Water in the Cratonic Mantle Lithosphere

The fact that Archean and Proterozoic cratons are underlain by the thickest (>200 km) lithosphere on Earth has always puzzled scientists because the dynamic convection of the surrounding asthenosphere would be expected to delaminate and erode these mantle lithospheric "keels" over time. Although density and temperature of the cratonic lithosphere certainly play a role in its strength and longevity, the role of water has only been recently addressed with data on actual mantle samples. Water in mantle lithologies (primarily peridotites and pyroxenites) is mainly stored in nominally anhydrous minerals (olivine, pyroxene, garnet) where it is incorporated as hydrogen bonded to structural oxygen in lattice defects. The property of hydrolytic weakening of olivine [4] has generated the hypothesis that olivine, the main mineral of the upper mantle, may be dehydrated in cratonic mantle lithospheres, contributing to its strength. This presentation will review the distribution of water concentrations in four cratonic lithospheres. The distribution of water contents in olivine from peridotite xenoliths found in kimberlites is different in each craton (Figure 1). The range of water contents of olivine, pyroxene and garnet at each xenolith location appears linked to local metasomatic events, some of which occurred later then the Archean and Proterozoic when these peridotites initially formed via melting. Although the low olivine water contents ( 6 GPa at the base of the Kaapvaal cratonic lithosphere may contribute to its strength, and prevent its delamination, the wide range of those from Siberian xenoliths is not compatible with providing a high enough viscosity contrast with the asthenophere. The water content in olivine inclusions from Siberian diamonds, on the other hand, have systematically low water contents (<20 ppm wt H2O). The xenoliths may represent a biased sample of the cratonic lithosphere with an over-abundance of metasomatized peridotites with high water contents. The olivine inclusions, however, may have been protected from metasomatism by their host diamond and record the overall low olivine water content of the cratonic lithosphere. Water may thus still play a role in cratonic keel longevity

Creepy (not KREEPy) Gold-Indium Intermetallic Compounds on Secondary Ion Mass Spectrometry Samples

A series of Secondary Ion Mass Spectrometry (SIMS) sessions to measure hydrogen (H) in Martian meteorite minerals was completed using the Cameca 6f SIMS and NanoSIMS 50L at Arizona State University (ASU). During these sessions, a creeping phenomenon has occurred, where the edges of samples pressed in indium are covered by a metal alloy. We summarize these observations herein, present a collection of preliminary data, and discuss explanations and concerns for future SIMS work. We conclude the report with a research plan for further study

H Diffusion in Olivine and Pyroxene from Peridotite Xenoliths and a Hawaiian Magma Speedometer

Hydrogen is present as a trace element in olivine and pyroxene and its content distribution in the mantle results from melting and metasomatic processes. Here we examine how these H contents can be disturbed during decompression. Hydrogen was analyzed by FTIR in olivine and pyroxene of spinel peridotite xenoliths from Salt Lake Crater (SLC) nephelinites which are part of the rejuvenated volcanism at Oahu (Hawaii) [1,2]. H mobility in pyroxene resulting from spinel exsolution during mantle upwelling Most pyroxenes in SLC peridotites exhibit exsolutions, characterized by spinel inclusions. Pyroxene edges where no exsolution are present have less H then their core near the spinel. Given that H does not enter spinel [3], subsolidus requilibration may have concentrated H in the pyroxene adjacent to the spinel exsolution during mantle upwelling. H diffusion in olivine during xenolith transport by its host magma and host magma ascent rates Olivines have lower water contents at the edge and near fractures compared to at their core, while the concentrations of all other chemical elements appear homogeneous. This suggests that some of the initial water has diffused out of the olivine. Water loss from the olivine is thought to occur during host-magma ascent and xenolith transport to the surface [4-6]. Diffusion modeling matches best the data when the initial water content used is that measured at the core of the olivines, implying that mantle water contents are preserved at the core of the olivines. The 3225 cm(sup -1) OH band at times varies independantly of other OH bands, suggesting uneven H distribution in olivine defects likely acquired during mantle metasomatism just prior to eruption and unequilibrated. Diffusion times (1-48 hrs) combined with depths of peridotite equilibration or of magma start of degassing allow to calculate ascent rates for the host nephelinite of 0.1 to 27 m/s

Tin Abundances Require that Chassignites Originated from Multiple Magmatic Bodies Distinct from Nakhlites

Meteorites from Mars lack field context but chemical and chronologic studies have revealed remarkable links between nakhlites and chassignites. A widely held consensus is that nakhlites and chassignites originated from a large, single differentiated flow or shallow intrusive [1-5]. An Ar-Ar study assumed multiple flows based on resolvable age differences between meteorites [6], but did not address the possibility of differential cooling in a large, shallowly emplaced intrusion [1]. REE abundances in pyroxenes from nakhlites and Chassigny led [7] to argue for derivation of these rocks from distinct magmas. Volatile abundances (F, Cl, OH) in chlorapatites indicated that the entire suite of nakhlites and chassignites experienced hydrothermal interaction with a single fluid supporting a single body origin [4]. The discovery of a new chassignite, NWA 8694, extended the Mg# range from 80-54, providing a closer link to nakhlites but revealed the petrological difficulty of fractionating a single body of liquid to yield a series of olivine cumulates with such a large Mg# range [8]. When mafic magmas are emplaced into the crust, crustal assimilation can impart distinct elemental signatures if the country rock has experienced sedimentary or hydrothermal processing [9]. In this work, we used Sn abundances of nakhlites and chassignites to show that these rocks were crystallized from distinct magma batches, providing vital contextual clues to their origin

Melt Inclusion Analysis of RBT 04262 with Relationship to Shergottites and Mars Surface Compositions

Martian meteorite RBT 04262 is in the shergottite class. It displays the two lithologies typically found in "lherzolitic shergottites": one with a poikilitic texture of large pyroxene enclosing olivine and another with non-poikilitic texture. In the case of RBT 04262, the latter strongly ressembles an olivine- phyric shergottite which led the initial classification of this meteorite in that class. RBT 04262 has been studied with regards to its petrology, geochemistry and cosmic ray exposure and belongs to the enriched oxidized end-member of the shergottites. Studies on RBT 04262 have primarily focused on the bulk rock composition or each of the lithologies independently. To further elucidate RBT 04262's petrology and use it to better understand Martian geologic history, an in-depth study of its melt inclusions (MI) is being conducted. The MI chosen for this study are found within olivine grains. MI are thought to be trapped melts of the crystallizing magma preserved by the encapsulating olivine and offer snapshots of the composition of the magma as it evolves. Some MI, in the most Mg-rich part of the olivine of olivine-pyric shergottites, may even be representative of the meteorite parent melt

A Multi-Sims Investigation of Water Content and D/H Ratios in Roberts Massif 04262 with Insight to Sources of Hydrogen in Maskelynite

We want to define the H2O content ([H2O]) and hydrogen (H) isotope composition of meteoritic material from Mars [1-3] with motivation to understand Mars volatile history, constrain geochemical signatures of interior water reservoirs (i.e. the Martian mantle) and explore effects of planetary (e.g. planet formation, magma ocean degassing) and local (e.g. volcanic degassing, impact melting and degassing) processes on H incorporated in minerals. Secondary ion mass spectrometry (SIMS) allows multiple avenues to address these questions. However, application to (1) precious astromaterials and (2) low level H measurements, pose specific challenges that are further complicated when combined. We present preliminary data of a multi-approach (SIMS vs. NanoSIMS) study of H in Roberts Massif 04262 (RBT 04262), an enriched lherzolitic shergottite with nonpoikilitic (NP) and poikilitic (P) lithologies [4]. We analyze olivine, pyrox-ene, and melt inclusions to compare indigenous mantle water, with impact-generated maskelynite to investigate H signatures due to shock

Mantle Water Contents Beneath the Rio Grande Rift (NM, USA): FTIR Analysis of Rio Puerco and Kilbourne Hole Peridotite Xenoliths

Peridotite xenoliths from the Rio Grande Rift (RGR) are being analyzed for H (sub 2) O contents by FTIR (Fourier Transform Infrared) as well as for major and trace element compositions. Nine samples are from the Rio Puerco Volcanic Field (RP) which overlaps the central RGR and southeastern Colorado Plateau; seventeen samples are from Kilbourne Hole (KH) in the southern RGR. Spinel Cr# (Cr/(Cr+Al)) (0.08-0.46) and olivine Mg# (Mg/(Mg plus Fe)) (0.883-0.911) of all RGR samples fall within the olivine-spinel mantle array from [1], an indicator that peridotites are residues of partial melting. Pyroxene H (sub 2) O in KH correlate with bulk rock and pyroxene Al (sub 2) O (sub 3).The KH clinopyroxene rare earth element (REE) variations fit models of 0-13 percent fractional melting of a primitive upper mantle. Most KH peridotites have bulk-rock light REE depleted patterns, but five are enriched in light REEs consistent with metasomatism. Variation in H (sub 2) O content is unrelated to REE enrichment. Metasomatism is seen in RP pyroxenite xenoliths [2] and will be examined in the peridotites studied here. Olivine H (sub 2) O contents are low (less than or equal to 15 parts per million), and decrease from core to rim within grains. This is likely due to H loss during xenolith transport by the host magma [3]. Diffusion models of H suggest that mantle H (sub 2) O contents are still preserved in cores of KH olivine, but not RP olivine. The average H (sub 2) O content of Colorado Plateau clinopyroxene (670 parts per million) [4] is approximately 300 parts per million higher than RGR clinopyroxene (350 parts per million). This upholds the hypothesis that hydration-induced lithospheric melting occurred during flat-slab subduction of the Farallon plate [5]. Numerical models indicate hydration via slab fluids is possible beneath the plateau, approximately 600 kilometers from the paleo-trench, but less likely approximately 850 kilometers away beneath the rift [6]

Hydrogen Isotope Fractionation During Impact Degassing of Pyroxene and Maskelynite in Shergottite Larkman Nunatak 06319

Hydrogen in nominally anhydrous minerals (NAMs) in meteorites provides insight to mantle sources of indigenous water on differentiated bodies: e.g. Peslier et al. 2017 [1], including Mars [2-4]. However, all meteorite samples, including Martian shergottites, record impact events as fractures, deformation, silicate darkening, shock melt veins and pockets, etc. The effect of shock on hydrogen in NAMs is poorly constrained, and must be understood prior to using these data to infer planetary indigenous water. Here we present water contents and D/H ratios (calculated as dD, i.e. the variation of the D/H ratio relative to a standard, in this case sea water "SMOW") in pyroxene, olivine and maskelynite in the olivine-phyric shergottite Larkman Nunatak 06319 (LAR 06319) as a function of proximity to impact melt. While the results suggest impact may have a role in fractionating H isotopes, the magmatic signature of H2O in Mars can be preserved in some pyroxene

Basaltic Shergottite NWA 856: Differentiation of a Martian Magma

NWA 856 or Djel Ibone, is a basaltic shergottite discovered as a single stone of 320 g in South Morocco in April, 2001. This meteorite is fresh, i.e. shows minimal terrestrial weathering for a desert find. No shergottite discovered in North Africa can be paired with NWA 856. The purpose of this study is to constrain its crystallization history using textural observations, crystallization sequence modeling and in-situ trace element analysis in order to understand differentiation in shergottite magmatic systems

Trace Element Abundances of Olivine-Hosted Melt Inclusions in Shergottites Northwest Africa 7397 and Robert Massif 04262

Olivine-hosted melt inclusions (MIs) may retain trapped parent magma compositions as well as record progressive differentiation while magmas crystallize and ascend towards the surface [1,2 and references therein]. Major element compositions of the MIs, especially Fe and Mg, can be affected by post-entrapment re-equilibration with their host olivine [1,2]. Therefore, Fe/Mg ratio correction is required to obtain MI bulk compositions following equilibrium with their host olivine. Partition coefficients of most of the trace elements in olivine are very low (i.e. DOL/melt<0.001). Thus, ratios of trace elements of olivine-hosted MIs are unlikely to be affected by post-entrapment re-equilibration and no correction is necessary [2]. Hence, tracking trace element behavior in MIs may constrain the composition of the parent magma and its evolution yielding insights on magma differentiation of shergottites. However, analyzing MIs for chemical compositions is a challenging task due to their low abundances and small sizes. Using a highly sensitive and precise micro-beam technique is essential to examine olivine-hosted MIs in order to measure trace element abundances. For this purpose, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an excellent tool due to its wide range of laser spot sizes (1-150 m), ability to obtain raster analysis (several mm2) and lower detection limits (0.1 ppb) [3]