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Day, JMD, Walker RJ, Warren JM.  2017.  Os-186-Os-187 and highly siderophile element abundance systematics of the mantle revealed by abyssal peridotites and Os-rich alloys. Geochimica et Cosmochimica Acta. 200:232-254.   10.1016/j.gca.2016.12.013   Abstract

Abyssal peridotites are oceanic mantle fragments that were recently processed through ridges and represent residues of both modern and ancient melting. To constrain the nature and timing of melt depletion processes, and the composition of the mantle, we report high-precision Os isotope data for abyssal peridotites from three ocean basins, as well as for Os-rich alloys, primarily from Mesozoic ophiolites. These data are complemented by whole-rock highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re), trace- and major-element abundances for the abyssal peridotites, which are from the Southwest Indian (SWIR), Central Indian (CIR), Mid-Atlantic (MAR) and Gakkel Ridges. The results reveal a limited role for melt refertilization or secondary alteration processes in modifying abyssal peridotite HSE compositions. The abyssal peridotites examined have experienced variable melt depletion (2% to >16%), which occurred >0.5 Ga ago for some samples. Abyssal peridotites typically exhibit low Pd/Ir and, combined with high-degrees of estimated total melt extraction, imply that they were relatively refractory residues prior to incorporation into their present ridge setting. Recent partial melting processes and mid-ocean ridge basalt (MORB) generation therefore played a limited role in the chemical evolution of their precursor mantle domains. The results confirm that many abyssal peridotites are not simple residues of recent MORB source melting, having a more complex and long-lived depletion history.

Peridotites from the Gakkel Ridge, SWIR, CIR and MAR indicate that the depleted MORB mantle has 186Os/188Os of 0.1198356 ±21 (2SD). The Phanerozoic Os-rich alloys yield an average 186Os/188Os within uncertainty of abyssal peridotites (0.1198361 ±20). Melt depletion trends defined between Os isotopes and melt extraction indices (e.g., Al2O3) allow an estimate of the primitive mantle (PM) composition, using only abyssal peridotites. This yields 187Os/188Os (0.1292 ±25), and 186Os/188Os of 0.1198388 ±29, both of which are within uncertainty of previous primitive mantle estimates. The 186Os/188Os composition of the PM is less radiogenic than for some plume-related lavas, with the latter requiring sources with high long-term time-integrated Pt/Os. Estimates of primitive mantle HSE concentrations using abyssal peridotites define chondritic Pd/Ir, which differs from previous supra-chondritic estimates for Pd/Ir based on peridotites from a range of tectonic settings. By contrast, estimates of PM yield non-chondritic Ru/Ir. The cause of enhanced Ru in the mantle remains enigmatic, but may reflect variable partitioning behaviour of Ru at high pressure and temperature.

Day, JMD, Walker RJ.  2015.  Highly siderophile element depletion in the Moon. Earth and Planetary Science Letters. 423:114-124.   10.1016/j.epsl.2015.05.001   Abstract

Coupled 187Os/188Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundance data are reported for Apollo 12 (12005, 12009, 12019, 12022, 12038, 12039, 12040), Apollo 15 (15555) and Apollo 17 (70135) mare basalts, along with mare basalt meteorites La Paz icefield (LAP) 04841 and Miller Range (MIL) 05035. These mare basalts have consistently low HSE abundances, at ∼2×10−5 to 2×10−7 the chondritic abundance. The most magnesian samples have broadly chondrite-relative HSE abundances and chondritic measured and calculated initial 187Os/188Os. The lower abundances and fractionated HSE compositions of more evolved mare basalts can be reproduced by modeling crystal–liquid fractionation using rock/melt bulk-partition coefficients of ∼2 for Os, Ir, Ru, Pt and Pd and ∼1.5 for Re. Lunar mare basalt bulk-partition coefficients are probably higher than for terrestrial melts as a result of more reducing conditions, leading to increased HSE compatibility. The chondritic-relative abundances and chondritic 187Os/188Os of the most primitive high-MgO mare basalts cannot readily be explained through regolith contamination during emplacement at the lunar surface. Mare basalt compositions are best modeled as representing ∼5–11% partial melting of metal-free sources with low Os, Ir, Ru, Pd (∼0.1 ng g−1), Pt (∼0.2 ng g−1), Re (∼0.01 ng g−1) and S (∼75 μg g−1), with sulphide-melt partitioning between 1000 and 10,000.

Apollo 12 olivine-, pigeonite- and ilmenite normative mare basalts define an imprecise 187Re–187Os age of 3.0±0.9 Ga with an initial 187Os/188Os of 0.107±0.010. This age is within uncertainty of 147Sm–143Nd ages for the samples. The initial Os isotopic composition of Apollo 12 samples indicates that the source of these rocks evolved with Re/Os within ∼10% of chondrite meteorites, from the time that the mantle source became a system closed to siderophile additions, to the time that the basalts erupted. Similarity in absolute HSE abundances between mare basalts from the Apollo 12, 15 and 17 sites, and from unknown regions of the Moon (La Paz mare basalts, MIL 05035), indicates relatively homogeneous and low HSE abundances within the lunar interior. Low absolute HSE abundances and chondritic Re/Os of mare basalts are consistent with a late accretion addition of ∼0.02 wt.% of the Moon's mass to the mantle, prior to the formation of the lunar crust. Late accretion must also have occurred significantly prior to cessation of lunar mantle differentiation (>4.4 Ga), to enable efficient mixing and homogenization within the mantle. Low lunar HSE abundances are consistent with proportionally 40 times more late accretion to Earth than the Moon. Disproportional late accretion to the two bodies is consistent with the small 182W excess (∼21–28 ppm) measured in lunar rocks, compared to the silicate Earth.

Day, JMD, Macpherson CG, Lowry D, Pearson DG.  2012.  Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al. Contributions to Mineralogy and Petrology. 164:177-183.   10.1007/s00410-012-0755-3   AbstractWebsite

Gurenko et al. (Contrib Mineral Petrol 162:349-363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) O-18/O-16 datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233-262, 1997; Day et al. Geology 37:555-558, 2009, Geochim Cosmochim Acta 74:6565-6589, 2010), these authors find variations in delta O-18(ol) (similar to 4.6-6.0 aEuro degrees) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231-241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349-363, 2011) speculate that delta O-18(ol) values for La Palma olivine grains measured by LF (Day et al. Geology 37:555-558, 2009, Geochim Cosmochim Acta 74:6565-6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in delta O-18(ol) values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349-363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that delta O-18(ol) is weakly correlated (R (2) = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514-524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member delta O-18 values for HIMU-peridotite (delta O-18 = 5.3 +/- A 0.3 aEuro degrees) and depleted pyroxenite (delta O-18 = 5.9 +/- A 0.3 aEuro degrees) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349-363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555-558, 2009, Geochim Cosmochim Acta 74:6565-6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226-234, 2011), there are significant differences in the predicted delta O-18 values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565-6589, 2010) proposed a mantle source for La Palma lavas with low-delta O-18 (< 5 aEuro degrees), rather than higher-delta O-18 (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349-363, 2011). Here we question the approach of using weakly correlated variations in delta O-18(ol) and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.

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.

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.

Day, JMD.  2016.  Extraordinary World. Nature. 537:310-311.   10.1038/537310a   Abstract

The isotopic compositions of objects that formed early in the evolution of the Solar System have been found to be similar to Earth's composition — overturning notions of our planet's chemical distinctiveness.

Day, JMD, Moynier F.  2014.  Evaporative fractionation of volatile stable isotopes and their bearing on the origin of the Moon. Phil. Trans. R. Soc. A. 20130259   10.1098/rsta.2013.0259   Abstract

The Moon is depleted in volatile elements relative to the Earth and Mars. Low abundances of volatile elements, fractionated stable isotope ratios of S, Cl, K and Zn, high mu (238U/204Pb) and long-term Rb/Sr depletion are distinguishing features of the Moon, relative to the Earth. These geochemical characteristics indicate both inheritance of volatile-depleted materials that formed the Moon and planets and subsequent evaporative loss of volatile elements that occurred during lunar formation and differentiation. Models of volatile loss through localized eruptive degassing are not consistent with the available S, Cl, Zn and K isotopes and abundance data for the Moon. The most probable cause of volatile depletion is global-scale evaporation resulting from a giant impact or a magma ocean phase where inefficient volatile loss during magmatic convection led to the present distribution of volatile elements within mantle and crustal reservoirs. Problems exist for models of planetary volatile depletion following giant impact. Most critically, in this model, the volatile loss requires preferential delivery and retention of late-accreted volatiles to the Earth compared with the Moon. Different proportions of late-accreted mass are computed to explain present-day distributions of volatile and moderately volatile elements (e.g. Pb, Zn; 5 to >10%) relative to highly siderophile elements (approx. 0.5%) for the Earth. Models of early magma ocean phases may be more effective in explaining the volatile loss. Basaltic materials (e.g. eucrites and angrites) from highly differentiated airless asteroids are volatile-depleted, like the Moon, whereas the Earth and Mars have proportionally greater volatile contents. Parent-body size and the existence of early atmospheres are therefore likely to represent fundamental controls on planetary volatile retention or loss.

Day, JMD, Pearson DG, Macpherson CG, Lowry D, Carracedo JC.  2010.  Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands. Geochimica Et Cosmochimica Acta. 74:6565-6589.   10.1016/j.gca.2010.08.021   AbstractWebsite

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (delta(18)O(olivine) = 5.17 +/- 0.08 parts per thousand; (87)Sr/(86)Sr = 0.7029 to 0.7031; epsilon(Nd) = +5.7 to +7.1; (187)Os/(188)Os = 0.1481 to 0.1750; (206)Pb/(204)Pb = 19.1 to 19.7; Pd/Ir = 6 +/- 3) versus those from La Palma (delta(18)Oo(livine) = 4.87 +/- 0.18 parts per thousand; (87)Sr/(86)Sr = 0.7031 to 0.7032; epsilon(Nd) = +5.0 to +6.4; (187)Os/(188)Os = 0.1421 to 0.1460; (206)Pb/(204)Pb = 19.5 to 20.2; Pd/Ir = 11 +/- 4) are revealed from the dataset. Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and USE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIM U-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (>= 110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 +/- 0.05 Os, 0.17 +/- 0.16 Ir, 0.34 +/- 0.32 Ru, 2.6 +/- 2.5 Pt, 1.4 +/- 1.2 Pd, 0.39 +/- 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai'ian tholeiites. The HIMU affinities of the lavas, in conjunction with the low delta(18)O(olivine) and high (206)Pb/(204)Pb for La Palma, and elevated (187)Os/(188)Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic (206)Pb/(204), (187)Os/(188)Os, elevated Re/Os and Pt/Os, and low-delta(18)O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (similar to 50 km). (C) 2010 Elsevier Ltd. All rights reserved.

Day, JMD, Qiu L, Ash RD, McDonough WF, Teng F-Z, Rudnick RL, Taylor LA.  2016.  Evidence for high-temperature fractionation of lithium isotopes during differentiation of the Moon. Meteoritics and Planetary Science. 51(6):1046-1062.   10.1111/maps.12643   Abstract

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low-Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low-Ti mare basalts have lower Li contents and lower δ7Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high-Ti mare basalts (δ7Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ7Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low-Ti mare basalt 15555, the highest concentrations of Li occur in late-stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ7Li in low- and high-Ti mare basalt sources broadly correlate negatively with 18O/16O and positively with 56Fe/54Fe (low-Ti: δ7Li ≤4‰; δ56Fe ≤0.04‰; δ18O ≥5.7‰; high-Ti: δ7Li >6‰; δ56Fe >0.18‰; δ18O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large-degree, high-temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ7Li in late-stage liquids, probably as a consequence of preferential retention of 7Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile-poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ7Li ranging between −2.5‰ and 4‰. The higher δ7Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.

Day, JMD.  2013.  Hotspot volcanism and highly siderophile elements. Chemical Geology. 341:50-74.   10.1016/j.chemgeo.2012.12.010   AbstractWebsite

Hotspot volcanic rocks are formed under conditions that differ from conventional plate tectonic boundary magmatic processes and are compositionally distinct from mid-oceanic ridge basalts. Hotspot volcanic rocks include - but are not limited to - ocean island basalts (OIB), continental flood basalts (CFB), komatiites, oceanic plateau and some intraplate alkaline volcanic rocks. Studies of the highly siderophile element (HSE) geochemistry of hotspot volcanic rocks have provided new perspectives into mantle convection, mantle heterogeneity, core-mantle interactions, crustal and mantle lithospheric recycling, melting processes and crust-mantle interactions. The HSE, comprising Os, Ir, Ru, Rh, Pt, Pd, Re and Au, have strong affinities for metal and sulphide relative to silicate. These elements also have variable partitioning behaviour between highly compatible Os, Ir, Ru and Rh relative to compatible Pt and Pd and to moderately incompatible Re and Au during melting and crysta! The HSE can be utilised to understand sub-aerial volcanic degassing and crustal assimilation processes in hotspot volcanic rocks such as CFB and OIB, as well as for quantitative assessment of fractional crystallisation. Mantle melting studies have highlighted the strong control of sulphide in the mantle prior to exhaustion of S and generation of Os Ir Ru metal alloys at similar to>25% partial melting; a behaviour of the HSE that is fundamental to understanding terrestrial hotspot volcanism. Perhaps the most exciting utility of the HSE, however, lies in their ability to reveal both short- and long-term fractionation processes acting on hotspot volcanic sources from inter-element HSE fractionations and Os-187/Os-188-Os-186/Os-188 systematics. The growing database for HSE abundances and Os-187/Os-188 in hotspot volcanic rocks is consistent with their generation from a heterogeneous upper mantle generated by melt differentiation and recycling of crust and mantle lithosphere d! The HSE provide geochemical evidence for how lithological and chemical heterogeneities are sampled within the mantle. Modeling of HSE abundances and Os isotopes show that large apparent recycled contributions (50% to 90%) in some OIB can be explained by the preferential melting of volumetrically minor (<10%) pyroxenite in their sources. Preferential melting of more fusible materials in the mantle also explains why low-degree partial melts, such as alkali basalts and basanites, may exhibit more extreme isotopic variations than tholeiites or komatiites, which likely contain a higher contribution from peridotite in a hybridised pyroxenite-peridotite mantle source. High-precision Os-188/Os-188 data for hotspot volcanism are limited, but the combined variations in long-term Re/Os and Pt/Os retained in some mantle sources may reflect either the long-term fractionation of Re and Pt from Os between the inner and outer core, or ancient sulphide segregation and lithological variati! Study of the HSE in hotspot volcanic rocks from Solar System bodies also informs on planetary-scale processes, indicating that Earth, the Moon, Mars and fully differentiated asteroids all have HSE abundances in their mantles that are higher than expected from low-pressure metal-silicate partitioning. Furthermore, the HSE are in broadly chondritic-relative abundances for these planetary bodies, at similar to 0.0002 (Moon), to similar to 0.007 (Mars), to similar to 0.009 (Earth) x carbonaceous chondrite Ivuna (CI) composition. The timing of addition of the HSE to planetary bodies preserved in their magmas and volcanic products is consistent with Solar-System-wide late accretion no later than 3.8 Ga for Earth, and even earlier based on evidence from the Moon (similar to 4.4 Ga), Mars (similar to 4.5 Ga) and asteroids (>4.56 Ga). (C) 2013 Elsevier B.V. All rights reserved.DELMON.A, 1972, AMERICAN JOURNAL OF SCIENCE, V272, P805

Day, JMD, Corder CA, Assayag N, Cartigny P.  2019.  Ferrous oxide-rich asteroid achondrites. Geochimica et Cosmochimica Acta.   Abstract

Ferrous oxide (FeO)-rich asteroid achondrites can be defined as asteroid-derived samples that experienced incipient partial melting processes in the early Solar System (>4.5 Ga) leading to melt-residues and cumulate and melt rocks that have high FeO in silicate grains (molar Mg/ [Mg + Fe] <80), implying relatively oxidative conditions (fO2 of IW +1 to +3). These achondrites include olivine-dominated brachinite and brachinite-like achondrite meteorites, ungrouped meteorites including Lewis Cliff 88763, Northwest Africa (NWA) 6693 and NWA 6704, Tafassasset, NWA 011/1296, and the oligoclase-rich meteorites Graves Nunataks (GRA) 06128 and GRA 06129. Ferrous oxide-rich asteroidal achondrites differ from other partially-melted achondrites, including ureilites and acapulcoite-lodranites in that the latter have higher molar Mg/ (Mg + Fe) in silicate grains, and lower fO2 (IW 0 to -2). New mineral chemical, whole-rock major- and trace-element and highly siderophile element (HSE: Re, Os, Ir, Ru, Rh, Pt, Pd, Au) abundance data, and O and Os isotope data are presented for FeO-rich achondrite meteorites Allan Hills 84025 (brachinite), Miller Range (MIL) 090206 and MIL 090405 (brachinite-like achondrites), and NWA 6693 (ungrouped). These results, combined with available data for FeO-rich asteroidal achondrites, reveal that these rocks include nearly-pure residues after partial melting, to samples formed by melt-rock reaction and as cumulates, requiring variable to extensive Fe-Ni-S partial melting, and between 1 to 20% silicate partial melting. The FeO-rich asteroidal achondrites originate from at least four distinct parent bodies, based on O-Cr-Ti isotope systematics, and occur in both carbonaceous and non-carbonaceous chondrite precursor sources. The initial water and volatile contents of FeO-rich asteroid achondrites were similar to carbonaceous chondrite groups, implying both carbonaceous and non-carbonaceous precursor materials generated water-rich partially-melted asteroidal bodies. The existence and recognition of FeO-rich asteroid achondrites explains the otherwise enigmatic nature of some iron meteorite groups (e.g., IVA, IVB) that require segregation from an oxidized asteroid parent body. The internal structure of some asteroid parent bodies was likely to be complex, reflecting early differentiation processes of nascent core formation, Fe-Ni-S melt pooling, variable silicate partial melting, igneous differentiation and the important role of melt-rock reaction, melt refertilization and late-stage C- (reduced bodies) or S-rich (oxidized bodies) fluid and vapor reactions.

Day, JMD, Pearson DG, Hulbert LJ.  2008.  Rhenium-osmium isotope and platinum-group element constraints on the origin and evolution of the 1.27 Ga Muskox layered intrusion. Journal of Petrology. 49:1255-1295.   10.1093/petrology/egn024   AbstractWebsite

Platinum-group element (PGE: Os, Ir, Ru, Pt, Pd) and Re-Os isotope systematics determined for the entire preserved stratigraphy of the 1.27 Ga Muskox intrusion provide an exceptional view of magma chamber processes and mineralization in the main plutonic system of the Mackenzie large igneous province (LIP). We present new Re-Os isotope data for the intrusion, together with PGE and trace element abundances, and oxygen and Sm-Nd isotope data on samples that include local crustal materials, layered series peridotites, stratiform chromitites, marginal and roof zone rocks, and the Muskox Keel feeder dyke. Intrusive rocks span wide ranges in initial isotopic compositions (gamma(Os)i=+1.0 to +87.6; epsilon(Nd)i = -0.4 to -6.6; delta(18)O(Ol) =+ 5.5 to + 6.9 parts per thousand) and highly siderophile element abundances (HSE: PGE and Re; Re =0.02-105 ppb; Pt =0.23-115 ppb; O(s)= 0.02 to > 200 ppb). HSE and fluid-immobile trace element abundance variations are consistent with relative compatibilities expected for cumulate rocks. The most radiogenic Os and unradiogenic Nd isotope compositions occur in the Muskox marginal and roof zones. Negative gamma(Os)i values in these rocks and their non-isochronous relations result from mobilization of Re in the intrusion through post-magmatic hydrothermal processes. The most significant process causing Os and Nd isotope variations in the layered series of the intrusion is crustal contamination of mantle-derived magma batches feeding individual cyclic units. This process may be directly responsible for formation of chromitite horizons within the intrusion. Accounting for crustal assimilation, the Muskox intrusion parental magma has gamma(Os)i = +1.2 +/- 0.3, epsilon(Nd)i > -1.0 +/- 0.4, delta(18)O similar to +5.5 parts per thousand and HSE abundances similar to those expected from >= 15% partial melting of the Mackenzie LIP mantle source. This composition is similar to that calculated for 1.27 Ga primitive upper mantle. Parental magmas were probably derived from a mantle source unaffected by long- term, large-scale melt depletion, with no appreciable input from recycled crust and lithosphere, or putative core contributions.

Day, JMD, Moynier F, Meshik AP, Pradivtseva OV, Pettit DR.  2017.  Evaporative fractionation of zinc during the first nuclear detonation. Science Advances. 3(2):e1602668.   10.1126/sciadv.1602668   Abstract

Volatile element and compound abundances vary widely in planets and were set during the earliest stages of solar system evolution. Experiments or natural analogs approximating these early conditions are limited. Using silicate glass formed from arkosic sands during the first nuclear detonation at the Trinity test site, New Mexico, we show that the isotopes of zinc were fractionated during evaporation. The green silicate glasses, termed “trinitite,” show +0.5 ± 0.1‰/atomic mass unit isotopic fractionation from ~200 m to within 10 m of ground zero of the detonation, corresponding to an α fractionation factor between 0.999 and 0.9995. These results confirm that Zn isotopic fractionation occurs through evaporation processes at high temperatures. Evidence for similar fractionations in lunar samples consequently implies a volatile-depleted bulk Moon, with evaporation occurring during a giant impact or in a magma ocean.

Day, JMD, Waters CL, Schaefer BF, Walker RJ, Turner S.  2016.  Use of Hydrofluoric Acid Desilicification in the Determination of Highly Siderophile Element Abundances and Re-Pt-Os Isotope Systematics in Mafic-Ultramafic Rocks. Geostandards and Geoanalytical Research. 40(1):49-65.   DOI: 10.1111/j.1751-908X.2015.00367.x   Abstract

Properly combining highly siderophile element (HSE: Re,Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding 187Os/188Os and 186Os/188Os measurements of rocks requires efficient digestion of finely-ground powders and complete spike-sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF-desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014)Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8to> 18% m/m, or as mass fractions, < 8 to> 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR-1, BHVO-2, TDB-1). To investigate the effect of HF-desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a‘standard acid digestion’ (2:1 mixture of concentrated HNO3 and HCl), and a standard acid digestion, followed by HF-desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF-desilicification. Desilicifi-cation procedures using HF do not improve liberation ofthe HSE from Azores basalts, or some RMs (e.g., WPR-1).We conclude that HF-desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re-Pt-Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF-desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured 187Os/188Os or 186Os/188Os.

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.

Day, JMD.  2018.  Geochemical constraints on residual metal and sulfide in the sources of lunar mare basalts. American Mineralogist. 103:1734-1740.   10.2138/am-2018-6368   Abstract

Low oxygen fugacity (fO2) in the lunar interior (one log unit below the iron-wüstite buffer [IW-1]) offers the possibility that stable Fe-metal and sulfide phases exist as restites within lunar mare basalt source regions. Metal and sulfide phases have high metal-melt and sulfide-melt partition coefficients for chalcophile, siderophile (>100), and highly siderophile elements (>>100,000 - HSE: Os, Ir, Ru, Rh, Pt, Pd, Re, Au). If these phases are residual after mare basalt extraction, they would be expected to retain significant quantities of these elements, likely generating non-chondritic HSE inter-element ratios, including Re/Os in the silicate magma. If such phases were present, the estimated HSE abundances of the bulk silicate Moon (BSM) would be proportionally higher than current estimates (0.00023 ±2 × CI chondrite), and perhaps closer to the bulk silicate Earth (BSE) estimate (0.009 ±2 × CI chondrite). Here I show that relationships between elements of similar incompatibility but with siderophile (W), chalcophile (Cu) and lithophile tendencies (Th, U, Yb) do not deviate from expected trends generated by magmatic differentiation during cooling and crystallization of mare basalts. These results, combined with chondrite-relative HSE abundances and near-chondritic measured 187Os/188Os compositions of primitive high-MgO mare basalts, imply that lunar mantle melts were generated from residual metal- and sulfide-free sources, or experienced complete exhaustion of metal and sulfides during partial melt extraction. Evidence for the loss of moderately volatile elements during lunar formation and early differentiation indicates that the BSM is >4 to 10 times more depleted in S than BSE. Because of an S-depleted BSM, mare basalt melts are unlikely to have reached S saturation, even if sulfide concentration at sulfide saturation (SCSS) was lowered relative to terrestrial values due to low lunar fO2. In the absence of residual sulfide or metal, resultant partial melt models indicate that a lunar mantle source with 25 to 75 ug g-1 S and high sulfide-melt partition coefficients can account for the chondritic relative abundances of the HSE in mare basalts from a BSM that experienced <0.02% by mass of late accretion.

Day, JMD, Taylor LA, Floss C, Patchen AD, Schnare DW, Pearson DG.  2006.  Comparative petrology, geochemistry, and petrogenesis of evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica. Geochimica Et Cosmochimica Acta. 70:1581-1600.   10.1016/j.gca.2005.11.015   AbstractWebsite

New data is presented for five evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica, LAP 02205, LAP 02224, LAP 02226, LAP 02436, and LAP 03632. These basalts have nearly identical mineralogies, textures, and geochemical compositions, and are therefore considered to be paired. The LaPaz basalts contain olivine (Fo(64-2)) and pyroxene (Fs(32)Wo(8)En(60) to Fs(84-86)Wo(15)En(2-0)) crystals that record extreme chemical fractionation to Fe-enrichment at the rims, and evidence for silicate liquid immiscibility and incompatible element enrichment in the mesostasis. The basalts also contain FeNi metals with unusually high Co and Ni contents, similar to some Apollo 12 basalts, and a single-phase network of melt veins and fusion crusts. The fusion crust has similar chemical characteristics to the whole rock for the LaPaz basalts, whereas the melt veins represent localized melting of the basalt and have an endogenous origin. The crystallization conditions and evolved nature of the LaPaz basalts are consistent with fractionation of olivine and chromite from a parental liquid similar in composition to some olivine-phyric Apollo 12 and Apollo 15 basalts or lunar low-Ti pyroclastic glasses. However, the young reported ages for the LaPaz mare basalts (similar to 2.9 Ga) and their relative incompatible element enrichment compared to Apollo mare basalts and pyroclastic glasses indicate they cannot be directly related. Instead, the LaPaz mare basalts may represent fractionated melts from a magmatic system fed by similar degrees of partial melting of a mantle source similar to that of the low-Ti Apollo mare basalts or pyroclastic glasses, but which possessed greater incompatible element enrichment. Despite textural differences, the LaPaz basalts and mare basalt meteorite NWA 032 have similar ages and compositions and may originate from the same magmatic system on the Moon. (c) 2005 Elsevier Inc. All rights reserved.

Day, JMD, O'Driscoll B, Strachan RA, Daly JS, Walker RJ.  2017.  Identification of mantle peridotite as a possible Iapetan ophiolite sliver in south Shetland, Scottish Caledonides. Journal of the Geological Society. 174(1):88-92.   Abstract

The Neoproterozoic Dunrossness Spilite Subgroup of south Shetland, Scotland, has been interpreted as a series of komatiitic and mafic lava flows formed in a marginal basin in response to Laurentian continental margin rifting. We show that ultramafic rocks previously identified as komatiites are depleted mantle peridotites that experienced seafloor hydrothermal alteration. The presence of positive Bouguer gravity and aeromagnetic anomalies extending from the Dunrossness Spilite Subgroup northward to the Shetland Ophiolite Complex suggests instead that these rocks may form part of an extensive ophiolite sliver, obducted during Iapetus Ocean closure in a forearc setting.

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.

Day, JMD, Walker RJ, James OB, Puchtel IS.  2010.  Osmium isotope and highly siderophile element systematics of the lunar crust. Earth and Planetary Science Letters. 289:595-605.   10.1016/j.epsl.2009.12.001   AbstractWebsite

Coupled (187)Os/(188)Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 +/- 0.3 pg g(-1) Os, 1.5 +/- 0.6 pg g(-1) Ir, 6.8 +/- 2.7 pg g(-1) Ru, 16 +/- 15 pg g(-1) Pt,33 +/- 30 pg g(-1) Pd and 0.29 +/- 0.10 pg g(-1) Re (similar to 0.00002 x Cl) and Re/Os ratios that were modestly elevated ((187)Re/(188)Os = 0.6 to 1.7) relative to Cl chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (similar to 0.00007 x Cl) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle-crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments. If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust-mantle concentration ratios (D-values) must be <= 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re.Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust-mantle HSE partitioning for the Earth and Moon are somewhat surprising. Low HSE abundances in the lunar crust, coupled with estimates of HSE concentrations in the lunar mantle implies there may be a 'missing component' of late-accreted materials (as much as 95%) to the Moon if the Earth/Moon mass-flux estimates are correct and terrestrial mantle HSE abundances were established by late accretion. (C) 2009 Elsevier B.V. All rights reserved.

Day, JMD, Koppers AAP, Mendenhall BC, Oller B.  2018.  The ‘Scripps Dike’ and its implications for mid-Miocene volcanism and tectonics of the California Continental Borderland. From the Mountains to the Abyss: The California Borderland as an Archive of Southern California Geologic Evolution - SEPM Special Publication. 110: Society for Sedimentary Geology   10.2110/sepmsp.110.02   Abstract

New field observations, petrology, geochemistry, and 40Ar/39Ar geochronology are reported for the Scripps Dike, which crops out at the coast north of La Jolla, California. The northeast–southwest-trending and laterally discontinuous dike has a basaltic–trachyandesite bulk composition,
with an emplacement age of 13.89 6 0.13 Ma. Modeling of the dike composition indicates that it formed from 0.5 to 1.5% partial melting of a primitive mantle-type source, metasomatized by slab fluids, predominantly in the garnet stability field. The composition of the dike, including relatively high MgO (6.6 wt.%) and Sr/Y (~105), makes it akin to magnesian andesites in Baja California, Mexico, termed ‘‘bajaites.’’ Field evidence indicates
that the current exposure of the dike is close to the original stalling depth, it was probably associated with explosive volcanism, and the dike flowed laterally. After accounting for alteration, the dike has an initial 87Sr/86Sr composition of 0.70390, with limited evidence for crustal contamination, consistent with derivation from a slab-fluid-metasomatized mantle source. The composition of the dike places it broadly in the range of Miocene California Continental Borderland (hereafter referred to as Borderland) volcanic rocks studied previously. A comparison of ages of volcanic rocks occurring along the Borderland margin reveals an approximately age-progressive trend to the southeast. This represents an opposite sense to the apparent ageprogressive trend for Miocene to Recent volcanic rocks north of the Western Transverse Ranges. Possible models to explain the compositions and age relationships of Miocene to Recent volcanic rocks of the Borderland region include southeasterly migration of volcanism in response to Rivera Triple Junction movement and slab window formation, or the presence of a weak ‘‘hotspot’’ that has been active since at least the Miocene. Identification of the process(es) responsible for Borderland volcanism is currently limited by dissection and northwestward movement of Borderland rocks in response to northwest–southeast shearing of the Pacific–North American plate boundary, and by the quality and quantity of reported age-dates and paleomagnetic information. The formation processes of volcanism in the Borderland have ramifications for palinspastic reconstruction of the margin, as well as for the thermal and magmatic evolution of western California in response to a change in plate motion in a subduction to transform setting. The Scripps Dike provides evidence that regions of the mantle beneath the California Continental Borderland were metasomatized by slab fluids in a manner similar to portions of mantle beneath central Baja California, Mexico.

Day, JMD, Hilton DR, Pearson DG, Macpherson CG, Kjarsgaard BA, Janney PE.  2005.  Absence of a high time-integrated He-3/(U+Th) source in the mantle beneath continents. Geology. 33:733-736.   10.1130/g21625.1   AbstractWebsite

Volcanic rocks from ocean island and continental flood basalt provinces can exhibit He-3/He-4 ratios greatly in excess of those of mid-oceanic-ridge basalts (MORB). High He-3/He-4 ratios must indicate derivation from a mantle source with high time-integrated He-3/(U+Th) relative to depleted MORB-source mantle. The location of the high He-3/He-4 mantle reservoir is a poorly resolved but important issue because of the constraints it places upon the structure and convective style of Earth's mantle. It has been proposed that the high He-3/He-4 reservoir resides in the upper mantle, rather than the lower mantle, because Earth should be volatile poor and highly differentiated, with incompatible elements (such as He) concentrated in the upper mantle and crust. This hypothesis can be tested using continental intraplate alkaline volcanics (CIAV) that are generated at or near the boundary between the conducting lithospheric and convecting asthenospheric mantle. Olivine and clinopyroxene phenocrysts from Cretaceous to Miocene CIAV from Canada, South Africa, and Uganda have He-3/He-4 ratios more radiogenic than MORB, strongly arguing against a widespread high He-3/He-4 source in the continental lithosphere or the underlying convecting upper mantle. Combined with a global data set of CIAV and continental lithosphere mantle xenoliths, these results provide no evidence for high He-3/He-4 in any samples known to originate from this environment. Therefore, volcanic rocks with He-3/He-4 greater than MORB He-3/He-4 are likely to sample a mantle source with high time-integrated He-3/(U+Th) that cannot exist within or below the continents. This reservoir is also unlikely to exist within the upper mantle as defined by the He-3/He-4 distribution in MORB.

Day, JMD.  2016.  Evidence against an ancient non-chondritic mantle source for North Atlantic Igneous Province lavas. Chemical Geology. 440:91-100.   10.1016/j.chemgeo.2016.07.002   Abstract

North Atlantic Igneous Province (NAIP) lavas host olivine with the highest 3He/4He ever measured for terrestrial
igneous rocks (up to 50 RA, or 4He/3He = ~15,300). The relationship of high-3He/4He with Pb isotope compositions
close to the terrestrial geochron and 143Nd/144Nd plausibly consistentwith supra-chondritic mantle Sm/Nd
in Baffin Island and West Greenland lavas has been interpreted to reflect an ancient ‘non-chondritic’ mantle
source signature. Alternatively, assimilation of continental crustal rocks with unradiogenic Pb isotope compositions
and low 143Nd/144Nd, into magmaswith high-3He/4He, and derived from variably depleted mantle sources,
could impart similar geochemical signatures. Radiogenic and stable isotope data for NAIP lavas are consistent
with origins as melts from upper mantle sources that contain low-18O/16O recycled lithosphere and/or hydrothermally
altered crust, or that have experienced pervasive contamination by crustal gneisses. Olivines from
NAIP lavas with 3He/4He spanning from 8 to 48 RA have δ18O ranging from 3.5 to 5.5‰. These compositions
are consistent with sources of ambient mantle and low-δ18O recycled lithosphere, or with concomitant crustal
assimilation and He-loss during fractional crystallization. Limited assimilation (≤1%) of incompatible element
rich crustal gneisses with low 206Pb/204Pb and 143Nd/144Nd by melts from variably depleted mantle sources
can explain Nd-Pb isotope compositions of Baffin Island and West Greenland picrites. Icelandic lavas provide
supporting evidence that the ancestral mantle plume responsible for generating NAIP magmatism sampled variably
enriched and depletedmantle,with no evidence for ancient non-chondriticmantle sources. Pervasive crustal
contamination and partial melting of heterogeneous mantle sources, generated by plate tectonic processes, can
account for the compositions of continental flood basalts (CFB),without the requirement of a non-chondritic terrestrial
reservoir. Combined with evidence that the 142Nd/144Nd composition of the bulk silicate Earth is due to
nucleosynthetic S-process deficits in chondrite meteorites, these observations cast doubt thatNAIP lavas sampled
a non-chondritic mantle source with Sm/Nd higher than in chondrites. If short-lived radiogenic (e.g.,
146Sm-142Nd, 182Hf-182W)isotope anomalies are found in CFB, theymust either reflect assimilation of isotopically
anomalous crustal materials, or partial melting of early-formed mantle heterogeneities produced by differentiation
and late accretion.

Day, JMD, Pearson GD, Hulbert LJ.  2013.  Highly siderophile element behaviour during flood basalt genesis and evidence for melts from intrusive chromitite formation in the Mackenzie large igneous province. Lithos. 182-183:242-258.   Abstract

The 1.27 Ga Coppermine continental flood basalt (CFB) province in northern Canada represents the extrusive manifestation of the 2.7 Mkm2 Mackenzie large igneous province (LIP) that includes the Mackenzie dyke swarm and the Muskox layered intrusion. New Re–Os isotope and highly siderophile element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundance data are reported together with whole-rock major- and trace-element abundances and Nd isotopes to examine the behaviour of the HSE during magmatic differentiation and to place constraints on the extent of crustal interaction with mantle-derived melts. Mineral chemistry and petrography are also reported for an unusual andesite glass flow (CM19; 4.9 wt.% MgO) found in close proximity to newly recognised picrites (> 20 wt.% MgO) in the lowermost stratigraphy of the Coppermine CFB. Compositions of mineral phases in CM19 are similar to the same phases found in Muskox Intrusion chromitites and the melt composition is equivalent to inclusions trapped within Muskox chromites. The apparently conflicting elevated HSE contents (e.g., 3.8 ppb Os) and mantle-like initial 187Os/188Os (γOs = + 2.2), versus stable isotope (δ18O = + 12‰) and lithophile element evidence (εNdi = − 12.8) for extensive crustal contamination, implicate an origin for CM19 as a magma mingling product formed within the Muskox Intrusion during chromitite genesis. Combined with Nd isotope data that places the feeder for lower Coppermine CFB picrites and basalts within the Muskox Intrusion, this result provides compelling evidence for direct processing of some CFB within upper-crustal magma chambers. The Coppermine CFB defines a 187Re–187Os isochron with an age of 1263 + 16/− 20 Ma and initial γOs = + 2.2 ± 0.8. The initial Os isotope composition for the Coppermine CFB is slightly higher than the near-primitive-mantle initial 187Os/188Os for the Muskox Intrusion (γOs = + 1.2 ± 0.3). This result is interpreted to reflect greater crustal contamination in extrusive CFB and the sensitivity of Os isotopes, compared with absolute HSE concentrations, for tracking crustal contributions.

Modelling of absolute and relative HSE abundances in global CFB reveals that HSE concentrations decrease with increasing fractionation for melts with < 8 ± 1 wt.% MgO, with picrites (> 13.5 wt.% MgO) from CFB (n = 98; 1.97 ± 1.77 ppb) having higher Os abundances than ocean island basalt (OIB) equivalents (n = 75; 0.95 ± 0.86 ppb). The differences between CFB and OIB picrite absolute Os abundances may result from higher degrees of partial melting to form CFB but may also reflect incorporation of trace sulphide in CFB picrites from magmas that reached S-saturation in upper-crustal magma chambers. Significant inter-element fractionation of (Re + Pt + Pd)/(Os + Ir + Ru) are generated during magmatic differentiation in response to strongly contrasting partitioning of these two groups of elements into sulphides and/or HSE-rich alloys. Furthermore, fractional crystallization has a greater role on absolute and relative HSE abundances than crustal contamination under conditions of CFB petrogenesis due to the dilution effect of continental crust, which has low total abundances of the HSE. Combined data for the basaltic and intrusive portions of the Mackenzie LIP indicate a mantle source broadly within the range of the primitive upper mantle. The majority of Archaean komatiites and Phanerozoic CFB also require mantle sources with primitive upper mantle to chondritic Re/Os evolution, with exceptions typically being from analyses of highly-fractionated MgO-poor basalts.

Day, JMD, Harvey RP, Hilton DR.  2019.  Melt-modified lithosphere beneath Ross Island and its role in the tectono-magmatic evolution of the West Antarctic Rift System. Chemical Geology. 518:45-54.   Abstract

Mantle lithosphere influences rift system tectonic evolution, yet the age and composition of rifted lithosphere is typically difficult to constrain due to limited sampling. In the West Antarctic Rift System (WARS), Cenozoic to recent alkaline volcanic rocks yield a variety of peridotite and pyroxenite xenoliths that allow sampling of lithosphere. We report osmium and helium isotope data, elemental abundances, and petrology, for a suite of xenoliths and lavas from the Hut Point Peninsula of Ross Island. Recently (<1.3 Ma) erupted basanites yield fresh dunite and harzburgite (olivine forsterite [Fo] 90.1-88.2), lherzolite (Fo90.6-87.4), and pyroxenite xenoliths (Fo89.3-87.3). The basanite lavas contain abundant large olivine xenocrysts (Fo89.7-88.0), with more ferroan matrix olivine grains (Fo83.7-81.2) and have HIMU-like incompatible trace-element signatures. The 3He/4He ratios (6.8 ±0.3RA; 2SD) defined by co-existing He-rich xenoliths indicate a mantle source distinct from high-3He/4He plume mantle. Pyroxenite and lherzolite xenoliths have similar relative abundances of incompatible trace elements to host lavas, whereas dunite xenoliths have refractory compositions. Melt-rock reaction occurring in the xenoliths is demonstrated by replacement by amphibole or clinopyroxene to form pyroxenite and lherzolite lithologies, or as amphibole-impregnated dunites. The 187Re-187Os systematics of the lavas, pyroxenites and lherzolites define an apparent isochron, with initial 187Os/188Os ratio of 0.1286 ±0.0001. The initial 187Os/188Os is within uncertainty of dunite and harzburgite xenolith Os isotope compositions (0.1279-0.1303). Pervasive evidence for melt-rock interaction indicates that the straight-line relationship in 187Re/188Os-187Os/188Os space is a mixing line between high Re/Os lavas with radiogenic 187Os/188Os, and dunite and harzburgite. Petrological and geochemical evidence indicates that dunite and harzburgite xenoliths represent young lithosphere, with rhenium depletion ages up to ~250 Ma. The timing of formation and composition of the Hut Point Peninsula xenoliths are consistent with both destruction and creation of mantle lithosphere during or after subduction along the Gondwana margin, prior to WARS formation. Modification of mantle lithosphere by subduction is also consistent with generation of HIMU-like metasomatized mantle reservoirs that fed Cenozoic to recent alkali volcanism of Mount Erebus and the WARS. The presence of young lithosphere within the WARS has collateral implications for rift dynamics and melting processes, especially beneath Mount Erebus, contrasting with older lithospheric mantle beneath the Trans-Antarctic Mountains and Marie Byrd Land.