spectra
516 nearly all show a silicon mass line and have been used by Hsu et al. (2015) for more detailed
517 compositional analysis. They find that they are almost metal-free with a composition in
518 agreement with pure silica (SiO2) rather than typical rock-forming silicates (e.g., olivine or
519 pyroxene). A size estimate derived from their dynamical properties by numerical modeling
520 (Hsu et al. 2011) agrees with the sizes inferred from the spectra signal of the silca grains on a
521 very confined size range with radii ranging 2 – 9 nm (Hsu et al. 2015). A rough quantitative
522 estimate by Hsu et al. (2015) gives a silica / water ice mixing ratio of 150 – 3500 ppm in the
523 material ejected from the plume into the E ring. This number is based on the assumption that
524 all nanograins detected by CDA are made of silica, although the composition can only
525 definitely be assessed for a fraction of them. In this sense, the mixing ratio given above
526 represents an upper limit. Note that this population is different from the nanograins observed
527 directly in the plume by CAPS (section 3.4).

528 Tables 4 and 5 give an overview on the E ring composition near Enceladus estimated from
529 CDA data. Table 5 also shows how concentrations inferred in the E ring might be
530 extrapolated to plume composition. The entries in Table 5 do come with some caveats, as
531 described in the caption. An additional ambiguity is introduced, but not considered in Table 5,
532 because CDA is not sensitive to grains below ≈ 0.2 µm in the E ring or the plume, yet CAPS
533 measurements show that these small grains are present (section 3.3). This situation becomes
534 even more complicated when assessing the overall composition including the vapor, because
535 it is important to consider the different gas / solid mass ratios in the plume and in the E ring.
536 In the plume this ratio is about 10 (section 8.1). However, only ≈ 10% the grains escape the
537 plume (Porco et al. 2006, Spahn et al. 2006, Schmidt et al. 2008, Kempf et al. 2010, Ingersoll
538 & Ewald 2011, Porco et al. 2017), increasing the gas / dust ratio injected into the E ring to
539 ≈ 100.

540
541 Table 4. Abundances of main ice grain Types as identified by CDA in the E ring and their
542 non-water constituents (Hillier et al. 2007, Postberg et al. 2008, 2009a, 2009b, 2011a, 2018).
543 Valid for particle radii for which the composition can be assessed by CDA (≈ 0.2 – 2 µm).
544 The fraction given in the table is size dependent because in larger grains Type I become less
545 frequent while the other two become more frequent. The abundances of the different Types
546 thus also depend on the minimum size threshold detectable by CDA, which again depends on
547 impact speed and instrument settings. Stream particle nano grains actually do not belong to
548 the E ring in a dynamical sense. However, their E ring origin was indirectly determined by
549 Hsu et al. (2011, 2012).

Type I Type II Type III Stream particle

nano grains

Number fraction 60 – 70 % 20 - 30% ≈ 10% -

Main non-water Na, K Organic Na and K SiO2

constituent (MNWC) salts

Typical MNWC < 0.0001% 0.000001 – 10% 0.5 – 2% high

concentration in
individual grains
550

551 Table 5. Integrated abundances of constituents found by CDA in the E ring. These estimates
552 require some assumptions. It is assumed that all compositional types have a similar ion yield
553 when impinging CDA and that Type II and III grains are on average more massive than
554 Type I grains by a factor of 5. The organic fraction is calculated based on the assumption that
555 most of the organics emitted into the E ring reside in a specific sub population that show
556 extraordinary high organic concentrations up to the percent level (Postberg et al. 2018). An
557 average organic concentration of 0.5 - 5% in these grains was assumed. The actual detection
558 frequency of this grain subtype in the E ring varies between 1% and 3% (Postberg et al.,
559 2018). These two factors determine the uncertainty for organics given in the table. The
560 number for SiO2 from stream particles is taken from Hsu et al. (2015) and constitutes an
561 upper limit as explained in the text. The water abundance is inferred from the abundances of
562 the non-water constituents and neglects the possibility that there might be further compounds
563 not seen by CDA. In this sense the value is an upper limit.

Water ice Organic Na and K SiO2

material Salts

Concentration in 99.0% – 99.9% 0.01 – 0.3 % 0.1 – 0.4% 0.015% – 0.35%

E ring solids (upper limit)

Concentration in decreasing increasing increasing similar (?)

plume solids

564

565 3.2 CDA measurements inside the plume

566 The compositional types identified in E ring ice grains are also found in the plume. Modeling
567 of the plume indicates that the plume is stratified in grain size (Schmidt et al., 2008), which
568 was observed by VIMS (Hedman et al., 2009) and the HRD subsystem of CDA (Kempf et al.
569 2008). So it is naturally interesting to see if this dynamical stratification comes along with a
570 compositional stratification. Normally the CDA’s maximum cadence of spectra transmission
571 (< 0.6/s) does not allow measurements with high spatial resolution in the plume. In 2008 a
572 special modification to the CDA’s processing software was made to allow a spectra
573 transmission rate of up to 5/s for a short time. However, the mass resolution and the mass
574 range of the CDA had to be reduced to accommodate this increased transmission rate. The
575 new mode was successfully executed during the highly inclined E5 flyby with a relative speed
576 of 17.7 km/s. The result is shown in Figure 6. Each data point of the profile can be compared
577 with the highly inclined spacecraft trajectory shown in Figure 7.

578
579 Figure 6: The compositional plume profile during E5 (modified from Postberg et al. 2011a).
580 Left panel: The relative frequencies of the compositional grain types (I, II, and III) are plotted. Each
581 data point represents an interval of ±4 seconds and includes ~40 spectra (≈ 5/sec) before closest
582 approach and slightly less afterwards. Error bars are one standard deviation from the mean derived
583 from counting statistics. CDA continuously recorded at its maximum rate, therefore the measured
584 frequencies reflect proportions and not absolute abundances. During the period of highest impact rate
585 between ~18 s and ~35 s after CA, too few useful spectra were obtained (hatched region) due to the
586 overload of the instrument. Similarly, unspecified selection effects may have led to fluctuations in the
587 statistics starting from ~11 s after closest approach. Although the data obtained during this time
588 interval (grey) may therefore have been affected by instrument performance issues, they exhibit a
589 stable trend matching the model predictions of Postberg et al. (2011a) shown on the right panel.
590
591 Right panel: Compositional profile of Type III grains with overlaying contours obtained from two
592 models. The dashed line shows a modelled uniform particle flux emerging from all four tiger stripes.
593 The solid line shows a model including eight faster and more collimated jet-like particle sources
594 observed by Spitale & Porco (2007). The contribution from the small jet particles helps fit the rapid
595 decrease of salt-rich grains when the spacecraft was entering the densest part of the plume, starting
596 about five seconds after closest approach. The model fit including fast sources is also considerably
597 better in matching the relatively low level of Type III grains after 40 s from closest approach, when
598 the spacecraft was still within range of the jets. The background flux of E ring grains is also part of
599 the model. It dominates until about ten seconds before closest approach.

600 Figure 6 shows that on E5 near closest approach (CA) to Enceladus (21 km) the proportions
601 of the three main types exhibited significant variations.

602 a) a steep increase in salt-rich Type III grains from near zero shortly before CA to a
603 maximum of >40% a few seconds after CA and a subsequent shallower decrease
604 towards the dense plume.

605 b) a corresponding simultaneous decrease in the Type I grain proportion with respect to
606 the E ring background shortly before CA.

607 c) a less pronounced increase in the proportion of Type II grains after CA with a
608 subsequent sharp maximum between +45s to +51s.

609 The most plausible explanation for the simultaneous increase of Type III and decrease of
610 Type I proportions in the fringe region of the plume (Figure 7) is that salt-rich grains are
611 ejected at slower speeds than salt-poor grains: The slow Type III grains are dominant at low
612 altitudes, whereas the faster Type I grains enriched at higher altitudes and in the E ring but
613 depleted close to Enceladus. In contrast, the increased ratio of organic-containing Type II ice
614 grains in the core region of the plume, does not seem to depend on altitude and thus ejection
615 speed.

616 Postberg et al. (2011a) suggest that different size distributions of Type I and III grains are
617 responsible for the different ejection speeds implied by the measurements. As a consequence
618 of the radius-dependent friction force that a grain experiences when accelerated by a gas in a
619 subsurface ice vent (Schmidt et al., 2008), ejection speeds of particles are size dependent.
620 This size dependence leads to the observed tendency of large particles preferentially
621 populating the lower regions of the plume (Kempf et al. 2008, Hedman et al. 2009). Figure 6
622 (right panel) shows the model fits to the E5 data, assuming size dependent ejection speeds in a
623 uniform particle flux emerging from all four tiger stripes. It qualitatively reproduces the rise
624 in the fraction of salt-rich grains around closest approach. An even better match could be
625 achieved if the eight faster and more collimated jet-like particle sources known at that time
626 (Spitale & Porco, 2007, Hansen et al., 2008) were added to the uniform flux. These jets are
627 modelled with a steeper particle size distribution, which therefore are richer in small grains
628 compared to the slower uniform particle flux, and, in this model, are preferably salt poor
629 (Postberg et al., 2011a). Figure 7 shows a graphical representation of the modelled plume
630 including the jets and the E ring background.
631
632 Figure 7: Graphical representation of the model plume, including the E ring background, as derived
633 from the E5 flyby data (modified from Postberg et al., 2011a). The background colors on the left panel
634 show the modelled proportion of salt-rich grains (Type III). Pure water ice (Type I) and organic
635 bearing grains (Type II) are subsumed as salt-poor in this model. Overlaid are contours of constant
636 mean particle radius obtained from the model. The projection used is in the plane of the E5 spacecraft
637 trajectory (solid black line, shown with 10 s intervals). It is expected to see both the largest particles
638 and the highest fraction of salt-rich grains, a few seconds after closest approach to Enceladus.
639 Structures of the three most relevant localized supersonic jets for this projection are clearly visible in
640 both the compositional profile and size contours. Note that the model only considers particles with
641 radii above the estimated instrument’s detection threshold (r ≥ 0.2 µm).

642 The profile of organic-bearing Type II grains does not seem to follow a trend where speed and
643 size are linked to composition as in the case of Type I and III grains. Their proportion is
644 slightly higher in the dense plume compared to the plume fringe region, in which the Type III
645 maximum of E5 lies (Figure 6, left panel). This implies a general enrichment of ice grains
646 containing organic material that could be associated with fast, collimated jets (Postberg et al.,
647 2011a). A second significant increase of Type II grains between 45 and 51 seconds after
648 closest approach coincides with the passage of jet source III identified by Spitale & Porco
649 (2007). This event also coincides with the time where Cassini’s ground track lies over the
650 Tiger Stripe fissure called Damascus sulcus and indicates a passage through a region
651 significantly enriched in organic-bearing ice grains. The short timing of this Type II increase
652 only agrees with a very collimated jet source with an opening angle of about 10° because the
653 spacecraft was already 600km above the surface at that point (Fig. 7). The implied organic
654 rich emission from Damascus sulcus is supported by VIMS observations of surface deposits
655 that show the strongest organic absorption at 3.44µm (Brown et al. 2006) on Enceladus
656 around Damascus sulcus (section 6). Moreover, plume grains emerging from Baghdad and
657 Damascus sulci show IR features in VIMS spectra not observed in emissions of the other two
658 fractures (section 3.4).

659 The high rate spectra recording mode employed during E5 turned out to be a risk to the CDA
660 instrument’s health and safety and therefore could not be used again. Despite the limits in
661 detection rate other attempts to map the plume stratification were done during E17, E18 in
662 2012 and E21 in 2015. Here the maximum spectral recording rate was limited to approx.
663 0.6/s, about ten times lower than during E5. Unlike E5 the trajectory of all three flybys were
664 not inclined and led Cassini almost horizontally over the south polar terrain. The flyby speeds
665 were less than half of E5: 7.5km/s on E17 and E18 and 8.5 km/s on E21. In terms of spatial
666 resolution, the lower speed partially compensated for the lower detection rate.

667 In contrast to E5, where the spacecraft trajectory was perpendicular to the Tiger Stripe
668 fractures, Cassini flew almost parallel to these surface features during E17 and E18 (Figure
669 8). With a mean anomaly of 146° (E17) and 153° (E18) the position in Enceladus’ orbit was
670 also very similar. Of these three low velocity flybys, E17 yielded the data set with the highest
671 quality. The compositional profile of E17 (Khawaja et al., 2017) is shown in Figure 8. When
672 entering the plume from the E ring background, the proportion of Type 1 goes down, whereas
673 the proportions of the other two groups go up. However, the increase in the proportion of
674 Type III grains is much less pronounced than in E5 reaching ≈ 18% around the closest
675 approach (≈ 7 % in the E ring), whereas at the same time the Type II proportion reaches 55%
676 (starting from ≈ 30% in the E ring).

677
678

679

680

681
682 Figure 8: Upper panels: The trajectories of E17 and E18 are similar. The ground tracks of
683 the spacecraft trajectories (black lines) are marked by time interval with respect to the time of
684 closest approach. Closest approach was at 76 km in both cases. Lower panel: The
685 compositional profile of E17. The grey area indicates the region where plume particles are
686 more abundant than the E ring background. The dark grey area marks the period when
687 Cassini was directly over the South Polar Terrain (below -70° latitude).

688 The domination of Type II grains in the plume on E17 might only be reconciled with the E5
689 findings when a general enrichment of these organic bearing grains inside a large number of
690 fast jets is assumed, which, at the same time, suppress the Type III proportion that are ejected
691 from slower sources. Efforts are ongoing to modify the E5 model in a way that it can be
692 reconciled with the E17 data. Compositional plume variations in time, between E5 (in 2008)
693 and E17 (in 2012), might also be a factor.

694 3.3 CAPS Measurements on Nanograins in the Plume

695
696 Two subsystems of the Cassini Plasma Spectrometer (CAPS), the Ion Mass Spectrometer
697 (IMS) and the Electron Spectrometer (ELS) (Young et al., 2004) frequently observed a
698 population of charged nanograins in the Enceladus plume (Jones et al 2009). The principle of
699 operation of ELS allows the detection of negatively charged nanograins, their energy per
700 charge (as ELS uses an electrostatic analyzer) and direction, using a microchannel plate
701 (MCP). For the Enceladus encounters, the flyby speed may be used to determine the mass per
702 charge via a conversion involving that speed. In the case of IMS, there is an additional linear
703 electric field time of flight (TOF) determination of mass, beyond the input electrostatic
704 analyzer, which operates similarly to ELS. Most of the results here refer to the analysis of
705 'START' MCP pulses beyond the IMS electrostatic section.
706
707 With a mass to charge ratio m/q ~ 103 to 104 u/q the detected grains are inside the mass-gap
708 between neutral and charged molecular species (sections 2 and 4) and larger, macroscopic (r >
709 0.2µm) solid ice grains observed by CDA (section 3.1 and 3.2) and VIMS (section 3.4)
710 (Figures 9 and 13b). During plume traversals the CDA is not sensitive enough to detect such
711 small grains and CAPS is the only instrument capable of observing this sub-population in the
712 plume. In contrast to the hyper-velocity SiO2 nanograins observed by CDA in Saturn’s
713 magnetosphere, the nanograins in the plume are generally assumed to be of icy composition
714 by comparison with the compositional analysis of gas (Hansen et al. 2008, 2011, Waite et al.
715 2017, section 2), ions (Coates et al. 2010a, 2010b, section 4) and larger grains observed by the
716 CDA (Postberg et al. 2011a, section 3.2). Thus the icy composition of nanograins is mainly
717 based on plausibility arguments but not on direct measurements.
718
719 The nano-particles are charged both negatively and positively and dominate the energy
720 spectra at ~1 keV and higher in the regions in which they are seen. Jones et al. (2009)
721 suggested that triboelectric charging during the plume emission process could provide the
722 charging mechanism. Detailed comparison of the observed fluxes with known jet emission
723 sites gave a good correspondence, and the oppositely charged species were seen to deflect in
724 Saturn’s electric and magnetic field.
725
726 The charged nanograin analysis of these heavy species (up to about 30,000 amu/q,
727 corresponding to ~2000 H2O molecules) was further pursued by Hill et al (2012). On this
728 basis they suggest that most of the grain charging occurs in the plume itself via electron
729 impact. They also argued for single charge on the grains. The measured density of negative
730 and positive nanograins near Enceladus is shown in Figure 9(d) from Hill et al. (2012) and
731 indicates that negative nanograins are clearly dominant near Enceladus.
732
733
(d)

734
735 Figure 9 – (a) ELS and (b) IMS spectrograms showing charged nanograins (high energy
736 signals) during the E3 encounter; (c) E3 and E5 trajectories with ELS nanograin data
737 superimposed and compared with the Cassini ground track (from Jones et al., 2009). (d)
738 shows the calculated density of negative (ELS) and positive (IMS) nanograins showing the
739 dominance of negatively charged grains (from Hill et al., 2012).
740
741 Charged nanograins can easily escape Enceladus’ gravity field on trajectories bent by Saturn’s
742 co-rotating electromagnetic field (Hill et al. 2012, Dong et al. 2015) and can provide a
743 significant source of material for the Enceladus torus and for the E ring. If one uses the
744 (uncertain) negative and positive nanograin densities from Hill et al. (2012) and assumes a
745 grain speed of ~500 ms-1 over an area πRE2 and an average mass of 10,000 amu, then an
746 approximate mass flux of negative and positive charged nano-phase dust grains of 5.6 kgs-1
747 can be estimated which is a mass flux comparable to those of grains with r > 0.6µm (Kempf et
748 al., this volume). Dong et al. (2015) further analyzed the CAPS nanograin data and combined
749 them with CDA and RPWS observations to provide a composite size distribution. This model
750 distribution was based on fitting a composite dust nanograin size distribution peaking at ~2nm
751 to the other observations. From these fits, the total mass production rate of all grains was
752 found to be ~20% of the INMS water vapor mass density at ~15-65 kgs-1 the majority of
753 which resides in grains with radii below 100nm. However, this estimate is controversial
754 because it assumes a continuous size distribution between grains of a few nanometers in size
755 up to micron -sized grains, which is ambiguous as Cassini’s instruments do not well constrain
756 the size distribution for radii between 4 nm and about 1 µm (Dong et al., 2015). Recent
757 calibration experiments indicate that Dong et al (2015) drastically underestimated the
758 nanograin detection efficiency of the CAPS sensor. If this underestimate is verified, the flux
759 would go down by a factor of 10 – 20 to not more than a few kg/s. In any case the mass flux
760 of nanograins could be close to the mass flux of macroscopic ice grains escaping into the E
761 ring and would therefore be an important source of matter into the E ring and Saturn’s
762 magnetosphere. For a detailed discussion see Kempf et al., this volume.
763

764 3.4 VIMS measurements of the plume

765 Information about the plume ice particle composition can also be derived from remote-
766 sensing spectral data. Challenges associated with these sorts of measurements are that the
767 plume has a low optical depth and the plume particles are strongly forward scattering. The
768 former means that the plume spectra have low signal-to-noise ratios while the latter means
769 that the observations with the highest signals do not typically exhibit strong absorption
770 signals. Indeed, the only clear spectral feature in near-infrared plume spectra is a dip at three
771 microns that is due to the extremely strong fundamental water-ice absorption band. Thus far,
772 no other component than water has been securely detected in near infrared plume spectra,
773 although efforts are ongoing.
774
775 While the CDA data contains much more information about the chemical composition of
776 plume particles, the VIMS spectral data provide important constraints on the physical
777 structure of the ice grains. For example, the position of the band minimum depends on
778 whether the ice is in an amorphous or crystalline state, and the observed spectra indicate that
779 the plume particles consist primarily of crystalline water ice (Figure 10). This crystalline state
780 implies that the grains formed at temperatures above 130 K, which is consistent with other
781 evidence that the plume sources are rather warm. Further studies of the spectral and
782 photometric properties of the plume particles could also reveal whether the plume particles
783 are compact grains or loose aggregates of smaller particles.
784
785
786
787 Figure 10 (Adapted from Dhingra et al. 2017): Character of ice in Enceladus' plume. Mie-
788 theory based model spectra for crystalline and amorphous ice compared with plume spectra
789 collected with the VIMS instrument onboard Cassini. The VIMS spectra are best fit with a
790 crystalline water ice spectrum.
791
792
793 VIMS solar occultation data obtained in 2010 together with UVIS measurements show that
794 the plume material above Baghdad and Damascus sulci has a dust-to-gas mass ratio that is
795 roughly an order of magnitude higher than the material above Alexandria and Cairo sulci
796 (Hedman et al. 2018). The highest-resolution near-infrared spectral data obtained by VIMS
797 can resolve material coming from three of the fissures, allowing spatial variations in plume
798 particle properties to be detected (Figure 11). The ice grains emerging from Baghdad, Cairo
799 and Damascus sulci all show a strong three-micron water-ice absorption band with a band
800 minimum position consistent with primarily crystalline water ice. However, the detailed shape
801 of this band, as well as the spectral slope at shorter wavelengths, does differ from fissure to
802 fissure. In particular, the spectra of the Cairo material seem to be distinct from those of the
803 material emerging from Baghdad and Damascus. This observation almost certainly reflects
804 differences in the particle size distributions of the material erupted from the different
805 fractures, but it could also imply variations in the structure and compositions of the grains
806 emerging from the different sources (Dhingra et al. 2017). The high amount of organic
807 bearing grains observed by CDA when flying over Damascus during the E5 flyby (Postberg et
808 al., 2011a) (section 3.2) might also reflect these compositional differences.
809
810
811

Damascu

Baghdad
Plume
Cairo

(a) (b) (c)

812
813

Damascus

Baghdad

Cairo

814
(c)
815 Figure 11: Spatial variability in the near-IR spectral properties of Enceladus' plume. (a)
816 Spatially-resolved VIMS observation of Enceladus' plume from the E10 encounter (cube:
817 V1652853941). Red, green and blue regions indicate sampled regions in the plume and
818 correspond to eruptions along Cairo, Baghdad and Damascus tiger stripes. Colors
819 correspond to the spectra shown in b and c. (b) Spectral character of eruptions along
820 individual tiger stripes. Note the differences in the spectral slope between 1-2.5 µm. (c) Same
821 spectra as in b but vertically offset for clarity. Note the spectral asymmetry (bump) present in
822 the Cairo spectrum (indicated by an orange arrow), which is not observed in spectra from
823 Baghdad and Damascus. Similarly, a spectral bump around 2.6 µm is only apparent on
824 Baghdad and Damascus. The magenta dotted line indicates the band minimum position,
825 which is the same for all three spectra and indicates crystalline water ice grains in the plume.
826 Uncertainties on individual data points are not plotted for the sake of clarity. Sizes of error
827 bars are typically comparable to those of the symbols, but they vary with wavelength. (See
828 Dhingra et al. 2017 for further details on the uncertainties associated with these spectral
829 observations).
830
831
832
833 4 COMPOSITION OF CHARGED PARTICLES
834
835 Two of Cassini’s instruments assessed the composition of charged particles emitted by
836 Enceladus. The positive ion composition was determined by the Cassini Plasma Spectrometer
837 (CAPS) Ion Mass Spectrometer (IMS, Young et al., 2004), which has a time of flight sub-
838 system. The principle of operation of Electron Spectrometer (ELS) allows the detection of
839 negatively charged species, their energy per charge (as ELS uses an electrostatic analyzer)
840 and direction, using a microchannel plate (MCP). Measurements have been performed from
841 inside the plume as well as from escaping material in Saturn’s magnetosphere. The analysis of
842 charged species in the magnetosphere has also been pursued using the Charge Energy Mass
843 Spectrometer (CHEMS) sensor of the Magnetospheric Imaging Instrument (MIMI).
844 In general, the sensitivity of Cassini instruments to minor species in ionized form is lower
845 than for neutral molecules or macroscopic ice grains. In fact, only the measurements in
846 Saturn’s magnetosphere allowed for long enough integration times (months to years) to
847 unambiguously identify non-water constituents. In some cases, quantification was possible,
848 nicely complementing the neutral gas and solid grains compositional measurements of
849 Enceladus’ plume material.

850
851 4.1 CAPS Measurements of Charged Molecules in the Plume
852
853 The discovery of the Enceladus plume via the magnetic field deflection (Dougherty et al.,
854 2006) and subsequent Cassini measurements (Spahn et al. 2006, Hansen et al. 2006, Porco et
855 al., 2006, Waite et al. 2006) provided the impetus to determine the plasma and neutral
856 interaction and composition of the plume. The first ion measurements were presented by
857 Tokar et al. (2006) who analyzed the plasma flow around Enceladus. The measured deflection
858 was initially compared to models developed for Io (Hill et al., 1998). The initial estimate for
859 the total plasma mass loading rate was ~3 x 1027 H2O s-1, corresponding to ~100 kg s-1. The
860 positive ion composition near the plume was found to be dominated by water group ions
861 including O+, OH+, H2O+ and H3O+. The presence of H3O+ shows that ion-neutral chemistry
862 occurs in the plume as charge exchange is required for its formation and is velocity dependent
863 with slower velocities favoring charge exchange.
864
865 The Radio and Plasma Wave Spectrometer (RPWS) and CAPS Electron Spectrometer (ELS)
866 observe a substantial plasma density increase near Enceladus (Morooka et al., 2011, Coates et
867 al., 2013) again indicating that the main mass loading process is charge exchange. Additional
868 ionization processes include electron impact ionization and photoionization. Charge exchange
869 provides energetic neutrals that create an expansion of the Enceladus-related neutral cloud
870 seen as a large-scale OH cloud from the Hubble Space Telescope (Shemansky et al., 1993)
871 and later from Cassini (Esposito et al, 2005).
872
873 Further analysis of positive ions in the plume itself was presented by Tokar et al. (2009) using
874 two close Enceladus encounters in 2008, E3 (52 km closest approach) and E5 (25 km). Cold
875 (<10 eV) ions were observed in the ram direction, indicating an almost stagnant plume
876 ionosphere produced from the plume’s neutral exosphere. Slowing of the plasma was
877 observed north of Enceladus at some 4-6 Enceladus radii (RE) away, while south of Enceladus
878 signatures were seen up to 22 RE away. The composition of the plume ionosphere was again
879 water group (O+, OH+, H2O+ and H3O+) ions and in addition heavier water dimer positive ions
880 were found ((HxO2)+) with x=1-4. These heavier ions, predicted by Johnson et al. (1989), may
881 be formed by charge exchange with a neutral dimer from the plume or via ion-molecule
882 interactions in the stagnant plasma. Figure 12a shows a mass spectrum of positive ions in the
883 Enceladus plume ionosphere.
884
885 The cold ions in the plume and the low relative speed between the ions and neutrals here
886 indicate that the initial ions are converted to fresh pickup ions via ion-molecule interactions,
887 consistent with the presence of H3O+. The ambient ions from the magnetosphere nearby (O+,
888 OH+, H2O+ and H3O+) interact with H2O in the plume itself giving H2O+ and H3O+, in a
889 similar process of H3O+ production to comets (Cravens et al., 2011). These initially stagnant
890 ions are gradually accelerated and move into the magnetospheric wake. They become the
891 principal source of H3O+ for the Saturnian magnetosphere and contribute to the ambient
892 plasma torus, which interacts via charge exchange with Saturn’s extended neutral cloud
893 (Tokar et al., 2006) and becomes redistributed through the magnetosphere (Johnson et al,
894 2006).
895
896 In addition to the positive water dimer ions, another remarkable discovery was that of
897 negative water cluster ions in the plume (Coates et al., 2010a). These cold ions were also seen
898 in the spacecraft ram direction and form part of the plume ionosphere. The ions have a short
899 lifetime and were inferred to be constantly produced from H2O or ice grains in the plume
900 itself. Enceladus thus joins Earth, comets Halley and Churyumov-Gerasimenko, and Titan, as
901 locations where negative ions have been detected. Figure 12b shows a mass spectrum of
902 negative ions in the Enceladus plume ionosphere, while Figure 9 (a)-(c) shows overviews of
903 the CAPS observations.
(a)

904
(b)

905
906 Figure 12 – (a) Positive ion spectra in the Enceladus plume ionosphere measured during the
907 E3 (top) and E5 (bottom) encounters, showing water group and dimer (with x=4) ion masses
908 (Tokar et al., 2009) (b) Negative ion spectrum measured during the E3 encounter showing
909 multiples of m=18 (adapted from Coates et al., 2010a). Nanograins can be seen at the high
910 mass end of the spectrum.
911
912 Water-associated negative ions (e.g. OH-, O-, H-) can be produced from H2O by dissociative
913 electron attachment. Peaks are visible in mass groups 9–27, 27–45, 45–70, 70–300 and 300–
914 500 u/q which may be (OH) n- or perhaps (OH-)(H2O)n with n=1,2,3,4…30. Considering the
915 very limited mass resolution of the measurement, the first three peaks are well centered
916 around masses of negative clusters (17u, 35u, 53u). However, the peaks visible in the higher
917 mass groups may include not only water-related clusters, but perhaps more complex carbon-
918 based species such as seen by CDA and INMS (see sections 3 and 5). The density of the
919 negative ions decreased with mass and can reach 50% of the total density of ambient
920 electrons. However, there is also evidence that the highest density of negative species is in the
921 charged dust grains in this region (see section 3.3). A further discussion of the negative ions
922 and comparison with Titan can be found in Coates et al., 2010b.
923
924 The complexity of the negatively charged population outside the plume but near Enceladus is
925 presented by Coates et al. (2013). The population includes cold magnetospheric electrons,
926 negative and positive water clusters, charged nanograins, “magnetospheric photoelectrons”
927 produced from ionization of neutrals throughout the magnetosphere near Enceladus, and
928 “plume photoelectrons” from photoionization in the plume. The plume and magnetospheric
929 photoelectrons provide a source of warm electrons with energy >20 eV, which can cause
930 electron impact ionization (>13eV is needed for this ionization). These warm electrons
931 increase the importance of this process in the region near Enceladus and probably throughout
932 Saturn’s inner magnetosphere.
933
934 The variability of water molecule production rate in the plume was studied using models and
935 Cassini CAPS, MIMI and INMS data by Smith et al (2010) who found at least a factor of 4
936 variation in the production rate of Enceladus in a 7-month period covering encounters E2, E3
937 and E5. The results are consistent with variability based on orbital location (Hedman et al.,
938 2013) as mentioned by Blanc et al., 2015 (see also chapter by Smith et al., this volume).
939
940
941 4.2 Compositional CAPS and MIMI Measurements of Ionized Plume Material in
942 Saturn’s Magnetosphere
943
944 The first measurements by CAPS at Saturn (Young et al., 2005) revealed that the dominant
945 species in the magnetosphere is water group ions (W+, corresponding to combinations of O+,
946 OH+, H2O+, H3O+). They also reported small concentrations of N+ between ~3.5-8 RS
947 indicating that, unexpectedly, something in the inner magnetosphere (rather than Titan, at 20
948 RS) was producing the N+.
949
950 Further analysis of the water group population has been performed. The dominance of the W+
951 density implied a dominant plasma source within 5.5 RS (Wilson et al., 2008). A more
952 comprehensive survey of plasma parameters including regions inside Enceladus’ orbit
953 (Thomsen et al, 2010) over 4.5 years showed that (1) the ratio of the density of H2+ to H+ is
954 higher near Titan’s orbit, indicating Titan as a source of H2+, and (2) W+ ions dominate in the
955 inner magnetosphere within ~3 Rs of the equatorial plane. Arridge et al. (2011) reviewed the
956 published plasma data and concluded that the inner magnetosphere is dominated by low
957 energy electrons and water group ions sourced from Enceladus. Figure 13 shows the densities
958 of various electron and ions species, collected by Arridge et al. (2011).
959
 Inner Middle Outer
108
107
n [m-3]

106
105
104
103

103
T [eV]

102

10

1
4 6 8 10 12 14 18 16 20
Radial distance [RS]
960
961 Figure 13 - Density and temperature in Saturn’s magnetosphere from various sources
962 collected by Arridge et al. (2011): (a) number densities of hot and cold electrons (Schippers
963 et al. 2008), and thermal ions (Thomsen et al. 2010); (b) plasma temperatures of hot and cold
964 electrons (Schippers et al. 2008), thermal ions (Thomsen et al. 2010; Wilson et al. 2008).
965
966 Pickup water group ions near Enceladus’ orbit were studied by Tokar et al (2008). They
967 suggest that the ions are formed by charge exchange near Enceladus between water group
968 neutrals (O, OH, H2O) and thermal ions corotating with Saturn. The velocity space
969 distribution of the pickup ions, assumed to be OH+, is ring-like in velocity space (see section
970 4.1), indicating that they are relatively new pickup ions. Their density corresponded to ~8%
971 of the total ion density between 4 to 4.5 RS. Related ion cyclotron waves were studied by
972 Leisner et al. (2006) who found that waves produced by W+ (O+, OH+, H2O+, H3O+) and also
973 O2+ were visible throughout the E-ring region.
974
975 Further analysis of the nitrogen population has also been pursued by Smith et al. (2005, 2007)
976 who confirmed a source in the inner magnetosphere, although the molecular source (N2 or
977 NH3) has not been determined yet. Subsequent work by Smith et al. (2008) using a
978 combination of data analysis and modeling showed that the most likely source is NHx+, likely
979 from ammonia, representing a fraction of a few % compared to water ions (see Figure 14). An
980 N2+ origin may additionally be present. However, the non-detection by UVIS in the neutral
981 plume gas restricts the N2 abundance to be below 0.5% of the emitted water vapor (Hansen et
982 al., 2011) and the INMS detects NH3 in the plume with a volume mixing ratio of 0.4% – 1.3%
983 (see section 2.2). It is currently unclear why charged nitrogen species appear to be more
984 abundant in the magnetosphere compared to what can be supplied by the known nitrogen
985 bearing neutral species. One possibility may be that NHx+ species have longer lifetimes than
986 water ions.
 987
988 Figure 14 - Concentrations for N2+ (solid black lines) and NHx+ (dotted line) from CAPS IMS
989 data. Percentages of all heavy ions are shown as a function of radial distance from Saturn
990 (Rs). For N2+ only an upper limit could be inferred. (From Smith et al., 2008).
991
992 The analysis of minor ions compared to W+ in the magnetosphere with integration times of
993 several years (Figure 15) has also been pursued using the CHEMS sensor of the MIMI
994 instrument (Krimigis et al. 2004), which detects energetic particles in the range 83-167 keV
995 (Christon et al. 2013, 2014). The presence of N+ (~2% compared to W+) confirmed the CAPS
996 detection of nitrogen bearing species. Furthermore, C+ indicates dissociation of abundant
997 organic material in agreement with the organic species found in the plume (section 2 and 3).
998 In particular, Christon et al. (2013, 2014) studied the 28M+ (<1% compared to W+) and O2+
999 (~2%). The main nearby source for the O2+ is photolysis of Saturn’s main rings, based on the
1000 observed seasonal variation that favors a ring-related source. For 28M+ the source may be
1001 Enceladus or the main rings, and C2H5+, HCNH+, N2+, Si+, and CO+ were suggested as
1002 possible species. Further seasonal variations are under study. Christon et al. (2015) studied an
1003 ion with mass 56 u with an abundance of ~10-4 compared with W+, identifying it as Fe+.
1004 However, they suggested that this ion may be produced from meteor ablation near Saturn’s
1005 mesosphere-ionosphere boundary, or perhaps from impacted interplanetary dust particles in
1006 the main rings and that Enceladus is probably not the source in this case.
1007
1008
1009 Figure 15 - From Christon et al. (2015)
1010 (a) Triple coincidence pulse height analysis events by MIMI-CHEMS measured in Saturn’s
1011 near-equatorial magnetosphere under certain selection criteria (see Christon et al. 2015)
1012 inside of 20 Rs or the magnetopause, whichever is closer to Saturn, from 2004 to 2013 are
1013 displayed in a Mass (M) versus Mass-per-Charge (M/Q), color spectrogram. The water group
1014 (W+) (mostly O+ at 16 amu/e, followed by roughly equal amounts of OH+ and H2O+ at 17 and
1015 18 amu/e, respectively, at about half the O+ abundance, along with a little H3O+), and the
1016 minor and rare heavy ion species are identified. C+ and N+ are the most abundant non-water
1017 species.
1018 (b) Histogram of the data plotted in (a). The histogram permits clearer identification of the
1019 minor ions like 28M and O2+ and the ‘rare group’ ions of CO2+ (44M+) and iron (56M+) and
1020 facilitates qualitative visual comparisons to W+ and the minor ions.
1021

1022

1023 5. SOURCES OF THE DIVERSE PLUME CONSTITUENTS

1024 5.1. Solid Compounds

1025 The distinct compositional ice grain families probably have very different origins and/or
1026 generation mechanisms. The composition of Type III particles matches the composition
1027 expected for liquid water within Enceladus (Zolotov, 2007), which has washed out salts from
1028 primordial rock inside the moon’s potentially porous (McKinnon, 2015) core (Postberg et al.,
1029 2009a, 2011a; Hsu et al., 2015). Postberg et al. (2009a) suggest that a spray of droplets is
1030 inevitably generated when bubbles reaching the water table of the ocean burst (e.g., Lhuissier
1031 & Villermaux, 2012). The bubbles can be formed either from water evaporating close to its
1032 triple point or upwelling volatile gases (Matson et al., 2012), like CO2, CH4, or H2. If the
1033 spray-droplets are sufficiently small, they will not fall back onto the water table but will be
1034 carried by vapour (emerging from the evaporating water) and follow the pressure gradient
1035 upwards through the cracks and vents into space (Postberg et al., 2009a). Following this
1036 model, Type III grains would be direct samples from the water table of the ocean. From their
1037 composition the ocean salinity would be above 0.5%, with NaCl as the most abundant
1038 dissolved component followed by about half the amount of NaHCO3 and/or NaCO3 (see the
1039 chapter by Glein et al. in this volume).

1040 By contrast, the salt poor (or salt free) Type I grains cannot be generated from ocean spray.
1041 Most of these grains are probably produced from vapor condensation (Schmidt et al., 2008,
1042 Yeoh et al. 2015). Whether the vapor stems from evaporating ocean-water or sublimated ice
1043 makes no noticeable difference in their composition, and both mechanisms are likely to
1044 contribute. However, most Type I spectra show traces of sodium (Na/H2O ≈ 10-7) that are in
1045 good agreement with the traces of salts that one expects to find in the gas phase of
1046 evaporating salt water (Postberg et al., 2009a). The observation of predominately crystalline
1047 ice grains in the plume (Dhingra et al. 2017 (see Figure 10, section 3.4)) implies that the
1048 grains formed at temperatures well above 130 K, which is consistent with other evidence that
1049 the conditions in the ice vents are rather warm (see chapter by Goldstein et al. in this volume).

1050 Vapor that rapidly moves upward inside the ice vents condenses to ice grains when narrow
1051 passages in the ice channels cause local supersaturation. This process naturally forms smaller
1052 grains than the freezing of ocean spray. Compared to the latter, these smaller salt-poor grains
1053 are accelerated to higher average speeds (for any given density and speed of the carrier gas)
1054 (Schmidt et al., 2008, Postberg et al., 2011a). Homogeneous vapor condensation can also
1055 occur during adiabatic cooling after the vapour left the vents. This condensation is limited to
1056 altitudes equivalent to 10 – 100 vent diameters (after which the gas becomes collisionless)
1057 and produces small grains from nanometer scales up to radii clearly below 1 µm for plausible
1058 vent diameters and gas velocities (Yeoh et al. 2015, also see chapter by Goldstein et al. this
1059 volume). This scenario is again consistent with salt-poor vapour condensates being
1060 preferentially smaller than grains formed from salt-rich ocean spray.

1061 The origin of the organic-enriched Type II grains is the least constrained of the three types.
1062 However, their great abundance and frequent detection during Cassini crossings of the
1063 Enceladean plume again suggest that Enceladus is their main source (Postberg et al., 2008,
1064 2011a; Khawaja et al., 2017, Postberg et al. 2018). Most of them are salt-poor, in agreement
1065 with a formation from condensing vapor. In this case, besides water, initially volatile organic
1066 compounds may have condensed onto ice grains as the vapor cooled on its way upwards
1067 through the icy channels. A small fraction of grains shows spectral features of Type II as well
1068 as Type III. These grains could be frozen salt-water droplets that may have incorporated
1069 organic compounds from the Enceladean ocean. Alternatively, organics that initially were in
1070 the gas phase could have condensed onto the salty ice grains in the vents.

1071 About 3% of Type II grains exhibit mass lines that stem from organic parent species with
1072 molecular masses in excess of 200u in particularly high concentration (Postberg et al., 2018).
1073 These organic species are too massive to be in the gas phase at plausible physical conditions
1074 above the evaporating water table (T ≤ 0°C), where the water is inevitably in contact with the
1075 ice crust. The refractory organic material has been detected mostly in salt poor ice grains and
1076 thus they did not form from the salty ocean spray which preserves the liquid composition.
1077 Consequently, the organic material was not dissolved in the ocean water when the ice grain
1078 formed. According to Postberg et al. (2018) the most plausible way to generate these ice
1079 grains containing abundant high-mass-organics is if the organic material exists as a separate
1080 phase, such as a thin film or layer of mostly refractory, insoluble organic species floating on
1081 top of the water table. When bubbles burst in such a scenario, they tear apart the organic film
1082 and, besides salty water droplets, throw up droplets or flakes rich in hydrophobic organic
1083 material (Fig. 16). They will then serve as efficient nucleation cores for ice condensation:
1084 droplets ascending in the icy vents become coated by water ice condensing from the vapor
1085 carrying the grains (Postberg et al., 2018). These high mass organics species potentially also
1086 have been observed by INMS in the plume during high speed flybys, where the high impact
1087 velocity of organic-bearing ice grains disintegrated large molecules to organic fragments
1088 small enough to show up in INMS limited mass range (< 100 u) (Postberg et al. 2018, see
1089 section 2). The observation of unspecified high mass molecular species in the plume by CAPS
1090 (Coates et al., 2010a, 2010b) might also be due to large fragment ions from these organic
1091 species (see section 4.1 and Figure 12).

1092
1093 Figure 16
1094 Schematic on the formation of ice grains from heterogenous nucleation (not to scale). From
1095 Postberg etal. (2018) with permission from Nature. (a) Ascending gas bubbles in the ocean
1096 efficiently transport organic material into water-filled cracks in the south polar ice crust. (b)
1097 Organics ultimately concentrate in a thin organic layer on top of the water table, located
1098 inside the icy vents. When gas bubbles burst, they form aerosols made of insoluble organic
1099 material that later serve as effi cient condensation cores for the production of an icy crust
1100 from water vapor, thereby forming HMOC-type particles. Another effect of the bubble
1101 bursting is that larger, pure saltwater droplets form, which freeze and are later detected as
1102 salt-rich type-3 ice particles in the plume and the E ring. The fi gure implies the parallel
1103 formation of both organic and saltwater spray, but their formation could actually be
1104 separated in space (e.g., at different tiger stripes cracks) or time (e.g., dependent on the
1105 varying tidal stresses working on the cracks) (Hedman et al., 2013; Kite and Rubin, 2016).
1106
1107 The nano - phase silica (SiO2) grains emitted from the E ring can be interpreted as silica
1108 colloids with radii of 2 - 9 nm that formed during the cooling of hydrothermal waters in the
1109 subsurface ocean of Enceladus (Hsu et al., 2015). Combined with long-term laboratory
1110 experiments, the composition and narrow size distribution of these grains argue for ongoing
1111 hydrothermal activities within Enceladus and place constraints on the temperature, alkalinity,
1112 and salinity of Enceladus' subsurface waters (Hsu et al., 2015; Sekine et al., 2015). For further
1113 details see chapter by Glein et al. in this volume. These nano-particles would be transported
1114 from hydrothermal reaction sites, probably located inside Enceladus’ porous rocky core to the
1115 water table (Hsu et al. 2015, Choblet et al. 2017) and then naturally become inclusions of
1116 salty ocean spray from which Type III ice grains form. Nano-silica might also be hovering in
1117 the vapor phase above the water table, dragged into ice vents and then become condensation
1118 cores for the formation of salt poor ice grains of the Types I and II. Interestingly MIMI-
1119 CHEMS observes a species with a mass of 28 u in Saturn’s magnetosphere with Enceladus
1120 being a possible source (section 3). Besides volatile gases (section 5.2), Si+ from eroded
1121 nanosilica grains might be a source.

1122 Other nano-phase species measured in the plume are charged grains, presumably made of
1123 water ice, observed by CAPS (Jones et al. 2009, Hill et al. 2012). These tiny grains inevitably
1124 form when the water vapor cools during adiabatic expansion into space (Yeoh et al. 2015,
1125 also see chapter by Goldstein et al. in this volume). They quickly become mostly negatively
1126 charged after leaving the vents (e.g. Hill et al. 2012, see section 3.3 for details). The CAPS
1127 measurements indicate a size of 1 - 3 nm and hence are even smaller than the silica nano
1128 grains. Although these grains are invisible in Cassini images, they might be as abundant by
1129 mass as macroscopic ice grains (see section 3.3).

1130

1131 5.2 Volatile Compounds

1132 With a mixing ratio above 95%, INMS and UVIS measurements clearly rank H2O vapor as
1133 the most abundant gaseous plume constituent (section 2). A large part likely comes from
1134 evaporation of ocean water, close to its triple point, that has hydrostatically ascended inside
1135 the ‘Tiger Stripe’ cracks through most of the south polar ice crust. With an ice shell thickness
1136 below 5 km at the south pole (Cadek et al. 2016, Le Gall et al., 2017) the evaporating water
1137 table lies less than 1000m below the surface (Postberg et al., 2016) (see chapter by Spencer et
1138 al. this volume). Ice sublimation will cause a currently unspecified but substantial
1139 contribution to the observed water vapor. Above the water table, ice in walls of the vents is
1140 warmed by the ascending gas. Even at the outlets, where the vents reach the moon’s surface,
1141 ice temperatures reach almost 200K, causing a non-negligible vapor pressure from
1142 sublimating ice (Goguen et al., 2013).

1143 Probably the most remarkable volatile plume constituent is H2, which during E21 has been
1144 detected in concentrations exceeding 0.3%. Its extreme volatility precludes “storage” over
1145 geological time scales on a small body like Enceladus and suggests that it is currently (or has
1146 been very recently) produced inside the moon. Its detection is highly suggestive of ongoing
1147 serpentinization reactions in hydrothermal systems within the ocean of Enceladus (Waite et
1148 al., 2017). Most importantly the data in Table 2 in section 2.2 allowed Waite et al. (2017) to
1149 calculate the chemical viability of H2 as the chemical energy source in the reaction 4H2 + CO2
1150 à CH4 + H2O – a reaction that expresses methanogenic metabolism in Earth’s hydrothermal
1151 systems. At moderate alkaline pH values, the chemical affinity is positive, thus verifying the
1152 habitability of the interior ocean (see chapter by Glein et al., this volume).

1153 Ammonia (NH3) is detected in the plume in similar mixing ratios (0.4 – 1.3%) as H2. It is a
1154 very reproducible constituent because it has been detected at all occasions when the INMS
1155 acquired plume composition and its presence also enhances the spectral fit for UVIS plume
1156 spectra (see section 2). The nitrogen-bearing ion species observed in Saturn’s magnetosphere
1157 (section 4.2) indicate even higher concentrations there. Possible sources for NH3 are
1158 numerous and are poorly constrained from Cassini measurements. For example, it can: 1)
1159 form from the dissolving gases in the ocean, 2) be a product of a chemical reaction in the
1160 ocean or hydrothermal sites, or 3) be released from clathrates that might reside deep in the icy
1161 crust (Kieffer et al. 2006).
1162 Similar considerations are true for methane (CH4), that has been frequently measured in the
1163 plume at concentrations of about 0.2 % (section 2.2). Bouquet et al. (2015) discuss methane
1164 contributions from clathrate decomposition as well as hydrothermal production and conclude
1165 that both scenarios are viable. Waite et al. (2017) suggest hydrothermal scenarios such as
1166 Sabatier or Fischer-Tropsch like processes as well thermogenesis.

1167 Carbon dioxide with a mixing ratio of about 0.5% likely is released when pressurized water
1168 saturated in CO2 ascends from the depth of the ocean. Matson et al. (2012) present a model
1169 where dissolved gases, mostly CO2, exsolves as the water moves toward the surface inside
1170 conduits in the south polar ice crust. Bubbles formed by exsolution can decrease the bulk
1171 density of the vertical column of water enough that the pressure at the bottom of the column is
1172 less than that at the top of the ocean. It is suggested that this pressure difference drives ocean
1173 water into and up the conduit toward the surface. CO2 saturated ocean water would be in good
1174 agreement with the substantial concentrations of carbonate salts found in the salt rich ice
1175 grains that are suggested to resemble ocean water composition (Postberg et al., 2009a), with
1176 more dissolved CO2 for a lower ocean pH (see chapter by Glein et al., this volume).

1177 The most controversial Cassini observation in the plume gas is the species with a mass of 28 u
1178 which could be attributed to CO, N2, C2H4 or even Si (as a cationic species, see below). Both
1179 INMS and UVIS measurements now agree that the abundance of CO and N2 lies below 0.5%.
1180 Whereas the latest INMS results exclude any intrinsic plume gas with mass 28 u at a level of
1181 0.1% (Waite et al., 2017), UVIS results indicate at least traces of ethylene (C2H4) to be
1182 present (Shemansky et al., 2016). These constraints are particularly interesting in the context
1183 of a 28 u cation species observed by MIMI-CHEMS in Saturn’s magnetosphere (Christon et
1184 al., 2014) (section 4.2). However, it cannot be differentiated if this species stems from a
1185 gaseous plume compound or dissociated silicates, like silica nano-grains or interplanetary dust
1186 (with the latter obviously not being of Enceladus origin).

1187
1188 6. SURFACE COMPOSITION

1189 6.1. Infrared observations

1190 Earth-based telescopic spectra of Enceladus already indicated the presence of water ice
1191 (Grundy et al., 1999; Cruikshank et al., 2005; Emery et al., 2005, Verbiscer et al., 2006). At
1192 opposition, the icy surface reflects more than 130% of the visible sunlight (geometric albedo
1193 = 1.375 ± 0.008 (Verbiscer et al. 2007), Bond albedo = 0.85 ± 0.11 (Pitman et al. 2010)),
1194 which makes Enceladus the body with the highest visible geometric albedo of all bodies in the
1195 solar system. The Bond albedo of the trailing hemisphere is higher (0.93 ± 0.11) than that of
1196 the leading hemisphere (0.77 ± 0.09) (Pitman et al. 2010). Grundy et al., Emery et al., and
1197 Verbiscer et al. reported detecting a weak absorption in the 2.2 to 2.4 µm region indicating a
1198 possible presence of NH3 or NH3 hydrate, but Cruikshank et al. did not detect the feature, and
1199 so far, it has not been definitively detected in Cassini’s VIMS data with the latest instrument
1200 calibration (Clark et al., 2016).

1201 Early studies by Cassini VIMS confirmed dominant water ice on Enceladus' surface (Figures
1202 17a, 17b). Trapped CO2 was found in most locations, including the Tiger Stripe region
1203 (Brown et al., 2006). Brown et al. also reported amorphous ice. However, this early work did
1204 not include the effects of diffraction by sub-micron ice grains that are common in the E-ring
1205 and in the plume (e.g., Kempf et al. 2008, Hedman at el. 2009, Postberg et al. 2011a, see
1206 section 3.4.). The signatures of sub-micron ice grains, probably from E ring deposition in
1207 most cases, can be observed throughout the Saturn system (Clark et al. 2012). Clark et al.
1208 (2012) showed that a radiative transfer model that included diffraction from sub-micron
1209 particles modified the spectral structure in a unique way, changing relative band depths and
1210 shifting band shapes toward longer wavelengths, and verified the effects with lab spectral of
1211 small ice grains. Amorphous ice shifts the bands to shorter wavelengths and changes the
1212 shapes differently than sub-micron grains. For further discussion on crystalline and
1213 amorphous surface ice see section 7.2.

1214

1215

1216 Figure 17a. VIMS average spectra of Enceladus show the signatures of crystalline water ice
1217 at 1.65 µm and 3.1 µm.
1218

1219 Figure 17b. VIMS spectra of Enceladus showing crystalline water ice (3.1 µm) and a CO2
1220 signature in some locations, predominantly in the Tiger Stripe region.

1221 Jaumann et al. (2008) mapped the grain size of ice across Enceladus' surface and found that
1222 the observed ice absorption strengths in Cassini VIMS spectra could be explained by pure
1223 crystalline ice of varying grain sizes. They found the largest grain sizes (~0.2 mm) in the
1224 south polar “Tiger Stripe” region. Jaumann et al. also found that the particle diameter of water
1225 ice grains increases toward younger tectonically altered surface units and the largest particles
1226 are found in relatively “fresh” surface material. The smallest ice grains were generally found
1227 in old, densely cratered terrains. They also found that the ice grain diameters are strongly
1228 correlated with geologic features and surface ages, indicating a stratigraphic evolution of the
1229 surface that is caused by plume deposition and distribution of materials from cratering events.
1230 A complicating factor in deriving grain sizes in the presence of sub-micron ice grains is that,
1231 as tiny ice grains become more abundant, the surface looks more like a block of ice and the
1232 absorption band depth increases. Fortunately, the presence of small grains is revealed by the
1233 modification of the shapes of the absorption bands (Clark et al., 2012), but a more
1234 sophisticated analysis of the spectral properties is needed than a simple calculation of band
1235 depth (Figure 18). Jaumann et al. (2008) completed their study before these effects were
1236 known. Some of the areas they found with larger ice grain sizes, especially those subject to
1237 large amounts of plume ‘snow’, are definitely affected by sub-micron ice grains and thus need
1238 to be re-evaluated. Scipioni et al., (2017) have begun that evaluation and have generally found
1239 much smaller grain sizes than Jaumann et al. (2008) and a correlation with plume deposition
1240 (see section 7.1 for a details). However, the highest spatial resolution data have yet to be
1241 analyzed at the native resolution.

1242 Additional work on the relation between band depth and grain size has been accomplished by
1243 Verbiscer et al. (2006) who demonstrated the effects of the photometric or scattering
1244 properties of surface particles on absorption band depths. Such analysis is further complicated
1245 by the relationship between band depth and phase angle (e.g. Pitman et al. 2017), which needs
1246 to be included in any modeling effort.
1247

1248 Figure 18. Ice band depth as a function of grain diameter with band depths observed on
1249 Enceladus. This graph does not include photometric effects or the effects of sub-micron ice
1250 grains, which will show enhanced band depths as the abundance of such grains increases.

1251 Derivation of compositional abundances from reflectance spectroscopy requires the

1252 identification of the components making up the surface, and a simultaneous solution of the
1253 grains sizes and abundances of each component. While water ice dominates Enceladus'
1254 surface, Brown et al., (2006) found trace organic compounds in the Tiger Stripe region
1255 (Figure 19). The band position of the organics is consistent with aliphatic hydrocarbons, but
1256 the signature is weak and a more specific identification could not be made. Detecting the
1257 presence of the organic absorptions is made more complex by the spectral curvature in the
1258 strong signatures of ice. A more sophisticated analysis than that performed by Brown et al.,
1259 with the latest VIMS calibration (Clark et al. 2016) needs to be done and might reveal more
1260 information on the nature of the organics. However, the signatures of organic trace
1261 compounds (Brown et al. 2006) are consistent with the detection of organic bearing ice grains
1262 and methane in the plume by CDA (Postberg et al. 2008, 2018) and INMS, respectively,
1263 (Waite et al. 2006, 2017) that are expected to be deposited primarily near the Tiger Stripes
1264 (section 7.1). Brown et al., (2006) also set an upper limit of 2% for solid NH3 global surface
1265 deposits. Hodyss et al., (2009) reported detecting methanol in VIMS spectra from Enceladus’
1266 surface but it has not been verified with the latest VIMS calibration.

1267
1268

1269 Figure 19. Cassini VIMS surface composition from Brown et al., (2006).

1270 Sodium salts (NaCl and NaHCO3/Na2CO3) have been reported in the ice grains in Enceladus'
1271 plume at the 0.1% - 1% level (Postberg et al. 2009a, 2011a, section 3.1, 3.2). It is possible
1272 that these salts could be detected by optical remote sensing. Carbonate salts have strong
1273 absorptions in the 2+ micron region due to C-O stretch-bend combinations. Sodium chloride,
1274 NaCl, is a naturally occurring mineral, halite. Halite is transparent in the VIMS spectral range
1275 unless the halite contains water. Adsorbed water absorption is shifted to shorter wavelengths
1276 than ice absorptions, but a high signal-to-noise ratio is needed to detect adsorbed water in
1277 small abundances. Halite shows a narrow 0.27-micron absorption (Clark et al., 2007), but this
1278 spectral region is not covered by any instrument on Cassini. Halite has not been measured in
1279 the deeper UV covered by the UVIS instrument. At present, the published VIMS spectra of
1280 the plumes have insufficient signal-to-noise ratios to constrain salt abundance. By averaging
1281 all VIMS spectra of the surface or the plume obtained over the entire mission might produce a
1282 high enough signal-to-noise ratio to constrain the salt abundance in the future.

1283 6.2 Ultraviolet and visible light observations.

1284 At far ultraviolet (FUV) and middle-ultraviolet (MUV) wavelengths, Enceladus’ reflectance
1285 drops precipitously. Figure 20a shows an Enceladus spectrum acquired by UVIS (Hendrix et
1286 al., 2010). Water ice has an absorption edge between 165 and 180 nm which is diagnostic of
1287 grain size. A combination of grain sizes can be found to fit the absorption edge of water ice to
1288 the UVIS spectrum, consistent with the water ice composition established by longer
1289 wavelength spectra. Anderson and van Dishoeck (2008) show that the ice absorption edge, in
1290 the UVIS spectral region, shifts to shorter wavelengths in amorphous ice relative to crystalline
1291 ice. While we do not have amorphous ice optical constants in the UVIS range at the
1292 temperatures of Enceladus, the crystalline optical constants provide a good match if the grain
1293 size is on the order of 10µm (Hendrix et al. 2010), consistent with the UV indicating the
1294 dominance of crystalline ice. For further discussion on crystalline and amorphous surface ice
1295 see section 7.2. There is an additional absorber(s) longward of 175 nm that reduces the
1296 reflectivity in the UVIS spectral range (Figure 20a).

1297
1298 Figure 20a (from Hendrix et al. 2010). This UVIS spectrum (grey) was acquired on 27 May
1299 2007 at a range of 620,000 km at a solar phase angle of 2°. In red and blue two model
1300 spectra of crystalline water ice with different grain sizes are shown (blue: areal mixture of
1301 70% 45 µm and 30% 400µm grains, red: areal mixture of two intimate ice grain mixtures of
1302 the two sizes). The mixture of grain sizes in the ice determines the precise location of the
1303 absorption edge between 165 and 180 nm. An additional absorber longward of ≈ 175 nm is
1304 required to fit the Enceladus spectrum.

1305
1306 Figure 20b UVIS FUV data are combined with a single MUV data point from HST at 275 nm
1307 (Verbiscer et al., 2005), the visible spectrum (plus signs) from Verbiscer et al (2005) and data
1308 from 800 to 1000 nm from Verbiscer et al (2006). The visible data were acquired at larger
1309 phase angles and thus do not reach the absolute albedo maximum of 1.375 ± 0.008 (Verbiscer
1310 et al. 2007).
1311 Figure 20b shows the spectrum of Enceladus when UVIS data are combined with the data at
1312 visible and near-infrared wavelengths from Verbiscer et al. (2005) and Verbiscer et al.
1313 (2006), as illustrated in Hendrix et al. (2010). With an I/F of > 1 Enceladus is very reflective
1314 at visible wavelengths >400 nm. At wavelengths shorter than 400 nm the disk-averaged I/F
1315 drops to 80% at 275 nm (Verbiscer et al., 2005), then to < 40% at 190 nm. The UVIS FUV
1316 spectrum exhibits a “ledge” from 175 to 185 nm with ~30% reflectivity, with an upturn
1317 between 185 and 190 nm. The final drop-off short of 175 nm is due to the presence of water
1318 ice.

1319 The spectrum of Enceladus at FUV and MUV wavelengths is not consistent with pure water
1320 ice. Some additional contaminant(s) must be present to darken the surface at wavelengths
1321 from 175 nm to 400 nm. The effort to identify this component(s) from the spectrum alone is
1322 hampered by a severe lack of laboratory data and optical constants in this wavelength range.
1323 There is, however, a fairly good idea of the constituents in the plume from INMS, UVIS, and
1324 CDA data. While gases escape (Hansen et al., 2006), the larger plume particles preferentially
1325 fall back to the surface of Enceladus (Kempf et al. 2010, Postberg et al., 2011a). Smaller
1326 plume particles tend to go into orbit forming the E ring, but they can be re-accreted on
1327 Enceladus’ surface (for details see section by Kempf et al, this volume). A logical approach is
1328 to model non-water species in the plume as the contaminants darkening Enceladus’ surface.

1329 INMS has identified 0.4 – 1.3% NH3 in the plume gas (Waite et al., 2017) and, although the
1330 CDA has not reported a detection of ammonia in the ice grains, it is possible that nitrogen-
1331 bearing compounds are also emitted in the solid phase as minor species. The addition of ~1%
1332 NH3 to water ice with larger grain size in the model surface spectra computed by Hendrix et
1333 al. (2010) reproduces the ledge seen in the UVIS spectrum from 175 to 185 nm and the upturn
1334 at ~185 nm (Figure 21). This finding was confirmed by UV observations with the Hubble
1335 Space Telescope (Zastrow et al., 2012). It is also in agreement with the upper limit of 2% NH3
1336 inferred from VIMS observations (Brown et al. 2006, see also section 6.1). Although NH3 is
1337 not expected to be stable to photolysis and radiolysis on Enceladus’ surface, ammonia hydrate
1338 may be, and is also consistent with ground-based near-infrared spectra (Verbiscer et al.,
1339 2006). Moreover, NH3 may not need to be stable over long timescales since it is probably
1340 constantly replenished. At wavelengths longer than 190 nm NH3 is no longer an absorber
1341 towards the visible portion of the spectrum and an additional component must be present to
1342 explain the drop-off in reflectivity between 190 and 400 nm.

1343
1344

1345
1346 Figure 21. (from Hendrix et al. 2010). Intimate mixtures of 99 % H2O (grain size 1µm) and
1347 1 % NH3 (varying grain sizes: blue 1 µm, green 15 µm, red & purple 30 µm). Models used
1348 NH3 data from Dawes et al. (2007) except purple line, which used NH3 data from Martonchik
1349 et al. (1984).

1350 The aliphatic hydrocarbons detected by Brown et al. (see section 6.1) generally do not have
1351 UV absorbers that can explain Enceladus' UV spectrum. However, it has been shown that
1352 mixtures of H2O + CH4 + NH3 ices which have been irradiated in the lab produce tholins
1353 (Thompson et al., 1987). Moreover, more complex organics have been detected in the plume
1354 by CDA (Postberg et al., 2008, 2018) and INMS (Waite et al., 2009) and these may be
1355 processed on Enceladus’ surface to form such tholins. Unfortunately, very limited spectral
1356 data have been published, however it does appear that some type of tholin material could be
1357 responsible for the darkening of Enceladus’ surface at MUV wavelengths (Hendrix et al.,
1358 2010).

1359 A plausible alternative to an organic UV absorber would be nanophase iron in space

1360 weathered meteoritic dust. Clark et al. (2012) showed common spectral characteristics of the
1361 visible to UV absorber at some locations on Iapetus with other icy satellite surfaces in the
1362 Saturn system including Enceladus, and in the Cassini Division in Saturn's rings. On Iapetus,
1363 the deposits of dark material are relatively pure, and the VIMS data definitively reject tholins,
1364 leaving the nanophase metallic iron and iron oxides as the best explanation. However, at
1365 present on Enceladus, the available spectral data are insufficient to definitively distinguish
1366 between the tholin versus nano-iron plus nano-iron oxide explanation because the UV
1367 absorber signatures are relatively weak (see chapter by Hendrix et al., this volume).

1368

1369 7 PLUME / SURFACE INTERACTION

1370 7.1. Constraints from grain size

1371 Water ice is the main component observed in the plume ejected from Enceladus' Tiger
1372 Stripes. Most of the icy dust particles and gas erupted from this region redeposit on the
1373 surface at a rate that decreases with increasing distance from the surface fractures. The
1374 deposition rate had been simulated by Kempf et al (2010) and Southworth et al. (2018) to be
1375 0.5 mm/yr close to the vents, and 10 µm/year at certain regions north of the equator assuming
1376 compact ice deposition (density ≈ 0.9 g/cm3). The plumes' deposits are broad below 45°S,
1377 then, due to interactions with Saturn’s gravity, they split into two patterns centered at ∼45°W
1378 and ∼225°W, respectively (Figure 22).

90° 10-1

Ice Deposition (mm/yr)

10-2

10-3
0°
10-4

10-5
−90° 10-6
360°W 180°W 0°W
1379
1380 Figure 22: Plume deposition on Enceladus surface as modeled by Southworth et al. (2018).
1381 The model assumes a homogenous distribution of sources all along the Tiger Stripe fractures.

1382 Scipioni et al. (2017) investigated whether the plume material that accumulates on the surface
1383 leaves a spectral signature that can be observed by analyzing data returned by VIMS between
1384 0.88-5.12 µm (Figure 23). VIMS-IR spectra are sampled in 256 spectral channels, with an
1385 average spectral sampling of 16.6 nm (Brown et al., 2004). In general, the depth of absorption
1386 features is influenced by the variation of water ice abundance and grain size. Larger grains
1387 generally cause a deeper absorption, whereas if water ice is mixed with a contaminant

Figure 23. VIMS Enceladus spectrum showing water ice absorption and reflection features
in the near infrared. The main water ice overtones and combinations in the near infrared
range are located at 1.04, 1.25, 1.5, 2.0, and 3.0 µm, while a reflectance peak arises at
3.6 µm.
1388 material, then band depths become shallower (Hapke et al., 1978; Clark, 1981a, 1981b).
1389 However, micron and sub-micron ice grains show enhanced band depths as the abundance of
1390 such grains increases (Figure 18) (Clark et al. 2012). Therefore, plume ice grain deposition,
1391 the sizes of which predominately lie in such a small size regime (Schmidt et al. 2008, Kempf
1392 et al. 2010, Postberg et al. 2011a), might increase band depth because of reduced scattering in
1393 closely packed small particles when the particles are much smaller than the wavelength (Clark
1394 et al., 2012). Although the grain sizes of up to ~0.2 mm inferred by Jaumann et al. (2008) are
1395 probably drastically overestimated due to the aforementioned effect, the general finding of
1396 Jaumann et al. that larger grains are observed closer to the plume sources is in agreement with
1397 the observed size stratification of the plume (e.g., Hedman et al. 2009, see section 3.2 and
1398 chapter by Kempf et al., this volume).

1399 To have a comprehensive view of the distribution of the abundance of the water ice and/or of
1400 the variation of the grain size across the surface, Scipioni et al. (2017) created spatially-
1401 resolved, cylindrically-projected maps of the selected water ice band depths and of the
1402 reflectance peak. From the comparison between model-predicted ice deposits and water ice
1403 distribution maps, the observation of deeper absorptions is expected where the plume
1404 deposition rate increases.

1405 Water ice spectral signatures vary little across the surface of Enceladus (Figure 24), and water
1406 ice band depths only have subtle variations across Enceladus on average. The most
1407 pronounced difference in band depths values involves the South Polar Terrain (SPT). Indeed,
1408 the Tiger Stripes, and the terrains surrounding them, up to about -60° latitude, show by far the
1409 deepest water ice absorption bands, and the smallest value of the 3.6-µm reflectance peak.
1410 Elsewhere on the surface, the band depths and the reflection peak show a longitudinal
1411 variation. The terrains with the lowest band depth values are located between 0°W and 45°W,
1412 between 315°W and 360°W, and around 180°W, and they have almost constant band depths
1413 across the latitudinal direction. A regional bright spot shows up in the leading side, centered
1414 at about 90°W and 30°N. The near infrared reflectance (Figure 24d) of the bright spot is
1415 relatively high, while this spectral index decreases to background levels moving towards 0°W
1416 and 180°W.

1417 To visualize the re-deposition processes taking place on the surface of Enceladus, the
1418 extracted level curves from the modeled deposition rate (Figure 22) are plotted on top of
1419 VIMS-derived maps in Figure 24. The water ice distribution maps show overall a good
1420 agreement with the predicted ejecta deposits in the SPT and in the eastern portion of the
1421 trailing hemisphere. The ice deposits along ∼225° W predicted by the model (Figure 22) are
1422 in fact reproduced by color changes observed in the VIMS maps. From 205°W to 360°W,
1423 there is a qualitative match between the model and the data but the “wedged” shape of the
1424 deposition map is not well reproduced. On parts of the leading side (0°W - 135°W), the map
1425 and the plume deposit prediction’s diverge. Although both the ejecta deposition rate and the
1426 water ice band depths show a longitudinal trend on the leading hemisphere, their positions in
1427 latitude do not exactly overlap. This divergence is at least partially caused by a regional bright
1428 spot centered at 30°N, 90°W. At this location, the deposition model predicts a rate below
1429 10µm/year (Kempf et al., 2010).

1430 The location of this bright spot on the leading hemisphere matches that of a microwave
1431 scattering anomaly (Ries & Jansen, 2015) found by Cassini’s RADAR instrument. The
1432 feature correlates with a tectonized terrain with very few craters, indicative of a recent (< 100
1433 Myr) resurfacing event, maybe caused by an ice diapir (Ries & Jansen, 2015). It is possible
1434 that this caused accumulation of fresh water ice, or annealing to bigger grain sizes, that would
1435 explain the deeper band depth in the near infrared observations and would mask the faint
1436 signature of the plumes' deposits in this region.

1437
1438 (a)

1439
1440 (b)

1441
1442 (c)
1443
1444 (d)

1445 Figure 24 Panels from top to bottom map the 1.25, 1.5, 2-µm band depth (a – c), and the
1446 strength of the 3.6-µm reflectance peak (d), respectively. Contour lines correspond to yearly
1447 plume deposition rate in millimeters (Southworth et al., 2018) under the, unrealistic,
1448 assumption of compact ice deposition with a density of 0.9 g/cm3.

1449 The near infrared data can be compared to four global, high spatial resolution color ratio maps
1450 form Cassini’s Imaging Science Subsystem (ISS) produced by Schenk et al. (2011) by
1451 cylindrically projecting and mosaicking ISS data in the IR3 (0.930 µm), GRN (0.586 µm) and
1452 UV3 (0.338 µm) filters.

1453 Except for the IR3/GRN ratio map, the maps displayed in Figure 25 agree with the plume
1454 deposition model very well. The position as well as the shape of the features in the ratio maps
1455 matches the deposition model. In contrast to the near infrared maps, the match is also good on
1456 the leading hemisphere and in general the match is more accurate for these visible maps
1457 (Figure 25) compared to the near infrared maps of Figure 24. The reason for this mismatch
1458 might be that in visible light, water ice is more transparent than in the near infrared, leading to
1459 a more apparent optical effect produced by a trace abundance of a non-ice component
1460 (discussed above), or due to a grain size difference between the non-ice components and the
1461 ice. The bright region in the leading hemisphere, observed in the near infrared water ice band
1462 depth maps, is only apparent in the GRN/UV3 and not as obvious in the IR3/UV3 map.

1463

1464
1465 a)
1466

1467
1468 (b)

1469

1470
1471 (c)

1472
1473 (d)

1474 Figure 25 The first three panels show three Cassini ISS ratio maps: GRN/UV3 (a), IR3/GRN
1475 (b), and IR3/UV3 (c) (Schenk et al. 2011). The last panel, 25d, represents the RGB
1476 combination of the three filters. In the a, b, and c color ratio maps, bright areas are
1477 associated with a positive slope relative to the ratioed bands. The bright regions in the a, c,
1478 and d combination resemble well the plume fallout outlined by deposits model (Southworth et
1479 al., 2018). The IR3/GRN map (25b) is smoother and does not resemble ejecta deposits.

1480

1481 7.2 Constraints from ice crystallinity

1482 Mapping the crystallinity of surface ices on Enceladus provides an alternative method to find
1483 indicators of plume deposition on its surface. At the average surface temperature on the icy
1484 Saturnian satellites, ~80 K, amorphous ice is stable against thermal recrystallization for long
1485 timescales (Mastrapa et al. 2013). Temperature enhancements beyond 135 K are known to
1486 cause a phase change in H2O ice from amorphous to crystalline; H2O ice can then re-
1487 amorphize over time when subjected to ion bombardment as shown by Mastrapa & Brown
1488 (2006) or by micrometeorite bombardment. Changes in H2O ice phase can thus be used to
1489 track variations in temperature and physical conditions on the surface, ideal to reveal past
1490 and/or present processes on the surface. In the case of Enceladus, H2O plume vapor deposited
1491 on a cold surface (≤130 K) might produce amorphous ice (Baragiola et al., 2008) while icy
1492 plume deposits are expected to be crystalline (Dhingra et al. (2017), also see section 3.4).
1493 Consequently, amorphous H2O ice at the SPT might mark the presence of a vapor deposition
1494 mechanism whereas crystalline ice would be indicative of deposition of plume ice grains as
1495 the dominant process. Moreover, amorphous ice further away from the SPT could indicate an
1496 “old” surface where secondary effects, like space weathering, are more efficient than plume
1497 deposition.

1498 Although early Cassini results by Brown et al. (2006) indicated amorphous ice, later work by
1499 Clark et al. (2012) indicated that the effects of diffraction from sub-micron ice grains might
1500 explain the observed VIMS spectra of Enceladus rather than amorphous ice. Brown et al.
1501 (2006) based amorphous ice detection on a decrease in strength of absorption at 1.65 µm, and
1502 a decrease in intensity of the 3.1-µm Fresnel peak. Clark et al., (2012) showed both of these
1503 effects are also caused by diffraction from sub-micron ice particles in the surface.

1504 The analysis of VIMS data in principle allows spatially resolved measurements but no results
1505 on the detection and distribution of amorphous ice have been published yet. However, various
1506 analyses to constrain the effects of plume deposition with a “crystallinity map” are currently
1507 ongoing (e.g., with the method established by Dalle Ore et al. 2015 but modified for the
1508 effects sub-micron ice grains).

1509

1510 8. CONCLUSIONS AND OPEN QUESTIONS

1511 8.1. Plume composition

1512 The Enceladean plume is composed of three different phases: Gas, solids (dust), and ions.
1513 Neutral gas is the most abundant component and is emitted with an average rate of 170 – 250
1514 kg/s (Hansen et al. 2017). The estimates for the emitted solid material vary much more. This
1515 estimate only partially reflects the orbital variation in emitted dust that appears to be larger
1516 than for gas (Hedman et al. 2013, Nimmo et al. 2014, Ingersoll & Ewald 2017, Hansen et al.
1517 2017) but also reflects the larger uncertainty of the dust flux estimates. Estimates range from
1518 about 3 - 5kg/s (Schmidt et al. 2008, Kempf et al. 2010) to 50 kg/s (Ingersoll & Ewald, 2011)
1519 or 15 – 65 kg/s (Dong et al. 2015). The arguably most robust value is given by Kempf et al.
1520 (this volume) with about 20 kg/s and yields a dust to gas ratio about 10% (for a detailed
1521 discussion see chapter by Kempf et al., this volume). The ejection speed of the gas is much
1522 larger than that of the dust grains (Schmidt et al. 2008, Hedman et al. 2009), therefore the gas
1523 almost completely escapes into space. The ionic component is picked up by Saturn’s
1524 magnetosphere and also escapes Enceladus’ gravitational influence. The abundant nanometer-
1525 sized grains observed by CAPS (Hill et al 2012, Dong et al. 2015) probably also almost
1526 completely escape. However, only a fraction (5 – 10%) of the solid material larger than ≈ 0.1
1527 µm in the plume escapes into the E ring, whereas the greater part is falling back to the surface
1528 (Porco et al. 2006, Spahn et al. 2006, Schmidt et al. 2008, Kempf et al. 2010, Ingersoll &
1529 Ewald 2011), a fact that strongly couples plume composition and surface composition (see
1530 section 8.3). The probability of escape is coupled to the grain size: larger grains are ejected at
1531 lower speeds, leading to the observed tendency of large particles preferentially populating the
1532 lower regions of the plume and smaller grains preferentially escaping into the E ring (Kempf
1533 et al. 2008, Hedman et al. 2009). This size dependence also causes a compositional plume
1534 stratification (Postberg et al. 2011a, Khawaja et al. 2017) (see 8.2).

1535 All three phases (gas, dust, and ionic) are primarily composed of water. For the neutral gas
1536 the water abundance is larger than 96%, for dust grains with r > 0.2 µm it is in the order of
1537 99%, whereas the water proportion in the ionic phase, though dominant, is less well
1538 constrained. The majority of ice grains in the plume are in a crystalline (and not amorphous)
1539 state (Dhingra et al., 2017) indicative of formation temperatures above 130K. Although the
1540 general interpretation that these grains are made of water ice is justified (e.g. Hill et al., 2012),
1541 the composition of the predominately negatively charged nano-grains in the plume is actually
1542 not known (see section 8.4. ‘Open Questions’).

1543 The main non-icy compounds in the solid phase (r > 0.2 µm) are sodium salts and organic
1544 material. Salts and organics are heterogeneously distributed over three compositional diverse
1545 main ice grain populations and can both reach percent level abundance in individual grains
1546 (Postberg et al. 2009a, 2011a, 2018). SiO2 is another important constituent (> 100 ppm) but
1547 was indirectly inferred by measurements in the outer Saturnian system (Hsu et al., 2011,
1548 2015). The most abundant volatiles are ammonia, molecular hydrogen, carbon dioxide, and
1549 organics. Each of these compounds is present in mixing ratios of fractions of a percent with
1550 upper limits of H2 and NH3 slightly above 1% (Waite et al. 2017). The D/H ratio is 2.9
1551 (+1.5/–0.7) x 10-4 and is approximately in the mid-range of observed cometary D/H values
1552 and much higher than in Saturn’s atmosphere (Waite et al., 2009). Methane (≈ 0.2%) is the
1553 most abundant organic compound in the gas phase with less abundant C2 and maybe C3
1554 species (Magee & Waite, 2017). In comparison, the ice grains carry more refractory organic
1555 material with atomic masses ranging from about 28 u up to at least 200 u (Postberg et al.
1556 2008, 2018). O- and N-bearing organic species might be present in both, neutral gas and ice
1557 grains (Magee & Waite 2017, Postberg et al. 2018). The tentative detection of ammonia in the
1558 surface ice of Enceladus (Emery et al. 2005, Verbiscer et al. 2006, Hendrix et al. 2010,
1559 section 4.2) supports the idea of nitrogen-bearing ice grains being emitted by the plume.
1560 In general, the sensitivity of Cassini instruments to minor species in ionized form is lower
1561 than for neutral molecules or macroscopic ice grains. Ions directly measured in the plume are
1562 composed almost exclusively of water and water products. Detected cations have the form
1563 HnO+ (n = 0 - 3) and respective dimers. Detected anions are dissociated water molecules
1564 (OH, H-, O-) or cluster of the form (H2O)nOH- (n = 1 - 3) (Tokar et al. 2009, Coates et al.
1565 2010a, 2010b). The only indication for ions other than from water are high-mass anions (>
1566 200 u) possibly in agreement with complex organics (Coates et al., 2010a, 2010b). In contrast,
1567 there is ample evidence for non-water ions from integrated measurements in Saturn’s
1568 magnetosphere that likely were emitted by Enceladus’ plume. The most apparent are N-
1569 bearing cations, in particular NH+ detected by CAPS, present on a level of a few percent
1570 (Smith et al. 2008), a proportion that seems to be difficult to reconcile with the lower
1571 abundance of N-bearing species in the plume (see section 8.4 for further discussion). The
1572 detection of N+ by the MIMI-CHEMS sensor supports this result. The instrument also finds
1573 C+ in similar abundance (≈ 1%) indicative of dissociation of organic plume constituents.
1574 Another ion species of possible plume origin detected in trace abundance, are cations with a
1575 mass of 28 u that could be C2H5+, HCNH+, N2+, Si+, and CO+ (Christon et al. 2014, 2015). See
1576 section 8.4 for further discussion.
1577 Possible origins of the different constituents in Enceladus’ interior are discussed in section 5
1578 and in the chapter by Glein et al. this volume.
1579

1580 8.2. Variability of the plume composition in space and time

1581 There is clear indication of spatial variation in the plume’s composition. Most apparent is the
1582 compositional stratification of the ice grains with r > 0.2 µm measured by the CDA. Ice grains
1583 containing significant amounts of sodium and potassium salts are significantly more abundant
1584 at low altitudes. This stratification is indicative of lower ejection speeds caused either by
1585 slower ejection speed of the carrier gas or by the larger size of these grains (Postberg et al.,
1586 2011a). In turn the almost pure water ice grains are more abundant at high altitudes and in the
1587 fraction that escapes into the E ring. Organic bearing grains appear to be most abundant in
1588 confined high velocity jets at all altitudes (Postberg et al. 2011a, Khawaja et al. 2017). The
1589 stratification outlined above is based on proportions, obviously the absolute abundance of ice
1590 grains of any composition increases with lower altitudes. The plume material above Baghdad
1591 and Damascus sulci has a dust-to-gas mass ratio that is roughly an order of magnitude higher
1592 than the material above Alexandria and Cairo sulci (Hedman et al. 2018). This difference
1593 suggests, but does not prove, that the there is a lateral variation in the ice grain composition
1594 (Postberg et al. 2011a, Dhingra et al., 2017). Organic bearing grains are possibly more
1595 abundant in emissions from Damascus sulcus than from the other sulci (Postberg et al. 2011a,
1596 Brown et al. 2006).
1597 The spatial density variation of the neutral gas inside the plume is substantial (Hansen et al.
1598 2008, Teolis et al., 2017). However, it is not known if a compositional variation is linked to
1599 this spatial variation. The only clue from Cassini is INMS measurements which indicate that
1600 heavier molecular species (e.g. CO2, 44 u) have a narrower lateral spread than lighter species
1601 (e.g., H2, 2 u) in a supersonic jet cone (Perry et al. 2015).
1602 Spatial variations in the composition of the ionized phase have not been reported. However,
1603 charged molecules and charged nano grains both will have very different trajectories
1604 compared to the ballistic trajectories of the neutral gas and larger grains. The plasma
1605 environment is dominated by the dynamics of the interactions between the plume neutral gas
1606 and the co-rotational plasma in Saturn’s magnetosphere (see chapter by Smith et al., this
1607 volume) Because the charge-to-mass ratios of nanograins are sufficiently large, their
1608 dynamics are strongly influenced by the Lorentz forces and thus sensitive to the local
1609 electromagnetic environment resulting from the plume-magnetosphere interactions. Grains
1610 with radii of a few nm with both polarities are found in the plume (Jones et al., 2009), and
1611 these grains are likely responsible for several features observed in the Cassini magnetic field
1612 and thermal plasma data (Simon et al., 2011, Hill et al., 2012, Meier et al., 2014, Meier et al.,
1613 2015, Dong et al., 2015). Fluxes of both plasma ions and charged nanograins emitted by
1614 Enceladus will strongly vary with magnetic field and co-rotational plasma conditions and
1615 could potentially be linked to a compositional variation.
1616 The plume is known to be time variable. The most apparent activity cycle is coupled to the
1617 moon’s orbital period (Hedman et al. 2013, Nimmo et al. 2014, Ingersoll & Ewald 2017). The
1618 plume brightness from emitted ice grains varies by about a factor of 4 between apocenter
1619 (maximum) and pericenter (minimum). This variation can be explained either by a change in
1620 total mass flux or by a drastic change in the grain size distribution or by a superposition of
1621 both effects (Hedman et al., 2013). A variation by a factor of four has also been observed for
1622 the nanograin flux (Smith et al. 2010, Blanc et al, 2015) (for detail see chapter by Smith et al.,
1623 this volume). There is also indication for brightness variations on the order of years (Hedman
1624 et al. 2013, Ingersoll & Ewald 2017). By contrast, the variations in the integrated emitted gas
1625 flux over time seem to be milder (Hansen et al. 2017, Teolis et al. 2017). Currently no
1626 compositional variation can be linked to either these variations (see section 8.4.).
1627
1628 8.3. Surface composition
1629 Enceladus exhibits the cleanest water ice surface with the highest visible albedo known in the
1630 solar system (Verbiscer at al. 2007). The only non-icy component that has been measured
1631 with certainty is CO2 that is trapped in surface water ice. CO2 appears to be most abundant in
1632 the south polar terrain (Brown et al. 2006). An absorption in the far UV consistent with NH3
1633 mixed in water ice has been identified in disk-averaged UVIS images (Hendrix et al. 2010)
1634 but is only in agreement with its absence in near infrared spectra at concentrations of less than
1635 2% (Emery et al. 2005, Verbiscer et al. 2006, Brown et al., 2006). Infrared bands consistent
1636 with aliphatic hydrocarbons have been identified along the tiger stripe fissures (Brown et al.
1637 2006). Suitable candidates for an absorption in the mid UV, also observed on other icy moons
1638 of Saturn (see chapter by Hendrix et al., this volume), might be some sort of tholins or traces
1639 of a mixture of nano-phase iron and iron oxide.
1640
1641 Deposition of plume material, especially micron-sized ice grains, happens on most of
1642 Enceladus surface. If E ring deposition is also taken into account, the entire surface is exposed
1643 to plume material (see chapter by Kempf et al., this volume) though deposition rates vary with
1644 surface location. The south polar terrain is subject to intense resurfacing by icy plume
1645 deposits and the composition there should be largely governed by the composition of the
1646 emitted ice grains. From deposition maps (Schenk et al. 2011, Scipioni et al. 2017) and plume
1647 dynamics (see section by Goldstein et al. this volume), the largest grains fall back onto the
1648 surface closest to their Tiger Stripe sources. CDA data indicate that these large grains are
1649 particularly rich in non-icy components, which make it likely that sodium salts, in particular
1650 chloride and carbonate/bicarbonate, and organic compounds are present in substantial
1651 quantities of up to ≈ 1% close to the Tiger Stripe fissures.
1652
1653 At present, the published VIMS spectra of the plumes have insufficient signal-to-noise ratios
1654 to constrain the salt abundance. Organic material is likely present near the tiger stripes
1655 (Brown et al., 2006) and “tholins” are tentatively indicated (Hendrix et al. 2010). If the latter
1656 are present, they could be the result of space weathering of organic precursors in the plume
1657 and can form on geological time scales. This process might be more efficient at regions
1658 further away from the south polar terrain which are not subject to the highest deposition rates
1659 of fresh plume material. Although the deposition of crystalline ice grains from the plume
1660 might argue for mostly crystalline surface ice, at least near the south polar terrain, the
1661 question of whether amorphous ice is present on Enceladus’ surface has not been fully
1662 resolved.
1663
1664
1665 8.4. Major open questions

1666 The only reduced carbon plume compound that can be identified with certainty is methane.
1667 Although there are definite measurements of further (unspecified) organic species with higher
1668 masses in the ice grains (Postberg et al. 2008, 2018) and the neutral plume gas (Waite et al.
1669 2009, Magee & Waite 2017), the actual organic compounds are poorly constrained
1670 qualitatively and quantitatively. In the plume gas, this uncertainty concerns unspecified
1671 species with up to three C-atoms whereas in the ice grains the organic molecules, at least
1672 occasionally, are much more complex (Postberg et al. 2018). It is also likely that the limited
1673 mass resolution of the CDA not only limits the detection and specification of organic
1674 compounds but also the detection of inorganic compounds, like minerals and salts other than
1675 the most abundant species reported by Postberg et al. (2009a). In particular, ammonia or other
1676 nitrogen-bearing species would be in agreement with observations of Enceladus’ surface
1677 (Hendrix et al. 2010). One of the major compositional uncertainties is the unidentified species
1678 at 28 u. There is no such species detected by the INMS in the plume with an upper limit
1679 below 0.1% (Waite et al. 2017). However, UVIS reports traces of organic species, attributed
1680 mostly to C2H4 (28 u), in the plume (Shemansky et al., 2016) and an unspecified ionic species
1681 with 28 u is detected in Saturn’s magnetosphere (Christon et al. 2013, 2014). Obviously, a
1682 better understanding of the organic as well as the inorganic plume inventory is a critical
1683 element for the investigation of Enceladus’ subsurface ocean by future missions (see chapter
1684 by Lunine et al., this volume).

1685 Cassini’s instruments could not directly measure the composition of nanograins in the plume.
1686 Although it is a plausible assumption that they are mostly or exclusively composed of water
1687 ice, the actual composition is in principle unknown. Nanograins play an important role in the
1688 overall emission of solid plume material (Hill et al. 2012), and they are in contrast to the
1689 larger grains (r > 0.1 µm) observed by CDA that completely escape into the Saturnian system.
1690 At least some of the emitted nanograins are composed of SiO2. Dynamical modeling indicates
1691 that these are different from the nano-grains directly observed in the plume (Hsu et al., 2011,
1692 2015, Hill et al., 2012). SiO2 grains might leave the vents primarily incorporated into
1693 macroscopic ice grains and are only released later by plasma sputter erosion of their carriers
1694 (Hsu et al. 2015) in the E ring, but it is actually unclear whether SiO2 nano-grains also exist as
1695 individual particles in the plume.

1696 The overabundance of N-bearing ions (in particular NHx+) from Enceladus in Saturn’s
1697 magnetosphere (Smith et al. 2008) compared to the apparent plume composition is a long-
1698 standing unresolved question. Possible explanations could be: a) NHx+ has a long lifetime
1699 compared with water ions and is therefore overrepresented in the ionic phase; b) abundant N-
1700 bearing species are emitted in the form of organic molecules (in the gas and in ice grains) that,
1701 after their dissociation, feed NHx+ into the magnetosphere; c) Nanograins are effective carriers
1702 of N-bearing species that are later released as ions into Saturn’s magnetosphere. The tentative
1703 detection of ammonia in the surface ices of Enceladus (Emery et al. 2005, Verbiscer et al.
1704 2006, Hendrix et al. 2010) supports the idea of nitrogen-bearing ice grains emitted by the
1705 plume.
1706 Except for the compositional stratification of the macroscopic ice grains in the plume
1707 (Postberg et al., 2011a), variations of the plume’s composition in space and time are not yet
1708 well constrained by Cassini measurements. However, given the rich dynamical fine structure
1709 (Hansen et al. 2008, 2017, Porco et al. 2014, Teolis et al. 2017, Southworth et al. 2018) and
1710 the quite drastic diurnal orbital variation in the plume brightness (Hedman et al., 2013,
1711 Nimmo et al., 2014, Ingersoll & Ewald 2017) it is highly likely that, yet unknown,
1712 compositional variations coincide with the variations in activity.
1713
1714 Sodium salts and organic compounds are currently poorly constrained on the Enceladean
1715 surface although their presence in quantities up to the percent level on the south polar terrain
1716 is highly likely. The effects of submicron grains on VIMS spectra have been underestimated
1717 at first and a new VIMS calibration was required for observations that occurred later in the
1718 mission (Clark et al. 2016). Therefore, a more sophisticated analysis of the VIMS data might
1719 reveal more information on organics in the near future. Ultimately, co-adding all VIMS
1720 spectra of the surface obtained over the entire Cassini mission may produce a spectrum with a
1721 sufficiently high signal-to-noise ratio to constrain salt abundances in the near future.
1722
1723 There is a non-water mid UV absorber on Enceladus. It seems to have similar properties to
1724 impurities observed on other icy moons (see chapter by Hendrix et al. this volume) and the
1725 main rings (e.g., Clark et al. 2012, Filacchione et al. 2012). At present, the available spectral
1726 data are insufficient to definitively distinguish between the two best candidates: tholins or a
1727 mixture of nano-phase iron and iron oxide. The latter could potentially indicate impact
1728 gardening by space weathered meteoritic dust.
1729
1730 The detection of amorphous water ice on Enceladus could reveal more of its surface history
1731 by identifying regions where ice condensed from vapor at low temperatures or locations
1732 where previous surface modification by particle bombardment is/was more efficient than the
1733 deposition of crystalline plume ice grains. Amorphous water ice may still be detected on the
1734 surface of Enceladus in Cassini VIMS spectra if the latest VIMS calibration (Clark et al.,
1735 2016) is applied, but such analyses have not been done at the full spatial resolution of the
1736 VIMS dataset.
1737
1738
1739
1740 Acknowledgements:
1741
1742 F.P. acknowledges funding from the European Research Council (ERC) under the European
1743 Union's Horizon 2020 research and innovation programme (Consolidator Grant 724908-
1744 Habitat OASIS).
1745
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