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2019
Inglis, EC, Moynier F, Creech J, Deng Z, Day JMD, Teng F-Z, Bizzarro M, Jackson M, Savage P.  2019.  Isotopic fractionation of zirconium during magmatic differentiation and the stable isotope composition of the silicate Earth. Geochimica et Cosmochimica Acta. 250:311-323.   10.1016/j.gca.2019.02.010   Abstract

High-precision double-spike Zr stable isotope measurements (expressed as δ94/90ZrIPGP-Zr, the permil deviation of the 94Zr/90Zr ratio from the IPGP-Zr standard) are presented for a range of ocean island basalts (OIB) and mid-ocean ridge basalts (MORB) to examine mass-dependent isotopic variations of zirconium in Earth. Ocean island basalt samples, spanning a range of radiogenic isotopic flavours (HIMU, EM) show a limited range in δ94/90ZrIPGP-Zr (0.046 ± 0.037‰; 2sd, n = 13). Similarly, MORB samples with chondrite-normalized La/Sm of >0.7 show a limited range in δ94/90ZrIPGP-Zr (0.053 ± 0.040‰; 2sd, n = 8). In contrast, basaltic lavas from mantle sources that have undergone significant melt depletion, such as depleted normal MORB (N-MORB) show resolvable variations in δ94/90ZrIPGP-Zr, from −0.045 ± 0.018 to 0.074 ± 0.023‰. Highly evolved igneous differentiates (>65 wt% SiO2) from Hekla volcano in Iceland are isotopically heavier than less evolved igneous rocks, up to 0.53‰. These results suggest that both mantle melt depletion and extreme magmatic differentiation leads to resolvable mass-dependent Zr isotope fractionation. We find that this isotopic fractionation is most likely driven by incorporation of light isotopes of Zr within the 8-fold coordinated sites of zircons, driving residual melts, with a lower coordination chemistry, towards heavier values. Using a Rayleigh fractionation model, we suggest a αzircon-melt of 0.9995 based on the whole rock δ94/90ZrIPGP-Zr values of the samples from Hekla volcano (Iceland). Zirconium isotopic fractionation during melt-depletion of the mantle is less well-constrained, but may result from incongruent melting and incorporation of isotopically light Zr in the 8-fold coordinated M2 site of orthopyroxene. Based on these observations lavas originating from the effect of melt extraction from a depleted mantle source (N-MORB) or that underwent zircon saturation (SiO2 > 65 wt%) are removed from the dataset to give an estimate of the primitive mantle Zr isotope composition of 0.048 ± 0.032‰; 2sd, n = 48. These data show that major controls on Zr fractionation in the Earth result from partial melt extraction in the mantle and by zircon fractionation in differentiated melts. Conversely, fertile mantle is homogenous with respect to Zr isotopes. Zirconium mass-dependent fractionation effects can therefore be used to trace large-scale mantle melt depletion events and the effects of felsic crust formation.

2014
Franz, HB, Kim ST, Farquhar J, Day JMD, Economos RC, McKeegan KD, Schmitt AK, Irving AJ, Hoek J, Dottin J.  2014.  Isotopic links between atmospheric chemistry and the deep sulphur cycle on Mars. Nature. 508:364-+.   10.1038/nature13175   AbstractWebsite

The geochemistry of Martian meteorites provides a wealth of information about the solid planet and the surface and atmospheric processes that occurred on Mars. The degree to which Martian magmas may have assimilated crustal material, thus altering the geochemical signatures acquired from their mantle sources, is unclear(1). This issue features prominently in efforts to understand whether the source of light rare-earth elements in enriched shergottites lies in crustal material incorporated into melts(1,2) or in mixing between enriched and depleted mantle reservoirs(3). Sulphur isotope systematics offer insight into some aspects of crustal assimilation. The presence of igneous sulphides in Martian meteorites with sulphur isotope signatures indicative of mass-independent fractionation suggests the assimilation of sulphur both during passage of magmas through the crust of Mars and at sites of emplacement. Here we report isotopic analyses of 40 Martian meteorites that represent more than half of the distinct known Martian meteorites, including 30 shergottites (28 plus 2 pairs, where pairs are separate fragments of a single meteorite), 8 nakhlites (5 plus 3 pairs), Allan Hills 84001 and Chassigny. Our data provide strong evidence that assimilation of sulphur into Martian magmas was a common occurrence throughout much of the planet's history. The signature of mass-independent fractionation observed also indicates that the atmospheric imprint of photochemical processing preserved in Martian meteoritic sulphide and sulphate is distinct from that observed in terrestrial analogues, suggesting fundamental differences between the dominant sulphur chemistry in the atmosphere of Mars and that in the atmosphere of Earth(4).

2012
Day, JMD, Walker RJ, Ash RD, Liu Y, Rumble D, Irving AJ, Goodrich CA, Tait K, McDonough WF, Taylor LA.  2012.  Origin of felsic achondrites Graves Nunataks 06128 and 06129, and ultramafic brachinites and brachinite-like achondrites by partial melting of volatile-rich primitive parent bodies. Geochimica Et Cosmochimica Acta. 81:94-128.   10.1016/j.gca.2011.12.017   AbstractWebsite

New major- and trace-element abundances, highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances, and oxygen and rhenium-osmium isotope data are reported for oligoclase-rich meteorites Graves Nunataks 06128 and 06129 (GRA 06128/9), six brachinites (Brachina; Elephant Morraine 99402/7; Northwest Africa (NWA) 1500; NWA 3151; NWA 4872; NWA 4882) and three olivine-rich achondrites, which are referred to here as brachinite-like achondrites (NWA 5400; NWA 6077; Zag (b)). GRA 06128/9 represent examples of felsic and highly-sodic melt products from an asteroid that may provide a differentiation complement to brachinites and/or brachinite-like achondrites. The new data, together with our petrological observations, are consistent with derivation of GRA 06128/9, brachinites and the three brachinite-like achondrites from nominally volatile-rich and oxidised 'chondritic' precursor sources within their respective parent bodies. Furthermore, the range of Delta O-17 values (similar to 0 parts per thousand to -0.3 parts per thousand) among the meteorites indicates generation from isotopically heterogeneous sources that never completely melted, or isotopically homogenised. It is possible to generate major-and trace-element compositions similar to brachinites and the three studied brachinite-like achondrites as residues of moderate degrees (13-30%) of partial melting of primitive chondritic sources. This process was coupled with inefficient removal of silica-saturated, high Fe/Mg felsic melts with compositions similar to GRA 06128/9. Melting of the parent bodies of GRA 06128/9, brachinites and brachinite-like achondrites halted well before extensive differentiation, possibly due to the exhaustion of the short-lived radionuclide Al-26 by felsic melt segregation. This mechanism provides a potential explanation for the cessation of run-away melting in asteroids to preserve achondrites such as GRA 06128/9, brachinites, brachinite-like achondrites, acapulcoite-lodranites, ureilites and aubrites. Moderate degrees of partial melting of chondritic material and generation of Fe-Ni-S-bearing melts are generally consistent with HSE abundances that are within factors of similar to 2-10 x CI-chondrite abundances for GRA 06128/9, brachinites and the three brachinite-like achondrites. However, in detail, brachinite-like achondrites NWA 5400, NWA 6077 and Zag (b) are interpreted to have witnessed single-stage S-rich metal segregation, whereas HSE in GRA 06128/9 and brachinites have more complex heritages. The HSE compositions of GRA 06128/9 and brachinites require either: (1) multiple phases in the residue (e. g., metal and sulphide); (2) fractionation after generation of an initial melt, again involving multiple phases; (3) fractional fusion, or; (4) a parent body with non-chondritic relative HSE abundances. Petrological and geochemical observations permit genetic links (i.e., same parent body) between GRA 06128/9 and brachinites and similar formation mechanisms for brachinites and brachinite-like achondrites. (C) 2011 Elsevier Ltd. All rights reserved.

Brandon, AD, Puchtel IS, Walker RJ, Day JMD, Irving AJ, Taylor LA.  2012.  Evolution of the martian mantle inferred from the Re-187-Os-187 isotope and highly siderophile element abundance systematics of shergottite meteorites. Geochimica Et Cosmochimica Acta. 76:206-235.   10.1016/j.gca.2011.09.047   AbstractWebsite

Shergottite meteorites are a suite of mafic to ultramafic igneous rocks whose parental magmas probably derived from the martian mantle. In this study, a suite of 23 shergottites, spanning their known range in bulk compositions, Rb-Sr, Sm-Nd, and Lu-Hf isotopes, were measured for Re-187-Os-187 isotopic systematics and highly siderophile element abundances (HSE: including Os, Ir, Ru, Pt, Pd, Re). The chief objective was to gain new insight on the chemical evolution of the martian mantle by unraveling the long-term HSE budget of its derivative melts. Possible effects upon HSEs related to crustal contamination, as well as terrestrial and/or martian surface alteration are also examined. Some of the shergottites are hot arid-desert finds. Their respective acetic acid leachates and residues show that both Re and Os display open-system behavior during sample residence at or near the martian and/or terrestrial surfaces. In some meteorites, the alteration effects can be circumvented by analysis of the leached residues. For those shergottites believed to record robust Re-Os isotopic systematics, calculated initial Os-187/Os-188 are well correlated with the initial Nd-143/Nd-144. Shergottites from mantle sources with long-term melt-depleted characteristics (initial epsilon Nd-143 of + 36 to + 40) have chondritic initial gamma Os-187 ranging from -0.5 to + 2.5. Shergottites with intermediate initial epsilon Nd-143 of + 8 to + 17 have a range in initial gamma Os-187 of -0.6 to + 2.3, which overlaps the range for depleted shergottites. Shergottites from long-term enriched sources, with initial epsilon Nd-143 of similar to-7, are characterized by suprachondritic gamma Os-187 values of + 5 to + 15. The initial gamma Os-187 variations for the shergottites do not show a correlation with indices of magmatic differentiation, such as MgO, or any systematic differences between hot arid-desert finds, Antarctic finds, or observed falls. The strong correlation between the initial epsilon Nd-143 and gamma Os-187 in shergottites from approximately + 40 and 0 to -7 and + 15, respectively, is assessed in models for mixing depleted mantle-derived melts with ancient crust (modeled to be similar to evolved shergottite in composition), and with assimilation-fractional crystallization. These models show that the correlation is unlikely to result from participation of martian crust. More likely, this correlation relates to contributions from depleted and enriched reservoirs formed in a martian magma ocean at ca. 4.5 Ga. These models indicate that the shergottite endmember sources were generated by mixing between residual melts and cumulates that formed at variable stages during solidification of a magma ocean. The expanded database for the HSE abundances in shergottites suggests that their martian mantle sources have similar HSE abundances to the terrestrial mantle, consistent with prior studies. The relatively high HSE abundances in both planetary mantles likely cannot be accounted for by high pressure-temperature metal-silicate partitioning at the bases of magma oceans, as has been suggested for Earth. If the HSE were instead supplied by late accretion, this event must have occurred prior to the crystallization of the last martian magma ocean. (C) 2011 Elsevier Ltd. All rights reserved.

2011
Riches, AJV, Liu Y, Day JMD, Puchtel IS, III RD, McSween HY, Walker RJ, Taylor LA.  2011.  Petrology and geochemistry of Yamato 984028: A cumulate lherzolitic shergottite with affinities to Y 000027, Y 000047, and Y 000097. Polar Science. 4(4):497-514.   10.1016/j.polar.2010.04.009   Abstract

We report the petrography, mineral and whole-rock chemistry (major-, trace-, and highly-siderophile element abundances, and osmium and oxygen isotope compositions) of a newly recognized lherzolitic shergottite, Yamato (Y) 984028. Oxygen isotopes (Δ17O = 0.218‰) confirm a martian origin for this meteorite. Three texturally distinctive internal zones and a partially devitrified fusion crust occur in the polished section of Y 984028 studied here. The zones include: 1) a poikilitic region with pyroxene enclosing olivine and chromite (Zone A); 2) a non-poikilitic zone with cumulate olivine, interstitial pyroxene, maskelynite and Ti-rich chromite (Zone B) and; 3) a monomict breccia (Zone C). The pyroxene oikocryst in Zone A is chemically zoned from Wo3–7En76–71 in the core region to Wo33–36En52–49 at the rim, and encloses more Mg-rich olivine (Fo74–70) in the core, as compared with olivines (Fo69–68) located at the oikocryst rim. Constraints from Fe–Mg partitioning between crystals and melt indicate that constituent minerals are not in equilibrium with the corresponding bulk-rock composition, implying that Y 984028 represents a cumulate. The whole-rock major- and trace-element compositions, and initial 187Os/188Os value (0.1281 ± 0.0002) of Y 984028 are similar to other lherzolitic shergottites and this sample is probably launch-paired with Y 793602, Y 000027, Y 000047, and Y 000097. The Os isotopic composition and highly-siderophile element (HSE) abundances of Y 984028 and other lherzolitic shergottites are consistent with derivation from a martian mantle source that evolved with chondritic Re/Os.