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Day, JMD, O'Driscoll B.  In Press.  Ancient high Pt/Os crustal contaminants can explain radiogenic 186Os in intraplate magmas. Earth and Planetary Science Letters. Abstract

The origin of variations in 186Os/188Os ratios amongst mantle-derived basaltic and komatiitic lavas remains controversial, with opposing models arguing for deep core-mantle versus shallow mantle sources. Crustal contamination has generally not been favoured due to the low Os contents of such sources, meaning that variations in 186Os/188Os would require involvement of extremely high proportions of crustal material. Here we re-examine crustal contamination as an effective means for generating significant 186Os/188Os variations in Earth materials. Using chromitites and peridotites from the Stillwater, Muskox and Rum layered intrusions, we show that radiogenic 186Os/188Os ratios are correlated with 187Os/188Os ratios and can only be explained by shallow-level mixing processes and crustal contamination. The samples have 186Os ([{(186Os/188Ossample[t]/186Os/188OsPM(t)) -1} × 1000], where the modern primitive mantle [PM] 186Os/188Os is 0.1198388) values ranging between 0.04 to 0.15 for the ~2.7 Ga Stillwater Igneous Complex, -0.05 to 0.17 for the ~1.27 Ga Muskox Intrusion, and 0.02 to 0.13 for the ~0.06 Ga Rum Layered Suite. The highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) contents of the chromitites and peridotites can be modelled through high sulfide-melt partitioning (typically >8000) and emphasise the role of S-saturation and HSE scavenging. Considering the high sulfide-melt partitioning and accounting for high silicate melt to sulfide melt ratios (R-factor), it is possible to explain the variations in 186Os-187Os in layered intrusions using calculated Os isotope crustal evolution growth models. These calculations indicate that <4% of ancient high Pt/Os crustal contributions can explain the composition of the chromitites and peridotites that were examined. Our observations are consistent with published models for chromitite genesis that invoke either crustal melt-primitive melt mixing, or cumulate assimilation. A crustal origin for radiogenic 186Os is a possible cause for 186Os/188Os ratio variations observed in some komatiites. It is more difficult to explain radiogenic 186Os/188Os measured in Hawaiian lavas by crustal contamination processes. Instead, ancient high Pt/Os oceanic crust, shallow mantle sources such as metasomatic sulfide, or metal-rich large low-shear wave velocity provinces at the core-mantle boundary, all remain valid explanations.

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.

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.

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

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

Day, JMD, Sossi PA, Shearer CK, Moynier F.  2019.  Volatile distributions in and on the Moon revealed by Cu and Fe isotopes in the ‘Rusty Rock’ 66095. Geochimica et Cosmochimica Acta.   10.1016/j.gca.2019.02.036   Abstract

The Apollo 16 ‘Rusty Rock’ impact melt breccia 66095 is a volatile-rich sample, with the volatiles inherited through vapor condensation from an internal lunar source formed during thermo-magmatic evolution of the Moon. We report Cu and Fe isotope data for 66095 and find that bulk-rocks, residues and acid leaches span a relatively limited range of compositions (3.0 ±1.3 wt.% FeO [range = 2.0-4.8 wt.%], 5.4 ±3.1 ppm Cu [range = 3-12 ppm], average δ56Fe of 0.15 ± 0.05‰ [weighted mean = 0.16‰] and δ65Cu of 0.72 ± 0.14‰ [weighted mean = 0.78‰]). In contrast to the extreme enrichment of light isotopes of Zn and heavy isotopes of Cl in 66095, δ65Cu and δ56Fe in the sample lie within the previously reported range for lunar mare basalts (0.92 ± 0.16‰ and 0.12 ± 0.02‰, respectively). The lack of extreme isotopic fractionation for Cu and Fe isotopes reflects compositions inherent to 66095, with condensation of a cooling gas from impact-generated fumarolic activity at temperatures too low to lead to the condensation of Cu and Fe, but higher than required to condense Zn. Together with thermodynamic models, these constraints suggest that the gas condensed within 66095 between 700 and 900 °C (assuming a pressure of 10-6 and an fO2 of IW-2). That the Cu and Fe isotopic compositions of sample 66095 are within the range of mare basalts removes the need for an exotic, volatile-enriched source. The enrichment in Tl, Br, Cd, Sn, Zn, Pb, Rb, Cs, Ga, B, Cl, Li relative to Bi, Se, Te, Ge, Cu, Ag, Sb, Mn, P, Cr and Fe in the ‘Rusty Rock’ is consistent with volcanic outgassing models and indicates that 66095 likely formed distal from the original source of the gas. The volatile-rich character of 66095 is consistent with impact-generated fumarolic activity in the region of the Cayley Plains, demonstrating that volatile-rich rocks can occur on the lunar surface from outgassing of a volatile-poor lunar interior. The ‘Rusty Rock’ indicates that the lunar interior is significantly depleted in volatile elements and compounds and that volatile-rich lunar surface rocks likely formed through vapor condensation. Remote sensing studies have detected volatiles on the lunar surface, attributing them dominantly to solar wind. Based on the ‘Rusty Rock’, some of these surface volatiles may also originate from the Moon’s interior.

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

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

Peters, BJ, Shahar A, Carlson RW, Day JMD, Mock TD.  2019.  A sulfide perspective on iron isotope fractionation during ocean island basalt petrogenesis. Geochimica et Cosmochimica Acta. 245:59-78.   Abstract

Iron isotopic compositions are demonstrably powerful tracers of foundational planetary processes, including crust and core formation. In many volcanic environments, however, geochemical vestiges of these processes are obscured by the effects of magmatic differentiation on Fe isotopic compositions. Recent decades have witnessed continued refinement of observational and experimental approaches to Fe isotope fractionation during silicate differentiation. In contrast, the influence of sulfide fractionation on Fe isotopic compositions in terrestrial environments is known only from theoretical approaches and limited experimental data for relatively siliceous magmatic systems. One reason for this may be that sulfide fractionation is difficult to definitively trace using traditional major and minor element variation patterns. We utilize well-characterized lavas and cumulate xenoliths from Piton de la Fournaise and Piton des Neiges, Réunion Island, that have previously been examined for their highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) contents to investigate the effect of sulfide fractionation on Fe isotopes. The Fe isotopic compositions of the basalts range from δ56Fe values of 0.04 to 0.15‰ (average: 0.10‰) and the compositions of the cumulate xenoliths range from δ56Fe values of -0.07 to 0.08‰ (average: 0‰). In the absence of metal, HSE preferentially partition into sulfide phases, making them important tracers of sulfide segregation during magmatic differentiation. We find that commonly-observed co-variations between Fe isotopic compositions and major element oxide abundances are relatively underdeveloped for Réunion lavas. The correlation between Fe isotopic composition and MgO, for example, has a similar statistical significance to the correlation between Fe isotopic composition and Pd/Ir ratios, suggesting an important role of sulfides during Fe isotopic fractionation. After accounting for sulfide segregation, we determine that the parental magma Fe isotopic composition calculated for Piton de la Fournaise would be overestimated by 0.04‰ (within propagated error, 0.01-0.06‰) when considering silicate differentiation alone. An analogous calculation for Kilauea Iki basalts, for which there is available Fe isotopic and HSE data, yields a somewhat smaller difference of 0.02‰ (0-0.03‰). These differences may partially explain Fe isotopic compositions in other settings that could not previously be reconciled with a dominantly peridotitic and/or chondritic mantle source. This discovery may warrant discussion of the apparent decoupling between Fe and radiogenic isotopes in ocean island basalts, where the latter shows significant global variations and the former may show little or none. Our work highlights the need for additional constraints on the behavior of Fe isotopes during crustal recycling processes and reinforces the notion that consideration must be given to the effect of magmatic differentiation on Fe isotopic compositions.

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, Tait KT, Udry A, Moynier F, Liu Y, Neal CR.  2018.  Martian magmatism from plume metasomatized mantle. Nature Communications. 9:4799.   10.1038/s41467-018-07191-0   Abstract

Direct analysis of the composition of Mars is possible through delivery of meteorites to Earth. Martian meteorites include ∼165 to 2400 Ma shergottites, originating from depleted to enriched mantle sources, and ∼1340 Ma nakhlites and chassignites, formed by low degree partial melting of a depleted mantle source. To date, no unified model has been proposed to explain the petrogenesis of these distinct rock types, despite their importance for understanding the formation and evolution of Mars. Here we report a coherent geochemical dataset for shergottites, nakhlites and chassignites revealing fundamental differences in sources. Shergottites have lower Nb/Y at a given Zr/Y than nakhlites or chassignites, a relationship nearly identical to terrestrial Hawaiian main shield and rejuvenated volcanism. Nakhlite and chassignite compositions are consistent with melting of hydrated and metasomatized depleted mantle lithosphere, whereas shergottite melts originate from deep mantle sources. Generation of martian magmas can be explained by temporally distinct melting episodes within and below dynamically supported and variably metasomatized lithosphere, by long-lived, static mantle plumes.

Udry, A, Day JMD.  2018.  1.34 billion-year-old magmatism on Mars evaluated from the co-genetic nakhlite and chassignite meteorites. Geochimica et Cosmochimica Acta. 238:292-315.   Abstract

Nakhlite and chassignite martian meteorites have similar crystallization (1340 ± 40 Ma) and ejection (∼11 Ma) ages, and 87Rb-87Sr and 143Sm-144Nd compositions. Using a near-comprehensive suite of these rocks, we place further constraints on nakhlite and chassignite petrogenesis, utilizing bulk rock and mineral major- and trace-element compositions, and quantitative textural data for 17 samples, including three recent finds (Northwest Africa [NWA] 10153, NWA 10645, and NWA 11013). Bulk rock and mineral compositions indicate that nakhlites and chassignites originated from <5% partial melting of a highly depleted source, in the presence of residual garnet. Significant fractionation of olivine and pyroxene from parental magmas led to formation of cumulate dunites (chassignites), and augite-rich cumulates with relatively low abundances of interstitial material (nakhlites). We show that two nakhlite groups exist with high and low absolute trace-element abundances, which are consistent with groupings from previous studies based on mesostasis content and volatile element contents. The discrepancy between the parental melt and cumulate bulk rock compositions indicates that a missing fractionated melt composition complementary to nakhlites and chassignites should exist on Mars. Quantitative textural analyses of both nakhlites and chassignites are consistent with emplacement as distinct lava flows and/or magmatic bodies close to the martian surface, rather than from a single sill or lava flow sequence. Although originating from the same parental melt to nakhlites, chassignites likely represent cumulates that were either erupted as xenoliths, or occurred as crystal settling pods within dikes or sills and thus represent a different batch of flow/magma from the nakhlites. Determination of an ancient 207Pb-206Pb age (3.95 ± 0.16 Ga) for an apatite grain in NWA 998 is consistent with hydrothermal alteration of nakhlites by ancient crustal-derived fluids immediately following their emplacement. We interpret the apatite age, which is highly distinct from the crystallization age of nakhlites, to indicate addition of Cl-rich fluids driven by hydrothermal circulation of martian crustal brines during emplacement of the nakhlites and chassignites. Although the spatial location of nakhlites and chassignites at the martian surface remains unconstrained, our results indicate similar emplacement features to those observed in terrestrial volcano-magmatic systems.

Sato, KN, Andersson AJ, Day JMD, Taylor JRA, Frank MB, Jung JY, McKittrick J, Levin LA.  2018.  Response of sea urchin fitness traits to environmental gradients across the Southern California oxygen minimum zone. Frontiers in Marine Science. 5   10.3389/fmars.2018.00258   AbstractWebsite

Marine calcifiers are considered to be among the most vulnerable taxa to climate-forced environmental changes occurring on continental margins with effects hypothesized to occur on microstructural, biomechanical, and geochemical properties of carbonate structures. Natural gradients in temperature, salinity, oxygen, and pH on an upwelling margin combined with the broad depth distribution (100-1,100 m) of the pink fragile sea urchin, Strongylocentrotus (formerly Allocentrotus) fragilis, along the southern California shelf and slope provide an ideal system to evaluate potential effects of multiple climate variables on carbonate structures in situ. We measured, for the first time, trait variability across four distinct depth zones using natural gradients as analogues for species-specific implications of oxygen minimum zone (OMZ) expansion, deoxygenation and ocean acidification. Although S. fragilis may likely be tolerant of future oxygen and pH decreases predicted during the twenty-first century, we determine from adults collected across multiple depth zones that urchin size and potential reproductive fitness (gonad index) are drastically reduced in the OMZ core (450-900 m) compared to adjacent zones. Increases in porosity and mean pore size coupled with decreases in mechanical nanohardness and stiffness of the calcitic endoskeleton in individuals collected from lower pH(Total) (7.57-7.59) and lower dissolved oxygen (13-42 mu mol kg(-1)) environments suggest that S. fragilis may be potentially vulnerable to crushing predators if these conditions become more widespread in the future. In addition, elemental composition indicates that S. fragilis has a skeleton composed of the low Mg-calcite mineral phase of calcium carbonate (mean Mg/Ca = 0.02 mol mol(-1)), with Mg/Ca values measured in the lower end of values reported for sea urchins known to date. Together these findings suggest that ongoing declines in oxygen and pH will likely affect the ecology and fitness of a dominant echinoid on the California margin.

Tait, KT, Day JMD.  2018.  Chondritic late accretion to Mars and the nature of shergottite reservoirs. Earth and Planetary Science Letters. 494:99-108.   AbstractFree for 50 days

Mars is considered to have formed as a planetary embryo that experienced extensive differentiation early in its history. Shergottite meteorites preserve evidence for this history, and for late accretion events that affected their mantle sources within Mars. Here we report the first coupled 187Re–187Os, 87Sr/86Sr, highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) and major element abundance dataset for martian shergottites that span a range of MgO contents, from 6.4 to 30.3 wt.%. The shergottites range from picro-basalt to basaltic-andesite compositions, have enriched to depleted incompatible trace-element compositions, and define fractional crystallization trends, enabling the determination of HSE compatibility for martian magmatism in the order: Os > Ir ≥ Ru ≫ Pt ≥ Pd ≥ Re. This order of compatibility is like that defined previously for Earth and the Moon, but the fractionation of strongly compatible Os, Ir and Ru appears to take place at higher MgO contents in martian magmas, due to early onset of sulfide fractionation. In general, enriched shergottites have lower MgO contents than intermediate or depleted shergottites and have fractionated HSE patterns (Re + Pd + Pt > Ru + Ir + Os) and more radiogenic measured 87Sr/86Sr (0.7127–0.7235) and 187Os/188Os (0.140–0.247) than intermediate or depleted shergottite meteorites (87Sr/86Sr = 0.7010–0.7132; 187Os/188Os = 0.127–0.141). Osmium isotope compositions, corrected for crystallization age, define compositions that are implausibly unradiogenic in some enriched shergottites, implying recent mobilization of Re in some samples. Filtering for the effects of alteration and high Re/Os through crystal-liquid fractionation leads to a positive correlation between age-corrected Sr and Os isotope compositions. Mixing between hypothetical martian crustal and mantle reservoirs are unable to generate the observed Sr–Os isotope compositions of shergottites, which require either distinct and discrete long-term incompatible-element depleted and enriched mantle sources, or originate from hybridized melting of deep melts with metasomatized martian lithosphere. Using MgO-regression methods, we obtain a modified estimate of the bulk silicate Mars HSE composition of (in ng g−1) 0.4 [Re], 7.4 [Pd], 9.6 [Pt], 6.2 [Ru], 3.7 [Ir], 4 [Os], and a long-term chondritic 187Os/188Os ratio (∼0.1312). This result does not permit existing models invoking high-pressure and temperature partitioning of the HSE. Instead, our estimate implies 0.6–0.7% by mass of late accretion of broadly chondritic material to Mars. Our results indicate that Mars could have accreted earlier than Earth, but that disproportional accretion of large bodies and a relative constant flux of accretion of available materials in the first 50–100 Ma of Solar System led to the broad similarity in HSE abundances between Earth and Mars.

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

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

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.

O'Driscoll, B, Walker RJ, Clay PL, Day JMD, Ash RD, Daly JS.  2018.  Length-scales of chemical and isotopic heterogeneity in the mantle section of the Shetland Ophiolite Complex, Scotland. Earth and Planetary Science Letters. 488:144-154.   Abstract

Kilometre to sub-metre scale heterogeneities have been inferred in the oceanic mantle based on sampling of both ophiolites and abyssal peridotites. The ∼492 Ma Shetland Ophiolite Complex (SOC) contains a well-preserved mantle section that is dominated by harzburgite (∼70 vol.%) previously reported to have variable major and trace element compositions, yet dominantly chondritic initial 187Os/188Os compositions. To assess the preservation of compositional heterogeneities at sub-metre length-scales in the oceanic mantle, a ∼45 m2 area of the SOC mantle section was mapped and sampled in detail. Harzburgites, dunites and a pyroxenite from this area were analysed for lithophile and highly-siderophile element (HSE) abundances, as well as for 187Os/188Os ratios. Lithophile element data for most rocks are characteristic of supra-subduction zone (SSZ) metasomatic processes. Two dunites have moderately fractionated HSE patterns and suprachondritic γOs(492 Ma) values (+5.1 and +7.5) that are also typical of ophiolitic dunites generated by SSZ melt–rock interactions. By contrast, six harzburgites and four dunites have approximately chondritic-relative abundances of Os, Ir and Ru, and γOs(492 Ma) values ranging only from −0.6 to +2.7; characteristics that imply no significant influence during SSZ processes. Two harzburgites are also characterised by significantly less radiogenic γOs(492 Ma) values (−3.5 and −4), and yield Mesoproterozoic time of Re depletion (TRD) model ages. The range of Os isotope compositions in the studied area is comparable to the range reported for a suite of samples representative of the entire SOC mantle section, and approaches the total isotopic variation of the oceanic mantle, as observed in abyssal peridotites. Mechanisms by which this heterogeneity can be formed and preserved involve inefficient and temporally distinct melt extraction events and strong localised channelling of these melts.

Amsellam, E, Moynier F, Day JMD, Moriera M, Puchtel IS, Teng F-Z.  2018.  The stable strontium isotopic composition of ocean island basalts, mid-ocean ridge basalts, and komatiites. Chemical Geology. 483:595-602.   Abstract

The radiogenic 87Rb-87Sr system has been widely applied to the study of geological and planetary processes. In contrast, the stable Sr isotopic composition of the bulk silicate Earth (BSE) and the effects of igneous differentiation on stable Sr isotopes are not well-established. Here we report the stable Sr isotope (88Sr/86Sr, reported as δ88/86Sr, in parts per mil relative to NIST SRM 987) compositions for ocean islands basalts (OIB), mid-ocean ridge basalts (MORB) and komatiites from a variety of locations. Stable Sr isotopes display limited fractionation in a OIB sample suite from the Kilauea Iki lava lake suggesting that igneous processes have limited effect on stable Sr isotope fractionation (±0.12‰ over 20% MgO variation; 2sd). In addition, OIB (δ88/86Sr = 0.16–0.46‰; average 0.28 ± 0.17‰), MORB (δ88/86Sr = 0.27–0.34‰; average 0.31 ± 0.05‰) and komatiites (δ88/86Sr = 0.20–0.97‰; average 0.41 ± 0.16‰) from global localities exhibit broadly similar Sr stable isotopic compositions. Heavy stable Sr isotope compositions (δ88/86Sr > 0.5‰) in some Barberton Greenstone belt komatiites may reflect Archean seawater alteration or metamorphic processes and preferential removal of the lighter isotopes of Sr. To first order, the similarity among OIBs from three different ocean basins suggests homogeneity of stable Sr isotopes in the mantle. Earth's mantle stable Sr isotopic composition is established from the data on OIB, MORB and komatiites to be δ88/86Sr = 0.30 ± 0.02‰ (2sd). The BSE δ88/86Sr value is identical, within uncertainties, to the composition of carbonaceous chondrites (δ88/86Sr = 0.29 ± 0.06‰; 2sd) measured in this study.

Peters, BJ, Carlson RW, Day JMD, Horan MF.  2018.  Hadean silicate differentiation preserved by anomalous 142Nd/144Nd ratios in the Réunion hotspot source. Nature. 555:89-93.   doi:10.1038/nature25754   Abstract

Active volcanic hotspots can tap into domains in Earth’s deep interior that were formed more than two billion years ago1,2. High-precision data on variability in tungsten isotopes have shown that some of these domains resulted from differentiation events that occurred within the first fifty million years of Earth history3,4. However, it has not proved easy to resolve analogous variability in neodymium isotope compositions that would track regions of Earth’s interior whose composition was established by events occurring within roughly the first five hundred million years of Earth history5,6. Here we report 142Nd/144Nd ratios for Réunion Island igneous rocks, some of which are resolvably either higher or lower than the ratios in modern upper-mantle domains. We also find that Réunion 142Nd/144Nd ratios correlate with helium-isotope ratios (3He/4He), suggesting parallel behaviour of these isotopic systems during very early silicate differentiation, perhaps as early as 4.39 billion years ago. The range of 142Nd/144Nd ratios in Réunion basalts is inconsistent with a single-stage differentiation process, and instead requires mixing of a conjugate melt and residue formed in at least one melting event during the Hadean eon, 4.56 billion to 4 billion years ago. Efficient post-Hadean mixing nearly erased the ancient, anomalous 142Nd/144Nd signatures, and produced the relatively homogeneous 143Nd/144Nd composition that is characteristic of Réunion basalts. Our results show that Réunion magmas tap into a particularly ancient, primitive source compared with other volcanic hotspots7,8,9,10, offering insight into the formation and preservation of ancient heterogeneities in Earth’s interior.

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

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

Truong, TB, Castillo PR, Hilton DR, Day JMD.  2018.  The trace element and Sr-Nd-Pb isotope geochemistry of Juan Fernandez lavas reveal variable contributions from a high-3He/4He mantle plume. Chemical Geology. 476:280-291.   10.1016/j.chemgeo.2017.11.024   Abstract

The Juan Fernandez Islands in the southeastern Pacific are an atypical linear volcanic chain that exhibits a considerable range in 3He/4He ratios (8 to 18 RA, where RA is the 3He/4He ratio of air), but limited ranges of 87Sr/86Sr and 143Nd/144Nd. Here we report new trace element abundance data and Sr-Nd-Pb isotope data for mafic lavas previously analyzed for their 3He/4He and He contents from the two main islands of Robinson Crusoe and Alexander Selkirk. Lavas from these islands have been previously grouped based on geochemical and petrological classification into Group I and III basalts, and Group II basanites. In general, samples have overlapping Sr-Nd-Pb isotope compositions that suggest a common, albeit slightly heterogeneous mantle source. In detail, the Group I and III tholeiitic and alkalic basalts have nearly identical incompatible trace element patterns, whereas the Group II basanites show elevated incompatible trace element abundances. Major and incompatible trace element modeling indicates that Group III basalts (3He/4He = 7.8–9.5 RA) from younger Alexander Selkirk Island were produced by the highest degree of partial melting (> 10%) of a common mantle source, followed by Group I basalts (13.6–18.0 RA) and Group II basanites (11.2–12.5 RA) from older Robinson Crusoe Island. The 206Pb/204Pb of Group I basalts and Group II basanites are slightly more radiogenic and limited in range (19.163 to 19.292) compared with those of Group III (18.939 to 19.221). The Group I and II lavas from Robinson Crusoe are consistent with an origin from the so-called focus zone (FOZO) mantle component, whereas the Alexander Selkirk basalts additionally contain contributions from a less-enriched or relatively depleted mantle component. Juan Fernandez lavas reveal limited ranges of Sr-Nd-Pb isotopes but variable 3He/4He as their parental magmas originated mainly from the FOZO component with high 3He/4He (> 9 RA) and variably polluted with a depleted component with lower 3He/4He (ca. 8 RA). Contributions from high-3He/4He mantle sources to ocean island basalts can therefore vary both spatially and temporally, over meter to kilometer lengths and hundred to million-year time scales, and may not be strongly correlated to radiogenic lithophile isotope systematics.

Dhaliwal, JK, Day JMD, Moynier F.  2018.  Volatile element loss during planetary magma ocean phases. Icarus. 300:249-260.   10.1016/j.icarus.2017.09.002   Abstract

Moderately volatile elements (MVE) are key tracers of volatile depletion in planetary bodies. Zinc is an especially useful MVE because of its generally elevated abundances in planetary basalts, relative to other MVE, and limited evidence for mass-dependent isotopic fractionation under high-temperature igneous processes. Compared with terrestrial basalts, which have δ66Zn values (per mille deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard) similar to some chondrite meteorites (∼+0.3‰), lunar mare basalts yield a mean δ66Zn value of +1.4 ± 0.5‰ (2 st. dev.). Furthermore, mare basalts have average Zn concentrations ∼50 times lower than in typical terrestrial basaltic rocks. Late-stage lunar magmatic products, including ferroan anorthosite, Mg- and Alkali-suite rocks have even higher δ66Zn values (+3 to +6‰). Differences in Zn abundance and isotopic compositions between lunar and terrestrial rocks have previously been interpreted to reflect evaporative loss of Zn, either during the Earth-Moon formatting Giant Impact, or in a lunar magma ocean (LMO) phase. To explore the mechanisms and processes under which volatile element loss may have occurred during a LMO phase, we developed models of Zn isotopic fractionation that are generally applicable to planetary magma oceans. Our objective was to identify conditions that would yield a δ66Zn signature of ∼ +1.4‰ within the lunar mantle. For the sake of simplicity, we neglect possible Zn isotopic fractionation during the Giant Impact, and assumed a starting composition equal to the composition of the present-day terrestrial mantle, assuming both the Earth and Moon had zinc ‘consanguinity’ following their formation. We developed two models: the first simulates evaporative fractionation of Zn only prior to LMO mixing and crystallization; the second simulates continued evaporative fractionation of Zn that persists until ∼75% LMO crystallization. The first model yields a relatively homogenous bulk solid LMO δ66Zn value, while the second results in a stratification of δ66Zn values within the LMO sequence. Loss and/or isolation mechanisms for volatiles are critical to these models; hydrodynamic escape was not a dominant process, but loss of a nascent lunar atmosphere or separation of condensates into a proto-lunar crust are possible mechanisms by which volatiles could be separated from the lunar interior. The results do not preclude models that suggest a lunar volatile depletion episode related to Giant Impact. Conversely, LMO models for volatile loss do not require loss of volatiles prior to lunar formation. Outgassing during planetary magma ocean phases likely played a profound part in setting the volatile inventories of planets, particularly for low mass bodies that experienced the greatest volatile loss. In turn, our result suggest that the initial compositions of planets that accreted from smaller, highly differentiated planetesimals were likely to be severely volatile depleted.

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.

Dhaliwal, JK, Day JMD, Corder CA, Tait KT, Marti K, Assayag N, Cartigny P, Rumble D, Taylor LA.  2017.  Early metal-silicate differentiation during planetesimal formation revealed by acapulcoite and lodranite meteorites. Geochimica et Cosmochimica Acta. 216:115-140.   10.1016/j.gca.2017.06.042   AbstractWebsite

In order to establish the role and expression of silicate-metal fractionation in early planetesimal bodies, we have conducted a highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundance and 187Re-187Os study of acapulcoite-lodranite meteorites. These data are reported with new petrography, mineral chemistry, bulk-rock major and trace element geochemistry, and oxygen isotopes for Acapulco, Allan Hills (ALHA) 81187, Meteorite Hills (MET) 01195, Northwest Africa (NWA) 2871, NWA 4833, NWA 4875, NWA 7474 and two examples of transitional acapulcoite-lodranites, Elephant Moraine (EET) 84302 and Graves Nunataks (GRA) 95209. These data support previous studies that indicate that these meteorites are linked to the same parent body and exhibit limited degrees (<2–7%) of silicate melt removal. New HSE and osmium isotope data demonstrate broadly chondritic relative and absolute abundances of these elements in acapulcoites, lower absolute abundances in lodranites and elevated (>2 × CI chondrite) HSE abundances in transitional acapulcoite-lodranite meteorites (EET 84302, GRA 95209). All of the meteorites have chondritic Re/Os with measured 187Os/188Os ratios of 0.1271 ± 0.0040 (2 St. Dev.). These geochemical characteristics imply that the precursor material of the acapulcoites and lodranites was broadly chondritic in composition, and were then heated and subject to melting of metal and sulfide in the Fe-Ni-S system. This resulted in metallic melt removal and accumulation to form lodranites and transitional acapulcoite-lodranites. There is considerable variation in the absolute abundances of the HSE, both among samples and between aliquots of the same sample, consistent with both inhomogeneous distribution of HSE-rich metal, and of heterogeneous melting and incomplete mixing of silicate material within the acapulcoite-lodranite parent body. Oxygen isotope data for acapulcoite-lodranites are also consistent with inhomogeneous melting and mixing of accreted components from different nebular sources, and do not form a well-defined mass-dependent fractionation line. Modeling of HSE inter-element fractionation suggests a continuum of melting in the Fe-Ni-S system and partitioning between solid metal and sulfur-bearing mineral melt, where lower S contents in the melt resulted in lower Pt/Os and Pd/Os ratios, as observed in lodranites. The transitional meteorites, EET 84302 and GRA 95209, exhibit the most elevated HSE abundances and do not follow modelled Pt/Os and Pd/Os solid metal-liquid metal partitioning trends. We interpret this to reflect metal melt pooling into domains that were sampled by these meteorites, suggesting that they may originate from deeper within the acapulcoite-lodranite parent body, perhaps close to a pooled metallic ‘core’ region. Petrographic examination of transitional samples reveals the most extensive melting, pooling and networking of metal among the acapulcoite-lodranite meteorites. Overall, our results show that solid metal-liquid metal partitioning in the Fe-Ni-S system in primitive achondrites follows a predictable sequence of limited partial melting and metal melt pooling that can lead to significant HSE inter-element fractionation effects in proto-planetary materials.

Peters, BJ, Day JMD.  2017.  A geochemical link between plume head and tail volcanism. Geochemical Perspective Letters. 5:29-34.   10.7185/geochemlet.1742   Abstract

Geodynamical models of mantle plumes often invoke initial, high volume plume ‘head’ magmatism, followed by lower volume plume ‘tails’. However, geochemical links between plume heads, represented by flood basalts such as the Deccan Traps, and plume tails, represented by ocean islands such as La Réunion, are ambiguous, challenging this classical view of mantle plume theory. Using Sr-Nd-Os isotope data, we demonstrate a geochemical link between archetypal plume head and tail volcanism in the Réunion hotspot. Similar plume head-tail relationships have not been definitively shown in previous geochemical studies for Réunion or other global hotspots. Such a link is enabled by use of compatible elements, such as Os, which can circumvent complexities introduced by magmatic assimilation of crust or lithosphere because these elements are scarce in crust compared to primary mantle melts. We calculate Sr-Nd-Os isotopic compositions for the Réunion primary magma and find these are identical to predictions for the Deccan primary magma. Our result provides geochemical evidence for a temporally stable mantle plume that samples a primitive reservoir associated with the African large low-shear-velocity province and with a heritage beginning at the Cretaceous-Palaeogene boundary.

Clay, PL, Burgess R, Busemann H, Ruzie-Hamilton L, Joachim B, Day JMD, Ballentine CJ.  2017.  Halogens in chondritic meteorites and terrestrial accretion. Nature. 551:614-618.   10.1038/nature24625   Abstract

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15–37 times lower, respectively, than previously reported and usually accepted estimates1. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass2,3,4,5, cannot solely account for present-day terrestrial halogen inventories6,7. It is estimated that 80–90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs7,8 and have not undergone the extreme early loss observed in atmosphere-forming elements9. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases10, the efficient extraction of halogen-rich fluids6 from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion5,11,12,13,14.

Peters, BJ, Day JMD, Greenwood RC, Hilton DR, Gibson J, Franchi IA.  2017.  Helium-oxygen-osmium isotopic and elemental constraints on the mantle sources of the Deccan Traps. Earth and Planetary Science Letters. 478:245-257.   10.1016/j.epsl.2017.08.042   Abstract

The Deccan Traps, a 65 million-year-old continental flood basalt province located in western India, is the result of one of the largest short-lived magmatic events to have occurred on Earth. The nature and composition of its mantle source(s), however, have been difficult to resolve due to extensive assimilation of continental crust into the ascending Traps magmas. To circumvent this issue, using high-precision electron microprobe analysis, we have analyzed olivine grains from MgO-rich (up to 15.7wt.%) lavas that likely erupted before substantial crustal assimilation occurred. We compare olivine, pyroxene and plagioclase mineral chemistry and He–O–Os isotope compositions with bulk rock major-and trace-element abundances and 187Os/188Os for both bulk-rocks and mineral separates. Helium isotope compositions for the olivine grains generally show strong influence from crustal assimilation (<3 RA), but one ankaramite from the Pavagadh volcanic complex has a 3He/4He ratio of 10.7 RA, which is slightly lower than the range of 3He/4He measured for present-day Réunion Island volcanism (∼12–14 RA). Olivine-dominated mineral separates span a more restricted range in 187Os/188Os (0.1267 to 0.1443) compared with their host lavas (0.1186 to 0.5010), with the separates reflecting a parental magma composition less affected by lithospheric or crustal interaction than for the bulk-rocks. Despite significant He–Os isotopic variations, D17O is relatively invariant (−0.008 ±0.014 per mil)and indistinguishable from the bulk mantle, consistent with high-3He/4He hotspots measured to-date.

Compositions of olivine grains indicate the presence of up to 25% of a pyroxenite source for Deccan parental magmas, in good agreement with ∼20% predicted from isotopic data for the same samples. Modeled pyroxenite signatures appear like geochemical signatures expected to arise due to other types of mantle differentiation or due to assimilation of continental crust; however, we show that crustal assimilation cannot account for all of the compositional features of the olivine. Weak correlations exist between a global compilation of Xpx(Deccan: 0.2–0.7) and 3He/4He, δ18O (Deccan olivine: 4.9–5.2 per mil) and 187Os/188Os. Robust relationships between these parameters may be precluded due to a lack of two-reservoir source mixing, instead involving multiple mantle domains with distinct compositions, or because Xpxmay reflect both source features and crustal assimilation. Notwithstanding, geochemical similarities exist between Deccan Traps olivine (3He/4He =10.7 RA; 187Os/188Osi=0.1313 ±45, 2σ) and Réunion igneous rocks (3He/4He =12–14 RA; 187Os/188Osi=0.1324 ±14). These relationships imply that a characteristic geochemical ‘fingerprint’ may have persisted in the mantle plume that fed the Deccan Traps, since its inception at 65 Ma, to ongoing eruptions occurring on Réunion up to the present-day.