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The compositions of ocean island basalts (OIB) can record signatures of ancient subducted crust that has been recycled through the mantle. Based on their radiogenic isotope, major and trace element compositions, several geochemically-extreme mantle compositions are suggested to host components of recycled crust. Barium (Ba) stable isotopes can serve as a tracer of crustal recycling into the mantle sources of OIB because 1) Ba isotopes are fractionated in surface crustal reservoirs and 2) Ba is highly enriched in crust relative to the mantle. Therefore, the Ba isotopic compositions of the subducted crust could be detected in OIB. Here, we characterized Ba isotopic compositions of fresh OIB from hotspots sampling a range of mantle compositions. We first explore δ 138/134Ba (permil deviation of the 138Ba/134Ba ratio from the standard SRM3104a) in a suite of Hekla samples and demonstrate that magmatic differentiation does not impact the δ 138/134Ba values of OIB over MgO concentrations from 2.3 to 8.0 wt%, and higher MgO lavas are unlikely to experience δ 138/134Ba fractionation. After excluding OIB samples that experienced low-temperature alteration—which may shift the δ 138/134Ba values of samples away from their mantle sources—the δ 138/134Ba values of Samoan (including EM2 and high 3He/4He) lavas range from -0.07 to 0.07‰, while for Cook-Austral (HIMU) lavas the δ 138/134Ba values range from 0.00 to 0.11‰, and for St. Helena (HIMU) samples the δ 138/134Ba values range from 0.02 to 0.05‰. High 3He/4He (> 20 Ra, ratio to atmosphere) lavas from Vestfirðir of Iceland (-0.09 to 0.14‰) and Samoa (-0.02 to 0.01‰) also exhibit Ba isotopic variability. An extreme EM2 lava examined here (143Nd/144Nd = 0.512582) has lighter Ba isotopic composition (-0.07 ± 0.02‰, 2SE) than the depleted mantle sampled by MORB (0.05 ± 0.05‰, 2SD). The Samoan lavas show a possible positive trend between δ 138/134Ba values and 143Nd/144Nd ratios, and can be modeled as a binary mixing between the high 3He/4He (FOZO) mantle and recycled heterogeneous continental crust. In contrast, the extreme HIMU composition (206Pb/204Pb > 21.7) shows heavier Ba isotope signatures (0.11 ± 0.02‰, 2SE); δ 138/134Ba values positively correlate strongly with 206Pb/204Pb ratios in HIMU lavas, consistent with a contribution from recycled oceanic crust. [ABSTRACT FROM AUTHOR]

Rubidium is a moderately volatile element with high incompatibility and fluid mobility. Its stable isotopes have great potential in tracing various geological processes. For example, lunar rocks are isotopically heavier than terrestrial ones, suggesting volatile loss by evaporation during or following the formation of the Moon. However, these studies rely on a poorly constrained estimate for the composition of the Earth's mantle and a poor understanding of high-temperature processes which may act to fractionate stable Rb isotopes. It is therefore important to precisely characterize different rock types that sample the Earth's mantle as well as to evaluate the importance of key isotopic fractionation processes. In order to address these issues, we established a high precision analytical method for Rb isotopic measurements using the Nu Sapphire CC-MC-ICP-MS (collision-cell multi-collector inductively coupled plasma mass spectrometer). In addition, we present a series of Rb isotopic data of volcanic rocks from Hekla volcano (Iceland) and MORB (mid-ocean ridge basalt) samples. We show that our method returns a high Rb sensitivity (∼500 V/μg·g−1 for 85Rb) and a long-term reproducibility of 0.03‰ on δ87Rb (the permil deviation of the 87Rb/85Rb ratio from the SRM 984 standard). This method uses a 2 ng/g Rb solution for analyses, allowing us to consume about 10 times less Rb to achieve similar or better precision than previous studies. Using this method, seven geostandards and one synthetic standard return Rb isotopic data consistent with previous work. Twenty-one Hekla volcanic rocks, spanning compositions from basalt to rhyolite, show limited Rb isotopic variation, with δ87Rb values varying from −0.17‰ to −0.07‰, demonstrating that magmatic evolution has an insignificant effect on Rb isotope ratios. A set of MORB samples (n = 15) from different mid-ocean ridges also span a limited Rb isotopic variation, displaying a range similar to the Hekla rock suite (−0.19 to −0.02‰). Combining our new data together with previously reported OIB data gives an average δ87Rb value of −0.12 ± 0.08‰ (2SD, n = 25), representing the current best estimate of the mantle's isotopic composition. Considering the δ87Rb values of the upper continental crust (−0.14 ± 0.01‰, 2SE, n = 73), as inferred from recent measurements of granites, loess and sediments, and assuming this value represents the whole crust, the revised Rb isotopic composition of the bulk silicate Earth (and by extension the bulk Earth, assuming no Rb partitioned into the core) is −0.13 ± 0.06‰ (2SD). [ABSTRACT FROM AUTHOR]

Abstract: In order to improve characterisation of volatiles in the EM1 and EM2 mantle sources, which are interpreted to contain subducted sedimentary or lithospheric components, we report electron microprobe, FTIR and SIMS CO2, H2O, S, F and Cl concentrations of variably enriched glasses from Pitcairn and Society seamounts in Polynesia. The analyses complement previously published Cl, Br and I data for some of the same glasses and all the techniques show reasonable agreement of better than 5–9% for S, Cl and H2O. The concentrations of H2O and all the halogens increase as a function of melt evolution with the highest values of 1.6wt.% H2O, 2100ppm F, 1500ppm Cl, 3.7ppm Br and 80ppb I in melts with <2wt.% MgO. In contrast, CO2 and S are strongly influenced by degassing and it is the least evolved melts that preserve the highest CO2 concentrations, that indicate CO2 oversaturation of some lavas. Comparison of volatile and non-volatile elements of similar compatibility (e.g. H2O/Ce, Cl/K) as a function of equilibration depth and 87Sr/86Sr, suggests H2O and halogens were not significantly degassed from melts equilibrated at >100bars and most of the variation in H2O/Ce reflects source composition. Despite their overall enrichment in volatiles, both the Pitcairn and Society EM1 and EM2 sources are depleted in H2O as well as Cl, Br, and I relative to Ce and K. Slightly different behaviour is suggested for F and a correlation between F/Cl and K/Cl in Pitcairn melts, could be explained by preferential subduction of F relative to Cl into the EM sources. The relative abundances of H2O, halogens and lithophile elements in melts from different tectonic settings indicate subduction-related H2O and Cl loss efficiencies are similar at ~90–96%; F is suggested to have a lower loss efficiency; whereas Br and I are lost more efficiently. Nonetheless, dehydrated lithosphere containing 5–10% of its original volatile content is interpreted as the most likely source of volatile enrichment in the Pitcairn and Society mantle sources. [Copyright &y& Elsevier]

Abstract: New measurements of high 3He/4He ratios in Samoan lavas from Ofu Island (19.5–33.8 times atmospheric) extend the known range for 3He/4He in the southern hemisphere mantle. The Ofu data suggest that the high 3He/4He mantle component thought to be common to all oceanic hotspots, called FOZO (Focus Zone), is not homogeneous. Sr, Nd and Pb isotopes in Ofu lavas indicate that the Samoan high 3He/4He component is isotopically distinct from the high 3He/4He lavas from Hawaii, Iceland and Galapagos. Along with Samoa, the highest 3He/4He sample from each southern hemisphere high 3He/4He hotspot exhibits lower 143Nd/144Nd ratios than their counterparts in the northern hemisphere (excluding lavas erupted in continental, back-arc, and submarine ridge environments). The observation of a large-scale isotopic enrichment (generally higher 87Sr/86Sr and lower 143Nd/144Nd) in the FOZO-A (austral) high 3He/4He mantle compared to the FOZO-B (boreal) high 3He/4He mantle is similar to the DUPAL anomaly, a globe-encircling feature of isotopic enrichment observed primarily in southern hemisphere ocean island basalts. Additionally, the recent discovery that terrestrial samples have 142Nd/144Nd ratios higher than chrondrites has potentially important implications for the origin of the FOZO reservoirs, and suggest that the high 3He/4He mantle has been re-enriched. [Copyright &y& Elsevier]

Major and trace element abundances, including highly siderophile elements, and 187Os and 182W isotopic compositions were determined for ca. 89 Ma mafic and ultramafic rocks from the islands of Gorgona (Colombia) and Curaçao (Dutch Caribbean). The volcanic systems of both islands were likely associated with a mantle plume that generated the Caribbean Large Igneous Provence. The major and lithophile trace element characteristics of the rocks examined are consistent with the results of prior studies, and indicate derivation from both a chemically highly-depleted mantle component, and an enriched, or less highly-depleted mantle component. Highly siderophile element abundances for these rocks are generally similar to rocks with comparable MgO globally, indicating that the major source components were not substantially enriched or depleted in these elements. Rhenium-Os isotopic systematics of most rocks of both islands indicate derivation from a mantle source with an initial 187Os/188Os ratio between that of the contemporaneous average depleted mid-ocean ridge mantle and bulk silicate Earth. The composition may reflect either an average lower mantle signature, or global-scale Os isotopic heterogeneity in the upper mantle. Some of the basalts, as well as two of the komatiites, are characterized by calculated initial 187Os/188Os ratios 10–15 % higher than the chondritic reference. These more radiogenic Os isotopic compositions do not correlate with major or trace element systematics, and indicate a mantle source component that was most likely produced by either sulfide metasomatism or ancient Re/Os fractionation. Tungsten-182 isotopic compositions measured for rocks from both islands are characterized by variable μ182W values ranging from modern bulk silicate Earth-like to strongly negative values. The μ182W values do not correlate with major/trace element abundances or initial 187Os/188Os compositions. As with some modern ocean island basalt systems, however, the lowest μ182W value (−53) measured, for a Gorgona olivine gabbro, corresponds with the highest 3He/4He previously measured from the suite (15.8 R/R A). Given the lack of correlation with other chemical/isotopic compositions, the mantle component characterized by negative μ182W and possibly high 3He/4He is most parsimoniously explained to have formed as a result of isotopic equilibration between the mantle and core at the core-mantle boundary. [ABSTRACT FROM AUTHOR]

Lithological heterogeneity is a widely accepted feature of the Earth's mantle, with recycled crustal material accounting for a significant part of heterogeneity in ocean island basalt (OIB) geochemistry. Fe isotopes have been used to link geochemical heterogeneity in OIB sources to distinct mantle lithologies due to their mineral-specific equilibrium fractionation effects, or their composition, such as incorporation of kinetically-fractionated core liquids entrained from the core-mantle boundary. Here we present Fe isotope data for Samoan shield, and Azores volcanoes, together with a combined phase-equilibria and equilibrium mineral-melt isotope fractionation model. These OIB lavas allow us to study the roles of core-derived and recycled mantle components in generating heavy δ 57Fe melts. Heavy δ 57Fe correlates with radiogenic isotope signatures of enrichment by a crustal component and not with Fe/Mn or any indicator of core involvement. However, single-stage melting of a MORB-like eclogitic pyroxenite cannot generate the heavy δ 57Fe seen in Pitcairn, Azores, and rejuvenated Samoa lavas. Melts of a reaction-zone pyroxenite (commonly suggested to form part of the OIB source), derived from eclogite melts hybridised with peridotite, also fail to generate the heaviest Fe isotopic compositions seen in OIB. Instead, the generation of heavy δ 57Fe melts in OIB requires: (1) processes that make subducted eclogite isotopically heavier than its pristine precursor MORB (e.g., hydrothermal alteration, metamorphism, sediment input); (2) lithospheric processing, such as remobilisation of previously frozen small-degree melts, or a contribution from lithospheric material metasomatised by silicate melts; and/or (3) melting conditions that limit the dilution of melts with heavy δ 57Fe by ambient lower δ 57Fe materials. No single process we consider can generate the heavy δ 57Fe seen in the Azores, Pitcairn, and rejuvenated Samoan lavas. Therefore, it cannot be assumed that a pyroxenite lithology derived from recycled crustal material is the sole producer of heavy δ 57Fe melts in OIB, nor can these signatures be related to contributions from the Earth's core. Instead, the observation of heavy δ 57Fe OIB melts cannot be ascribed to a unique source or process. This ambiguity reflects the multitude of processes operating from the generation of recycled lithologies through to their mantle melting: from MORB generation, its low temperature alteration, through mantle heterogeneity development and lithospheric processing, to eruption at ocean islands. [ABSTRACT FROM AUTHOR]

The Indian-type mantle (i.e., above the north hemisphere reference line on the plot of 208 Pb/ 204 Pb vs. 206 Pb/ 204 Pb) has been considered as a “Southern Hemisphere” geochemical signature, whose origin remains enigmatic. The South China Sea is an extensional basin formed after rifting of the Euro-Asia continent in the Northern Hemisphere, however, the geochemical nature of the igneous crust remains unexplored. For the first time, IODP Expedition 349 has recovered seafloor basalts covered by the thick sediments in the Southwest sub-basin (Sites U1433 and U1434) and the East sub-basin (Site U1431). The Southwest sub-basin consists of enriched (E)-MORB type basalts, and the East sub-basin consists of both normal (N)-MORB-type and E-MORB-type basalts based on trace element compositions. The basalts of the two sub-basins are Indian-type MORBs based on Sr–Nd–Pb–Hf isotope compositions, and the Southwest sub-basin basalts show isotopic compositions (i.e., 206 Pb/ 204 Pb of 17.59–17.89) distinctly different from the East sub-basin (i.e., 206 Pb/ 204 Pb of 18.38–18.57), suggesting a sub-basin scale mantle compositional heterogeneity and different histories of mantle compositional evolution. Two different enriched mantle end-members (EM1 and EM2) are responsible for the genesis of the Indian-type mantle in the South China Sea. We have modeled the influences of Hainan mantle plume and lower continental crust based on Sr–Nd–Pb–Hf isotope compositions. The results indicate that the influence of Hainan plume can explain the elevated 206 Pb/ 204 Pb of the East sub-basin basalts, and the recycling of lower continental crust can explain the low 206 Pb/ 204 Pb of the Southwest sub-basin basalts. Based on the strong geochemical imprints of Hainan plume in the ridge magmatism, we propose that the Hainan plume might have promoted the opening of the South China Sea, during which the Hainan plume contributed enriched component to the sub-ridge mantle and caused thermal erosion and return of lower continental crust to the convective mantle. These results imply an in situ origin of the Indian-type mantle that can help understand the genesis of the “Southern Hemisphere” geochemical anomaly in the Northern Hemispheric extensional basin. [ABSTRACT FROM AUTHOR]

The study of silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to discern between different models for the origins of geochemical heterogeneities in the mantle. Relatively large (∼several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes relative to the dissolved Si. In contrast, only a limited range (∼tenths of a per mil) of Si isotope fractionation has been observed from high-temperature igneous processes. Therefore, Si isotopes may be useful as tracers for the presence of crustal material within OIB mantle source regions that experienced relatively low-temperature surface processes in a manner similar to other stable isotope systems, such as oxygen. Characterizing the isotopic composition of the mantle is also of central importance to the use of the Si isotope system as a basis for comparisons with other planetary bodies (e.g., Moon, Mars, asteroids). Here we present the first comprehensive suite of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIB. Samples originate from ocean islands in the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. On average, δ 30 Si values for OIB (−0.32 ± 0.09‰, 2 sd) are in general agreement with previous estimates for the δ 30 Si value of Bulk Silicate Earth (−0.29 ± 0.07‰, 2 sd; Savage et al., 2014). Nonetheless, some small systematic variations are present; specifically, most HIMU-type (Mangaia; Cape Verde; La Palma, Canary Islands) and Iceland OIB are enriched in the lighter isotopes of Si (δ 30 Si values lower than MORB), consistent with recycled altered oceanic crust and lithospheric mantle in their mantle sources. [ABSTRACT FROM AUTHOR]

Stable sulfur isotope ratios of mid-ocean ridge and ocean island basalts (MORBs and OIBs) preserve unique information about early Earth processes and the long-term volatile cycles between Earth's mantle and the surface. Icelandic basalts present ideal material to examine the oldest known terrestrial mantle reservoir, accessed through a deep-rooted mantle plume, but their multiple sulfur isotope systematics have not been explored previously. Here, we present new sulfur concentration (30–1570 ppm) and isotope data (δ 34 S = −2.5 to +3.8‰ and Δ 33 S = −0.045 to +0.016‰; vs. Canyon Diablo Troilite) from a sample suite (n = 62) focused on subglacially erupted basaltic glasses obtained from Iceland's neovolcanic zones. Using these data along with trace element systematics to account for the effects of magmatic processes (degassing and immiscible sulfide melt formation) on δ 34 S, we show that primitive (MgO > 6 wt.%), least degassed glasses accurately record the δ 34 S signatures of their mantle sources. Compared to the depleted MORB source mantle (DMM; δ 34 S = −1.3±0.3‰), the Iceland mantle is shown to have a greater range of δ 34 S values between −2.5 and −0.1%. Similarly, Icelandic basalts are characterized by more variable and negatively shifted Δ 33 S values (−0.035 to +0.013‰) relative to DMM (0.004±006‰). Negative δ 34 S- Δ 33 S signatures are most prominent in basalts from the Snæfellsnes Volcanic Zone and the Kverkfjöll volcanic system, which also have the lowest, most MORB-like 3He/4He (8–9 R/R A , where R A is the 3He/4He of air) and the highest Ba/La (up to 12) in Iceland. We propose that subduction fluid-enriched, mantle wedge type material, possibly present in the North Atlantic upper mantle, constitutes a low- δ 34 S- Δ 33 S component in the Icelandic mantle. This suggests that volatile heterogeneity in Iceland, and potentially at other OIBs, may originate not only from diverse plume-associated mantle components, but also from a heterogeneous ambient upper mantle. By contrast, a set of samples with high 3He/4He (up to 25.9 R/R A) and negative μ 182 W anomalies define an ancient lower mantle reservoir with a near-chondritic Δ 33 S and δ 34 S signature of ∼0‰. The difference between DMM and the high high-3He/4He mantle may reflect separate conditions during core-mantle differentiation, or a previously unidentified flux of sulfur from the core to the high-3He/4He reservoir. • Multiple sulfur isotope data presented for 62 Icelandic lavas. • Effects of degassing and sulfide immiscibility on δ 34 S evaluated. • Undegassed Icelandic basalts show greater S isotopic variability than MORBs. • Negative δ 34 S- Δ 33 S values tied to a subduction fluid-modified mantle component. • A near-chondritic S isotopic signature suggested for the primordial mantle. [ABSTRACT FROM AUTHOR]

• Hg isotopic composition of terrestrial igneous rocks and chondrites overlaps. • This shows that Earth's Hg may have been be dominated by late accretion. • Hg isotopic composition of eucrite meteorites reflects evaporation under equilibrium. Variations in the abundances of moderately volatile elements (MVE) are one of the most fundamental geochemical differences between the terrestrial planets. Whether these variations are the consequence of nebular processes, planetary volatilization, differentiation or late accretion is still unresolved. The element mercury is the most volatile of the MVE and is a strongly chalcophile element. It is one of the few elements that exhibit large mass-dependent (MDF) and mass-independent (MIF) isotopic fractionations for both odd (odd-MIF, Δ 199 Hg and Δ 201 Hg) and even (even-MIF, Δ 200 Hg) Hg isotopes in nature, which is traditionally used to trace Hg biogeochemical cycling in surface environments. However, the Hg isotopic composition of Earth and meteorites is not well constrained. Here, we present Hg isotopic data for terrestrial basaltic, trachytic and granitic igneous samples. These rocks are isotopically lighter (δ 202 Hg = −3.3 ± 0.9‰; 1 standard deviation) than sedimentary rocks that have previously been considered to represent the terrestrial Hg isotope composition (δ 202 Hg = − 0.7 ± 0.5 ‰ ; 1 standard deviation). We show degassing during magma emplacement induces MIF that are consistent with kinetic fractionation in these samples. Also presented is a more complete dataset for chondritic (carbonaceous, ordinary and enstatite) meteorites, which are consistent with previous work for carbonaceous chondrites (positive odd-MIF) and ordinary chondrites (no MIF), and demonstrate that some enstatite chondrites exhibit positive odd-MIF, similar to carbonaceous chondrites. The terrestrial igneous rocks fall within the range of chondritic compositions for both MIF and MDF. Given the fact that planetary differentiation (core formation, evaporation) would contribute to Hg loss from the silicate portion of Earth and would likely fractionate Hg isotopes from chondritic compositions, we suggest that the budget of the mantle Hg is dominated by late accretion of chondritic materials to Earth, as also suggested for other volatile chalcophile elements (S, Se, Te). Considering the Hg isotopic signatures, materials with compositions similar to CO chondrites or ordinary chondrites are the most likely late accretion source candidates. Finally, eucrite meteorites, which are highly depleted in volatile elements, are isotopically heavier than chondrites and exhibit negative odd-MIF. The origin of volatile depletion in eucrites has been vigorously debated. We show that Δ 199 Hg versus Δ 201 Hg relationships point toward an equilibrium nuclear field shift effect, suggesting that volatile loss occurred during a magma ocean phase at the surface of the eucrite parent body, likely the asteroid 4-Vesta. [ABSTRACT FROM AUTHOR]

• Isotopic links between S, W, He, and Pb suggest mixing between several components. • One component is primordial with Δ 33 S = 0. • Primordial sulfur is linked to a dense, undegassed basal reservoir (ULVZ). • Additional components are recycled with variable Δ 33 S. • Recycled sulfur is linked to material with EMII and HIMU characteristics. Understanding present-day mantle heterogeneity is key to understanding the geochemical evolution of our planet. The Samoan islands are the type locality for the Enriched Mantle (II) reservoir that is thought to be produced from the subduction and recycling of marine sediment from upper continental crust. In addition to hosting extreme radiogenic isotope compositions from the EM II reservoir, Samoa also exhibits contributions from other mantle reservoirs in a dilute form including the EM (I) (recycled continental material), HIMU (recycled oceanic crust), and DMM (depleted upper mantle) mantle reservoirs. The plume system feeding the Samoan islands sits above a seismically imaged Large Low Shear Velocity Province (LLSVP) and an Ultra-Low Velocity Zone (ULVZ) that is thought to contribute, in addition to recycled components, the recently discovered early-formed (primordial) components with negative μ 182 W and high 3He/4He. Recent work measuring sulfur isotopes in ocean island basalts has established that recycled oceanic and continental crust host unique S-isotope compositions that can be identified at various hotspot localities. Here we document previously unknown relationships between Δ 33 S and radiogenic tungsten, helium and lead isotopes from 7 Samoan basalts (from the islands of Ofu, Vailulu'u and Malumalu) that suggest mixing between several endmembers. One, a HIMU influence that has slight positive Δ 33 S and positive δ 34 S; another, related to EM II that has near zero Δ 33 S and positive δ 34 S; a third, which is primordial with negative μ 182 W, high 3He/4He, that has Δ 33 S = 0 and negative δ 34 S. From this, we conclude that the indistinguishable Δ 33 S of the primordial endmember from that of the convective mantle indicates that sulfur isotopes were homogenized early in Earth's history. The Vailulu'u sample with HIMU characteristics, carries a small but resolvable Δ 33 S that allows, but does not require mass-independent Archean Δ 33 S to shift the Δ 33 S. The observed correlations involving Δ 33 S support arguments linking Pb, He, and W geochemistry to a deep mantle process and places constraints on questions related to the sources of mantle geochemical heterogeneity. [ABSTRACT FROM AUTHOR]