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Cabral, RA, Jackson MG, Rose-Koga EF, Koga KT, Whitehouse MJ, Antonelli MA, Farquhar J, Day JMD, Hauri EH.  2013.  Anomalous sulphur isotopes in plume lavas reveal deep mantle storage of Archaean crust. Nature. 496:490-+.   10.1038/nature12020   AbstractWebsite

Basaltic lavas erupted at some oceanic intraplate hotspot volcanoes are thought to sample ancient subducted crustal materials(1,2). However, the residence time of these subducted materials in the mantle is uncertain and model-dependent(3), and compelling evidence for their return to the surface in regions of mantle upwelling beneath hotspots is lacking. Here we report anomalous sulphur isotope signatures indicating mass-independent fractionation (MIF) in olivine-hosted sulphides from 20-million-year-old ocean island basalts from Mangaia, Cook Islands (Polynesia), which have been suggested to sample recycled oceanic crust(3,4). Terrestrial MIF sulphur isotope signatures (in which the amount of fractionation does not scale in proportion with the difference in the masses of the isotopes) were generated exclusively through atmospheric photochemical reactions until about 2.45 billion years ago(5-7). Therefore, the discovery of MIF sulphur in these young plume lavas suggests that sulphur-probably derived from hydrothermally altered oceanic crust-was subducted into the mantle before 2.45 billion years ago and recycled into the mantle source of Mangaia lavas. These new data provide evidence for ancient materials, with negative Delta S-33 values, in the mantle source for Mangaia lavas. Our data also complement evidence for recycling of the sulphur content of ancient sedimentary materials to the subcontinental lithospheric mantle that has been identified in diamond-hosted sulphide inclusions(8,9). This Archaean age for recycled oceanic crust also provides key constraints on the length of time that subducted crustal material can survive in the mantle, and on the timescales of mantle convection from subduction to upwelling beneath hotspots.

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, Ash RD, Liu Y, Bellucci JJ, Rumble D, McDonough WF, Walker RJ, Taylor LA.  2009.  Asteroids and andesites. Nature. 459:E2.   doi:10.1038/nature08078   Abstract

Arculus et al.1 raise an important question regarding the use of terrestrial rock nomenclature to characterize extraterrestrial materials. Here the issue relates to the definition of ‘andesite’, and whether the felsic achondrite meteorites GRA 06128 and GRA 06129 (GRA 06128/9) can and should be classified using this term2. More broadly, the question is whether extraterrestrial rocks should be classified using standard petrologic and geochemical criteria, such as mineralogy and major-element bulk composition, developed for the description of terrestrial rocks3,4. The approach of Arculus et al.1 is that petrogenetic process is of equal or greater importance when classifying a rock. This question must ultimately be decided by the scientific community.

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‰.

Hyde, BC, Day JMD, Tait KT, Ash RD, Holdsworth DW, Moser DE.  2014.  Characterization of weathering and heterogeneous mineral phase distribution in brachinite Northwest Africa 4872. Meteoritics and Planetary Science. 49(7):1141-1156.   10.1111/maps.12320   Abstract

Terrestrial weathering of hot desert achondrite meteorite finds and heterogeneous phase distributions in meteorites can complicate interpretation of petrological and geochemical information regarding parent-body processes. For example, understanding the effects of weathering is important for establishing chalcophile and siderophile element distributions within sulfide and metal phases in meteorites. Heterogeneous mineral phase distribution in relatively coarsely grained meteorites can also lead to uncertainties relating to compositional representativeness. Here, we investigate the weathering and high-density (e.g., sulfide, spinel, Fe-oxide) phase distribution in sections of ultramafic achondrite meteorite Northwest Africa (NWA) 4872. NWA 4872 is an olivine-rich brachinite (Fo63.6 ± 0.5) with subsidiary pyroxene (Fs9.7 ± 0.1Wo46.3 ± 0.2), Cr-spinel (Cr# = 70.3 ± 1.1), and weathered sulfide and metal. Raman mapping confirms that weathering has redistributed sulfur from primary troilite, resulting in the formation of Fe-oxide (-hydroxide) and marcasite (FeS2). From Raman mapping, NWA 4872 is composed of olivine (89%), Ca-rich pyroxene (0.4%), and Cr-spinel (1.1%), with approximately 7% oxidized metal and sulfide and 2.3% marcasite-dominated sulfide. Microcomputed tomography (micro-CT) observations reveal high-density regions, demonstrating heterogeneities in mineral distribution. Precision cutting of the largest high-density region revealed a single 2 mm Cr-spinel grain. Despite the weathering in NWA 4872, rare earth element (REE) abundances of pyroxene determined by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) indicate negligible modification of these elements in this mineral phase. The REE abundances of mineral grains in NWA 4872 are consistent with formation of the meteorite as the residuum of the partial melting process that occurred on its parent body. LA-ICP-MS analyses of sulfide and alteration products demonstrate the mobility of Re and/or Os; however, highly siderophile element (HSE) abundance patterns remain faithful recorders of processes acting on the brachinite parent body(ies). Detailed study of weathering and phase distribution offers a powerful tool for assessing the effects of low-temperature alteration and for identifying robust evidence for parent-body processes.

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.

Day, JMD, Ash RD, Liu Y, Bellucci JJ, Rumble D, McDonough WF, Walker RJ, Taylor LA.  2009.  Early formation of evolved asteroidal crust. Nature. 457:179-182.   10.1038/nature07651   AbstractWebsite

Mechanisms for the formation of crust on planetary bodies remain poorly understood(1). It is generally accepted that Earth's andesitic continental crust is the product of plate tectonics(1,2), whereas the Moon acquired its feldspar- rich crust by way of plagioclase flotation in a magma ocean(3,4). Basaltic meteorites provide evidence that, like the terrestrial planets, some asteroids generated crust and underwent large- scale differentiation processes(5). Until now, however, no evolved felsic asteroidal crust has been sampled or observed. Here we report age and compositional data for the newly discovered, paired and differentiated meteorites Graves Nunatak ( GRA) 06128 and GRA 06129. These meteorites are feldspar- rich, with andesite bulk compositions. Their age of 4.5+/-0.06 Gyr demonstrates formation early in Solar System history. The isotopic and elemental compositions, degree of metamorphic re-equilibration and sulphide- rich nature of the meteorites are most consistent with an origin as partial melts from a volatile- rich, oxidized asteroid. GRA 06128 and 06129 are the result of a newly recognized style of evolved crust formation, bearing witness to incomplete differentiation of their parent asteroid and to previously unrecognized diversity of early- formed materials in the Solar System.

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.

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, Floss C, Taylor LA, Anand M, Patchen AD.  2006.  Evolved mare basalt magmatism, high Mg/Fe feldspathic crust, chondritic impactors, and the petrogenesis of Antarctic lunar breccia meteorites Meteorite Hills 01210 and Pecora Escarpment 02007. Geochimica Et Cosmochimica Acta. 70:5957-5989.   10.1016/j.gca.2006.05.001   AbstractWebsite

Antarctic lunar meteorites Meteorite Hills 01210 and Pecora Escarpment 02007 are breccias that come from different regolith lithologies on the Moon. MET 01210 is composed predominantly of fractionated low-Ti basaltic material and is classified as an immature, predominantly basaltic glassy matrix regolith breccia. PCA 02007 is a predominantly feldspathic regolith breccia consisting of metamorphosed feldspathic, noritic, troctolitic and noritic-anorthosite clasts, agglutinate and impact-glasses, as well as a number of basaltic clasts with mare and possible non-mare affinities. The basalt clasts in MET 0 12 10 have undergone 'Fenner' trend enrichments in iron and may also have witnessed late-stage crystallization of zircon or a zirconium-rich mineral. Some of the features of MET 0 1210 are similar to other basaltic lunar breccia meteorites (e.g., Northwest Africa 773; Elephant Moraine 87521/96008; Yamato 793274/981031), but it is not paired with them. The presence of metamorphic anorthositic clasts as well as agglutinates indicates a small regolith component. Similarities with previously discovered evolved (e.g., LaPaz Icefield 02205; Northwest Africa 032) and ferroan (e.g., Asuka 881757; Yamato 793169) basaltic lunar meteorites suggest a similar mare source region for MET 01210. Despite lack of evidence for pairing, PCA 02007 shares many features with other feldspathic regolith breccias (e.g., Yamato 791197, Queen Alexandra Range 94281), including a high Mg/Fe whole-rock composition, glass spherules, agglutinate fragments and a diverse clast inventory spanning the range of ferroan anorthosite and high magnesium suite rocks. Some of the basalt fragments in this sample are fractionated and have an igneous origin. However, the majority of the basalt fragments are impact melt clasts. PCA 02007 supports previous studies of feldspathic lunar meteorites that have suggested an aluminous crust for the Moon, with compositions more similar to magnesium granulite breccias than ferroan anorthosites. A 'chondrule-like' fragment found in PCA 02007 and unlike any previously described lunar material is described and tentatively identified as the remnants of a chondritic lunar impactor. This clast is porphyritic with equant olivines that have forsterite-rich cores (Fo(> 98)), extreme normal zonation to more fayalitic rims (Fo(> 44)), and a mineral assemblage with rare earth element abundances distinct from described lunar material and more similar to chondrules found in ordinary or carbonaceous chondrites. Its discovery and description is significant for understanding the composition of lunar impactors. Previously, the main evidence for chondritic lunar impactors was from chondritic relative abundances and near chondritic ratios of highly siderophile elements in lunar impact melt breccias. However, the presence of this clast, along with two other chondritic clasts from Apollo soils 12037 and 15602, provides clues to the identity of ancient meteorite impactors on the Moon. (c) 2006 Elsevier Inc. All rights reserved.

Day, JMD, Corder CA, Assayag N, Cartigny P.  2019.  Ferrous oxide-rich asteroid achondrites. Geochimica et Cosmochimica Acta.   j.gca.2019.04.005   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.

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.

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).

Pernet-Fisher, JF, Barry PH, Day JMD, Pearson DG, Woodland S, Agashev AM, Pokhilenko LN, Pokhilenko NP.  2019.  Heterogeneous kimberlite metasomatism revealed from a combined He-Os isotope study of Siberian megacrystalline dunite xenoliths. Geochimica et Cosmochimica Acta.   https://doi.org/10.1016/j.gca.2019.07.054   Abstract

The Siberian sub-continental lithospheric mantle (SCLM) is regionally heterogeneous due to the complex modification of ancient cratonic material by various metasomatic fluids and interaction with the Siberian plume at ∼250 Ma. Here, we assess the extent and origin of this heterogeneity by analysis of helium isotopes, rhenium-osmium isotopes, trace-element, and highly siderophile element [HSE: Os, Ir, Ru, Pt, Pd, Re] abundances in a suite of mantle-derived megacrystalline dunite xenoliths from the 360 Ma Udachnaya East kimberlite pipe, Siberia. This enables assessment of the style and extent of metasomatism acting to modify the volatile budget of the Siberian SCLM. The olivine megacrysts have 3He/4He values that range from 2.3 to 7.4 RA (where RA = the 3He/4He of air), outside the canonical range for the lithospheric mantle (6.1 ± 2.1 RA; Day et al., 2015). High [He] and low U + Th concentrations in these olivine megacrysts indicate that the Udachnaya megacrystalline dunite xenolith suite has undergone minimal post-eruptive modification of He isotopes by 4He recoil. We instead interpret He isotope variations to reflect pre- or syn-eruptive metasomatic signatures during kimberlite emplacement. The dunites can be divided into two groups, ultimately reflecting modification by two distinct metasomatic styles. Group 1 dunites are characterized by highly unradiogenic Os isotope compositions (γOs360Ma -16 to -13) and ancient melt depletion ages (∼3 Ga) typical of ancient cratonic lithospheric mantle; yet display a range of He isotope ratios (2.3 to 5.9 RA). This indicates that group 1 dunites are modified by gas-rich metasomatic fluids acting to modify He abundances and isotope ratios, while preserving unradiogenic Os isotope and HSE abundance systematics. Group 2 dunites extend to significantly more radiogenic Os isotope signatures and higher He isotope values (γOs360Ma > -5 to +53; 3He/4He from 3.7 to 7.4 RA). These two groups define a negative hyperbolic array between Os and He isotopes which we interpret to result from metasomatism by variable mixtures between: (1) a gas-rich and HSE-poor fluid (similar to the fluids acting to modify Group 1 dunites) with helium isotope compositions above the MORB range (> 8 RA) derived from the asthenosphere, and: (2) strongly radiogenic fluids (∼ 2 RA; 187Os/188Os > 0.25) likely sourced from within the SCLM. Thee Udachnaya megacrystalline dunite xenolith suite provides insight into how mantle-plume derived fluids interact with metasomatic fluids within the SCLM.

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.   https://doi.org/10.1016/j.epsl.2018.02.020   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.

Magna, T, Day JMD, Mezger K, Fehr MA, Dohmen R, Aoudjehane HC, Agee CB.  2015.  Lithium isotope constraints on crust–mantle interactions and surface processes on Mars. Geochimica et Cosmochimica Acta. 162:46-65.   10.1016/j.gca.2015.04.029   Abstract

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (−0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member.

The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl–S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars (BSM) to be 4.2 ± 0.9‰ (2σ). This value is at the higher end of estimates for the Bulk Silicate Earth (BSE; 3.5 ± 1.0‰, 2σ), but overlaps within uncertainty.

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

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

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.

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.   https://doi.org/10.1016/j.chemgeo.2018.03.030   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.

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.