Temporal helium isotopic variations within Hawaiian volcanoes: Basalts from Mauna Loa and Haleakala

Helium isotope ratios in basalts spanning the subaerial eruptive history of Mauna Loa and Haleakala vary systematically with eruption age. In both volcanoes, olivine mineral separates from the oldest samples have the highest ³He/⁴He ratios. The Haleakala samples studied range in age from roughly one million years to historic time, while the Mauna Loa samples are radiocarbon dated flows younger than 30.000 years old. The Honomanu tholeiites are the oldest samples from Haleakala and have ³He/⁴ ratios that range from 13 to 16.8× atmospheric, while the younger Kula and Hana series alkali basalts all have ³He/⁴ close to 8×atmospheric. A similar range is observed on Mauna Loa; the oldest samples (roughly 30,000 years) have ³He/⁴ ratios of 15 to 20 × atmospheric, with a relatively smooth decrease to 8 × atmospheric with decreasing age. The consistent trend of decreasing ³He/⁴He ratio with time in both volcanoes, coherence between the helium and Sr and Nd isotopes (for Haleakala), and the similarity of ³He/⁴ in the late stage basalts to depleted mid-ocean ridge basalt (MORB) helium, argue against the decrease being the result of radiogenic ingrowth of ⁴He. The data strongly suggest an undegassed (i.e., high ³He/(Th + U)) mantle source for the early shield building stages of Hawaiian volcanism. and are consistent with the hotspot/mantle plume model. The data are difficult to reconcile with models for Hawaiian volcanism that require recycled oceanic crust or derivation from a MORB-related upper mantle source. We interpret the decrease in ³He/⁴ with volcano evolution to result from an increasing involvement of depleted mantle and/or lithosphere during the late stages of Hawaiian volcanism.     

Os-Os systematics of Hawaiian picrites revisited: New insights into Os isotopic variations in ocean island basalts

Eighteen picrites (MgO > 13 wt.%) and three related basalts from six Hawaiian volcanoes were analyzed for ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os. Variations in these ratios reflect long-term Re/Os and Pt/Os differences in the mantle source regions of these volcanoes. ¹⁸⁷Os/¹⁸⁸Os ratios vary from ∼0.129 to 0.136, consistent with the range defined by previous studies of Hawaiian picrites and basalts. Samples with lower ¹⁸⁷Os/¹⁸⁸Os are mainly from Kea trend volcanoes (Mauna Kea and Kilauea), and the more radiogenic samples are mainly from Loa trend volcanoes (Mauna Loa, Hualalai, Koolau and Loihi). As previously suggested, differences in ¹⁸⁷Os/¹⁸⁸Os between volcanic centers are most consistent with the presence of variable proportions of recycled materials and/or pyroxenitic components in the Hawaiian source.¹⁸⁶Os/¹⁸⁸Os ratios vary from 0.1198332 ± 26 to 0.1198480 ± 20, with some samples having ratios that are significantly higher than current estimates for the ambient upper mantle. Although the range of ¹⁸⁶Os/¹⁸⁸Os for the Hawaiian suite is consistent with that reported by previous studies, the new data reveal significant heterogeneities among picrites from individual volcanoes. The linear correlation between ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os reported by a previous study is no longer apparent with the larger dataset. The postulated recycled materials and pyroxenites responsible for the dominant variations in ¹⁸⁷Os/¹⁸⁸Os are likely not responsible for the variations in ¹⁸⁶Os/¹⁸⁸Os. Such materials are typically characterized by both insufficiently high Os concentrations and Pt/Os to account for the ¹⁸⁶Os/¹⁸⁸Os heterogeneities. The lack of correspondence between ¹⁸⁶Os/¹⁸⁸Os variations and the Kea and Loa trends supports this conclusion.The primary cause of ¹⁸⁶Os/¹⁸⁸Os variations are evaluated within the framework of two mixing scenarios: (1) metasomatic transport of Pt and/or ¹⁸⁶Os-rich Os into some portions of the Hawaiian source, and (2) interaction between an isotopically complex plume source with a common, Os- and ¹⁸⁶Os-enriched reservoir (COs). Both scenarios require large scale, selective transport of Pt, Re and/or Os. Current estimates of HSE concentrations in the mantle source of these rocks, however, provide little evidence for either process, so the dominant cause of the ¹⁸⁶Os/¹⁸⁸Os variations remains uncertain.     

Rare Earth Element Inversions and Percolation Models for Hawaii

A detailed study has been made of the evolution with time ofthe mantle source and degree of melting required to producea typical Hawaiian volcano. The preshield stage involves a changefrom a depleted to a primitive mantle source and an increasein the melt fraction. Important intra- and inter-volcano variationsoccur during the shield stage which may be related to melt transportprocesses. With time, Mauna Loa's lavas show depletion in increasinglycompatible elements, a result which is consistent with percolationprocesses. Postshield magmas are generated by very small degreesof melting of a depleted mantle source and may be importantin the development of posterosional volcanism. Posterosionallavas can be generated by variable degrees of melting of anamphibole-bearing source that has been enriched by postshieldmagma. A simple percolation model is consistent with the isotopic evolutionof Hawaiian volcanoes. All of the observed isotopic variationseen between Hawaiian volcanoes may be produced from only twomantle sources by small variations in the percolation processes. ^* Present address: Department of Earth Sciences, Parks Road, Oxford OX1 3PR, UK.     

Trace element abundances of high-MgO glasses from Kilauea, Mauna Loa and Haleakala volcanoes, Hawaii

We performed an ion-microprobe study of eleven high-MgO (6.7–14.8 wt%) tholeiite glasses from the Hawaiian volcanoes Kilauea, Mauna Loa and Haleakala. We determined the rare earth (RE), high field strength, and other selected trace element abundances of these glasses, and used the data to establish their relationship to typical Hawaiian shield tholeiite and to infer characteristics of their source. The glasses have trace element abundance characteristics generally similar to those of typical shield tholeiites, e.g. L(light)REE/H(heavy)REE_C1 < 1. The Kilauea and Mauna Loa glasses, however, display trace and major element characteristics that cross geochemical discriminants observed between Kilauea and Mauna Loa shield lavas. The glasses contain a blend of these discriminating chemical characteristics, and are not exactly like the typical shield lavas from either volcano. The production of these hybrid magmas likely requires a complexly zoned source, rather than two unique sources. When corrected for olivine fractionation, the glass data show correlations between CaO concentration and incompatible trace element abundances, indicating that CaO may behave incompatibly during melting of the tholeiite source. Furthermore, the tholeiite source must contain residual garnet and clinopyroxene to account for the variation in trace element abundances of the Kilauea glasses. Inversion modeling indicates that the Kilauea source is flat relative to C1 chondrites, and has a higher bulk distribution coefficient for the HREE than the LREE. Received: 4 February 1997 / Accepted: 27 August 1997     

Ages,rare-earth element enrichment,and petrogenesis of tholeiitic and alkalic basalts from Kahoolawe Island,Hawaii

Kahoolawe Island, Hawaii (18×11 km), is a basaltic shield volcano with caldera-filling lavas, seven identified postshield vents, and at least two occurrences of apparent rejuvenated-stage eruptive. We examined 42 samples that represent all stages of Kahoolawe volcano stratigraphy for their petrography, whole-rock major-and trace-element contents, mineral compositions, and K–Ar ages. The two oldest shield samples have an average age of 1.34±0.08 Ma, and four postshield samples (3 are alkalic) average 1.15±0.03 Ma; ages of 1.08 and 0.99 Ma for two additional tholeiitic samples probably are minimum ages. Whole-rock major- and trace-element and mineral compositions of Kahoolawe shield and caldera-fill laves are generally similar to the lavas forming Kilauea and Mauna Loa tholeiitic shields, but in detail, Kahoolawe shield lavas have distinctive compositions. An unusual aspect of many postshield Ka-hoolawe lavas is anomalously high REE and Y abundances (up to 200 ppm La and 175 ppm Y) and negative Ce anomalies. These enrichments reflect surficial processes, where weathering and soil development promoted REE-Y transport at the weathering front. Major element abundances (MgO, 10–6 wt.%) for shield and caldera-fill basalts are consistent with fractionation of ol+px+pl in frequently replenished magma reservoirs. In general, tholeiitic basalts erupted from late vents are higher in SiO₂ than the shield lavas, and temporal differences in parental magma compositions are the likely explanation. Alkalic basalts that erupted from vents are comparable in composition to those at other Hawaiian volcanoes. Trace-element abundance ratios indicate that alkalic basalts represent either relatively lower degrees of melting of the shield source or a distinct source. Apparent rejuvenated-stage basalts (i.e., emplaced after substantial Kahoolawe erosion) are tholeiitic, unlike the rejuvenated-stages at other Hawaiian volcanoes (alkalic). Kahoolawe, like several other Hawaiian volcanoes, has intercalated tholeiitic and alkalic basalts in the postshield stage, but it is the only volcano that appears to have produced tholeiitic rejuvenated-stage lavas.     

Stable calcium isotopic compositions of Hawaiian shield lavas: Evidence for recycling of ancient marine carbonates into the mantle

We report high-precision ⁴⁴Ca/⁴⁰Ca measurements (2σ_m < 0.06‰) of Hawaiian shield stage tholeiites. Our data reveal ∼0.3‰ variation in their ⁴⁴Ca/⁴⁰Ca, which comprises ∼20% of the ⁴⁴Ca/⁴⁰Ca variation observed in global carbonates. The ⁴⁴Ca/⁴⁰Ca variation is correlated with Sr/Nb and ⁸⁷Sr/⁸⁶Sr, and this pattern is best explained by adding up to 4% ancient carbonate into the Hawaiian plume. Mass-balance calculations show that up to 40% of the Ca budget and 65% of the Sr budget in some Hawaiian (Makapuu-stage Koolau) lavas are derived from recycled carbonates. Our finding demonstrates, for the first time with the application of Ca isotopes, that ancient recycled carbonates are important components of mantle plumes which feed some of the largest terrestrial volcanoes. Thus, recycling of carbonates into the mantle is an essential part of the global Ca and C cycles.     

Constraints on the Source Components of Lavas Forming the Hawaiian North Arch and Honolulu Volcanics

Hawaiian volcanoes, dominantly shields of tholeiitic basalt,form as the Pacific Plate migrates over a hotspot in the mantle.As these shields migrate away from the hotspot, highly alkaliclavas, forming the rejuvenated stage of volcanism, may eruptafter an interval of erosion lasting for 0·25–2·5Myr. Alkalic lavas with geochemical characteristics similarto rejuvenated- stage lavas erupted on the sea floor north ofOahu along the Hawaiian Arch. The variable Tb/Yb, Sr/Ce, K/Ce,Rb/La, Ba/La, Ti/Eu and Zr/Sm ratios in lavas forming the NorthArch and the rejuvenated-stage Honolulu Volcanics were controlledduring partial melting by residual garnet, clinopyroxene, Fe–Tioxides and phlogopite. However, the distinctively high Ba/Thand Sr/Nd ratios of lava forming the North Arch and HonoluluVolcanics reflect source characteristics. These characteristicsare also associated with shield tholeiitic basalt; hence theyarise from the Hawaiian hotspot, which is interpreted to bea mantle plume. Inversion of the batch melting equation usingabundances of highly incompatible elements, such as Th and La,requires enriched sources with 10–55% clinopyroxene and5–25% garnet for North Arch lavas. The ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Ndratios in lavas forming the North Arch and Honolulu Volcanicsare consistent with mixing between the Hawaiian plume and adepleted component related to mid-ocean ridge basalts. Specifically,the enrichment of incompatible elements coupled with low ⁸⁷Sr/⁸⁶Srand high ¹⁴³Nd/¹⁴⁴Nd relative to bulk Earth ratios is best explainedby derivation from depleted lithosphere recently metasomatizedby incipient melt (<2% melting) from the Hawaiian plume.In this metasomatized source, the incompatible element abundances,as well as Sr and Nd isotopic ratios, are controlled by incipientmelts. In contrast, the large range of published ¹⁸⁷Os/¹⁸⁸Osdata (0·134–0·176) reflects heterogeneitycaused by various proportions of pyroxenite veins residing ina depleted peridotite matrix. KEY WORDS: Hawaiian plume; Honolulu Volcanics; North Arch; plume–lithosphere interaction; rejuvenated stage; trace element geochemistry; alkalic lavas     

Isotope Compositions of Submarine Hana Ridge Lavas, Haleakala Volcano, Hawaii: Implications for Source Compositions, Melting Process and the Structure of the Hawaiian Plume

We report Sr, Nd, and Pb isotope compositions for 17 bulk-rocksamples from the submarine Hana Ridge, Haleakala volcano, Hawaii,collected by three dives by ROV Kaiko during a joint Japan–USHawaiian cruise in 2001. The Sr, Nd, and Pb isotope ratios forthe submarine Hana Ridge lavas are similar to those of Kilauealavas. This contrasts with the isotope ratios from the subaerialHonomanu lavas of the Haleakala shield, which are similar toMauna Loa lavas or intermediate between the Kilauea and MaunaLoa fields. The observation that both the Kea and Loa componentscoexist in individual shields is inconsistent with the interpretationthat the location of volcanoes within the Hawaiian chain controlsthe geographical distribution of the Loa and Kea trend geochemicalcharacteristics. Isotopic and trace element ratios in Haleakalashield lavas suggest that a recycled oceanic crustal gabbroiccomponent is present in the mantle source. The geochemical characteristicsof the lavas combined with petrological modeling calculationsusing trace element inversion and pMELTS suggest that the meltingdepth progressively decreases in the mantle source during shieldgrowth, and that the proportion of the recycled oceanic gabbroiccomponent sampled by the melt is higher in the later stagesof Hawaiian shields as the volcanoes migrate away from the centralaxis of the plume. KEY WORDS: submarine Hana Ridge; isotope composition; melting depth; Hawaiian mantle plume     

The Fe/Mn ratio in MORB and OIB determined by ICP-MS

Variations in the abundance of iron in the mantle may have important consequences for mantle dynamics and geochemistry. The abundance of iron in lavas derived from mantle source regions varies during partial melting and subsequent fractionation, so that source heterogeneities are not easily resolved in iron abundances alone. However, manganese is a geochemically similar element, so that the planetary Fe/Mn ratio is approximately constant. Here, we report new Fe/Mn results for mid-oceanic ridge basalts (MORBs), oceanic island basalts (OIBs) and komatiites using a precise inductively coupled plasma mass spectrometric (ICP-MS) method to measure Fe/Mn to better than 0.5% (2σ). As a measure of reproducibility of Fe/Mn, five olivine and five orthopyroxene grains from a Kilbourne Hole peridotite xenolith yielded Fe/Mn 69.8 ± 0.4 and 44.3 ± 0.2, respectively. To avoid ubiquitous secondary Fe-Mn oxides, Fe/Mn ratios in Pacific, Atlantic, and Indian MORBs were determined by Laser Ablation ICP-MS. MORB Fe/Mn (53-56) corrected for crystal fractionation yielded a value of 54.0 ± 1.2 (1σ). Icelandic basalts and picrites (MgO 10-29%) had Fe/Mn ratios 56-61, with a single exception. Six relatively fresh komatiites from Belingwe (MgO 20-29%) yielded Fe/Mn values of 58.3 ± 0.2 (1σ). Basalts from Tahiti and Reunion exhibited high Fe/Mn (>65), like Hawaii. This implies that the mantle source regions of Tahiti and Reunion lavas may have been enriched in Fe relative to other mantle reservoirs (e.g., MORBs, Iceland, Belingwe). Combined with previous results for Hawaii, we now find that Fe/Mn > 65 is characteristic of at least two plumes from the Pacific Superswell. It is conceivable that this is evidence for excess Fe due to core-mantle interaction in these mantle plumes, although partial melting of secondary pyroxenites may cause similar variations in Fe/Mn. Heterogeneity of Fe/Mn in mantle-derived lavas is now clearly documented.     

Os and Os enrichments and high-He/He sources in the Earth’s mantle: Evidence from Icelandic picrites

Picrites from the neovolcanic zones in Iceland display a range in ¹⁸⁷Os/¹⁸⁸Os from 0.1297 to 0.1381 (γ_Os = + 2.1 to +8.7) and uniform ¹⁸⁶Os/¹⁸⁸Os of 0.1198375 ± 32 (2σ). The value for ¹⁸⁶Os/¹⁸⁸Os is within uncertainty of the present-day value for the primitive upper mantle of 0.1198398 ± 16. These Os isotope systematics are best explained by ancient recycled crust or melt enrichment in the mantle source region. If so, then the coupled enrichments displayed in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os from lavas of other plume systems must result from an independent process, the most viable candidate at present remains core-mantle interaction. While some plumes with high ³He/⁴He, such as Hawaii, appear to have been subjected to detectable addition of Os (and possibly He) from the outer core, others such as Iceland do not.A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He from 9.6 to 19 Ra in Iceland picrites is best modeled as mixtures of 1 Ga or older ancient recycled crust mixed with primitive mantle or incompletely degassed depleted mantle isolated since 1-1.5 Ga, which preserves the high ³He/⁴He of the depleted mantle at the time. These mixtures create a hybrid source region that subsequently mixes with the present-day convecting MORB mantle during ascent and melting. This multistage mixing scenario requires convective isolation in the deep mantle for hundreds of million years or more to maintain these compositionally distinct hybrid sources. The ³He/⁴He of lavas derived from the Iceland plume changed over time, from a maximum of 50 Ra at 60 Ma, to approximately 25-27 Ra at present. The changes are coupled with distinct compositional gaps between the different aged lavas when ³He/⁴He is plotted versus various geochemical parameters such as ¹⁴³Nd/¹⁴⁴Nd and La/Sm. These relationships can be interpreted as an increase in the proportion of ancient recycled crust in the upwelling plume over this time period.The positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He demonstrates that the Iceland lava He isotopic compositions do not result from simple melt depletion histories and consequent removal of U and Th in their mantle sources. Instead their He isotopic compositions reflect mixtures of heterogeneous materials formed at different times with different U and Th concentrations. This hybridization is likely prevalent in all ocean island lavas derived from deep mantle sources.     

Boron isotopic constraints on the source of Hawaiian shield lavas

Boron isotopic compositions of lavas from three representative Hawaiian shield volcanoes (Kilauea, Mauna Loa, and Koolau) were analyzed by thermal ionization mass spectrometry. The boron isotopic composition of each sample was analyzed twice, once with and once without acid leaching to evaluate the effect of posteruptive boron contamination. Our acid-leaching procedure dissolved glass, olivine, secondary zeolite, and adsorbed boron; this dissolved boron was completely removed from the residue, which was comprised of plagioclase, pyroxenes, and newly formed amorphous silica. We confirmed that an appropriate acid-leaching process can eliminate adsorbed and incorporated boron contamination from all submarine samples without modifying the original ¹¹B/¹⁰B ratio. On the other hand, when the sample was weathered, i.e., the olivine had an iddingsite rim, ¹¹B/¹⁰B of the acid-resistant minerals are also modified, thus it is impossible to get the preeruptive ¹¹B/¹⁰B value from the weathered samples. Through this elimination and evaluation procedure of posteruptive contamination, preeruptive δ¹¹B values for the shield lavas are −4.5 to −5.4‰ for Koolau (N = 8), −3.6 to −4.6‰ for Kilauea (N = 11), and −3.0 to −3.8‰ for Mauna Loa (N = 6).Historical Kilauea lavas show a systematic temporal trend for B content and Nb/B coupled with other radiogenic isotopic ratios and trace element ratios, at constant δ¹¹B, indicating little or no assimilation of crustal materials in these lavas. Uncorrelated B content and δ¹¹B in Koolau and Mauna Loa lavas may also indicate little or no effect of crustal assimilation in these lavas. The source of KEA-component (identical to the so-called Kea end member in Hawaiian lavas) of the Hawaiian source mantle, represented by Kilauea, should be derived from lower part of subducted oceanic crust or refractory peridotite in the recycled subducted slab. The systematic trend from Kilauea to Koolau—decreasing δ¹¹B coupled with decreasing εNd as well as increasing ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb—is consistent with involvement of subducted sediment components in the EMK(enriched Makapuu)-component, represented by Makapuu-stage of Koolau lavas.     

Geochemistry of tholeiites from Lanai,Hawaii

Lanai is the third smallest of the fifteen principal subaerial shield volcanoes of the Hawaiian hotspot. This volcano apparently became extinct during the shield-building stage of volcanism, as shown by the absence of both alkalic cap and post-erosional lavas. Major and trace element analyses of 22 new samples collected primarily from 3 stratigraphic sections show that Lanai tholeiites span a large range in composition. Some Lanai lavas are unique geochemically among Hawaiian tholeiites in having the lowest abundances of incompatible trace elements of any Hawaiian lavas and well-developed positive Eu anomalies. The geochemical characteristics of these low-abundance Lanai tholeiites are not the result of alteration, differences in mantle source modal mineralogy, the presence of residual accessory mantle phases or fractional crystallization of such phases, assimilation of depleted [MORB] wall-rock, or accumulation/resorption of phenocrysts or xenocrysts. Incompatible trace element ratios (e.g., Nb/La, Nb/Th, La/Th, La/Hf, Ce/Pb) in Lanai tholeiites span considerable ranges and form coherent trends with each other and with absolute abundances of these elements. Large variations in La/Sm, La/Yb, and absolute REE abundances at constant MgO suggest that Lanai tholeiites formed by variable amounts of partial melting. However, large ranges in incompatible element ratios cannot be explained solely by variations in partial melting of a geochemically homogeneous source, but must reflect geochemical heterogeneities in the Lanai source. Partial melting modeling indicates that the mixed Lanai source is probably LREE-enriched [i.e., (La/Yb)_CN>1]. One component in the Lanai source, exemplified by the low-abundance tholeiites, has markedly lower REE/HFSE, Th/HFSE, alkali/HFSE, and Ce/Pb ratios than other Lanai or Hawaiian tholeiites and may indicate the presence of recycled residual subduction zone materials in the Hawaiian plume source. The positive Eu anomalies that characterize the low-abundance Lanai tholeiites are not the result of plagioclase accumulation or assimilation but are a feature of this source component. Progressive temporal geochemical variations in Lanai tholeiites from 2 stratigraphic sections indicate that the source composition of these lavas probably evolved over time. This change could have resulted from a progressive decrease in the extent of partial melting of the Lanai source. The compositional variability of Lanai tholeiites suggests that geochemical heterogeneities in their source are larger than the scale of partial melting. Lanai tholeiites could not have formed by smaller degrees of partial melting of plume material than did the larger-volume Hawaiian shields. Therefore, volume differences between Hawaiian shields must be controlled primarily by differences in the volume of supplied plume material rather than by differences in the degree of partial melting. The premature cessation of eruptive activity at Lanai may be attributed to relatively large degrees of partial melting of a small plume.     

Lithium isotopes in Guatemalan and Franciscan HP-LT rocks: Insights into the role of sediment-derived fluids during subduction

High-pressure, low-temperature (HP-LT) rocks from a Cretaceous age subduction complex occur as tectonic blocks in serpentinite mélange along the Motagua Fault (MF) in central Guatemala. Eclogite and jadeitite among these are characterized by trace element patterns with enrichments in fluid mobile elements, similar to arc lavas. Eclogite is recrystallized from MORB-like altered oceanic crust, presumably at the boundary between the down-going plate and overlying mantle wedge. Eclogite geochemistry, mineralogy and petrography suggest a two step petrogenesis of (1) dehydration during prograde metamorphism at low temperatures (<500 °C) followed by (2) partial rehydration/fertilization at even lower T during exhumation. In contrast, Guatemalan jadeitites are crystallized directly from low-T aqueous fluid as veins in serpentinizing mantle during both subduction and exhumation. The overall chemistry and mineralogy of Guatemalan eclogites are similar to those from the Franciscan Complex, California, implying similar P-T-x paths.Li concentrations (?90 ppm) in mineral separates and whole rocks (WR) from Guatemalan and Franciscan HP-LT rocks are significantly higher than MORB (4-6 ppm), but similar to HP-LT rocks globally. Li isotopic compositions range from −5‰ to +5‰ for Guatemalan HP-LT rocks, and −4‰ to +1‰ for Franciscan eclogites, overlapping previous findings for other HP-LT suites. The combination of Li concentrations greater than MORB, and Li isotopic values lighter than MORB are inconsistent with a simple dehydration model. We prefer a model in which Li systematics in Guatemalan and Franciscan eclogites reflect reequilibration with subduction fluids during exhumation. Roughly 5-10% of the Li in these fluids is derived from sediments.Model results predict that the dehydrated bulk ocean crust is isotopically lighter (δ⁷Li ? +1 ± 3‰) than the depleted mantle (∼+3.5 ± 0.5‰), while the mantle wedge beneath the arc is the isotopic complement of the bulk crust. A subduction fluid with an AOC-GLOSS composition over the full range of model temperatures (50-600 °C) gives an average fluid δ⁷Li (∼+7 ± 5‰ 1σ) that is isotopically heavier than the depleted mantle. If the lowest temperature steps are excluded (50-260 °C) as too cold to participate in circulation of the mantle wedge, then the average subduction fluid (δ⁷Li = +4 ± 2.3‰ 1σ, is indistinguishable from depleted mantle. Because of the relatively compatible nature of Li in metamorphic minerals, the most altered part of the crust (uppermost extrusives), may retain a Li isotopic signature (∼+5 ± 3‰) heavier than the bulk crust. The range of Li isotopic values for OIB, IAB and MORB overlap, making it is difficult to resolve which of these components may contribute to the recycled component in the mantle using δ⁷Li alone.     

Tungsten isotopes as tracers of core-mantle interactions: The influence of subducted sediments

The postulated difference in W isotopic composition of the Earth’s core of ∼2 ε_W units, compared to the bulk silicate earth (BSE) has previously been used to search for evidence of core-mantle interaction (CMI) in ocean island basalts (OIB). The absence of W isotope anomalies has thus been taken as evidence that CMI does not occur. However, the addition of subducted sediment with high W to the sources of OIB could obscure a core signature. This possibility brings into question the utility of W isotopes as tracers for CMI. To accurately consider the effects of sediment addition to mantle sources of OIB with respect to W requires improved constraints on the abundances of W in subducting sediment. Here, we present high-precision W abundance data (and other HFSE) for a suite of sediments from the Banda subduction regime in East Indonesia. Subducting East Indonesian sediments have trace element concentrations that resemble those of average upper continental crust (UCC), making these sediments valuable to consider as typical of subducted sediments. Average W abundances of 2.1 ppm, corrected for carbon content coupled with current models of 0.5% core addition and 1% sediment addition to EM1 or HIMU plume, suggest that a model hybrid source should exhibit values of ε_W = −0.24 with ∼25 ppb W. Prior studies have not reported such low W isotopic compositions or high estimated W concentrations present in the sources of either Hawaiian or French Polynesian lavas, so such large additions of core material to these plume sources seems unlikely. Given these constraints, core contributions to these source, if present, can be no more than ∼0.1%.     

Rhenium and chalcophile elements in basaltic glasses from Ko’olau and Moloka’i volcanoes: Magmatic outgassing and composition of the Hawaiian plume

The behavior of chalcophile metals in volcanic environments is important for a variety of economic and environmental applications, and for understanding large-scale processes such as crustal recycling into the mantle. In order to better define the behavior of chalcophile metals in ocean island volcanoes, we measured the concentrations of Re, Cd, Bi, Cu, Pb, Zn, Pt, S, and a suite of major elements and lithophile trace elements in moderately evolved (6-7% MgO) tholeiitic glasses from Ko’olau and Moloka’i volcanoes. Correlated variations in the Re, Cd, and S contents of these glasses are consistent with loss of these elements as volatile species during magmatic outgassing. Bismuth also shows a good correlation with S in the Ko’olau glasses, but undegassed glasses from Moloka’i have unexpectedly low Bi contents. Rhenium appears to have been more volatile than either Cd or Bi in these magmas.Undegassed glasses with 880-1400 ppm S have 1.2-1.5 ppb Re and 130-145 ppb Cd. In contrast, outgassed melts with low S (<200 ppm) are depleted in these elements by factors of 2-5. Key ratios such as Re/Yb and Cu/Re are fractionated significantly from mantle values. Copper, Pb, and Pt contents of these glasses show no correlation with S, ruling out segregation of an immiscible magmatic sulfide phase as the cause of these variations. Undegassed Hawaiian tholeiites have Re/Yb ratios significantly higher than those of MORB, and extend to values greater than that of the primitive mantle. Loss of Re during outgassing of ocean island volcanoes, may help resolve the apparent paradox of low Re/Os ratios in ocean island basalts with radiogenic Os isotopic compositions. Plume source regions with Re/Yb ratios greater than that of the primitive mantle may provide at least a partial solution to the “missing Re” problem in which one or more reservoirs with high Re/Yb are required to balance the low Re/Yb of MORB.Lithophile trace element compositions of most Ko’olau and Moloka’i tholeiites are consistent with variable degrees of melting of fertile mantle peridotite. However, light rare earth element (LREE)-enriched glasses have trace element compositions more consistent with a garnet-rich source having a distinctive trace element composition. This provides additional evidence for a unique source component possibly related to recycled oceanic crust contributing to Ko’olau tholeiites.     

High-pressure partial melting of gabbro and its role in the Hawaiian magma source

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4–9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ≈10× greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: insights from olivine phenocrysts

A relatively narrow range of oxygen isotopic ratios (?? ¹⁸O?=?5.0?C5.4??) is preserved in olivine of mantle xenoliths, mid-ocean ridge (MORB), and most ocean island basalts (OIB). The values in excess of this range are generally attributed either to the presence of a recycled component in the Earth??s mantle or to shallow level contamination processes. A viable way forward to trace source heterogeneity is to find a link between chemical (elemental and isotopic) composition of the earlier crystallized mineral phases (olivine) and the composition of their parental magmas, then using them to reconstruct the composition of source region. The Canary hotspot is one of a few that contains ~1- to 2-Ga-old recycled ocean crust that can be traced to the core-mantle boundary using seismic tomography and whose origin is attributed to the mixing of at least three main isotopically distinct mantle components i.e. HIMU, DMM, and EM. This work reports ion microprobe and single crystal laser fluorination oxygen isotope data of 148 olivine grains also analyzed for major and minor elements in the same spot. The olivines are from 20 samples resembling the most primitive shield stage picrite through alkali basalt to basanite series erupted on Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro, Canary Islands, for which shallow level contamination processes were not recognized. A broad range of ?? ¹⁸O_olivine values from 4.6 to 6.1?? was obtained and explained by stable, long-term oxygen isotope heterogeneity of crystal cumulates present under different volcanoes. These cumulates are thought to have crystallized from mantle-derived magmas uncontaminated at crustal depth, representing oxygen isotope heterogeneity of source region. A relationship between Ni?×?FeO/MgO and ?? ¹⁸O_olivine values found in one basanitic lava erupted on El Hierro, the westernmost island of the Canary Archipelago, was used to estimate oxygen isotope compositions of partial melts presumably originated from peridotite (HIMU-type component inherited its radiogenic isotope composition from ancient, ~1 to 2?Ga, recycled ocean crust) and pyroxenite (young, <1?Ga, recycled oceanic crust preserved as eclogite with depleted MORB-type isotopic signature) components of the Canary plume. The model calculations yield 5.2 and 5.9?±?0.3?? for peridotite- and pyroxenite-derived melts, respectively, which appeared to correspond closely to the worldwide HIMU-type OIB and upper limit N-MORB ?? ¹⁸O values. This difference together with the broad range of ?? ¹⁸O variations found in the Canarian olivines cannot be explained by thermodynamic effects of oxygen isotopic fractionation and are believed to represent true variations in the mantle, due to oceanic crust and continental lithosphere recycling.     

Geochemistry of Lavas from the Emperor Seamounts, and the Geochemical Evolution of Hawaiian Magmatism from 85 to 42 Ma

The Hawaiian–Emperor Seamount Chain (ESC), in the northernPacific Ocean, was produced during the passage of the PacificPlate over the Hawaiian hotspot. Major and trace element concentrationsand Sr–Nd–Pb isotopic compositions of shield andpost-shield lavas from nine of the Emperor Seamounts providea 43 Myr record of the chemistry of the oldest preserved Hawaiianmagmatism during the Late Mesozoic and Early Cenozoic (from85 to 42 Ma). These data demonstrate that there were large variationsin the composition of Hawaiian magmatism over this period. Tholeiiticbasalts from Meiji Seamount (85 Ma), at the northernmost endof the ESC, have low concentrations of incompatible trace elements,and unradiogenic Sr isotopic compositions, compared with youngerlavas from the volcanoes of the Hawaiian Chain (<43 Ma).Lavas from Detroit Seamount (81 Ma) have highly depleted incompatibletrace element and Sr–Nd isotopic compositions, which aresimilar to those of Pacific mid-ocean ridge basalts. Lavas fromthe younger Emperor Seamounts (62–42 Ma) have trace elementcompositions similar to those of lavas from the Hawaiian Islands,but initial ⁸⁷Sr/⁸⁶Sr ratios extend to lower values. From 81to 42 Ma there was a systematic increase in ⁸⁷Sr/⁸⁶Sr of boththoleiitic and alkalic lavas. The age of the oceanic lithosphereat the time of seamount formation decreases northwards alongthe Emperor Seamount Chain, and the oldest Emperor Seamountswere built upon young, thin lithosphere close to a former spreadingcentre. However, the inferred distance of the Hawaiian plumefrom a former spreading centre, and the isotopic compositionsof the oldest Emperor lavas appear to rule out plume–ridgeinteraction as an explanation for their depleted compositions.We suggest that the observed temporal chemical and isotopicvariations may instead be due to variations in the degree ofmelting of a heterogeneous mantle, resulting from differencesin the thickness of the oceanic lithosphere upon which the EmperorSeamounts were constructed. During the Cretaceous, when theHawaiian plume was situated beneath young, thin lithosphere,the degree of melting within the plume was greater, and incompatibletrace element depleted, refractory mantle components contributedmore to melting. KEY WORDS: Emperor Seamounts; Hawaiian plume; lava geochemistry; lithosphere thickness; mantle heterogeneity     

Heterogeneous mantle melting and magmatic processes at the East Pacific Rise (2.6–3.1°S): Evidence from mid-ocean ridge basalt geochemistry and Sr–Nd–Pb isotopes

ABSTRACT

We present the major and trace elements and Sr, Nd, and Pb isotopes in mid-ocean ridge basalts (MORB) from the East Pacific Rise (EPR) at 2.6–3.1°S. These samples are low-K tholeiites and show significant variation in their major element compositions (e.g. 4.60–8.18 wt% MgO, 8.34–12.12 wt% CaO, 9.78–14.25 wt% Fe₂O₃, and 0.06–0.34 K₂O wt%). Trace element abundances of the 2.6–3.1°S MORB are variably depleted (e.g. (La/Sm), _N = 0.51–0.78, Zr/Y = 2.35–3.42, Th/La = 0.035–0.056, and Ce/Yb = 2.38–3.96) but closely resemble the average N-MORB. In the compatible elements (Ni and Cr) against incompatible element Zr plots, the 2.6–3.1°S MORB show well-defined negative correlations, together with a liquid line of descent (LLD) modelling and petrographic observations, implying a significant role of olivine, plagioclase and clinopyroxene fractionation during magma evolution. When compared to global MORB and peridotites, the 2.6–3.1°S MORB and most of the other axial lavas from the South EPR show similar Zn/Fe, Zn/Mn, and Fe/Mn ratios, attesting to a peridotite-dominated mantle lithology. However, the relationships between incompatible trace element ratios, such as Zr/Rb and Nb/Sm, and the negative correlation between Zr/Nb and ⁸⁷Sr/⁸⁶Sr indicate a geochemically heterogeneous mantle source. The mantle beneath the South EPR likely consists of two components, with the enriched component residing as physically distinct domains (e.g. veins or dikes) in the depleted peridotite matrix. In the Sr–Nd–Pb isotope space, the South EPR MORB lie along the mixing lines between the depleted MORB mantle (DMM) and the ‘C’-like Pukapuka endmember. We infer that low-F melts derived from these enriched materials may cause localized mantle heterogeneity (veins or dikes) via an infiltration process. Subsequent melting of the refertilized mantle may impart an isotopically distinct characteristic to South EPR MORB.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).