Early mantle heterogeneities in the Réunion hotspot source inferred from highly siderophile elements in cumulate xenoliths

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Early mantle heterogeneities in the Réunion hotspot source inferred from highly siderophile elements in cumulate xenoliths Bradley J. Peters a,∗ , James M.D. Day a , Lawrence A. Taylor b a b

Scripps Isotope Geochemistry Laboratory, Geosciences Research Division, Scripps Institution of Oceanography, UCSD, La Jolla, CA 92093, USA Planetary Geosciences Institute, Department of Earth and Planetary Sciences, University of Tennessee, Knoxville, TN 37996, USA

a r t i c l e

i n f o

Article history: Received 20 February 2016 Received in revised form 5 May 2016 Accepted 9 May 2016 Available online xxxx Editor: B. Marty Keywords: non-chondritic mantle highly siderophile elements Os isotopes ocean island basalts Réunion hotspot cumulate xenoliths

a b s t r a c t Ultramafic cumulate rocks form during intrusive crystallization of high-MgO magmas, incorporating relatively high abundances of compatible elements, including Cr and Ni, and high abundances of the highly siderophile elements (HSE: Os, Ir, Ru, Pt, Pd, Re). Here, we utilize a suite of cumulate xenoliths from Piton de la Fournaise, La Réunion (Indian Ocean), to examine the mantle source composition of the Réunion hotspot using HSE abundances and Os isotopes. Dunite and wherlite xenoliths and associated lavas from the Piton de la Fournaise volcanic complex span a range of MgO contents (46 to 7 wt.%), yet exhibit remarkably homogeneous 187 Os/188 Os (0.1324 ± 0.0014, 2σ ), representing the Osisotopic composition of Réunion hotspot primary melts. A significant fraction of the xenoliths also have primitive upper-mantle (PUM) normalized HSE patterns with elevated Ru and Pd (PUM-normalized Ru/Ir and Pd/Ir of 0.8–6.3 and 0.2–7.2, respectively). These patterns are not artifacts of alteration, fractional crystallization, or partial melting processes, but rather require a primary magma with similar relative enrichments. Some highly olivine-phyric (>40 modal percent olivine) Piton de la Fournaise lavas also preserve these relative Ru and Pd enrichments, while others preserve a pattern that is likely related to sulfur saturation in evolved melts. The estimate of HSE abundances in PUM indicates high Ru/Ir and Pd/Pt values relative to carbonaceous, ordinary and enstatite chondrite meteorite groups. Thus, the existence of cumulate rocks with even more fractionated HSE patterns relative to PUM suggests that the Réunion hotspot samples a yet unrecognized mantle source. The origin of fractionated HSE patterns in Réunion melts may arise from sampling of a mantle source that experienced limited late accretion (<0.2% by mass) compared with PUM (0.5–0.8%), possibly involving impactors that were distinct from present-day chondrites, or limited core–mantle interactions. Given the remarkably homogeneous Os, Pb, and noble-gas isotopic signatures of Réunion, which plot near the convergence point of isotopic data for many hotspots, such a conclusion provides evidence for an early differentiated and subsequently isolated mantle domain that may be partially sampled by some ocean island basalts. © 2016 Elsevier B.V. All rights reserved.

1. Introduction Geochemical studies of lavas from hotspot volcanoes have yielded information that is foundational to knowledge about Earth’s deep mantle. In particular, high-3 He/4 He (e.g., Kurz et al., 1982; Hilton et al., 1999; Stuart et al., 2003), solar-like 20 Ne/22 Ne (Moreira and Kurz, 2001) (Fig. 1), or coupled 186 Os–187 Os enrichments in some ocean-island basalt (OIB) lavas (e.g., Walker et al., 1995; Brandon et al., 1998, 1999; Ireland et al., 2011) have been interpreted as potential indicators of deep-mantle

*

Corresponding author. Tel.: +1 858 534 8580. E-mail address: [email protected] (B.J. Peters).

http://dx.doi.org/10.1016/j.epsl.2016.05.015 0012-821X/© 2016 Elsevier B.V. All rights reserved.

source signatures (e.g., Craig and Lupton, 1976; Kurz et al., 1982; Humayun, 2011). However, these signatures have not been clearly linked to early-formed, relatively primitive or minimally depleted reservoirs that are distinct from the upper, depleted MORB mantle (DMM). Positive identification of deep- or primitive-mantle sources to volcanism has proven difficult because, apart from noble gases, the majority of isotope systems measured routinely in OIB (e.g., Sr–Nd–Hf–Pb) are broadly lithophile in character. As a result, they tend to be enriched in crustal or sedimentary rocks (μg g−1 ) which, when they are assimilated into magmas, can overwhelm isotopic or elemental signatures imparted from ‘peridotitic’ mantle sources (<μg g−1 ). One way to circumvent this problem is to measure highly siderophile elements (HSE: Os, Ir, Ru, Pt, Pd, Re), many of which exhibit compatible behav-

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Fig. 1. (A) The Sr–Nd–Pb isotope mantle tetrahedron, showing the location of Mauritius (white field) and Réunion (Piton de la Fournaise – black field superimposed on the Mauritius field) relative to other selected OIB locations; (B) noble-gas characteristics of Réunion basalts (Kaneoka et al., 1986; Staudacher et al., 1990) compared with Loihi basalts (Honda et al., 1993) and the solar noble gas signature (Moreira and Kurz, 2001); (C) 206 Pb/204 Pb–207 Pb/204 Pb characteristics of Réunion and Mauritius basalts compared to those of other hotspots, isochrons calculated using μ = 8.0; (D) 206 Pb/204 Pb–208 Pb/204 Pb characteristics of Réunion and Mauritius basalts compared to those of other OIB (κ = 232 Th/238 Pb = 4.0).

ior, in OIB. The HSE represent a suite of geochemically similar, highly to moderately compatible elements, which can be dominated by mantle (peridotite/pyroxenite) components in OIB, due to the corresponding low concentrations of these elements in crustal rocks (Day, 2013). The potential for using the HSE and the radiogenic 187 Re–187 Os and 190 Pt–186 Os systems that are embedded within the HSE to examine deep-mantle contributions to hotspot volcanic rocks has been previously recognized (Walker et al., 1994, 1995; Brandon et al., 1998, 1999; Ireland et al., 2011; Humayun, 2011). However, a significant impediment has been that relatively low concentrations of these elements are preserved in many OIB lavas, since the HSE are efficiently removed during fractional crystallization. This leads to compatible HSE (Os, Ir, Ru) concentrations about an order of magnitude less in OIB lavas than in their mantle sources and complicates interpretations of HSE signatures (Day, 2013). A novel means with which to elucidate the composition of hotspot mantle sources is to use cumulate rocks that can be found as xenoliths within OIB lavas. Cumulate xenoliths are formed by fractional crystallization of early-crystallizing mineral phases such as spinel, olivine, and pyroxene during the ascent of mantle-derived melts to the surface, and may additionally host HSE-bearing sulfides. For this reason, cumulate rocks tend to be relatively enriched in compatible elements and leave a magma residuum that possesses a significantly different composition than before fractional crystallization, becoming progressively depleted in compatible major-, minor-, and trace-elements as crystallization progresses (e.g., Wager et al., 1960; Jackson and Wright, 1970). Additionally, because cumulate phases are fractionated early in magma ascent, they are less susceptible to crustal contamina-

tion than extrusive lavas. The abundance of cumulate rocks at many hotspots, including Hawaii (e.g., Clague, 1988), the Canary Islands (e.g., Widom et al., 1999; Day et al., 2010), the Azores (Mattioli et al., 1997), and Réunion (e.g., Babkine et al., 1966; Upton and Wadsworth, 1972) provides a means to quantitatively evaluate the composition of hotspot parental magmas. In this contribution, we appraise aspects of the composition of the Réunion primary magma through combined analysis of cumulate xenoliths and associated lavas. Compared with other oceanisland locations, the Réunion hotspot has been noted for its remarkable isotopic homogeneity in terms of He (e.g., Graham et al., 1990; Füri et al., 2011), Sr (e.g., McDougall and Compston, 1965; Albarède and Tamagnan, 1988; Fisk et al., 1988; Albarède et al., 1997), Nd (e.g., Fisk et al., 1988; Albarède et al., 1997; Luais, 2004; Bosch et al., 2008), Pb (e.g., Vlastélic et al., 2005, 2007, 2009), and Os isotopes (Roy-Barman and Allègre, 1995; Schiano et al., 2012; Gannoun et al., 2015) signatures that persist even in submarine strata (Fretzdorff and Haase, 2002). Additionally, Réunion plots near the center of the Sr–Nd–Pb isotopic arrays of hotspots (Bosch et al., 2008), rather than displaying a pronounced affinity for one or more of the recognized mantle end-members (Fig. 1). Geochemical evidence, including limited 187 Os/188 Os variations that are marginally more radiogenic than modern-day chondrites (Roy-Barman and Allègre, 1995; Schiano et al., 2012; Gannoun et al., 2015), and a broadly chondritic Th/U signature (Vlastélic et al., 2006) supports a negligible role for recycled materials in the Réunion mantle source. Rather than channeling a mixed signal from multiple mantle-source domains, as inferred for many other OIB, it is possible that Réunion magmas are derivates of a mantle source that has been effectively isolated from recycling processes through

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much of Earth history. Consistent with this hypothesis, Réunion magmatic products lie on a ∼4.4 Ga geochron in Pb isotope space (Fig. 1C; Supplementary Materials). We show that this ancient source also preserves early mantle HSE heterogeneities and Re/Os that make it distinct from the bulk silicate Earth estimate derived from mantle peridotites (Becker et al., 2006). 2. Samples and methods A total of 29 cumulate and 13 associated basaltic lava samples from Piton de la Fournaise were selected for study. Petrography and modal analysis were performed at the Scripps Isotope Geochemistry Laboratory (SIGL), Scripps Institution of Oceanography, using identical protocols to those described in Day et al. (2014). Majorand minor-element mineral compositions were obtained primarily from polished mounts containing olivine, clinopyroxene, and spinel, and as polished-thick sections, at the University of Tennessee using a Cameca SX 100 electron microprobe analyzer. A total of 430 olivine, 294 clinopyroxene, and 246 spinel grains were analyzed in cumulate xenolith samples. Bulk-rock major- and select trace-element abundance analyses were performed by X-ray fluorescence (XRF) at Franklin and Marshall University using a PW 2404 PANalytical XRF vacuum spectrometer, following the procedures outlined in Boyd and Mertzman (1987). Trace-element mineral and bulk-rock analyses were performed at the SIGL. Silicate, oxide, and sulfide phases were measured for the HSE, Cu and W by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in samples CH0701Dunite and CH0706B. Bulk-rock trace-element abundances were determined on 100 mg of homogenized powder, using analytical procedures similar to those described in Day et al. (2014), and utilizing a ThermoScientific iCAPq-c quadrupole inductively coupled plasma mass spectrometer (ICP-MS) in standard mode. Bulk-rock osmium isotope and HSE abundance analyses were performed on ∼1 g of homogenized powder according to methods described in Day et al. (2016) and were appropriately oxide and blank corrected. Precision for 187 Os/188 Os, determined by repeated measurement of a 35 pg UMCP Johnson–Matthey standard was better than ±0.3% for cumulate runs (2σ ; 0.11381 ± 0.00032; n = 12). Repeated measurement of this standard during analyses of RU07 and RU15 samples, which took place several months after analyses of CH07 samples, averaged 187 Os/188 Os = 0.11408 ± 0.00017 (n = 5) and samples measured at this time were normalized to a standard measurement of 0.11381 to enable comparisons between these data. Run statistics for HSE generally indicate <5% relative standard deviation. Average HSE blanks for cumulate analyses were (in pg): 14.5 ± 14 [Os], 74.8 ± 86 [Ir], 109 ± 34 [Ru], 50.5 ± 18.7 [Pt], 37.3 ± 57.4 [Pd], and 8.9 ± 4.6 [Re]. Full methods information along with tabulated run statistics can be found in the Supplementary Materials. 3. Results Tabulated whole-rock and mineral geochemical and isotopic data and associated figures are provided in the Supplementary Materials. Most of the studied Piton Chisny cumulate xenoliths are equigranular dunites with low clinopyroxene contents (0.6–3.1 modal %). Two samples, CH0701Dunite and CH0703Dunite, have relatively high abundances of clinopyroxene (∼2–3 modal %). Sample CH0703B is the sole wherlite of the suite, and possesses distinct mineral chemistry. Approximately one-third of the dunites have a yellow–green color, and the remaining samples are weakly to strongly discolored with a reddish–purple hue. There are, however, no clear distinctions between the bulk chemistry of any of the dunite samples (Supplementary Materials). Roughly one-third of the cumulate xenoliths contain trace sulfide that is observable

Fig. 2. Example of major-element variations for Piton Chisny lavas (circles) and Piton de la Fournaise lavas (squares).

in thin section. Sulfide grains occur primarily as silicate-hosted grains (generally <10 μm diameter) with rare, larger interstitial sulfide (up to 50 μm diameter). The large sulfides typically display subequal proportions of pentlandite and pyrrhotite, with rare chalcopyrite occurring exclusively in olivine-hosted grains. Forsterite contents of the cumulate xenoliths span a restricted range from Fo80 to Fo89 and are generally more Mg-rich than those of Piton de la Fournaise lavas (Fo84.0±0.9 ) (Füri et al., 2011); wherlite sample CH0703B has the lowest forsterite contents (Fo82.0±0.9 ), while discolored dunite sample CH0706A has the highest forsterite contents (Fo88.1±0.3 ). Olivine formula units of Ca average 0.03 and are consistent across samples. Ranges for pyroxene compositions are En44–51 Wo39–49 Fs5–11 , with no distinguishable differences between rock type or coloration. Spinels are highly chromian, with an average Cr# of 57 ± 5 (1σ ). Piton Chisny xenoliths have high bulk-rock MgO contents (33.1 to 46.4 wt.%, Fig. 2) and low SiO2 contents (37.5 to 41.1 wt.%), with a range of Mg-numbers (82.7 to 91.0). Most samples have low CaO contents (0.26 to 1.08 wt.%), except those with significant clinopyroxene accumulation (e.g., CH0701Dunite, CH0703B and CH0703Dunite; 1.81 to 7.74 wt.%). Wherlite sample CH0703B has lower proportions of Fe2 O3 (T) and MgO compared with the other Piton Chisny xenoliths, reflecting greater accumulation of pyroxene and/or amphibole relative to olivine. Correlations between MgO and Fe2 O3 (T), along with elevated concentrations of Ni and Cr, reflect the importance of olivine accumulation over the accumulation of other mineral phases. Relatively high levels of moderately incompatible elements (e.g., Sc, V, Zn) may reflect additional influence from Cr-spinel and clinopyroxene fractionation. For many major- and trace-element systems, the xenolith and lava samples share a common differentiation trend (e.g., Fig. 2). A brief discussion of the major-element characteristics of Piton de la Fournaise lavas is provided in the Supplementary Materials. Concentrations of the rare earth elements (REE) in the cumulate xenoliths are depleted relative to Réunion lavas and to primitive mantle (Fig. 3). The xenoliths display a dominant trough-like pattern, reflecting REE compatibility in olivine and a subordinate, concave-down pattern, reflecting REE compatibility in clinopyroxene. Lava samples display a range in absolute REE concentrations, but highly consistent relative abundances of the REE with primitive mantle-normalized La/Yb varying from 5.0 to 6.9. Concentrations of elements enriched in crustal materials, such as W (1–50 ng g−1 ) are low in the cumulate xenoliths. The xenoliths 0.5 have positive Ta anomalies (Ta/Ta∗ = [Ta/(Th × La)]PM = 0.91–2.92; PM indicates normalization to primitive mantle for the respective elements) (McDonough and Sun, 1995), variable Pb anomalies 0.5 (Pb/Pb∗ = [Pb/(La × Nd)]PM = 0.06–28.9) and negative Sr anoma-

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Fig. 3. Primitive mantle-normalized trace element variation and rare earth element diagrams for Piton Chisny cumulate xenoliths (A, B) and Piton de la Fournaise lavas (C, D). Primitive-mantle normalization from McDonough and Sun (1995).

0.5 lies (Sr/Sr∗ = [Sr/(Pr × Hf)]PM = 0.13–1.01). Lavas preserve positive ∗ Ta anomalies (Ta/Ta = 1.67–1.86) and flat-to-negative Sr anomalies (Sr/Sr∗ = 0.84–0.95), but possess strongly negative Pb anomalies (Pb/Pb∗ = 0.26–0.45) that do not correlate with chalcophileelement abundances (Supplementary Materials). Differences between “canonical” trace-element ratios in Réunion OIB compared to other OIB indicate that mineral fractionation processes have a dominant effect on incompatible-element compositions; for example, Nb/U values (37.0–42.5) are relatively low with respect to typical OIB (Nb/U = 52 ± 11) (Hofmann, 2007). Correlations between Cu and ratios of chalcophile elements indicate that sulfide phases exert control over the abundances of certain trace elements in all samples (Fig. 4, Supplementary Materials), despite a lack of observed sulfide in some polished thin sections. In situ measurements of oxides by LA-ICP-MS indicate that these phases contain appreciable Cu and may be partially responsible for Cu abundances in the cumulate xenoliths (Supplementary Information). Piton Chisny cumulate xenoliths contain between 0.27 to 3.9 ng g−1 Os ([Os/Ir]PUM = 2.7 ± 1.5, 1σ ) and generally elevated abundances of Ru (0.9 to 5.93 ng g−1 , [Ru/Ir]PUM = 2.6 ± 1.4) and Pd (0.21 to 21.3 ng g−1 , [Pd/Ir]PUM = 2.1 ± 1.9, 2σ ). Iridium abundances range from 0.14 to 3.1 ng g−1 , and Re abundances are generally low, ranging from 0.001 to 0.266 ng g−1 . Abundances of Pt in xenoliths vary widely from 0.08 to 13.3, with [Pt/Ir]PUM = 1.0 ± 1.0. Host lavas show a similar relative range of HSE abundances, but have generally lower absolute abundances (Ru = 0.156 to 1.42 ng g−1 ; Pd = 0.65 to 10 ng g−1 ). Concentrations of Re in the lavas are generally higher (0.045 to 2.48 ng g−1 ) than in the cumulate xenoliths. Primitive upper-mantle-normalized HSE patterns for

the majority of cumulate xenoliths exhibit a dominant “sawtooth” pattern with relative enrichments in Ru and Pd, and subordinate patterns lacking relative Pd enrichments or containing relative Re enrichments (Fig. 5). Parameterizations of these patterns show no relationship to each other, or to tracers of lithophile and chalcophile differentiation processes, or long-term Re/Os fractionation (Supplementary Materials). The PUM-normalized HSE patterns of lavas show that some samples have similar sawtooth patterns to the cumulate xenoliths; others have hyperbolic distributions of the HSE, with high relative enrichments in Re, and some are a hybrid of these two patterns (Fig. 5). Cumulate xenoliths and lavas have a narrow range of 187 Os/ 188 Os values that are indistinguishable from one another (0.1324 ± 0.0014, n = 33, and 0.1325 ± 0.0015, n = 11, respectively; standard deviations are 2σ ). These values are consistent with published Osisotopic data for Réunion lavas (0.1325 ± 0.0029, n = 57) (Schiano et al., 2012; Gannoun et al., 2015), indicating that magmatic fractionation is unlikely to affect the Os-isotopic compositions of Piton de la Fournaise lavas (e.g., Gannoun et al., 2015). Measured 187 Os/188 Os values are greater than both the estimate of the primitive upper mantle [187 Os/188 Os = 0.1296 ± 0.0008; e.g., Meisel et al., 2001] and chondrites (e.g., Horan et al., 2003), with average cumulate and lava γ Os1 values of 3.8 ± 1.1 and 3.9 ± 1.2, respectively, relative to chondrite (187 Os/188 Os = 0.12757). Nonetheless, the Réunion hotspot source is less radiogenic than 187 Os/188 Os measured at many other hotspot localities, in particular HIMU-

187

1

γ Os = [

( 188 Os )Sample ( T ) (

Os 187 O s ) (T ) 188 O s Mantle

− 1] · 100, T indicates isotopic compositions at time, T .

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Pd and Re enrichments measured in Piton Chisny cumulate xenoliths. 4.1. Post-magmatic alteration and petrogenetic controls on cumulate xenoliths and lavas

Fig. 4. Co-variations of Cu and chalcophile element ratios in Piton Chisny cumulate xenoliths. Symbols as in Fig. 2. Correlation coefficients are (A) r 2 = 0.77 and (B) r 2 = 0.86.

type OIB (e.g., Hauri and Kurz, 1997; Mukhopadhyay et al., 2003; Lassiter et al., 2003; Gaffney et al., 2005; Day et al., 2009, 2010; Ireland et al., 2009, 2011; Day, 2013), but are more radiogenic than classic EM2-type OIB lavas from Samoa (e.g., Jackson and Shirey, 2011). 4. Discussion The petrological and geochemical characteristics of the ultramafic xenoliths found at Piton Chisny are consistent with an accumulative origin. They exhibit petrological characteristics of cumulate rocks including association of olivine and clinopyroxene and lack of orthopyroxene, which is more common in upper mantle rocks. Olivine in equilibrium with depleted upper mantle are expected to have ∼Fo89.5 (Workman and Hart, 2005) or greater, while the average of Piton Chisny xenoliths is less than Fo85 . This average is indistinguishable from cumulates extracted in the Grand Brûlé drill core, which records a continuous sequence of basalt–gabbro–dunite/wherlite under the Piton de la Fournaise terrain (Augé et al., 1989; Rançon et al., 1989). Most importantly, the xenoliths and lavas share common differentiation trajectories (Fig. 2, Supplementary Materials), implying that they share a mutual primary-magma composition. The conclusion that the xenoliths are cumulate rocks is consistent with assumptions of noble-gas studies that have employed Piton Chisny xenoliths to study Réunion mantle sources, showing high-3 He/4 He and near-Solar 20 Ne/22 Ne (Trieloff et al., 2002; Buikin et al., 2005; Füri et al., 2011). In the following discussion, post-magmatic alteration effects and cumulate petrogenetic processes are considered, followed by an assessment of the possible causes for relative Ru,

In Piton Chisny cumulate xenoliths, the most obvious effect of alteration is the strong red to purple discoloration present in some xenoliths. Although the discoloration is not clearly correlated with changes in modal mineralogy, it is most commonly found in intergranular spaces, implying it resulted from fluid-mediated alteration processes. The similarity in the bulk geochemistry of fresh and discolored cumulate xenoliths demonstrates that this modification was largely isochemical, but that it caused local oxidation to some cumulate xenoliths. For example, average Fe2+ /Fe∗ (molar proportion of ferrous to total Fe) is essentially indistinguishable between discolored and fresh samples (0.92 ± 0.03 versus 0.88 ± 0.05), and both types of xenolith exhibit relatively low levels of oxidation compared to lavas (0.1 to 0.97). Bulk-rock abundances of transition metals and spinel Fe3+ contents are also similar between the fresh and discolored groups. However, intergrowth patterns occur on silicate-spinel boundaries, which may arise from replacement of ferrous Fe near the edges of olivine grains (Supplementary Materials). Small quantities of these oxidized minerals, therefore, appear capable of producing the large color difference observed in the cumulate xenoliths, without significantly affecting their bulk chemistry. Critically, 187 Os/188 Os values and the HSE-pattern sub-groups do not vary systemically between the fresh and the discolored xenoliths, suggesting that late-stage alteration to some cumulate xenoliths did not strongly affect HSE compositions. Post-emplacement infiltration of basaltic melt can also affect the bulk geochemistry of cumulate rocks before they have fully compacted (e.g., Mathez, 1995; Holness et al., 2007), and may equally disturb the geochemistry of an entire sample suite. Mineralogical evidence for this process, such as the presence of plagioclase or other fine-grained material, is absent in Piton Chisny cumulate xenoliths. Piton Chisny cumulate xenoliths have low Al2 O3 (<1 wt.%, except wherlite sample CH0703B, which has 1.72 wt.%), and this element is uncorrelated to HSE abundances or Ru/Ir, Pd/Pt and Re/Pd. This excludes the possibility that the HSE patterns are affected by basaltic-melt infiltration processes. Additionally, concentrations of all HSE are uncorrelated to 187 Os/188 Os, diminishing the possibility that Os isotopes were perturbed by melt infiltration. For the lavas, it is likely that some Re loss has occurred through degassing under high f O2 conditions (e.g., Bennett et al., 2000; Lassiter et al., 2003; Norman et al., 2004; Day et al., 2010; Gannoun et al., 2015), but this is probably not a concern for the deeply crystallized cumulates (Supplementary Materials). Rare earth element patterns show clear mineralogical control and many of the features of major- and trace-element concentrations in the cumulate xenoliths can be attributed to element compatibility in olivine (Supplementary Materials). Those dunites that contain little clinopyroxene have concave-up patterns, whereas the three samples with significant clinopyroxene have concave-down patterns. This latter pattern is consistent with element compatibility in clinopyroxene, which is known to have a preference for the middle REE relative to the light and heavy REE (e.g., Fujimaki et al., 1984) compared to olivine. The REE are also generally more incompatible in olivine than in clinopyroxene, meaning that even a small modal volume of clinopyroxene can control the REE composition of a dunite. Concentrations of the lightest and heaviest REE are broadly similar between the two groups, demonstrating that mineral fractionation alone is insufficient to overcome pervasive negatively sloped REE patterns likely present in the OIB parental magma. Indeed, normalized REE abundances in Piton de la Fournaise lavas are remarkably smooth with limited variation

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Fig. 5. Primitive upper-mantle normalized highly siderophile element patterns for Piton Chisny cumulate xenoliths (A–C, symbol colors as in Fig. 2) and Piton de la Fournaise lavas (D–F, symbols color coded according to modal proportion of olivine using the scale in panel D). Primitive mantle normalization from Becker et al. (2006).

in absolute abundances (LaN /YbN = 5.0–6.9; Fig. 3), highlighting the homogeneity of Réunion partial melts. Ubiquitous positive Ti anomalies in cumulate xenoliths (Ti/Ti∗ = 1.01–6.89), which are mediated by olivine and spinel accumulation, reflect the regularity of mineral fractionation in these rocks. Sulfides also clearly affect xenolith compositions (Fig. 4, Supplementary Information). Thus, many trace-element variations observed in the Piton Chisny xenoliths can be reasonably explained by fractional crystallization and/or partial-melting processes occurring during Réunion magmatism. 4.2. HSE in Réunion lavas and cumulate xenoliths Most Piton Chisny cumulate xenoliths display saw-toothed HSE patterns with relative depletions in Ir, Pt, and Re (high Ru/Ir and Pd/Pt), when normalized to either CI chondrite (Horan et al., 2003), or the estimate for the primitive upper mantle (PUM) (Becker et al., 2006). These patterns are not analytical artifacts. We used identical methods to those employed by Day et al. (2016), who have shown that identical results are obtained using conventional digestion or HF-desilicification methods in volcanic rocks spanning a range of compositions. Further, standard peridotite and lava reference materials analyzed using these methods do not exhibit the

characteristic patterns observed in the Chisny cumulate xenoliths. Here, we conceptually equate PUM to the bulk silicate earth (BSE), since the terrestrial crust hosts a minor fraction of the total HSE (1%). Consequently, relative fractionation of the HSE in the cumulate xenoliths is greater than that in the PUM, or the BSE. Either a hitherto-unrecognized petrogenetic process causes significant HSE inter-element fractionation, or the cumulate xenoliths inherited this signature from their mantle source. There are also cumulate xenoliths with relative enrichments in Re and/or Pt relative to Pd (Fig. 5), and we first focus on explaining the causes of the HSE patterns from these xenoliths. Most OIB lavas are known to have highly variable inter-element fractionations of the HSE, but generally have PUM-normalized Ru/Ir and Pd/Pt values <1, and have high Re/Os (e.g., Ireland et al., 2009; Day et al., 2010), which contrasts strongly with the patterns measured for the majority of Piton Chisny xenoliths. In basaltic magmas, HSE are highly compatible (Os, Ir, Ru) to compatible (Pt, Pd), or moderately incompatible (Re). These elements typically exhibit parallel liquid lines of descent, controlled by olivine and spinel fractionation (Crocket, 2000; Puchtel and Humayun, 2001; Puchtel et al., 2004; Jamais et al., 2008; Ireland et al., 2009; Day, 2013). The HSE also have strong but variable affinities for sul-

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fide (Barnes et al., 1985; Hart and Ravizza, 1996; Burton et al., 1999; Ballhaus et al., 2006; Gannoun et al., 2007), leading to relatively high Re/Os value in sulfide-residual melts (Roy-Barman et al., 1998; Alard et al., 2000; Gannoun et al., 2004; Day, 2013). Thus, cumulate xenoliths with Re enrichments (Fig. 5B) may represent relatively late-stage differentiates in the subsurface cumulate pile. In situ analysis of Re in the cumulate xenoliths shows relative enrichment of Re in oxide phases that may explain the corresponding enrichments in Re observed for some samples (Supplementary Information). Relative enrichments in Pt, or the absence of strong depletions in Pt, are more difficult to explain by such a mechanism. Cumulate xenoliths from Piton Chisny that have the greatest enrichments in Pt are also generally the most HSE-enriched (Fig. 5). In addition, all clinopyroxene-bearing dunites have flat-to positive trends across Pt. The same trend, however, is also observed in samples without appreciable clinopyroxene. Current knowledge of Pt partitioning underscores the relatively low incompatibility of Pt in tholeiitic melts (Jamais et al., 2008; Pitcher et al., 2009; Ireland et al., 2009) relative to alkali basalts (Day, 2013), particularly in relatively evolved melts (Jamais et al., 2008). However, while evolved melts occur on Réunion (Supplementary Materials), they are not well-represented in the suite of lavas that we measured. Furthermore, the relatively high HSE abundances in some of the Pt-enriched xenoliths, and their similar forsterite contents to the other measured cumulate xenoliths, indicate that singular fractionation processes involving either silicate phases, such as clinopyroxene, or Pt-based alloys may be responsible for these variations. Alard et al. (2000) noted that interstitial sulfides host strong relative enrichments in Pd that may influence bulk-rock Pd/Pt in the opposite direction to that seen in the Chisny cumulate xenoliths. Indeed, the majority of sulfides observed in Chisny xenoliths are olivine-hosted rather than interstitial, and the magnitude of relative Pd enrichments noted for this type of sulfide are significantly less than for interstitial sulfides. In situ analysis of oxides, sulfides, and silicates in samples CH0701 Dunite and CH0706B reveal PUM-normalized Pd/Pt values >1 in all cumulate mineral phases; this strongly argues for a similar relative enrichment in the Réunion parental magma (Supplementary Information). Given that cumulate xenoliths with relative Re and Pt enrichments can be explained by petrogenetic processes, we investigate the possibility that the general saw-toothed shape of PUMnormalized patterns of some Piton Chisny xenoliths reflects similar processes. We present a null-hypothesis fractional-crystallization model utilizing empirically determined partition coefficients and assuming a parental melt that is relatively unfractionated, with respect to the HSE (Fig. 6A). The results permit the generation of a cumulate from a parental melt with relative enrichments in Ru and Pd; however, the model also predicts significant depletion in the incompatible HSE (e.g., Pt, Pd, Re), relative to the compatible HSE (Os, Ir, Ru), which is not observed in the Piton Chisny xenoliths. Correspondingly, these calculations also mean that partial melting is not likely to be responsible for the HSE fractionations, as a reversely fractionated signature would be implied under the conditions of partial melting assumed for Réunion when using the same partition coefficients (e.g., Rehkämper et al., 1999; Day, 2013). Fractional crystallization or partial melting models, therefore, fail to explain the characteristic sawtooth patterns of many of the Piton Chisny xenoliths. Instead, the HSE signatures must be imparted from the Réunion mantle source. Petrological modeling utilizing the same partition coefficients demonstrates that a source with pre-existing relative enrichments in Ru, Pd, and Re can produce a cumulate and residual magma with compositions that closely match those observed in the Reenriched cumulate xenoliths and lavas with hyperbolic HSE patterns, respectively (Fig. 6B). This result provides compelling ev-

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Fig. 6. (A) Modeled average compositions of cumulate precipitated by fractional crystallization (gray lines) from a primary magma (heavy black line) that lacks Ru/Ir, Pd/Pt and Re/Pd enrichments (composition from Day, 2013) and the composition of a corresponding residual melt after fractional crystallization (black lines). Gray region: range of Piton Chisny cumulate compositions; percentages: mass proportion of primary magma lost to fractional crystallization. Partition coefficients are those for 12 wt.% MgO parental melt to alkali basalt as reported in Day (2013). Primitive mantle normalization from Becker et al. (2006). (B) Fractional crystallization model for a theoretical Réunion primary magma (heavy black line) possessing elevated Ru/Ir, Pd/Pt and Re/Pd. Compositions of the residual melt and the average composition of the cumulate xenoliths are shown by the black and gray lines, respectively; measured HSE compositions for cumulate xenoliths and lavas are shown in the dark and light gray shaded regions, respectively. Percentages refer to mass loss from primary magma. The effect of these models on lava HSE compositions are discussed in the Supplementary Materials.

idence that Piton de la Fournaise lavas preserve HSE fractionations from a parental magma that inherited Ru/Ir and Pd/Pt fractionations from their mantle source. The presence of similar sawtooth HSE patterns in lavas with high modal proportions of olivine also implies that this signature was acquired within accumulative olivine. For example, a simple arithmetic model indicates 10–60% accumulation of olivine, which is comparable to the modal abundance of olivine in the appropriate samples, can account for the sawtooth patterns present in lavas (Supplementary Materials). Samples with intermediate abundances of modal olivine may preserve features of the sawtooth fractionated pattern or the hyperbolic pattern; this is dependent on the proportion of accumulated to late-crystallizing olivine. These results strongly support the mode-of-origin for the fractionated HSE patterns preserved in the majority of Piton Chisny xenoliths as being inherited directly from their parental magma. 4.3. A non-chondritic source for Réunion The possibility that the Réunion mantle source was segregated early in Earth’s history and remained relatively unaffected by recycling processes has been suggested previously. In particular, relatively low time-integrated Th/U (Vlastélic et al., 2006), 3 He/4 He

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Fig. 7. Correlation of MgO to Ir for Hawaiian lavas (Ireland et al., 2009) and Piton de la Fournaise lavas that do not display the hyperbolic HSE patterns noted in the text. Least-squares regression lines and fit statistics for the two sample suites (Hawaii, black; Réunion, gray) are provided for reference.

(e.g., Trieloff et al., 2002; Füri et al., 2011), 187 Os/188 Os (e.g., Schiano et al., 2012; Gannoun et al., 2015), Ne (e.g., Trieloff et al., 2002), and Sr–Nd–Pb isotopic compositions (Bosch et al., 2008) might indicate that the Réunion mantle source derives from a relatively undifferentiated reservoir. Using the MgO and Ir composition of Piton de la Fournaise lavas that have not experienced S saturation, we calculate the Ir composition of the Réunion parental magma to be 0.41 ng g−1 (0.29–0.54 ng g−1 , 1σ propagated error) at 35 wt.% MgO, and lower than for other hotspots (e.g., Fig. 7). Using the HSE/Ir values of the same samples, we calculate the concentrations of Os, Ru, Pt, Pd and Re to be 1.01 (0.36–2.0), 0.42 (0.29–0.54), 1.09 (0.49–1.9), 4.18 (0–11), 11 (0–36) and 0.64 (0–2.0) ng g−1 , respectively (1σ propagated error). These estimated concentrations are consistent with fractionated Ru/Ir, Pd/Pt, and Re/Pd relative to PUM observed in the cumulates, but are generally lower in abundance compared to PUM and similarly calculated parental compositions of other OIB. If this signature represents the composition of the Réunion mantle source, its composition is certainly non-chondritic. The relatively unradiogenic 187 Os/188 Os signature of Réunion (0.1324 ± 0.0014) compared to other OIB also supports the idea that its mantle source is non-chondritic. If a Réunion mantle source, represented by CI chondrites (Horan et al., 2003), were isolated at 4.4 Ga (Vlastélic et al., 2006), its present-day Osisotopic signature requires a 187 Re/188 Os value that is approximately 22 percent higher than that measured for Chondrite Ivuna in order to evolve to its current 187 Os/188 Os value. If this mantle source subsequently interacted with depleted mantle domains (e.g., Gannoun et al., 2015), then we overestimate the HSE concentrations of the source and underestimate the age at which it was isolated from the rest of the mantle. Thus, the Réunion mantle source would be even more geochemically unique than we suggest. The unique, highly fractionated HSE pattern observed in Piton de la Fournaise xenoliths are dissimilar to patterns measured in oceanic crust and lithosphere (e.g. Rehkämper et al., 1999; Luguet et al., 2003) or continental crust and lithosphere (e.g., Peucker-Ehrenbrink and Jahn, 2001; Ackerman et al., 2009), which may be present in the sources of other hotspots. Indeed, the unique geochemistry of the Réunion source material may also indicate it melts deeper in the mantle than other hotspot sources (Supplementary Materials). Given these conditions, we explore the possible origins of an early-formed, non-chondritic Réunion mantle source and the implications for the existence of such a source. We propose two possibilities to explain the highly fractionated HSE patterns of the Réunion source. First, if the source of the Réunion primary magma is ultimately in the deepest mantle, chemical

Fig. 8. (A) Modeled HSE composition of core after 25% extraction of Earth’s mass into the core (solid gray line) from an initially chondritic body (solid black line) (Horan et al., 2003) based on silicate–metal partitioning experiments of Mann et al. (2012), P of 60 GPa and T of 4250 K. Dashed gray lines are compositions of solid metal precipitated from small amounts of liquid metal entrained from the core into the residual mantle (e.g., Humayun, 2011) based on liquid metal–solid metal partitioning experiments of Chabot and Jones (2003); percentages represent degree of solidification. (B) Curves for mixing between solid metal precipitated as 1% by mass of liquid metal (as in panel a) and a calculated residual silicate mantle left behind after core formation. Percentages refer to proportion solid metal involved in the metal–silicate mixing. (C) Mixing between 99.99% residual silicate mantle and 0.01% solid metal (as in panel B) and chondrite (Horan et al., 2003), simulating late accretion. Calculated composition of primary Réunion magma shown for reference (see text for details). Symbols as in Fig. 2.

contributions from Earth’s core could impart a strongly fractionated HSE pattern on a source-domain later insulated from the geochemical effects of chondritic late accretion. Results of highpressure experiments indicate that liquid silicate–metal partitioning is not equivalent for all of the HSE, and core formation may have left a mantle residuum with elevated Ru/Ir and Pd/Pt values, but extremely low absolute HSE abundances (e.g., Mann et al., 2012). If a small amount of liquid metal from the core were re-entrained into a deep-mantle domain and then cooled (e.g.,

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Humayun, 2011), this could partially replenish HSE abundances and still maintain elevated Pd/Pt and Re/Pd values. Mixing between a solid metal formed by this process and the mantle residuum left over after core formation could produce a domain that has similar HSE fractionations to measured Piton Chisny cumulate xenoliths (Fig. 8A–B). However, extremely high calculated metal/silicate partition coefficients for the most compatible HSE (Os, Ir, Ru, e.g., DOs = 8064) mean that these elements are entirely stripped from Earth’s mantle during core differentiation, thus preserving the original chondritic relative proportions in the core. Mixing between the residual mantle and metallic core material, therefore, causes the mantle to immediately re-acquire the chondritic Ru/Ir signature of the metal, even at vanishingly small added masses. This problem may be avoided by incorporating quantitative constraints on HSE fractionation by sulfide liquid at high temperatures and pressures, which may also cause Ru/Ir fractionation (e.g., Laurenz et al., 2015). For the less-compatible and incompatible HSE (Pt, Pd and Re), the model predicts retention of a fractionated signature with elevated Pd/Pt and Re/Pd in the mantle, after a limited degree of remixing between the mantle and solid metal from the core. If this mantle domain were subjected to a low degree (<0.2% by mass) of chondritic late accretion, its composition would closely match Ir, Ru, and Pt abundances calculated for the Réunion source (Fig. 8C). Second, the source could represent a mantle domain that was differentiated during or after late accretion by non-chondritic or heterogeneous materials in an open silicate system. Previous workers have suggested that late-accretion materials may not be wellrepresented by measured chondrites, but rather reflect a population of impactors that are no longer preserved in the meteorite collection (e.g., Pattou et al., 1996; Becker et al., 2006; Puchtel et al., 2008). For example, similar HSE patterns to the PUM, with elevated Ru/Ir and Pd/Pt values have been observed in lunar breccias (e.g., Puchtel et al., 2008; Sharp et al., 2014). Alternatively, recent constraints provided by refined geochemical modeling (e.g., Rubie et al., 2011) and geochemical data (Walker et al., 2015), indicate that the Earth may have resided in a chemically heterogeneous proto-planetary disk. Accretion of asteroidal material possessing variable chemistry may produce anomalously fractionated HSE patterns, relative to fractionations observed in a single meteorite family. Additionally, mixing of highly fractionated or heterogeneous-accreted material with primitive Earth material hosting little or no HSE fractionation relative to chondrites, could produce domains of variable HSE fractionation, effectively erasing a homogeneous chondritic or non-chondritic signature existing before late accretion. Importantly, the two proposed models of lower mantle processes and non-chondritic late accretion are not mutually exclusive. For example, a deep-mantle domain that inherited a fractionated HSE signature from core–mantle interaction may also have experienced variable contributions from non-chondritic late impactors; however, the degree of this accretion would be unknown without constraints on the HSE compositions of the impactors themselves. The unique contributions of the two alternatives are that the first does not require that late accretion was non-chondritic, whereas the second does not require that the Réunion source experienced core contributions. However, both explanations can account for the unusually low calculated HSE abundances in the Réunion source, which cannot otherwise easily be explained by conventional lateaccretion models. Evidence from the HSE, therefore, strongly supports the notion that the Réunion source represents an early differentiated mantle domain that became chemically isolated from the bulk silicate Earth before the termination of late accretion. Future high-pressure and temperature metal–silicate and sulfidepartitioning data may be able to fully account for the magnitude of calculated HSE abundances in the lower mantle during core forma-

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tion. If this were the case, it could mean that the Réunion mantle source was isolated even earlier, before the onset of late accretion. Heterogeneous distribution of the daughter isotopes to shortlived radiogenic isotope systems (e.g., 146 Sm–142 Nd and 182 Hf–182 W) have provided complementary evidence for the existence of persistent, distinct mantle domains that formed early in Earth’s history (e.g., Caro et al., 2003, 2006; Caro and Bourdon, 2010; Boyet and Carlson, 2005; Bennett et al., 2007; Willbold et al., 2011; Touboul et al., 2012, 2014; Debaille et al., 2013; Rizo et al., 2013). If the Réunion mantle source experienced minimal contributions from late accretion, Réunion igneous rocks may also possess modestly positive ε 142 Nd, but either positive or negative μ182 W, depending on the relative contribution of core material to the extant Hf–W system. However, the lack of correlation between Ru/Ir, Pd/Pt and Re/Pd values (Supplementary Materials) implies that there were multiple processes involved in the formation of the Réunion source-domain. If this were the case, it may provide a mechanism by which the source could simultaneously contain elevated Ru/Ir, Pd/Pt, and Re/Pd values, but also lack positive ε 142 Nd and μ182 W. 5. Conclusions Piton Chisny cumulate xenoliths preserve evidence for nonchondritic HSE inter-element fractionations in the Réunion mantle source. Combined with the unique features of Réunion’s radiogenic isotopic signature, this evidence may be a repercussion of a strong influence from a deep, primitive source that is less refractory than either ambient upper mantle or other mantle sources to hotspot magmas. The origin of fractionated patterns in Piton Chisny cumulate xenoliths requires further investigation from studies of extinct radionuclides and nucleosynthetic effects, but may be due to either: (1) addition of a non-chondritic exogenous component during late accretion, or (2) limited contribution from core material after Earth differentiation that was insulated from the geochemical consequences of late accretion. In either case, these results demonstrate that the Réunion hotspot has the greatest potential of all OIB studied to date for sampling a mantle domain that has been effectively isolated from the convecting upper mantle through much of Earth’s history. Acknowledgements The authors thank Richard Walker for discussions and Allan Patchen for technical assistance with EMP analyses. We are grateful to two anonymous reviewers and EPSL editor Dr. Bernard Marty for their thoughtful comments, which substantially improved the quality of this work. Field work was supported by the National Geographic Society (NGS 8330-07), the Geological Society of America (GSA 10539-14) and by a generous donation from Dr. Robert Rex. General support was provided from NSF EAR Grants 1116089 and 1447130 to JMDD and the Devendra and Aruna Lal Fellowship to BJP. These sources of funding are gratefully acknowledged. The authors declare no conflicts of interest. Appendix A. Supplementary material Supplementary material related to this article can be found online at http://dx.doi.org/10.1016/j.epsl.2016.05.015. References Ackerman, L., Walker, R.J., Puchtel, I.S., Pitcher, L., Jelínek, E., Strnad, L., 2009. Effects of melt percolation on highly siderophile elements and Os isotopes in subcontinental lithospheric mantle: a study of the upper mantle profile beneath Central Europe. Geochim. Cosmochim. Acta 73, 2400–2414.

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