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ArticleVolume 13, Number 919 September 2012Q09009, doi:10.1029/2012GC004268ISSN: 1525-2027Major element variations in Hawaiian shield lavas: Sourcefeatures and perspectives from global ocean island basalt(OIB) systematicsMatthew G. JacksonDepartment of Earth Sciences, Boston University, 675 Commonwealth Avenue, Boston, Massachusetts02215, USA (jacksonm@bu.edu)Dominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences,University of British Columbia, 6339 Stores Road, Vancouver, British Columbia V6T1Z4, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, 20 Oxford Street, Cambridge,Massachusetts 02138, USA[1] Among volcanic hot spots globally, Hawaii has the highest magma flux, yet there is significant contro-versy surrounding the composition of the mantle sourcing Hawaiian lavas. In order to place constraints onthe source lithologies of Hawaiian lavas, we explore relationships between major elements and radiogenicisotopes in tholeiitic, shield-building lavas. Olivine-fractionation corrected lava compositions reveal cleartrends between radiogenic isotopes and major elements. Individual data points exhibit remarkable trendsand there is no need to average the data by volcano. Data form arrays that are anchored by Koolau lava atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2, and Na2O/TiO2, and low143Nd/144Nd, 206Pb/204Pb, TiO2,CaO and CaO/Al2O3) and by Kea and Loihi lavas at the other (with low87Sr/86Sr, 187Os/188Os, SiO2, andNa2O/TiO2, and high143Nd/144Nd, 206Pb/204Pb, TiO2, CaO and CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with radiogenic isotopes. The Hawaiian data set exhibits correlations that mirrorthe best correlations between major elements and radiogenic isotope in the global ocean island basalt (OIB)database. We suggest that the mechanism driving the correlations in Hawaii illustrates, in microcosm, alarger global process that generates major element variability in mantle plumes. Like the global arrays, theHawaiian lavas with radiogenic Pb and SiO2-poor lavas are sourced by a SiO2-poor mafic component (pyrox-enite) admixed with peridotite, while Hawaiian lavas with unradiogenic Pb and high SiO2 are sourced by aSiO2-rich mafic component (eclogite). The variable SiO2 in the mafic component may result from differentdegrees of SiO2-extraction from the slab during subduction.Components: 14,700 words, 10 figures, 1 table.Keywords: Hawaii; eclogite; hotspot; isotopes; mantle plume; pyroxenite.Index Terms: 1025 Geochemistry: Composition of the mantle; 1033 Geochemistry: Intra-plate processes (3615, 8415); 1038Geochemistry: Mantle processes (3621).Received 4 June 2012; Revised 25 July 2012; Accepted 10 August 2012; Published 19 September 2012.?2012. American Geophysical Union. All Rights Reserved. 1 of 24Jackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features andperspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.1. Introduction[2] Oceanic plates?including mafic crust, depletedlithospheric peridotite, and a thin veneer of marinesediments?are sent into the mantle at subductionzones, thereby contributing to the compositionalheterogeneity of Earth?s mantle [Hofmann andWhite, 1982; White and Hofmann, 1982; Iwamoriet al., 2010]. Buoyantly upwelling regions of themantle are thought to return parts of these subductedoceanic plates to the shallow mantle, where theypartially melt beneath hot spots like Hawaii. Lavaserupted at hot spots therefore reveal clues about thedynamic history and composition of the mantle[Zindler and Hart, 1986; Hofmann, 1997]. Thecompositions of hot spot lavas suggest that recyclingof ancient subducted oceanic plates is a commonprocess that has affected the geochemistry of themantle over geologic time [e.g., Hofmann andWhite, 1982; Sobolev et al., 2005].[3] However, significant controversy surrounds thefinal fate of recycled oceanic crust in the mantle[Eggins, 1992; Hauri, 1996; Wagner and Grove,1998; Putirka, 1999; Sobolev et al., 2005, 2007;Gaffney et al., 2005; Huang and Frey, 2005; Huanget al., 2007; Herzberg, 2006, 2011; Putirka et al.,2011; Niu et al., 2012]. Following billion-yeartimescales of residence in the mantle, oceanic crustis likely stretched, thinned, and its geochemicalsignal is greatly attenuated [e.g., Ottino, 1989; VanKeken et al., 2004]. While distinct mafic litholo-gies may survive mantle convection to be meltedbeneath hot spots like Hawaii [Hauri, 1996; Sobolevet al., 2005, 2007, 2008; Huang and Frey, 2005;Huang et al., 2007; Herzberg, 2006, 2011], thesurvival of distinct mafic lithologies into the man-tle beneath Hawaii has been questioned [Putirka,1999; Salters et al., 2006; Putirka et al., 2011].Putirka [1999] and Putirka et al. [2011] argue thatperidotite melting can explain the geochemistry ofHawaiian lavas, and a distinct mafic lithology in themantle source of Hawaiian lavas is not required.[4] Hawaii is arguably the most-studied oceanic hotspot, and the abundance of geochemical data obtainedfrom Hawaiian lavas makes it an ideal location forevaluating the presence of recycled oceanic crust inthe mantle source. While a multitude of componentshave been identified in the Hawaiian mantle, mostof the isotopic variability in Hawaiian shield-buildinglavas can be described with just three components,as shown by principal component analysis [Hauri,1996; Eiler et al., 1996a]. These componentsinclude the Koolau, Loihi and Kea components(Figure 2) [Stille et al., 1986; West and Leeman,1987; Eiler et al., 1996b; Hauri, 1997; Gaffneyet al., 2005; Huang et al., 2005; Weis et al., 2011].The small volumes of low-degree melts sampled bypost-shield and rejuvenated lavas require the pres-ence of a fourth, depleted component, distinct fromPacific MORB [Mukhopadhyay et al., 2003; Freyet al., 2005; Fekiacova et al., 2007; Garcia et al.,2010; Hanano et al., 2010], but post-shield andrejuvenated-stage lavas are volumetrically insignif-icant compared to the shield-building lavas andthese lavas are not considered here. Hawaii is thearchetypal high 3He/4He hot spot, and lavas fromLoihi seamount define the Loihi component andhost 3He/4He ratios in excess of 30 Ra (ratio toatmosphere) [Kurz et al., 1982; Rison and Craig,1983; Kurz et al., 1983; Staudigel et al., 1984;Sarda et al., 1988; Honda et al., 1993; Valbrachtet al., 1997; Eiler et al., 1998; Jackson et al., 2008].TheKoolau component, defined byKoolauMakapuu-stage lavas, is a lower 3He/4He end-member charac-terized by the lowest 143Nd/144Nd and 206Pb/204Pband highest 87Sr/86Sr in Hawaii and constitutes theenriched Loa trend volcanic end-member (see below)[Tanaka et al., 2008]. This end-member is sampledin diluted form at several Hawaiian volcanoes andlikely hosts a component of recycled oceanic crustand sediment [e.g., Hauri, 1996; Lassiter andHauri, 1998; Blichert-Toft et al., 1999; Normanet al., 2002; Sobolev et al., 2005; Huang et al.,2005, 2011a; Herzberg, 2011; Putirka et al., 2011].The origin of the Kea component, best exemplifiedby lavas from Mauna Kea, W. Maui and Kilauea, isless clear. The Kea component, which hosts thehighest 143Nd/144Nd and 206Pb/204Pb and the lowest87Sr/86Sr in Hawaii, is relatively homogeneous rel-ative to the Koolau component, leading to modelssuggesting a MORB-source, Pacific oceanic litho-sphere source or entrained asthenospheric source inKea lavas, but recycled lower oceanic crust andmantle lithosphere also have been suggested [Chenand Frey, 1985; Frey and Rhodes, 1993; Hauri,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042682 of 241996; Eiler et al., 1996a, 1996b; Lassiter and Hauri,1998; Blichert-Toft et al., 2003; Gaffney et al., 2005].The Kea component dominates the Kea volcanictrend (see below).[5] The distribution of the Loa and Kea componentsis organized geographically along the hot spot(Figure 1). Hawaiian shield volcanoes erupted duringthe past 5 Ma tend to be oriented along two en ech-elon volcanic trends that exhibit distinct isotopic [e.g.,Jackson et al., 1972; Tatsumoto, 1978; Abouchamiet al., 2005; Tanaka et al., 2008; Farnetani andHofmann, 2010; Weis et al., 2011; Huang et al.,2011b] and major element [Hauri, 1996; Greeneet al., 2010] compositions. Volcanoes along thenorthern geographic trend erupt Kea-type lavas andsouthern-trend volcanoes tend to erupt Loa-typelavas. The origin of this geographic and geochemi-cal separation is the source of significant discussion[e.g., Hieronymus and Bercovici, 1999; Abouchamiet al., 2005; Ren et al., 2005; Marske et al., 2007;Weis et al., 2011; Huang et al., 2011b]. Under-standing the origin of the different major elementcompositions of shield-stage lavas between the Loaand Kea trends [Hauri, 1996] may provide impor-tant clues about the structure of the Hawaiian plume,including the possible organization of lithologicheterogeneities within the plume conduit [Blichert-Toft et al., 2003; Abouchami et al., 2005] and inthe deep mantle [Weis et al., 2011; Huang et al.,2011b].[6] Frey and Rhodes [1993] systematically docu-mented major element variations among differentHawaiian shields and attributed them to mantlesource variability. However, correlations betweenmajor elements and isotopes can strengthen con-clusions that major element variations in hot spotlavas reflect mantle source lithological heterogene-ity [Hauri, 1996; Sobolev et al., 2008; Jackson andDasgupta, 2008]. Hauri [1996] showed correlatedmajor element and isotopic variations in composi-tional and isotopic averages of Hawaiian volcanoes,and on this basis, argued for major element vari-ability in the Hawaiian mantle and for the impor-tance of eclogite in the petrogenesis of Hawaiianshield lavas. Jackson and Dasgupta [2008] extentsuch major element-isotope correlation to the globalOIB data set. Here we show that the original ele-ment-isotope correlations observed by Hauri [1996]are ?mirrored? by the global OIB data set [Jacksonand Dasgupta, 2008]. These data document themajor element variability in the Hawaiian plume,constrain source lithologies, and place the majorelement variability in the Hawaiian plume in thecontext of global OIB variability.2. Treatment of Geochemical Data[7] The geochemical data used in this study wereobtained from the Georoc database (georoc.mpch-mainz.gwdg.de/georoc) on December 26, 2011.Only tholeiitic lavas are considered. All non-tholeiitic lavas [Macdonald and Katsura, 1964] areexcluded, as are lavas that are explicitly described aspost-shield or rejuvenated. Only lavas with a com-plete set of major elements (SiO2, TiO2, Al2O3,FeOtotal, MnO, MgO, CaO, Na2O, K2O, P2O5) areconsidered. A sample is excluded if it does not haveat least one of the following isotopic measurements:87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb), 187Os/188Os, 176Hf/177Hf, or3He/4He. Compared to Sr, Nd and Pb isotopes, andHf isotopes to a lesser extent, measurements ofHe and Os isotopes are still relatively rare. Lavaswith low Os concentrations are susceptible to con-tamination by assimilation of materials with radio-genic Os. Therefore, Os-poor (Os < 40 ppt) lavas areexcluded [Class et al., 2009]. Similarly, lavas withlow helium concentrations are susceptible to reduc-tion of 3He/4He by post-eruptive radiogenic ingrowthof 4He or crustal assimilation, and analyses of He-poor olivines and glasses (less than 2*108 cc/g STP4He) are excluded [Garcia et al., 1990; Hilton et al.,1995; Kurz et al., 2004; Class and Goldstein, 2005].Only 3He/4He measurements obtained by crushingolivines and glasses are used. Much of the heliumisotopic data available for Hawaiian lavas are elimi-nated using the concentration filter, but we feel thatthe filter yields a data set that better reflects mantle3He/4He compositions. However, all 3He/4He mea-surements are preserved in Data Set S1 in theauxiliary material, regardless of 4He concentration, aslong as the associated whole rock major elementanalyses do not indicate excessive alteration ormagmatic evolution.1[8] As a filter for alteration, samples with K2O/P2O5< 1, low dry totals (<97 wt.%) or high dry totals(>101 wt.%) were excluded [e.g., Frey et al., 1994].Leaching is necessary to reduce alteration compo-nents in lavas that most strongly influence Sr and Pbisotopic ratios but not Nd and Hf isotopic ratios[Nobre Silva et al., 2009, 2010]. However, it is notalways known which samples were leached in acid1Auxiliary material data sets are available at ftp://ftp.agu.org/apend/gc/2012gc004268. Other auxiliary materials are available inthe HTML. doi:10.1029/2012GC004268.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042683 of 24prior to isotopic analyses, as this is not consistentlyreported in the literature. Fortunately, Sr and Pbisotopic ratios show excellent correlations with Ndand Hf isotopic ratios in Hawaiian volcanoes(Figure 2). Owing to these correlations, we show Ndand Pb isotopic data, but not Sr and Hf isotopic data,in subsequent figures. Sr and Hf isotopic data,where available, are preserved in Data Set S1.[9] Low MgO lavas (<6.5 wt.%) were not includedin the filtered data set. Such lavas can suffer fromclinopyroxene and plagioclase fractionation [e.g.,Rhodes and Vollinger, 2004; Rhodes et al., 2012].Lavas with MgO > 6.5 wt.% are affected primar-ily by fractionation or accumulation of olivine Cr-spinel [Hauri, 1996].[10] The lavas remaining (n = 551) after thesefiltering steps were renormalized to 100 wt.% totals(on a dry basis) with all Fe reported as FeOtotal(see Data Set S1). The lavas were then corrected forolivine fractionation to a constant MgO of 16 wt.%by adding or subtracting equilibrium olivine in 0.01wt.% increments, similar to Langmuir et al. [1992].Equilibrium olivines were generated using theolivine-melt Kd of 0.3 [Roeder and Emslie, 1970;Ford et al., 1983] assuming 10% of the total iron isFe3+. Correcting the lavas for olivine fractionation/addition until they are in equilibrium with a mantleolivine (forsterite 90) does not change our conclu-sions (see Table 1, Figure S1, and Data Set S1). Anolivine-melt Kd of 0.34 has been suggested forMauna Kea lavas [e.g., Matzen et al., 2011], whichdoes not change our conclusions (see Figure S1 andData Set S1). For cumulates (MgO > 20 wt.%), wefollow the procedure of Hauri [1996] and subtractan olivine composition of forsterite 87 until the bulklava has 16 wt.%MgO. All of the major element andisotopic data, and major element data corrected forolivine fractionation, are reported in Data Set S1for individual samples and in Table 1 as volcanoaverages.3. Observations3.1. Radiogenic Isotopes[11] The panels of Figure 2 show the variability inradiogenic isotopes in the lavas considered in thisstudy. Every lava considered in this study has bothmajor element data (n = 551) and at least one radio-genic isotope system measured (87Sr/86Sr [n = 444],143Nd/144Nd [n = 417], 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb) [n = 452], 176Hf/177Hf [n = 229],187Os/188Os [n = 86], 3He/4He [n = 152 for all 4Heconcentrations, or 48 for samples with 4He > 2*108cc STP/g]). The radiogenic isotopic data shown inFigure 2 are intended to show the isotopic variabilityin the freshest, least evolved Hawaiian shield lavasthat we examined in this study, and therefore the datain the figures do not encompass the complete radio-genic isotopic variability in Hawaiian lavas.Figure 1. Map of Hawaiian hot spot from Loihi to Kauai showing individual volcanoes (map made usingGeoMapApp, http://www.geomapapp.org).GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042684 of 24Table1(Sample).MeanIsotopicandMajorElementCompositionsforHawaiianVolcanoesExaminedinThisStudya[ThefullTable1isavailableintheHTMLversionofthisarticle]VolcanoIsland143Nd/144NdAverage2SD87Sr/86SrAverage2SD206Pb/204 PbAverage2SD207Pb/204PbAverage2SD208Pb/204PbAverage2SD187Os/188OsAverage2SDLoa-trendLoihi(tholeiitic)BigIsland0.5129530.0000700.7035810.00013118.3760.13315.4680.03038.1180.1220.13330.0046MaunaLoaBigIsland0.5129060.0000740.7038090.00066818.1680.17615.4600.02437.9080.1380.13560.0030HualalaiBigIsland0.5129030.0000510.7037270.00008618.1820.13215.4590.02537.9510.1590.13480.0016MahukonaBigIsland0.5129620.0000680.7036390.00015518.2530.22215.4690.01437.9410.152NAKahoolaweMauiNui0.5128480.0000990.7041200.00031818.0420.31415.4360.03037.8290.2190.1439LanaiMauiNui0.5127700.0001210.7041810.00031617.9220.09815.4370.01637.7530.057NAWestMolokaiMauiNui0.5129430.0002160.7038190.00039418.2530.44515.4600.02537.9390.254NAKoolau(Makapuu)Oahu0.5127570.0000770.7040820.00031517.8540.07415.4380.02637.7730.0710.14260.0075Koolau(KSDP)Oahu0.5129170.0000830.7037600.00017318.0630.08115.4530.00737.8370.051NAKoolau(NuuanuLandslide)Oahu0.5129720.0000590.7035680.00016118.2040.36615.4480.01737.8830.2400.13370.0056WaianaeOahu0.5129750.0001260.7036480.00019418.1460.20615.4610.03737.8560.117NAKauaiKauai0.5129690.0000560.7036710.00022918.2280.16615.4510.01537.9390.0980.13680.0038Kea-trendKilaueaBigIsland0.5129580.0000270.7035840.00009918.4640.20515.4830.05538.1040.1890.13100.0017MaunaKeaBigIsland0.5129680.0000360.7035840.00009418.4970.18115.4830.02538.1040.1710.12970.0011KohalaBigIsland0.5130150.0000000.7037100.00008718.1700.27615.4600.04137.8450.1480.13650.0115HaleakalaMauiNui0.5129580.0000400.7036450.00019418.5410.22015.4800.01938.1540.1830.13040.0000WestMauiMauiNui0.5130250.0000480.7035500.00014018.4310.14215.4830.03137.9570.1280.13210.0011EastMolokaiMauiNui0.5129810.0000830.7035650.00020718.4370.41015.4800.03238.0600.255NAa Meansandthestandarddeviations(SD,2sigma)arefromDataSetS1.Ifthestandarddeviationisnotreported,itisbecauseonlyasinglemeasurementisavailable.Majorelementcompositionsarecorrectedforolivinefractionation/additiontoaconstantMgO(16wt.%)ortobeinequilibriumwithaforsterite90olivinecomposition(butthetwodifferentcorrectionschemesyieldsimilarmajorelementcompositions).Anolivine-meltKdof0.30isusedforcorrection.Dataforsamplesareexcludedifthewholerockisaltered,highlyevolved,orifthemajorelementdataareincompleteortheanalysesyieldshighorlowtotals(seetextforfiltersapplied).HeliumandOsisotopedataexistformanyofthevolcanoeslistedasNAinthetable,butinseveralcases,correspondingmajorelementdatadoesnotexist,orindicatesexcessivemagmaticevolutionorpost-eruptivealteration,andtheHeandOsdataarenotreported.Sr,Nd,PbandHfisotopesarenotfilteredbasedontraceelementconcentrations.Inonecolumn,heliumisotopicratiosforsampleswithlowheliumconcentrations(<2*10-8cc4He/gSTP)arenotreported(?HighHeconc?).However,heliumisotopicratioswithlowerconcentrationsarepreservedinthenextcolumn(?AllHeconc?)andinDataSetS1.OsisotopesareexcludediftheOsconcentrationis<40ppt.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042685 of 24Figure 2GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042686 of 24[12] The radiogenic isotopic compositions of Hawai-ian shield lavas have been discussed at great length inthe literature (for a recent review, see Weis et al.[2011]). We outline some of the most outstandingfeatures of the radiogenic isotopic geochemistry ofHawaiian lavas in Figure 2. In general, Loa-trendlavas have lower 206Pb/204Pb, 143Nd/144Nd and176Hf/177Hf and higher 187Os/188Os, 87Sr/86Sr and208Pb*/206Pb* (208Pb*/206Pb* = (208Pb/204Pb -29.475)/(206Pb/204Pb - 9.306) [Hofmann, 2003]) thanKea-trend lavas (Figure 2).[13] In isotope space, Hawaiian lavas define cleararrays that resolve the Loa- and Kea-trends. Forexample, in 208Pb/204Pb versus 206Pb/204Pb isotopespace (Figure 2), Kea-trend volcanoes tend to havemore radiogenic 206Pb/204Pb values than Loa-trendvolcanoes. Kea-trend volcanoes?including MaunaKea, Kilauea, Haleakala, E. Molokai and W. Maui?define the most radiogenic Pb-isotopic compositionsin Hawaii. By contrast, Loa-trend volcanoes tend tohave less radiogenic 206Pb/204Pb (and a higher208Pb/204Pb for a given 206Pb/204Pb) than Kea-trendvolcanoes. Koolau, Kahoolawe and Lanai, theHawaiian volcanoes with the most geochemicallyenriched 143Nd/144Nd and 87Sr/86Sr, also have theleast radiogenic 206Pb/204Pb. However, Loihi, theyoungest Loa-trend volcano, has depleted (high)143Nd/144Nd and (low) 87Sr/86Sr signatures andradiogenic Pb-isotopic compositions, similar to Kea-trend volcanoes. The Pb-isotopic compositions inLoihi lavas extend to values encountered only in theKea trend volcanoes, including Mauna Kea andKilauea (and the Hilina-stage of Kileaua in particular[Kimura et al., 2006]). However, Loihi generally hasa higher 208Pb/204Pb at a given 206Pb/204Pb, andtherefore higher 208Pb*/206Pb*, than Kea-trend vol-canoes. In general, all other Loa-trend volcanoes plotbetween Loihi and the geochemically extremeKoolau-component lavas from Koolau, Kahoolaweand Lanai.3.2. Major Element Variation Diagrams[14] Plots of whole rock MgO concentrations ver-sus the other major element oxides (Figure 3)?including SiO2, TiO2, CaO, Al2O3, FeOtotal andNa2O?are useful for showing enrichments ordepletions of these elements at various stages ofmagmatic evolution. The Loa- and Kea- trend vol-canoes, which exhibit different isotopic character-istics, also tend to follow different trends in severalof the major element variation diagrams.[15] At a given MgO content, Loa-trend volca-noes tend to have higher SiO2 and lower TiO2and CaO contents than Kea-trend volcanoes. How-ever, Loihi seamount, another Loa-trend volcano,has among the lowest SiO2 and the highest TiO2 andCaO concentrations in Hawaii. Loihi lavas overlapcompositionally with the major element composi-tions found in the extreme Kea-component volca-noes, Mauna Kea and Kilauea. Al2O3 exhibits littlevariability among volcanoes at a given MgO. It ispossible that the Loa-trend volcanoes with thelowest 143Nd/144Nd?Koolau, Lanai and Kahoo-lawe?have slightly higher Al2O3 and Na2O andlower FeOtotal contents than Loihi and the Kea-trendvolcanoes, but the differences, if real, are small (SeeSection 3.3).[16] In Figure 3, we show that 208Pb*/206Pb* exhibitsno relationship with MgO. This suggests that magmaevolution and crustal assimilation, which can modifyMgO abundances, are not responsible for generatingthe variability in 208Pb*/206Pb*, which is a sourcefeature [e.g., Hofmann, 2003]. This observation isimportant, as several major element oxides (SiO2,CaO, TiO2) exhibit clear relationships with208Pb*/206Pb* (See Section 3.3, Figure 4) after cor-rections for olivine fractionation/addition are made.3.3. Major Elements Versus Isotopes[17] The Loa- and Kea-trend volcanoes exhibitisotopic (Section 3.1) andmajor element (Section 3.2)differences. The isotopic variations in Hawaiianshield lavas also exhibit clear relationships witholivine fractionation-corrected major element oxideabundances.[18] Fractionation-corrected SiO2, CaO and TiO2concentrations and Nd and Pb isotopic ratios showFigure 2. Plots of radiogenic isotope ratios for data included in this study. Note that the radiogenic isotope data in thefigures includes only samples with the major element data indicating that the lavas are not highly evolved or altered.Koolau lavas are divided into three groups: Makapuu (MAK), Koolau scientific drilling project (KSDP), and theNuuanu landslide (NUU). The approximate isotopic composition of the 3 geochemical components in Hawaii (as iden-tified in lavas) are labeled in the figure: Koolau, Loihi and Kea. Many lavas have only one of the radiogenic isotopedata and do not appear in any of the panels (but lavas with a single radiogenic isotope ratio do appear in the other datafigures). Similarly, lavas that do not possess the full suite of radiogenic isotopic compositions appear in some, but notall, of the panels.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042687 of 24Figure 3. Major element variation diagrams plotting MgO against SiO2, Al2O3, FeOtotal, Na2O, CaO and TiO2.A plot of MgO versus 208Pb*/206Pb* is also shown. The major elements in the panels of this figure have not been cor-rected for olivine fractionation or addition. Lavas with MgO lower than 6.5 wt.% are not considered in this study, andare not shown in the diagrams. K2O, P2O5 andMnO are not shown, but data are available in Data Set S1. Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042688 of 24the clearest relationships, and define arrays in theHawaiian data set [Hauri, 1996] (Figure 4). Lavasfrom the Makapuu-stage of Koolau, Lanai andKahoolawe anchor one extreme of the arrays, andhave the lowest 143Nd/144Nd, 206Pb/204Pb, CaOand TiO2 and the highest SiO2 and208Pb*/206Pb*.The other end of the Hawaiian array is anchoredby Loihi and the extreme Kea-trend volcanoes,Mauna Kea and Kilauea, which define the highest143Nd/144Nd, 206Pb/204Pb, CaO and TiO2 and thelowest 208Pb*/206Pb* and SiO2 (Figure 4).[19] Contrary to the findings of Hauri [1996], theother fractionation-correctedmajor element oxides?FeOtotal, Al2O3 and Na2O?do not exhibit clearrelationships with Nd and Pb-isotopic compositions(Figure 5). When plotted against 206Pb/204Pb, theFigure 4. Olivine fractionation-corrected SiO2, TiO2, and CaO oxide abundances are plotted against143Nd/144Ndand 208Pb*/206Pb*. SiO2, TiO2, and CaO exhibit similar relationships with87Sr/86Sr and 176Hf/177Hf (not shown).An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to 16 wt.% MgO. See Table 1, Figure S1, andData Set S1 for alternative olivine fractionation/addition schemes. Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042689 of 24fractionation-corrected FeOtotal concentrations of theextreme low 143Nd/144Nd Loa-trend lavas?all fromKoolau, Kahoolawe and Lanai?appear to be shiftedto slightly lower values than Kea-trend volcanoesand Loihi. Fractionation-corrected Al2O3 and Na2Oconcentrations appear to be offset to somewhathigher values in most of Loa-trend lavas, whileHawaiian lavas with the highest 143Nd/144Nd,including Loihi and Kea-trend volcanoes, tend tohave slightly lower Al2O3 and Na2O abundances.However, care must be taken when generalizingabout relationships between radiogenic isotopes andFeOtotal, Al2O3 and Na2O, as there is significantscatter in the data and the trends (if any) are not asclear as with SiO2, CaO and TiO2.[20] Two major element ratios not affected byolivine fractionation, CaO/Al2O3 and Na2O/TiO2,exhibit striking relationships with Nd and Pb-isotopiccompositions (Figure 6), as noted previously[Hauri, 1996; Putirka, 1999]. CaO/Al2O3 ratios arelowest and Na2O/TiO2 ratios are highest in the mostextreme low 143Nd/144Nd Loa-trend lavas fromFigure 5. Olivine fractionation-corrected FeOtotal, Al2O3and Na2O abundances are plotted against206Pb/204Pb. Thecorrelations (if any) are poor. 143Nd/144Nd, 87Sr/86Sr and176Hf/177Hf also fail to exhibit clear relationships withFeOtotal, Al2O3, and Na2O (not shown). An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.Figure 6. CaO/Al2O3 and Na2O/TiO2 oxide ratios areplotted against 208Pb*/206Pb*. 143Nd/144Nd, 87Sr/86Srand 176Hf/177Hf exhibit similar relationships with CaO/Al2O3 and Na2O/TiO2 (not shown). Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426810 of 24Koolau, Kahoolawe and Lanai. Loihi lavas andextreme Kea-trend lavas from Mauna Kea andKilauea have the highest CaO/Al2O3 and the lowestNa2O/TiO2.[21] Helium and Os isotopic ratios show clear rela-tionships with fractionation-corrected major elementcompositions and major element ratios. 3He/4Heexhibits trends with SiO2, CaO, Al2O3, CaO/Al2O3and FeOtotal [Kurz et al., 2004; Herzberg, 2011;Hauri, 1996], but not with TiO2 and Na2O abun-dances or with Na2O/TiO2 ratios (Figure 8). High3He/4He lavas from Loihi anchor the low-SiO2 andAl2O3 and high-CaO, CaO/Al2O3 and FeOtotalportions of the arrays. When plotted against olivinefractionation corrected major element abundancesand major element ratios, extreme Loa-componentlavas with the highest 187Os/188Os (and high SiO2,Al2O3, Na2O and Na2O/TiO2, and low TiO2, FeOtotal,CaO, and CaO/Al2O3) anchor one portion of the arrayand Loihi and the extreme Kea-component lavas withlow 187Os/188Os (and low SiO2, Al2O3, Na2O andNa2O/TiO2 and high TiO2, FeOtotal, CaO and CaO/Al2O3) anchor the other extreme of the arrays.4. Origin of Major Element Variabilityin Hawaiian Lavas[22] While assimilation of oceanic crust has beensuggested to modify the isotopic compositions ofoxygen [Wang et al., 2003], heavy noble gases[e.g., Kent et al., 1999] and 187Os/188Os (in Os-poorlavas [e.g., Martin et al., 1994]) in some Hawaiianlavas, shallow processes operating in the oceaniccrust are not likely to be responsible for the observedrelationships between radiogenic isotopes andfractionation-corrected major element abundancesin the filtered data set. First, highly evolved lavas,which are most susceptible to being modified byassimilation, are not considered in this study.Second, radiogenic isotopes exhibit no relationshipwith MgO (Figure 3), a proxy for magmatic evolu-tion. This suggests that crustal assimilation is notresponsible for generating variability in radiogenicisotopes and major elements. Third, the Sr-Nd-Pb-Hfisotopic compositions of altered oceanic crust andoceanic sediment in the Hawaiian region are unlikeHawaiian lavas or geochemical end-member com-positions sampled by Hawaiian lavas [Hauri, 1996;Lassiter and Hauri, 1998; Blichert-Toft et al., 1999;Hanano et al., 2010]. Therefore, assimilation of localoceanic crust and sediments is not the mechanismresponsible for driving relationships between majorelements and radiogenic isotopes in Hawaiian lavas.Consequently, the observed major element-isotopeFigure 7. Olivine fractionation-corrected SiO2 andTiO2 oxide abundances and Na2O/TiO2 ratios are plottedagainst 187Os/188Os. Olivine fractionation correctedFeOtotal, Na2O, Al2O3 and CaO oxide abundances andCaO/Al2O3 ratios also exhibit relationships with187Os/188Os, but are not shown here. An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426811 of 24Figure 8. Olivine fractionation-corrected SiO2, CaO, Al2O3 and FeOtotal oxide abundances and CaO/Al2O3 ratios areplotted against 3He/4He. Olivine fractionation corrected Na2O and TiO2 oxide abundances and Na2O/TiO2 ratios exhibitno relationships with 3He/4He and are not shown here. An olivine-melt Kd of 0.30 is used for olivine fractionation/additionto 16 wt.%MgO. See Table 1, Figure S1, and Data Set S1 for alternative olivine fractionation/addition schemes. Colors anddata symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426812 of 24correlations in Hawaiian shield lavas (Figures 4and 6?8) reflect mantle source heterogeneity. Herewe examine each of the three Hawaiian componentsin turn?Koolau, Loihi and Kea?and evaluate theorigin of the major element variability and discusspossible mechanisms that drive the observed rela-tionships between radiogenic isotopes and olivine-fractionation corrected major element compositions.4.1. The Koolau Component:The Enigmatic Eclogite4.1.1. Bulk Lava Major Element CompositionsFrom Peridotite or Eclogite Melts?[23] Makapuu stage lavas from Koolau volcanoexhibit the most enriched 143Nd/144Nd in Hawaiiand sample the end-member Koolau-componentcompositions [Roden et al., 1994], and they anchorthe low CaO, high SiO2 portion of the arrays formedin major element versus isotope space in Figure 4.Makapuu-stage Koolau lavas play a central role inthe debate on the role of eclogite melting in theHawaiian plume [e.g., Hauri, 1996; Huang andFrey, 2005; Salters et al., 2006; Huang et al.,2007; Sobolev et al., 2005, 2007; Herzberg, 2011;Putirka et al., 2011], and we explore the argumentssurrounding eclogite versus peridotite melting.[24] One argument against the generation ofMakapuu-stage Koolau melts by peridotite melting hinges onhigh pressure and temperature experiments performedon a Kilauea high-MgO glass composition. Eggins[1992] and Wagner and Grove [1998] showedexperimentally that the major element compositionsof the high MgO Kilauea glasses cannot be in equi-librium with both garnet and olivine (i.e., garnetperidotite). This is important because Hawaiianshield lavas exhibit heavy rare earth element(HREE) depletions and, after correction for olivinefractionation, relatively constant concentrations ofHREE [Hofmann et al., 1984], which require resid-ual garnet in the mantle source of the lavas[Hofmann et al., 1984; Huang and Frey, 2005].Instead, Eggins [1992] and Wagner and Grove[1998] found that Kilauea glasses are in equilib-rium with a harzburgite (olivine + orthopyroxene)residue, but this phase assemblage will not generatethe residual garnet signature observed in Hawaiianlavas.[25] The SiO2 contents of Kilauea glasses are alsotoo high to be melts of garnet peridotite [Hauri,1996; Wagner and Grove, 1998], and KoolauMakapuu-stage lavas have even higher SiO2 thanthe Kilauea lavas, which excludes garnet peridotiteas a source for the Koolau component (Figure 4).Similarly, the FeOtotal versus SiO2 systematics ofMakapuu-stage Koolau lavas are inconsistent withexperimentally derived partial melts of peridotite atgarnet stability field pressures [Hauri, 1996]. Whilelow pressure (1?1.5 GPa) partial melts of perido-tites can yield the high SiO2 contents found in theselavas, the FeOtotal of low pressure partial melts istoo low. There are at least two reasons why suchlow pressures of melting are not feasible. First, lowpressures of melting (1?1.5 GPa) are below thoseof the field of garnet stability and will not generatethe residual garnet signature observed in Hawaiianlavas [Hofmann et al., 1984; Huang and Frey,2005]. Second, the lithosphere beneath Hawaii istoo thick to permit such shallow melting (<45 km)[Hauri, 1996].[26] Water addition to peridotite can increase theSiO2 content of melts at low pressures of melting[Parman and Grove, 2004]. However, wet meltingof garnet peridotite does not increase the melt SiO2concentration [Tenner et al., 2012], and existingwet melting experiments of garnet peridotite cannotexplain the high SiO2 in Koolau lavas.[27] Nonetheless, Putirka et al. [2011] suggest thateclogite/garnet pyroxenite are not required for thepetrogenesis of Hawaiian lavas, and that peridotitemelting can generate the entire observed composi-tional range. Using a compilation of experimentalmelt data generated from a range of peridotiticcompositions at different pressure and temperatureconditions, they argue that the major elementcompositions of parental magmas of Makapuu-stage Koolau lavas can be explained by mixing ofpartial melts from different peridotite meltingexperiments. However, there is no single experi-mental melt that matches the extreme compositionof Makapuu-stage Koolau lavas (i.e., high SiO2,low FeO and CaO). While Putirka et al. [2011]argued that the primary magma composition ofMakapuu-stage Koolau lavas can be reproduced bymixing three experimental melts [see Putirkaet al., 2011, equation 6], the three experimentalmelts (i.e., H154 from Kinzler and Grove [1992],T-762 from Falloon et al. [1988], and T-3572from Falloon and Danyushevsky [2000]) are all low-pressure melts (1?2 GPa) and have only olivine andorthopyroxene as residual phases. Consequently,these experiments are inconsistent with REE con-centrations and patterns in Hawaiian lavas, whichrequire garnet as a residual phase during melting.[28] In summary, existing experimental peridotitemelt data and melt-rock reaction models do notGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426813 of 24explain the composition of Makapuu-stage Koolaulavas. While we cannot exclude the possibility thatfuture peridotite melting experiments may match theunusual major element compositions of Makapuu-stage Koolau, we note that eclogite melting in theHawaiian mantle source may provide a mechanismfor generating the highest SiO2 Hawaiian lavas.Eclogite has been invoked to explain the combinedresidual garnet signature and high SiO2 content ofMakapuu-stage Koolau lavas [Hauri, 1996; Huangand Frey, 2005; Sobolev et al., 2005, 2007]. Thelow CaO contents of Makapuu-stage Koolau lavasare also consistent with partial melting of eclogite[Huang and Frey, 2005; Herzberg, 2006]. Herzberg[2006] parameterized the peridotite melting experi-ments of Walter [1998] and argued that mostHawaiian shield lavas have CaO contents that aretoo low to be partial melts of peridotite [Pertermannand Hirschmann, 2003]. Since Makapuu-stageKoolau lavas have the lowest CaO contents at agiven MgO content among Hawaiian lavas [Freyet al., 1994] (Figures 3 and 4), Huang and Frey[2005] and Sobolev et al. [2005] suggested thatthey contain the largest contribution from partialmelts of eclogite/garnet pyroxenite. Additionally,Makapuu-stage lavas and olivines have the lowestMnO contents among Hawaiian lavas [Huang et al.,2007; Sobolev et al., 2007], consistent with partialmelting of eclogite [Pertermann and Hirschmann,2003], as MnO is relatively compatible in garnet.Finally, Makapuu-stage lavas have the among low-est TiO2 contents in the Hawaiian tholeiitic suite[Frey et al., 1994] (Figures 3 and 4). Such lowmagmatic TiO2 is distinctive feature of dacitic meltsof eclogite with residual rutile [Pertermann andHirschmann, 2003, Figure 9].4.1.2. High SiO2 Lavas From Melt-RockReaction Between Peridotite Melts andPeridotite Mantle?[29] Melt-rock reaction between peridotite meltsand harzburgite/peridotite (i.e., assimilation oforthopyroxene+clinopyroxene and precipitation ofolivine [Kelemen et al., 1992]) has also beenproposed as a model to explain the high SiO2-content in Hawaiian lavas [Eggins, 1992; Wagnerand Grove, 1998; Stolper et al., 2004; Putirkaet al., 2011]. The peridotite reacting with the meltcould be a melt-residue of the rising mantle plume[Wagner and Grove, 1998, Figure 5a] or in situlithospheric mantle [Wagner and Grove, 1998,Figure 5b]. Hauri [1996] noted that, if the elevatedSiO2 in Koolau were a result of melt-rock reactionwith the mantle lithosphere, it would be reflectedby a lithospheric imprint on the Koolau lavas,including unradiogenic 187Os/188Os and high143Nd/144Nd ratios typical of the oceanic mantlelithosphere [e.g., Shirey and Walker, 1998;Warren et al., 2009]. This is not observed. KoolauMakapuu-state lavas have radiogenic 187Os/188Osand low 143Nd/144Nd (Figure 2), an observationthat is inconsistent with extensive melt-rock reactionin the oceanic mantle lithosphere. Further, a melt-mantle reaction predicts that CaO/Al2O3 willincrease with SiO2 as pyroxene is dissolved andolivine is precipitated: olivine precipitation from themelt will drive up melt SiO2, and clinopyroxene(and/or orthopyroxene) dissolution from the mantlewill increase melt SiO2 and CaO/Al2O3. However,this is inconsistent with the negative relationshipobserved between CaO/Al2O3 and high SiO2 inHawaiian lavas (Figure 9), indicating that a mecha-nism other than melt-rock reaction is responsible forthe increased SiO2 in Koolau lavas.Figure 9. CaO/Al2O3 versus SiO2 in the Hawaiianmagmatic suite considered in this study. Melt-rock reac-tion between the shallow mantle lithosphere and amantle melt tends to increase SiO2 in the melt as clino-pyroxene from the mantle lithosphere is dissolved intothe melt while olivine from the melt is precipitated.This melt-rock reaction would be manifested as a posi-tive trend in SiO2 versus CaO/Al2O3 space. However,Hawaiian lavas with the highest SiO2 have the lowestCaO/Al2O3, a signature that is inconsistent with meltrock reaction. The lavas in the figure have been correctedfor olivine fractionation to a constant MgO of 16 wt.%.An olivine-melt Kd of 0.30 is used for olivine fraction-ation/addition. Lavas with high 206Pb/204Pb have lowSiO2 and high CaO/Al2O3, and lavas with high low206Pb/204Pb have high SiO2 and low CaO/Al2O3. Colorsand data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426814 of 24[30] Melt-rock reaction with the mantle plume alsofails to explain the observed residual garnet signature,i.e., and relatively constant HREE contents (aftercorrection for olivine fractionation or accumulation)in Hawaiian tholeiites [e.g., Hofmann et al., 1984;Huang and Frey, 2005]. This is because melt-rockreaction is likely to generate variable HREE abun-dances. Previous studies invoking melt-rock reac-tion considered high LREE/HREE ratios alone toreflect a residual garnet signature [e.g., Eggins,1992; Wagner and Grove, 1998; Putirka et al.,2011], but the variable HREE abundances result-ing from melt-rock reaction do not match the rela-tively constant abundances in Hawaiian lavas.Therefore, a melt-mantle reaction occurring withinthe plume, proposed to explain the high SiO2 con-tent in Hawaiian lavas, cannot explain the observedresidual garnet signature.4.1.3. Peridotite Versus Eclogite Melting:Evidence From Ni in Olivine?[31] Ni concentrations in olivines play a key role inthe debate surrounding eclogite melting in theHawaiian plume, particularly beneath Koolau vol-cano. Olivines in Makapuu-stage Koolau lavas haveunusually high Ni abundances [e.g., Clague et al.,1991; Garcia, 2002]. Sobolev et al. [2005, 2007]and Herzberg [2011] argued that the high Ni con-tents in Hawaiian olivines and lavas imply an oliv-ine-free, secondary garnet pyroxenite source forHawaiian lavas. Wang and Gaetani [2008] suggestthat the high olivine Ni contents are caused by highDNiol/melt that results from a melt with a high SiO2content, which implies an important role of eclogitein the petrogenesis of Hawaiian lavas.[32] However, Putirka et al. [2011] and Rhodeset al. [2012] suggest that there are large uncertain-ties in the model predicted DNiol/melt values and Nivariations in peridotites. They argued that Ni con-centrations in olivines and lavas may not be used asdiscriminators between eclogite melting and peri-dotite melting. Putirka et al. [2011] argue that, athigh temperature, DNiol/melt is low, and hot peridotitemelting yields Ni-rich melts. Following transport toshallower depths, DNiol/melt is higher owing to lowerambient temperatures, and crystallizing olivines areNi-rich. Further experiments parameterizing theeffects of temperature, pressure and melt composi-tion on Ni partitioning between olivine and melt areneeded to evaluate these contrasting hypotheses.[33] In summary, there is active debate surroundingthe interpretation of the elevated Ni abundances inHawaiian magmatic olivines and whole rocks, andfurther experiments parameterizing the effects oftemperature, pressure and melt composition on Nipartitioning between olivine and melt are needed toevaluate the contrasting hypotheses. However, thedistinctive geochemical characteristics of Makapuu-stage Koolau lavas?high SiO2, low CaO, TiO2 andMnO, and REE patterns showing residual garnetsignature?are consistent with partial melting ofeclogite [Hauri, 1996; Pertermann and Hirschmann,2003; Herzberg, 2006; Dasgupta et al., 2010], butare not matched by melt compositions from existingexperimental peridotite melting studies.4.2. The Loihi Component: The ParadoxicalPyroxenite4.2.1. Lithology of the Loihi Mantle Source[34] Lavas from the Hawaiian Loa-trend describearrays that suggest binary mixing between twoextreme compositions (Figures 2 and 4?8): Makapuu-stage Koolau lavas anchor the low 143Nd/144Nd and206Pb/204Pb portion of the Loa array, and high3He/4He lavas from Loihi define the portion withdepleted 143Nd/144Nd and 87Sr/86Sr signatures andradiogenic 206Pb/204Pb. While Koolau lavas havehigh SiO2 and low TiO2, CaO and CaO/Al2O3,Loihi lavas exhibit the lowest SiO2 and highestTiO2, CaO and CaO/Al2O3 in the Loa-trend suite.Unlike the Koolau Makapuu source, which is likelyto contain an eclogite component, the Loihi mantlesource is generally agreed to be peridotitic [e.g.,Sobolev et al., 2005, 2007; Putirka et al., 2011;Herzberg, 2006, 2011]. Nonetheless, there are keygeochemical features of high 3He/4He Loihi lavassuggesting that the source peridotite is enriched as aresult of the addition a mafic component [e.g.,Sobolev et al., 2005; Putirka et al., 2011; Herzberg,2011]?likely a SiO2-poor pyroxenite?and thefinal, hybrid mixture is still a peridotite.[35] Evidence that a mafic component was added tothe Loihi peridotite source comes from elevatedTiO2 contents in fractionation-corrected Loihi lavas,which are too high to be generated by peridotitemelting at the degrees of melting inferred forHawaiian shield lavas. Prytulak and Elliot [2007]showed that, after correcting lavas to 16 wt.% MgO,the fractionation-corrected TiO2 abundances of lavasfrom many Hawaiian volcanoes (>1.8 wt%) can onlybe generated by low degrees (<3%) of partialmelting of a primitive peridotite (840?1200 ppm Ti)[McDonough and Sun, 1995; Carlson and Boyet,2008] or a depleted mantle source (657?798, ppmTi) [Workman and Hart, 2005; Salters and Stracke,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426815 of 242004]. Such low degrees of partial melting areinconsistent with their tholeiitic bulk compositions,and there is evidence that Hawaiian lavas are gen-erated at higher degrees of melting (?5%) [McKenzieand O?Nions, 1991; Watson and McKenzie, 1991;Garcia et al., 1995]. Therefore, Prytulak and Elliot[2007] concluded that the mantle sources beneaththese Hawaiian volcanoes have been enriched by theaddition of a Ti-rich component, and the most likelymaterial to host sufficient Ti is a recycled maficcomponent. Loihi tholeiites have among the highestTiO2 concentrations?2.1 wt. % TiO2 at 16 wt.%MgO?in the Hawaiian tholeiite suite (Figures 3and 4) [Garcia et al., 1995; Hauri, 1996] indicat-ing that the dominantly peridotitic Loihi source hasincorporated a mafic lithology during its history inthe mantle.[36] Pb isotopic compositions offer a second line ofevidence for the addition of a mafic component tothe peridotitic Loihi mantle source. Loihi lavas havethe highest 206Pb/204Pb and 208Pb/204Pb among Loatrend volcanoes, and only extreme Kea-trend lavashave more radiogenic Pb isotopic ratios. The Pb-isotopic compositions of Loihi lavas plot well to theright of the geochron, which has been attributed tothe presence of a mafic material [Lassiter andHauri, 1998; Jackson et al., 2010; Jackson andCarlson, 2011] with high U/Pb following seaflooralteration (U addition) and subduction zone pro-cessing (Pb loss) [Hofmann and White, 1982; Kelleyet al., 2005].[37] A third line of evidence supporting a maficcomponent in the Loihi mantle source comes fromelevated 187Os/188Os ratios (up to 0.138) in Loihilavas. Roy-Barman et al. [1998] identified a positivecorrelation between 3He/4He and 187Os/188Os inLoihi, which led the authors to suggest that themantle beneath Loihi hosts a component withradiogenic Os that is somehow related to the end-member component found in Makapuu-stageKoolau lavas. (A similar correlation between 3He/4Heand 187Os/188Os is Iceland led Brandon et al. [2007]to suggest the presence of a mafic componentadmixed with high 3He/4He peridotite in the source ofhigh 3He/4He Icelandic lavas.) However, owing to themuch higher 3He/4He and more depleted 87Sr/86Srand 143Nd/144Nd ratios in Loihi lavas compared toKoolau lavas, we consider it unlikely that the high187Os/188Os mafic components in Loihi and Koolaulavas are the same.[38] The radiogenic Os and Pb, and high Ti con-centration in Loihi lavas are consistent with thepresence of a mafic component added to theperidotitic mantle source of Loihi lavas, yet petro-logic models for the Loihi source indicate thatperidotite melting is occurring [e.g., Putirka et al.,2011; Herzberg, 2011]. This raises an importantquestion, which relates to the paradox of pyroxenitein the Loihi mantle source: How can the mixture ofthe peridotite and pyroxenite result in a mantlesource that generates melts that appear petrologi-cally to have been sourced by a peridotite? Owing tothe high TiO2 in Loihi lavas, Putirka et al. [2011]invoked the Prytulak and Elliot [2007] Ti model tosuggest the incorporation of a mafic component inthe Loihi source, but argued that it no longer existsas a distinct lithology. Putirka et al. [2011] sug-gested that the mafic source has been mixed com-pletely into the peridotite, so that the final lithologyis an enriched peridotite. If true, the final mixture, aperidotite, would inherit elevated TiO2 and radio-genic Os and Pb from the mafic lithology. However,mixing of the pyroxenite into the peridotite mightnot take place in the solid state.Gaffney et al. [2005]proposed a model for melting a mafic component inthe presence of peridotite, while keeping the petro-logic signature of the mafic component ?hidden.?They suggested that the eclogite melt would infil-trate and react with the peridotite and generate afertile peridotite, similar to that observed in eclogite-peridotite ?sandwich? experiments [Yaxley andGreen, 1998; Takahashi and Nakajima, 2002].The resulting fertile peridotite will be rich in ortho-pyroxene, as a result of eclogite melt reaction witholivine in the peridotite. Gaffney et al. [2005] sug-gested that melting of the fertilized peridotite willyield melts with a major element composition thatreflects peridotite melting [Hirschmann et al.,2003], even though they possess isotopic and traceelement geochemical signatures that reflect a con-tribution from a mafic component. The Putirka et al.[2011] and Gaffney et al. [2005] models may helpexplain the paradox of a mafic component in theLoihi mantle source that is essentially ?invisible? topetrologic models that suggest derivation of Loihilavas from a peridotitic source.4.2.2. Mantle Source Lithological DifferencesBetween the Loa-Trend Extremes: Comparingthe Loihi Mantle Source to the KoolauMakapuu Mantle[39] The association of high 3He/4He with a mantlesource that hosts a mafic component at Loihi isparadoxical. Owing to the highly incompatiblenature of U and Th during mantle melting, maficmaterials should in general have higher U and Ththan peridotitic materials. Therefore, over time,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426816 of 24mafic materials will generate more 4He than peri-dotites, resulting in lower 3He/4He in the formerrelative to the latter. As a result, a mafic componentadded to the peridotitic source should result in low3He/4He in Loihi lavas, not high 3He/4He. How-ever, if the SiO2-undersaturated pyroxenite inferredto have been added to the peridotitic Loihi sourcesuffered melt extraction in a paleo-subduction zone,then incompatible elements like U and Th will havebeen effectively removed from the pyroxenite, thusreducing its potential to generate 4He over time.Jackson et al. [2008] observed that 3He/4He ratioscorrelate with the magnitude of positive Ti, Ta andNb (TITAN) anomalies (where anomalies of theTITAN elements?calculated relative to elementsof similar compatibility in peridotite on a primitivemantle normalized spidergram?are not to be con-fused with the absolute concentrations of theseelements) in Hawaiian lavas, where Loihi exhibitsthe largest Ti anomalies and highest 3He/4He ratios.Owing to the ubiquitous presence of rutile in eclo-gite, trace elements compatible in rutile, includingthe TITAN elements, are residually enriched rela-tive to other trace elements during melt extractionfrom and dehydration of the downing-going slab;incompatible elements not sequestered into rutile?including the radiogenic helium-producing elements,U and Th?will be lost from the slab, togetherwith SiO2. For such a model to explain the radio-genic Pb isotopes in Loihi lavas, Pb would have to bepreferentially removed from the slab relative to U andTh, which is likely [Kelley et al., 2005]. The residualSiO2-poor mafic material?a pyroxenite?is TITAN-enriched and depleted in U and Th, and will contrib-ute little 4He to the peridotite with which it mixes,including high 3He/4He peridotites. Such a modelmight explain the association of TITAN enrichmentand high 3He/4He in SiO2-poor Loihi lavas.[40] By contrast, Makapuu-stage Koolau lavas havehigher SiO2, lower3He/4He and less radiogenic Pb.These lavas sample a SiO2-rich eclogite (Section 4.1)that has not suffered severe SiO2 and incompatibleelement depletion in a subduction zone, as evidencedby the silica-rich character of Koolau lavas. Such aneclogite will have retained its complement of U andTh (and Pb, thereby preserving a low U/Pb ratio) andwill producemore 4He over time that will ?infect? thesurrounding peridotite mantle?including the litho-logic reservoir hosting high 3He/4He peridotite[e.g., Parman et al., 2005; Albar?de, 2008; Hartet al., 2008; Jackson et al., 2008]?with low3He/4He. A host of possible mafic lithologies existin nature, and the presence of two distinct maficcomponents?a SiO2-poor pyroxenite and a SiO2-rich eclogite?in the Hawaiian plume might recon-cile the geochemical differences between the twoLoa-trend mantle components, Loihi and Koolau-Makapuu.4.3. The Kea Component[41] A third major isotopic end-member observed inHawaiian shield lavas?the Kea component?issampled by volcanoes that define the Kea en eche-lon volcanic trend. The Kea-trend volcanoes havemore homogeneous Sr, Nd and Hf isotopes that arealso generally more depleted [e.g., Stille et al.,1986] than their Loa-trend equivalents [DePaoloet al., 2001; Weis et al., 2011]. This has led tomodels suggesting a depleted peridotite source?MORB-source, Pacific oceanic lithosphere, entrainedasthenosphere, or recycled mantle lithosphere?forKea-component lavas [West et al., 1987; Chen andFrey, 1985; Hauri, 1996; Eiler et al., 1996a, 1996b;Lassiter et al., 1996]. However, the low 176Hf/177Hfof the Kea end-member suggests that asthenosphericor lithospheric materials are not present in the sourceof Kea-type lavas [Blichert-Toft et al., 1999].Recycled lower oceanic crust has also been sug-gested to source Kea-component lavas, but only incombination with recycled lithospheric peridotite[Lassiter and Hauri, 1998].[42] With the exception of 3He/4He and 208Pb*/206Pb*,Kea- and Loihi-component lavas are more similar toeach other than to Koolau-component lavas, and thefractionation-corrected major element compositions ofKea lavas are remarkably similar to Loihi-componentlavas, as observed previously [Hauri, 1996]. In fact, theKea-component exhibits several geochemical similari-ties with the Loihi-component that suggest that theformer also hosts a mafic component in its mantlesource. For example, Kea-component lavas hosthigh TiO2 contents, consistent with the addition of apyroxenite component in the source of Kea-component lavas (Mauna Kea and Kilauea have>2 wt.% TiO2 at 16 wt.% MgO (Table 1) [Prytulakand Elliot, 2007]). However, information fromradiogenic isotopes does not permit a clear resolu-tion of the debate over source lithologies contribut-ing to the Kea mantle source. On the one hand, Pbisotopic compositions in Kea-component lavas areamong the most radiogenic in Hawaii. If radiogenicPb is associated with a recycled mafic component,then Kilauea lavas should host a significant maficcomponent. This is contradicted by the generallyunradiogenic 187Os/188Os in Kea-trend lavas(<0.133, with the exception of a single Kohala lava;Figure 7). One possible explanation for this apparentGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426817 of 24disagreement is that there is a greater contribution ofrecycled sediment to the Loa-trend mantle than tothe Kea-trend source: Sediment generally has higher187Os/188Os than mafic lithologies, so it is possiblefor a mantle source with a sediment and a maficcomponent (like the Loa-trend mantle) to have ahigher 187Os/188Os than the a mantle source withjust a mafic component (like the Kea-trend mantle)[Lassiter and Hauri, 1998; Huang et al., 2005].5. Major Element Versus IsotopeCorrelations in Hawaii in the Contextof Global OIBs[43] The broad correlations between major elementsand isotopes in Hawaiian lavas form arrays anchoredby Loihi and Kea-component lavas (with high143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and low87Sr/86Sr) at one end and by Koolau lavas (with low143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and high87Sr/86Sr) at the other. Information from olivine-fractionation corrected major element data suggeststhat the correlations in the Hawaiian data set areanchored on both ends by different types of maficcomponent that coexist (and interact) with peridotitein the Hawaiian plume: a silica-poor pyroxeniteanchors the Loihi and Kea-component portion of theHawaiian array (Section 4.2 and 4.3), and a silica-rich eclogite anchors the enriched portion (Koolau)of the Hawaiian array (Section 4.1). A host of pos-sible mafic lithologies exist in nature, and the SiO2content of the mafic materials in the source ofthe Loihi, Kea and Koolau components may bethe defining difference among these components.However, in order to understand the origin of thesecontrasting mafic sources, they must first be placedin the context of global OIB geochemical variability.[44] Broad relationships between major elementsand radiogenic isotopes in the global OIB data setmay help constrain the mantle source compositionsof the Loihi, Kea and Koolau components. Jacksonand Dasgupta [2008] show that global OIB lavaswith the most radiogenic Pb have the lowest SiO2and the highest CaO/Al2O3 (Figure 10). SiO2 andCaO/Al2O3 also exhibit some of the clearest cor-relations with 206Pb/204Pb in Hawaiian lavas, andthese correlations mimic the global trend (Figure 10).Like the global OIB data set, FeOtotal, Al2O3 andNa2O abundances in Hawaii exhibit little or nocorrelation with radiogenic isotopes. In summary,the correlations between Pb isotopes and majorelements in Hawaii appear to broadly reflect theglobal trends, and we suggest that the mechanismthat drives the correlations between major elementsand isotopes in Hawaii illustrates, in microcosm, alarger global process.[45] Hauri [1996] suggested that SiO2-rich(50 wt.%) Koolau lavas resulted from melting ofSiO2-saturated mafic material (which we refer toabove as eclogite), while the mantle sources of thelow SiO2 lavas (40 wt.%) in the Pacific Islandswith the most radiogenic Pb are thought to hostSiO2-poor mafic material (which we refer to aspyroxenite) [Hirschmann et al., 2003; Kogiso et al.,2003; Kogiso and Hirschmann, 2006; Dasguptaet al., 2006; Jackson and Dasgupta, 2008]. Apply-ing this model to the Hawaiian magmatic suite, weinfer that Loihi and Kea-component lavas, whichexhibit the most radiogenic Pb compositions and thelowest SiO2 concentrations in Hawaiian shieldlavas, are derived from a peridotitic mantle sourcethat incorporated a small portion of a SiO2-poormafic component with radiogenic Pb.[46] Subduction zone processes can modify thecomposition of the downgoing oceanic crust byvariably removing SiO2 (and fractionating traceelement ratios, such as U, Th and Pb) [Hauri, 1996;Jackson and Dasgupta, 2008]. As a result, SiO2-richand SiO2-poor mafic lithologies exist in the mantlethat are likely to host distinct time-integrated isoto-pic ratios. Low SiO2 lavas from Mangaia andTubuaii and the high SiO2 lavas from Hawaii?sKoolau Makapuu-stage anchor the high 206Pb/204Pband low 206Pb/204Pb portions of the global array,respectively (Figure 10) [Jackson and Dasgupta,2008]. SiO2-deficient eclogites suggested for thesource of SiO2-poor OIB lavas with radiogenic Pbmust have somehow attained higher U/Pb ratios,likely via Pb-loss from the slab [Kelley et al., 2005](i.e., the same subduction zone processes reduced theSiO2 of the downgoing crust and increased U/Pb).The variability within the Hawaiian array may begenerated in a similar manner, where the Hawaiianplume hosts both SiO2-rich eclogites (with low206Pb/204Pb) and SiO2-poor pyroxenites (with high206Pb/204Pb) that mix in the peridotite matrix of theplume to generate the correlations between majorelements and radiogenic isotopes in Hawaii. Thus,processes operating in subduction zones that modifythe downgoing oceanic crust may be responsible forgenerating much of the major element variabilityobserved in Hawaii and in OIBs in general [Hauri,1996].6. Conclusions[47] From this review study, we draw the followingconclusions:GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426818 of 24[48] 1. Data for tholeiitic Hawaiian shield lavasform arrays in plots of radiogenic isotopes versusolivine-corrected major element oxides. Individualdata points exhibit remarkable trends and there isno need to average the data by volcano.[49] 2. The trends are anchored by Koolau lavas atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2,Figure 10. Olivine fractionation-corrected SiO2 concentrations and CaO/Al2O3 ratios are plotted against206Pb/204Pbfor Hawaiian lavas and the global OIB data set. The correlations in the Hawaiian data set mimics, in microcosm, thelarger global correlation. The global OIB data set is from Jackson and Dasgupta [2008] and includes only lavas withMgO > 8 wt.% MgO, as many non-Hawaiian OIB lavas experience clinopyroxene fractionation at lower MgO abun-dances (see Data Set S1 for compositions). An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. HIMU (or high-m, or 238U/204Pb) represents the mantle reservoir with radiogenic Pb-isotopes [e.g.,Hauri and Hart, 1993; Woodhead, 1996; Hanyu et al., 2011].GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426819 of 24and Na2O/TiO2, and low143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaO and CaO/Al2O3) and byKea and Loihi lavas at the other (low 87Sr/86Sr,187Os/188Os, SiO2, and Na2O/TiO2, and high143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaOand CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with Sr, Nd, Pb or Hfisotope compositions.[50] 3. In Hawaiian tholeiitic lavas, 3He/4He showsa remarkably good relationship with SiO2, CaO,Al2O3, CaO/Al2O3 and FeOtotal. High3He/4He lavasfrom Loihi anchor the low SiO2 and Al2O3 and highCaO, CaO/Al2O3 and FeOtotal portions of the arrays.3He/4He exhibits no clear relationships with TiO2and Na2O abundances or with Na2O/TiO2 ratios.[51] 4. The Loihi source is likely peridotitic, but hasbeen infused with a SiO2-poor mafic componentsuch that the final mixture is an enriched peridotite.Loihi and Kea-component lavas exhibit similarmajor element characteristics (low SiO2 and Na2O/TiO2 and high TiO2, CaO and CaO/Al2O3), whichmay suggest lithologically similar mantle sources.The composition of SiO2-rich Koolau-componentlavas is not easily explained by available data forperidotite melting experiments (wet or dry) or bymelt-rock reaction of peridotite melts with the oce-anic mantle lithosphere. Instead, Koolau-componentlavas are likely derived from melts of a SiO2-richeclogite that has variably interacted with peridotite.[52] 5. Correlations between major elements andradiogenic isotopes in Hawaiian lavas mimic thebest correlations observed in the global OIB data setbetween Pb isotopic ratios and SiO2 and CaO/Al2O3. We suggest that the mechanism that drivesthe correlations between major elements and iso-topes in Hawaii illustrates, in microcosm, a largerglobal process. Variable processing of slabs insubduction zones yields SiO2-poor pyroxenites(with high U/Pb) and SiO2-rich eclogites (with lowU/Pb) that evolve radiogenic and unradiogenic Pbisotopic compositions, respectively. 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Hart (2005), Major and trace ele-ment composition of the depleted MORB mantle (DMM),Earth Planet. Sci. Lett., 231, 53?72, doi:10.1016/j.epsl.2004.12.005.Yaxley, G. M., and D. H. Green (1998), Reactions betweeneclogite and peridotite: Mantle refertilisation by subductionof oceanic crust, Schweiz. Mineral. Petrogr. Mitt., 78,243?255.Zindler, A., and S. R. Hart (1986), Chemical geodynamics,Annu. Rev. Earth Planet. Sci., 14, 493?571, doi:10.1146/annurev.ea.14.050186.002425.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426824 of 24 ArticleVolume 13, Number 919 September 2012Q09009, doi:10.1029/2012GC004268ISSN: 1525-2027Major element variations in Hawaiian shield lavas: Sourcefeatures and perspectives from global ocean island basalt(OIB) systematicsMatthew G. JacksonDepartment of Earth Sciences, Boston University, 675 Commonwealth Avenue, Boston, Massachusetts02215, USA (jacksonm@bu.edu)Dominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences,University of British Columbia, 6339 Stores Road, Vancouver, British Columbia V6T1Z4, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, 20 Oxford Street, Cambridge,Massachusetts 02138, USA[1] Among volcanic hot spots globally, Hawaii has the highest magma flux, yet there is significant contro-versy surrounding the composition of the mantle sourcing Hawaiian lavas. In order to place constraints onthe source lithologies of Hawaiian lavas, we explore relationships between major elements and radiogenicisotopes in tholeiitic, shield-building lavas. Olivine-fractionation corrected lava compositions reveal cleartrends between radiogenic isotopes and major elements. Individual data points exhibit remarkable trendsand there is no need to average the data by volcano. Data form arrays that are anchored by Koolau lava atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2, and Na2O/TiO2, and low143Nd/144Nd, 206Pb/204Pb, TiO2,CaO and CaO/Al2O3) and by Kea and Loihi lavas at the other (with low87Sr/86Sr, 187Os/188Os, SiO2, andNa2O/TiO2, and high143Nd/144Nd, 206Pb/204Pb, TiO2, CaO and CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with radiogenic isotopes. The Hawaiian data set exhibits correlations that mirrorthe best correlations between major elements and radiogenic isotope in the global ocean island basalt (OIB)database. We suggest that the mechanism driving the correlations in Hawaii illustrates, in microcosm, alarger global process that generates major element variability in mantle plumes. Like the global arrays, theHawaiian lavas with radiogenic Pb and SiO2-poor lavas are sourced by a SiO2-poor mafic component (pyrox-enite) admixed with peridotite, while Hawaiian lavas with unradiogenic Pb and high SiO2 are sourced by aSiO2-rich mafic component (eclogite). The variable SiO2 in the mafic component may result from differentdegrees of SiO2-extraction from the slab during subduction.Components: 14,700 words, 10 figures, 1 table.Keywords: Hawaii; eclogite; hotspot; isotopes; mantle plume; pyroxenite.Index Terms: 1025 Geochemistry: Composition of the mantle; 1033 Geochemistry: Intra-plate processes (3615, 8415); 1038Geochemistry: Mantle processes (3621).Received 4 June 2012; Revised 25 July 2012; Accepted 10 August 2012; Published 19 September 2012.?2012. American Geophysical Union. All Rights Reserved. 1 of 24Jackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features andperspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.1. Introduction[2] Oceanic plates?including mafic crust, depletedlithospheric peridotite, and a thin veneer of marinesediments?are sent into the mantle at subductionzones, thereby contributing to the compositionalheterogeneity of Earth?s mantle [Hofmann andWhite, 1982; White and Hofmann, 1982; Iwamoriet al., 2010]. Buoyantly upwelling regions of themantle are thought to return parts of these subductedoceanic plates to the shallow mantle, where theypartially melt beneath hot spots like Hawaii. Lavaserupted at hot spots therefore reveal clues about thedynamic history and composition of the mantle[Zindler and Hart, 1986; Hofmann, 1997]. Thecompositions of hot spot lavas suggest that recyclingof ancient subducted oceanic plates is a commonprocess that has affected the geochemistry of themantle over geologic time [e.g., Hofmann andWhite, 1982; Sobolev et al., 2005].[3] However, significant controversy surrounds thefinal fate of recycled oceanic crust in the mantle[Eggins, 1992; Hauri, 1996; Wagner and Grove,1998; Putirka, 1999; Sobolev et al., 2005, 2007;Gaffney et al., 2005; Huang and Frey, 2005; Huanget al., 2007; Herzberg, 2006, 2011; Putirka et al.,2011; Niu et al., 2012]. Following billion-yeartimescales of residence in the mantle, oceanic crustis likely stretched, thinned, and its geochemicalsignal is greatly attenuated [e.g., Ottino, 1989; VanKeken et al., 2004]. While distinct mafic litholo-gies may survive mantle convection to be meltedbeneath hot spots like Hawaii [Hauri, 1996; Sobolevet al., 2005, 2007, 2008; Huang and Frey, 2005;Huang et al., 2007; Herzberg, 2006, 2011], thesurvival of distinct mafic lithologies into the man-tle beneath Hawaii has been questioned [Putirka,1999; Salters et al., 2006; Putirka et al., 2011].Putirka [1999] and Putirka et al. [2011] argue thatperidotite melting can explain the geochemistry ofHawaiian lavas, and a distinct mafic lithology in themantle source of Hawaiian lavas is not required.[4] Hawaii is arguably the most-studied oceanic hotspot, and the abundance of geochemical data obtainedfrom Hawaiian lavas makes it an ideal location forevaluating the presence of recycled oceanic crust inthe mantle source. While a multitude of componentshave been identified in the Hawaiian mantle, mostof the isotopic variability in Hawaiian shield-buildinglavas can be described with just three components,as shown by principal component analysis [Hauri,1996; Eiler et al., 1996a]. These componentsinclude the Koolau, Loihi and Kea components(Figure 2) [Stille et al., 1986; West and Leeman,1987; Eiler et al., 1996b; Hauri, 1997; Gaffneyet al., 2005; Huang et al., 2005; Weis et al., 2011].The small volumes of low-degree melts sampled bypost-shield and rejuvenated lavas require the pres-ence of a fourth, depleted component, distinct fromPacific MORB [Mukhopadhyay et al., 2003; Freyet al., 2005; Fekiacova et al., 2007; Garcia et al.,2010; Hanano et al., 2010], but post-shield andrejuvenated-stage lavas are volumetrically insignif-icant compared to the shield-building lavas andthese lavas are not considered here. Hawaii is thearchetypal high 3He/4He hot spot, and lavas fromLoihi seamount define the Loihi component andhost 3He/4He ratios in excess of 30 Ra (ratio toatmosphere) [Kurz et al., 1982; Rison and Craig,1983; Kurz et al., 1983; Staudigel et al., 1984;Sarda et al., 1988; Honda et al., 1993; Valbrachtet al., 1997; Eiler et al., 1998; Jackson et al., 2008].TheKoolau component, defined byKoolauMakapuu-stage lavas, is a lower 3He/4He end-member charac-terized by the lowest 143Nd/144Nd and 206Pb/204Pband highest 87Sr/86Sr in Hawaii and constitutes theenriched Loa trend volcanic end-member (see below)[Tanaka et al., 2008]. This end-member is sampledin diluted form at several Hawaiian volcanoes andlikely hosts a component of recycled oceanic crustand sediment [e.g., Hauri, 1996; Lassiter andHauri, 1998; Blichert-Toft et al., 1999; Normanet al., 2002; Sobolev et al., 2005; Huang et al.,2005, 2011a; Herzberg, 2011; Putirka et al., 2011].The origin of the Kea component, best exemplifiedby lavas from Mauna Kea, W. Maui and Kilauea, isless clear. The Kea component, which hosts thehighest 143Nd/144Nd and 206Pb/204Pb and the lowest87Sr/86Sr in Hawaii, is relatively homogeneous rel-ative to the Koolau component, leading to modelssuggesting a MORB-source, Pacific oceanic litho-sphere source or entrained asthenospheric source inKea lavas, but recycled lower oceanic crust andmantle lithosphere also have been suggested [Chenand Frey, 1985; Frey and Rhodes, 1993; Hauri,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042682 of 241996; Eiler et al., 1996a, 1996b; Lassiter and Hauri,1998; Blichert-Toft et al., 2003; Gaffney et al., 2005].The Kea component dominates the Kea volcanictrend (see below).[5] The distribution of the Loa and Kea componentsis organized geographically along the hot spot(Figure 1). Hawaiian shield volcanoes erupted duringthe past 5 Ma tend to be oriented along two en ech-elon volcanic trends that exhibit distinct isotopic [e.g.,Jackson et al., 1972; Tatsumoto, 1978; Abouchamiet al., 2005; Tanaka et al., 2008; Farnetani andHofmann, 2010; Weis et al., 2011; Huang et al.,2011b] and major element [Hauri, 1996; Greeneet al., 2010] compositions. Volcanoes along thenorthern geographic trend erupt Kea-type lavas andsouthern-trend volcanoes tend to erupt Loa-typelavas. The origin of this geographic and geochemi-cal separation is the source of significant discussion[e.g., Hieronymus and Bercovici, 1999; Abouchamiet al., 2005; Ren et al., 2005; Marske et al., 2007;Weis et al., 2011; Huang et al., 2011b]. Under-standing the origin of the different major elementcompositions of shield-stage lavas between the Loaand Kea trends [Hauri, 1996] may provide impor-tant clues about the structure of the Hawaiian plume,including the possible organization of lithologicheterogeneities within the plume conduit [Blichert-Toft et al., 2003; Abouchami et al., 2005] and inthe deep mantle [Weis et al., 2011; Huang et al.,2011b].[6] Frey and Rhodes [1993] systematically docu-mented major element variations among differentHawaiian shields and attributed them to mantlesource variability. However, correlations betweenmajor elements and isotopes can strengthen con-clusions that major element variations in hot spotlavas reflect mantle source lithological heterogene-ity [Hauri, 1996; Sobolev et al., 2008; Jackson andDasgupta, 2008]. Hauri [1996] showed correlatedmajor element and isotopic variations in composi-tional and isotopic averages of Hawaiian volcanoes,and on this basis, argued for major element vari-ability in the Hawaiian mantle and for the impor-tance of eclogite in the petrogenesis of Hawaiianshield lavas. Jackson and Dasgupta [2008] extentsuch major element-isotope correlation to the globalOIB data set. Here we show that the original ele-ment-isotope correlations observed by Hauri [1996]are ?mirrored? by the global OIB data set [Jacksonand Dasgupta, 2008]. These data document themajor element variability in the Hawaiian plume,constrain source lithologies, and place the majorelement variability in the Hawaiian plume in thecontext of global OIB variability.2. Treatment of Geochemical Data[7] The geochemical data used in this study wereobtained from the Georoc database (georoc.mpch-mainz.gwdg.de/georoc) on December 26, 2011.Only tholeiitic lavas are considered. All non-tholeiitic lavas [Macdonald and Katsura, 1964] areexcluded, as are lavas that are explicitly described aspost-shield or rejuvenated. Only lavas with a com-plete set of major elements (SiO2, TiO2, Al2O3,FeOtotal, MnO, MgO, CaO, Na2O, K2O, P2O5) areconsidered. A sample is excluded if it does not haveat least one of the following isotopic measurements:87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb), 187Os/188Os, 176Hf/177Hf, or3He/4He. Compared to Sr, Nd and Pb isotopes, andHf isotopes to a lesser extent, measurements ofHe and Os isotopes are still relatively rare. Lavaswith low Os concentrations are susceptible to con-tamination by assimilation of materials with radio-genic Os. Therefore, Os-poor (Os < 40 ppt) lavas areexcluded [Class et al., 2009]. Similarly, lavas withlow helium concentrations are susceptible to reduc-tion of 3He/4He by post-eruptive radiogenic ingrowthof 4He or crustal assimilation, and analyses of He-poor olivines and glasses (less than 2*108 cc/g STP4He) are excluded [Garcia et al., 1990; Hilton et al.,1995; Kurz et al., 2004; Class and Goldstein, 2005].Only 3He/4He measurements obtained by crushingolivines and glasses are used. Much of the heliumisotopic data available for Hawaiian lavas are elimi-nated using the concentration filter, but we feel thatthe filter yields a data set that better reflects mantle3He/4He compositions. However, all 3He/4He mea-surements are preserved in Data Set S1 in theauxiliary material, regardless of 4He concentration, aslong as the associated whole rock major elementanalyses do not indicate excessive alteration ormagmatic evolution.1[8] As a filter for alteration, samples with K2O/P2O5< 1, low dry totals (<97 wt.%) or high dry totals(>101 wt.%) were excluded [e.g., Frey et al., 1994].Leaching is necessary to reduce alteration compo-nents in lavas that most strongly influence Sr and Pbisotopic ratios but not Nd and Hf isotopic ratios[Nobre Silva et al., 2009, 2010]. However, it is notalways known which samples were leached in acid1Auxiliary material data sets are available at ftp://ftp.agu.org/apend/gc/2012gc004268. Other auxiliary materials are available inthe HTML. doi:10.1029/2012GC004268.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042683 of 24prior to isotopic analyses, as this is not consistentlyreported in the literature. Fortunately, Sr and Pbisotopic ratios show excellent correlations with Ndand Hf isotopic ratios in Hawaiian volcanoes(Figure 2). Owing to these correlations, we show Ndand Pb isotopic data, but not Sr and Hf isotopic data,in subsequent figures. Sr and Hf isotopic data,where available, are preserved in Data Set S1.[9] Low MgO lavas (<6.5 wt.%) were not includedin the filtered data set. Such lavas can suffer fromclinopyroxene and plagioclase fractionation [e.g.,Rhodes and Vollinger, 2004; Rhodes et al., 2012].Lavas with MgO > 6.5 wt.% are affected primar-ily by fractionation or accumulation of olivine Cr-spinel [Hauri, 1996].[10] The lavas remaining (n = 551) after thesefiltering steps were renormalized to 100 wt.% totals(on a dry basis) with all Fe reported as FeOtotal(see Data Set S1). The lavas were then corrected forolivine fractionation to a constant MgO of 16 wt.%by adding or subtracting equilibrium olivine in 0.01wt.% increments, similar to Langmuir et al. [1992].Equilibrium olivines were generated using theolivine-melt Kd of 0.3 [Roeder and Emslie, 1970;Ford et al., 1983] assuming 10% of the total iron isFe3+. Correcting the lavas for olivine fractionation/addition until they are in equilibrium with a mantleolivine (forsterite 90) does not change our conclu-sions (see Table 1, Figure S1, and Data Set S1). Anolivine-melt Kd of 0.34 has been suggested forMauna Kea lavas [e.g., Matzen et al., 2011], whichdoes not change our conclusions (see Figure S1 andData Set S1). For cumulates (MgO > 20 wt.%), wefollow the procedure of Hauri [1996] and subtractan olivine composition of forsterite 87 until the bulklava has 16 wt.%MgO. All of the major element andisotopic data, and major element data corrected forolivine fractionation, are reported in Data Set S1for individual samples and in Table 1 as volcanoaverages.3. Observations3.1. Radiogenic Isotopes[11] The panels of Figure 2 show the variability inradiogenic isotopes in the lavas considered in thisstudy. Every lava considered in this study has bothmajor element data (n = 551) and at least one radio-genic isotope system measured (87Sr/86Sr [n = 444],143Nd/144Nd [n = 417], 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb) [n = 452], 176Hf/177Hf [n = 229],187Os/188Os [n = 86], 3He/4He [n = 152 for all 4Heconcentrations, or 48 for samples with 4He > 2*108cc STP/g]). The radiogenic isotopic data shown inFigure 2 are intended to show the isotopic variabilityin the freshest, least evolved Hawaiian shield lavasthat we examined in this study, and therefore the datain the figures do not encompass the complete radio-genic isotopic variability in Hawaiian lavas.Figure 1. Map of Hawaiian hot spot from Loihi to Kauai showing individual volcanoes (map made usingGeoMapApp, http://www.geomapapp.org).GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042684 of 24Table1(Sample).MeanIsotopicandMajorElementCompositionsforHawaiianVolcanoesExaminedinThisStudya[ThefullTable1isavailableintheHTMLversionofthisarticle]VolcanoIsland143Nd/144NdAverage2SD87Sr/86SrAverage2SD206Pb/204 PbAverage2SD207Pb/204PbAverage2SD208Pb/204PbAverage2SD187Os/188OsAverage2SDLoa-trendLoihi(tholeiitic)BigIsland0.5129530.0000700.7035810.00013118.3760.13315.4680.03038.1180.1220.13330.0046MaunaLoaBigIsland0.5129060.0000740.7038090.00066818.1680.17615.4600.02437.9080.1380.13560.0030HualalaiBigIsland0.5129030.0000510.7037270.00008618.1820.13215.4590.02537.9510.1590.13480.0016MahukonaBigIsland0.5129620.0000680.7036390.00015518.2530.22215.4690.01437.9410.152NAKahoolaweMauiNui0.5128480.0000990.7041200.00031818.0420.31415.4360.03037.8290.2190.1439LanaiMauiNui0.5127700.0001210.7041810.00031617.9220.09815.4370.01637.7530.057NAWestMolokaiMauiNui0.5129430.0002160.7038190.00039418.2530.44515.4600.02537.9390.254NAKoolau(Makapuu)Oahu0.5127570.0000770.7040820.00031517.8540.07415.4380.02637.7730.0710.14260.0075Koolau(KSDP)Oahu0.5129170.0000830.7037600.00017318.0630.08115.4530.00737.8370.051NAKoolau(NuuanuLandslide)Oahu0.5129720.0000590.7035680.00016118.2040.36615.4480.01737.8830.2400.13370.0056WaianaeOahu0.5129750.0001260.7036480.00019418.1460.20615.4610.03737.8560.117NAKauaiKauai0.5129690.0000560.7036710.00022918.2280.16615.4510.01537.9390.0980.13680.0038Kea-trendKilaueaBigIsland0.5129580.0000270.7035840.00009918.4640.20515.4830.05538.1040.1890.13100.0017MaunaKeaBigIsland0.5129680.0000360.7035840.00009418.4970.18115.4830.02538.1040.1710.12970.0011KohalaBigIsland0.5130150.0000000.7037100.00008718.1700.27615.4600.04137.8450.1480.13650.0115HaleakalaMauiNui0.5129580.0000400.7036450.00019418.5410.22015.4800.01938.1540.1830.13040.0000WestMauiMauiNui0.5130250.0000480.7035500.00014018.4310.14215.4830.03137.9570.1280.13210.0011EastMolokaiMauiNui0.5129810.0000830.7035650.00020718.4370.41015.4800.03238.0600.255NAa Meansandthestandarddeviations(SD,2sigma)arefromDataSetS1.Ifthestandarddeviationisnotreported,itisbecauseonlyasinglemeasurementisavailable.Majorelementcompositionsarecorrectedforolivinefractionation/additiontoaconstantMgO(16wt.%)ortobeinequilibriumwithaforsterite90olivinecomposition(butthetwodifferentcorrectionschemesyieldsimilarmajorelementcompositions).Anolivine-meltKdof0.30isusedforcorrection.Dataforsamplesareexcludedifthewholerockisaltered,highlyevolved,orifthemajorelementdataareincompleteortheanalysesyieldshighorlowtotals(seetextforfiltersapplied).HeliumandOsisotopedataexistformanyofthevolcanoeslistedasNAinthetable,butinseveralcases,correspondingmajorelementdatadoesnotexist,orindicatesexcessivemagmaticevolutionorpost-eruptivealteration,andtheHeandOsdataarenotreported.Sr,Nd,PbandHfisotopesarenotfilteredbasedontraceelementconcentrations.Inonecolumn,heliumisotopicratiosforsampleswithlowheliumconcentrations(<2*10-8cc4He/gSTP)arenotreported(?HighHeconc?).However,heliumisotopicratioswithlowerconcentrationsarepreservedinthenextcolumn(?AllHeconc?)andinDataSetS1.OsisotopesareexcludediftheOsconcentrationis<40ppt.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042685 of 24Figure 2GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042686 of 24[12] The radiogenic isotopic compositions of Hawai-ian shield lavas have been discussed at great length inthe literature (for a recent review, see Weis et al.[2011]). We outline some of the most outstandingfeatures of the radiogenic isotopic geochemistry ofHawaiian lavas in Figure 2. In general, Loa-trendlavas have lower 206Pb/204Pb, 143Nd/144Nd and176Hf/177Hf and higher 187Os/188Os, 87Sr/86Sr and208Pb*/206Pb* (208Pb*/206Pb* = (208Pb/204Pb -29.475)/(206Pb/204Pb - 9.306) [Hofmann, 2003]) thanKea-trend lavas (Figure 2).[13] In isotope space, Hawaiian lavas define cleararrays that resolve the Loa- and Kea-trends. Forexample, in 208Pb/204Pb versus 206Pb/204Pb isotopespace (Figure 2), Kea-trend volcanoes tend to havemore radiogenic 206Pb/204Pb values than Loa-trendvolcanoes. Kea-trend volcanoes?including MaunaKea, Kilauea, Haleakala, E. Molokai and W. Maui?define the most radiogenic Pb-isotopic compositionsin Hawaii. By contrast, Loa-trend volcanoes tend tohave less radiogenic 206Pb/204Pb (and a higher208Pb/204Pb for a given 206Pb/204Pb) than Kea-trendvolcanoes. Koolau, Kahoolawe and Lanai, theHawaiian volcanoes with the most geochemicallyenriched 143Nd/144Nd and 87Sr/86Sr, also have theleast radiogenic 206Pb/204Pb. However, Loihi, theyoungest Loa-trend volcano, has depleted (high)143Nd/144Nd and (low) 87Sr/86Sr signatures andradiogenic Pb-isotopic compositions, similar to Kea-trend volcanoes. The Pb-isotopic compositions inLoihi lavas extend to values encountered only in theKea trend volcanoes, including Mauna Kea andKilauea (and the Hilina-stage of Kileaua in particular[Kimura et al., 2006]). However, Loihi generally hasa higher 208Pb/204Pb at a given 206Pb/204Pb, andtherefore higher 208Pb*/206Pb*, than Kea-trend vol-canoes. In general, all other Loa-trend volcanoes plotbetween Loihi and the geochemically extremeKoolau-component lavas from Koolau, Kahoolaweand Lanai.3.2. Major Element Variation Diagrams[14] Plots of whole rock MgO concentrations ver-sus the other major element oxides (Figure 3)?including SiO2, TiO2, CaO, Al2O3, FeOtotal andNa2O?are useful for showing enrichments ordepletions of these elements at various stages ofmagmatic evolution. The Loa- and Kea- trend vol-canoes, which exhibit different isotopic character-istics, also tend to follow different trends in severalof the major element variation diagrams.[15] At a given MgO content, Loa-trend volca-noes tend to have higher SiO2 and lower TiO2and CaO contents than Kea-trend volcanoes. How-ever, Loihi seamount, another Loa-trend volcano,has among the lowest SiO2 and the highest TiO2 andCaO concentrations in Hawaii. Loihi lavas overlapcompositionally with the major element composi-tions found in the extreme Kea-component volca-noes, Mauna Kea and Kilauea. Al2O3 exhibits littlevariability among volcanoes at a given MgO. It ispossible that the Loa-trend volcanoes with thelowest 143Nd/144Nd?Koolau, Lanai and Kahoo-lawe?have slightly higher Al2O3 and Na2O andlower FeOtotal contents than Loihi and the Kea-trendvolcanoes, but the differences, if real, are small (SeeSection 3.3).[16] In Figure 3, we show that 208Pb*/206Pb* exhibitsno relationship with MgO. This suggests that magmaevolution and crustal assimilation, which can modifyMgO abundances, are not responsible for generatingthe variability in 208Pb*/206Pb*, which is a sourcefeature [e.g., Hofmann, 2003]. This observation isimportant, as several major element oxides (SiO2,CaO, TiO2) exhibit clear relationships with208Pb*/206Pb* (See Section 3.3, Figure 4) after cor-rections for olivine fractionation/addition are made.3.3. Major Elements Versus Isotopes[17] The Loa- and Kea-trend volcanoes exhibitisotopic (Section 3.1) andmajor element (Section 3.2)differences. The isotopic variations in Hawaiianshield lavas also exhibit clear relationships witholivine fractionation-corrected major element oxideabundances.[18] Fractionation-corrected SiO2, CaO and TiO2concentrations and Nd and Pb isotopic ratios showFigure 2. Plots of radiogenic isotope ratios for data included in this study. Note that the radiogenic isotope data in thefigures includes only samples with the major element data indicating that the lavas are not highly evolved or altered.Koolau lavas are divided into three groups: Makapuu (MAK), Koolau scientific drilling project (KSDP), and theNuuanu landslide (NUU). The approximate isotopic composition of the 3 geochemical components in Hawaii (as iden-tified in lavas) are labeled in the figure: Koolau, Loihi and Kea. Many lavas have only one of the radiogenic isotopedata and do not appear in any of the panels (but lavas with a single radiogenic isotope ratio do appear in the other datafigures). Similarly, lavas that do not possess the full suite of radiogenic isotopic compositions appear in some, but notall, of the panels.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042687 of 24Figure 3. Major element variation diagrams plotting MgO against SiO2, Al2O3, FeOtotal, Na2O, CaO and TiO2.A plot of MgO versus 208Pb*/206Pb* is also shown. The major elements in the panels of this figure have not been cor-rected for olivine fractionation or addition. Lavas with MgO lower than 6.5 wt.% are not considered in this study, andare not shown in the diagrams. K2O, P2O5 andMnO are not shown, but data are available in Data Set S1. Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042688 of 24the clearest relationships, and define arrays in theHawaiian data set [Hauri, 1996] (Figure 4). Lavasfrom the Makapuu-stage of Koolau, Lanai andKahoolawe anchor one extreme of the arrays, andhave the lowest 143Nd/144Nd, 206Pb/204Pb, CaOand TiO2 and the highest SiO2 and208Pb*/206Pb*.The other end of the Hawaiian array is anchoredby Loihi and the extreme Kea-trend volcanoes,Mauna Kea and Kilauea, which define the highest143Nd/144Nd, 206Pb/204Pb, CaO and TiO2 and thelowest 208Pb*/206Pb* and SiO2 (Figure 4).[19] Contrary to the findings of Hauri [1996], theother fractionation-correctedmajor element oxides?FeOtotal, Al2O3 and Na2O?do not exhibit clearrelationships with Nd and Pb-isotopic compositions(Figure 5). When plotted against 206Pb/204Pb, theFigure 4. Olivine fractionation-corrected SiO2, TiO2, and CaO oxide abundances are plotted against143Nd/144Ndand 208Pb*/206Pb*. SiO2, TiO2, and CaO exhibit similar relationships with87Sr/86Sr and 176Hf/177Hf (not shown).An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to 16 wt.% MgO. See Table 1, Figure S1, andData Set S1 for alternative olivine fractionation/addition schemes. Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042689 of 24fractionation-corrected FeOtotal concentrations of theextreme low 143Nd/144Nd Loa-trend lavas?all fromKoolau, Kahoolawe and Lanai?appear to be shiftedto slightly lower values than Kea-trend volcanoesand Loihi. Fractionation-corrected Al2O3 and Na2Oconcentrations appear to be offset to somewhathigher values in most of Loa-trend lavas, whileHawaiian lavas with the highest 143Nd/144Nd,including Loihi and Kea-trend volcanoes, tend tohave slightly lower Al2O3 and Na2O abundances.However, care must be taken when generalizingabout relationships between radiogenic isotopes andFeOtotal, Al2O3 and Na2O, as there is significantscatter in the data and the trends (if any) are not asclear as with SiO2, CaO and TiO2.[20] Two major element ratios not affected byolivine fractionation, CaO/Al2O3 and Na2O/TiO2,exhibit striking relationships with Nd and Pb-isotopiccompositions (Figure 6), as noted previously[Hauri, 1996; Putirka, 1999]. CaO/Al2O3 ratios arelowest and Na2O/TiO2 ratios are highest in the mostextreme low 143Nd/144Nd Loa-trend lavas fromFigure 5. Olivine fractionation-corrected FeOtotal, Al2O3and Na2O abundances are plotted against206Pb/204Pb. Thecorrelations (if any) are poor. 143Nd/144Nd, 87Sr/86Sr and176Hf/177Hf also fail to exhibit clear relationships withFeOtotal, Al2O3, and Na2O (not shown). An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.Figure 6. CaO/Al2O3 and Na2O/TiO2 oxide ratios areplotted against 208Pb*/206Pb*. 143Nd/144Nd, 87Sr/86Srand 176Hf/177Hf exhibit similar relationships with CaO/Al2O3 and Na2O/TiO2 (not shown). Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426810 of 24Koolau, Kahoolawe and Lanai. Loihi lavas andextreme Kea-trend lavas from Mauna Kea andKilauea have the highest CaO/Al2O3 and the lowestNa2O/TiO2.[21] Helium and Os isotopic ratios show clear rela-tionships with fractionation-corrected major elementcompositions and major element ratios. 3He/4Heexhibits trends with SiO2, CaO, Al2O3, CaO/Al2O3and FeOtotal [Kurz et al., 2004; Herzberg, 2011;Hauri, 1996], but not with TiO2 and Na2O abun-dances or with Na2O/TiO2 ratios (Figure 8). High3He/4He lavas from Loihi anchor the low-SiO2 andAl2O3 and high-CaO, CaO/Al2O3 and FeOtotalportions of the arrays. When plotted against olivinefractionation corrected major element abundancesand major element ratios, extreme Loa-componentlavas with the highest 187Os/188Os (and high SiO2,Al2O3, Na2O and Na2O/TiO2, and low TiO2, FeOtotal,CaO, and CaO/Al2O3) anchor one portion of the arrayand Loihi and the extreme Kea-component lavas withlow 187Os/188Os (and low SiO2, Al2O3, Na2O andNa2O/TiO2 and high TiO2, FeOtotal, CaO and CaO/Al2O3) anchor the other extreme of the arrays.4. Origin of Major Element Variabilityin Hawaiian Lavas[22] While assimilation of oceanic crust has beensuggested to modify the isotopic compositions ofoxygen [Wang et al., 2003], heavy noble gases[e.g., Kent et al., 1999] and 187Os/188Os (in Os-poorlavas [e.g., Martin et al., 1994]) in some Hawaiianlavas, shallow processes operating in the oceaniccrust are not likely to be responsible for the observedrelationships between radiogenic isotopes andfractionation-corrected major element abundancesin the filtered data set. First, highly evolved lavas,which are most susceptible to being modified byassimilation, are not considered in this study.Second, radiogenic isotopes exhibit no relationshipwith MgO (Figure 3), a proxy for magmatic evolu-tion. This suggests that crustal assimilation is notresponsible for generating variability in radiogenicisotopes and major elements. Third, the Sr-Nd-Pb-Hfisotopic compositions of altered oceanic crust andoceanic sediment in the Hawaiian region are unlikeHawaiian lavas or geochemical end-member com-positions sampled by Hawaiian lavas [Hauri, 1996;Lassiter and Hauri, 1998; Blichert-Toft et al., 1999;Hanano et al., 2010]. Therefore, assimilation of localoceanic crust and sediments is not the mechanismresponsible for driving relationships between majorelements and radiogenic isotopes in Hawaiian lavas.Consequently, the observed major element-isotopeFigure 7. Olivine fractionation-corrected SiO2 andTiO2 oxide abundances and Na2O/TiO2 ratios are plottedagainst 187Os/188Os. Olivine fractionation correctedFeOtotal, Na2O, Al2O3 and CaO oxide abundances andCaO/Al2O3 ratios also exhibit relationships with187Os/188Os, but are not shown here. An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426811 of 24Figure 8. Olivine fractionation-corrected SiO2, CaO, Al2O3 and FeOtotal oxide abundances and CaO/Al2O3 ratios areplotted against 3He/4He. Olivine fractionation corrected Na2O and TiO2 oxide abundances and Na2O/TiO2 ratios exhibitno relationships with 3He/4He and are not shown here. An olivine-melt Kd of 0.30 is used for olivine fractionation/additionto 16 wt.%MgO. See Table 1, Figure S1, and Data Set S1 for alternative olivine fractionation/addition schemes. Colors anddata symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426812 of 24correlations in Hawaiian shield lavas (Figures 4and 6?8) reflect mantle source heterogeneity. Herewe examine each of the three Hawaiian componentsin turn?Koolau, Loihi and Kea?and evaluate theorigin of the major element variability and discusspossible mechanisms that drive the observed rela-tionships between radiogenic isotopes and olivine-fractionation corrected major element compositions.4.1. The Koolau Component:The Enigmatic Eclogite4.1.1. Bulk Lava Major Element CompositionsFrom Peridotite or Eclogite Melts?[23] Makapuu stage lavas from Koolau volcanoexhibit the most enriched 143Nd/144Nd in Hawaiiand sample the end-member Koolau-componentcompositions [Roden et al., 1994], and they anchorthe low CaO, high SiO2 portion of the arrays formedin major element versus isotope space in Figure 4.Makapuu-stage Koolau lavas play a central role inthe debate on the role of eclogite melting in theHawaiian plume [e.g., Hauri, 1996; Huang andFrey, 2005; Salters et al., 2006; Huang et al.,2007; Sobolev et al., 2005, 2007; Herzberg, 2011;Putirka et al., 2011], and we explore the argumentssurrounding eclogite versus peridotite melting.[24] One argument against the generation ofMakapuu-stage Koolau melts by peridotite melting hinges onhigh pressure and temperature experiments performedon a Kilauea high-MgO glass composition. Eggins[1992] and Wagner and Grove [1998] showedexperimentally that the major element compositionsof the high MgO Kilauea glasses cannot be in equi-librium with both garnet and olivine (i.e., garnetperidotite). This is important because Hawaiianshield lavas exhibit heavy rare earth element(HREE) depletions and, after correction for olivinefractionation, relatively constant concentrations ofHREE [Hofmann et al., 1984], which require resid-ual garnet in the mantle source of the lavas[Hofmann et al., 1984; Huang and Frey, 2005].Instead, Eggins [1992] and Wagner and Grove[1998] found that Kilauea glasses are in equilib-rium with a harzburgite (olivine + orthopyroxene)residue, but this phase assemblage will not generatethe residual garnet signature observed in Hawaiianlavas.[25] The SiO2 contents of Kilauea glasses are alsotoo high to be melts of garnet peridotite [Hauri,1996; Wagner and Grove, 1998], and KoolauMakapuu-stage lavas have even higher SiO2 thanthe Kilauea lavas, which excludes garnet peridotiteas a source for the Koolau component (Figure 4).Similarly, the FeOtotal versus SiO2 systematics ofMakapuu-stage Koolau lavas are inconsistent withexperimentally derived partial melts of peridotite atgarnet stability field pressures [Hauri, 1996]. Whilelow pressure (1?1.5 GPa) partial melts of perido-tites can yield the high SiO2 contents found in theselavas, the FeOtotal of low pressure partial melts istoo low. There are at least two reasons why suchlow pressures of melting are not feasible. First, lowpressures of melting (1?1.5 GPa) are below thoseof the field of garnet stability and will not generatethe residual garnet signature observed in Hawaiianlavas [Hofmann et al., 1984; Huang and Frey,2005]. Second, the lithosphere beneath Hawaii istoo thick to permit such shallow melting (<45 km)[Hauri, 1996].[26] Water addition to peridotite can increase theSiO2 content of melts at low pressures of melting[Parman and Grove, 2004]. However, wet meltingof garnet peridotite does not increase the melt SiO2concentration [Tenner et al., 2012], and existingwet melting experiments of garnet peridotite cannotexplain the high SiO2 in Koolau lavas.[27] Nonetheless, Putirka et al. [2011] suggest thateclogite/garnet pyroxenite are not required for thepetrogenesis of Hawaiian lavas, and that peridotitemelting can generate the entire observed composi-tional range. Using a compilation of experimentalmelt data generated from a range of peridotiticcompositions at different pressure and temperatureconditions, they argue that the major elementcompositions of parental magmas of Makapuu-stage Koolau lavas can be explained by mixing ofpartial melts from different peridotite meltingexperiments. However, there is no single experi-mental melt that matches the extreme compositionof Makapuu-stage Koolau lavas (i.e., high SiO2,low FeO and CaO). While Putirka et al. [2011]argued that the primary magma composition ofMakapuu-stage Koolau lavas can be reproduced bymixing three experimental melts [see Putirkaet al., 2011, equation 6], the three experimentalmelts (i.e., H154 from Kinzler and Grove [1992],T-762 from Falloon et al. [1988], and T-3572from Falloon and Danyushevsky [2000]) are all low-pressure melts (1?2 GPa) and have only olivine andorthopyroxene as residual phases. Consequently,these experiments are inconsistent with REE con-centrations and patterns in Hawaiian lavas, whichrequire garnet as a residual phase during melting.[28] In summary, existing experimental peridotitemelt data and melt-rock reaction models do notGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426813 of 24explain the composition of Makapuu-stage Koolaulavas. While we cannot exclude the possibility thatfuture peridotite melting experiments may match theunusual major element compositions of Makapuu-stage Koolau, we note that eclogite melting in theHawaiian mantle source may provide a mechanismfor generating the highest SiO2 Hawaiian lavas.Eclogite has been invoked to explain the combinedresidual garnet signature and high SiO2 content ofMakapuu-stage Koolau lavas [Hauri, 1996; Huangand Frey, 2005; Sobolev et al., 2005, 2007]. Thelow CaO contents of Makapuu-stage Koolau lavasare also consistent with partial melting of eclogite[Huang and Frey, 2005; Herzberg, 2006]. Herzberg[2006] parameterized the peridotite melting experi-ments of Walter [1998] and argued that mostHawaiian shield lavas have CaO contents that aretoo low to be partial melts of peridotite [Pertermannand Hirschmann, 2003]. Since Makapuu-stageKoolau lavas have the lowest CaO contents at agiven MgO content among Hawaiian lavas [Freyet al., 1994] (Figures 3 and 4), Huang and Frey[2005] and Sobolev et al. [2005] suggested thatthey contain the largest contribution from partialmelts of eclogite/garnet pyroxenite. Additionally,Makapuu-stage lavas and olivines have the lowestMnO contents among Hawaiian lavas [Huang et al.,2007; Sobolev et al., 2007], consistent with partialmelting of eclogite [Pertermann and Hirschmann,2003], as MnO is relatively compatible in garnet.Finally, Makapuu-stage lavas have the among low-est TiO2 contents in the Hawaiian tholeiitic suite[Frey et al., 1994] (Figures 3 and 4). Such lowmagmatic TiO2 is distinctive feature of dacitic meltsof eclogite with residual rutile [Pertermann andHirschmann, 2003, Figure 9].4.1.2. High SiO2 Lavas From Melt-RockReaction Between Peridotite Melts andPeridotite Mantle?[29] Melt-rock reaction between peridotite meltsand harzburgite/peridotite (i.e., assimilation oforthopyroxene+clinopyroxene and precipitation ofolivine [Kelemen et al., 1992]) has also beenproposed as a model to explain the high SiO2-content in Hawaiian lavas [Eggins, 1992; Wagnerand Grove, 1998; Stolper et al., 2004; Putirkaet al., 2011]. The peridotite reacting with the meltcould be a melt-residue of the rising mantle plume[Wagner and Grove, 1998, Figure 5a] or in situlithospheric mantle [Wagner and Grove, 1998,Figure 5b]. Hauri [1996] noted that, if the elevatedSiO2 in Koolau were a result of melt-rock reactionwith the mantle lithosphere, it would be reflectedby a lithospheric imprint on the Koolau lavas,including unradiogenic 187Os/188Os and high143Nd/144Nd ratios typical of the oceanic mantlelithosphere [e.g., Shirey and Walker, 1998;Warren et al., 2009]. This is not observed. KoolauMakapuu-state lavas have radiogenic 187Os/188Osand low 143Nd/144Nd (Figure 2), an observationthat is inconsistent with extensive melt-rock reactionin the oceanic mantle lithosphere. Further, a melt-mantle reaction predicts that CaO/Al2O3 willincrease with SiO2 as pyroxene is dissolved andolivine is precipitated: olivine precipitation from themelt will drive up melt SiO2, and clinopyroxene(and/or orthopyroxene) dissolution from the mantlewill increase melt SiO2 and CaO/Al2O3. However,this is inconsistent with the negative relationshipobserved between CaO/Al2O3 and high SiO2 inHawaiian lavas (Figure 9), indicating that a mecha-nism other than melt-rock reaction is responsible forthe increased SiO2 in Koolau lavas.Figure 9. CaO/Al2O3 versus SiO2 in the Hawaiianmagmatic suite considered in this study. Melt-rock reac-tion between the shallow mantle lithosphere and amantle melt tends to increase SiO2 in the melt as clino-pyroxene from the mantle lithosphere is dissolved intothe melt while olivine from the melt is precipitated.This melt-rock reaction would be manifested as a posi-tive trend in SiO2 versus CaO/Al2O3 space. However,Hawaiian lavas with the highest SiO2 have the lowestCaO/Al2O3, a signature that is inconsistent with meltrock reaction. The lavas in the figure have been correctedfor olivine fractionation to a constant MgO of 16 wt.%.An olivine-melt Kd of 0.30 is used for olivine fraction-ation/addition. Lavas with high 206Pb/204Pb have lowSiO2 and high CaO/Al2O3, and lavas with high low206Pb/204Pb have high SiO2 and low CaO/Al2O3. Colorsand data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426814 of 24[30] Melt-rock reaction with the mantle plume alsofails to explain the observed residual garnet signature,i.e., and relatively constant HREE contents (aftercorrection for olivine fractionation or accumulation)in Hawaiian tholeiites [e.g., Hofmann et al., 1984;Huang and Frey, 2005]. This is because melt-rockreaction is likely to generate variable HREE abun-dances. Previous studies invoking melt-rock reac-tion considered high LREE/HREE ratios alone toreflect a residual garnet signature [e.g., Eggins,1992; Wagner and Grove, 1998; Putirka et al.,2011], but the variable HREE abundances result-ing from melt-rock reaction do not match the rela-tively constant abundances in Hawaiian lavas.Therefore, a melt-mantle reaction occurring withinthe plume, proposed to explain the high SiO2 con-tent in Hawaiian lavas, cannot explain the observedresidual garnet signature.4.1.3. Peridotite Versus Eclogite Melting:Evidence From Ni in Olivine?[31] Ni concentrations in olivines play a key role inthe debate surrounding eclogite melting in theHawaiian plume, particularly beneath Koolau vol-cano. Olivines in Makapuu-stage Koolau lavas haveunusually high Ni abundances [e.g., Clague et al.,1991; Garcia, 2002]. Sobolev et al. [2005, 2007]and Herzberg [2011] argued that the high Ni con-tents in Hawaiian olivines and lavas imply an oliv-ine-free, secondary garnet pyroxenite source forHawaiian lavas. Wang and Gaetani [2008] suggestthat the high olivine Ni contents are caused by highDNiol/melt that results from a melt with a high SiO2content, which implies an important role of eclogitein the petrogenesis of Hawaiian lavas.[32] However, Putirka et al. [2011] and Rhodeset al. [2012] suggest that there are large uncertain-ties in the model predicted DNiol/melt values and Nivariations in peridotites. They argued that Ni con-centrations in olivines and lavas may not be used asdiscriminators between eclogite melting and peri-dotite melting. Putirka et al. [2011] argue that, athigh temperature, DNiol/melt is low, and hot peridotitemelting yields Ni-rich melts. Following transport toshallower depths, DNiol/melt is higher owing to lowerambient temperatures, and crystallizing olivines areNi-rich. Further experiments parameterizing theeffects of temperature, pressure and melt composi-tion on Ni partitioning between olivine and melt areneeded to evaluate these contrasting hypotheses.[33] In summary, there is active debate surroundingthe interpretation of the elevated Ni abundances inHawaiian magmatic olivines and whole rocks, andfurther experiments parameterizing the effects oftemperature, pressure and melt composition on Nipartitioning between olivine and melt are needed toevaluate the contrasting hypotheses. However, thedistinctive geochemical characteristics of Makapuu-stage Koolau lavas?high SiO2, low CaO, TiO2 andMnO, and REE patterns showing residual garnetsignature?are consistent with partial melting ofeclogite [Hauri, 1996; Pertermann and Hirschmann,2003; Herzberg, 2006; Dasgupta et al., 2010], butare not matched by melt compositions from existingexperimental peridotite melting studies.4.2. The Loihi Component: The ParadoxicalPyroxenite4.2.1. Lithology of the Loihi Mantle Source[34] Lavas from the Hawaiian Loa-trend describearrays that suggest binary mixing between twoextreme compositions (Figures 2 and 4?8): Makapuu-stage Koolau lavas anchor the low 143Nd/144Nd and206Pb/204Pb portion of the Loa array, and high3He/4He lavas from Loihi define the portion withdepleted 143Nd/144Nd and 87Sr/86Sr signatures andradiogenic 206Pb/204Pb. While Koolau lavas havehigh SiO2 and low TiO2, CaO and CaO/Al2O3,Loihi lavas exhibit the lowest SiO2 and highestTiO2, CaO and CaO/Al2O3 in the Loa-trend suite.Unlike the Koolau Makapuu source, which is likelyto contain an eclogite component, the Loihi mantlesource is generally agreed to be peridotitic [e.g.,Sobolev et al., 2005, 2007; Putirka et al., 2011;Herzberg, 2006, 2011]. Nonetheless, there are keygeochemical features of high 3He/4He Loihi lavassuggesting that the source peridotite is enriched as aresult of the addition a mafic component [e.g.,Sobolev et al., 2005; Putirka et al., 2011; Herzberg,2011]?likely a SiO2-poor pyroxenite?and thefinal, hybrid mixture is still a peridotite.[35] Evidence that a mafic component was added tothe Loihi peridotite source comes from elevatedTiO2 contents in fractionation-corrected Loihi lavas,which are too high to be generated by peridotitemelting at the degrees of melting inferred forHawaiian shield lavas. Prytulak and Elliot [2007]showed that, after correcting lavas to 16 wt.% MgO,the fractionation-corrected TiO2 abundances of lavasfrom many Hawaiian volcanoes (>1.8 wt%) can onlybe generated by low degrees (<3%) of partialmelting of a primitive peridotite (840?1200 ppm Ti)[McDonough and Sun, 1995; Carlson and Boyet,2008] or a depleted mantle source (657?798, ppmTi) [Workman and Hart, 2005; Salters and Stracke,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426815 of 242004]. Such low degrees of partial melting areinconsistent with their tholeiitic bulk compositions,and there is evidence that Hawaiian lavas are gen-erated at higher degrees of melting (?5%) [McKenzieand O?Nions, 1991; Watson and McKenzie, 1991;Garcia et al., 1995]. Therefore, Prytulak and Elliot[2007] concluded that the mantle sources beneaththese Hawaiian volcanoes have been enriched by theaddition of a Ti-rich component, and the most likelymaterial to host sufficient Ti is a recycled maficcomponent. Loihi tholeiites have among the highestTiO2 concentrations?2.1 wt. % TiO2 at 16 wt.%MgO?in the Hawaiian tholeiite suite (Figures 3and 4) [Garcia et al., 1995; Hauri, 1996] indicat-ing that the dominantly peridotitic Loihi source hasincorporated a mafic lithology during its history inthe mantle.[36] Pb isotopic compositions offer a second line ofevidence for the addition of a mafic component tothe peridotitic Loihi mantle source. Loihi lavas havethe highest 206Pb/204Pb and 208Pb/204Pb among Loatrend volcanoes, and only extreme Kea-trend lavashave more radiogenic Pb isotopic ratios. The Pb-isotopic compositions of Loihi lavas plot well to theright of the geochron, which has been attributed tothe presence of a mafic material [Lassiter andHauri, 1998; Jackson et al., 2010; Jackson andCarlson, 2011] with high U/Pb following seaflooralteration (U addition) and subduction zone pro-cessing (Pb loss) [Hofmann and White, 1982; Kelleyet al., 2005].[37] A third line of evidence supporting a maficcomponent in the Loihi mantle source comes fromelevated 187Os/188Os ratios (up to 0.138) in Loihilavas. Roy-Barman et al. [1998] identified a positivecorrelation between 3He/4He and 187Os/188Os inLoihi, which led the authors to suggest that themantle beneath Loihi hosts a component withradiogenic Os that is somehow related to the end-member component found in Makapuu-stageKoolau lavas. (A similar correlation between 3He/4Heand 187Os/188Os is Iceland led Brandon et al. [2007]to suggest the presence of a mafic componentadmixed with high 3He/4He peridotite in the source ofhigh 3He/4He Icelandic lavas.) However, owing to themuch higher 3He/4He and more depleted 87Sr/86Srand 143Nd/144Nd ratios in Loihi lavas compared toKoolau lavas, we consider it unlikely that the high187Os/188Os mafic components in Loihi and Koolaulavas are the same.[38] The radiogenic Os and Pb, and high Ti con-centration in Loihi lavas are consistent with thepresence of a mafic component added to theperidotitic mantle source of Loihi lavas, yet petro-logic models for the Loihi source indicate thatperidotite melting is occurring [e.g., Putirka et al.,2011; Herzberg, 2011]. This raises an importantquestion, which relates to the paradox of pyroxenitein the Loihi mantle source: How can the mixture ofthe peridotite and pyroxenite result in a mantlesource that generates melts that appear petrologi-cally to have been sourced by a peridotite? Owing tothe high TiO2 in Loihi lavas, Putirka et al. [2011]invoked the Prytulak and Elliot [2007] Ti model tosuggest the incorporation of a mafic component inthe Loihi source, but argued that it no longer existsas a distinct lithology. Putirka et al. [2011] sug-gested that the mafic source has been mixed com-pletely into the peridotite, so that the final lithologyis an enriched peridotite. If true, the final mixture, aperidotite, would inherit elevated TiO2 and radio-genic Os and Pb from the mafic lithology. However,mixing of the pyroxenite into the peridotite mightnot take place in the solid state.Gaffney et al. [2005]proposed a model for melting a mafic component inthe presence of peridotite, while keeping the petro-logic signature of the mafic component ?hidden.?They suggested that the eclogite melt would infil-trate and react with the peridotite and generate afertile peridotite, similar to that observed in eclogite-peridotite ?sandwich? experiments [Yaxley andGreen, 1998; Takahashi and Nakajima, 2002].The resulting fertile peridotite will be rich in ortho-pyroxene, as a result of eclogite melt reaction witholivine in the peridotite. Gaffney et al. [2005] sug-gested that melting of the fertilized peridotite willyield melts with a major element composition thatreflects peridotite melting [Hirschmann et al.,2003], even though they possess isotopic and traceelement geochemical signatures that reflect a con-tribution from a mafic component. The Putirka et al.[2011] and Gaffney et al. [2005] models may helpexplain the paradox of a mafic component in theLoihi mantle source that is essentially ?invisible? topetrologic models that suggest derivation of Loihilavas from a peridotitic source.4.2.2. Mantle Source Lithological DifferencesBetween the Loa-Trend Extremes: Comparingthe Loihi Mantle Source to the KoolauMakapuu Mantle[39] The association of high 3He/4He with a mantlesource that hosts a mafic component at Loihi isparadoxical. Owing to the highly incompatiblenature of U and Th during mantle melting, maficmaterials should in general have higher U and Ththan peridotitic materials. Therefore, over time,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426816 of 24mafic materials will generate more 4He than peri-dotites, resulting in lower 3He/4He in the formerrelative to the latter. As a result, a mafic componentadded to the peridotitic source should result in low3He/4He in Loihi lavas, not high 3He/4He. How-ever, if the SiO2-undersaturated pyroxenite inferredto have been added to the peridotitic Loihi sourcesuffered melt extraction in a paleo-subduction zone,then incompatible elements like U and Th will havebeen effectively removed from the pyroxenite, thusreducing its potential to generate 4He over time.Jackson et al. [2008] observed that 3He/4He ratioscorrelate with the magnitude of positive Ti, Ta andNb (TITAN) anomalies (where anomalies of theTITAN elements?calculated relative to elementsof similar compatibility in peridotite on a primitivemantle normalized spidergram?are not to be con-fused with the absolute concentrations of theseelements) in Hawaiian lavas, where Loihi exhibitsthe largest Ti anomalies and highest 3He/4He ratios.Owing to the ubiquitous presence of rutile in eclo-gite, trace elements compatible in rutile, includingthe TITAN elements, are residually enriched rela-tive to other trace elements during melt extractionfrom and dehydration of the downing-going slab;incompatible elements not sequestered into rutile?including the radiogenic helium-producing elements,U and Th?will be lost from the slab, togetherwith SiO2. For such a model to explain the radio-genic Pb isotopes in Loihi lavas, Pb would have to bepreferentially removed from the slab relative to U andTh, which is likely [Kelley et al., 2005]. The residualSiO2-poor mafic material?a pyroxenite?is TITAN-enriched and depleted in U and Th, and will contrib-ute little 4He to the peridotite with which it mixes,including high 3He/4He peridotites. Such a modelmight explain the association of TITAN enrichmentand high 3He/4He in SiO2-poor Loihi lavas.[40] By contrast, Makapuu-stage Koolau lavas havehigher SiO2, lower3He/4He and less radiogenic Pb.These lavas sample a SiO2-rich eclogite (Section 4.1)that has not suffered severe SiO2 and incompatibleelement depletion in a subduction zone, as evidencedby the silica-rich character of Koolau lavas. Such aneclogite will have retained its complement of U andTh (and Pb, thereby preserving a low U/Pb ratio) andwill producemore 4He over time that will ?infect? thesurrounding peridotite mantle?including the litho-logic reservoir hosting high 3He/4He peridotite[e.g., Parman et al., 2005; Albar?de, 2008; Hartet al., 2008; Jackson et al., 2008]?with low3He/4He. A host of possible mafic lithologies existin nature, and the presence of two distinct maficcomponents?a SiO2-poor pyroxenite and a SiO2-rich eclogite?in the Hawaiian plume might recon-cile the geochemical differences between the twoLoa-trend mantle components, Loihi and Koolau-Makapuu.4.3. The Kea Component[41] A third major isotopic end-member observed inHawaiian shield lavas?the Kea component?issampled by volcanoes that define the Kea en eche-lon volcanic trend. The Kea-trend volcanoes havemore homogeneous Sr, Nd and Hf isotopes that arealso generally more depleted [e.g., Stille et al.,1986] than their Loa-trend equivalents [DePaoloet al., 2001; Weis et al., 2011]. This has led tomodels suggesting a depleted peridotite source?MORB-source, Pacific oceanic lithosphere, entrainedasthenosphere, or recycled mantle lithosphere?forKea-component lavas [West et al., 1987; Chen andFrey, 1985; Hauri, 1996; Eiler et al., 1996a, 1996b;Lassiter et al., 1996]. However, the low 176Hf/177Hfof the Kea end-member suggests that asthenosphericor lithospheric materials are not present in the sourceof Kea-type lavas [Blichert-Toft et al., 1999].Recycled lower oceanic crust has also been sug-gested to source Kea-component lavas, but only incombination with recycled lithospheric peridotite[Lassiter and Hauri, 1998].[42] With the exception of 3He/4He and 208Pb*/206Pb*,Kea- and Loihi-component lavas are more similar toeach other than to Koolau-component lavas, and thefractionation-corrected major element compositions ofKea lavas are remarkably similar to Loihi-componentlavas, as observed previously [Hauri, 1996]. In fact, theKea-component exhibits several geochemical similari-ties with the Loihi-component that suggest that theformer also hosts a mafic component in its mantlesource. For example, Kea-component lavas hosthigh TiO2 contents, consistent with the addition of apyroxenite component in the source of Kea-component lavas (Mauna Kea and Kilauea have>2 wt.% TiO2 at 16 wt.% MgO (Table 1) [Prytulakand Elliot, 2007]). However, information fromradiogenic isotopes does not permit a clear resolu-tion of the debate over source lithologies contribut-ing to the Kea mantle source. On the one hand, Pbisotopic compositions in Kea-component lavas areamong the most radiogenic in Hawaii. If radiogenicPb is associated with a recycled mafic component,then Kilauea lavas should host a significant maficcomponent. This is contradicted by the generallyunradiogenic 187Os/188Os in Kea-trend lavas(<0.133, with the exception of a single Kohala lava;Figure 7). One possible explanation for this apparentGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426817 of 24disagreement is that there is a greater contribution ofrecycled sediment to the Loa-trend mantle than tothe Kea-trend source: Sediment generally has higher187Os/188Os than mafic lithologies, so it is possiblefor a mantle source with a sediment and a maficcomponent (like the Loa-trend mantle) to have ahigher 187Os/188Os than the a mantle source withjust a mafic component (like the Kea-trend mantle)[Lassiter and Hauri, 1998; Huang et al., 2005].5. Major Element Versus IsotopeCorrelations in Hawaii in the Contextof Global OIBs[43] The broad correlations between major elementsand isotopes in Hawaiian lavas form arrays anchoredby Loihi and Kea-component lavas (with high143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and low87Sr/86Sr) at one end and by Koolau lavas (with low143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and high87Sr/86Sr) at the other. Information from olivine-fractionation corrected major element data suggeststhat the correlations in the Hawaiian data set areanchored on both ends by different types of maficcomponent that coexist (and interact) with peridotitein the Hawaiian plume: a silica-poor pyroxeniteanchors the Loihi and Kea-component portion of theHawaiian array (Section 4.2 and 4.3), and a silica-rich eclogite anchors the enriched portion (Koolau)of the Hawaiian array (Section 4.1). A host of pos-sible mafic lithologies exist in nature, and the SiO2content of the mafic materials in the source ofthe Loihi, Kea and Koolau components may bethe defining difference among these components.However, in order to understand the origin of thesecontrasting mafic sources, they must first be placedin the context of global OIB geochemical variability.[44] Broad relationships between major elementsand radiogenic isotopes in the global OIB data setmay help constrain the mantle source compositionsof the Loihi, Kea and Koolau components. Jacksonand Dasgupta [2008] show that global OIB lavaswith the most radiogenic Pb have the lowest SiO2and the highest CaO/Al2O3 (Figure 10). SiO2 andCaO/Al2O3 also exhibit some of the clearest cor-relations with 206Pb/204Pb in Hawaiian lavas, andthese correlations mimic the global trend (Figure 10).Like the global OIB data set, FeOtotal, Al2O3 andNa2O abundances in Hawaii exhibit little or nocorrelation with radiogenic isotopes. In summary,the correlations between Pb isotopes and majorelements in Hawaii appear to broadly reflect theglobal trends, and we suggest that the mechanismthat drives the correlations between major elementsand isotopes in Hawaii illustrates, in microcosm, alarger global process.[45] Hauri [1996] suggested that SiO2-rich(50 wt.%) Koolau lavas resulted from melting ofSiO2-saturated mafic material (which we refer toabove as eclogite), while the mantle sources of thelow SiO2 lavas (40 wt.%) in the Pacific Islandswith the most radiogenic Pb are thought to hostSiO2-poor mafic material (which we refer to aspyroxenite) [Hirschmann et al., 2003; Kogiso et al.,2003; Kogiso and Hirschmann, 2006; Dasguptaet al., 2006; Jackson and Dasgupta, 2008]. Apply-ing this model to the Hawaiian magmatic suite, weinfer that Loihi and Kea-component lavas, whichexhibit the most radiogenic Pb compositions and thelowest SiO2 concentrations in Hawaiian shieldlavas, are derived from a peridotitic mantle sourcethat incorporated a small portion of a SiO2-poormafic component with radiogenic Pb.[46] Subduction zone processes can modify thecomposition of the downgoing oceanic crust byvariably removing SiO2 (and fractionating traceelement ratios, such as U, Th and Pb) [Hauri, 1996;Jackson and Dasgupta, 2008]. As a result, SiO2-richand SiO2-poor mafic lithologies exist in the mantlethat are likely to host distinct time-integrated isoto-pic ratios. Low SiO2 lavas from Mangaia andTubuaii and the high SiO2 lavas from Hawaii?sKoolau Makapuu-stage anchor the high 206Pb/204Pband low 206Pb/204Pb portions of the global array,respectively (Figure 10) [Jackson and Dasgupta,2008]. SiO2-deficient eclogites suggested for thesource of SiO2-poor OIB lavas with radiogenic Pbmust have somehow attained higher U/Pb ratios,likely via Pb-loss from the slab [Kelley et al., 2005](i.e., the same subduction zone processes reduced theSiO2 of the downgoing crust and increased U/Pb).The variability within the Hawaiian array may begenerated in a similar manner, where the Hawaiianplume hosts both SiO2-rich eclogites (with low206Pb/204Pb) and SiO2-poor pyroxenites (with high206Pb/204Pb) that mix in the peridotite matrix of theplume to generate the correlations between majorelements and radiogenic isotopes in Hawaii. Thus,processes operating in subduction zones that modifythe downgoing oceanic crust may be responsible forgenerating much of the major element variabilityobserved in Hawaii and in OIBs in general [Hauri,1996].6. Conclusions[47] From this review study, we draw the followingconclusions:GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426818 of 24[48] 1. Data for tholeiitic Hawaiian shield lavasform arrays in plots of radiogenic isotopes versusolivine-corrected major element oxides. Individualdata points exhibit remarkable trends and there isno need to average the data by volcano.[49] 2. The trends are anchored by Koolau lavas atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2,Figure 10. Olivine fractionation-corrected SiO2 concentrations and CaO/Al2O3 ratios are plotted against206Pb/204Pbfor Hawaiian lavas and the global OIB data set. The correlations in the Hawaiian data set mimics, in microcosm, thelarger global correlation. The global OIB data set is from Jackson and Dasgupta [2008] and includes only lavas withMgO > 8 wt.% MgO, as many non-Hawaiian OIB lavas experience clinopyroxene fractionation at lower MgO abun-dances (see Data Set S1 for compositions). An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. HIMU (or high-m, or 238U/204Pb) represents the mantle reservoir with radiogenic Pb-isotopes [e.g.,Hauri and Hart, 1993; Woodhead, 1996; Hanyu et al., 2011].GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426819 of 24and Na2O/TiO2, and low143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaO and CaO/Al2O3) and byKea and Loihi lavas at the other (low 87Sr/86Sr,187Os/188Os, SiO2, and Na2O/TiO2, and high143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaOand CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with Sr, Nd, Pb or Hfisotope compositions.[50] 3. In Hawaiian tholeiitic lavas, 3He/4He showsa remarkably good relationship with SiO2, CaO,Al2O3, CaO/Al2O3 and FeOtotal. High3He/4He lavasfrom Loihi anchor the low SiO2 and Al2O3 and highCaO, CaO/Al2O3 and FeOtotal portions of the arrays.3He/4He exhibits no clear relationships with TiO2and Na2O abundances or with Na2O/TiO2 ratios.[51] 4. The Loihi source is likely peridotitic, but hasbeen infused with a SiO2-poor mafic componentsuch that the final mixture is an enriched peridotite.Loihi and Kea-component lavas exhibit similarmajor element characteristics (low SiO2 and Na2O/TiO2 and high TiO2, CaO and CaO/Al2O3), whichmay suggest lithologically similar mantle sources.The composition of SiO2-rich Koolau-componentlavas is not easily explained by available data forperidotite melting experiments (wet or dry) or bymelt-rock reaction of peridotite melts with the oce-anic mantle lithosphere. Instead, Koolau-componentlavas are likely derived from melts of a SiO2-richeclogite that has variably interacted with peridotite.[52] 5. Correlations between major elements andradiogenic isotopes in Hawaiian lavas mimic thebest correlations observed in the global OIB data setbetween Pb isotopic ratios and SiO2 and CaO/Al2O3. We suggest that the mechanism that drivesthe correlations between major elements and iso-topes in Hawaii illustrates, in microcosm, a largerglobal process. Variable processing of slabs insubduction zones yields SiO2-poor pyroxenites(with high U/Pb) and SiO2-rich eclogites (with lowU/Pb) that evolve radiogenic and unradiogenic Pbisotopic compositions, respectively. 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JacksonDepartment of Earth Sciences, Boston University, Boston, Massachusetts, USADominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, British Columbia, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts, USAJackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features and perspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.Introduction:The supplement referred to in the text includes a worksheet in a single Excel 2004 (.xls) file, and a PDF (.pdf) file with figures illustrating the effects of different olivine fractionation correction schemes modify the composition of a melt.  The worksheet contains all geochemical data from Hawaiian lavas from Georoc--including major element abundances (both raw abundances and abundances following olivine fractionation correction) and isotopic ratios--remaining after applying the filters described in the text. The global OIB dataset used in Jackson and Dasgupta (2008) are also included for comparison.  Major element abundances for different olivine fractionation correction schemes are also included in the spreadsheet.  1. 2012gc004268-ds01.xlsData Set S1. All geochemical data and for Hawaiian lavas presented in the manuscript.2. 2012gc004268-fs01.pdfFigure S1. Hawaiian shield lavas are corrected for olivine fractionation/addition using three different methods. In the first column, lavas are corrected to a constant MgO (16 wt.%) using an olivine-melt Kd of 0.30. In the second column, lavas are corrected to a constant MgO (16 wt.%) using an olivine-melt Kd of 0.34.  In the third column, lavas are corrected to be in equilibrium with forsterite 90 olivine using an olivine-melt Kd of 0.30. Cumulates (Mg>20 wt.%) are corrected in the same manner in all plots by subtracting olivine of forsterite 87 composition. As shown in the figure, the correction scheme used does not greatly change the major element concentrations and the sense of the correlations is preserved. Symbols are the same as the manuscript.ReferencesJackson, M.G., and R. Dasgupta (2008), Compositions of HIMU, EM1, and EM2 from global trends between radiogenic isotopes and major elements in ocean island basalts, Earth Planet. Sci. Lett., 276, 175-186. ArticleVolume 13, Number 919 September 2012Q09009, doi:10.1029/2012GC004268ISSN: 1525-2027Major element variations in Hawaiian shield lavas: Sourcefeatures and perspectives from global ocean island basalt(OIB) systematicsMatthew G. JacksonDepartment of Earth Sciences, Boston University, 675 Commonwealth Avenue, Boston, Massachusetts02215, USA (jacksonm@bu.edu)Dominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences,University of British Columbia, 6339 Stores Road, Vancouver, British Columbia V6T1Z4, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, 20 Oxford Street, Cambridge,Massachusetts 02138, USA[1] Among volcanic hot spots globally, Hawaii has the highest magma flux, yet there is significant contro-versy surrounding the composition of the mantle sourcing Hawaiian lavas. In order to place constraints onthe source lithologies of Hawaiian lavas, we explore relationships between major elements and radiogenicisotopes in tholeiitic, shield-building lavas. Olivine-fractionation corrected lava compositions reveal cleartrends between radiogenic isotopes and major elements. Individual data points exhibit remarkable trendsand there is no need to average the data by volcano. Data form arrays that are anchored by Koolau lava atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2, and Na2O/TiO2, and low143Nd/144Nd, 206Pb/204Pb, TiO2,CaO and CaO/Al2O3) and by Kea and Loihi lavas at the other (with low87Sr/86Sr, 187Os/188Os, SiO2, andNa2O/TiO2, and high143Nd/144Nd, 206Pb/204Pb, TiO2, CaO and CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with radiogenic isotopes. The Hawaiian data set exhibits correlations that mirrorthe best correlations between major elements and radiogenic isotope in the global ocean island basalt (OIB)database. We suggest that the mechanism driving the correlations in Hawaii illustrates, in microcosm, alarger global process that generates major element variability in mantle plumes. Like the global arrays, theHawaiian lavas with radiogenic Pb and SiO2-poor lavas are sourced by a SiO2-poor mafic component (pyrox-enite) admixed with peridotite, while Hawaiian lavas with unradiogenic Pb and high SiO2 are sourced by aSiO2-rich mafic component (eclogite). The variable SiO2 in the mafic component may result from differentdegrees of SiO2-extraction from the slab during subduction.Components: 14,700 words, 10 figures, 1 table.Keywords: Hawaii; eclogite; hotspot; isotopes; mantle plume; pyroxenite.Index Terms: 1025 Geochemistry: Composition of the mantle; 1033 Geochemistry: Intra-plate processes (3615, 8415); 1038Geochemistry: Mantle processes (3621).Received 4 June 2012; Revised 25 July 2012; Accepted 10 August 2012; Published 19 September 2012.?2012. American Geophysical Union. All Rights Reserved. 1 of 24Jackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features andperspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.1. Introduction[2] Oceanic plates?including mafic crust, depletedlithospheric peridotite, and a thin veneer of marinesediments?are sent into the mantle at subductionzones, thereby contributing to the compositionalheterogeneity of Earth?s mantle [Hofmann andWhite, 1982; White and Hofmann, 1982; Iwamoriet al., 2010]. Buoyantly upwelling regions of themantle are thought to return parts of these subductedoceanic plates to the shallow mantle, where theypartially melt beneath hot spots like Hawaii. Lavaserupted at hot spots therefore reveal clues about thedynamic history and composition of the mantle[Zindler and Hart, 1986; Hofmann, 1997]. Thecompositions of hot spot lavas suggest that recyclingof ancient subducted oceanic plates is a commonprocess that has affected the geochemistry of themantle over geologic time [e.g., Hofmann andWhite, 1982; Sobolev et al., 2005].[3] However, significant controversy surrounds thefinal fate of recycled oceanic crust in the mantle[Eggins, 1992; Hauri, 1996; Wagner and Grove,1998; Putirka, 1999; Sobolev et al., 2005, 2007;Gaffney et al., 2005; Huang and Frey, 2005; Huanget al., 2007; Herzberg, 2006, 2011; Putirka et al.,2011; Niu et al., 2012]. Following billion-yeartimescales of residence in the mantle, oceanic crustis likely stretched, thinned, and its geochemicalsignal is greatly attenuated [e.g., Ottino, 1989; VanKeken et al., 2004]. While distinct mafic litholo-gies may survive mantle convection to be meltedbeneath hot spots like Hawaii [Hauri, 1996; Sobolevet al., 2005, 2007, 2008; Huang and Frey, 2005;Huang et al., 2007; Herzberg, 2006, 2011], thesurvival of distinct mafic lithologies into the man-tle beneath Hawaii has been questioned [Putirka,1999; Salters et al., 2006; Putirka et al., 2011].Putirka [1999] and Putirka et al. [2011] argue thatperidotite melting can explain the geochemistry ofHawaiian lavas, and a distinct mafic lithology in themantle source of Hawaiian lavas is not required.[4] Hawaii is arguably the most-studied oceanic hotspot, and the abundance of geochemical data obtainedfrom Hawaiian lavas makes it an ideal location forevaluating the presence of recycled oceanic crust inthe mantle source. While a multitude of componentshave been identified in the Hawaiian mantle, mostof the isotopic variability in Hawaiian shield-buildinglavas can be described with just three components,as shown by principal component analysis [Hauri,1996; Eiler et al., 1996a]. These componentsinclude the Koolau, Loihi and Kea components(Figure 2) [Stille et al., 1986; West and Leeman,1987; Eiler et al., 1996b; Hauri, 1997; Gaffneyet al., 2005; Huang et al., 2005; Weis et al., 2011].The small volumes of low-degree melts sampled bypost-shield and rejuvenated lavas require the pres-ence of a fourth, depleted component, distinct fromPacific MORB [Mukhopadhyay et al., 2003; Freyet al., 2005; Fekiacova et al., 2007; Garcia et al.,2010; Hanano et al., 2010], but post-shield andrejuvenated-stage lavas are volumetrically insignif-icant compared to the shield-building lavas andthese lavas are not considered here. Hawaii is thearchetypal high 3He/4He hot spot, and lavas fromLoihi seamount define the Loihi component andhost 3He/4He ratios in excess of 30 Ra (ratio toatmosphere) [Kurz et al., 1982; Rison and Craig,1983; Kurz et al., 1983; Staudigel et al., 1984;Sarda et al., 1988; Honda et al., 1993; Valbrachtet al., 1997; Eiler et al., 1998; Jackson et al., 2008].TheKoolau component, defined byKoolauMakapuu-stage lavas, is a lower 3He/4He end-member charac-terized by the lowest 143Nd/144Nd and 206Pb/204Pband highest 87Sr/86Sr in Hawaii and constitutes theenriched Loa trend volcanic end-member (see below)[Tanaka et al., 2008]. This end-member is sampledin diluted form at several Hawaiian volcanoes andlikely hosts a component of recycled oceanic crustand sediment [e.g., Hauri, 1996; Lassiter andHauri, 1998; Blichert-Toft et al., 1999; Normanet al., 2002; Sobolev et al., 2005; Huang et al.,2005, 2011a; Herzberg, 2011; Putirka et al., 2011].The origin of the Kea component, best exemplifiedby lavas from Mauna Kea, W. Maui and Kilauea, isless clear. The Kea component, which hosts thehighest 143Nd/144Nd and 206Pb/204Pb and the lowest87Sr/86Sr in Hawaii, is relatively homogeneous rel-ative to the Koolau component, leading to modelssuggesting a MORB-source, Pacific oceanic litho-sphere source or entrained asthenospheric source inKea lavas, but recycled lower oceanic crust andmantle lithosphere also have been suggested [Chenand Frey, 1985; Frey and Rhodes, 1993; Hauri,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042682 of 241996; Eiler et al., 1996a, 1996b; Lassiter and Hauri,1998; Blichert-Toft et al., 2003; Gaffney et al., 2005].The Kea component dominates the Kea volcanictrend (see below).[5] The distribution of the Loa and Kea componentsis organized geographically along the hot spot(Figure 1). Hawaiian shield volcanoes erupted duringthe past 5 Ma tend to be oriented along two en ech-elon volcanic trends that exhibit distinct isotopic [e.g.,Jackson et al., 1972; Tatsumoto, 1978; Abouchamiet al., 2005; Tanaka et al., 2008; Farnetani andHofmann, 2010; Weis et al., 2011; Huang et al.,2011b] and major element [Hauri, 1996; Greeneet al., 2010] compositions. Volcanoes along thenorthern geographic trend erupt Kea-type lavas andsouthern-trend volcanoes tend to erupt Loa-typelavas. The origin of this geographic and geochemi-cal separation is the source of significant discussion[e.g., Hieronymus and Bercovici, 1999; Abouchamiet al., 2005; Ren et al., 2005; Marske et al., 2007;Weis et al., 2011; Huang et al., 2011b]. Under-standing the origin of the different major elementcompositions of shield-stage lavas between the Loaand Kea trends [Hauri, 1996] may provide impor-tant clues about the structure of the Hawaiian plume,including the possible organization of lithologicheterogeneities within the plume conduit [Blichert-Toft et al., 2003; Abouchami et al., 2005] and inthe deep mantle [Weis et al., 2011; Huang et al.,2011b].[6] Frey and Rhodes [1993] systematically docu-mented major element variations among differentHawaiian shields and attributed them to mantlesource variability. However, correlations betweenmajor elements and isotopes can strengthen con-clusions that major element variations in hot spotlavas reflect mantle source lithological heterogene-ity [Hauri, 1996; Sobolev et al., 2008; Jackson andDasgupta, 2008]. Hauri [1996] showed correlatedmajor element and isotopic variations in composi-tional and isotopic averages of Hawaiian volcanoes,and on this basis, argued for major element vari-ability in the Hawaiian mantle and for the impor-tance of eclogite in the petrogenesis of Hawaiianshield lavas. Jackson and Dasgupta [2008] extentsuch major element-isotope correlation to the globalOIB data set. Here we show that the original ele-ment-isotope correlations observed by Hauri [1996]are ?mirrored? by the global OIB data set [Jacksonand Dasgupta, 2008]. These data document themajor element variability in the Hawaiian plume,constrain source lithologies, and place the majorelement variability in the Hawaiian plume in thecontext of global OIB variability.2. Treatment of Geochemical Data[7] The geochemical data used in this study wereobtained from the Georoc database (georoc.mpch-mainz.gwdg.de/georoc) on December 26, 2011.Only tholeiitic lavas are considered. All non-tholeiitic lavas [Macdonald and Katsura, 1964] areexcluded, as are lavas that are explicitly described aspost-shield or rejuvenated. Only lavas with a com-plete set of major elements (SiO2, TiO2, Al2O3,FeOtotal, MnO, MgO, CaO, Na2O, K2O, P2O5) areconsidered. A sample is excluded if it does not haveat least one of the following isotopic measurements:87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb), 187Os/188Os, 176Hf/177Hf, or3He/4He. Compared to Sr, Nd and Pb isotopes, andHf isotopes to a lesser extent, measurements ofHe and Os isotopes are still relatively rare. Lavaswith low Os concentrations are susceptible to con-tamination by assimilation of materials with radio-genic Os. Therefore, Os-poor (Os < 40 ppt) lavas areexcluded [Class et al., 2009]. Similarly, lavas withlow helium concentrations are susceptible to reduc-tion of 3He/4He by post-eruptive radiogenic ingrowthof 4He or crustal assimilation, and analyses of He-poor olivines and glasses (less than 2*108 cc/g STP4He) are excluded [Garcia et al., 1990; Hilton et al.,1995; Kurz et al., 2004; Class and Goldstein, 2005].Only 3He/4He measurements obtained by crushingolivines and glasses are used. Much of the heliumisotopic data available for Hawaiian lavas are elimi-nated using the concentration filter, but we feel thatthe filter yields a data set that better reflects mantle3He/4He compositions. However, all 3He/4He mea-surements are preserved in Data Set S1 in theauxiliary material, regardless of 4He concentration, aslong as the associated whole rock major elementanalyses do not indicate excessive alteration ormagmatic evolution.1[8] As a filter for alteration, samples with K2O/P2O5< 1, low dry totals (<97 wt.%) or high dry totals(>101 wt.%) were excluded [e.g., Frey et al., 1994].Leaching is necessary to reduce alteration compo-nents in lavas that most strongly influence Sr and Pbisotopic ratios but not Nd and Hf isotopic ratios[Nobre Silva et al., 2009, 2010]. However, it is notalways known which samples were leached in acid1Auxiliary material data sets are available at ftp://ftp.agu.org/apend/gc/2012gc004268. Other auxiliary materials are available inthe HTML. doi:10.1029/2012GC004268.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042683 of 24prior to isotopic analyses, as this is not consistentlyreported in the literature. Fortunately, Sr and Pbisotopic ratios show excellent correlations with Ndand Hf isotopic ratios in Hawaiian volcanoes(Figure 2). Owing to these correlations, we show Ndand Pb isotopic data, but not Sr and Hf isotopic data,in subsequent figures. Sr and Hf isotopic data,where available, are preserved in Data Set S1.[9] Low MgO lavas (<6.5 wt.%) were not includedin the filtered data set. Such lavas can suffer fromclinopyroxene and plagioclase fractionation [e.g.,Rhodes and Vollinger, 2004; Rhodes et al., 2012].Lavas with MgO > 6.5 wt.% are affected primar-ily by fractionation or accumulation of olivine Cr-spinel [Hauri, 1996].[10] The lavas remaining (n = 551) after thesefiltering steps were renormalized to 100 wt.% totals(on a dry basis) with all Fe reported as FeOtotal(see Data Set S1). The lavas were then corrected forolivine fractionation to a constant MgO of 16 wt.%by adding or subtracting equilibrium olivine in 0.01wt.% increments, similar to Langmuir et al. [1992].Equilibrium olivines were generated using theolivine-melt Kd of 0.3 [Roeder and Emslie, 1970;Ford et al., 1983] assuming 10% of the total iron isFe3+. Correcting the lavas for olivine fractionation/addition until they are in equilibrium with a mantleolivine (forsterite 90) does not change our conclu-sions (see Table 1, Figure S1, and Data Set S1). Anolivine-melt Kd of 0.34 has been suggested forMauna Kea lavas [e.g., Matzen et al., 2011], whichdoes not change our conclusions (see Figure S1 andData Set S1). For cumulates (MgO > 20 wt.%), wefollow the procedure of Hauri [1996] and subtractan olivine composition of forsterite 87 until the bulklava has 16 wt.%MgO. All of the major element andisotopic data, and major element data corrected forolivine fractionation, are reported in Data Set S1for individual samples and in Table 1 as volcanoaverages.3. Observations3.1. Radiogenic Isotopes[11] The panels of Figure 2 show the variability inradiogenic isotopes in the lavas considered in thisstudy. Every lava considered in this study has bothmajor element data (n = 551) and at least one radio-genic isotope system measured (87Sr/86Sr [n = 444],143Nd/144Nd [n = 417], 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb) [n = 452], 176Hf/177Hf [n = 229],187Os/188Os [n = 86], 3He/4He [n = 152 for all 4Heconcentrations, or 48 for samples with 4He > 2*108cc STP/g]). The radiogenic isotopic data shown inFigure 2 are intended to show the isotopic variabilityin the freshest, least evolved Hawaiian shield lavasthat we examined in this study, and therefore the datain the figures do not encompass the complete radio-genic isotopic variability in Hawaiian lavas.Figure 1. Map of Hawaiian hot spot from Loihi to Kauai showing individual volcanoes (map made usingGeoMapApp, http://www.geomapapp.org).GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042684 of 24Table1(Sample).MeanIsotopicandMajorElementCompositionsforHawaiianVolcanoesExaminedinThisStudya[ThefullTable1isavailableintheHTMLversionofthisarticle]VolcanoIsland143Nd/144NdAverage2SD87Sr/86SrAverage2SD206Pb/204 PbAverage2SD207Pb/204PbAverage2SD208Pb/204PbAverage2SD187Os/188OsAverage2SDLoa-trendLoihi(tholeiitic)BigIsland0.5129530.0000700.7035810.00013118.3760.13315.4680.03038.1180.1220.13330.0046MaunaLoaBigIsland0.5129060.0000740.7038090.00066818.1680.17615.4600.02437.9080.1380.13560.0030HualalaiBigIsland0.5129030.0000510.7037270.00008618.1820.13215.4590.02537.9510.1590.13480.0016MahukonaBigIsland0.5129620.0000680.7036390.00015518.2530.22215.4690.01437.9410.152NAKahoolaweMauiNui0.5128480.0000990.7041200.00031818.0420.31415.4360.03037.8290.2190.1439LanaiMauiNui0.5127700.0001210.7041810.00031617.9220.09815.4370.01637.7530.057NAWestMolokaiMauiNui0.5129430.0002160.7038190.00039418.2530.44515.4600.02537.9390.254NAKoolau(Makapuu)Oahu0.5127570.0000770.7040820.00031517.8540.07415.4380.02637.7730.0710.14260.0075Koolau(KSDP)Oahu0.5129170.0000830.7037600.00017318.0630.08115.4530.00737.8370.051NAKoolau(NuuanuLandslide)Oahu0.5129720.0000590.7035680.00016118.2040.36615.4480.01737.8830.2400.13370.0056WaianaeOahu0.5129750.0001260.7036480.00019418.1460.20615.4610.03737.8560.117NAKauaiKauai0.5129690.0000560.7036710.00022918.2280.16615.4510.01537.9390.0980.13680.0038Kea-trendKilaueaBigIsland0.5129580.0000270.7035840.00009918.4640.20515.4830.05538.1040.1890.13100.0017MaunaKeaBigIsland0.5129680.0000360.7035840.00009418.4970.18115.4830.02538.1040.1710.12970.0011KohalaBigIsland0.5130150.0000000.7037100.00008718.1700.27615.4600.04137.8450.1480.13650.0115HaleakalaMauiNui0.5129580.0000400.7036450.00019418.5410.22015.4800.01938.1540.1830.13040.0000WestMauiMauiNui0.5130250.0000480.7035500.00014018.4310.14215.4830.03137.9570.1280.13210.0011EastMolokaiMauiNui0.5129810.0000830.7035650.00020718.4370.41015.4800.03238.0600.255NAa Meansandthestandarddeviations(SD,2sigma)arefromDataSetS1.Ifthestandarddeviationisnotreported,itisbecauseonlyasinglemeasurementisavailable.Majorelementcompositionsarecorrectedforolivinefractionation/additiontoaconstantMgO(16wt.%)ortobeinequilibriumwithaforsterite90olivinecomposition(butthetwodifferentcorrectionschemesyieldsimilarmajorelementcompositions).Anolivine-meltKdof0.30isusedforcorrection.Dataforsamplesareexcludedifthewholerockisaltered,highlyevolved,orifthemajorelementdataareincompleteortheanalysesyieldshighorlowtotals(seetextforfiltersapplied).HeliumandOsisotopedataexistformanyofthevolcanoeslistedasNAinthetable,butinseveralcases,correspondingmajorelementdatadoesnotexist,orindicatesexcessivemagmaticevolutionorpost-eruptivealteration,andtheHeandOsdataarenotreported.Sr,Nd,PbandHfisotopesarenotfilteredbasedontraceelementconcentrations.Inonecolumn,heliumisotopicratiosforsampleswithlowheliumconcentrations(<2*10-8cc4He/gSTP)arenotreported(?HighHeconc?).However,heliumisotopicratioswithlowerconcentrationsarepreservedinthenextcolumn(?AllHeconc?)andinDataSetS1.OsisotopesareexcludediftheOsconcentrationis<40ppt.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042685 of 24Figure 2GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042686 of 24[12] The radiogenic isotopic compositions of Hawai-ian shield lavas have been discussed at great length inthe literature (for a recent review, see Weis et al.[2011]). We outline some of the most outstandingfeatures of the radiogenic isotopic geochemistry ofHawaiian lavas in Figure 2. In general, Loa-trendlavas have lower 206Pb/204Pb, 143Nd/144Nd and176Hf/177Hf and higher 187Os/188Os, 87Sr/86Sr and208Pb*/206Pb* (208Pb*/206Pb* = (208Pb/204Pb -29.475)/(206Pb/204Pb - 9.306) [Hofmann, 2003]) thanKea-trend lavas (Figure 2).[13] In isotope space, Hawaiian lavas define cleararrays that resolve the Loa- and Kea-trends. Forexample, in 208Pb/204Pb versus 206Pb/204Pb isotopespace (Figure 2), Kea-trend volcanoes tend to havemore radiogenic 206Pb/204Pb values than Loa-trendvolcanoes. Kea-trend volcanoes?including MaunaKea, Kilauea, Haleakala, E. Molokai and W. Maui?define the most radiogenic Pb-isotopic compositionsin Hawaii. By contrast, Loa-trend volcanoes tend tohave less radiogenic 206Pb/204Pb (and a higher208Pb/204Pb for a given 206Pb/204Pb) than Kea-trendvolcanoes. Koolau, Kahoolawe and Lanai, theHawaiian volcanoes with the most geochemicallyenriched 143Nd/144Nd and 87Sr/86Sr, also have theleast radiogenic 206Pb/204Pb. However, Loihi, theyoungest Loa-trend volcano, has depleted (high)143Nd/144Nd and (low) 87Sr/86Sr signatures andradiogenic Pb-isotopic compositions, similar to Kea-trend volcanoes. The Pb-isotopic compositions inLoihi lavas extend to values encountered only in theKea trend volcanoes, including Mauna Kea andKilauea (and the Hilina-stage of Kileaua in particular[Kimura et al., 2006]). However, Loihi generally hasa higher 208Pb/204Pb at a given 206Pb/204Pb, andtherefore higher 208Pb*/206Pb*, than Kea-trend vol-canoes. In general, all other Loa-trend volcanoes plotbetween Loihi and the geochemically extremeKoolau-component lavas from Koolau, Kahoolaweand Lanai.3.2. Major Element Variation Diagrams[14] Plots of whole rock MgO concentrations ver-sus the other major element oxides (Figure 3)?including SiO2, TiO2, CaO, Al2O3, FeOtotal andNa2O?are useful for showing enrichments ordepletions of these elements at various stages ofmagmatic evolution. The Loa- and Kea- trend vol-canoes, which exhibit different isotopic character-istics, also tend to follow different trends in severalof the major element variation diagrams.[15] At a given MgO content, Loa-trend volca-noes tend to have higher SiO2 and lower TiO2and CaO contents than Kea-trend volcanoes. How-ever, Loihi seamount, another Loa-trend volcano,has among the lowest SiO2 and the highest TiO2 andCaO concentrations in Hawaii. Loihi lavas overlapcompositionally with the major element composi-tions found in the extreme Kea-component volca-noes, Mauna Kea and Kilauea. Al2O3 exhibits littlevariability among volcanoes at a given MgO. It ispossible that the Loa-trend volcanoes with thelowest 143Nd/144Nd?Koolau, Lanai and Kahoo-lawe?have slightly higher Al2O3 and Na2O andlower FeOtotal contents than Loihi and the Kea-trendvolcanoes, but the differences, if real, are small (SeeSection 3.3).[16] In Figure 3, we show that 208Pb*/206Pb* exhibitsno relationship with MgO. This suggests that magmaevolution and crustal assimilation, which can modifyMgO abundances, are not responsible for generatingthe variability in 208Pb*/206Pb*, which is a sourcefeature [e.g., Hofmann, 2003]. This observation isimportant, as several major element oxides (SiO2,CaO, TiO2) exhibit clear relationships with208Pb*/206Pb* (See Section 3.3, Figure 4) after cor-rections for olivine fractionation/addition are made.3.3. Major Elements Versus Isotopes[17] The Loa- and Kea-trend volcanoes exhibitisotopic (Section 3.1) andmajor element (Section 3.2)differences. The isotopic variations in Hawaiianshield lavas also exhibit clear relationships witholivine fractionation-corrected major element oxideabundances.[18] Fractionation-corrected SiO2, CaO and TiO2concentrations and Nd and Pb isotopic ratios showFigure 2. Plots of radiogenic isotope ratios for data included in this study. Note that the radiogenic isotope data in thefigures includes only samples with the major element data indicating that the lavas are not highly evolved or altered.Koolau lavas are divided into three groups: Makapuu (MAK), Koolau scientific drilling project (KSDP), and theNuuanu landslide (NUU). The approximate isotopic composition of the 3 geochemical components in Hawaii (as iden-tified in lavas) are labeled in the figure: Koolau, Loihi and Kea. Many lavas have only one of the radiogenic isotopedata and do not appear in any of the panels (but lavas with a single radiogenic isotope ratio do appear in the other datafigures). Similarly, lavas that do not possess the full suite of radiogenic isotopic compositions appear in some, but notall, of the panels.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042687 of 24Figure 3. Major element variation diagrams plotting MgO against SiO2, Al2O3, FeOtotal, Na2O, CaO and TiO2.A plot of MgO versus 208Pb*/206Pb* is also shown. The major elements in the panels of this figure have not been cor-rected for olivine fractionation or addition. Lavas with MgO lower than 6.5 wt.% are not considered in this study, andare not shown in the diagrams. K2O, P2O5 andMnO are not shown, but data are available in Data Set S1. Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042688 of 24the clearest relationships, and define arrays in theHawaiian data set [Hauri, 1996] (Figure 4). Lavasfrom the Makapuu-stage of Koolau, Lanai andKahoolawe anchor one extreme of the arrays, andhave the lowest 143Nd/144Nd, 206Pb/204Pb, CaOand TiO2 and the highest SiO2 and208Pb*/206Pb*.The other end of the Hawaiian array is anchoredby Loihi and the extreme Kea-trend volcanoes,Mauna Kea and Kilauea, which define the highest143Nd/144Nd, 206Pb/204Pb, CaO and TiO2 and thelowest 208Pb*/206Pb* and SiO2 (Figure 4).[19] Contrary to the findings of Hauri [1996], theother fractionation-correctedmajor element oxides?FeOtotal, Al2O3 and Na2O?do not exhibit clearrelationships with Nd and Pb-isotopic compositions(Figure 5). When plotted against 206Pb/204Pb, theFigure 4. Olivine fractionation-corrected SiO2, TiO2, and CaO oxide abundances are plotted against143Nd/144Ndand 208Pb*/206Pb*. SiO2, TiO2, and CaO exhibit similar relationships with87Sr/86Sr and 176Hf/177Hf (not shown).An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to 16 wt.% MgO. See Table 1, Figure S1, andData Set S1 for alternative olivine fractionation/addition schemes. Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042689 of 24fractionation-corrected FeOtotal concentrations of theextreme low 143Nd/144Nd Loa-trend lavas?all fromKoolau, Kahoolawe and Lanai?appear to be shiftedto slightly lower values than Kea-trend volcanoesand Loihi. Fractionation-corrected Al2O3 and Na2Oconcentrations appear to be offset to somewhathigher values in most of Loa-trend lavas, whileHawaiian lavas with the highest 143Nd/144Nd,including Loihi and Kea-trend volcanoes, tend tohave slightly lower Al2O3 and Na2O abundances.However, care must be taken when generalizingabout relationships between radiogenic isotopes andFeOtotal, Al2O3 and Na2O, as there is significantscatter in the data and the trends (if any) are not asclear as with SiO2, CaO and TiO2.[20] Two major element ratios not affected byolivine fractionation, CaO/Al2O3 and Na2O/TiO2,exhibit striking relationships with Nd and Pb-isotopiccompositions (Figure 6), as noted previously[Hauri, 1996; Putirka, 1999]. CaO/Al2O3 ratios arelowest and Na2O/TiO2 ratios are highest in the mostextreme low 143Nd/144Nd Loa-trend lavas fromFigure 5. Olivine fractionation-corrected FeOtotal, Al2O3and Na2O abundances are plotted against206Pb/204Pb. Thecorrelations (if any) are poor. 143Nd/144Nd, 87Sr/86Sr and176Hf/177Hf also fail to exhibit clear relationships withFeOtotal, Al2O3, and Na2O (not shown). An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.Figure 6. CaO/Al2O3 and Na2O/TiO2 oxide ratios areplotted against 208Pb*/206Pb*. 143Nd/144Nd, 87Sr/86Srand 176Hf/177Hf exhibit similar relationships with CaO/Al2O3 and Na2O/TiO2 (not shown). Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426810 of 24Koolau, Kahoolawe and Lanai. Loihi lavas andextreme Kea-trend lavas from Mauna Kea andKilauea have the highest CaO/Al2O3 and the lowestNa2O/TiO2.[21] Helium and Os isotopic ratios show clear rela-tionships with fractionation-corrected major elementcompositions and major element ratios. 3He/4Heexhibits trends with SiO2, CaO, Al2O3, CaO/Al2O3and FeOtotal [Kurz et al., 2004; Herzberg, 2011;Hauri, 1996], but not with TiO2 and Na2O abun-dances or with Na2O/TiO2 ratios (Figure 8). High3He/4He lavas from Loihi anchor the low-SiO2 andAl2O3 and high-CaO, CaO/Al2O3 and FeOtotalportions of the arrays. When plotted against olivinefractionation corrected major element abundancesand major element ratios, extreme Loa-componentlavas with the highest 187Os/188Os (and high SiO2,Al2O3, Na2O and Na2O/TiO2, and low TiO2, FeOtotal,CaO, and CaO/Al2O3) anchor one portion of the arrayand Loihi and the extreme Kea-component lavas withlow 187Os/188Os (and low SiO2, Al2O3, Na2O andNa2O/TiO2 and high TiO2, FeOtotal, CaO and CaO/Al2O3) anchor the other extreme of the arrays.4. Origin of Major Element Variabilityin Hawaiian Lavas[22] While assimilation of oceanic crust has beensuggested to modify the isotopic compositions ofoxygen [Wang et al., 2003], heavy noble gases[e.g., Kent et al., 1999] and 187Os/188Os (in Os-poorlavas [e.g., Martin et al., 1994]) in some Hawaiianlavas, shallow processes operating in the oceaniccrust are not likely to be responsible for the observedrelationships between radiogenic isotopes andfractionation-corrected major element abundancesin the filtered data set. First, highly evolved lavas,which are most susceptible to being modified byassimilation, are not considered in this study.Second, radiogenic isotopes exhibit no relationshipwith MgO (Figure 3), a proxy for magmatic evolu-tion. This suggests that crustal assimilation is notresponsible for generating variability in radiogenicisotopes and major elements. Third, the Sr-Nd-Pb-Hfisotopic compositions of altered oceanic crust andoceanic sediment in the Hawaiian region are unlikeHawaiian lavas or geochemical end-member com-positions sampled by Hawaiian lavas [Hauri, 1996;Lassiter and Hauri, 1998; Blichert-Toft et al., 1999;Hanano et al., 2010]. Therefore, assimilation of localoceanic crust and sediments is not the mechanismresponsible for driving relationships between majorelements and radiogenic isotopes in Hawaiian lavas.Consequently, the observed major element-isotopeFigure 7. Olivine fractionation-corrected SiO2 andTiO2 oxide abundances and Na2O/TiO2 ratios are plottedagainst 187Os/188Os. Olivine fractionation correctedFeOtotal, Na2O, Al2O3 and CaO oxide abundances andCaO/Al2O3 ratios also exhibit relationships with187Os/188Os, but are not shown here. An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426811 of 24Figure 8. Olivine fractionation-corrected SiO2, CaO, Al2O3 and FeOtotal oxide abundances and CaO/Al2O3 ratios areplotted against 3He/4He. Olivine fractionation corrected Na2O and TiO2 oxide abundances and Na2O/TiO2 ratios exhibitno relationships with 3He/4He and are not shown here. An olivine-melt Kd of 0.30 is used for olivine fractionation/additionto 16 wt.%MgO. See Table 1, Figure S1, and Data Set S1 for alternative olivine fractionation/addition schemes. Colors anddata symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426812 of 24correlations in Hawaiian shield lavas (Figures 4and 6?8) reflect mantle source heterogeneity. Herewe examine each of the three Hawaiian componentsin turn?Koolau, Loihi and Kea?and evaluate theorigin of the major element variability and discusspossible mechanisms that drive the observed rela-tionships between radiogenic isotopes and olivine-fractionation corrected major element compositions.4.1. The Koolau Component:The Enigmatic Eclogite4.1.1. Bulk Lava Major Element CompositionsFrom Peridotite or Eclogite Melts?[23] Makapuu stage lavas from Koolau volcanoexhibit the most enriched 143Nd/144Nd in Hawaiiand sample the end-member Koolau-componentcompositions [Roden et al., 1994], and they anchorthe low CaO, high SiO2 portion of the arrays formedin major element versus isotope space in Figure 4.Makapuu-stage Koolau lavas play a central role inthe debate on the role of eclogite melting in theHawaiian plume [e.g., Hauri, 1996; Huang andFrey, 2005; Salters et al., 2006; Huang et al.,2007; Sobolev et al., 2005, 2007; Herzberg, 2011;Putirka et al., 2011], and we explore the argumentssurrounding eclogite versus peridotite melting.[24] One argument against the generation ofMakapuu-stage Koolau melts by peridotite melting hinges onhigh pressure and temperature experiments performedon a Kilauea high-MgO glass composition. Eggins[1992] and Wagner and Grove [1998] showedexperimentally that the major element compositionsof the high MgO Kilauea glasses cannot be in equi-librium with both garnet and olivine (i.e., garnetperidotite). This is important because Hawaiianshield lavas exhibit heavy rare earth element(HREE) depletions and, after correction for olivinefractionation, relatively constant concentrations ofHREE [Hofmann et al., 1984], which require resid-ual garnet in the mantle source of the lavas[Hofmann et al., 1984; Huang and Frey, 2005].Instead, Eggins [1992] and Wagner and Grove[1998] found that Kilauea glasses are in equilib-rium with a harzburgite (olivine + orthopyroxene)residue, but this phase assemblage will not generatethe residual garnet signature observed in Hawaiianlavas.[25] The SiO2 contents of Kilauea glasses are alsotoo high to be melts of garnet peridotite [Hauri,1996; Wagner and Grove, 1998], and KoolauMakapuu-stage lavas have even higher SiO2 thanthe Kilauea lavas, which excludes garnet peridotiteas a source for the Koolau component (Figure 4).Similarly, the FeOtotal versus SiO2 systematics ofMakapuu-stage Koolau lavas are inconsistent withexperimentally derived partial melts of peridotite atgarnet stability field pressures [Hauri, 1996]. Whilelow pressure (1?1.5 GPa) partial melts of perido-tites can yield the high SiO2 contents found in theselavas, the FeOtotal of low pressure partial melts istoo low. There are at least two reasons why suchlow pressures of melting are not feasible. First, lowpressures of melting (1?1.5 GPa) are below thoseof the field of garnet stability and will not generatethe residual garnet signature observed in Hawaiianlavas [Hofmann et al., 1984; Huang and Frey,2005]. Second, the lithosphere beneath Hawaii istoo thick to permit such shallow melting (<45 km)[Hauri, 1996].[26] Water addition to peridotite can increase theSiO2 content of melts at low pressures of melting[Parman and Grove, 2004]. However, wet meltingof garnet peridotite does not increase the melt SiO2concentration [Tenner et al., 2012], and existingwet melting experiments of garnet peridotite cannotexplain the high SiO2 in Koolau lavas.[27] Nonetheless, Putirka et al. [2011] suggest thateclogite/garnet pyroxenite are not required for thepetrogenesis of Hawaiian lavas, and that peridotitemelting can generate the entire observed composi-tional range. Using a compilation of experimentalmelt data generated from a range of peridotiticcompositions at different pressure and temperatureconditions, they argue that the major elementcompositions of parental magmas of Makapuu-stage Koolau lavas can be explained by mixing ofpartial melts from different peridotite meltingexperiments. However, there is no single experi-mental melt that matches the extreme compositionof Makapuu-stage Koolau lavas (i.e., high SiO2,low FeO and CaO). While Putirka et al. [2011]argued that the primary magma composition ofMakapuu-stage Koolau lavas can be reproduced bymixing three experimental melts [see Putirkaet al., 2011, equation 6], the three experimentalmelts (i.e., H154 from Kinzler and Grove [1992],T-762 from Falloon et al. [1988], and T-3572from Falloon and Danyushevsky [2000]) are all low-pressure melts (1?2 GPa) and have only olivine andorthopyroxene as residual phases. Consequently,these experiments are inconsistent with REE con-centrations and patterns in Hawaiian lavas, whichrequire garnet as a residual phase during melting.[28] In summary, existing experimental peridotitemelt data and melt-rock reaction models do notGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426813 of 24explain the composition of Makapuu-stage Koolaulavas. While we cannot exclude the possibility thatfuture peridotite melting experiments may match theunusual major element compositions of Makapuu-stage Koolau, we note that eclogite melting in theHawaiian mantle source may provide a mechanismfor generating the highest SiO2 Hawaiian lavas.Eclogite has been invoked to explain the combinedresidual garnet signature and high SiO2 content ofMakapuu-stage Koolau lavas [Hauri, 1996; Huangand Frey, 2005; Sobolev et al., 2005, 2007]. Thelow CaO contents of Makapuu-stage Koolau lavasare also consistent with partial melting of eclogite[Huang and Frey, 2005; Herzberg, 2006]. Herzberg[2006] parameterized the peridotite melting experi-ments of Walter [1998] and argued that mostHawaiian shield lavas have CaO contents that aretoo low to be partial melts of peridotite [Pertermannand Hirschmann, 2003]. Since Makapuu-stageKoolau lavas have the lowest CaO contents at agiven MgO content among Hawaiian lavas [Freyet al., 1994] (Figures 3 and 4), Huang and Frey[2005] and Sobolev et al. [2005] suggested thatthey contain the largest contribution from partialmelts of eclogite/garnet pyroxenite. Additionally,Makapuu-stage lavas and olivines have the lowestMnO contents among Hawaiian lavas [Huang et al.,2007; Sobolev et al., 2007], consistent with partialmelting of eclogite [Pertermann and Hirschmann,2003], as MnO is relatively compatible in garnet.Finally, Makapuu-stage lavas have the among low-est TiO2 contents in the Hawaiian tholeiitic suite[Frey et al., 1994] (Figures 3 and 4). Such lowmagmatic TiO2 is distinctive feature of dacitic meltsof eclogite with residual rutile [Pertermann andHirschmann, 2003, Figure 9].4.1.2. High SiO2 Lavas From Melt-RockReaction Between Peridotite Melts andPeridotite Mantle?[29] Melt-rock reaction between peridotite meltsand harzburgite/peridotite (i.e., assimilation oforthopyroxene+clinopyroxene and precipitation ofolivine [Kelemen et al., 1992]) has also beenproposed as a model to explain the high SiO2-content in Hawaiian lavas [Eggins, 1992; Wagnerand Grove, 1998; Stolper et al., 2004; Putirkaet al., 2011]. The peridotite reacting with the meltcould be a melt-residue of the rising mantle plume[Wagner and Grove, 1998, Figure 5a] or in situlithospheric mantle [Wagner and Grove, 1998,Figure 5b]. Hauri [1996] noted that, if the elevatedSiO2 in Koolau were a result of melt-rock reactionwith the mantle lithosphere, it would be reflectedby a lithospheric imprint on the Koolau lavas,including unradiogenic 187Os/188Os and high143Nd/144Nd ratios typical of the oceanic mantlelithosphere [e.g., Shirey and Walker, 1998;Warren et al., 2009]. This is not observed. KoolauMakapuu-state lavas have radiogenic 187Os/188Osand low 143Nd/144Nd (Figure 2), an observationthat is inconsistent with extensive melt-rock reactionin the oceanic mantle lithosphere. Further, a melt-mantle reaction predicts that CaO/Al2O3 willincrease with SiO2 as pyroxene is dissolved andolivine is precipitated: olivine precipitation from themelt will drive up melt SiO2, and clinopyroxene(and/or orthopyroxene) dissolution from the mantlewill increase melt SiO2 and CaO/Al2O3. However,this is inconsistent with the negative relationshipobserved between CaO/Al2O3 and high SiO2 inHawaiian lavas (Figure 9), indicating that a mecha-nism other than melt-rock reaction is responsible forthe increased SiO2 in Koolau lavas.Figure 9. CaO/Al2O3 versus SiO2 in the Hawaiianmagmatic suite considered in this study. Melt-rock reac-tion between the shallow mantle lithosphere and amantle melt tends to increase SiO2 in the melt as clino-pyroxene from the mantle lithosphere is dissolved intothe melt while olivine from the melt is precipitated.This melt-rock reaction would be manifested as a posi-tive trend in SiO2 versus CaO/Al2O3 space. However,Hawaiian lavas with the highest SiO2 have the lowestCaO/Al2O3, a signature that is inconsistent with meltrock reaction. The lavas in the figure have been correctedfor olivine fractionation to a constant MgO of 16 wt.%.An olivine-melt Kd of 0.30 is used for olivine fraction-ation/addition. Lavas with high 206Pb/204Pb have lowSiO2 and high CaO/Al2O3, and lavas with high low206Pb/204Pb have high SiO2 and low CaO/Al2O3. Colorsand data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426814 of 24[30] Melt-rock reaction with the mantle plume alsofails to explain the observed residual garnet signature,i.e., and relatively constant HREE contents (aftercorrection for olivine fractionation or accumulation)in Hawaiian tholeiites [e.g., Hofmann et al., 1984;Huang and Frey, 2005]. This is because melt-rockreaction is likely to generate variable HREE abun-dances. Previous studies invoking melt-rock reac-tion considered high LREE/HREE ratios alone toreflect a residual garnet signature [e.g., Eggins,1992; Wagner and Grove, 1998; Putirka et al.,2011], but the variable HREE abundances result-ing from melt-rock reaction do not match the rela-tively constant abundances in Hawaiian lavas.Therefore, a melt-mantle reaction occurring withinthe plume, proposed to explain the high SiO2 con-tent in Hawaiian lavas, cannot explain the observedresidual garnet signature.4.1.3. Peridotite Versus Eclogite Melting:Evidence From Ni in Olivine?[31] Ni concentrations in olivines play a key role inthe debate surrounding eclogite melting in theHawaiian plume, particularly beneath Koolau vol-cano. Olivines in Makapuu-stage Koolau lavas haveunusually high Ni abundances [e.g., Clague et al.,1991; Garcia, 2002]. Sobolev et al. [2005, 2007]and Herzberg [2011] argued that the high Ni con-tents in Hawaiian olivines and lavas imply an oliv-ine-free, secondary garnet pyroxenite source forHawaiian lavas. Wang and Gaetani [2008] suggestthat the high olivine Ni contents are caused by highDNiol/melt that results from a melt with a high SiO2content, which implies an important role of eclogitein the petrogenesis of Hawaiian lavas.[32] However, Putirka et al. [2011] and Rhodeset al. [2012] suggest that there are large uncertain-ties in the model predicted DNiol/melt values and Nivariations in peridotites. They argued that Ni con-centrations in olivines and lavas may not be used asdiscriminators between eclogite melting and peri-dotite melting. Putirka et al. [2011] argue that, athigh temperature, DNiol/melt is low, and hot peridotitemelting yields Ni-rich melts. Following transport toshallower depths, DNiol/melt is higher owing to lowerambient temperatures, and crystallizing olivines areNi-rich. Further experiments parameterizing theeffects of temperature, pressure and melt composi-tion on Ni partitioning between olivine and melt areneeded to evaluate these contrasting hypotheses.[33] In summary, there is active debate surroundingthe interpretation of the elevated Ni abundances inHawaiian magmatic olivines and whole rocks, andfurther experiments parameterizing the effects oftemperature, pressure and melt composition on Nipartitioning between olivine and melt are needed toevaluate the contrasting hypotheses. However, thedistinctive geochemical characteristics of Makapuu-stage Koolau lavas?high SiO2, low CaO, TiO2 andMnO, and REE patterns showing residual garnetsignature?are consistent with partial melting ofeclogite [Hauri, 1996; Pertermann and Hirschmann,2003; Herzberg, 2006; Dasgupta et al., 2010], butare not matched by melt compositions from existingexperimental peridotite melting studies.4.2. The Loihi Component: The ParadoxicalPyroxenite4.2.1. Lithology of the Loihi Mantle Source[34] Lavas from the Hawaiian Loa-trend describearrays that suggest binary mixing between twoextreme compositions (Figures 2 and 4?8): Makapuu-stage Koolau lavas anchor the low 143Nd/144Nd and206Pb/204Pb portion of the Loa array, and high3He/4He lavas from Loihi define the portion withdepleted 143Nd/144Nd and 87Sr/86Sr signatures andradiogenic 206Pb/204Pb. While Koolau lavas havehigh SiO2 and low TiO2, CaO and CaO/Al2O3,Loihi lavas exhibit the lowest SiO2 and highestTiO2, CaO and CaO/Al2O3 in the Loa-trend suite.Unlike the Koolau Makapuu source, which is likelyto contain an eclogite component, the Loihi mantlesource is generally agreed to be peridotitic [e.g.,Sobolev et al., 2005, 2007; Putirka et al., 2011;Herzberg, 2006, 2011]. Nonetheless, there are keygeochemical features of high 3He/4He Loihi lavassuggesting that the source peridotite is enriched as aresult of the addition a mafic component [e.g.,Sobolev et al., 2005; Putirka et al., 2011; Herzberg,2011]?likely a SiO2-poor pyroxenite?and thefinal, hybrid mixture is still a peridotite.[35] Evidence that a mafic component was added tothe Loihi peridotite source comes from elevatedTiO2 contents in fractionation-corrected Loihi lavas,which are too high to be generated by peridotitemelting at the degrees of melting inferred forHawaiian shield lavas. Prytulak and Elliot [2007]showed that, after correcting lavas to 16 wt.% MgO,the fractionation-corrected TiO2 abundances of lavasfrom many Hawaiian volcanoes (>1.8 wt%) can onlybe generated by low degrees (<3%) of partialmelting of a primitive peridotite (840?1200 ppm Ti)[McDonough and Sun, 1995; Carlson and Boyet,2008] or a depleted mantle source (657?798, ppmTi) [Workman and Hart, 2005; Salters and Stracke,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426815 of 242004]. Such low degrees of partial melting areinconsistent with their tholeiitic bulk compositions,and there is evidence that Hawaiian lavas are gen-erated at higher degrees of melting (?5%) [McKenzieand O?Nions, 1991; Watson and McKenzie, 1991;Garcia et al., 1995]. Therefore, Prytulak and Elliot[2007] concluded that the mantle sources beneaththese Hawaiian volcanoes have been enriched by theaddition of a Ti-rich component, and the most likelymaterial to host sufficient Ti is a recycled maficcomponent. Loihi tholeiites have among the highestTiO2 concentrations?2.1 wt. % TiO2 at 16 wt.%MgO?in the Hawaiian tholeiite suite (Figures 3and 4) [Garcia et al., 1995; Hauri, 1996] indicat-ing that the dominantly peridotitic Loihi source hasincorporated a mafic lithology during its history inthe mantle.[36] Pb isotopic compositions offer a second line ofevidence for the addition of a mafic component tothe peridotitic Loihi mantle source. Loihi lavas havethe highest 206Pb/204Pb and 208Pb/204Pb among Loatrend volcanoes, and only extreme Kea-trend lavashave more radiogenic Pb isotopic ratios. The Pb-isotopic compositions of Loihi lavas plot well to theright of the geochron, which has been attributed tothe presence of a mafic material [Lassiter andHauri, 1998; Jackson et al., 2010; Jackson andCarlson, 2011] with high U/Pb following seaflooralteration (U addition) and subduction zone pro-cessing (Pb loss) [Hofmann and White, 1982; Kelleyet al., 2005].[37] A third line of evidence supporting a maficcomponent in the Loihi mantle source comes fromelevated 187Os/188Os ratios (up to 0.138) in Loihilavas. Roy-Barman et al. [1998] identified a positivecorrelation between 3He/4He and 187Os/188Os inLoihi, which led the authors to suggest that themantle beneath Loihi hosts a component withradiogenic Os that is somehow related to the end-member component found in Makapuu-stageKoolau lavas. (A similar correlation between 3He/4Heand 187Os/188Os is Iceland led Brandon et al. [2007]to suggest the presence of a mafic componentadmixed with high 3He/4He peridotite in the source ofhigh 3He/4He Icelandic lavas.) However, owing to themuch higher 3He/4He and more depleted 87Sr/86Srand 143Nd/144Nd ratios in Loihi lavas compared toKoolau lavas, we consider it unlikely that the high187Os/188Os mafic components in Loihi and Koolaulavas are the same.[38] The radiogenic Os and Pb, and high Ti con-centration in Loihi lavas are consistent with thepresence of a mafic component added to theperidotitic mantle source of Loihi lavas, yet petro-logic models for the Loihi source indicate thatperidotite melting is occurring [e.g., Putirka et al.,2011; Herzberg, 2011]. This raises an importantquestion, which relates to the paradox of pyroxenitein the Loihi mantle source: How can the mixture ofthe peridotite and pyroxenite result in a mantlesource that generates melts that appear petrologi-cally to have been sourced by a peridotite? Owing tothe high TiO2 in Loihi lavas, Putirka et al. [2011]invoked the Prytulak and Elliot [2007] Ti model tosuggest the incorporation of a mafic component inthe Loihi source, but argued that it no longer existsas a distinct lithology. Putirka et al. [2011] sug-gested that the mafic source has been mixed com-pletely into the peridotite, so that the final lithologyis an enriched peridotite. If true, the final mixture, aperidotite, would inherit elevated TiO2 and radio-genic Os and Pb from the mafic lithology. However,mixing of the pyroxenite into the peridotite mightnot take place in the solid state.Gaffney et al. [2005]proposed a model for melting a mafic component inthe presence of peridotite, while keeping the petro-logic signature of the mafic component ?hidden.?They suggested that the eclogite melt would infil-trate and react with the peridotite and generate afertile peridotite, similar to that observed in eclogite-peridotite ?sandwich? experiments [Yaxley andGreen, 1998; Takahashi and Nakajima, 2002].The resulting fertile peridotite will be rich in ortho-pyroxene, as a result of eclogite melt reaction witholivine in the peridotite. Gaffney et al. [2005] sug-gested that melting of the fertilized peridotite willyield melts with a major element composition thatreflects peridotite melting [Hirschmann et al.,2003], even though they possess isotopic and traceelement geochemical signatures that reflect a con-tribution from a mafic component. The Putirka et al.[2011] and Gaffney et al. [2005] models may helpexplain the paradox of a mafic component in theLoihi mantle source that is essentially ?invisible? topetrologic models that suggest derivation of Loihilavas from a peridotitic source.4.2.2. Mantle Source Lithological DifferencesBetween the Loa-Trend Extremes: Comparingthe Loihi Mantle Source to the KoolauMakapuu Mantle[39] The association of high 3He/4He with a mantlesource that hosts a mafic component at Loihi isparadoxical. Owing to the highly incompatiblenature of U and Th during mantle melting, maficmaterials should in general have higher U and Ththan peridotitic materials. Therefore, over time,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426816 of 24mafic materials will generate more 4He than peri-dotites, resulting in lower 3He/4He in the formerrelative to the latter. As a result, a mafic componentadded to the peridotitic source should result in low3He/4He in Loihi lavas, not high 3He/4He. How-ever, if the SiO2-undersaturated pyroxenite inferredto have been added to the peridotitic Loihi sourcesuffered melt extraction in a paleo-subduction zone,then incompatible elements like U and Th will havebeen effectively removed from the pyroxenite, thusreducing its potential to generate 4He over time.Jackson et al. [2008] observed that 3He/4He ratioscorrelate with the magnitude of positive Ti, Ta andNb (TITAN) anomalies (where anomalies of theTITAN elements?calculated relative to elementsof similar compatibility in peridotite on a primitivemantle normalized spidergram?are not to be con-fused with the absolute concentrations of theseelements) in Hawaiian lavas, where Loihi exhibitsthe largest Ti anomalies and highest 3He/4He ratios.Owing to the ubiquitous presence of rutile in eclo-gite, trace elements compatible in rutile, includingthe TITAN elements, are residually enriched rela-tive to other trace elements during melt extractionfrom and dehydration of the downing-going slab;incompatible elements not sequestered into rutile?including the radiogenic helium-producing elements,U and Th?will be lost from the slab, togetherwith SiO2. For such a model to explain the radio-genic Pb isotopes in Loihi lavas, Pb would have to bepreferentially removed from the slab relative to U andTh, which is likely [Kelley et al., 2005]. The residualSiO2-poor mafic material?a pyroxenite?is TITAN-enriched and depleted in U and Th, and will contrib-ute little 4He to the peridotite with which it mixes,including high 3He/4He peridotites. Such a modelmight explain the association of TITAN enrichmentand high 3He/4He in SiO2-poor Loihi lavas.[40] By contrast, Makapuu-stage Koolau lavas havehigher SiO2, lower3He/4He and less radiogenic Pb.These lavas sample a SiO2-rich eclogite (Section 4.1)that has not suffered severe SiO2 and incompatibleelement depletion in a subduction zone, as evidencedby the silica-rich character of Koolau lavas. Such aneclogite will have retained its complement of U andTh (and Pb, thereby preserving a low U/Pb ratio) andwill producemore 4He over time that will ?infect? thesurrounding peridotite mantle?including the litho-logic reservoir hosting high 3He/4He peridotite[e.g., Parman et al., 2005; Albar?de, 2008; Hartet al., 2008; Jackson et al., 2008]?with low3He/4He. A host of possible mafic lithologies existin nature, and the presence of two distinct maficcomponents?a SiO2-poor pyroxenite and a SiO2-rich eclogite?in the Hawaiian plume might recon-cile the geochemical differences between the twoLoa-trend mantle components, Loihi and Koolau-Makapuu.4.3. The Kea Component[41] A third major isotopic end-member observed inHawaiian shield lavas?the Kea component?issampled by volcanoes that define the Kea en eche-lon volcanic trend. The Kea-trend volcanoes havemore homogeneous Sr, Nd and Hf isotopes that arealso generally more depleted [e.g., Stille et al.,1986] than their Loa-trend equivalents [DePaoloet al., 2001; Weis et al., 2011]. This has led tomodels suggesting a depleted peridotite source?MORB-source, Pacific oceanic lithosphere, entrainedasthenosphere, or recycled mantle lithosphere?forKea-component lavas [West et al., 1987; Chen andFrey, 1985; Hauri, 1996; Eiler et al., 1996a, 1996b;Lassiter et al., 1996]. However, the low 176Hf/177Hfof the Kea end-member suggests that asthenosphericor lithospheric materials are not present in the sourceof Kea-type lavas [Blichert-Toft et al., 1999].Recycled lower oceanic crust has also been sug-gested to source Kea-component lavas, but only incombination with recycled lithospheric peridotite[Lassiter and Hauri, 1998].[42] With the exception of 3He/4He and 208Pb*/206Pb*,Kea- and Loihi-component lavas are more similar toeach other than to Koolau-component lavas, and thefractionation-corrected major element compositions ofKea lavas are remarkably similar to Loihi-componentlavas, as observed previously [Hauri, 1996]. In fact, theKea-component exhibits several geochemical similari-ties with the Loihi-component that suggest that theformer also hosts a mafic component in its mantlesource. For example, Kea-component lavas hosthigh TiO2 contents, consistent with the addition of apyroxenite component in the source of Kea-component lavas (Mauna Kea and Kilauea have>2 wt.% TiO2 at 16 wt.% MgO (Table 1) [Prytulakand Elliot, 2007]). However, information fromradiogenic isotopes does not permit a clear resolu-tion of the debate over source lithologies contribut-ing to the Kea mantle source. On the one hand, Pbisotopic compositions in Kea-component lavas areamong the most radiogenic in Hawaii. If radiogenicPb is associated with a recycled mafic component,then Kilauea lavas should host a significant maficcomponent. This is contradicted by the generallyunradiogenic 187Os/188Os in Kea-trend lavas(<0.133, with the exception of a single Kohala lava;Figure 7). One possible explanation for this apparentGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426817 of 24disagreement is that there is a greater contribution ofrecycled sediment to the Loa-trend mantle than tothe Kea-trend source: Sediment generally has higher187Os/188Os than mafic lithologies, so it is possiblefor a mantle source with a sediment and a maficcomponent (like the Loa-trend mantle) to have ahigher 187Os/188Os than the a mantle source withjust a mafic component (like the Kea-trend mantle)[Lassiter and Hauri, 1998; Huang et al., 2005].5. Major Element Versus IsotopeCorrelations in Hawaii in the Contextof Global OIBs[43] The broad correlations between major elementsand isotopes in Hawaiian lavas form arrays anchoredby Loihi and Kea-component lavas (with high143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and low87Sr/86Sr) at one end and by Koolau lavas (with low143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and high87Sr/86Sr) at the other. Information from olivine-fractionation corrected major element data suggeststhat the correlations in the Hawaiian data set areanchored on both ends by different types of maficcomponent that coexist (and interact) with peridotitein the Hawaiian plume: a silica-poor pyroxeniteanchors the Loihi and Kea-component portion of theHawaiian array (Section 4.2 and 4.3), and a silica-rich eclogite anchors the enriched portion (Koolau)of the Hawaiian array (Section 4.1). A host of pos-sible mafic lithologies exist in nature, and the SiO2content of the mafic materials in the source ofthe Loihi, Kea and Koolau components may bethe defining difference among these components.However, in order to understand the origin of thesecontrasting mafic sources, they must first be placedin the context of global OIB geochemical variability.[44] Broad relationships between major elementsand radiogenic isotopes in the global OIB data setmay help constrain the mantle source compositionsof the Loihi, Kea and Koolau components. Jacksonand Dasgupta [2008] show that global OIB lavaswith the most radiogenic Pb have the lowest SiO2and the highest CaO/Al2O3 (Figure 10). SiO2 andCaO/Al2O3 also exhibit some of the clearest cor-relations with 206Pb/204Pb in Hawaiian lavas, andthese correlations mimic the global trend (Figure 10).Like the global OIB data set, FeOtotal, Al2O3 andNa2O abundances in Hawaii exhibit little or nocorrelation with radiogenic isotopes. In summary,the correlations between Pb isotopes and majorelements in Hawaii appear to broadly reflect theglobal trends, and we suggest that the mechanismthat drives the correlations between major elementsand isotopes in Hawaii illustrates, in microcosm, alarger global process.[45] Hauri [1996] suggested that SiO2-rich(50 wt.%) Koolau lavas resulted from melting ofSiO2-saturated mafic material (which we refer toabove as eclogite), while the mantle sources of thelow SiO2 lavas (40 wt.%) in the Pacific Islandswith the most radiogenic Pb are thought to hostSiO2-poor mafic material (which we refer to aspyroxenite) [Hirschmann et al., 2003; Kogiso et al.,2003; Kogiso and Hirschmann, 2006; Dasguptaet al., 2006; Jackson and Dasgupta, 2008]. Apply-ing this model to the Hawaiian magmatic suite, weinfer that Loihi and Kea-component lavas, whichexhibit the most radiogenic Pb compositions and thelowest SiO2 concentrations in Hawaiian shieldlavas, are derived from a peridotitic mantle sourcethat incorporated a small portion of a SiO2-poormafic component with radiogenic Pb.[46] Subduction zone processes can modify thecomposition of the downgoing oceanic crust byvariably removing SiO2 (and fractionating traceelement ratios, such as U, Th and Pb) [Hauri, 1996;Jackson and Dasgupta, 2008]. As a result, SiO2-richand SiO2-poor mafic lithologies exist in the mantlethat are likely to host distinct time-integrated isoto-pic ratios. Low SiO2 lavas from Mangaia andTubuaii and the high SiO2 lavas from Hawaii?sKoolau Makapuu-stage anchor the high 206Pb/204Pband low 206Pb/204Pb portions of the global array,respectively (Figure 10) [Jackson and Dasgupta,2008]. SiO2-deficient eclogites suggested for thesource of SiO2-poor OIB lavas with radiogenic Pbmust have somehow attained higher U/Pb ratios,likely via Pb-loss from the slab [Kelley et al., 2005](i.e., the same subduction zone processes reduced theSiO2 of the downgoing crust and increased U/Pb).The variability within the Hawaiian array may begenerated in a similar manner, where the Hawaiianplume hosts both SiO2-rich eclogites (with low206Pb/204Pb) and SiO2-poor pyroxenites (with high206Pb/204Pb) that mix in the peridotite matrix of theplume to generate the correlations between majorelements and radiogenic isotopes in Hawaii. Thus,processes operating in subduction zones that modifythe downgoing oceanic crust may be responsible forgenerating much of the major element variabilityobserved in Hawaii and in OIBs in general [Hauri,1996].6. Conclusions[47] From this review study, we draw the followingconclusions:GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426818 of 24[48] 1. Data for tholeiitic Hawaiian shield lavasform arrays in plots of radiogenic isotopes versusolivine-corrected major element oxides. Individualdata points exhibit remarkable trends and there isno need to average the data by volcano.[49] 2. The trends are anchored by Koolau lavas atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2,Figure 10. Olivine fractionation-corrected SiO2 concentrations and CaO/Al2O3 ratios are plotted against206Pb/204Pbfor Hawaiian lavas and the global OIB data set. The correlations in the Hawaiian data set mimics, in microcosm, thelarger global correlation. The global OIB data set is from Jackson and Dasgupta [2008] and includes only lavas withMgO > 8 wt.% MgO, as many non-Hawaiian OIB lavas experience clinopyroxene fractionation at lower MgO abun-dances (see Data Set S1 for compositions). An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. HIMU (or high-m, or 238U/204Pb) represents the mantle reservoir with radiogenic Pb-isotopes [e.g.,Hauri and Hart, 1993; Woodhead, 1996; Hanyu et al., 2011].GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426819 of 24and Na2O/TiO2, and low143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaO and CaO/Al2O3) and byKea and Loihi lavas at the other (low 87Sr/86Sr,187Os/188Os, SiO2, and Na2O/TiO2, and high143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaOand CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with Sr, Nd, Pb or Hfisotope compositions.[50] 3. In Hawaiian tholeiitic lavas, 3He/4He showsa remarkably good relationship with SiO2, CaO,Al2O3, CaO/Al2O3 and FeOtotal. High3He/4He lavasfrom Loihi anchor the low SiO2 and Al2O3 and highCaO, CaO/Al2O3 and FeOtotal portions of the arrays.3He/4He exhibits no clear relationships with TiO2and Na2O abundances or with Na2O/TiO2 ratios.[51] 4. The Loihi source is likely peridotitic, but hasbeen infused with a SiO2-poor mafic componentsuch that the final mixture is an enriched peridotite.Loihi and Kea-component lavas exhibit similarmajor element characteristics (low SiO2 and Na2O/TiO2 and high TiO2, CaO and CaO/Al2O3), whichmay suggest lithologically similar mantle sources.The composition of SiO2-rich Koolau-componentlavas is not easily explained by available data forperidotite melting experiments (wet or dry) or bymelt-rock reaction of peridotite melts with the oce-anic mantle lithosphere. Instead, Koolau-componentlavas are likely derived from melts of a SiO2-richeclogite that has variably interacted with peridotite.[52] 5. Correlations between major elements andradiogenic isotopes in Hawaiian lavas mimic thebest correlations observed in the global OIB data setbetween Pb isotopic ratios and SiO2 and CaO/Al2O3. We suggest that the mechanism that drivesthe correlations between major elements and iso-topes in Hawaii illustrates, in microcosm, a largerglobal process. Variable processing of slabs insubduction zones yields SiO2-poor pyroxenites(with high U/Pb) and SiO2-rich eclogites (with lowU/Pb) that evolve radiogenic and unradiogenic Pbisotopic compositions, respectively. 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Hart (2005), Major and trace ele-ment composition of the depleted MORB mantle (DMM),Earth Planet. Sci. Lett., 231, 53?72, doi:10.1016/j.epsl.2004.12.005.Yaxley, G. M., and D. H. Green (1998), Reactions betweeneclogite and peridotite: Mantle refertilisation by subductionof oceanic crust, Schweiz. Mineral. Petrogr. Mitt., 78,243?255.Zindler, A., and S. R. Hart (1986), Chemical geodynamics,Annu. Rev. Earth Planet. Sci., 14, 493?571, doi:10.1146/annurev.ea.14.050186.002425.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426824 of 24 file:///C|/Documents%20and%20Settings/bugeaud/Desktop/ggge2264-sup-0001-readme.txt[5/14/2014 11:10:22 AM]Auxiliary Material for Paper 2012GC004268Major element variations in Hawaiian shield lavas: Source features and perspectives from global ocean island basalt (OIB) systematicsMatthew G. JacksonDepartment of Earth Sciences, Boston University, Boston, Massachusetts, USADominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, British Columbia, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts, USAJackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features and perspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.Introduction:The supplement referred to in the text includes a worksheet in a single Excel 2004 (.xls) file, and a PDF (.pdf) file with figures illustrating the effects of different olivine fractionation correction schemes modify the composition of a melt.  The worksheet contains all geochemical data from Hawaiian lavas from Georoc--including major element abundances (both raw abundances and abundances following olivine fractionation correction) and isotopic ratios--remaining after applying the filters described in the text. The global OIB dataset used in Jackson and Dasgupta (2008) are also included for comparison.  Major element abundances for different olivine fractionation correction schemes are also included in the spreadsheet.  1. 2012gc004268-ds01.xlsData Set S1. All geochemical data and for Hawaiian lavas presented in the manuscript.2. 2012gc004268-fs01.pdfFigure S1. Hawaiian shield lavas are corrected for olivine fractionation/addition using three different methods. In the first column, lavas are corrected to a constant MgO (16 wt.%) using an olivine-melt Kd of 0.30. In the second column, lavas are corrected to a constant MgO (16 wt.%) using an olivine-melt Kd of 0.34.  In the third column, lavas are corrected to be in equilibrium with forsterite 90 olivine using an olivine-melt Kd of 0.30. Cumulates (Mg>20 wt.%) are corrected in the same manner in all plots by subtracting olivine of forsterite 87 composition. As shown in the figure, the correction scheme used does not greatly change the major element concentrations and the sense of the correlations is preserved. Symbols are the same as the manuscript.ReferencesJackson, M.G., and R. Dasgupta (2008), Compositions of HIMU, EM1, and EM2 from global trends between radiogenic isotopes and major elements in ocean island basalts, Earth Planet. Sci. Lett., 276, 175-186. 0.92 0.93 0.94 0.95 0.96 0.97 0.98 44 45 46 47 48 49 50 51 52 53 SiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5 2.7 208  Pb*/  206Pb*TiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 5 6 7 8 9 10 11 12 208  Pb*/  206 Pb*        CaO (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 8 9 10 11 12 13 14 15 208  Pb*/  206 Pb*        FeO (wt.%, at 16% MgO) Corrected to MgO=16 wt %using an olivine-melt Kd = 0.300.92 0.93 0.94 0.95 0.96 0.97 0.98 44 45 46 47 48 49 50 51 52 53 SiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5 2.7 TiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 5 6 7 8 9 10 11 12 CaO (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 8 9 10 11 12 13 14 15 FeO (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 44 45 46 47 48 49 50 51 52 53 SiO2 (wt.%, at forsterite 90) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5 2.7 TiO2 (wt.%, at forsterite 90) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 5 6 7 8 9 10 11 12 CaO (wt.%, at forsterite 90) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 8 9 10 11 12 13 14 15 FeO (wt.%, at forsterite 90)Corrected to MgO=16 wt %using an olivine-melt Kd = 0.34Corrected to be in equilibrium with forsterite 90 olivineusing an olivine-melt Kd = 0.30 208  Pb*/  206 Pb*          Jackson et al (2012), Fig. S1 ArticleVolume 13, Number 919 September 2012Q09009, doi:10.1029/2012GC004268ISSN: 1525-2027Major element variations in Hawaiian shield lavas: Sourcefeatures and perspectives from global ocean island basalt(OIB) systematicsMatthew G. JacksonDepartment of Earth Sciences, Boston University, 675 Commonwealth Avenue, Boston, Massachusetts02215, USA (jacksonm@bu.edu)Dominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences,University of British Columbia, 6339 Stores Road, Vancouver, British Columbia V6T1Z4, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, 20 Oxford Street, Cambridge,Massachusetts 02138, USA[1] Among volcanic hot spots globally, Hawaii has the highest magma flux, yet there is significant contro-versy surrounding the composition of the mantle sourcing Hawaiian lavas. In order to place constraints onthe source lithologies of Hawaiian lavas, we explore relationships between major elements and radiogenicisotopes in tholeiitic, shield-building lavas. Olivine-fractionation corrected lava compositions reveal cleartrends between radiogenic isotopes and major elements. Individual data points exhibit remarkable trendsand there is no need to average the data by volcano. Data form arrays that are anchored by Koolau lava atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2, and Na2O/TiO2, and low143Nd/144Nd, 206Pb/204Pb, TiO2,CaO and CaO/Al2O3) and by Kea and Loihi lavas at the other (with low87Sr/86Sr, 187Os/188Os, SiO2, andNa2O/TiO2, and high143Nd/144Nd, 206Pb/204Pb, TiO2, CaO and CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with radiogenic isotopes. The Hawaiian data set exhibits correlations that mirrorthe best correlations between major elements and radiogenic isotope in the global ocean island basalt (OIB)database. We suggest that the mechanism driving the correlations in Hawaii illustrates, in microcosm, alarger global process that generates major element variability in mantle plumes. Like the global arrays, theHawaiian lavas with radiogenic Pb and SiO2-poor lavas are sourced by a SiO2-poor mafic component (pyrox-enite) admixed with peridotite, while Hawaiian lavas with unradiogenic Pb and high SiO2 are sourced by aSiO2-rich mafic component (eclogite). The variable SiO2 in the mafic component may result from differentdegrees of SiO2-extraction from the slab during subduction.Components: 14,700 words, 10 figures, 1 table.Keywords: Hawaii; eclogite; hotspot; isotopes; mantle plume; pyroxenite.Index Terms: 1025 Geochemistry: Composition of the mantle; 1033 Geochemistry: Intra-plate processes (3615, 8415); 1038Geochemistry: Mantle processes (3621).Received 4 June 2012; Revised 25 July 2012; Accepted 10 August 2012; Published 19 September 2012.?2012. American Geophysical Union. All Rights Reserved. 1 of 24Jackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features andperspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.1. Introduction[2] Oceanic plates?including mafic crust, depletedlithospheric peridotite, and a thin veneer of marinesediments?are sent into the mantle at subductionzones, thereby contributing to the compositionalheterogeneity of Earth?s mantle [Hofmann andWhite, 1982; White and Hofmann, 1982; Iwamoriet al., 2010]. Buoyantly upwelling regions of themantle are thought to return parts of these subductedoceanic plates to the shallow mantle, where theypartially melt beneath hot spots like Hawaii. Lavaserupted at hot spots therefore reveal clues about thedynamic history and composition of the mantle[Zindler and Hart, 1986; Hofmann, 1997]. Thecompositions of hot spot lavas suggest that recyclingof ancient subducted oceanic plates is a commonprocess that has affected the geochemistry of themantle over geologic time [e.g., Hofmann andWhite, 1982; Sobolev et al., 2005].[3] However, significant controversy surrounds thefinal fate of recycled oceanic crust in the mantle[Eggins, 1992; Hauri, 1996; Wagner and Grove,1998; Putirka, 1999; Sobolev et al., 2005, 2007;Gaffney et al., 2005; Huang and Frey, 2005; Huanget al., 2007; Herzberg, 2006, 2011; Putirka et al.,2011; Niu et al., 2012]. Following billion-yeartimescales of residence in the mantle, oceanic crustis likely stretched, thinned, and its geochemicalsignal is greatly attenuated [e.g., Ottino, 1989; VanKeken et al., 2004]. While distinct mafic litholo-gies may survive mantle convection to be meltedbeneath hot spots like Hawaii [Hauri, 1996; Sobolevet al., 2005, 2007, 2008; Huang and Frey, 2005;Huang et al., 2007; Herzberg, 2006, 2011], thesurvival of distinct mafic lithologies into the man-tle beneath Hawaii has been questioned [Putirka,1999; Salters et al., 2006; Putirka et al., 2011].Putirka [1999] and Putirka et al. [2011] argue thatperidotite melting can explain the geochemistry ofHawaiian lavas, and a distinct mafic lithology in themantle source of Hawaiian lavas is not required.[4] Hawaii is arguably the most-studied oceanic hotspot, and the abundance of geochemical data obtainedfrom Hawaiian lavas makes it an ideal location forevaluating the presence of recycled oceanic crust inthe mantle source. While a multitude of componentshave been identified in the Hawaiian mantle, mostof the isotopic variability in Hawaiian shield-buildinglavas can be described with just three components,as shown by principal component analysis [Hauri,1996; Eiler et al., 1996a]. These componentsinclude the Koolau, Loihi and Kea components(Figure 2) [Stille et al., 1986; West and Leeman,1987; Eiler et al., 1996b; Hauri, 1997; Gaffneyet al., 2005; Huang et al., 2005; Weis et al., 2011].The small volumes of low-degree melts sampled bypost-shield and rejuvenated lavas require the pres-ence of a fourth, depleted component, distinct fromPacific MORB [Mukhopadhyay et al., 2003; Freyet al., 2005; Fekiacova et al., 2007; Garcia et al.,2010; Hanano et al., 2010], but post-shield andrejuvenated-stage lavas are volumetrically insignif-icant compared to the shield-building lavas andthese lavas are not considered here. Hawaii is thearchetypal high 3He/4He hot spot, and lavas fromLoihi seamount define the Loihi component andhost 3He/4He ratios in excess of 30 Ra (ratio toatmosphere) [Kurz et al., 1982; Rison and Craig,1983; Kurz et al., 1983; Staudigel et al., 1984;Sarda et al., 1988; Honda et al., 1993; Valbrachtet al., 1997; Eiler et al., 1998; Jackson et al., 2008].TheKoolau component, defined byKoolauMakapuu-stage lavas, is a lower 3He/4He end-member charac-terized by the lowest 143Nd/144Nd and 206Pb/204Pband highest 87Sr/86Sr in Hawaii and constitutes theenriched Loa trend volcanic end-member (see below)[Tanaka et al., 2008]. This end-member is sampledin diluted form at several Hawaiian volcanoes andlikely hosts a component of recycled oceanic crustand sediment [e.g., Hauri, 1996; Lassiter andHauri, 1998; Blichert-Toft et al., 1999; Normanet al., 2002; Sobolev et al., 2005; Huang et al.,2005, 2011a; Herzberg, 2011; Putirka et al., 2011].The origin of the Kea component, best exemplifiedby lavas from Mauna Kea, W. Maui and Kilauea, isless clear. The Kea component, which hosts thehighest 143Nd/144Nd and 206Pb/204Pb and the lowest87Sr/86Sr in Hawaii, is relatively homogeneous rel-ative to the Koolau component, leading to modelssuggesting a MORB-source, Pacific oceanic litho-sphere source or entrained asthenospheric source inKea lavas, but recycled lower oceanic crust andmantle lithosphere also have been suggested [Chenand Frey, 1985; Frey and Rhodes, 1993; Hauri,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042682 of 241996; Eiler et al., 1996a, 1996b; Lassiter and Hauri,1998; Blichert-Toft et al., 2003; Gaffney et al., 2005].The Kea component dominates the Kea volcanictrend (see below).[5] The distribution of the Loa and Kea componentsis organized geographically along the hot spot(Figure 1). Hawaiian shield volcanoes erupted duringthe past 5 Ma tend to be oriented along two en ech-elon volcanic trends that exhibit distinct isotopic [e.g.,Jackson et al., 1972; Tatsumoto, 1978; Abouchamiet al., 2005; Tanaka et al., 2008; Farnetani andHofmann, 2010; Weis et al., 2011; Huang et al.,2011b] and major element [Hauri, 1996; Greeneet al., 2010] compositions. Volcanoes along thenorthern geographic trend erupt Kea-type lavas andsouthern-trend volcanoes tend to erupt Loa-typelavas. The origin of this geographic and geochemi-cal separation is the source of significant discussion[e.g., Hieronymus and Bercovici, 1999; Abouchamiet al., 2005; Ren et al., 2005; Marske et al., 2007;Weis et al., 2011; Huang et al., 2011b]. Under-standing the origin of the different major elementcompositions of shield-stage lavas between the Loaand Kea trends [Hauri, 1996] may provide impor-tant clues about the structure of the Hawaiian plume,including the possible organization of lithologicheterogeneities within the plume conduit [Blichert-Toft et al., 2003; Abouchami et al., 2005] and inthe deep mantle [Weis et al., 2011; Huang et al.,2011b].[6] Frey and Rhodes [1993] systematically docu-mented major element variations among differentHawaiian shields and attributed them to mantlesource variability. However, correlations betweenmajor elements and isotopes can strengthen con-clusions that major element variations in hot spotlavas reflect mantle source lithological heterogene-ity [Hauri, 1996; Sobolev et al., 2008; Jackson andDasgupta, 2008]. Hauri [1996] showed correlatedmajor element and isotopic variations in composi-tional and isotopic averages of Hawaiian volcanoes,and on this basis, argued for major element vari-ability in the Hawaiian mantle and for the impor-tance of eclogite in the petrogenesis of Hawaiianshield lavas. Jackson and Dasgupta [2008] extentsuch major element-isotope correlation to the globalOIB data set. Here we show that the original ele-ment-isotope correlations observed by Hauri [1996]are ?mirrored? by the global OIB data set [Jacksonand Dasgupta, 2008]. These data document themajor element variability in the Hawaiian plume,constrain source lithologies, and place the majorelement variability in the Hawaiian plume in thecontext of global OIB variability.2. Treatment of Geochemical Data[7] The geochemical data used in this study wereobtained from the Georoc database (georoc.mpch-mainz.gwdg.de/georoc) on December 26, 2011.Only tholeiitic lavas are considered. All non-tholeiitic lavas [Macdonald and Katsura, 1964] areexcluded, as are lavas that are explicitly described aspost-shield or rejuvenated. Only lavas with a com-plete set of major elements (SiO2, TiO2, Al2O3,FeOtotal, MnO, MgO, CaO, Na2O, K2O, P2O5) areconsidered. A sample is excluded if it does not haveat least one of the following isotopic measurements:87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb), 187Os/188Os, 176Hf/177Hf, or3He/4He. Compared to Sr, Nd and Pb isotopes, andHf isotopes to a lesser extent, measurements ofHe and Os isotopes are still relatively rare. Lavaswith low Os concentrations are susceptible to con-tamination by assimilation of materials with radio-genic Os. Therefore, Os-poor (Os < 40 ppt) lavas areexcluded [Class et al., 2009]. Similarly, lavas withlow helium concentrations are susceptible to reduc-tion of 3He/4He by post-eruptive radiogenic ingrowthof 4He or crustal assimilation, and analyses of He-poor olivines and glasses (less than 2*108 cc/g STP4He) are excluded [Garcia et al., 1990; Hilton et al.,1995; Kurz et al., 2004; Class and Goldstein, 2005].Only 3He/4He measurements obtained by crushingolivines and glasses are used. Much of the heliumisotopic data available for Hawaiian lavas are elimi-nated using the concentration filter, but we feel thatthe filter yields a data set that better reflects mantle3He/4He compositions. However, all 3He/4He mea-surements are preserved in Data Set S1 in theauxiliary material, regardless of 4He concentration, aslong as the associated whole rock major elementanalyses do not indicate excessive alteration ormagmatic evolution.1[8] As a filter for alteration, samples with K2O/P2O5< 1, low dry totals (<97 wt.%) or high dry totals(>101 wt.%) were excluded [e.g., Frey et al., 1994].Leaching is necessary to reduce alteration compo-nents in lavas that most strongly influence Sr and Pbisotopic ratios but not Nd and Hf isotopic ratios[Nobre Silva et al., 2009, 2010]. However, it is notalways known which samples were leached in acid1Auxiliary material data sets are available at ftp://ftp.agu.org/apend/gc/2012gc004268. Other auxiliary materials are available inthe HTML. doi:10.1029/2012GC004268.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042683 of 24prior to isotopic analyses, as this is not consistentlyreported in the literature. Fortunately, Sr and Pbisotopic ratios show excellent correlations with Ndand Hf isotopic ratios in Hawaiian volcanoes(Figure 2). Owing to these correlations, we show Ndand Pb isotopic data, but not Sr and Hf isotopic data,in subsequent figures. Sr and Hf isotopic data,where available, are preserved in Data Set S1.[9] Low MgO lavas (<6.5 wt.%) were not includedin the filtered data set. Such lavas can suffer fromclinopyroxene and plagioclase fractionation [e.g.,Rhodes and Vollinger, 2004; Rhodes et al., 2012].Lavas with MgO > 6.5 wt.% are affected primar-ily by fractionation or accumulation of olivine Cr-spinel [Hauri, 1996].[10] The lavas remaining (n = 551) after thesefiltering steps were renormalized to 100 wt.% totals(on a dry basis) with all Fe reported as FeOtotal(see Data Set S1). The lavas were then corrected forolivine fractionation to a constant MgO of 16 wt.%by adding or subtracting equilibrium olivine in 0.01wt.% increments, similar to Langmuir et al. [1992].Equilibrium olivines were generated using theolivine-melt Kd of 0.3 [Roeder and Emslie, 1970;Ford et al., 1983] assuming 10% of the total iron isFe3+. Correcting the lavas for olivine fractionation/addition until they are in equilibrium with a mantleolivine (forsterite 90) does not change our conclu-sions (see Table 1, Figure S1, and Data Set S1). Anolivine-melt Kd of 0.34 has been suggested forMauna Kea lavas [e.g., Matzen et al., 2011], whichdoes not change our conclusions (see Figure S1 andData Set S1). For cumulates (MgO > 20 wt.%), wefollow the procedure of Hauri [1996] and subtractan olivine composition of forsterite 87 until the bulklava has 16 wt.%MgO. All of the major element andisotopic data, and major element data corrected forolivine fractionation, are reported in Data Set S1for individual samples and in Table 1 as volcanoaverages.3. Observations3.1. Radiogenic Isotopes[11] The panels of Figure 2 show the variability inradiogenic isotopes in the lavas considered in thisstudy. Every lava considered in this study has bothmajor element data (n = 551) and at least one radio-genic isotope system measured (87Sr/86Sr [n = 444],143Nd/144Nd [n = 417], 206Pb/204Pb (and 207Pb/204Pband 208Pb/204Pb) [n = 452], 176Hf/177Hf [n = 229],187Os/188Os [n = 86], 3He/4He [n = 152 for all 4Heconcentrations, or 48 for samples with 4He > 2*108cc STP/g]). The radiogenic isotopic data shown inFigure 2 are intended to show the isotopic variabilityin the freshest, least evolved Hawaiian shield lavasthat we examined in this study, and therefore the datain the figures do not encompass the complete radio-genic isotopic variability in Hawaiian lavas.Figure 1. Map of Hawaiian hot spot from Loihi to Kauai showing individual volcanoes (map made usingGeoMapApp, http://www.geomapapp.org).GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042684 of 24Table1(Sample).MeanIsotopicandMajorElementCompositionsforHawaiianVolcanoesExaminedinThisStudya[ThefullTable1isavailableintheHTMLversionofthisarticle]VolcanoIsland143Nd/144NdAverage2SD87Sr/86SrAverage2SD206Pb/204 PbAverage2SD207Pb/204PbAverage2SD208Pb/204PbAverage2SD187Os/188OsAverage2SDLoa-trendLoihi(tholeiitic)BigIsland0.5129530.0000700.7035810.00013118.3760.13315.4680.03038.1180.1220.13330.0046MaunaLoaBigIsland0.5129060.0000740.7038090.00066818.1680.17615.4600.02437.9080.1380.13560.0030HualalaiBigIsland0.5129030.0000510.7037270.00008618.1820.13215.4590.02537.9510.1590.13480.0016MahukonaBigIsland0.5129620.0000680.7036390.00015518.2530.22215.4690.01437.9410.152NAKahoolaweMauiNui0.5128480.0000990.7041200.00031818.0420.31415.4360.03037.8290.2190.1439LanaiMauiNui0.5127700.0001210.7041810.00031617.9220.09815.4370.01637.7530.057NAWestMolokaiMauiNui0.5129430.0002160.7038190.00039418.2530.44515.4600.02537.9390.254NAKoolau(Makapuu)Oahu0.5127570.0000770.7040820.00031517.8540.07415.4380.02637.7730.0710.14260.0075Koolau(KSDP)Oahu0.5129170.0000830.7037600.00017318.0630.08115.4530.00737.8370.051NAKoolau(NuuanuLandslide)Oahu0.5129720.0000590.7035680.00016118.2040.36615.4480.01737.8830.2400.13370.0056WaianaeOahu0.5129750.0001260.7036480.00019418.1460.20615.4610.03737.8560.117NAKauaiKauai0.5129690.0000560.7036710.00022918.2280.16615.4510.01537.9390.0980.13680.0038Kea-trendKilaueaBigIsland0.5129580.0000270.7035840.00009918.4640.20515.4830.05538.1040.1890.13100.0017MaunaKeaBigIsland0.5129680.0000360.7035840.00009418.4970.18115.4830.02538.1040.1710.12970.0011KohalaBigIsland0.5130150.0000000.7037100.00008718.1700.27615.4600.04137.8450.1480.13650.0115HaleakalaMauiNui0.5129580.0000400.7036450.00019418.5410.22015.4800.01938.1540.1830.13040.0000WestMauiMauiNui0.5130250.0000480.7035500.00014018.4310.14215.4830.03137.9570.1280.13210.0011EastMolokaiMauiNui0.5129810.0000830.7035650.00020718.4370.41015.4800.03238.0600.255NAa Meansandthestandarddeviations(SD,2sigma)arefromDataSetS1.Ifthestandarddeviationisnotreported,itisbecauseonlyasinglemeasurementisavailable.Majorelementcompositionsarecorrectedforolivinefractionation/additiontoaconstantMgO(16wt.%)ortobeinequilibriumwithaforsterite90olivinecomposition(butthetwodifferentcorrectionschemesyieldsimilarmajorelementcompositions).Anolivine-meltKdof0.30isusedforcorrection.Dataforsamplesareexcludedifthewholerockisaltered,highlyevolved,orifthemajorelementdataareincompleteortheanalysesyieldshighorlowtotals(seetextforfiltersapplied).HeliumandOsisotopedataexistformanyofthevolcanoeslistedasNAinthetable,butinseveralcases,correspondingmajorelementdatadoesnotexist,orindicatesexcessivemagmaticevolutionorpost-eruptivealteration,andtheHeandOsdataarenotreported.Sr,Nd,PbandHfisotopesarenotfilteredbasedontraceelementconcentrations.Inonecolumn,heliumisotopicratiosforsampleswithlowheliumconcentrations(<2*10-8cc4He/gSTP)arenotreported(?HighHeconc?).However,heliumisotopicratioswithlowerconcentrationsarepreservedinthenextcolumn(?AllHeconc?)andinDataSetS1.OsisotopesareexcludediftheOsconcentrationis<40ppt.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042685 of 24Figure 2GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042686 of 24[12] The radiogenic isotopic compositions of Hawai-ian shield lavas have been discussed at great length inthe literature (for a recent review, see Weis et al.[2011]). We outline some of the most outstandingfeatures of the radiogenic isotopic geochemistry ofHawaiian lavas in Figure 2. In general, Loa-trendlavas have lower 206Pb/204Pb, 143Nd/144Nd and176Hf/177Hf and higher 187Os/188Os, 87Sr/86Sr and208Pb*/206Pb* (208Pb*/206Pb* = (208Pb/204Pb -29.475)/(206Pb/204Pb - 9.306) [Hofmann, 2003]) thanKea-trend lavas (Figure 2).[13] In isotope space, Hawaiian lavas define cleararrays that resolve the Loa- and Kea-trends. Forexample, in 208Pb/204Pb versus 206Pb/204Pb isotopespace (Figure 2), Kea-trend volcanoes tend to havemore radiogenic 206Pb/204Pb values than Loa-trendvolcanoes. Kea-trend volcanoes?including MaunaKea, Kilauea, Haleakala, E. Molokai and W. Maui?define the most radiogenic Pb-isotopic compositionsin Hawaii. By contrast, Loa-trend volcanoes tend tohave less radiogenic 206Pb/204Pb (and a higher208Pb/204Pb for a given 206Pb/204Pb) than Kea-trendvolcanoes. Koolau, Kahoolawe and Lanai, theHawaiian volcanoes with the most geochemicallyenriched 143Nd/144Nd and 87Sr/86Sr, also have theleast radiogenic 206Pb/204Pb. However, Loihi, theyoungest Loa-trend volcano, has depleted (high)143Nd/144Nd and (low) 87Sr/86Sr signatures andradiogenic Pb-isotopic compositions, similar to Kea-trend volcanoes. The Pb-isotopic compositions inLoihi lavas extend to values encountered only in theKea trend volcanoes, including Mauna Kea andKilauea (and the Hilina-stage of Kileaua in particular[Kimura et al., 2006]). However, Loihi generally hasa higher 208Pb/204Pb at a given 206Pb/204Pb, andtherefore higher 208Pb*/206Pb*, than Kea-trend vol-canoes. In general, all other Loa-trend volcanoes plotbetween Loihi and the geochemically extremeKoolau-component lavas from Koolau, Kahoolaweand Lanai.3.2. Major Element Variation Diagrams[14] Plots of whole rock MgO concentrations ver-sus the other major element oxides (Figure 3)?including SiO2, TiO2, CaO, Al2O3, FeOtotal andNa2O?are useful for showing enrichments ordepletions of these elements at various stages ofmagmatic evolution. The Loa- and Kea- trend vol-canoes, which exhibit different isotopic character-istics, also tend to follow different trends in severalof the major element variation diagrams.[15] At a given MgO content, Loa-trend volca-noes tend to have higher SiO2 and lower TiO2and CaO contents than Kea-trend volcanoes. How-ever, Loihi seamount, another Loa-trend volcano,has among the lowest SiO2 and the highest TiO2 andCaO concentrations in Hawaii. Loihi lavas overlapcompositionally with the major element composi-tions found in the extreme Kea-component volca-noes, Mauna Kea and Kilauea. Al2O3 exhibits littlevariability among volcanoes at a given MgO. It ispossible that the Loa-trend volcanoes with thelowest 143Nd/144Nd?Koolau, Lanai and Kahoo-lawe?have slightly higher Al2O3 and Na2O andlower FeOtotal contents than Loihi and the Kea-trendvolcanoes, but the differences, if real, are small (SeeSection 3.3).[16] In Figure 3, we show that 208Pb*/206Pb* exhibitsno relationship with MgO. This suggests that magmaevolution and crustal assimilation, which can modifyMgO abundances, are not responsible for generatingthe variability in 208Pb*/206Pb*, which is a sourcefeature [e.g., Hofmann, 2003]. This observation isimportant, as several major element oxides (SiO2,CaO, TiO2) exhibit clear relationships with208Pb*/206Pb* (See Section 3.3, Figure 4) after cor-rections for olivine fractionation/addition are made.3.3. Major Elements Versus Isotopes[17] The Loa- and Kea-trend volcanoes exhibitisotopic (Section 3.1) andmajor element (Section 3.2)differences. The isotopic variations in Hawaiianshield lavas also exhibit clear relationships witholivine fractionation-corrected major element oxideabundances.[18] Fractionation-corrected SiO2, CaO and TiO2concentrations and Nd and Pb isotopic ratios showFigure 2. Plots of radiogenic isotope ratios for data included in this study. Note that the radiogenic isotope data in thefigures includes only samples with the major element data indicating that the lavas are not highly evolved or altered.Koolau lavas are divided into three groups: Makapuu (MAK), Koolau scientific drilling project (KSDP), and theNuuanu landslide (NUU). The approximate isotopic composition of the 3 geochemical components in Hawaii (as iden-tified in lavas) are labeled in the figure: Koolau, Loihi and Kea. Many lavas have only one of the radiogenic isotopedata and do not appear in any of the panels (but lavas with a single radiogenic isotope ratio do appear in the other datafigures). Similarly, lavas that do not possess the full suite of radiogenic isotopic compositions appear in some, but notall, of the panels.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042687 of 24Figure 3. Major element variation diagrams plotting MgO against SiO2, Al2O3, FeOtotal, Na2O, CaO and TiO2.A plot of MgO versus 208Pb*/206Pb* is also shown. The major elements in the panels of this figure have not been cor-rected for olivine fractionation or addition. Lavas with MgO lower than 6.5 wt.% are not considered in this study, andare not shown in the diagrams. K2O, P2O5 andMnO are not shown, but data are available in Data Set S1. Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042688 of 24the clearest relationships, and define arrays in theHawaiian data set [Hauri, 1996] (Figure 4). Lavasfrom the Makapuu-stage of Koolau, Lanai andKahoolawe anchor one extreme of the arrays, andhave the lowest 143Nd/144Nd, 206Pb/204Pb, CaOand TiO2 and the highest SiO2 and208Pb*/206Pb*.The other end of the Hawaiian array is anchoredby Loihi and the extreme Kea-trend volcanoes,Mauna Kea and Kilauea, which define the highest143Nd/144Nd, 206Pb/204Pb, CaO and TiO2 and thelowest 208Pb*/206Pb* and SiO2 (Figure 4).[19] Contrary to the findings of Hauri [1996], theother fractionation-correctedmajor element oxides?FeOtotal, Al2O3 and Na2O?do not exhibit clearrelationships with Nd and Pb-isotopic compositions(Figure 5). When plotted against 206Pb/204Pb, theFigure 4. Olivine fractionation-corrected SiO2, TiO2, and CaO oxide abundances are plotted against143Nd/144Ndand 208Pb*/206Pb*. SiO2, TiO2, and CaO exhibit similar relationships with87Sr/86Sr and 176Hf/177Hf (not shown).An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to 16 wt.% MgO. See Table 1, Figure S1, andData Set S1 for alternative olivine fractionation/addition schemes. Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC0042689 of 24fractionation-corrected FeOtotal concentrations of theextreme low 143Nd/144Nd Loa-trend lavas?all fromKoolau, Kahoolawe and Lanai?appear to be shiftedto slightly lower values than Kea-trend volcanoesand Loihi. Fractionation-corrected Al2O3 and Na2Oconcentrations appear to be offset to somewhathigher values in most of Loa-trend lavas, whileHawaiian lavas with the highest 143Nd/144Nd,including Loihi and Kea-trend volcanoes, tend tohave slightly lower Al2O3 and Na2O abundances.However, care must be taken when generalizingabout relationships between radiogenic isotopes andFeOtotal, Al2O3 and Na2O, as there is significantscatter in the data and the trends (if any) are not asclear as with SiO2, CaO and TiO2.[20] Two major element ratios not affected byolivine fractionation, CaO/Al2O3 and Na2O/TiO2,exhibit striking relationships with Nd and Pb-isotopiccompositions (Figure 6), as noted previously[Hauri, 1996; Putirka, 1999]. CaO/Al2O3 ratios arelowest and Na2O/TiO2 ratios are highest in the mostextreme low 143Nd/144Nd Loa-trend lavas fromFigure 5. Olivine fractionation-corrected FeOtotal, Al2O3and Na2O abundances are plotted against206Pb/204Pb. Thecorrelations (if any) are poor. 143Nd/144Nd, 87Sr/86Sr and176Hf/177Hf also fail to exhibit clear relationships withFeOtotal, Al2O3, and Na2O (not shown). An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.Figure 6. CaO/Al2O3 and Na2O/TiO2 oxide ratios areplotted against 208Pb*/206Pb*. 143Nd/144Nd, 87Sr/86Srand 176Hf/177Hf exhibit similar relationships with CaO/Al2O3 and Na2O/TiO2 (not shown). Colors and datasymbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426810 of 24Koolau, Kahoolawe and Lanai. Loihi lavas andextreme Kea-trend lavas from Mauna Kea andKilauea have the highest CaO/Al2O3 and the lowestNa2O/TiO2.[21] Helium and Os isotopic ratios show clear rela-tionships with fractionation-corrected major elementcompositions and major element ratios. 3He/4Heexhibits trends with SiO2, CaO, Al2O3, CaO/Al2O3and FeOtotal [Kurz et al., 2004; Herzberg, 2011;Hauri, 1996], but not with TiO2 and Na2O abun-dances or with Na2O/TiO2 ratios (Figure 8). High3He/4He lavas from Loihi anchor the low-SiO2 andAl2O3 and high-CaO, CaO/Al2O3 and FeOtotalportions of the arrays. When plotted against olivinefractionation corrected major element abundancesand major element ratios, extreme Loa-componentlavas with the highest 187Os/188Os (and high SiO2,Al2O3, Na2O and Na2O/TiO2, and low TiO2, FeOtotal,CaO, and CaO/Al2O3) anchor one portion of the arrayand Loihi and the extreme Kea-component lavas withlow 187Os/188Os (and low SiO2, Al2O3, Na2O andNa2O/TiO2 and high TiO2, FeOtotal, CaO and CaO/Al2O3) anchor the other extreme of the arrays.4. Origin of Major Element Variabilityin Hawaiian Lavas[22] While assimilation of oceanic crust has beensuggested to modify the isotopic compositions ofoxygen [Wang et al., 2003], heavy noble gases[e.g., Kent et al., 1999] and 187Os/188Os (in Os-poorlavas [e.g., Martin et al., 1994]) in some Hawaiianlavas, shallow processes operating in the oceaniccrust are not likely to be responsible for the observedrelationships between radiogenic isotopes andfractionation-corrected major element abundancesin the filtered data set. First, highly evolved lavas,which are most susceptible to being modified byassimilation, are not considered in this study.Second, radiogenic isotopes exhibit no relationshipwith MgO (Figure 3), a proxy for magmatic evolu-tion. This suggests that crustal assimilation is notresponsible for generating variability in radiogenicisotopes and major elements. Third, the Sr-Nd-Pb-Hfisotopic compositions of altered oceanic crust andoceanic sediment in the Hawaiian region are unlikeHawaiian lavas or geochemical end-member com-positions sampled by Hawaiian lavas [Hauri, 1996;Lassiter and Hauri, 1998; Blichert-Toft et al., 1999;Hanano et al., 2010]. Therefore, assimilation of localoceanic crust and sediments is not the mechanismresponsible for driving relationships between majorelements and radiogenic isotopes in Hawaiian lavas.Consequently, the observed major element-isotopeFigure 7. Olivine fractionation-corrected SiO2 andTiO2 oxide abundances and Na2O/TiO2 ratios are plottedagainst 187Os/188Os. Olivine fractionation correctedFeOtotal, Na2O, Al2O3 and CaO oxide abundances andCaO/Al2O3 ratios also exhibit relationships with187Os/188Os, but are not shown here. An olivine-meltKd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. See Table 1, Figure S1, and Data Set S1for alternative olivine fractionation/addition schemes.Colors and data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426811 of 24Figure 8. Olivine fractionation-corrected SiO2, CaO, Al2O3 and FeOtotal oxide abundances and CaO/Al2O3 ratios areplotted against 3He/4He. Olivine fractionation corrected Na2O and TiO2 oxide abundances and Na2O/TiO2 ratios exhibitno relationships with 3He/4He and are not shown here. An olivine-melt Kd of 0.30 is used for olivine fractionation/additionto 16 wt.%MgO. See Table 1, Figure S1, and Data Set S1 for alternative olivine fractionation/addition schemes. Colors anddata symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426812 of 24correlations in Hawaiian shield lavas (Figures 4and 6?8) reflect mantle source heterogeneity. Herewe examine each of the three Hawaiian componentsin turn?Koolau, Loihi and Kea?and evaluate theorigin of the major element variability and discusspossible mechanisms that drive the observed rela-tionships between radiogenic isotopes and olivine-fractionation corrected major element compositions.4.1. The Koolau Component:The Enigmatic Eclogite4.1.1. Bulk Lava Major Element CompositionsFrom Peridotite or Eclogite Melts?[23] Makapuu stage lavas from Koolau volcanoexhibit the most enriched 143Nd/144Nd in Hawaiiand sample the end-member Koolau-componentcompositions [Roden et al., 1994], and they anchorthe low CaO, high SiO2 portion of the arrays formedin major element versus isotope space in Figure 4.Makapuu-stage Koolau lavas play a central role inthe debate on the role of eclogite melting in theHawaiian plume [e.g., Hauri, 1996; Huang andFrey, 2005; Salters et al., 2006; Huang et al.,2007; Sobolev et al., 2005, 2007; Herzberg, 2011;Putirka et al., 2011], and we explore the argumentssurrounding eclogite versus peridotite melting.[24] One argument against the generation ofMakapuu-stage Koolau melts by peridotite melting hinges onhigh pressure and temperature experiments performedon a Kilauea high-MgO glass composition. Eggins[1992] and Wagner and Grove [1998] showedexperimentally that the major element compositionsof the high MgO Kilauea glasses cannot be in equi-librium with both garnet and olivine (i.e., garnetperidotite). This is important because Hawaiianshield lavas exhibit heavy rare earth element(HREE) depletions and, after correction for olivinefractionation, relatively constant concentrations ofHREE [Hofmann et al., 1984], which require resid-ual garnet in the mantle source of the lavas[Hofmann et al., 1984; Huang and Frey, 2005].Instead, Eggins [1992] and Wagner and Grove[1998] found that Kilauea glasses are in equilib-rium with a harzburgite (olivine + orthopyroxene)residue, but this phase assemblage will not generatethe residual garnet signature observed in Hawaiianlavas.[25] The SiO2 contents of Kilauea glasses are alsotoo high to be melts of garnet peridotite [Hauri,1996; Wagner and Grove, 1998], and KoolauMakapuu-stage lavas have even higher SiO2 thanthe Kilauea lavas, which excludes garnet peridotiteas a source for the Koolau component (Figure 4).Similarly, the FeOtotal versus SiO2 systematics ofMakapuu-stage Koolau lavas are inconsistent withexperimentally derived partial melts of peridotite atgarnet stability field pressures [Hauri, 1996]. Whilelow pressure (1?1.5 GPa) partial melts of perido-tites can yield the high SiO2 contents found in theselavas, the FeOtotal of low pressure partial melts istoo low. There are at least two reasons why suchlow pressures of melting are not feasible. First, lowpressures of melting (1?1.5 GPa) are below thoseof the field of garnet stability and will not generatethe residual garnet signature observed in Hawaiianlavas [Hofmann et al., 1984; Huang and Frey,2005]. Second, the lithosphere beneath Hawaii istoo thick to permit such shallow melting (<45 km)[Hauri, 1996].[26] Water addition to peridotite can increase theSiO2 content of melts at low pressures of melting[Parman and Grove, 2004]. However, wet meltingof garnet peridotite does not increase the melt SiO2concentration [Tenner et al., 2012], and existingwet melting experiments of garnet peridotite cannotexplain the high SiO2 in Koolau lavas.[27] Nonetheless, Putirka et al. [2011] suggest thateclogite/garnet pyroxenite are not required for thepetrogenesis of Hawaiian lavas, and that peridotitemelting can generate the entire observed composi-tional range. Using a compilation of experimentalmelt data generated from a range of peridotiticcompositions at different pressure and temperatureconditions, they argue that the major elementcompositions of parental magmas of Makapuu-stage Koolau lavas can be explained by mixing ofpartial melts from different peridotite meltingexperiments. However, there is no single experi-mental melt that matches the extreme compositionof Makapuu-stage Koolau lavas (i.e., high SiO2,low FeO and CaO). While Putirka et al. [2011]argued that the primary magma composition ofMakapuu-stage Koolau lavas can be reproduced bymixing three experimental melts [see Putirkaet al., 2011, equation 6], the three experimentalmelts (i.e., H154 from Kinzler and Grove [1992],T-762 from Falloon et al. [1988], and T-3572from Falloon and Danyushevsky [2000]) are all low-pressure melts (1?2 GPa) and have only olivine andorthopyroxene as residual phases. Consequently,these experiments are inconsistent with REE con-centrations and patterns in Hawaiian lavas, whichrequire garnet as a residual phase during melting.[28] In summary, existing experimental peridotitemelt data and melt-rock reaction models do notGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426813 of 24explain the composition of Makapuu-stage Koolaulavas. While we cannot exclude the possibility thatfuture peridotite melting experiments may match theunusual major element compositions of Makapuu-stage Koolau, we note that eclogite melting in theHawaiian mantle source may provide a mechanismfor generating the highest SiO2 Hawaiian lavas.Eclogite has been invoked to explain the combinedresidual garnet signature and high SiO2 content ofMakapuu-stage Koolau lavas [Hauri, 1996; Huangand Frey, 2005; Sobolev et al., 2005, 2007]. Thelow CaO contents of Makapuu-stage Koolau lavasare also consistent with partial melting of eclogite[Huang and Frey, 2005; Herzberg, 2006]. Herzberg[2006] parameterized the peridotite melting experi-ments of Walter [1998] and argued that mostHawaiian shield lavas have CaO contents that aretoo low to be partial melts of peridotite [Pertermannand Hirschmann, 2003]. Since Makapuu-stageKoolau lavas have the lowest CaO contents at agiven MgO content among Hawaiian lavas [Freyet al., 1994] (Figures 3 and 4), Huang and Frey[2005] and Sobolev et al. [2005] suggested thatthey contain the largest contribution from partialmelts of eclogite/garnet pyroxenite. Additionally,Makapuu-stage lavas and olivines have the lowestMnO contents among Hawaiian lavas [Huang et al.,2007; Sobolev et al., 2007], consistent with partialmelting of eclogite [Pertermann and Hirschmann,2003], as MnO is relatively compatible in garnet.Finally, Makapuu-stage lavas have the among low-est TiO2 contents in the Hawaiian tholeiitic suite[Frey et al., 1994] (Figures 3 and 4). Such lowmagmatic TiO2 is distinctive feature of dacitic meltsof eclogite with residual rutile [Pertermann andHirschmann, 2003, Figure 9].4.1.2. High SiO2 Lavas From Melt-RockReaction Between Peridotite Melts andPeridotite Mantle?[29] Melt-rock reaction between peridotite meltsand harzburgite/peridotite (i.e., assimilation oforthopyroxene+clinopyroxene and precipitation ofolivine [Kelemen et al., 1992]) has also beenproposed as a model to explain the high SiO2-content in Hawaiian lavas [Eggins, 1992; Wagnerand Grove, 1998; Stolper et al., 2004; Putirkaet al., 2011]. The peridotite reacting with the meltcould be a melt-residue of the rising mantle plume[Wagner and Grove, 1998, Figure 5a] or in situlithospheric mantle [Wagner and Grove, 1998,Figure 5b]. Hauri [1996] noted that, if the elevatedSiO2 in Koolau were a result of melt-rock reactionwith the mantle lithosphere, it would be reflectedby a lithospheric imprint on the Koolau lavas,including unradiogenic 187Os/188Os and high143Nd/144Nd ratios typical of the oceanic mantlelithosphere [e.g., Shirey and Walker, 1998;Warren et al., 2009]. This is not observed. KoolauMakapuu-state lavas have radiogenic 187Os/188Osand low 143Nd/144Nd (Figure 2), an observationthat is inconsistent with extensive melt-rock reactionin the oceanic mantle lithosphere. Further, a melt-mantle reaction predicts that CaO/Al2O3 willincrease with SiO2 as pyroxene is dissolved andolivine is precipitated: olivine precipitation from themelt will drive up melt SiO2, and clinopyroxene(and/or orthopyroxene) dissolution from the mantlewill increase melt SiO2 and CaO/Al2O3. However,this is inconsistent with the negative relationshipobserved between CaO/Al2O3 and high SiO2 inHawaiian lavas (Figure 9), indicating that a mecha-nism other than melt-rock reaction is responsible forthe increased SiO2 in Koolau lavas.Figure 9. CaO/Al2O3 versus SiO2 in the Hawaiianmagmatic suite considered in this study. Melt-rock reac-tion between the shallow mantle lithosphere and amantle melt tends to increase SiO2 in the melt as clino-pyroxene from the mantle lithosphere is dissolved intothe melt while olivine from the melt is precipitated.This melt-rock reaction would be manifested as a posi-tive trend in SiO2 versus CaO/Al2O3 space. However,Hawaiian lavas with the highest SiO2 have the lowestCaO/Al2O3, a signature that is inconsistent with meltrock reaction. The lavas in the figure have been correctedfor olivine fractionation to a constant MgO of 16 wt.%.An olivine-melt Kd of 0.30 is used for olivine fraction-ation/addition. Lavas with high 206Pb/204Pb have lowSiO2 and high CaO/Al2O3, and lavas with high low206Pb/204Pb have high SiO2 and low CaO/Al2O3. Colorsand data symbols as in Figure 2.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426814 of 24[30] Melt-rock reaction with the mantle plume alsofails to explain the observed residual garnet signature,i.e., and relatively constant HREE contents (aftercorrection for olivine fractionation or accumulation)in Hawaiian tholeiites [e.g., Hofmann et al., 1984;Huang and Frey, 2005]. This is because melt-rockreaction is likely to generate variable HREE abun-dances. Previous studies invoking melt-rock reac-tion considered high LREE/HREE ratios alone toreflect a residual garnet signature [e.g., Eggins,1992; Wagner and Grove, 1998; Putirka et al.,2011], but the variable HREE abundances result-ing from melt-rock reaction do not match the rela-tively constant abundances in Hawaiian lavas.Therefore, a melt-mantle reaction occurring withinthe plume, proposed to explain the high SiO2 con-tent in Hawaiian lavas, cannot explain the observedresidual garnet signature.4.1.3. Peridotite Versus Eclogite Melting:Evidence From Ni in Olivine?[31] Ni concentrations in olivines play a key role inthe debate surrounding eclogite melting in theHawaiian plume, particularly beneath Koolau vol-cano. Olivines in Makapuu-stage Koolau lavas haveunusually high Ni abundances [e.g., Clague et al.,1991; Garcia, 2002]. Sobolev et al. [2005, 2007]and Herzberg [2011] argued that the high Ni con-tents in Hawaiian olivines and lavas imply an oliv-ine-free, secondary garnet pyroxenite source forHawaiian lavas. Wang and Gaetani [2008] suggestthat the high olivine Ni contents are caused by highDNiol/melt that results from a melt with a high SiO2content, which implies an important role of eclogitein the petrogenesis of Hawaiian lavas.[32] However, Putirka et al. [2011] and Rhodeset al. [2012] suggest that there are large uncertain-ties in the model predicted DNiol/melt values and Nivariations in peridotites. They argued that Ni con-centrations in olivines and lavas may not be used asdiscriminators between eclogite melting and peri-dotite melting. Putirka et al. [2011] argue that, athigh temperature, DNiol/melt is low, and hot peridotitemelting yields Ni-rich melts. Following transport toshallower depths, DNiol/melt is higher owing to lowerambient temperatures, and crystallizing olivines areNi-rich. Further experiments parameterizing theeffects of temperature, pressure and melt composi-tion on Ni partitioning between olivine and melt areneeded to evaluate these contrasting hypotheses.[33] In summary, there is active debate surroundingthe interpretation of the elevated Ni abundances inHawaiian magmatic olivines and whole rocks, andfurther experiments parameterizing the effects oftemperature, pressure and melt composition on Nipartitioning between olivine and melt are needed toevaluate the contrasting hypotheses. However, thedistinctive geochemical characteristics of Makapuu-stage Koolau lavas?high SiO2, low CaO, TiO2 andMnO, and REE patterns showing residual garnetsignature?are consistent with partial melting ofeclogite [Hauri, 1996; Pertermann and Hirschmann,2003; Herzberg, 2006; Dasgupta et al., 2010], butare not matched by melt compositions from existingexperimental peridotite melting studies.4.2. The Loihi Component: The ParadoxicalPyroxenite4.2.1. Lithology of the Loihi Mantle Source[34] Lavas from the Hawaiian Loa-trend describearrays that suggest binary mixing between twoextreme compositions (Figures 2 and 4?8): Makapuu-stage Koolau lavas anchor the low 143Nd/144Nd and206Pb/204Pb portion of the Loa array, and high3He/4He lavas from Loihi define the portion withdepleted 143Nd/144Nd and 87Sr/86Sr signatures andradiogenic 206Pb/204Pb. While Koolau lavas havehigh SiO2 and low TiO2, CaO and CaO/Al2O3,Loihi lavas exhibit the lowest SiO2 and highestTiO2, CaO and CaO/Al2O3 in the Loa-trend suite.Unlike the Koolau Makapuu source, which is likelyto contain an eclogite component, the Loihi mantlesource is generally agreed to be peridotitic [e.g.,Sobolev et al., 2005, 2007; Putirka et al., 2011;Herzberg, 2006, 2011]. Nonetheless, there are keygeochemical features of high 3He/4He Loihi lavassuggesting that the source peridotite is enriched as aresult of the addition a mafic component [e.g.,Sobolev et al., 2005; Putirka et al., 2011; Herzberg,2011]?likely a SiO2-poor pyroxenite?and thefinal, hybrid mixture is still a peridotite.[35] Evidence that a mafic component was added tothe Loihi peridotite source comes from elevatedTiO2 contents in fractionation-corrected Loihi lavas,which are too high to be generated by peridotitemelting at the degrees of melting inferred forHawaiian shield lavas. Prytulak and Elliot [2007]showed that, after correcting lavas to 16 wt.% MgO,the fractionation-corrected TiO2 abundances of lavasfrom many Hawaiian volcanoes (>1.8 wt%) can onlybe generated by low degrees (<3%) of partialmelting of a primitive peridotite (840?1200 ppm Ti)[McDonough and Sun, 1995; Carlson and Boyet,2008] or a depleted mantle source (657?798, ppmTi) [Workman and Hart, 2005; Salters and Stracke,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426815 of 242004]. Such low degrees of partial melting areinconsistent with their tholeiitic bulk compositions,and there is evidence that Hawaiian lavas are gen-erated at higher degrees of melting (?5%) [McKenzieand O?Nions, 1991; Watson and McKenzie, 1991;Garcia et al., 1995]. Therefore, Prytulak and Elliot[2007] concluded that the mantle sources beneaththese Hawaiian volcanoes have been enriched by theaddition of a Ti-rich component, and the most likelymaterial to host sufficient Ti is a recycled maficcomponent. Loihi tholeiites have among the highestTiO2 concentrations?2.1 wt. % TiO2 at 16 wt.%MgO?in the Hawaiian tholeiite suite (Figures 3and 4) [Garcia et al., 1995; Hauri, 1996] indicat-ing that the dominantly peridotitic Loihi source hasincorporated a mafic lithology during its history inthe mantle.[36] Pb isotopic compositions offer a second line ofevidence for the addition of a mafic component tothe peridotitic Loihi mantle source. Loihi lavas havethe highest 206Pb/204Pb and 208Pb/204Pb among Loatrend volcanoes, and only extreme Kea-trend lavashave more radiogenic Pb isotopic ratios. The Pb-isotopic compositions of Loihi lavas plot well to theright of the geochron, which has been attributed tothe presence of a mafic material [Lassiter andHauri, 1998; Jackson et al., 2010; Jackson andCarlson, 2011] with high U/Pb following seaflooralteration (U addition) and subduction zone pro-cessing (Pb loss) [Hofmann and White, 1982; Kelleyet al., 2005].[37] A third line of evidence supporting a maficcomponent in the Loihi mantle source comes fromelevated 187Os/188Os ratios (up to 0.138) in Loihilavas. Roy-Barman et al. [1998] identified a positivecorrelation between 3He/4He and 187Os/188Os inLoihi, which led the authors to suggest that themantle beneath Loihi hosts a component withradiogenic Os that is somehow related to the end-member component found in Makapuu-stageKoolau lavas. (A similar correlation between 3He/4Heand 187Os/188Os is Iceland led Brandon et al. [2007]to suggest the presence of a mafic componentadmixed with high 3He/4He peridotite in the source ofhigh 3He/4He Icelandic lavas.) However, owing to themuch higher 3He/4He and more depleted 87Sr/86Srand 143Nd/144Nd ratios in Loihi lavas compared toKoolau lavas, we consider it unlikely that the high187Os/188Os mafic components in Loihi and Koolaulavas are the same.[38] The radiogenic Os and Pb, and high Ti con-centration in Loihi lavas are consistent with thepresence of a mafic component added to theperidotitic mantle source of Loihi lavas, yet petro-logic models for the Loihi source indicate thatperidotite melting is occurring [e.g., Putirka et al.,2011; Herzberg, 2011]. This raises an importantquestion, which relates to the paradox of pyroxenitein the Loihi mantle source: How can the mixture ofthe peridotite and pyroxenite result in a mantlesource that generates melts that appear petrologi-cally to have been sourced by a peridotite? Owing tothe high TiO2 in Loihi lavas, Putirka et al. [2011]invoked the Prytulak and Elliot [2007] Ti model tosuggest the incorporation of a mafic component inthe Loihi source, but argued that it no longer existsas a distinct lithology. Putirka et al. [2011] sug-gested that the mafic source has been mixed com-pletely into the peridotite, so that the final lithologyis an enriched peridotite. If true, the final mixture, aperidotite, would inherit elevated TiO2 and radio-genic Os and Pb from the mafic lithology. However,mixing of the pyroxenite into the peridotite mightnot take place in the solid state.Gaffney et al. [2005]proposed a model for melting a mafic component inthe presence of peridotite, while keeping the petro-logic signature of the mafic component ?hidden.?They suggested that the eclogite melt would infil-trate and react with the peridotite and generate afertile peridotite, similar to that observed in eclogite-peridotite ?sandwich? experiments [Yaxley andGreen, 1998; Takahashi and Nakajima, 2002].The resulting fertile peridotite will be rich in ortho-pyroxene, as a result of eclogite melt reaction witholivine in the peridotite. Gaffney et al. [2005] sug-gested that melting of the fertilized peridotite willyield melts with a major element composition thatreflects peridotite melting [Hirschmann et al.,2003], even though they possess isotopic and traceelement geochemical signatures that reflect a con-tribution from a mafic component. The Putirka et al.[2011] and Gaffney et al. [2005] models may helpexplain the paradox of a mafic component in theLoihi mantle source that is essentially ?invisible? topetrologic models that suggest derivation of Loihilavas from a peridotitic source.4.2.2. Mantle Source Lithological DifferencesBetween the Loa-Trend Extremes: Comparingthe Loihi Mantle Source to the KoolauMakapuu Mantle[39] The association of high 3He/4He with a mantlesource that hosts a mafic component at Loihi isparadoxical. Owing to the highly incompatiblenature of U and Th during mantle melting, maficmaterials should in general have higher U and Ththan peridotitic materials. Therefore, over time,GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426816 of 24mafic materials will generate more 4He than peri-dotites, resulting in lower 3He/4He in the formerrelative to the latter. As a result, a mafic componentadded to the peridotitic source should result in low3He/4He in Loihi lavas, not high 3He/4He. How-ever, if the SiO2-undersaturated pyroxenite inferredto have been added to the peridotitic Loihi sourcesuffered melt extraction in a paleo-subduction zone,then incompatible elements like U and Th will havebeen effectively removed from the pyroxenite, thusreducing its potential to generate 4He over time.Jackson et al. [2008] observed that 3He/4He ratioscorrelate with the magnitude of positive Ti, Ta andNb (TITAN) anomalies (where anomalies of theTITAN elements?calculated relative to elementsof similar compatibility in peridotite on a primitivemantle normalized spidergram?are not to be con-fused with the absolute concentrations of theseelements) in Hawaiian lavas, where Loihi exhibitsthe largest Ti anomalies and highest 3He/4He ratios.Owing to the ubiquitous presence of rutile in eclo-gite, trace elements compatible in rutile, includingthe TITAN elements, are residually enriched rela-tive to other trace elements during melt extractionfrom and dehydration of the downing-going slab;incompatible elements not sequestered into rutile?including the radiogenic helium-producing elements,U and Th?will be lost from the slab, togetherwith SiO2. For such a model to explain the radio-genic Pb isotopes in Loihi lavas, Pb would have to bepreferentially removed from the slab relative to U andTh, which is likely [Kelley et al., 2005]. The residualSiO2-poor mafic material?a pyroxenite?is TITAN-enriched and depleted in U and Th, and will contrib-ute little 4He to the peridotite with which it mixes,including high 3He/4He peridotites. Such a modelmight explain the association of TITAN enrichmentand high 3He/4He in SiO2-poor Loihi lavas.[40] By contrast, Makapuu-stage Koolau lavas havehigher SiO2, lower3He/4He and less radiogenic Pb.These lavas sample a SiO2-rich eclogite (Section 4.1)that has not suffered severe SiO2 and incompatibleelement depletion in a subduction zone, as evidencedby the silica-rich character of Koolau lavas. Such aneclogite will have retained its complement of U andTh (and Pb, thereby preserving a low U/Pb ratio) andwill producemore 4He over time that will ?infect? thesurrounding peridotite mantle?including the litho-logic reservoir hosting high 3He/4He peridotite[e.g., Parman et al., 2005; Albar?de, 2008; Hartet al., 2008; Jackson et al., 2008]?with low3He/4He. A host of possible mafic lithologies existin nature, and the presence of two distinct maficcomponents?a SiO2-poor pyroxenite and a SiO2-rich eclogite?in the Hawaiian plume might recon-cile the geochemical differences between the twoLoa-trend mantle components, Loihi and Koolau-Makapuu.4.3. The Kea Component[41] A third major isotopic end-member observed inHawaiian shield lavas?the Kea component?issampled by volcanoes that define the Kea en eche-lon volcanic trend. The Kea-trend volcanoes havemore homogeneous Sr, Nd and Hf isotopes that arealso generally more depleted [e.g., Stille et al.,1986] than their Loa-trend equivalents [DePaoloet al., 2001; Weis et al., 2011]. This has led tomodels suggesting a depleted peridotite source?MORB-source, Pacific oceanic lithosphere, entrainedasthenosphere, or recycled mantle lithosphere?forKea-component lavas [West et al., 1987; Chen andFrey, 1985; Hauri, 1996; Eiler et al., 1996a, 1996b;Lassiter et al., 1996]. However, the low 176Hf/177Hfof the Kea end-member suggests that asthenosphericor lithospheric materials are not present in the sourceof Kea-type lavas [Blichert-Toft et al., 1999].Recycled lower oceanic crust has also been sug-gested to source Kea-component lavas, but only incombination with recycled lithospheric peridotite[Lassiter and Hauri, 1998].[42] With the exception of 3He/4He and 208Pb*/206Pb*,Kea- and Loihi-component lavas are more similar toeach other than to Koolau-component lavas, and thefractionation-corrected major element compositions ofKea lavas are remarkably similar to Loihi-componentlavas, as observed previously [Hauri, 1996]. In fact, theKea-component exhibits several geochemical similari-ties with the Loihi-component that suggest that theformer also hosts a mafic component in its mantlesource. For example, Kea-component lavas hosthigh TiO2 contents, consistent with the addition of apyroxenite component in the source of Kea-component lavas (Mauna Kea and Kilauea have>2 wt.% TiO2 at 16 wt.% MgO (Table 1) [Prytulakand Elliot, 2007]). However, information fromradiogenic isotopes does not permit a clear resolu-tion of the debate over source lithologies contribut-ing to the Kea mantle source. On the one hand, Pbisotopic compositions in Kea-component lavas areamong the most radiogenic in Hawaii. If radiogenicPb is associated with a recycled mafic component,then Kilauea lavas should host a significant maficcomponent. This is contradicted by the generallyunradiogenic 187Os/188Os in Kea-trend lavas(<0.133, with the exception of a single Kohala lava;Figure 7). One possible explanation for this apparentGeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426817 of 24disagreement is that there is a greater contribution ofrecycled sediment to the Loa-trend mantle than tothe Kea-trend source: Sediment generally has higher187Os/188Os than mafic lithologies, so it is possiblefor a mantle source with a sediment and a maficcomponent (like the Loa-trend mantle) to have ahigher 187Os/188Os than the a mantle source withjust a mafic component (like the Kea-trend mantle)[Lassiter and Hauri, 1998; Huang et al., 2005].5. Major Element Versus IsotopeCorrelations in Hawaii in the Contextof Global OIBs[43] The broad correlations between major elementsand isotopes in Hawaiian lavas form arrays anchoredby Loihi and Kea-component lavas (with high143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and low87Sr/86Sr) at one end and by Koolau lavas (with low143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb and high87Sr/86Sr) at the other. Information from olivine-fractionation corrected major element data suggeststhat the correlations in the Hawaiian data set areanchored on both ends by different types of maficcomponent that coexist (and interact) with peridotitein the Hawaiian plume: a silica-poor pyroxeniteanchors the Loihi and Kea-component portion of theHawaiian array (Section 4.2 and 4.3), and a silica-rich eclogite anchors the enriched portion (Koolau)of the Hawaiian array (Section 4.1). A host of pos-sible mafic lithologies exist in nature, and the SiO2content of the mafic materials in the source ofthe Loihi, Kea and Koolau components may bethe defining difference among these components.However, in order to understand the origin of thesecontrasting mafic sources, they must first be placedin the context of global OIB geochemical variability.[44] Broad relationships between major elementsand radiogenic isotopes in the global OIB data setmay help constrain the mantle source compositionsof the Loihi, Kea and Koolau components. Jacksonand Dasgupta [2008] show that global OIB lavaswith the most radiogenic Pb have the lowest SiO2and the highest CaO/Al2O3 (Figure 10). SiO2 andCaO/Al2O3 also exhibit some of the clearest cor-relations with 206Pb/204Pb in Hawaiian lavas, andthese correlations mimic the global trend (Figure 10).Like the global OIB data set, FeOtotal, Al2O3 andNa2O abundances in Hawaii exhibit little or nocorrelation with radiogenic isotopes. In summary,the correlations between Pb isotopes and majorelements in Hawaii appear to broadly reflect theglobal trends, and we suggest that the mechanismthat drives the correlations between major elementsand isotopes in Hawaii illustrates, in microcosm, alarger global process.[45] Hauri [1996] suggested that SiO2-rich(50 wt.%) Koolau lavas resulted from melting ofSiO2-saturated mafic material (which we refer toabove as eclogite), while the mantle sources of thelow SiO2 lavas (40 wt.%) in the Pacific Islandswith the most radiogenic Pb are thought to hostSiO2-poor mafic material (which we refer to aspyroxenite) [Hirschmann et al., 2003; Kogiso et al.,2003; Kogiso and Hirschmann, 2006; Dasguptaet al., 2006; Jackson and Dasgupta, 2008]. Apply-ing this model to the Hawaiian magmatic suite, weinfer that Loihi and Kea-component lavas, whichexhibit the most radiogenic Pb compositions and thelowest SiO2 concentrations in Hawaiian shieldlavas, are derived from a peridotitic mantle sourcethat incorporated a small portion of a SiO2-poormafic component with radiogenic Pb.[46] Subduction zone processes can modify thecomposition of the downgoing oceanic crust byvariably removing SiO2 (and fractionating traceelement ratios, such as U, Th and Pb) [Hauri, 1996;Jackson and Dasgupta, 2008]. As a result, SiO2-richand SiO2-poor mafic lithologies exist in the mantlethat are likely to host distinct time-integrated isoto-pic ratios. Low SiO2 lavas from Mangaia andTubuaii and the high SiO2 lavas from Hawaii?sKoolau Makapuu-stage anchor the high 206Pb/204Pband low 206Pb/204Pb portions of the global array,respectively (Figure 10) [Jackson and Dasgupta,2008]. SiO2-deficient eclogites suggested for thesource of SiO2-poor OIB lavas with radiogenic Pbmust have somehow attained higher U/Pb ratios,likely via Pb-loss from the slab [Kelley et al., 2005](i.e., the same subduction zone processes reduced theSiO2 of the downgoing crust and increased U/Pb).The variability within the Hawaiian array may begenerated in a similar manner, where the Hawaiianplume hosts both SiO2-rich eclogites (with low206Pb/204Pb) and SiO2-poor pyroxenites (with high206Pb/204Pb) that mix in the peridotite matrix of theplume to generate the correlations between majorelements and radiogenic isotopes in Hawaii. Thus,processes operating in subduction zones that modifythe downgoing oceanic crust may be responsible forgenerating much of the major element variabilityobserved in Hawaii and in OIBs in general [Hauri,1996].6. Conclusions[47] From this review study, we draw the followingconclusions:GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426818 of 24[48] 1. Data for tholeiitic Hawaiian shield lavasform arrays in plots of radiogenic isotopes versusolivine-corrected major element oxides. Individualdata points exhibit remarkable trends and there isno need to average the data by volcano.[49] 2. The trends are anchored by Koolau lavas atone end (with high 87Sr/86Sr, 187Os/188Os, SiO2,Figure 10. Olivine fractionation-corrected SiO2 concentrations and CaO/Al2O3 ratios are plotted against206Pb/204Pbfor Hawaiian lavas and the global OIB data set. The correlations in the Hawaiian data set mimics, in microcosm, thelarger global correlation. The global OIB data set is from Jackson and Dasgupta [2008] and includes only lavas withMgO > 8 wt.% MgO, as many non-Hawaiian OIB lavas experience clinopyroxene fractionation at lower MgO abun-dances (see Data Set S1 for compositions). An olivine-melt Kd of 0.30 is used for olivine fractionation/addition to16 wt.% MgO. HIMU (or high-m, or 238U/204Pb) represents the mantle reservoir with radiogenic Pb-isotopes [e.g.,Hauri and Hart, 1993; Woodhead, 1996; Hanyu et al., 2011].GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426819 of 24and Na2O/TiO2, and low143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaO and CaO/Al2O3) and byKea and Loihi lavas at the other (low 87Sr/86Sr,187Os/188Os, SiO2, and Na2O/TiO2, and high143Nd/144Nd, 176Hf/177Hf,206Pb/204Pb, TiO2, CaOand CaO/Al2O3). FeOtotal, Al2O3 and Na2O con-centrations do not correlate with Sr, Nd, Pb or Hfisotope compositions.[50] 3. In Hawaiian tholeiitic lavas, 3He/4He showsa remarkably good relationship with SiO2, CaO,Al2O3, CaO/Al2O3 and FeOtotal. High3He/4He lavasfrom Loihi anchor the low SiO2 and Al2O3 and highCaO, CaO/Al2O3 and FeOtotal portions of the arrays.3He/4He exhibits no clear relationships with TiO2and Na2O abundances or with Na2O/TiO2 ratios.[51] 4. The Loihi source is likely peridotitic, but hasbeen infused with a SiO2-poor mafic componentsuch that the final mixture is an enriched peridotite.Loihi and Kea-component lavas exhibit similarmajor element characteristics (low SiO2 and Na2O/TiO2 and high TiO2, CaO and CaO/Al2O3), whichmay suggest lithologically similar mantle sources.The composition of SiO2-rich Koolau-componentlavas is not easily explained by available data forperidotite melting experiments (wet or dry) or bymelt-rock reaction of peridotite melts with the oce-anic mantle lithosphere. Instead, Koolau-componentlavas are likely derived from melts of a SiO2-richeclogite that has variably interacted with peridotite.[52] 5. Correlations between major elements andradiogenic isotopes in Hawaiian lavas mimic thebest correlations observed in the global OIB data setbetween Pb isotopic ratios and SiO2 and CaO/Al2O3. We suggest that the mechanism that drivesthe correlations between major elements and iso-topes in Hawaii illustrates, in microcosm, a largerglobal process. Variable processing of slabs insubduction zones yields SiO2-poor pyroxenites(with high U/Pb) and SiO2-rich eclogites (with lowU/Pb) that evolve radiogenic and unradiogenic Pbisotopic compositions, respectively. These two end-member mafic components interact variably withperidotite and anchor the extreme ends (i.e., highSiO2 and low SiO2) of the global array (Figure 10).Acknowledgments[53] This work was supported by start-up funds from BostonUniversity (to MGJ), and by NSERC DG to Dominique Weis.We acknowledge thoughtful and helpful reviews from KeithPutirka and Francis Albar?de, and Joel Baker for editorial han-dling. The three authors are deeply indebted to Fred Frey forhis impact on the study of oceanic volcanism.ReferencesAbouchami, W., A. W. Hofmann, S. J. G. Galer, F. A. Frey,J. Eisele, and M. Feigenson (2005), Lead isotopes revealbilateral asymmetry and vertical continuity in the Hawaiian man-tle plume, Nature, 434, 851?856, doi:10.1038/nature03402.Albar?de, F. (2008), Rogue mantle helium and neon, Science,319, 943?945, doi:10.1126/science.1150060.Blichert-Toft, J., F. A. Frey, and F. 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Hart (2005), Major and trace ele-ment composition of the depleted MORB mantle (DMM),Earth Planet. Sci. Lett., 231, 53?72, doi:10.1016/j.epsl.2004.12.005.Yaxley, G. M., and D. H. Green (1998), Reactions betweeneclogite and peridotite: Mantle refertilisation by subductionof oceanic crust, Schweiz. Mineral. Petrogr. Mitt., 78,243?255.Zindler, A., and S. R. Hart (1986), Chemical geodynamics,Annu. Rev. Earth Planet. Sci., 14, 493?571, doi:10.1146/annurev.ea.14.050186.002425.GeochemistryGeophysicsGeosystems G3 JACKSON ET AL.: MAJOR ELEMENT VARIATIONS IN HAWAIIAN LAVAS 10.1029/2012GC00426824 of 24 file:///C|/Documents%20and%20Settings/bugeaud/Desktop/ggge2264-sup-0001-readme.txt[5/14/2014 11:10:22 AM]Auxiliary Material for Paper 2012GC004268Major element variations in Hawaiian shield lavas: Source features and perspectives from global ocean island basalt (OIB) systematicsMatthew G. JacksonDepartment of Earth Sciences, Boston University, Boston, Massachusetts, USADominique WeisPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, British Columbia, CanadaShichun HuangDepartment of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts, USAJackson, M. G., D. Weis, and S. Huang (2012), Major element variations in Hawaiian shield lavas: Source features and perspectives from global ocean island basalt (OIB) systematics, Geochem. Geophys. Geosyst., 13, Q09009, doi:10.1029/2012GC004268.Introduction:The supplement referred to in the text includes a worksheet in a single Excel 2004 (.xls) file, and a PDF (.pdf) file with figures illustrating the effects of different olivine fractionation correction schemes modify the composition of a melt.  The worksheet contains all geochemical data from Hawaiian lavas from Georoc--including major element abundances (both raw abundances and abundances following olivine fractionation correction) and isotopic ratios--remaining after applying the filters described in the text. The global OIB dataset used in Jackson and Dasgupta (2008) are also included for comparison.  Major element abundances for different olivine fractionation correction schemes are also included in the spreadsheet.  1. 2012gc004268-ds01.xlsData Set S1. All geochemical data and for Hawaiian lavas presented in the manuscript.2. 2012gc004268-fs01.pdfFigure S1. Hawaiian shield lavas are corrected for olivine fractionation/addition using three different methods. In the first column, lavas are corrected to a constant MgO (16 wt.%) using an olivine-melt Kd of 0.30. In the second column, lavas are corrected to a constant MgO (16 wt.%) using an olivine-melt Kd of 0.34.  In the third column, lavas are corrected to be in equilibrium with forsterite 90 olivine using an olivine-melt Kd of 0.30. Cumulates (Mg>20 wt.%) are corrected in the same manner in all plots by subtracting olivine of forsterite 87 composition. As shown in the figure, the correction scheme used does not greatly change the major element concentrations and the sense of the correlations is preserved. Symbols are the same as the manuscript.ReferencesJackson, M.G., and R. Dasgupta (2008), Compositions of HIMU, EM1, and EM2 from global trends between radiogenic isotopes and major elements in ocean island basalts, Earth Planet. Sci. Lett., 276, 175-186. 0.92 0.93 0.94 0.95 0.96 0.97 0.98 44 45 46 47 48 49 50 51 52 53 SiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5 2.7 208  Pb*/  206Pb*TiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 5 6 7 8 9 10 11 12 208  Pb*/  206 Pb*        CaO (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 8 9 10 11 12 13 14 15 208  Pb*/  206 Pb*        FeO (wt.%, at 16% MgO) Corrected to MgO=16 wt %using an olivine-melt Kd = 0.300.92 0.93 0.94 0.95 0.96 0.97 0.98 44 45 46 47 48 49 50 51 52 53 SiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5 2.7 TiO2 (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 5 6 7 8 9 10 11 12 CaO (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 8 9 10 11 12 13 14 15 FeO (wt.%, at 16% MgO) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 44 45 46 47 48 49 50 51 52 53 SiO2 (wt.%, at forsterite 90) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5 2.7 TiO2 (wt.%, at forsterite 90) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 5 6 7 8 9 10 11 12 CaO (wt.%, at forsterite 90) 0.92 0.93 0.94 0.95 0.96 0.97 0.98 8 9 10 11 12 13 14 15 FeO (wt.%, at forsterite 90)Corrected to MgO=16 wt %using an olivine-melt Kd = 0.34Corrected to be in equilibrium with forsterite 90 olivineusing an olivine-melt Kd = 0.30 208  Pb*/  206 Pb*          Jackson et al (2012), Fig. S1 file:///C|/Documents%20and%20Settings/bugeaud/Desktop/ggge2264-sup-0004-t01.txt[5/14/2014 11:25:52 AM]Table 1. Mean Isotopic and Major Element Compositions for Hawaiian Volcanoes Examined in This StudyaVolcano Island  143Nd/144Nd Average +/- 2SD     87Sr/86Sr Average +/- 2SD       206Pb/204Pb Average +/- 2SD     207Pb/204Pb Average +/- 2SD     208Pb/204Pb Average +/- 2SD     187Os/188Os Average +/- 2SD     176Hf/177Hf Average +/- 2SD     3He/4He (Ra) Average +/- 2SD    SiO2 (wt.%), 16% MgO, Average +/- 2SD   TiO2 (wt.%), 16% MgO, Average +/- 2SD   Al2O3 (wt.%), 16% MgO, Average +/- 2SD  FeO (wt.%), 16% MgO, Average +/- 2SD    MnO (wt.%), 16% MgO, Average +/- 2SD    MgO (wt.%), 16% MgO     CaO (wt.%), 16% MgO, Average +/- 2SD    Na2O (wt.%), 16% MgO, Average +/- 2SD   K2O (wt.%), 16% MgO, Average +/- 2SD    P2O5 (wt.%), 16% MgO, Average +/- 2SD   SiO2 (wt.%), Forsterite 90, Average +/- 2SD     TiO2 (wt.%), Forsterite 90, Average +/- 2SD     Al2O3 (wt.%), Forsterite 90, Average +/- 2SD    FeO (wt.%), Forsterite 90, Average +/- 2SD      MnO (wt.%), Forsterite 90, Average +/- 2SD      MgO (wt.%), Forsterite 90, Average +/- 2SD      CaO (wt.%), Forsterite 90, Average +/- 2SD      Na2O (wt.%), Forsterite 90, Average +/- 2SD     K2O (wt.%), Forsterite 90, Average +/- 2SD      P2O5 (wt.%), Forsterite 90, Average +/- 2SDHigh He Conc.   All He Conc.Loa-trend   Loihi (tholeiitic)   Big Island      0.512953 +/- 0.000070   0.703581 +/- 0.000131   18.376 +/- 0.133        15.468 +/- 0.030        38.118 +/- 0.122        0.1333 +/- 0.0046       0.283111 +/- 0.000013   27.3 +/- 7.3    27.2 +/- 7.0    47.19 +/- 1.48  2.06 +/- 0.28   10.32 +/- 0.70  12.19 +/- 0.98  0.17 +/- 0.09   16      9.59 +/- 1.33   1.88 +/- 0.31   0.40 +/- 0.21   0.19 +/- 0.05   46.94 +/- 1.72  1.97 +/- 0.25   9.90 +/- 1.31   12.10 +/- 0.93  0.16 +/- 0.08   17.36 +/- 2.50  9.18 +/- 1.39   1.80 +/- 0.37   0.38 +/- 0.20   0.19 +/- 0.05   Mauna Loa    Big Island      0.512906 +/- 0.000074   0.703809 +/- 0.000668   18.168 +/- 0.176        15.460 +/- 0.024        37.908 +/- 0.138        0.1356 +/- 0.0030       0.283078 +/- 0.000034   13.1 +/- 8.9    12.4 +/- 8.9    49.48 +/- 0.82  1.70 +/- 0.23   10.78 +/- 0.43  11.19 +/- 0.82  0.16 +/- 0.08   16      8.44 +/- 0.58   1.76 +/- 0.25   0.29 +/- 0.11   0.18 +/- 0.05   49.55 +/- 1.04  1.70 +/- 0.25   10.85 +/- 0.77  11.19 +/- 0.78  0.16 +/- 0.07   15.82 +/- 1.51  8.49 +/- 0.68   1.77 +/- 0.29   0.29 +/- 0.11   0.18 +/- 0.05   Hualalai     Big Island      0.512903 +/- 0.000051   0.703727 +/- 0.000086   18.182 +/- 0.132        15.459 +/- 0.025        37.951 +/- 0.159        0.1348 +/- 0.0016       0.283085 +/- 0.000034   NA      NA      49.60 +/- 0.49  1.71 +/- 0.10   10.76 +/- 0.47  10.92 +/- 0.62  0.17 +/- 0.08   16      8.59 +/- 0.41   1.75 +/- 0.15   0.31 +/- 0.12   0.17 +/- 0.03   49.71 +/- 0.77  1.72 +/- 0.13   10.87 +/- 0.85  10.90 +/- 0.59  0.17 +/- 0.07   15.70 +/- 1.71  8.68 +/- 0.65   1.77 +/- 0.18   0.31 +/- 0.12   0.17 +/- 0.03   Mahukona     Big Island      0.512962 +/- 0.000068   0.703639 +/- 0.000155   18.253 +/- 0.222        15.469 +/- 0.014        37.941 +/- 0.152        NA      0.283107 +/- 0.000041   21      18.2 +/- 9.3    48.42 +/- 2.54  1.92 +/- 0.53   11.04 +/- 1.01  11.41 +/- 1.52  0.16 +/- 0.04   16      8.56 +/- 1.57   1.89 +/- 0.30   0.35 +/- 0.14   0.22 +/- 0.09   48.48 +/- 2.78  1.93 +/- 0.51   11.07 +/- 1.43  11.34 +/- 1.39  0.16 +/- 0.04   15.97 +/- 2.37  8.59 +/- 1.86   1.90 +/- 0.33   0.35 +/- 0.13   0.22 +/- 0.09   Kahoolawe    Maui Nui        0.512848 +/- 0.000099   0.704120 +/- 0.000318   18.042 +/- 0.314        15.436 +/- 0.030        37.829 +/- 0.219        0.1439  0.282986 +/- 0.000043   NA      NA      49.01 +/- 1.62  1.74 +/- 0.38   10.93 +/- 0.72  11.67 +/- 1.22  0.15 +/- 0.03   16      8.20 +/- 0.98   1.84 +/- 0.26   0.25 +/- 0.13   0.18 +/- 0.05   49.02 +/- 1.94  1.73 +/- 0.36   10.89 +/- 1.08  11.59 +/- 1.09  0.15 +/- 0.03   16.20 +/- 1.67  8.17 +/- 1.19   1.83 +/- 0.23   0.25 +/- 0.12   0.18 +/- 0.04   Lanai        Maui Nui        0.512770 +/- 0.000121   0.704181 +/- 0.000316   17.922 +/- 0.098        15.437 +/- 0.016        37.753 +/- 0.057        NA      0.283002 +/- 0.000098   NA      NA      49.75 +/- 1.20  1.61 +/- 0.26   11.03 +/- 0.60  11.25 +/- 0.50  0.13 +/- 0.03   16      7.83 +/- 0.79   1.93 +/- 0.18   0.28 +/- 0.17   0.18 +/- 0.05   49.85 +/- 1.32  1.62 +/- 0.24   11.14 +/- 0.65  11.27 +/- 0.45  0.13 +/- 0.03   15.69 +/- 0.70  7.90 +/- 0.81   1.95 +/- 0.19   0.28 +/- 0.17   0.18 +/- 0.05   West Molokai Maui Nui        0.512943 +/- 0.000216   0.703819 +/- 0.000394   18.253 +/- 0.445        15.460 +/- 0.025        37.939 +/- 0.254        NA      0.283100 +/- 0.000137   NA      NA      49.18 +/- 1.25  1.87 +/- 0.17   10.87 +/- 0.12  11.01 +/- 1.20  0.15 +/- 0.04   16      8.53 +/- 1.21   1.85 +/- 0.37   0.29 +/- 0.18   0.20 +/- 0.07   49.47 +/- 1.55  1.92 +/- 0.20   11.17 +/- 0.66  10.93 +/- 1.20  0.16 +/- 0.05   15.19 +/- 1.82  8.76 +/- 1.48   1.91 +/- 0.43   0.30 +/- 0.18   0.21 +/- 0.07   Koolau (Makapuu)     Oahu    0.512757 +/- 0.000077   0.704082 +/- 0.000315   17.854 +/- 0.074        15.438 +/- file:///C|/Documents%20and%20Settings/bugeaud/Desktop/ggge2264-sup-0004-t01.txt[5/14/2014 11:25:52 AM]0.026        37.773 +/- 0.071        0.1426 +/- 0.0075       0.282962 +/- 0.000042   NA      13.1 +/- 3.5    50.22 +/- 0.87  1.70 +/- 0.23   11.01 +/- 0.64  10.87 +/- 1.22  0.13 +/- 0.04   16      7.26 +/- 0.95   2.16 +/- 0.40   0.40 +/- 0.19   0.23 +/- 0.06   50.44 +/- 1.31  1.73 +/- 0.23   11.26 +/- 1.15  10.90 +/- 1.08  0.13 +/- 0.04   15.28 +/- 1.88  7.42 +/- 1.03   2.21 +/- 0.47   0.41 +/- 0.19   0.23 +/- 0.06   Koolau (KSDP)        Oahu    0.512917 +/- 0.000083   0.703760 +/- 0.000173   18.063 +/- 0.081        15.453 +/- 0.007        37.837 +/- 0.051        NA      0.283048 +/- 0.000057   NA      NA      49.53 +/- 1.17  1.75 +/- 0.24   10.96 +/- 0.48  10.99 +/- 0.60  0.15 +/- 0.05   16      8.25 +/- 0.58   1.90 +/- 0.19   0.28 +/- 0.11   0.17 +/- 0.05   49.73 +/- 1.41  1.79 +/- 0.21   11.20 +/- 0.65  11.01 +/- 0.61  0.15 +/- 0.05   15.30 +/- 0.92  8.42 +/- 0.50   1.94 +/- 0.21   0.29 +/- 0.12   0.18 +/- 0.05   Koolau (Nuuanu Landslide)    Oahu    0.512972 +/- 0.000059   0.703568 +/- 0.000161   18.204 +/- 0.366        15.448 +/- 0.017        37.883 +/- 0.240        0.1337 +/- 0.0056       0.283108 +/- 0.000039   NA      NA      48.43 +/- 1.33  1.91 +/- 0.24   10.94 +/- 0.34  11.48 +/- 0.76  0.16 +/- 0.05   16      8.76 +/- 0.65   1.82 +/- 0.15   0.28 +/- 0.16   0.18 +/- 0.05   48.49 +/- 1.49  1.91 +/- 0.29   10.94 +/- 0.83  11.37 +/- 0.75  0.16 +/- 0.04   16.08 +/- 2.06  8.77 +/- 1.02   1.82 +/- 0.21   0.29 +/- 0.16   0.18 +/- 0.06   Waianae      Oahu    0.512975 +/- 0.000126   0.703648 +/- 0.000194   18.146 +/- 0.206        15.461 +/- 0.037        37.856 +/- 0.117        NA      NA      NA      NA      48.29 +/- 1.81  2.15 +/- 0.31   11.26 +/- 1.01  11.34 +/- 1.13  0.13 +/- 0.03   16      8.05 +/- 1.35   2.01 +/- 0.44   0.47 +/- 0.23   0.27 +/- 0.16   48.35 +/- 2.02  2.17 +/- 0.26   11.33 +/- 0.98  11.34 +/- 0.93  0.13 +/- 0.02   15.81 +/- 1.41  8.11 +/- 1.49   2.03 +/- 0.43   0.47 +/- 0.21   0.27 +/- 0.15   Kauai        Kauai   0.512969 +/- 0.000056   0.703671 +/- 0.000229   18.228 +/- 0.166        15.451 +/- 0.015        37.939 +/- 0.098        0.1368 +/- 0.0038       0.283081 +/- 0.000039   NA      22.6 +/- 6.2    48.95 +/- 1.72  1.95 +/- 0.26   10.71 +/- 0.52  11.57 +/- 1.69  0.17 +/- 0.08   16      8.31 +/- 0.92   1.81 +/- 0.29   0.29 +/- 0.16   0.21 +/- 0.06   48.87 +/- 2.47  1.93 +/- 0.33   10.56 +/- 1.51  11.52 +/- 1.62  0.16 +/- 0.06   16.50 +/- 3.42  8.17 +/- 1.06   1.79 +/- 0.40   0.29 +/- 0.17   0.21 +/- 0.06Kea-trend   Kilauea      Big Island      0.512958 +/- 0.000027   0.703584 +/- 0.000099   18.464 +/- 0.205        15.483 +/- 0.055        38.104 +/- 0.189        0.1310 +/- 0.0017       0.283101 +/- 0.000018   11.6 +/- 2.0    12.5 +/- 4.1    48.62 +/- 0.89  1.99 +/- 0.27   10.61 +/- 0.40  11.51 +/- 0.68  0.15 +/- 0.04   16      8.74 +/- 0.58   1.79 +/- 0.23   0.36 +/- 0.09   0.20 +/- 0.04   48.62 +/- 1.05  1.99 +/- 0.25   10.59 +/- 0.68  11.48 +/- 0.62  0.15 +/- 0.03   16.10 +/- 1.17  8.72 +/- 0.61   1.79 +/- 0.26   0.36 +/- 0.09   0.20 +/- 0.04   Mauna Kea    Big Island      0.512968 +/- 0.000036   0.703584 +/- 0.000094   18.497 +/- 0.181        15.483 +/- 0.025        38.104 +/- 0.171        0.1297 +/- 0.0011       0.283122 +/- 0.000028   13.7 +/- 8.7    12.4 +/- 7.2    48.54 +/- 1.19  2.06 +/- 0.28   10.55 +/- 0.53  11.47 +/- 0.68  0.18 +/- 0.07   16      8.87 +/- 0.86   1.78 +/- 0.25   0.31 +/- 0.16   0.21 +/- 0.05   48.55 +/- 1.44  2.05 +/- 0.28   10.50 +/- 0.97  11.39 +/- 0.65  0.18 +/- 0.06   16.24 +/- 1.83  8.82 +/- 0.93   1.77 +/- 0.26   0.31 +/- 0.16   0.21 +/- 0.05   Kohala       Big Island      0.513015 +/- 0.000000   0.703710 +/- 0.000087   18.170 +/- 0.276        15.460 +/- 0.041        37.845 +/- 0.148        0.1365 +/- 0.0115       NA      NA      NA      48.42 +/- 2.86  1.89 +/- 0.47   11.31 +/- 1.30  11.30 +/- 1.07  0.16 +/- 0.04   16      8.69 +/- 0.33   1.67 +/- 0.37   0.33 +/- 0.16   0.21 +/- 0.12   48.43 +/- 2.96  1.89 +/- 0.43   11.30 +/- 1.36  11.28 +/- 1.04  0.15 +/- 0.04   16.06 +/- 1.46  8.69 +/- 0.57   1.66 +/- 0.35   0.33 +/- 0.15   0.21 +/- 0.11   Haleakala    Maui Nui        0.512958 +/- 0.000040   0.703645 +/- 0.000194   18.541 +/- 0.220        15.480 +/- 0.019        38.154 +/- 0.183        0.1304 +/- 0.0000       NA      17.6 +/- 2.8    18.5 +/- 4.3    48.33 +/- 1.38  2.17 +/- 0.39   10.78 +/- 0.59  11.56 +/- 1.13  0.17 +/- 0.09   16      8.66 +/- 0.89   1.75 +/- 0.27   0.33 +/- 0.11   0.22 +/- 0.06   48.30 +/- 1.81  2.15 +/- 0.47   10.67 +/- 1.03  11.49 +/- 1.07  0.17 +/- 0.07   16.36 +/- 2.52  8.57 +/- 1.01   1.73 +/- 0.35   0.33 +/- 0.12   0.22 +/- 0.06   West Maui    Maui Nui        0.513025 +/- 0.000048   0.703550 +/- 0.000140   18.431 +/- 0.142        15.483 +/- 0.031        37.957 +/- 0.128        0.1321 +/- 0.0011       0.283127 +/- 0.000027   NA      NA      47.36 +/- 1.50  2.04 +/- 0.35   10.76 +/- 0.86  12.19 +/- 1.34  0.16 +/- 0.06   16      9.08 +/- 1.14   1.84 +/- 0.35   0.32 +/- 0.21   0.23 +/- 0.08   47.20 +/- 1.80  1.98 +/- 0.33   10.43 +/- 1.45  12.07 +/- 1.18  0.15 +/- 0.05   17.07 +/- 2.33  8.79 +/- 1.11   1.78 +/- 0.38   0.31 +/- 0.20   0.22 +/- 0.07   East Molokai Maui Nui        0.512981 +/- 0.000083   0.703565 +/- 0.000207   18.437 +/- 0.410        15.480 +/- 0.032        38.060 +/- 0.255        NA      0.283125 +/- 0.000052   NA      NA      48.51 +/- 0.99  1.92 +/- 0.23   10.87 +/- 0.68  11.26 +/- 1.19  0.15 +/- 0.08   16      8.99 +/- 1.23   1.77 +/- 0.32   0.31 +/- 0.24   0.20 +/- 0.08   48.51 +/- 1.25  1.92 +/- 0.28   10.86 +/- 1.48  11.27 +/- 1.14  0.15 +/- 0.06   16.05 +/- 2.54  8.97 +/- 1.46   1.76 +/- 0.37   0.30 +/- 0.23   0.20 +/- 0.07file:///C|/Documents%20and%20Settings/bugeaud/Desktop/ggge2264-sup-0004-t01.txt[5/14/2014 11:25:52 AM]aMeans and the standard deviations (SD, 2 sigma) are from Data Set S1. If the standard deviation is not reported, it is because only a single measurement is available. Major element compositions are corrected for olivine fractionation/addition to a constant MgO (16 wt.%) or to be in equilibrium with a forsterite 90 olivine composition (but the two different correction schemes yield similar major element compositions). An olivine-melt Kd of 0.30 is used for correction. Data for samples are excluded if the whole rock is altered, highly evolved, or if the major element data are incomplete or the analyses yields high or low totals (see text for filters applied). Helium and Os isotope data exist for many of the volcanoes listed as NA in the table, but in several cases, corresponding major element data does not exist, or indicates excessive magmatic evolution or post-eruptive alteration, and the He and Os data are not reported. Sr, Nd, Pb and Hf isotopes are not filtered based on trace element concentrations. In one column, helium isotopic ratios for samples with low helium concentrations (<2*10-8 cc 4 He/g STP) are not reported ("High He conc"). However, helium isotopic ratios with lower concentrations are preserved in the next column ("All He conc") and in Data Set S1. Os isotopes are excluded if the Os concentration is <40 ppt.

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