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2017
Amsellam, E, Moynier F, Pringle EA, Bouvier A, Chen H, Day JMD.  2017.  Testing the chondrule-rich accretion model for planetary embryos using calcium isotopes. Earth and Planetary Science Letters. 469:75-83.   10.1016/j.epsl.2017.04.022   Abstract

Understanding the composition of raw materials that formed the Earth is a crucial step towards
understanding the formation of terrestrial planets and their bulk composition. Calcium is the fifth most
abundant element in terrestrial planets and, therefore, is a key element with which to trace planetary
composition. However, in order to use Ca isotopes as a tracer of Earth’s accretion history, it is first
necessary to understand the isotopic behavior of Ca during the earliest stages of planetary formation.
Chondrites are some of the oldest materials of the Solar System, and the study of their isotopic
composition enables understanding of how and in what conditions the Solar System formed. Here we
present Ca isotope data for a suite of bulk chondrites as well as Allende (CV) chondrules. We show that
most groups of carbonaceous chondrites (CV, CI, CR and CM) are significantly enriched in the lighter Ca
isotopes (δ44/40Ca= +0.1 to +0.93) compared with bulk silicate Earth (δ44/40Ca= +1.05 ± 0.04,
Huang et al., 2010) or Mars, while enstatite chondrites are indistinguishable from Earth in Ca isotope
composition (δ44/40Ca = +0.91 to +1.06). Chondrules from Allende are enriched in the heavier
isotopes of Ca compared to the bulk and the matrix of the meteorite (δ44/40Ca = +1.00 to +1.21).
This implies that Earth and Mars have Ca isotope compositions that are distinct from most carbonaceous
chondrites but that may be like chondrules. This Ca isotopic similarity between Earth, Mars, and
chondrules is permissive of recent dynamical models of planetary formation that propose a chondrulerich
accretion model for planetary embryos.

Mundl, A, Touboul M, Jackson MG, Day JMD, Kurz MD, Lekic V, Helz RT, Walker RJ.  2017.  Tungsten-182 heterogeneity in modern ocean island basalts. Science. 356(6333):66-69.   10.1126/science.aal4179   Abstract

New tungsten isotope data for modern ocean island basalts (OIB) from Hawaii, Samoa, and Iceland reveal variable 182W/184W, ranging from that of the ambient upper mantle to ratios as much as 18 parts per million lower. The tungsten isotopic data negatively correlate with 3He/4He. These data indicate that each OIB system accesses domains within Earth that formed within the first 60 million years of solar system history. Combined isotopic and chemical characteristics projected for these ancient domains indicate that they contain metal and are repositories of noble gases. We suggest that the most likely source candidates are mega–ultralow-velocity zones, which lie beneath Hawaii, Samoa, and Iceland but not beneath hot spots whose OIB yield normal 182W and homogeneously low 3He/4He.

Lowder, KB, Allen MC, Day JMD, Deheyn DD, Taylor JRA.  2017.  Assessment of ocean acidification and warming on the growth, calcification, and biophotonics of a California grass shrimp. ICES Journal of Marine Science.   doi:10.1093/icesjms/fsw246   Abstract

Cryptic colouration in crustaceans, important for both camouflage and visual communication, is achieved through physiological and morphological mechanisms that are sensitive to changes in environmental conditions. Consequently, ocean warming and ocean acidification can affect crustaceans’ biophotonic appearance and exoskeleton composition in ways that might disrupt colouration and transparency. In the present study, we measured growth, mineralization, transparency, and spectral reflectance (colouration) of the caridean grass shrimp Hippolyte californiensis in response to pH and temperature stressors. Shrimp were exposed to ambient pH and temperature (pH 8.0, 17 °C), decreased pH (pH 7.5, 17 °C), and decreased pH/increased temperature (pH 7.5, 19 °C) conditions for 7 weeks. There were no differences in either Mg or Ca content in the exoskeleton across treatments nor in the transparency and spectral reflectance. There was a small but significant increase in percent growth in the carapace length of shrimp exposed to decreased pH/increased temperature. Overall, these findings suggest that growth, calcification, and colour of H. californiensis are unaffected by decreases of 0.5 pH units. This tolerance might stem from adaptation to the highly variable pH environment that these grass shrimp inhabit, highlighting the multifarious responses to ocean acidification, within the Crustacea.

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.

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

Pernet-Fisher, JF, Day JMD, Howarth GH, Ryabov VV, Taylor LA.  2017.  Atmospheric outgassing and native-iron formation during carbonaceous sediment–basalt melt interactions. Earth and Planetary Science Letters. 460:201-212.   http://dx.doi.org/10.1016/j.epsl.2016.12.022   Abstract

Organic carbon-rich sediment assimilation by basaltic magmas leads to enhanced emission of greenhouse gases during continental flood basalt eruptions. A collateral effect of these interactions is the generation of low oxygen fugacities (fO2)(below the iron-wüstite [IW] buffer curve) during magmatic crystallization, resulting in the precipitation of native-iron. The occurrence of native-iron bearing terrestrial basaltic rocks are rare, having been identified at three locations: Siberia, West Greenland, and Central Germany. We report the first combined study of Re–Os isotopes, highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re), and trace-element abundances for these three occurrences, in addition to host sediments at West Greenland. To quantify the amount of crustal assimilation experienced by the magmas, we present combined crystallization and assimilation models, together with fractional crystallization models, to assess how relative abundances of the HSE have been modified during crystallization. The radiogenic osmium isotopic compositions (γOsinitial +15 to +193) of mafic igneous samples are consistent with assimilation of old high Re/Os crustal contaminants with radiogenic 187Os/188Os, whereas the HSE inter-element fractionations (Pd/Os 2 to >10,000) suggest that some Siberian samples underwent an early stage of sulfide removal.

Metalliferous samples from the Siberian intrusions of Khungtukun and Dzhaltul (associated with the Siberian flood basalts) yield internal 187Re–187Os ages of 266 ±83 Ma and 249 ±50 Ma, respectively, reflecting late-Permian emplacement ages. These results imply that crustal assimilation took place prior to crystallization of native-Fe. In contrast, metalliferous samples from Disko Island and Bühl (associated with the West Greenland flood basalts, and the Central European Volcanic Province, respectively) have trends in 187Re/188Os–187Os/188Os space corresponding to apparent ages older than their reported crystallization ages. These anomalous ages probably reflect concurrent assimilation of high Re/Os, radiogenic 187Os crust during crystallization of native-Fe, consistent with the character of local West Greenland sediments. In all three locations, calculations of combined assimilation of crustal sediments and fractional crystallization indicate between 1–7% assimilation can account for the Os-isotope systematics. In the case of Siberian samples, incompatible trace-element abundances indicate that lower crustal assimilation may have also occurred, consistent with the suggestion that crustal assimilation took place prior to native-Fe precipitation. The extent of local crustal contamination at Siberia, West Greenland, and Bühl necessitates that significant quantities of CH4, CO, CO2, SO2and H2O were released during assimilation of carbonaceous sediments. Consequently, carbonaceous sediment–basalt melt interactions have collateral effects on total gas output from flood basalt volcanism into the atmosphere. However, the amount of carbonaceous sediment contamination experienced by melts forming the Khungtukun and Dzhaltul intrusions alone, cannot explain the major C-isotope excursions at the Permo–Triassic mass-extinction event. Instead, further unsampled intrusions that also experienced significant carbonaceous sediment–melt interactions would be required. Enhanced greenhouse gas-emission during the Permo–Triassic mass extinction may have been facilitated by a combination of mantle melting and carbonaceous sediment–melt interactions, together with other proposed mechanisms, including wildfires, or by microbial metabolic exhalation.

Day, JMD, Corder CA, Cartigny P, M. SA, Assayag N, Rumble D, Taylor LA.  2017.  A carbon-rich region in Miller Range 091004 and implications for ureilite petrogenesis. Geochimica et Cosmochimica Acta. 198:379-395.   10.1016/j.gca.2016.11.026   Abstract

Ureilite meteorites are partially melted asteroidal-peridotite residues, or more rarely, cumulates that can contain greater than three weight percent carbon. Here we describe an exceptional C-rich lithology, composed of 34 modal% large (up to 0.8 mm long) crystalline graphite grains, in the Antarctic ureilite meteorite Miller Range (MIL) 091004. This C-rich lithology is embedded within a silicate region composed dominantly of granular olivine with lesser quantities of low-Ca pyroxene, and minor FeNi metal, high-Ca pyroxene, spinel, schreibersite and troilite. Petrological evidence indicates that the graphite was added after formation of the silicate region and melt depletion. Associated with graphite is localized reduction of host olivine (Fo88-89) to nearly pure forsterite (Fo99), which is associated with FeNi metal grains containing up to 11 wt.% Si. The main silicate region is typical of ureilite composition, with highly siderophile element (HSE) abundances ∼0.3 × chondrite, 187Os/188Os of 0.1260 to 0.1262 and Δ17O of -0.81 ±0.16‰. Mineral trace-element analyses reveal that the rare earth elements (REE) and the HSE are controlled by pyroxene and FeNi metal phases in the meteorite, respectively. Modelling of bulk-rock REE and HSE abundances indicates that the main silicate region experienced ∼6% silicate and >50% sulfide melt extraction, which is at the lower end of partial melt removal estimated for ureilites. Miller Range 091004 demonstrates heterogeneous distribution of carbon at centimeter scales and a limited range in Mg/(Mg+Fe) compositions of silicate grain cores, despite significant quantities of carbon. These observations demonstrate that silicate rim reduction was a rapid disequilibrium process, and came after silicate and sulfide melt removal in MIL 091004. The petrography and mineral chemistry of MIL 091004 is permissive of the graphite representing late-stage C-rich melt that pervaded silicates, or carbon that acted as a lubricant during anatexis and impact disruption in the parent body. Positive correlation of Pt/Os ratios with olivine core compositions, but a wide range of oxygen isotope compositions, indicates that ureilites formed from a compositionally heterogeneous parent body that experienced variable sulfide and metal melt-loss that is most pronounced in relatively oxidized ureilites with Δ17O between -1.5 and ∼0‰.

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, 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.   http://dx.doi.org/10.1144/jgs2016-074   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.

2016
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.  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.

Pringle, EA, Moynier F, Savage PS, Jackson MG, Moriera M, Day JMD.  2016.  Silicon isotopes reveal recycled altered oceanic crust in the mantle sources of Ocean Island Basalts. Geochimica et Cosmochimica Acta. 189:282-295.   10.1016/j.gca.2016.06.008   Abstract

The study of silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to discern between different models for the origins of geochemical heterogeneities in the mantle. Relatively large (several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes relative to the dissolved Si. In contrast, only a limited range (tenths of a per mil) of Si isotope fractionation has been observed from high-temperature igneous processes. Therefore, Si isotopes may be useful as tracers for the presence of crustal material within OIB mantle source regions that experienced relatively low-temperature surface processes in a manner similar to other stable isotope systems, such as oxygen.

Characterizing the isotopic composition of the mantle is also of central importance to the use of the Si isotope system as a basis for comparisons with other planetary bodies (e.g., Moon, Mars, asteroids). Here we present the first comprehensive suite of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIB. Samples originate from ocean islands in the Pacific, Atlantic, and Indian Ocean basins and include representative endmembers for the EM-1, EM-2, and HIMU mantle components. On average, d30Si values for OIB (0.32 ± 0.09‰, 2 sd) are in general agreement with previous estimates for the d30Si value of Bulk Silicate Earth (0.29 ± 0.07‰, 2 sd; Savage et al., 2014). Nonetheless, some small systematic variations are present; specifically, most HIMU-type (Mangaia; Cape Verde; La Palma, Canary Islands) and Iceland OIB are enriched in the lighter isotopes of Si (d30Si values lower than MORB), consistent with recycled altered oceanic crust and lithospheric mantle in their mantle sources.

Peters, BJ, Day JMD, Taylor LA.  2016.  Early mantle heterogeneities in the Réunion hotspot source inferred from highly siderophile elements in cumulate xenoliths. Earth and Planetary Science Letters. 448:150-160.   10.1016/j.epsl.2016.05.015   Abstract

Ultramafic cumulate rocks form during intrusive crystallization of high-MgO magmas, incorporating relatively high abundances of compatible elements, including Cr and Ni, and high abundances of the highly siderophile elements (HSE: Os, Ir, Ru, Pt, Pd, Re). Here, we utilize a suite of cumulate xenoliths from Piton de la Fournaise, La Réunion (Indian Ocean), to examine the mantle source composition of the Réunion hotspot using HSE abundances and Os isotopes. Dunite and wherlite xenoliths and associated lavas from the Piton de la Fournaise volcanic complex span a range of MgO contents (46 to 7 wt.%), yet exhibit remarkably homogeneous 187Os/188Os (0.1324±0.0014, 2σ), representing the Os-isotopic composition of Réunion hotspot primary melts. A significant fraction of the xenoliths also have primitive upper-mantle (PUM) normalized HSE patterns with elevated Ru and Pd (PUM-normalized Ru/Ir and Pd/Ir of 0.8–6.3 and 0.2–7.2, respectively). These patterns are not artifacts of alteration, fractional crystallization, or partial melting processes, but rather require a primary magma with similar relative enrichments. Some highly olivine-phyric (>40 modal percent olivine) Piton de la Fournaise lavas also preserve these relative Ru and Pd enrichments, while others preserve a pattern that is likely related to sulfur saturation in evolved melts.

The estimate of HSE abundances in PUM indicates high Ru/Ir and Pd/Pt values relative to carbonaceous, ordinary and enstatite chondrite meteorite groups. Thus, the existence of cumulate rocks with even more fractionated HSE patterns relative to PUM suggests that the Réunion hotspot samples a yet unrecognized mantle source. The origin of fractionated HSE patterns in Réunion melts may arise from sampling of a mantle source that experienced limited late accretion (<0.2% by mass) compared with PUM (0.5–0.8%), possibly involving impactors that were distinct from present-day chondrites, or limited core–mantle interactions. Given the remarkably homogeneous Os, Pb, and noble-gas isotopic signatures of Réunion, which plot near the convergence point of isotopic data for many hotspots, such a conclusion provides evidence for an early differentiated and subsequently isolated mantle domain that may be partially sampled by some ocean island basalts.

Day, JMD.  2016.  Siderophile Elements. Encyclopedia of Geochemistry. ( White WM, Ed.).: Springer   10.1007/978-3-319-39193-9_234-1  
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, 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.

Harvey, J, Day JMD.  2016.  Highly siderophile and strongly chalcophile elements in high temperature geochemistry and cosmochemistry. (81):774pp.: Mineralogical Society of America   10.2138/rmg.2015.81.00  
Gannoun, A, Burton KW, Day JMD, Harvey J, Schiano P, Parkinson I.  2016.  Highly Siderophile Element and Os Isotope Systematics of Volcanic Rocks at Divergent and Convergent Plate Boundaries and in Intraplate Settings. Reviews in Mineralogy and Geochemistry. 81:651-724.   10.2138/rmg.2016.81.11   Abstract

Terrestrial magmatism is dominated by basaltic compositions. This definition encompasses mid-ocean ridge basalts (MORB), which account for more than eighty percent of Earth’s volcanic products and which are formed at divergent oceanic plate margins, as well as intraplate volcanic rocks such as ocean island basalts (OIB), continental flood basalts (CFB) and continental rift-related basalts, and highly magnesian ultramafic volcanic rocks that dominantly occur in Archean terranes, termed komatiites. All of these broadly basaltic rocks are considered to form by partial melting of the upper mantle, followed by extraction from their source regions and emplacement at the Earth’s surface. For these reasons, basalts can be used to examine the nature and extent of partial melting in the mantle, the compositions of mantle sources, and the interactions between the crust and mantle. Because much of Earth’s mantle is inaccessible, basalts offer some of the best ‘proxies’ for examining mantle composition, mantle convection and crust–mantle interactions. By contrast, at arcs, volcanism is dominated by andesitic rock compositions. While some arcs do have basaltic and picritic magmatism, these magma types are rare in convergent plate margin settings and reflect the complex fractional crystallization and often associated concomitant assimilation processes occurring in arcs. Despite the limited occurrence of high MgO magmas in arc volcanic rocks, magmas from this tectonic setting are also important for elucidating the behavior of the HSE from creation of basaltic compositions at mid-ocean ridges to the subduction of this crust beneath arcs at convergent plate margins.

Day, JMD, Brandon AD, Walker RJ.  2016.  Highly Siderophile Elements in Earth, Mars, the Moon, and Asteroids. Reviews in Mineralogy and Geochemistry. 81:161-238.   10.2138/rmg.2016.81.04   Abstract

The highly siderophile elements (HSE: Os, Ir, Ru, Rh, Pt, Pd, Re, Au) are key tracers of planetary accretion and differentiation processes due to their affinity for metal relative to silicate. Under low-pressure conditions the HSE are defined by having metal–silicate partition coefficients in excess of 104 (e.g., Kimura et al. 1974; Jones and Drake 1986; O’Neill et al. 1995; Borisov and Palme 1997; Mann et al. 2012). The HSE are geochemically distinct in that, with the exception of Au, they have elevated melting points relative to iron (1665 K), low vapour pressures, and are resistant to corrosion or oxidation. Under solar nebular conditions, Re, Os, Ir, Ru, Rh, and Pt, along with the moderately siderophile elements (MSE) Mo and W, condense as refractory-metal alloys. Palladium and Au are not as refractory and condense in solid solution with FeNi metal (Palme 2008). Assuming abundances of the HSE in materials that made up the bulk Earth were broadly similar to modern chondrite meteorites, mass balance calculations suggest that >98% of these elements reside in the metallic core (O’Neill and Palme 1998). In practical terms, the resultant low HSE abundance inventories in differentiated silicate crusts and mantles enables the use of these elements in order to effectively track metallic core formation and the subsequent additions of HSE-rich impactors to planets and asteroids (Fig. 1). In detail, the absolute and relative abundances of the HSE in planetary materials are also affected by mantle and crustal processes including melting, metasomatism, fractional crystallization, and crust-mantle remixing, as well as later impact processing, volatility of Re under oxidizing conditions, and low-temperature secondary alteration (cf., Day 2013; Gannoun et al. 2016, this volume). In the absence of metal, the HSE are chalcophile, so these elements are also affected by processes

2015
Day, JMD, Corder CA, Rumble D, Assayag N, Cartigny P, Taylor LA.  2015.  Differentiation processes in FeO-rich asteroids revealed by the achondrite Lewis Cliff 88763. Meteoritics & Planetary Science. 50:1750-1766.   10.1111/maps.12509   AbstractWebsite

Olivine-dominated (70-80 modal %) achondrite meteorite Lewis Cliff (LEW) 88763 originated from metamorphism and limited partial melting of a FeO-rich parent body. The meteorite experienced some alteration on Earth, evident from subchondritic Re/Os, and redistribution of rhenium within the sample. LEW 88763 is texturally similar to winonaites, has a Delta O-17 value of -1.19 +/- 0.10 parts per thousand, and low bulk-rock Mg/(Mg+Fe) (0.39), similar to the FeO-rich cumulate achondrite Northwest Africa (NWA) 6693. The similar bulk-rock major-, minor-, and trace-element abundances of LEW 88763, relative to some carbonaceous chondrites, including ratios of Pd/Os, Pt/Os, Ir/Os, and Os-187/Os-188 (0.1262), implies a FeO-and volatile-rich precursor composition. Lack of fractionation of the rare earth elements, but a factor of approximately two lower highly siderophile element abundances in LEW 88763, compared with chondrites, implies limited loss of Fe-Ni-S melts during metamorphism and anatexis. These results support the generation of high Fe/Mg, sulfide, and/or metal-rich partial melts from FeO-rich parent bodies during partial melting. In detail, however, LEW 88763 cannot be a parent composition to any other meteorite sample, due to highly limited silicate melt loss (0 to << 5%). As such, LEW 88763 represents the least-modified FeO-rich achondrite source composition recognized to date and is distinct from all other meteorites. LEW 88763 should be reclassified as an anomalous achondrite that experienced limited Fe, Ni-FeS melt loss. Lewis Cliff 88763, combined with a growing collection of FeO-rich meteorites, such as brachinites, brachinite-like achondrites, the Graves Nunataks (GRA) 06128/9 meteorites, NWA 6693, and Tafassasset, has important implications for understanding the initiation of planetary differentiation. Specifically, regardless of precursor compositions, partial melting and differentiation processes appear to be similar on asteroidal bodies spanning a range of initial oxidation states and volatile contents.

Kato, C, Moynier F, Valdes M, Dhaliwal JK, Day JMD.  2015.  Extensive volatile loss during formation and differentiation of the Moon. Nature Communications. 6(7617)   10.1038/ncomms8617   Abstract

Low estimated lunar volatile contents, compared with Earth, are a fundamental observation for Earth–Moon system formation and lunar evolution. Here we present zinc isotope and abundance data for lunar crustal rocks to constrain the abundance of volatiles during the final stages of lunar differentiation. We find that ferroan anorthosites are isotopically heterogeneous, with some samples exhibiting high d66Zn, along with alkali and magnesian suite samples. Since the plutonic samples were formed in the lunar crust, they were not subjected to degassing into vacuum. Instead, their compositions are consistent with enrichment of the silicate portions of the Moon in the heavier Zn isotopes. Because of the difference in d66Zn between bulk silicate Earth and lunar basalts and crustal rocks, the volatile loss likely occurred in two stages: during the proto-lunar disk stage, where a fraction of lunar volatiles accreted onto Earth, and from degassing of a differentiating lunar magma ocean, implying the possibility of isolated, volatile-rich regions in the Moon’s interior.

O'Driscoll, B, Walker RJ, Day JMD, Ash RD, Daly JS.  2015.  Generations of Melt Extraction, Melt–Rock Interaction and High-Temperature Metasomatism Preserved in Peridotites of the∼ 497 Ma Leka Ophiolite Complex, Norway. Journal of Petrology. 56(9):1797-1828.   10.1093/petrology/egv055   Abstract

Ophiolites allow spatial and temporal assessment of the causes and length-scales of upper mantle compositional heterogeneity because they permit field-based observations to be coupled with geochemical investigations of upper mantle lithologies. The ∼497 Ma Leka Ophiolite Complex (Norway) comprises a section of early Palaeozoic (Iapetus) oceanic lithosphere with well-exposed mantle and lower crustal sections and generally low degrees of serpentinization. The Leka upper mantle section is heterogeneous at the centimetre to metre scale, manifested by abundant dunite lenses and sheets in harzburgitic host-rock, especially within ∼500 m of the palaeo Moho. Abundant chromitite (≥60 vol. % Cr-spinel) and pyroxenite lenses and layers also occur in the uppermost 200–300 m of the mantle section. These diverse mantle lithologies probably developed in a suprasubduction-zone (SSZ) setting, as a result of fluid-assisted melt extraction, offering an opportunity to interrogate the nature of chemical heterogeneities developed in such rocks. At ∼497 Ma, the Os isotopic compositions of Leka harzburgites averaged ∼2% more radiogenic than the projected average for abyssal peridotites at that time, yet they exhibit nearly chondritic relative abundances of the highly siderophile elements (HSE). Several of the harzburgites are characterized by low initial 187Os/188Os (<0·121), reflecting Proterozoic melt depletion. Preservation of Os isotopic compositions consistent with ancient (<0·5 to 2 Ga) melt depletion episodes is a common characteristic of melt-depleted oceanic peridotites. There is no clear evidence that SSZ melt extraction had a discernible impact on the bulk Os isotopic composition of the Iapetus oceanic mantle, as represented by the Leka harzburgites. By contrast, non-harzburgitic lithologies are generally characterized by more radiogenic initial 187Os/188Os and more variable HSE abundances. The dunites, chromitites and pyroxenites of the LOC can be separated into two groups on the basis of their trace element geochemistry and the Re-Os isotope errorchrons that they define, yielding ages of 485 ± 32 Ma and 589 ± 15 Ma, respectively. The former age corresponds, within error, to the accepted age of the ophiolite (497 ± 2 Ma). The meaning of the latter age is uncertain, but possibly corresponds to the early stages of Iapetus opening. The Leka ophiolite reveals the importance of oceanic lithosphere formation processes for mantle heterogeneity at metre to kilometre scales, but also emphasizes the robustness of Os isotopes in recording older melt-depletion events.

Day, JMD, Barry PH, Hilton DR, Burgess R, Pearson DG, Taylor LA.  2015.  The helium flux from the continents and ubiquity of low-3He/4He recycled crust and lithosphere. Geochimica et Cosmochimica Acta. 153:116-133.   http://dx.doi.org/10.1016/j.gca.2015.01.008   AbstractWebsite

New helium isotope and trace-element abundance data are reported for pyroxenites and eclogites from South Africa, Siberia, and the Beni Bousera Massif, Morocco that are widely interpreted to form from recycled oceanic crustal protoliths. The first He isotope data are also presented for Archaean peridotites from the Kaapvaal (South Africa), Slave (Canada), and Siberian cratons, along with recently emplaced off-craton peridotite xenoliths from Kilbourne Hole, San Carlos (USA) and Vitim (Siberia), to complement existing 3He/4He values obtained for continental and oceanic peridotites. Helium isotope compositions of peridotite xenoliths vary from 7.3 to 9.6 RA in recently (<10 kyr) emplaced xenoliths, to
0.05 RA in olivine from cratonic peridotite xenoliths of the 1179 Ma Premier kimberlite, South Africa. The helium isotope compositions of the peridotites can be explained through progressive sampling of 4He produced from radiogenic decay of U and Th in the mineral lattice in the older emplaced peridotite xenoliths. Ingrowth of 4He is consistent with generally higher 4He concentrations measured in olivine from older emplaced peridotite xenoliths relative to those from younger peridotite xenoliths. Collectively, the new data are consistent with pervasive open-system behaviour of He in peridotite xenoliths from cratons, mobile belts and tectonically-active regions. However, there is probable bias in the estimate of the helium isotope composition of the continental lithospheric mantle (6.1 ± 2.1 RA), since previously published databases were largely derived from peridotite xenoliths from non-cratonic lithosphere, or phenocrysts/xenocrysts obtained within continental intraplate alkaline volcanics that contain a contribution from asthenospheric sources. Using the new He isotope data for cratonic peridotites and assuming that significant portions (>50%) of the Archaean and Proterozoic continental lithospheric mantle are stable and unaffected by melt or fluid infiltration on geological timescales (>0.1 Ga), and that U and Th contents vary between cratonic lithosphere and non-cratonic lithosphere, calculations yield a 3He flux of 0.25–2.2 atoms/s/cm2 for the continental lithospheric mantle. These estimates differ by a factor of ten from non-cratonic lithospheric mantle and are closer to the
observed 3He flux from the continents (<1 atoms/s/cm2). Pyroxenites and eclogites from the continental regions are all characterized by 3He/4He (0.03–5.6 RA) less than the depleted upper mantle, and relatively high U and Th contents. Together with oceanic and continental lithospheric peridotites, these materials represent reservoirs with low time-integrated 3He/(U + Th) in the mantle. Pyroxenites and eclogites are also characterized by higher Fe/Mg, more radiogenic Os–Pb isotope compositions, and more variable d18O values (3 to 7 per mille), compared with peridotitic mantle. These xenoliths are widely interpreted to be the metamorphic/metasomatic equivalents of
recycled oceanic crustal protoliths. The low-3He/4He values of these reservoirs and their distinctive compositions make themprobable end-members to explain the compositions of some low-3He/4He OIB, and provide an explanation for the low-3He/4He measured in most HIMU lavas. Continental lithospheric mantle and recycled oceanic crust protoliths are not reservoirs for high-3He/4He and so alternative, volumetrically significant, He-rich reservoirs, such as less-degassed (lower?) mantle, are required to explain high-3He/4He signatures measured in some intraplate lavas. Recycling of oceanic crust represents a fundamental process for the generation of radiogenic noble gases in the mantle, and can therefore be used effectively as tracers for volatile recycling.

Barry, PH, Hilton DR, Day JMD, Pernet-Fisher JF, Howarth GH, Magna T, Agashev AM, Pokhilenko NP, Pokhilenko LH, Taylor LA.  2015.  Helium isotopic evidence for modification of the cratonic lithosphere during the Permo-Triassic Siberian flood basalt event. Lithos. 216-217:73-80.   10.1016/j.lithos.2014.12.001   Abstract

Major flood basalt emplacement events can dramatically alter the composition of the sub-continental lithospheric mantle (SCLM). The Siberian craton experienced one of the largest flood basalt events preserved in the geologic record — eruption of the Permo-Triassic Siberian flood basalts (SFB) at ~250 Myr in response to upwelling of a deep-rooted mantle plume beneath the Siberian SCLM. Here,we present helium isotope (3He/4He) and concentration data for petrologically-distinct suites of peridotitic xenoliths recovered from two temporally-separated kimberlites:
the 360 Ma Udachnaya and 160 Ma Obnazhennaya pipes, which erupted through the Siberian SCLM and bracket the eruption of the SFB. Measured 3He/4He ratios span a range from 0.1 to 9.8 RA (where RA = air 3He/4He) and fall into two distinct groups: 1) predominantly radiogenic pre-plume Udachnaya samples (mean clinopyroxene 3He/4He = 0.41 ± 0.30 RA (1σ); n = 7 excluding 1 outlier), and 2) ‘mantle-like’ post plume Obnazhennaya samples (mean clinopyroxene 3He/4He=4.20±0.90 RA (1σ); n=5 excluding 1 outlier). Olivine separates from both kimberlite pipes tend to have higher 3He/4He than clinopyroxenes (or garnet). Helium contents in Udachnaya samples ([He] = 0.13–1.35 μcm3STP/g; n = 6) overlap with those of Obnazhennaya
([He]=0.05–1.58 μcm3STP/g; n = 10), but extend to significantly higher values in some instances ([He]=49–349 μcm3STP/g; n = 4). Uranium and thorium contents are also reported for the crushed material from which He was extracted in order to evaluate the potential for He migration from the mineral matrix to fluid inclusions. The wide range in He content, together with consistently radiogenic He-isotope values in Udachnaya peridotites suggests that crustal-derived fluids have incongruently metasomatized segments of the Siberian SCLM, whereas high 3He/4He values in Obnazhennaya peridotites show that this section of the SCLM has been overprinted by Permo-Triassic (plume-derived) basaltic fluids. Indeed, the stark contrast between pre- and post-plume 3He/4He ratios in peridotite xenoliths highlights the potentially powerful utility of He-isotopes for differentiating between various types of metasomatism (i.e., crustal versus basaltic fluids).