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Constraints on the Water, Chlorine, and Fluorine Content of the Martian Mantle

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Constraints on the Water, Chlorine, and Fluorine Content of the Martian Mantle Meteoritics & Planetary Science 1–13 (2016) doi: 10.1111/maps.12624 Constraints on the water, chlorine, and fluorine content of the Martian mantle 1* 2,3 4 Justin FILIBERTO , Juliane GROSS , and Francis M. MCCubbin 1Department of Geology, Southern Illinois University, 1259 Lincoln Dr, MC 4324, Carbondale, Illinois 62901, USA 2Department of Earth and Planetary Sciences, Rutgers University, 610 Taylor Road, Piscataway, New Jersey 08854, USA 3Department of Earth and Planetary Sciences, The American Museum of Natural History, New York, New York 10024, USA 4NASA Johnson Space Center, Mail Code XI2, 2101 NASA Parkway, Houston, Texas 77058, USA *Corresponding author. E-mail: fi[email protected] (Received 30 July 2015; revision accepted 22 January 2016) Abstract–Previous estimates of the volatile contents of Martian basalts, and hence their source regions, ranged from nearly volatile-free through estimates similar to those found in terrestrial subduction zones. Here, we use the bulk chemistry of Martian meteorites, along with Martian apatite and amphibole chemistry, to constrain the volatile contents of the Martian interior. Our estimates show that the volatile content of the source region for the Martian meteorites is similar to the terrestrial Mid-Ocean-Ridge Mantle source. Chlorine is enriched compared with the depleted terrestrial mantle but is similar to the terrestrial enriched source region; fluorine is similar to the terrestrial primitive mantle; and water is consistent with the terrestrial mantle. Our results show that Martian magmas were not volatile saturated; had water/chlorine and water/fluorine ratios ~0.4–18; and are most similar, in terms of volatiles, to terrestrial MORBs. Presumably, there are variations in volatile content in the Martian interior as suggested by apatite compositions, but more bulk chemical data, especially for fluorine and water, are required to investigate these variations. Finally, the Noachian Martian interior, as exemplified by surface basalts and NWA 7034, may have had higher volatile contents. INTRODUCTION et al. 2013). However, Martian magmas may have partly degassed upon eruption and lost water and/or There is considerable debate about the pre-eruptive halogens to the surface (e.g., McSween and Harvey magmatic volatile (H2O, F, and Cl) contents of Martian 1993) and because of this uncertainty, estimates of the basalts and hence their source regions (see Filiberto pre-eruptive water contents of Martian magmas range et al. Forthcoming). The bulk water contents of the from essentially dry to 2 wt% H2O (e.g., Dann et al. Martian meteorites are rather low compared to 2001; Jones 2004; Nekvasil et al. 2007; McCubbin terrestrial basalts (<350 ppm H2O released at et al. 2010a, 2012; Usui et al. 2012, 2015; Giesting et al. T > 350 °C [e.g., Leshin et al. 1996]), as are the 2015). Experimental studies suggest that up to 2 wt% magmatic water contents of glassy olivine-hosted melt H2O may be required to reproduce the mineralogy and inclusions in primitive basaltic shergottites (<251 ppm temperatures of crystallization of shergotittes and H2O [Usui et al. 2012, 2015]). Comparable terrestrial chassignites (Dann et al. 2001; Nekvasil et al. 2007, basaltic rocks typically contain much higher 2009; Filiberto 2008). Further, studies of Li, Be, and B concentrations of H2O(~2000–20,000 ppm [e.g., zoning in pyroxenes and lithium isotopes, which are Johnson et al. 1994; Dixon and Clague 2001; Saal et al. thought to be geochemical proxies for fluid movement, 2002]). Bulk fluorine and chlorine contents of the have revealed conflicting results (e.g., Herd et al. 2004; unaltered Martian basalts are similar to those of Beck et al. 2006b; Magna et al. 2006, 2015; Seitz et al. terrestrial tholeiites (29–41 ppm F and 14–137 ppm Cl; 2006; Treiman et al. 2006; Filiberto et al. 2012a; Udry Dreibus and Wanke€ 1987; Bogard et al. 2010; Burgess et al. 2016). These studies have suggested degassing of 1 © The Meteoritical Society, 2016. 2 J. Filiberto et al. potentially hydrous magmas (Lentz et al. 2001; (or at least codominant with H2O; e.g., Filiberto and McSween et al. 2001; Beck et al. 2004; Herd et al. 2005; Treiman 2009b). Further, recent investigations of Udry et al. 2016), but bulk Li isotopes are not apatite in lunar rocks showed that apatite is not a consistent with degassing for many of the Martian robust hygrometer if it forms as a result of fractional meteorites (Magna et al. 2006; Seitz et al. 2006; crystallization, and using the F:Cl:OH ratio of such Filiberto et al. 2012a) and many shergottites and apatite to calculate the parental magma volatile nakhlites have been affected by post-crystallization concentration may overestimate the H2O content of the diffusion of Li, complicating the use of Li to constrain parental magma (Boyce et al. 2014). degassing (e.g., Beck et al. 2006b; Treiman et al. 2006; There has been much less focus given to amphibole Udry et al. 2016). Results from geochemical modeling in Martian meteorites and there are few direct analyses studies also suggest that water may be required to of water in Martian amphiboles (Watson et al. 1994b; explain Martian meteorite bulk chemistry, mineralogy, McCubbin et al. 2010a; Giesting et al. 2015). and temperatures of crystallization (McSween et al. Kaersutitic amphibole in Chassigny has 0.1 wt% Cl and 2001; McCubbin et al. 2010a, 2012; Balta and McSween 0.5 wt% F from EMP (electron microprobe) analyses, 2013; He et al. 2013). However, recent experimental but SIMS (secondary ion mass spectrometry) analyses work (Filiberto and Treiman 2009a; Filiberto et al. have yielded two distinctly different results for water 2012b, 2014a; Giehl et al. 2014; Farcy et al. content: 0.1–0.2 wt% H2O and 0.41–0.74 wt% H2O Forthcoming) has shown that chlorine and fluorine (Watson et al. 1994b; McCubbin et al. 2010a; Giesting affect crystallization temperatures of magmas in similar et al. 2015). Kaersutitic amphibole in the chassignite ways to water. Thus, the observed mineralogy and NWA 2737 has F and Cl concentrations (0.45–0.58 and crystallization temperatures of the Martian meteorites 0.09–0.13 wt% by EMP) that are similar to those in may not be due to water alone, which would lower the Chassigny, and ~0.1 wt% H2O measured by SIMS required dissolved water concentrations. Therefore, (Beck et al. 2006a; Treiman et al. 2007; Giesting et al. there is an unresolved debate about the pre-eruptive 2015) but may have been affected by shock water, chlorine, and fluorine bulk contents of Martian dehydrogenation (Giesting et al. 2015). Kaersutitic magmas and hence their source regions. Here we use amphiboles in Zagami and Shergotty have ~0.1–0.2 the bulk chemistry of Martian meteorites along with wt% H2O measured by SIMS but <0.1 wt% F and Cl parental magma compositions calculated from apatite measured by EMP (Treiman 1985; Watson et al. 1994a). and amphibole chemistry, to calculate the average volatile content of the Martian meteorite mantle source METHODS FOR CALCULATING VOLATILE region. ABUNDANCES OF PARENTAL MAGMAS TO AMPHIBOLE AND APATITE MARTIAN APATITE AND AMPHIBOLE CHEMISTRY Volatile-bearing minerals can be used to calculate volatile ratios (F/OH, Cl/OH, and F/Cl) of their Many studies have focused on using the OH- parental magma (e.g., Patino~ Douce and Roden 2006; bearing phases amphibole and apatite to constrain the Patino~ Douce et al. 2011; Giesting and Filiberto 2014; Martian igneous volatile history and budget (e.g., McCubbin et al. 2014, McCubbin et al. 2015b, Greenwood et al. 2003; Patino~ Douce and Roden 2006; Forthcoming). Patino~ Douce and Roden (2006), Patino~ Filiberto and Treiman 2009b; Patino~ Douce et al. 2011; Douce et al. (2011), Gross et al. (2013), and Howarth McCubbin et al. 2012; Giesting et al. 2015; Giesting et al. (2015) used thermodynamic calculations to show and Filiberto, Forthcoming; McCubbin et al. that volatile fugacity ratios of parental magmas can be Forthcoming). Apatite in Martian meteorites range calculated from apatite analyses and then compared on a from OH-bearing, F-apatite to almost pure endmember global and planetary basis. However, calculating exact Cl-apatite, which suggests a range in volatile contents of parental magma volatile concentrations requires primary magmas with some being potentially rich in partition coefficients relevant to planetary compositions. H2O (e.g., McCubbin et al. 2012; Gross et al. 2013). Recently, McCubbin et al. (2015b) provided experimental However, the majority of Martian apatite are chlorine- F-Cl-OH apatite-melt partition coefficients for a rich and typically plot in or near the field of chlorine- shergottite bulk composition, which will be used in this ~ dominant parental magmas (Patino Douce and Roden work to calculate the H2O/Cl and Cl/F ratio of magmas 2006; Filiberto and Treiman 2009b; McCubbin et al. parental to the Martian meteorites, rather than relying 2013; Howarth et al. 2015), suggesting that the majority on the volatile fugacity ratios as has previously been of magmas that crystallized apatite are chlorine-rich and done. Giesting and Filiberto (Forthcoming) provide a some may even have chlorine as the dominant volatile regression equation for volatile element partitioning Constraints on the volatile content of the Martian mantle 3 between amphibole and basaltic glass, which has been the Earth (Bogard et al. 2010; Burgess et al. 2013). used to calculate the Cl/OH ratio of magmas parental to However, in order to compare bulk compositions of the chassignites (Giesting et al. 2015). We will use these different planetary bodies, it is not enough to compare values in our modeling below. concentrations of elements. Instead, we must compare ratios of similarly incompatible elements, which PARENTAL MAGMA COMPOSITIONS accounts for differences in magmatic processes such as partial melting and fractional crystallization, as well as Estimates of Martian magma compositions range degassing and secondary alteration (e.g., Dreibus and from drier than terrestrial magmas to similar water Wanke€ 1987).
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