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Howarth, GH, Udry A, Day JMD.  2018.  Petrogenesis of basaltic shergottite Northwest Africa 8657: Implications for fO2 correlations and element redistribution during shock melting in shergottites. Meteoritics and Planetary Science. 53:249-267.   10.1111/maps.12999   AbstractWebsite

Northwest Africa (NWA) 8657 is an incompatible trace element-enriched, low-Al basaltic shergottite, similar in texture and chemistry to Shergotty, Zagami, and NWA 5298. It is composed of zoned pyroxene, maskelynite, merrillite, and Ti-oxide minerals with minor apatite, silica, and pyrrhotite. Pyroxene grains are characterized by patchy zoning, with pigeonite or augite cores zoned to Fe-rich pigeonite mantles. The cores have rounded morphologies and irregular margins. Combined with the low Ti/Al of the cores, the morphology and chemistry of the pyroxene grains are consistent with initial crystallization at depth (30–70 km) followed by partial resorption en route to the surface. Enriched rare earth element (REE) equilibrium melt compositions and calculated oxygen fugacities (fO2) conditions for pigeonite cores indicate that the original parent melts were enriched shergottite magmas that staged in chambers at depth within the Martian crust. NWA 8657 does not represent a liquid but rather entrained a proportion of pyroxene crystals from magma chambers where fractional crystallization was occurring at depth. Variation between fO2 and bulk-rock (La/Yb)N of the enriched and intermediate shergottites suggests that oxidation conditions and degree of incompatible element enrichment in the source may not be correlated, as thought previously. Shock melt pockets are characterized by an absence of phosphates and oxide minerals. It is likely that these phases were melted during shock. REEs were redistributed during this process into maskelynite and to a lesser extent the shock melt; however, the overall normalized REE profile of the shock melt is like that of the bulk-rock, but at lower absolute concentrations. Overall, shock melting has had a significant effect on the mineralogy of NWA 8657, especially the distribution of phosphates, which may be significant for geochronological applications of this meteorite and other Martian meteorites with extensive shock melt.

Liu, Y, Floss C, Day JMD, Hill E, Taylor LA.  2009.  Petrogenesis of lunar mare basalt meteorite Miller Range 05035. Meteoritics & Planetary Science. 44:261-284. AbstractWebsite

Miller Range (MIL) 05035 is a low-Ti mare basalt that consists predominantly of pyroxene (62.3 vol%) and plagioclase (26.4 vol%). Pyroxenes are strongly shocked and complexly zoned from augite (Wo(33)) and pigeonite (Wo(17)) cores with Mg# = 50-54 to hedenbergite rims. Coexisting pyroxene core compositions reflect crystallization temperatures of 1000 to 1100 degrees C. Plagioclase has been completely converted to maskelynite with signs of recrystallization. Maskelynite is relatively uniform in composition (An(94)Ab(6)-An(91)Ab(9)), except at contacts with late-stage mesostasis areas (elevated K contents, An(82)Ab(15)Or(3)). Symplectites (intergrowth of Fe-augite, fayalite, and silica) of different textures and bulk compositions in MIL 05035 suggest formation by decomposition of Ferro-pyroxene during shock-induced heating, which is Supported by the total maskelynitization of plagioclase, melt pockets, and the presence of a relict pyroxferroite grain. Petrography and mineral chemistry imply that crystallization of MIL 05035 Occurred in the sequence of Fe-poor pyroxenes (Mg# = 50-54), followed by plagioclase and Fe-rich pyroxenes (Mg# = 20-50), and finally hedenbergite, Fe-Ti oxides, and minor late-stage phases. Petrography, bulk chemistry, mineral compositions, and the age of MIL 05035 Suggest it is possibly Source crater-paired with Asuka (A-) 881757 and Yamato (Y-) 793169, and may also be launch-paired with Meteorite Hills (MET) 01210. MIL 05035 represents an old (similar to 3.8-3.9 Ga), incompatible element-depleted low-Ti basalt that was not sampled during the Apollo or Luna missions. The light-REE depleted nature and lack of Eu anomalies For this meteorite are consistent with an origin distant from the Procellarum KREEP Terrane, and genesis from an early Cumulate mantle-source region generated by extensive differentiation of the Moon.

Sarbadhikari, AB, Day JMD, Liu Y, Rumble D, Taylor LA.  2009.  Petrogenesis of olivine-phyric shergottite Larkman Nunatak 06319: Implications for enriched components in martian basalts. Geochimica Et Cosmochimica Acta. 73:2190-2214.   10.1016/j.gca.2009.01.012   AbstractWebsite

We report on the petrography and geochemistry of the newly discovered olivine-phyric shergottite Larkman Nunatak (LAR) 06319. The meteorite is porphyritic, consisting of megacrysts of olivine (<= 2.5 mm in length, F(O77-52)) and prismatic zoned pyroxene crystals with Wo(3)En(71) in the cores to Wo(8-30)En(23-45) at the rims. The groundmass is composed of finer grained olivine (<0.25 mm, Fo(62-46)), Fe-rich augite and pigeonite, maskelynite and minor quantities of chromite, ulvospinel, magnetite, ilmenite, phosphates, sulfides and glass. Oxygen fugacity estimates, derived from the olivine-pyroxene-spinel geo-barometer, indicate that LAR 06319 formed under more oxidizing conditions (QFM -1.7) than for depleted shergottites. The whole-rock composition of LAR 06319 is also enriched in incompatible trace elements relative to depleted shergottites, with a trace-element pattern that is nearly identical to that of olivine-phyric shergottite NWA 1068. The oxygen isotope composition of LAR 06319 (Delta(17)O = 0.29 +/- 0.03) confirms its martian origin. Olivine megacrysts in LAR 06319 are phenocrystic, with the most Mg-rich megacryst olivine being close to equilibrium with the bulk rock. A notable feature of LAR 06319 is that its olivine megacryst grains contain abundant melt inclusions hosted within the forsterite cores. These early-trapped melt inclusions have similar trace element abundances and patterns to that of the whole-rock, providing powerful evidence for closed-system magmatic behavior for LAR 06319. Calculation of the parental melt trace element composition indicates a whole-rock composition for LAR 06319 that was controlled by pigeonite and augite during the earliest stages of crystallization and by apatite in the latest stages. Crystal size distribution and spatial distribution pattern analyses of olivine indicate at least two different crystal populations. This is most simply interpreted as crystallization of megacryst olivine in magma conduits, followed by eruption and subsequent crystallization of groundmass olivine. LAR 06319 shows close affinity in mineral and whole-rock chemistry to olivine-phyric shergottite, NWA 1068 and the basaltic shergottite NWA 4468. The remarkable features of these meteorites are that they have relatively similar quantities of mafic minerals compared with olivine-phyric shergottites (e.g., Y-980459, Dho 019), but flat and elevated rare earth element patterns more consistent with the LREE-enriched basaltic shergottites (e.g., Shergotty, Los Angeles). This relationship can be interpreted as arising from partial melting of an enriched mantle source and subsequent crystal-liquid fractionation to form the enriched olivine-phyric and basaltic shergottites, or by assimilation of incompatible-element enriched martian crust. The similarity in the composition of early-trapped melt inclusions and the whole-rock for LAR 06319 indicates that any crustal assimilation must have occurred prior to crystallization of megacryst olivine, restricting such processes to the deeper portions of the crust. Thus, we favor LAR06319 forming from partial melting of an "enriched" and oxidized mantle reservoir, with fractional crystallization of the parent melt upon leaving the mantle. (c) 2009 Elsevier Ltd. All rights reserved.

Day, JMD, Taylor LA, Floss C, McSween HY.  2006.  Petrology and chemistry of MIL 03346 and its significance in understanding the petrogenesis of nakhlites on Mars. Meteoritics & Planetary Science. 41:581-606. AbstractWebsite

Antarctic meteorite Miller Range (MIL) 03346 is a nakhlite composed of 79% clinopyroxene, similar to 1% olivine, and 20% vitrophyric intercumulus material. We have performed a petrological and geochemical study of MIL 03346, demonstrating a petrogenetic history similar to previously discovered naklilites. Quantitative textural study of MIL 03346 indicates long (> 1 x 10(1) yr) residence times for the Cumulus augite, whereas the skeletal Fe-Ti oxide, fayalite, and sulfide in the vitrophyric intercumulus matrix suggest rapid cooling, probably as a lava flow. From the relatively high forsterite contents of olivine (up to Fo(43)) compared with other nakhlites and compositions of augite cores (Wo(38-42)En(35-40)Fs(22-28)) and their hedenbergite rims, we suggest that MIL 03346 is part of the same or a similar Martian Cumulate-rich lava flow as other nakhlites. However, MIL 03346 has experienced less equilibration and faster cooling than other nakhlites discovered to date. Calculated trace element concentrations based upon modal abundances of MIL 03346 and its constituent minerals are identical to whole rock trace element abundances. Parental melts for augite have REE patterns that are approximately parallel with whole rock and intercumulus melt using experimentally defined partition coefficients. This parallelism reflects closed-system crystallization for MIL 03346, where the only significant petrogenetic process between formation of augite and eruption and emplacement of the nakhlite flow has been fractional crystallization. A model for the petrogenesis of MIL 03346 and the naklilites (Nakhla, Governador Valadares, Lafayette, Yamato-000593, Northwest Africa (NWA) 817, NWA 998) Would include: 1) partial melting and ascent of melt generated from a long-term LREE depleted mantle Source, 2) crystallization of cumulus augite (+/- olivine, +/- magnetite) in a shallow-level Martian magma chamber, 3) eruption of the crystal-laden naklilite magma onto the surface of Mars, 4) cooling, crystal settling, overgrowth, and partial equilibration to different extents within the flow, 5) secondary alteration through hydrothermal processes, possibly immediately succeeding or during emplacement of the flow. This model might apply to single-or multiple-flow models for the nakhlites. Ultimately, MIL 03346 and the other nakhlites preserve a record of magmatic processes in volcanic rocks oil Mars with analogous petrogenetic histories to pyroxene-rich terrestrial lava flows and to komatiites.

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.

Herzberg, C, Cabral RA, Jackson MG, Vidito C, Day JMD, Hauri EH.  2014.  Phantom Archean crust in Mangaia hotspot lavas and the meaning of heterogeneous mantle. Earth and Planetary Science Letters. 396:97-106.   10.1016/j.epsl.2014.03.065   Abstract

Lavas from Mangaia in the Cook–Austral island chain, Polynesia, define an HIMU (or high μ , where View the MathML source) global isotopic end-member among ocean island basalts (OIB) with the highest 206,207,208Pb/204Pb. This geochemical signature is interpreted to reflect a recycled oceanic crust component in the mantle source. Mass independently fractionated (MIF) sulfur isotopes indicate that Mangaia lavas sampled recycled Archean material that was once at the Earth's surface, likely hydrothermally-modified oceanic crust. Recent models have proposed that crust that is subducted and then returned to the surface in a mantle plume is expected to transform to pyroxenite/eclogite during transit through the mantle. Here we examine this hypothesis for Mangaia using high-precision electron microprobe analysis on olivine phenocrysts. Contrary to expectations of a crustal component and, hence pyroxenite, results show a mixed peridotite and pyroxenite source, with peridotite dominating. If the isotopic compositions were inherited from subduction of recycled oceanic crust, our work shows that this source has phantom-like properties in that it can have its lithological identity destroyed while its isotope ratios are preserved. This may occur by partial melting of the pyroxenite and injection of its silicic melts into the surrounding mantle peridotite, yielding a refertilized peridotite. Evidence from one sample reveals that not all pyroxenite in the melting region was destroyed. Identification of source lithology using olivine phenocryst chemistry can be further compromised by magma chamber fractional crystallization, recharge, and mixing. We conclude that the commonly used terms mantle “heterogeneities” and “streaks” are ambiguous, and distinction should be made of its lithological and isotopic properties.

Day, JMD.  2015.  Planet formation processes revealed by meteorites. Geology Today. 31(1):12-20.   10.1111/gto.12082   Abstract

The history of the solar system is locked within the planets, asteroids and other objects that orbit the Sun. While remote observations of these celestial bodies are essential for understanding planetary processes, much of the geological and geochemical information regarding solar system heritage comes directly from the study of rocks and other materials originating from them. The diversity of materials available for study from planetary bodies largely comes from meteorites; fragments of rock that fall through Earth’s atmosphere after impact-extraction from their parent planet or asteroid. These extra-terrestrial objects are fundamental scientific materials, providing information on past conditions within planets, and on their surfaces, and revealing the timing of key events that affected a planet’s evolution. Meteorites can be sub-divided into four main groups: (1) chondrites, which are unmelted and variably metamorphosed ‘cosmic sediments’ composed of particles that made up the early solar nebula; (2) achondrites, which represent predominantly silicate materials from asteroids and planets that have partially to fully melted, from a broadly chondritic initial composition; (3) iron meteorites, which represent Fe-Ni samples from the cores of asteroids and planetesimals; and (4) stony-iron meteorites such as pallasites and mesosiderites, which are mixtures of metal and dominantly basaltic materials. Meteorite studies are rapidly expanding our understanding of how the solar system formed and when and how key events such as planetary accretion and differentiation occurred. Together with a burgeoning collection of classified meteorites, these scientific advances herald an unprecedented period of further scientific challenges and discoveries, an exciting prospect for understanding our origins.

Moynier, F, Day JMD, Okui W, Yokoyama T, Bouvier A, Walker RJ, Podosek FA.  2012.  Planetary-Scale Strontium Isotopic Heterogeneity and the Age of Volatile Depletion of Early Solar System Materials. The Astrophysical Journal. 758(1):45.   doi:10.1088/0004-637X/758/1/45   Abstract

Isotopic anomalies in planetary materials reflect both early solar nebular heterogeneity inherited from presolar stellar sources and processes that generated non-mass-dependent isotopic fractionations. The characterization of isotopic variations in heavy elements among early solar system materials yields important insight into the stellar environment and formation of the solar system, and about initial isotopic ratios relevant to long-term chronological applications. One such heavy element, strontium, is a central element in the geosciences due to wide application of the long-lived 87Rb-87Sr radioactive as a chronometer. We show that the stable isotopes of Sr were heterogeneously distributed at both the mineral scale and the planetary scale in the early solar system, and also that the Sr isotopic heterogeneities correlate with mass-independent oxygen isotope variations, with only CI chondrites plotting outside of this correlation. The correlation implies that most solar system material formed by mixing of at least two isotopically distinct components: a CV-chondrite-like component and an O-chondrite-like component, and possibly a distinct CI-chondrite-like component. The heterogeneous distribution of Sr isotopes may indicate that variations in initial 87Sr/86Sr of early solar system materials reflect isotopic heterogeneity instead of having chronological significance, as interpreted previously. For example, given the differences in 84Sr/86Sr between calcium aluminum inclusions and eucrites (ε84Sr > 2), the difference in age between these materials would be ~6 Ma shorter than previously interpreted, placing the Sr chronology in agreement with other long- and short-lived isotope systems, such as U-Pb and Mn-Cr.

O'Driscoll, B, Garwood R, Day JMD, Wogelius RA.  2018.  Platinum-group element remobilisation and concentration in the Cliff chromitites of the Shetland Ophiolite Complex, Scotland. Mineralogical Magazine. 82:471-490.   Abstract

The ~492 Ma Shetland Ophiolite Complex (SOC) contains an extensive mantle section, within which numerous podiform chromitite bodies formed during melt percolation in a supra-subduction zone setting. One of the SOC chromitite localities has an unusual style of platinum-group element (PGE) mineralisation. Specifically, the Cliff chromitite suite has relatively high (>250 ppm) Pt plus Pd, compared to other SOC chromitites. In this study, we use petrographic observation, mineral chemistry and X-ray microtomography to elucidate the petrogenesis of PGE-bearing phases at Cliff. The combined data reveal that the PGE at Cliff have likely been fractionated by an As-rich fluid, concentrating Pt and Ir into visible (0.1-1 μm) platinum-group minerals (PGM) such as sperrylite and irarsite, respectively. The high (>1 ppm) bulk rock concentrations of the other PGE (e.g., Os) in the Cliff chromitites suggests the presence of abundant fine-grained unidentified PGM in the serpentinised groundmass. The spatial association of arsenide phases and PGM with alteration rims on Cr-spinel grains suggests that the high Pt and Pd abundances at Cliff result from a late-stage low-temperature (e.g., 200-300°C) hydrothermal event. This conclusion highlights the potential effects that secondary alteration processes can have on modifying and upgrading the tenor of PGE deposits.

Chen, H, Meshik AP, Pravdivtseva OV, Day JMD, Wang K.  2019.  Potassium isotope fractionation during the high-temperature evaporation determined from the Trinity nuclear test. Chemical Geology.   Abstract

Trinitite materials are the post-detonation glassy residues formed from melting and evaporation of arkosic sands during the first nuclear detonation at the Trinity test site, New Mexico on 16th July, 1945. These trinitites provide useful materials for studying elemental and isotopic behaviors associated with high temperature melting and evaporation that is otherwise difficult to be achieved under laboratory conditions. Using a high-precision method, we measured the potassium (K) isotopic compositions of six bulk trinitite samples taken at different distances from the epicenter of detonation of the Gadget (ground zero). 15 leachates and etchates of trinitite samples were also analyzed to examine the distribution of K within the samples. All trinitites but IF_m (taken within 10 m from the epicenter) show no resolvable K loss and span a narrow range in K isotopic compositions (δ41K: -0.42 ± 0.05‰ to -0.48 ± 0.05‰), revealing no discernible K isotopic fractionation from the Bulk Silicate Earth (BSE) value (-0.48 ± 0.03‰). Residues and etchates of the trinitite material are identical in composition to the bulk samples implying that K isotopes were homogeneous with the arkosic sand at the Trinity test site prior to the nuclear detonation. The most strongly melted green trinitite IF_m, is the only trinitite that shows loss of K (~7%) coupled with resolvable heavier K isotope composition (0.2‰ higher in δ41K than the BSE value). This coupled K loss and isotopic fractionation corresponds to a 55 fractionation factor(avapor-melt) between 0.995 and 0.998 during the Trinity nuclear detonation. These results confirm that K isotopic fractionation occurs through evaporation processes at high temperatures. We also show that, compared with Zn isotopes measured in the same samples, the isotopes of K were significantly less fractionated during evaporation, indicating that K is less volatile during processes such as magma ocean degassing, volcanic outgassing, and impact volatile loss with the relative order of sensitivity being Cu > Zn > K. Our findings support the concept that the heavy K isotopic composition observed in lunar mare basalts reflects the primary signature imprinted by the Moon-forming giant impact event.

Day, JMD, Maria-Benavides J, McCubbin FM, Zeigler RA.  2018.  The potential for metal contamination during Apollo lunar sample curation. Meteoritics and Planetary Science. 53:1283-1291.   Abstract

Curation and preparation of samples for chemical analysis can occasionally lead to significant contamination. This issue is of concern in the study of lunar samples, especially those from the Apollo sample collection, where available masses are finite. Here we present compositional data for stainless steels that have commonly been used in the processing of Apollo lunar samples at NASA Johnson Space Center, including a chisel and a vessel typically used to transfer Apollo samples to principal investigators. The Type 304 stainless steels are Cr-rich, with high concentrations of Mn (4000–18,000 ug g1), Cu (1000–22,900 ug g1), Mo (1030–1120 ug g1), and W (72-193 ug g1). They have elevated highly siderophile element (HSE) concentrations (up to 92 ng g1 Os), 187Os/188Os ranging from 0.1310 to 0.1336, and negligible lithophile element abundances. We find that, while metal contamination is possible, significant (≫0.01% by mass) addition of stainless steel is required to strongly affect the composition of the HSE, W, Mo, Cr, or Cu for most Apollo lunar samples. Nonetheless, careful appraisal on a case-by-case basis should take place to ensure contamination introduced through sample processing during curation is at acceptably low levels. A survey of lunar mare basalts and crustal rocks indicates that metal contamination plays a negligible role in the compositional variability of the HSE and W compositions preserved in these samples. Further work to constrain contamination for other properties of Apollo samples is required (e.g., organics, microbes, water, noble gases, and magnetics), but the effect of metal contamination can be well-constrained for the Apollo lunar collection.

Howarth, GH, Day JMD, Pernet-Fisher JF, Goodrich CA, Pearson DG, Luo Y, Ryabov VV, Taylor LA.  2017.  Precious metal enrichment at low-redox in terrestrial native Fe-bearing basalts investigated using laser-ablation ICP-MS. Geochimica et Cosmochimica Acta.   10.1016/j.gca.2017.01.003   Abstract

Primary native Fe is a rare crystallizing phase from terrestrial basaltic magmas, requiring highly reducing conditions (fO2

Day, JMD, Pearson DG, Macpherson CG, Lowry D, Carracedo JC.  2009.  Pyroxenite-rich mantle formed by recycled oceanic lithosphere: Oxygen-osmium isotope evidence from Canary Island lavas. Geology. 37:555-558.   10.1130/g25613a.1   AbstractWebsite

Plate tectonic processes result in recycling of crust and lithosphere into Earth's mantle. Evidence for long-term preservation of recycled reservoirs in the mantle comes from the enriched isotopic character of oceanic island basalt (OIB) lavas. Although recycled constituents can explain much of the geochemical variation in the OIB-source mantle, it has been shown that direct melting of these components would lead to magmas with evolved compositions, unlike OIB. Instead, it has been argued that either metasomatic pyroxene-rich peridotite that has inherited the trace element and isotopic character of subducted materials, or high-temperature intramantle metasomatism of lithosphere can explain OIB compositions. To test these models, we present new oxygen and osmium isotope data for lavas from the Canary Islands of El Hierro and La Palma. These islands have distinct (18)O/(16)O and (187)Os/(188)Os compositions that can be explained through melting of pyroxenite-enriched peridotite mantle containing <10% recycled oceanic lithosphere. We also assess O-Os isotope systematics of lavas from Hawai'i and the Azores and show that they also conform to addition of distinct recycled oceanic components, including lithosphere and pelagic sediment. We conclude that enriched isotopic signatures of some OIBs are consistent with pyroxenite-rich mantle sources metasomatized by recycled components.