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Earth and Planetary Science Letters 286 (2009) 446–455 Contents lists available at ScienceDirect Earth and Planetary Science Letters j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e p s l Compositions of Mercury's earliest crust from magma ocean models Stephanie M. Brown a,⁎, Linda T. Elkins-Tanton b,1 a b Massachusetts Institute of Technology, Dept. Earth, Atmospheric, and Planetary Sciences, Building 54-823, 77 Massachusetts Avenue, Cambridge, MA 02139, United States Massachusetts Institute of Technology, Dept. Earth, Atmospheric, and Planetary Sciences, Building 54-824, 77 Massachusetts Avenue, Cambridge, MA 02139, United States a r t i c l e i n f o Article history: Received 21 January 2009 Received in revised form 22 June 2009 Accepted 4 July 2009 Available online 4 August 2009 Editor: R.W.Carlson Keywords: Mercury magma ocean crustal composition giant impact core a b s t r a c t The size of the Mercurian core and the low ferrous iron bearing silicate content of its crust offer constraints on formation models for the planet. Here we consider a bulk composition that allows endogenous formation of the planet's large core, and by processing the mantle through a magma ocean, would produce a low-iron oxide crust consistent with observations. More Earth-like bulk compositions require silicate removal, perhaps by a giant impact, to create the planet's large core fraction. We find that the endogenous model can produce a large core with either a plagioclase flotation crust or a low-iron oxide magmatic crust. Because a magma ocean creates a gradient in iron oxide content in the resulting planetary mantle, the parts of the mantle removed by a putative giant impact could result in either a high-iron oxide mantle in contradiction to current crustal measurements, or a low-iron oxide mantle consistent with the current understanding of Mercury. If a giant impact cannot preferentially remove shallow mantle material then the proto-Mercury must have had a bulk low iron-oxide composition. Thus a specific bulk composition is required to make Mercury endogenously, and either a specific process or a specific composition is required to make it exogenously through giant impact. Measurements taken by the MESSENGER mission, when compared to predictions given here, may help resolve Mercury's formation process. © 2009 Elsevier B.V. All rights reserved. 1. Introduction We model magma ocean solidification of several hypothetical bulk mantle compositions of Mercury and predict the compositions of their corresponding first crust, part of which may remain today. It may be possible to compare our predicted crusts with measured compositions from the MESSENGER mission and thus further constrain Mercury formation mechanisms. 1.1. Surface and interior composition constrains Data collected from Earth-based observation and by the three flybys of Mariner 10 show that Mercury's surface is low in iron-bearing silicates, containing between 0 and 3–4 wt.% FeO in the silicates (Solomon, 2003; Denevi and Robinson, 2008). Mid-infrared spectra have detected the presence of calcic plagioclase feldspar and low-FeO pyroxene (Robinson and Lucey, 1997; Robinson and Taylor, 2001; Solomon, 2003; Sprague et al., 2009). Recent measurements by the flybys of Mercury MESSENGER are consistent with these ground-based observations and limit total iron content to be less than 6 wt.% (Solomon et al., 2008), with iron oxide in silicates at less than 2–3 wt.% ⁎ Corresponding author. Tel.: +1 617 253 1902. E-mail addresses: [email protected] (S.M. Brown), [email protected] (L.T. Elkins-Tanton). 1 Tel.: + 1 617 253 1902. 0012-821X/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.epsl.2009.07.010 (Robinson et al., 2008; McClintock et al., 2008). Recent observations indicate the presence of a possible global darkening agent, thought to be an opaque oxide, a non-silicate mineral (Denevi and Robinson, 2008; Robinson et al., 2008; McClintock et al., 2008). While Mercury's surface silicates are iron oxide-poor, the bulk planet contains a high metallic iron fraction. Mercury's high density (Newcomb, 1895; Rabe, 1950; Anderson 1975; Anderson et al., 1987) indicates a massive core (Urey, 1952; Anderson and Kovach, 1967; Reynolds and Summers, 1969; Siegfried and Solomon, 1974). Uncertainties in the core radius and mass have been explored in response to the recent finding that the outer core is molten (Solomon, 2007; Margot et al., 2007), indicating the presence of a possible light alloying element (Harder and Schubert, 2001; Hauck et al., 2007; Riner et al., 2008). Core radius values range from 1675 km to 2075 km with a corresponding 53–78% of the mass of the planet (Riner et al., 2008). 1.2. Mercury formation mechanisms During the late 1970s and the 1980s, after Mariner 10, several hypotheses for the origin of Mercury were motivated by Mercury's high core fraction when compared to the other terrestrial planets. These different hypotheses are based upon either planetary accretion from compositions inherently high in metallic iron and low in silicates (endogenous) or silicate removal from an initially larger Mercury (exogenous). We consider three hypotheses as the most plausible and distinct in recent literature (Solomon, 2003) and discuss them here. (See Taylor and Scott, 2003 for details on the hypotheses.) S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 In 1978, Weidenschilling proposed that aerodynamic drag in the early solar system had a different effect on silicates than on the iron that endogenously formed Mercury. Weidenschilling's aerodynamic sorting hypothesis, based upon a nebular condensation model, culminates with a crust produced by a crystal–liquid fractionation of a silicate magma ocean (Weidenschilling, 1978; Solomon, 2003). The remaining two hypotheses modify Mercury after planetary accretion by removing silicates from the differentiated, cooled mantle. The first relies on a giant impact to remove the silicates from a Mercury 2.25 times the mass it is today (Benz et al., 1988, 2007). The giant impact is the favored hypothesis among many researchers (Boss, 1998; Taylor and Scott, 2003) for the formation of Mercury in part due to its similarities with the current theory of the formation of the Moon. The giant impact hypothesis relies upon accretion across a wide radius of the protoplanetary disk in order to account for the high relative velocity of the impactor. However, the other terrestrial planets all have higher iron oxide contents in their crusts than does Mercury; if the impactor came from a wide feeding range, crustal composition would be expected to be more similar (Taylor and Scott, 2003). In the final model discussed here, 70 to 80% of the silicate mantle is vaporized by radiation from the hot young Sun and is then removed by a strong solar wind (Cameron, 1985a; Fegley and Cameron, 1987). Temperatures at the distance of Mercury would have to reach between 2500 K and 3500 K to vaporize the mantle. Cameron proposes a model that forms the cores of the terrestrial planets before the Sun begins to form, placing Mercury's core between the necessary high temperatures (1982; Decampli and Cameron, 1979, Cameron, 1985a,b, 1988; Cameron et al., 1987). This Solar System formation model is not consistent with more modern models reviewed and discussed by Boss (1998, 2003) and Chambers (2003, 2004). Cameron himself realized the unlikely conditions necessary to form a Mercury depleted in silicates with this method and posits that the giant impact hypothesis as more probable (Cameron, 1988). 1.3. Structure of models With a view toward the likely formation processes of the other terrestrial planets, we propose that Mercury's large core and iron oxide-poor surface may be consistent with planetary formation from a bulk composition richer in metallic iron than that inferred for the Earth or Mars, rather than by solar ablation (Cameron, 1985a; Fegley and Cameron, 1987) or giant impact (Benz et al., 1988, 2007). The hypothesis presented here is parallel to Weidenschilling's (1978) sorting theory in that we propose a primary bulk composition of Mercury produced its large core, but rather than sorting alone, we suggest that high temperatures and highly reducing conditions in the early Solar System helped produce a Mercurian bulk composition that would eventually accrete to form a large iron core with low-iron oxide silicate mantle. Reducing conditions are expected at high temperatures, when metallic iron and sulfur will condense. At distances close to the young Sun, material had the opportunity to become reduced because temperatures were around 2500 K to 3500 K as Cameron (1985a,b) notes. This material would have an unusual metallic iron fraction by reducing iron otherwise bound into silicates. However, the Solar System has been cooling since it once reached these high temperatures. Safronov (1972) places disk temperatures between 115 K and 186 K in the zone of Mercury based on solar radiation calculations. We consider the situation in which Mercury was later accreted, at lower temperatures, from material reduced at high temperatures. The creation of Mercury's high metal fraction by accretion of metal-rich chondrites material has previously been proposed and briefly investigated by Taylor and Scott (2003). Mercury likely formed from materials condensed at a range of major axes from the Sun, but we suggest that high temperatures 447 around Mercury's orbit may have reduced their iron, regardless of their origin. Equilibrium condensation (discussed by Latimer, 1950; Lewis, 1972; Urey, 1952) predicts volatility and iron oxide content to increase with increasing helicocentric distances. We are effectively reconsidering the equilibrium condensation hypothesis within the framework of radial mixing, which is the major prediction from dynamical models of planetary accretion. We are not, however, presenting a specific new nebular model here. We present the results of models for the formation of Mercury that use known chondritic meteorite compositions to match the large core fraction of the planet and follow self-consistent models of magma ocean solidification to produce predictions for Mercury's crustal composition. Our hypothesis accounts for the large metallic iron fraction of Mercury and predicts a bulk mantle and crust composition low in iron oxide and volatiles and with refractory elemental abundances similar to chondrites (none enriched). The results of these models may be compared to the existing observations, and await further data from the MESSENGER mission. 2. Models The observations of Mercury's surface composition and its core size offer an initial constraint on early planet- and crust-forming processes. We assume that a magma ocean existed after the accretion of the planet. We model the solidification of the magma ocean and investigate the consequences of differing initial bulk compositions. Significant changes in bulk compositions result in alterations in final mineralogy and structure of the planet as well as initial crustal compositions. 2.1. Compositions The Mercury formation hypothesis presented here is motivated in part by the discovery of chondrites with an unusually high metallic iron composition: Bencubbinite (CB) chondrites. This rare primitive material contains at least 60 wt.% metallic iron (Weisberg et al., 2000). Should Mercury have been built from a CB-like bulk composition, its metallic iron fraction may be entirely explained without further iron reduction. Taylor and Scott (2003) propose that the accretion of metal-rich CB chondritic planetesimals is a plausible alternative to previous hypotheses for the formation of Mercury. Other chondrite classes could not create Mercury even if all their constituent iron was metallic (Fig. 1). Because Mercury orbits near the Sun, however, ejection of its bulk planet-building material (possibly the CB material composition) out to Earth's orbit is far less likely than is our obtaining samples of bulk material consistent with building the Earth and Mars, and we would therefore have fewer examples of its material (Wetherill, 1984; Love and Keil, 1995; Gladman et al., 1996). Current models of planetary accretion indicate that planets' feeding zones extend over a range of distances from the Sun (Raymond et al., 2006; O'Brien et al., 2006). Formation from a single meteorite composition is therefore highly unlikely. The CB chondrites offer an example composition with sufficient iron to build Mercury's large core and possibly a resulting mantle with interestingly high silica, but we do not argue that any planet is formed from any one primitive composition. As the constraints on Mercury's composition are few, we consider a range of initial bulk compositions. In this study we use four potential mantle compositions for Mercury. The first is the silica-rich composition that results from removing all iron oxide (reduced into a putative core) from the average CB chondrite composition (Weisberg et al., 2000; Lauretta et al., 2007). As the amount of iron oxide in this composition relies upon the extent of the reducing conditions, we consider a varying amount of iron oxide in our starting bulk magma ocean compositions, while holding the remaining oxides constant. This first CB chondrite composition is created by averaging the 448 S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 Fig. 1. Natural bulk metallic iron content for selected meteorite classes, and their metallic iron content if all iron oxide was also reduced to metallic iron. The metallic iron is presented in combination with NiS as we assume in a simplistic way that the bulk of the nickel and sulfur enter the core. In these compositions, NiS ranges from 0 to 2.28 mass percent of the planet. Only the CB chondrites have sufficient metallic iron to create Mercury's core through endogenous processes. Data: Lodders and Fegley (1998): CI, CO, CK, CR, EH, and EL; Jarosewich (1990): CM, CV, L, LL, and eucrites; Kenkyujo et al. (1995): H; CB compositions averaged from Lauretta et al. (2007) and Weisberg et al. (2001). compositions given in Lauretta et al. (2007) and Weisberg et al. (2000), and results in a composition with superchondritic Si/Mg. Because this may reflect sampling bias, we also use a CB chondrite composition created by averaging the Weisberg et al. (2000) and Lauretta et al. (2007) compositions that have chondritic Si/Mg. These two compositions are referred to as “chondritic CB” and “nonchondritic CB,” respectively. The third is a modeled average Earth mantle from Hart and Zindler (1986) (Table 1). The Hart and Zindler (1986) composition is derived from measured compositions of Earth mantle lherzolites (undepleted fertile mantle rocks). Morgan and Anders (1980) provides the fourth composition, produced from an assumed fractionation in the nebula of solar elemental abundances from an equilibrium condensation model; certain values were filled in by using lunar abundances and inferences for Mercury. From equilibrium condensation and this specific fractionation, all metal percentages increase nearer to the Sun in the Morgan and Anders (1980) model, and therefore Cr2O3 is notably higher than in the other compositions. The resulting mantle mineral assemblages differ from other bulk compositions and thus produce different predictions for the mantle and early crustal compositions of the planet. The Hart and Zindler (1986) composition and the Taylor and Scott (2003) CB composition fall between the CB chondritic and the CB non-chondritic composition. Therefore we did not run another Table 1 Bulk mantle compositions used in models. Oxide in wt.% Morgan and Anders (1980) Chondritic CB Weisberg et al. (2000, 2001), Lauretta et al. (2007) Hart and Zindler (1986) Earth model mantle Taylor and Scott (2003) CB Nonchondritic CB Weisberg et al. (2000, 2001), Lauretta et al. (2007) SiO2 Al2O3 MgO CaO TiO2 Cr2O3 FeO Mg # Si/Mg 47.1 6.4 33.7 5.2 0.3 3.3 3.7 94.20 1.1 47 5.5 42 4 0.2 1 0–7 91–100 1.1 46.3 3.96 38.4 3.2 0.2 0.5 7.7 89.89 0.9 50.8 5.2 37.4 3.6 0.2 0.7 2 97.09 1.1 63 3.7 29 3 0.15 1 0–7 87–100 2.2 model with the CB composition of Taylor and Scott (2003). These initial bulk compositions are given in Table 1. 2.2. Magma ocean solidification processes We assume that the energy of accretion and core formation is converted into enough heat to melt the planet, producing a wholemantle magma ocean with an initial depth of 600 km, from a radius of 1840 km at the core–mantle boundary to 2440 km at the surface. Although magma oceans are not a certainty of planetary formation, they are a likelihood, and here we start with the simplest assumption, a whole-mantle magma ocean. Magma ocean solidification proceeds through two major phases. First, because the slope of the adiabat in the well-mixed magma ocean is steeper than the slope of the solidus of the bulk magma ocean, as cooling proceeds the adiabat first intersects the solidus at depth. Thus the solidification of the magma ocean proceeds from the core–mantle boundary to the surface (Solomatov, 2000; Elkins-Tanton et al., 2003). The majority of mantle cumulate minerals possess a crystal site that incorporates either magnesium or iron. Because magnesium is incorporated preferentially, evolving magma ocean liquids, and therefore later-solidifying minerals, are enriched in iron. This process can produce solid mantle cumulates with densities that increase with radius through iron enrichment, and this iron enrichment process is critical for flotation of buoyant minerals in the magma ocean. Density gradients in the solid cumulate can also be produced by mineral phase changes. In the second stage of magma ocean solidification, the gravitationally unstable solidified silicate mantle cumulates overturn to a stable configuration as discussed in Elkins-Tanton et al. (2003, 2005a,b) and Elkins-Tanton (2008). During this process, low-density cumulates that originated at depth rise buoyantly and regions will melt adiabatically as they near the surface, potentially producing an earliest igneous crust. Simultaneously, higher iron oxide cumulates sink into the planetary interior. Overturn creates a mantle that is gravitationally stable and therefore resistant to the onset of thermal convection. If overturn does not allow rising cumulates to melt, and no flotation crust has formed, then the young planet will be left with a magmatic crust produced by solidification of the magma ocean. This crust would consist of the solidified last fractions of magma ocean S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 evolved liquids, and it would not resemble a basaltic magma produced by melting conventional mantle materials. Mantle overturn is driven by the density instabilities that are produced during mantle solidification. The density instabilities are commonly produced by the incorporation of magnesium over iron into the structures of the minerals. The final, near-surface layers in these models contain significant fractions of titanium-, chromium- or iron-bearing oxide minerals that will also drive overturn, as has been suggested for the Moon (Hess and Parmentier, 1995). In the case of low iron oxide in the original bulk composition, overturn is driven by this opaque-bearing layer. However, its viscosity may be sufficiently high to prevent wholesale overturn and opaque-bearing cumulates may partially remain (Elkins-Tanton et al., 2002; Riner et al., 2009), a possible outcome not modeled here, but discussed in Section 4.3. Note in addition that any unstable density gradient is sufficient to drive overturn, as long as viscosities are low enough to allow flow. 2.3. Modeling solidification To model solidification we use existing magma ocean evolution code from Elkins-Tanton et al. (2003, 2005a,b) and Elkins-Tanton (2008), modified for Mercury. This code requires an a priori set of assumptions about the mineral assemblages being solidified at every step, and these assemblages are specific for each of our bulk compositions. To predict crystallizing assemblages for Mercury we used John Longhi's magma ocean code FXMO, which is a Gibbs free energy minimization program for magma ocean solidification, along with existing experimental data. The magma ocean evolution code then calculates the equilibrium compositions and densities of each fractionating increment of mantle cumulates, and tracks the composition of the evolving residual magma ocean liquids. These mineral assemblages are reasonably simplifications of what can only be determined through series of experiments on bulk and then evolving magma ocean compositions. Results of these models, however, are not highly sensitive to small changes in mineralogy. In the non-chondritic CB bulk composition, high silica produces mantle cumulate phases including quartz (Fig. 2). The Earth mantle and other compositions contain far less silica and thus quartz is not stable in its magma ocean solidification evolution. All models end with evolved liquids rich in titanium and chromium, and thus solidify a layer near the planetary surface that is rich in opaque minerals. The solidus that we assume for all models is similar to that of a terrestrial peridotite over the pressure range appropriate for Mercury's magma ocean. For the soilidus equation and other details of model calculations, see Elkins-Tanton (2008). In these models the solidus determines the temperatures of the newly solidified mantle cumulates. Their temperatures in turn contribute to calculations of cumulate density through the thermal expansivities of the minerals. Solidi for a range of compositions do not vary enough to significantly change the predictions of these models. Mineral densities are calculated based on their temperature, pressure, and composition (thermochemical parameters are given in Elkins-Tanton (2008)). The model tracks the evolving magma ocean liquid and atmospheric mass and composition. One percent interstitial liquid is retained throughout solidification in each model. All solids are assumed to retain their solidus temperatures during the entirety of magma ocean solidification because the speed of solidification is fast compared to thermal diffusion in the solid. 3. Results There are two major opportunities for the formation of an early crust through magma ocean processes. In the first, as hypothesized for the Moon, plagioclase or other buoyant minerals float in a denser coexisting magma ocean liquid and form a conductive lid. Iron oxide enrichment creating progressively denser evolving magma ocean 449 liquids is the major contributor to plagioclase flotation (Wood et al., 1970; Smith et al., 1970; Warren, 1985). The second process that may produce an initial crust is cumulate overturn in the solid state following magma ocean solidification, in which buoyant cumulates rise from depth and melt adiabatically, producing secondary magmas that erupt onto the planet's surface. 3.1. Flotation crusts The planetary body most associated with a magma ocean is the Moon, thought to have been produced from a body the size of Mars impacting the Earth (Hartmann and Davis, 1975; Cameron and Ward, 1976). During solidification of the lunar magma ocean, plagioclase became buoyant and floated to the surface to form the initial crust. This plagioclase flotation has been suggested as a definitive marker of a magma ocean, but flotation will only occur if the plagioclase is less dense than its coexisting magma and if plagioclase stability is reached before a significant crystal fraction forms (the network of crystals would then prevent flotation). For the N7 wt.% FeO Earth-like (Hart and Zindler, 1986) mantle composition, plagioclase is stable and sufficiently buoyant to float in the magma ocean liquids from the point it becomes a crystallizing phase (Fig. 3e), assuming there is no crystal network to impede flotation. The moderate iron and high chromium content of the Morgan and Anders model composition similarly always produces a liquid dense enough to float plagioclase (Fig. 3f). In contrast, depending upon their iron contents, the iron oxide-poor magma ocean liquids in the chondritic and non-chondritic CB composition models do not always reach densities high enough to float plagioclase (Fig. 3c, d). To test the sensitivity of plagioclase flotation to iron oxide content in the initial magma ocean bulk composition for the four compositions, we started at 0 wt.% FeO and incrementally added iron oxide into the bulk composition (Figs. 3 and 4), and tested for plagioclase buoyancy. Noting that our model results are dependent on bulk composition and temperature, and limited by current understandings of melt densities, we posit that buoyant minerals will not float in the magma ocean unless its initial bulk FeO content is at least 2 wt.%–7 wt.% (Figs. 3 and 4), depending upon the rest of the bulk composition. With these higher initial iron oxide contents, in the case of the non-chondritic CB composition, both plagioclase and quartz float in the Mercurian magma ocean, creating a novel iron oxide-poor, silica-rich earliest crust. The chondritic CB composition produces a simple plagioclase flotation crust. 3.2. Volcanic crusts In a second mechanism for creating an early crust, adiabatic melting in upwelling solids during compositionally-driven overturn can produce a melt that erupts onto the planetary surface. Even in an initial magma ocean with insufficient iron oxide to float plagioclase, sufficient cumulate density gradients are produced by titanium or chromium enrichment to cause gravitationally driven solid-state overturn following solidification. The solidification model produces predictions for the original depth and composition of cumulates that, during gravitationally driven overturn, rise sufficiently to melt (Fig. 5 shows results for the chondritic CB composition). Their exact melt compositions cannot be calculated precisely because specific experimental studies would be required, but approximations can be made based on the source bulk composition using the free energy minimization program pMELTS (Ghiorso et al., 2002). When the bulk magma ocean FeO content is below the critical 2 to 7 wt.% value, the earliest planetary crust is likely formed by erupting lava that originates from melt during overturn. In all models one or two regions that form at depth during solidification are sufficiently buoyant and hot that they may melt adiabatically during overturn and 450 S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 contribute to this posited earliest igneous crust. Calculating the exact melt composition is unrealistic first because of the simplicity of the models and second because the melting behavior of these compositions is unknown, but rough estimates may be informative when compared to surface spectral data. In the chondritic CB composition model, low-FeO olivine + orthopyroxene cumulates that originated below 300 km depth rise sufficiently that they would partially melt during gravitationallydriven overturn (Fig. 6). Melts from this region would produce a very low iron basaltic composition (Table 2). The non-chondritic CB-like bulk composition with sufficiently low iron oxide to avoid producing a flotation crust may form a second interesting high-silica volcanic crustal composition (Table 2). In this case, the mineralogy of the surface can be predicted to some degree by calculating the mineral modes of the melt, solidified and equilibrated at the surface (Table 2). The deep melting region produces an albite– olivine–clinopyroxene rich crustal rock, perhaps a troctolite. The shallow melting region produces a lava composed mostly of quartz and some smaller amounts of clinopyroxene, anorthite, and spinel. Each region contributes to about half of the melt volume. Both of these Fig. 2. Cross-sections of the model Mercuries after crystallization and prior to overturn. The magma ocean solidifies from the core to the surface with the mineral assemblages shown. S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 volcanic crusts, produced during magma ocean cumulate overturn, would have very low iron oxide content in their silicate minerals. In summary, by modeling solidification of a Mercury magma ocean, it is possible to predict the composition of the planet's initial crust, which may remain today. Using a CB chondrite composition successfully reproduces Mercury's core fraction and creates a mantle very low in iron oxide. Unless FeO exceeds 2 to 7 wt.% in the bulk mantle, plagioclase will not float and form an earliest crust. The initial crust on such a planet will consist of high-magnesia lava erupted from melting produced during solid-state mantle overturn. With higher initial iron 451 oxide fractions, the non-chondritic CB chondrite composition will create an initial flotation crust of quartz and plagioclase, but dominated by quartz, in contrast to the Moon. Mantle compositions more similar to the Earth will likely produce a plagioclase flotation crust. These scenarios create distinct and measurable predictions. 4. Discussion The strongest existing constraints on Mercurian formation models are its very low iron bearing crustal silicates (Robinson and Lucey, Fig. 3. Density of minerals crystallizing from the magma ocean as a function of depth. The dotted line shows the density of the evolving coexisting magma ocean liquid. In some cases plagioclase or plagioclase and quartz become less dense than the liquid and can float. Flotation is only suppressed in compositions with less than ~ 2–7 wt.% iron. 452 S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 Fig. 4. The sensitivity of the non-chondritic CB bulk composition to FeO. The lines show the density of evolving magma ocean liquids as a function of radius and iron content. Initial iron content is marked on each curve; liquid density changes primarily because iron is enriched in liquids as low-pressure minerals are fractionated from it (see Fig. 3). The plagioclase and the quartz lines are the densities of these minerals as a function of pressure in the planet. For this specific composition, ~ 1.5 wt.% FeO is necessary to float the shown minerals, the lowest of all the compositions. Across all bulk compositions, 2–7 wt.% FeO is necessary to float buoyant minerals. Near the end of solidification high crystal fraction may prevent flotation, though the physics of this process are poorly understood, so the depth of buoyancy required to allow flotation is unconstrained. 1997; Robinson and Taylor, 2001; Solomon, 2003; Denevi and Robinson, 2008; Sprague et al., 2009) and the large metallic iron core (Urey, 1952; Anderson and Kovach, 1967; Reynolds and Summers, 1969; Siegfried and Solomon, 1974). In our magma ocean models, there are two opportunities to produce an earliest crust that may remain on the planet today and can be compared to observed constraints. The first is through flotation of buoyant minerals during magma ocean solidification, and the second is through eruptions of magma produced by adiabatic melting during solid-state cumulate mantle overturn after magma ocean solidification. 4.1. Endogenous models for producing a low-iron oxide silicate crust There are similarly two processes that may create a low-iron oxide crust: plagioclase may float in a magma ocean, or mantle source regions themselves low in iron oxide may melt and erupt a low-iron oxide crust. Previous researchers have estimated that the amount of iron oxide in the lavas on the surface of Mercury directly reflects the amount of iron oxide within the melting mantle source regions of the Fig. 5. Mercurian cumulate mantle density profiles of chondritic CB bulk composition with 0.2 wt.% FeO after magma ocean solidification (dashed line), and following gravitational overturn to stability (solid line). The mineral labels correspond to the dashed, pre-overturn density profile. planet, because iron oxide has a partial melt partition coefficient ~ 1 (Robinson and Taylor, 2001). On a planet the size of Mercury any of the bulk mantle compositions considered create a plagioclase or plagioclase + quartz flotation crust, provided the bulk composition has at least 2–7 wt.% FeO. Thus a chondritic CB Mercury with N2 to 7 wt.% FeO in its mantle, or a Mercury with a Hart and Zindler (1986) Earth-like mantle, or a Morgan and Anders (1980) model mantle might all present a low iron oxide ancient crust through flotation of buoyant phases (Table 2). The lavas produced by adiabatic melting during solid-state overturn would not likely erupt through a plagioclase flotation crust in the absence of crustal thinning, for example, from giant impacts. Should a flotation crust not form, as in the case of a low-FeO silicate mantle, then the lavas may erupt to form the earliest crust. A low-iron CB chondritic Mercurian mantle would likely produce a low-iron oxide earliest igneous crust and would be entirely consistent with the existing data on Mercury's surface. Taylor and Scott (2003) produce crustal composition predictions from a series of possible Mercury bulk compositions, including those of Morgan and Anders (1980), the vaporization model by Fegley and Cameron (1987), Goettel (1988), and a CB-chondrite like composition. Fig. 6. Bulk mantle composition for chondritic CB starting composition after overturn to gravitational stability. The shaded regions are hot enough to experience adiabatic decompression melting as they rise during overturn and would produce a low-iron oxide silicate crust. S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 453 Table 2 Earliest crustal compositions resulting from magma ocean models. Bulk Mercurian mantle composition Non-chondritic CB avg. b ~ 2 wt% FeO Source of crustal material CB chondritic average Chondritic CB avg b ~ 2 wt.% FeO Chondritic CB avg. N ~ 2 wt.% FeO Hart and Zindler (1986) Earth Morgan and Anders (1980) Morgan and Anders (1980) Adiabatic melting Adiabatic melting Flotation crust of overturning of overturning deep cumulates shallow cumulates Adiabatic melting of overturning cumulates Flotation crust Adiabatic melting of overturning cumulates Adiabatic melting of overturning cumulates 10% melt of 10% melt of bulk bulk composition composition Reference This study This study This study This study This study This study This study Taylor and Scott (2003)a Taylor and Scott (2003)a Flotation crust mineralogy None None Quartz N plagioclase None Plagioclase Plagioclase Plagioclase None None 56 43 Trace 1 Trace 0.1 Not modeled 0.1 5 – 50 71 15 7 6 Trace 0.5 Not modeled 0.1 5 – 50 49.2 10.9 14.4 18.5 1.7 1.6 0.3 3.7 44.7 19 13.1 18.8 0.9 0.3 Volcanic crust: SiO2 MgO Al2O3 CaO TiO2 Cr2O3 Na2O FeO Resulting crustal Thickness (km) a Non-chondritic CB avg. N2 wt.% FeO ~ 40 – 60 43–48 52–57 Trace–0.2 Trace–0.5 Trace Trace Not modeled 0.1 – 0.2 10 – 100 ~ 40 – 60 ~ 30 3.2 ~ 30 No flotation was considered in these models. They calculate a 10% partial melt at 1 GPa of the bulk compositions using John Longhi's phase-equilibria program MAGPOX. The igneous crust produced in our models contain much lower aluminum and calcium content than the Taylor and Scott (2003) lava predictions, and in the non-chondritic CB bulk composition case, much higher silica. These differences arise from the material that melts: Our models incorporate a differentiated planet, while the Taylor and Scott (2003) model assumes a homogeneous bulk mantle composition. If the mantle is heterogeneous, as our models indicate, Mercury may carry a relatively high iron oxide fraction at depth following magma ocean overturn, while crustal lavas contain little iron, reflecting their low-iron source regions (Fig. 7). This may be evident on the Moon, as various bulk compositions (Dreibus and Wänke, 1985; Longhi, 2003) range between 7.5% and 14% FeO, while measured lava basalts contain 15.5%–22% FeO (Papike et al., 1998). Thus, the bulk mantle density of Mercury would still be low and consistent with estimates, but regions within the interior may contain more iron oxide and have a higher density. Harder and Schubert (2001) have shown that the modeled size of Mercury's core depends directly upon assumptions of its composition. Models of the internal structure of Mercury are constrained only by the radius and mean density, but improvements on characterization of the moment of inertia and the gravitational field of the planet will help determine the size of the core if we assume densities for the crust, mantle, and core (Solomon, 2007; Margot et al., 2007). In Mercury interior models a mantle containing higher iron oxide fraction at depth might predict a smaller core radius. It may be difficult to distinguish the effect of the mantle density, however, as the uncertainties in the core composition may dominate the size of the core (Hauck et al., 2007; Riner et al., 2008). Note, though, that the low-iron oxide bulk mantle compositions favored in this modeling predict mantle densities between 3000 and 3100 kg m− 3, within a range of some of the models of Hauck et al. (2007). 4.2. Exogenous models for producing a low-iron oxide crust To make Mercury with the observed core and crust characteristics from a more Earthlike bulk composition, one of the exogenous models Fig. 7. Iron oxide content of mantle cumulates following solidification but before overturn, for chondritic CB bulk composition with 1 wt.% FeO in bulk composition. Fractionation produces higher iron oxide in cumulates solidifying last, nearer the surface (though these will likely sink during gravitationally-driven overturn). This figure demonstrates the ability of magma ocean fractionation to create heterogeneous mantle source regions for later melting. 454 S.M. Brown, L.T. Elkins-Tanton / Earth and Planetary Science Letters 286 (2009) 446–455 must be considered. Here we examine the Benz et al. (1988, 2007) giant impact model. If the proto-Mercury had a core fraction similar to the Earth's, then the proto-Mercury was a planet about the size of Mars, with a radius of ~ 3400 km. The position of high-iron oxide mantle cumulates at the time of impact may determine whether the resulting Mercury has a high-iron oxide or a low-iron oxide crust. During such a giant impact it is possible that the shallower mantle will be lost preferentially to the deep mantle (Kokubo, personal communication, and Andrews-Hanna et al., 2009). If the giant impact occurs after cumulate overturn when high-iron oxide cumulates had sunk into the planetary interior, the deep mantle may be the part of the proto-planet retained for the new, less massive mantle, and it will be rich in iron oxide. The energy of impact will likely create a second magma ocean, and flotation of buoyant low-iron phases such as plagioclase may be possible. An igneous crust created in this secondary magma ocean, however, will be too iron oxide-rich to match observations of Mercury. Alternatively, the giant impact may occur at or toward the end of magma ocean solidification. In this second scenario iron oxide has been enriched in evolving magma ocean liquids and resides largely near the surface of the planet and overturn has not begun to carry the iron oxide-rich mineral assemblages to depth. If the impact occurs at that moment a majority of the iron oxide may be lost from the planet, and any secondary igneous crust will therefore contain silicate minerals low in iron oxide. This may describe how a Mercury formed by giant impact produced a crust low in iron-bearing silicates, previously unexplained (Taylor and Scott, 2003). The timeframe required for this scenario is relatively well defined; impact must occur after a majority of the magma ocean is solidified, perhaps within 50,000 years of the last giant accretionary impact, and before cumulate overturn begins, in less than one million years (Elkins-Tanton, 2008). This is a generous interval during which protoMercury may have experienced another giant impact following an initial magma ocean in this accretion scenario. If a giant impact can preferentially remove the shallow mantle, therefore, then a giant impact on a newly-solidified and not yet overturned cumulate mantle can result in a low-iron oxide mantle consistent with surface observations. If a giant impact necessarily mixes the mantle, then Mercury must have an inherently low-iron oxide bulk silicate composition; otherwise its surface would consist of either plagioclase flotation or higher-iron oxide lavas. 4.3. Opaques on the surface of Mercury Our models indicate that an oldest volcanic crust on Mercury may form with few or no opaque minerals. Instead, these opaque phases solidify in a layer toward the end of the magma ocean solidification, analogously to models of the lunar magma ocean, and reside in the uppermost mantle at the end of solidification. In these models the source regions for ilmenite and chromite solidify between the surface and 120 km depth (Figs. 2, 3, and 5). These late, high-titanium and high-chromium cumulates will not crystallize until temperatures have fallen to about 1150 °C (Hess and Parmentier, 1995; Van Orman and Grove, 2000). By the time the dense material has finished solidifying and any gravitational instabilities begun to form, the temperature would have fallen farther. These low temperatures near the Mercurian surface produce high viscosity in the opaque-bearing layer. The viscosity may be sufficient, in fact, to prevent their overturn (Elkins-Tanton et al., 2002) and leave them near the planetary surface. Riner et al. (2009) discuss the possibility that the spectra of the low reflectance material seen on Mercury's surface reflect this magma ocean oxide layer, excavated by later impacts (see also Robinson and Lucey, 1997; Robinson and Taylor, 2001). The material could also be delivered to the surface by later magmatic activity, either from standard planetary convection or from impacts. This is a topic of ongoing work. 5. Conclusions Here we have considered a range of initial Mercurian mantle compositions, from an Earth-like composition to a non-chondritic CB high silica composition. Models of conditions in the early solar system may inform the likelihood of these compositions. During planetary formation the Sun's emissions in the visible were far weaker than they are today; however, high-energy emissions were much stronger (Ribas et al., 2005). This strong solar wind and X-ray flux may have produced a more metallic iron-rich composition nearer the Sun. Conversely, dynamical models of planetary formation indicate that radial mixing of planetary embryos during oligarchic accretion is ubiquitous, though less extreme nearest the Sun (O'Brien et al., 2006). Taken together, a more reduced, CB-like composition at Mercury's radius is a reasonable hypothesis, though more Earth-like bulk compositions are also reasonable given the likelihood of radial mixing. Highly reducing conditions near the Sun in the early solar system might have important implications for the composition of Mercury's core: under highly reducing conditions iron is likely to form bonds with alternative anions, such as sulfur. FeS is likely to participate in core formation. Such conditions might encourage the formation of a planetary core with an unusual fraction of light alloys, and thus allow the preservation of today's molten core (Harder and Schubert, 2001; Hauck et al., 2007; Riner et al., 2008). Formation of Mercury from a low-iron oxide CB bulk composition would create a planet with a sufficiently large metallic iron core and low iron oxide crust to match observations of Mercury. A low-iron oxide ancient crust can be made by plagioclase flotation, and in the case of a non-chondritic CB composition, a plagioclase plus quartz flotation crust. These crusts are only possible, however, if the bulk mantle composition has more than 2 to 7 wt.% FeO and can thus produce a dense magma ocean liquid. Formation from compositions with these iron oxide contents would also create at least portions of the planetary mantle with high iron oxide through fractionation in the magma ocean. Later melting of these regions would produce a higher-iron oxide volcanic crust, which would be a critical clue to mantle compositional variations and thus formation processes if later found by remote sensing. If all the magmatic crust is low in iron oxides in its silicate fraction, then all the mantle source regions they represent are similarly low in iron oxide. A giant impact model that preferentially removes shallow mantle cumulates may also be consistent with the low iron-bearing crustal silicates found on Mercury, but this requires one of two conditions. In the first, Mercury can be formed from a higher-iron oxide bulk composition, but the giant impact preferentially removes the higher iron cumulates from the upper half of the mantle before gravitationallydriven cumulate overturn carries them to depth. Alternatively, the proto-Mercury already had an unusually low-iron oxide bulk silicate composition. Evidence for a plagioclase flotation crust on Mercury found by MESSENGER would be consistent both with an endogenous model with N2 to 7 wt.% FeO in the bulk mantle, or with an exogenous giant impact model. If, conversely, the low-iron oxide silicate crust is not primarily plagioclase and is ubiquitous, then Mercury's bulk mantle composition must be low in iron oxide and would be consistent with formation from a low-iron oxide CB-like reduced bulk composition. Acknowledgements A suggestion from Paul Hess was the initial inspiration for this research. 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