Lunar and Planetary Science XXXIV (2003) 1686.pdf

Vapor , Composition and Fractional Vaporization of High Lavas on Io. B. Fegley, Jr.1, L. Schaefer1, and J. S. Kargel2, 1Planetary Chemistry Laboratory, Department of Earth and Planetary Sciences, Washington University, St. Louis, MO 63130-4899, 2 U.S. Geological Survey, Flagstaff, AZ 86001. E- mail: [email protected] , [email protected] and [email protected]

Introduction: Observations show that Io’s atmosphere We found that the total is not diagnostic of is dominated by SO2 and other sulfur and sulfur oxide lava composition. For instance, at 1900 K, the range of species, with minor amounts of Na, K, and Cl . vapor for tholeiites is 10-2.8 to 10-2.7 bars whereas Theoretical modeling [1-3] and recent observations [4] show the range for komatiites is 10-3.3 to 10-2.6 bars. that NaCl, which is produced volcanically, is a constituent of Initial Vapor Composition: Figure 1 shows the initial the atmosphere. Recent Galileo, HST and ground-based vapor composition over tholeiitic basalt and Barberton observations show that some volcanic hot spots on Io have komatiite lavas. The initial vapor composition for all lavas extremely high , in the range 1400-1900 K [5- studied is dominated by Na, K, O2, and O. These gases are 7]. At similar temperatures in laboratory experiments, molten more abundant than all other species by several orders of silicates and oxides have significant vapor pressures of Na, magnitude. Over the temperature range plotted, the K, SiO, Fe, Mg, and other gases. Thus vaporization of these abundances of Na, K, and O2 are essentially temperature- species from high temperature lavas on Io seems likely. We independent, whereas the abundance of every other species is therefore modeled the vaporization of silicate and oxide lavas temperature-dependent. suggested for Io. Our results for vapor chemistry are reported At the low end of our temperature range (1700-1900 K), here. The effects of fractional vaporization on lava chemistry the fifth most abundant is the e-(gas) produced by are given in a companion abstract by Kargel et al. [8] thermal of Na (g) and K (g) to Na+ (g) and K+ (g). Method: We use the MAGMA code developed by At these lower temperatures, K+ (g) is always more abundant Fegley and Cameron [9]. The MAGMA code simultaneously than Na+(g). However, there is a temperature-dependent solves for the activity coefficients of the oxides in a non- relationship for the extent of thermal ionization: ideal melt, vapor-melt equilibrium, and vapor + + = , where K and K are the (K / K)/(Na / Na) K2 / K1 1 2 equilibrium. Thirty gases and 36 melt species of the elements temperature-dependent equilibrium constants for the Si, Mg, Fe, Al, Ca, Ti, Na, and K are included in our ionization reactions for Na (g) and K (g), respectively. modeling. A list of these species and thermodynamic data is Observations of these four species could therefore help given by Fegley and Cameron [9]. constrain the temperature of the volcanic gas. We considered: (1) vaporization of erupted lavas without As temperature increases, however, the abundances of any fractional vaporization and (2) continuous fractional other metal gases exceeds that of the thermal ionization vaporization of lavas. Fractional vaporization is modeled by products. Particularly important are FeO (g), Fe (g), and SiO incrementally removing vapor (after complete equilibration), (g), which are the first three gases to become more abundant recomputing the bulk elemental composition of the magma than the electron gas. For ultramafic lavas such as and vapor, and reequilibrating the system. The actual komatiites, Mg (g) is also abundant as temperature increases. behavior of lavas on Io is plausibly somewhere between Note that the two graphs in Fig. 1 are nearly identical, except these two extremes as lavas erupted at 1400 K and higher for the magnesium gases, which are significantly more probably lose some volatiles. abundant above the komatiite than above the tholeiite. We made computations for a wide variety of lava Detection of Mg (g) during an eruption on Io would indicate compositions over 1700-3000 K. The MAGMA code an ultramafic composition. assumes a completely molten system, so we restricted our As of yet, there has been no detection of any of the calculations to temperatures above the liquidus temperatures metals Fe, Si, Mg in the Io torus. Na et al. [13] set an of the lavas modeled. The 95 compositions studied included: upper limit for the abundances of these metals relative to rhyolite, basalt (tholeiitic and alkali), komatiite, dunite, other sodium based upon the non-detection of the neutral atoms. ultramafic compositions, and calcium-aluminum rich The abundances of the metal gases which we are predicting inclusions (CAIs). The literature analyses were recomputed are, however, well below the upper limit set in [13] by on a volatile-free basis. Elements other than those listed several orders of magnitude for either lava in Fig. 1. above were also excluded. Here we focus on basalts and Fractional Vaporization: Figure 2 shows the evolution of komatiites. We describe results for CAI-type magmas in [8]. the vapor composition over a lava which is losing mass due Results: We first discuss the total vapor pressure over to vaporization at 1900 K. The alkalis which dominate the the evaporating lavas. We then discuss the initial vapor initial vapor are lost from the system after a small amount of composition. Finally, we describe the fractional vaporization fractional vaporization: by ~7% vaporized for the tholeiite of the systems. and ~4% vaporized for the komatiite. The pressure drops Equilibrium Vapor Pressure: The initial vapor pressures several orders of magnitude after the loss of alkalis and of the lavas are temperature-dependent and increase with becomes dominated by silicon, iron and magnesium gases as increasing temperature. At 1900 K, the vapor pressure of a -2.7 well as O2 and O. continental tholeiitic basalt [10] composition is 10 bars Iron is the next element to be lost from the system, after and the vapor pressure of a Barberton-type komatiite [11] is the alkalis. This produces Mg-rich residual compositions. 10-2.8 bars. These pressures are orders of magnitude larger -8 Above the depleted lavas, as shown in Fig. 2, Fe(g) is more than the ambient atmospheric pressure of Io (10 bars [12]). abundant than FeO(g), though the reverse is true in the initial Lunar and Planetary Science XXXIV (2003) 1686.pdf

LAVA VAPORIZATION ON IO: L. Schaefer and B. Fegley, Jr.

vapor (see Fig. 1 at 1900 K). For basaltic compositions, recommend searching for these species above high SiO(g) is the most abundant gas throughout most of the temperature volcanic hot spots such as Pele and Pillan during + + vaporization, followed by O2 and O. For ultramafic lavas, eruptions: Na, Na , K, K , SiO, O2, O, Mg, Fe, FeO. We call Mg(g) is also very abundant and becomes more abundant out SiO (g) in particular and suggest searches at millimeter, than SiO(g) as the Si abundance in the melt decreases. For IR, and UV wavelengths for this important gas. some ultramafic compositions, such as dunite and Acknowledgements: This work was supported by meimechites, Mg(g) is always more abundant than SiO(g). NASA Grant NAG5-11958. Summary: We predict that basaltic and komatiitic lavas References: [1] Fegley, Jr., B. and Zolotov, M. Yu. (2000) erupted at temperatures P 1700 K have total vapor pressures Icarus, 148, 193–210. [2] Moses, J. I. et al. (2002) Icarus, significantly greater than the ambient atmospheric pressure 156, 76-106. [3] Moses, J. I. et al. (2002) Icarus, 156, 107- of ~10-8 bars on Io. The vapor over the lavas is initially 135. [4] Lellouch, E. et al. (2002) Nature, 421, 45-47. [5] dominated by Na, K, O2, and O gases. At temperatures of hot Lopes, R. M. C. et al. (2001) J. Geophys. Res., 106, 33,053- spots such as Pele and Pillan [5,6] the next most abundant 33,078. [6] Davies, A. G. et al. (2001) J. Geophys. Res., 106, species is the e-(gas) from thermal ionization of Na and K. 33,079-33,103. [7] Kargel, J. S. et al. (2003) EOS, submitted. Other important gases are FeO, Fe, SiO, and for ultramafic [8] Kargel et al. (2003) LPS XXXIV, this volume. [9] Fegley, compositions, Mg gas. Fractional vaporization depletes the Jr., B. and Cameron, A. G. W. (1987) EPSL, 82, 207-222. vapor and lava in alkalis and decreases the total vapor [10] Murase, T. and A. R. McBirney (1973) Geol. Soc. Am. pressure by several orders of magnitude to about 10-6 bars. Bull., 84, 3563-3592. [11] Arndt, N., personal comm. [12] Then major vapor species are SiO, O2, Fe, O, FeO, and Mg, Lellouch, E. (1996) Icarus, 124, 1-21. [13] Na, C.Y. et al. with the latter more abundant over ultramafic lavas. (1998) Icarus, 131, 449-453. Continued fractional vaporization depletes Fe and Si, leading to more refractory compositions discussed in [8]. We

Figure 1: Initial vapor composition over: (a) a tholeiitic basalt, and (b) a Barberton-type komatiite.

0 0 Na Na O Tholeiite Komatiite 2 O2

-1 -1

K K n n o o i i t t

c -2

c -2

a O O a r r SiO

F 2 F

e e l l O o i o Mg S

M O M

i S

g -3 g -3 o o l l O 2 Si O O Fe + Fe -4 + + K a -4 K N Na2 - + e Na Na2 e- g e aO M e O O F N F Na Mg -5 -5 1800 2000 2200 2400 1800 2000 2200 2400 Temperature (K) Temperature (K) Figure 2: Vapor composition due to fractional vaporization of : (a) a tholeiitic basalt and (b) a Barberton-type komatiite. The alkalis, Na and K, are lost from the systems by (a) ~7% vaporized and (b) ~4% vaporized. Total % vaporized Total % vaporized 20 40 0 20 40 60 1.2 5.0 Tholeiite Komatiite

1.0 4.0 )

7 SiO -

SiO 0 1 )

6 · - 0.8 0 s r 1

a · Mg

b 3.0 s (

r e a r b ( u

0.6 s e s r e u r s O2 P s 2.0 r e

r O 2 o P

0.4 p Fe a O V

1.0 0.2 O FeO Fe FeO Mg

0 20 40 60 80 0 20 40 60 80

mol % SiO2 vaporized mol % SiO2 vaporized