Derivation of Hawaiian rejuvenated magmas from deep carbonated mantle sources: A review of experimental and natural constraints

Earth-Science Reviews 222 (2021) 103819 Available online 30 September 2021 0012-8252/© 2021 Elsevier B.V. All rights reserved. Derivation of Hawaiian rejuvenated magmas from deep carbonated mantle sources: A review of experimental and natural constraints Anastassia Y. Borisova a , b , * , Romain Tilhac c a G´ eosciences Environnement Toulouse, GET - UMR 5563 - OMP - CNRS, 14 Avenue E. Belin, 31400 Toulouse, France b Geological Department, Lomonosov Moscow State University, MGU, Vorobievu Gori, 119991 Moscow, Russia c Instituto Andaluz de Ciencias de la Tierra (IACT), CSIC – Universidad de Granada, 18100 Armilla, Granada, Spain ARTICLE INFO Keywords: Review Rejuvenated stage Hawaiian magmatism Carbonatite metasomatism Mantle sources of carbonatite melts Open-system melting Pyroxenite ABSTRACT The role of carbon-rich or carbonatitic melts as an important metasomatizing agent in the Earth's mantle is supported by direct and indirect evidence of their involvement, ranging from the presence of erupted carbonatitic lavas to metasomatic reactions documented in minerals and melt inclusions from mantle xenoliths. Carbonatite metasomatism in hot-spot settings, and more particularly in the mantle sources of rejuvenated Hawaiian lavas, has long been suspected. However, an unequivocal geochemical tracer of carbonated mantle sources in alkaline volcanic suites is still missing. We here examine high-quality majorand trace-element compositions of ~400 primitive Hawaiian lavas (MgO =8.5–21 wt%, SiO 2 =37–50 wt%) and associated xenoliths, focusing on those erupted during rejuvenated stages of activity of the Hawaiian hot spot, Pacific Ocean. The rejuvenated-stage alkaline lavas are the most enriched in volatile elements among the four-stage Hawaiian lavas. Our compilation shows that these rejuvenated-stage lavas range from melilite/nephelinite to transitional basalts and are characterized by low-Si and high-Na, -K and -Ca contents, along with the enrichment of REE, Th and Ba relative to K, Hf, Zr, Ti and Nb. Their trace-element systematics argues against derivation from a homogeneous lherzolitic or pyroxenitic source, regardless of the involvement of residual garnet or hydrous phases. Based on a comprehensive review of natural and experimental constraints on partitioning between carbonatites and mantle minerals and numerical simulations of open-system melting, we show that it is rather consistent with carbonatite metasomatism in their source. Variations in SiO 2 , CaO, alkali contents and trace-element proxies such as Hf/Sm also specify temporal variations in the depth of melting and/or the respective contribution of lherzolites and pyroxenites in a hybrid (probably asthenospheric) source fluxed by carbonatitic melts. We suggest that this episode took place ≤4.2 Ma at temperatures and pressures in excess of 1100 ◦C and 2 GPa. The lowsolidus carbonatite melts were likely generated following a time lag which allowed for cooling of the plume and likely derived from an ancient (>1Ga), recycled mantle, or lower mantle, source in the Hawaiian plume, in good agreement with Sr-Nd-Hf-Os isotope systematics and other chemical and mineralogical features of Hawaiian rejuvenated lavas and xenoliths. The identification of a deep carbonated mantle source for Hawaiian rejuvenated volcanic series is also in line with noble gas and light stable isotope systematics and suggests that the interaction between carbonatite melts and peridotites/pyroxenites may be a critical process explaining the compositional variability of many oceanic island magmas. 1. Introduction The presence of significant amounts of carbon in mantle plumes is well established (Trull et al., 1993; Hofmann et al., 2011; Anderson and Poland, 2017; Tucker et al., 2019). Direct and indirect evidence for carbon-rich or carbonatitic melts and fluids has been widely documented in oceanic hot-spot settings (e.g., Salters and Shimizu, 1988; Schmidt and Weidendorfer, 2018 and references therein). Erupted carbonatite melts are, for instance, reported from the Cape Verde and Canary Islands (All` egre et al., 1971; Silva et al., 1981; Barrera et al., 1981; Gerlach et al., 1988; Hoernle et al., 2002). Metasomatic reactions between carbonatitic fluids and mantle rocks are observed in xenoliths from the Solomon (Nixon and Boyd, 1979), Canary, Kerguelen or Fernando de Noronha Islands (e.g., Kogarko et al., 1995, 2001; Schiano * Corresponding author at: G´ eosciences Environnement Toulouse UMR 5563, Observatoire Midi Pyr´ en´ ees, 14 Avenue E. Belin, 31400 Toulouse, France. E-mail address: [email protected] (A.Y. Borisova). Contents lists available at ScienceDirect Earth-Science Reviews journal homepage: www.elsevier.com/locate/earscirev https://doi.org/10.1016/j.earscirev.2021.103819 Received 8 April 2021; Received in revised form 13 September 2021; Accepted 24 September 2021 Earth-Science Reviews 222 (2021) 103819 2 et al., 1994) and Hawaii (Wirth and Rocholl, 2003). Furthermore, based on the compositions of peridotite minerals and melt inclusions, Hauri et al. (1993), Kogarko et al. (1995), Coltorti et al. (1999), Schiano et al. (1994), Mattielli et al. (1999), Hassler (1999), Gr´ egoire et al. (2000), Kogarko et al. (2001) and Hoernle et al. (2002) inferred that ultramafic xenolith suites affected by carbonatite metasomatism are widespread in oceanic environments (e.g. Savai'i, Tubuai, Canary, Fernando de Noronha, Grande Comore and Kerguelen). Carbonatite and CO 2 -rich silicate melts play an important role as metasomatizing agents in the mantle lithosphere, as documented by newly formed clinopyroxene (Cpx) (Mattielli et al., 1999; Gr´ egoire et al., 2000), apatite (Hassler, 1999), phlogopite and amphibole (Gr´ egoire et al., 2000), and melt inclusions (Schiano et al., 1994) in metasomatized peridotites from the Kerguelen Archipelago. In fact, there is ubiquitous evidence of the involvement of carbonatites from mantle xenoliths, implying that carbonated mantle probably plays a major role in the source geochemistry of oceanic hotspot magmas. Metasomatism by kimberlites, carbon-rich melts and carbonatites in the mantle sources of rejuvenated Hawaiian lavas has long been suspected (e.g., Salters and Zindler, 1995; Keshlav and Sen, 2003, 2004; Wirth and Rocholl, 2003; Sen et al., 2005; Frezzotti and Peccerillo, 2007; Dixon et al., 2008; Hofmann et al., 2011; Hofmann and Farnetani, 2013; Rocholl et al., 2015; Schmidt and Weidendorfer, 2018 and references therein; Rocholl et al., 2019). Alternative models for the origin of these lavas involve partial melting of garnet (Grt)-bearing lherzolites and pyroxenites leaving residual apatite, phlogopite and titanite/Fe-Ti oxides in a mixed lithosphere-plume source (e.g., Class and Goldstein, 1997; Clague and Frey, 1982; Lassiter et al., 2000; Frey et al., 2000; Sen et al., 2005; Clague et al., 2006; Garcia et al., 2016). In contrast, based on the geochemistry of the primitive Kiekie lavas and glasses from the Niihau island, Dixon et al. (2008) proposed that low-degree partial melting of the Hawaiian plume led to silicate and carbonatite metasomatism along the depleted-mantle plume margins at sub-lithospheric depths. Compositional heterogeneities of mantle sources consequent to carbonatite metasomatism are generally inferred in intraplate magmas from Hf/rare earth elements (REE) and Zr/Hf variations (e.g., Dupuy et al., 1992; Hauri et al., 1993; Hoernle et al., 2002). However, these variations can be controlled by fractional crystallization of Cpx and Grt and other authors propose that fractionation may also occur during OIB and MORB generation due to increasing bulk partitioning coefficients D Sm <D Hf <D Eu between mantle minerals and basaltic melts (e.g., David et al., 2000). An unequivocal geochemical tracer of carbonated mantle sources in alkaline volcanic suites is thus missing. To constrain the role of carbonatite metasomatism and/or hybrid peridotite/pyroxenite sources in the generation of the volatile-rich rejuvenated-stage Hawaiian magmas, we here present an extensive dataset of majorand traceelement compositions compiled from the literature since 1982. For that purpose, we particularly focus on high-quality analytical data on incompatible trace-elements compositions of bulk rocks (lavas), glasses and mineral samples and discuss trace-element partitioning between minerals and silicate and carbonatite melts as well as the trace-element compositions of carbonatite magmas, melts and carbonated peridotite xenoliths worldwide. These data along with the decoupled Nd-Hf isotope systematics documented in the Salt Lake Crater (SLC) mantle xenoliths (e.g., Bizimis et al., 2005, 2013 and references therein) are consistent with carbonatite metasomatism derived from a deep, potentially lower-mantle, source containing ancient recycled material (>1 Ga) within the Hawaiian plume. 2. Data compilation 2.1. Sample systematics and analytical data selected for this study Four volcanic stages have been distinguished in the HawaiianEmperor volcanic chain (Fig. 1a,b): (1) alkalic preshield (3% in volume), (2) tholeiitic shield (98–95%), (3) alkalic postshield (<1%) and (4) alkalic rejuvenated stages (<1%) (Clague, 1987a; Sobolev and Nikogosian, 1994). The rejuvenated-stage alkaline lavas are the most enriched in volatile elements but also the most isotopically depleted (and the most homogeneous) with highly radiogenic Nd and Hf and unradiogenic Sr (e.g., Lassiter et al., 2000; Fekiacova et al., 2007; Dixon et al., 2008; Bizimis et al., 2013; B´ eguelin et al., 2019; Harrison et al., 2020). To constrain the role of carbonatite fluxing and/or hybrid mantle sources in the generation of their parental magmas, we have compiled a dataset of ~400 primitive lavas and glasses with SiO 2 ≤50 wt% and MgO ≥8.5 wt% (Fig. 2) from Honolulu (Oahu), Haleakala (Maui), Koloa (Kauai), the submarine Wailau landslide on Molokai, the North Arch volcanic field, lavas from West Maui and Mauna Kea as well as from volcanoes on Molokai, Niihau, Kauai, Oahu, and Kaula and other Hawaiian Islands. The volcanic activity of the selected localities is mostly related to the rejuvenated stage (Clague and Frey, 1982; Frey and Clague, 1983; Chen and Frey, 1985; Clague and Dalrymple, 1988; Maaløe et al., 1992; Chen et al., 1991; Reiners and Nelson, 1998; Frey et al., 2000; Dixon and Clague, 2001; Clague and Moore, 2002; Gaffney et al., 2004; Clague et al., 2006; Dixon et al., 2008; Cousens and Clague, 2015; Phillips et al., 2016) (Table 1). The lavas and glasses are classified as ijolites, melilite nephelinites, nepheline melilites, nepheline basanites and alkaline olivine (Ol) basalts, as well as some transitional-type basalts (Fig. 2; Table 1; Supplementary Dataset 1). These alkaline to transitional lavas were erupted after an erosion interval of 0.25–2.7 Ma following the shield-stage volcanism (Clague, 1987b; Garcia et al., 2016 and references therein). Petrographic description of these lavas can be found elsewhere (e.g., Clague and Frey, 1982; Garcia et al., 1986; Clague and Dalrymple, 1988). Analytical data were primarily selected based on the quality of the majorand trace-element analyses, but also aiming for sample representativity and limited or absence of secondary alteration features. Various analytical techniques performed in different laboratories were used, so we preferentially included analyses obtained using neutron activation or inductively coupled plasma mass spectrometry (ICP-MS) for Hf, Ta, Th and REE and X-ray fluorescence for Zr, Nb and Y. Following on previous compilations (e.g., Clague and Frey, 1982; Frey and Clague, 1983; Clague and Dalrymple, 1988; Chen et al., 1991; Frey et al., 2000), we consider that “old” data on Zr, Hf, Nb, Ba, REE, Ta and Th have an analytical precision of ±15 to 20%, and up to 25% only (e.g., Yang et al., 2003) for the Th contents of Frey et al. (2000). In contrast, recent trace-element analyses performed by ICP-MS have 2 σ precision of 3–5% (Reiners and Nelson, 1998) and better than 0.5% for major elements. For instance, major-element compositions acquired by X-ray fluorescence (XRF) and ICP-MS trace-element analyses carried out at the Washington State University GeoAnalytical Laboratory yielded a 2 σ precision mostly <3% based on repeated analyses of the BCR-P standard, reaching 6–7% for incompatible lithophile elements and <15% for Ni, Sc and Ga (Gaffney et al., 2004; Dixon et al., 2008). 2.2. Compositional features of the Hawaiian rejuvenated-stage lavas The selected samples are characterized by a wide range of Zr (69–260 ppm), Hf (1.7–6.9 ppm), La (8.5–109 ppm), Sm (3.3–17 ppm) and Lu (0.05–0.61 ppm) abundances (Fig. 3). Where missing, Hf concentrations were calculated from Zr contents assuming the average Zr/ Hf (43 ±10) of rejuvenated-stage lavas (as detailed below). This is the case for the database of Reiners and Nelson (1998) on rejuvenated-stage basalts from Kauai, which shows similar trace-element ratios and primitive mantle (PM)-normalized (Sun and McDonough, 1989) patterns compared with other rejuvenated-stage Hawaiian lavas. Hawaiian lava series are characterized by positive correlations between (Hf/Sm) n [or (Zr/Sm) n ] and (Ti/Eu) n , particularly marked in the rejuvenated-stage lavas (Fig. 3a), and negative correlations between (Hf/Sm) n and (La/K) n ; the latter reach particularly high values (up to 10) in lavas from Oahu and Kauai islands (Fig. 3b). These observations A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 3 Alkalic Preshield Stage Tholeiitic Shield Stage Alkalic Postshield Stage Alkalic Rejuvenated Stage Ocean crust ' ' O c e a n c r u s t ' ' ' ' O c e a n c r u s t ' ' ' ' O c e a n c r u s t ' ' Spinel lherzolite Spinel lherzolite Spinel lherzolite Spinel lherzolite Garnet lherzolite Garnet lherzolite Garnet lherzolite Garnet lherzolite Magma accumulation Magma accumulation Magma accumulation Magma accumulation S 5 SL 10 20 30 40 50 60 70 80 90 100 DEPTH (KM) 26° 25° 24° 23° 22° 21° 20° 19° 18° 198° 199° 200° 201° 202° 203° 205°204° 206° North Arch Volcanic Field Niihau Kauai Oahu W. Molokai E. Molokai Lanai W. Maui Kahoolawe Haleakala Mahukona Kohala Hualalai Mauna Kea Mauna Loa Kilauea Loihi Kea-trend volcano Loa-trend volcano -6 -4 -2 0 2 4 (x 103 m) A B Fig. 1. (A). Map showing the locations of the Hawaii, Maui, Molokai, Oahu, Kauai, Niihau Islands and of the North Arch Volcanic Field. The Kea and Loa-trends are also indicated. Modified after Hofmann and Farnetani (2013). (B) Schematic representation of the main petrological aspects of the four stages of Hawaiian volcanism (see text for further detail). Modified after Clague (1987a, 1987b). A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 4 Alkaline basalts Nephelinites 34 38 46 5042 0 2 6 8 10 Preshield-stage lavas Shield- & postshield-stage lavas Chen et al. (1991) Haleakala volcano, Maui island Gaffney et al. (2004) West Maui island Phillips et al. (2016) Haleakala volcano, Maui island DeFelice et al. (2019) - Mauna kea volcano, Hawaii Rejuvenated-stage lavas Clague & Frey (1982) Honolulu volcano, Oahu island Maaloe et al. (1992) Koloa volcano, Kauai island Reiners & Nelson (1998) Kauai island Frey et al. (2000) North Arch field Clague & Moore (2002) Wailau landslide, Molokai Dixon et al. (2008) Kiekie, Niihau island Cousens & Clague (2015) Kauai island Garcia et al. (2016) Kaula island SiO2 (wt %) 4 K2O + Na2O (wt %) Basanites Transitional basalts Clague et al. (2006) - Honolulu volcano, Oahu island Frey & Clague (1983) - Loihi seamout Clague & Dalrymple (1988) - Kauai island Fig. 2. K 2 O +Na 2 O vs SiO 2 contents classification diagram for Hawaiian island lava series (nephelinites, basanites, alkaline Ol basalts and transitional basalts). The classification is after Cox et al. (1979). The compositional database includes analyses of volcanic rocks from Honolulu (Oahu), Haleakala (Maui), Koloa (Kauai), the submarine Wailau landslide on Molokai, the North Arch volcanic field , as well as lavas from West Maui and Mauna Kea, and also from volcanoes on Molokai, Niihau, Kauai and other Hawaiian Islands. For the high-Ca basalts from Mauna Kea, Hawaii island, 48 wt% SiO 2 is assumed. The volcanic series plotted here are related to the rejuvenatedand postshield-stages of volcanic activity (Clague and Frey, 1982; Frey and Clague, 1983; Clague and Dalrymple, 1988; Maaløe et al., 1992; Chen et al., 1991; Reiners and Nelson, 1998; Frey et al., 2000; Clague and Moore, 2002; Yang et al., 2003; Gaffney et al., 2004; Clague et al., 2006; Dixon et al., 2008; Cousens and Clague, 2015; Phillips et al., 2016; Garcia et al., 2016). The data source is given in Table 1 and summarized in Supplementary Dataset 1. Table 1 Location, age and characteristics of the selected Hawaiian lavas and glasses. Volcanic stage Location Type of samples Age Reference Post-erosional or rejuvenated* Honolulu volcano, Oahu island nepheline melilitite; nephelinite; nephelinite with rare melilite; basanite; alkali Ol basalt <0.58 Ma Clague and Frey, 1982 Preshield** Loihi basanite and alkali basalt 5 ±4 to 102 ±13 ka Frey and Clague, 1983 Postshield and rejuvenated Kauai island alkalic basalt, basanite, nephelinite, and nepheline melilitite between 3.7 and 0.52 Ma Clague and Dalrymple, 1988 Postshield*** Haleakala volcano, Maui island alkalic basalts 0.5–0.1 Ma Chen et al., 1991 Post-erosional or rejuvenated Koloa volcano, Kauai island melilitite; nephelinite; basanite; alkali Ol basalt a peak in the activity at 1.2 Ma Maaløe et al., 1992 Rejuvenated Kauai island basanites, alkali basalts from about 3.5 to 0.5 Ma Reiners and Nelson, 1998 Rejuvenated North Arch volcanic field alkalic basalt to nephelinite 1.15–0.5 Ma Frey et al., 2000 Rejuvenated submarine Wailau landslide, Molokai basanites and alkaline basalts between 1.5 and 1.4 Ma Clague and Moore, 2002 Rejuvenated Hawaiian North Arch and Honolulu Volcanics melilitite; nephelinite; basanite; alkali basalt <0.5 to 1.5 Ma Yang et al., 2003 Postshield and rejuvenated West Maui Ol basalts 0.6–0.4 Ma Gaffney et al., 2004 Rejuvenated* Honolulu volcano, Oahu island alkalic basalt to nephelinite <0.58 Ma Clague et al., 2006 Rejuvenated Kiekie basalt, Niihau island basalt glasses 3.5–0.35 Ma Dixon et al., 2008 Rejuvenated Kaula island nephelinites and associated xenoliths 4.22 ±0.22? Ma Bizimis et al., 2013 Rejuvenated Kauai island transitional basalt to nephelinite 2.3–0.3 Ma Cousens and Clague, 2015 Postshield*** Haleakala, Maui island basanites <0.15 Ma Phillips et al., 2016 Shield Hawaii island basalts – DeFelice et al., 2019 Rejuvenated Kaula Island alkalic basalt to basanite <1.95 Ma Garcia et al., 2016 * Lanphere and Dalrymple (1980). ** Guillou et al. (1997). *** Sherrod et al. (2003). A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 5 (Ba/Th)N 0123456 A F GP P G 2 3 1 F (Hf/Sm)N 1.0 1.5 2.0 0.5 0123 (Nb/Th)N 0 A F P GP P 2 3 1 F (Hf/Sm)N 0 1.0 0.5 1.5 (La/Sm)N 02468 10 1*** F A F GP P G (K/Th)N 123 2 3 1F A F P GP G (Ba/K)N 135791113 A P 2 3 1 F F (Hf/Sm)N 0 1.0 0.5 1.5 (Zr/Hf)N 1.4 1.9 1* A P GP G F F (La/K)N 2460810 2 3 1F G A P GP F (Ti/Eu)N 0.5 1.0 1.5 0 (Hf/Sm)N 0 1.0 0.5 1.5 2 3 1 F G A P GP F 3 - low influx (Grt pyr.) 1 - low influx Numerical models (A) Amp-bearing (P) Phl-bearing (G) Grt-bearing (GP) Grt pyroxenites lherzolites Batch melts (PM source) Open-system melts (PM source + carbonatite flux) 2 - high influx (a) (b) (c) (e) (d) (f) (g) (h) Fig. 3. Primitive-mantle-normalized trace-element ratios of the alkaline Hawaiian island volcanic series: (Hf/Sm) n vs (a) (Ti/Eu) n ; (b) (La/K) n ; (c) (Zr/Hf) n ; (d) (Ba/ K) n ; (e) (La/Sm) n ; (f) (K/Th) n ; (g) (Nb/Th) n ; (h) (Ba/Th) n . The dataset used here is given in Supplementary Dataset 1 and Table 1. Purple and magenta symbols indicate rejuvenated stage lavas and glasses. Blue symbols correspond to the preshield-stage lavas, postshield stage samples; note that one series of primitive Ca-rich basalts from the shield stage (DeFelice et al., 2019) is also shown. Black dashed lines are trace-element ratios calculated in partial melts derived from Grt lherzolite (G), Amp (amphibole)-bearing (A), Phl(phlogopite)-bearing (P) lherzolites and garnet pyroxenites (GP). Continuous lines in yellow, orange and red are the instantaneous melt compositions calculated from OSM models simulating carbonatitic flux melting (Models 1, 2 and 3). Arrows along the curves indicate the increasing degree of melting (F) for both types of models. See text and Appendix for more details on the batch modeling parameters. Primitive-mantle composition after Sun and McDonough (1989). Other symbols as in Fig. 1. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.) A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 6 reflect coherent K, Zr, Hf and Ti depletion relative to REE compared to the PM. Negative correlations between (Hf/Sm) n and (Zr/Hf) n are also observed in some of the lavas from Honolulu volcano and Kauai (Fig. 3c). The rejuvenated-stage lava series exhibit a clear negative correlation between (Hf/Sm) n and (La/Sm) n , reflecting coherent light rare earth element (LREE) enrichment and Hf depletion (Fig. 3e). Two trends of (Hf/Sm) n versus (Nb/Th) n and (K/Th) n reflect two types of correlations between (Hf/Sm) n [or (Zr/Sm) n ] and (Nb/Th) n and between (Hf/Sm) n and (K/Th) n (Fig. 3f & g). In such cases, Hf depletion is accompanied by variable K and Nb depletion. Additionally, (Ba/Th) n , and to a lesser extent (Ba/K) n , vary widely, showing an absence of coherence between K, Ba and Th behavior, but the broad negative correlation between (Ba/K) n and (Hf/Sm) n suggests that the most Hf depleted lavas and glasses tend to be enriched in Ba (Fig. 3d & h). Three geochemical groups may be distinguished among Hawaiian late-stage lavas on the primitive mantle (PM)-normalized trace-element diagrams. (1) PM-normalized trace-element patterns of the postshieldstage lavas show no distinctive anomalies for “critical” elements like K, Zr, Hf, Ti, corresponding to (La/K) n , (Hf/Sm) n and (Ti/Eu) n ratios close to 1 (Fig. 4). Postshield-stage lavas with moderate (La/Sm) n show different degrees of Rb and Th depletion relative to LREE. In contrast, two types of rejuvenated-stage series with low (Hf/Sm) n <1 may be distinguished based on characteristic anomalies in PM-normalized patterns. Both types variously exhibit K, Zr, Hf and Ti anomalies. (2) On the one hand, PM-normalized trace-element patterns of the Honolulu rejuvenated-stage lavas with low (Hf/Sm) n (<1) and high (La/Sm) n (>3.3) show strongly negative Rb, K, Zr, Hf and Ti and positive Ba anomalies, and variable Th contents (Fig. 4). These anomalies are expressed in variably low (La/K) n , (Hf/Sm) n , (Ti/Eu) n and (Ba/Th) n ratios. (3) On the other hand, the Niihau rejuvenated-stage basaltic series is characterized by variable Th depletion relative to Ba and a weak Zr, Hf depletions relative to REE and an absence of pronounced K and Ti depletion. 3. Discussion The high MgO contents (8.5–21 wt%) of the Hawaiian volcanic series suggest that their compositions are probably not far from that of primary melts and that the effect of fractional crystallization is negligible. Nickel contents (200–600 ppm) show broadly positive correlations with MgO contents in most Hawaiian lava series, reflecting some extent of fractional crystallization/accumulation. In contrast, the absence of such correlation for Sc concentrations, which are restricted to 10–30 ppm, excludes significant Cpx fractionation (Figs. A1, A2). The trace-element fractionation trends observed are thus considered below in terms of variations in source mineralogy and composition and melting processes before to envisage their geological significance. 3.1. Source mineralogy 3.1.1. An anhydrous garnet lherzolite source? Partial melting of anhydrous Grt lherzolite/pyroxenite has been invoked in the source of Hawaiian lavas by various workers (Lassiter et al., 2000; Sobolev et al., 2005, 2007; Borghini and Fumagalli, 2020). Experimental data on trace-element partitioning (Table 2) in the presence of basaltic/basanite melts show that: (1) K dHf and K dSm values are similar among mantle minerals, (2) the K dZr of Cpx (0.09–0.27) are comparable to K dHf (0.1–0.55) and K dSm (0.09–0.67); (3) K d vary with temperature, pressure and melt composition but remain as follows: K dZr ≤K dHf ≈K dSm or K dHf ≤K dZr ≈K dSm in Cpx, Grt and other silicates (Table 2). This is, for instance, the case between Grt and basanitic melt (Adam and Green (2006). Corgne and Wood (2004), Corgne et al. (2012) and Bobrov et al. (2014)) also demonstrated that Hf is significantly more compatible compared to Sm in majoritic Grt suggesting that Hf depletion relative to Sm would be expected upon fractionation of majorite garnet or derivation of primary alkaline melts from such majorite Grt-bearing mantle source. We used a batch melting model (Fig. 3, Fig. A3a–A3d) to simulate the trace-element fractionation associated with partial melting of a Grt lherzolite. The results show that Hf/Sm and Ba/Th in partial melts remain constant relative to the source, with a weak Ba fractionation relative to Th (Fig. A3c). Most Hawaiian rejuvenated-stage lavas exhibit such fractionation but variable K, Hf, Zr and Ti depletion (i.e. low Hf/ Sm, Zr/Sm, Ti/Eu and high La/K, Zr/Hf relative to the PM) are observed (Fig. 3a–h), which probably excludes the involvement of Grt in an anhydrous lherzolite source and instead requires additional mineral/ melt phase(s) and/or REE enrichment by metasomatism. Similarly, the observed fractionation of Ba from Th, Nb and Ta could not be solely explained by the presence of majoritic Grt, owing to the similarity of its partition coefficients for these elements. The strong variations in (Ba/ Th) n at nearly constant (Hf/Sm) n observed, for instance, in Niihau basaltic series is clearly incompatible with the presence of majoritic Grt in their mantle source. It is currently considered that partial melting of mantle peridotite is a dynamic process, involving differential flow of melt and residual matrix (e.g., Oliveira et al., 2020, and references therein). However, when trace elements show similar bulk distribution coefficients (e.g., Dy and Yb) between mantle minerals and melts, only limited additional fractionation is expected from dynamic melting models compared to the predictions of batch melting (Eggins, 1992). Dynamic incongruent melting/ mineral dissolution can produce noticeable differences only when the partition coefficients of the produced mineral are sufficiently different from those of the reacting minerals (Zou and Reid, 2001). Dynamic melting of anhydrous lherzolitic assemblages is unable to cause any substantial trace-element fractionation in melts (e.g., Hf vs Sm, Zr vs Sm, La vs K, K vs Ba) considering the similarity of their bulk partition coefficients (Fig. 3a–h). We conclude that the strong trace-element Fig. 4. Primitive-mantle-normalized trace-element patterns of Hawaiian (1) postshield-stage lava samples (Ho-12 and Ho-14) with high (Hf/Sm) n and low (La/Sm) n and (2) rejuvenated-stage lava samples (69KAL1 and 69KAL2) with low (Hf/Sm) n and high (La/Sm) n ; (3) rejuvenated-stage basaltic lavas (70Nii10, 69Nii-9; T318-R19; T318-R2). Data sources are Clague and Frey (1982), Chen et al. (1991) and Dixon et al. (2008). Instantaneous melt compositions calculated from OSM (Model 2) simulating carbonatitic flux melting are shown for comparison. Bulk compositional field of extrusive carbonatite magmas and carbonatite melts are from Nelson et al. (1988), Woolley et al. (1991), Beccaluva et al. (1992), and Tayoda et al. (1994). Primitive mantle composition is after Sun and McDonough (1989). A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 7 variations from PM values observed among the alkaline lavas of Hawaii rejuvenated-stage volcanism cannot be explained by simple batch nor dynamic melting models from a homogeneous, anhydrous lherzolite source, whether or not Grt (including majoritic Grt) is present. 3.1.2. Hydrous silicate phases Trace-element contents of ocean-island basalts may be controlled by the presence of hydrated phases such amphibole (Amp) or phlogopite (Phl) during partial melting (e.g., Clague and Frey, 1982; Class and Goldstein, 1997; Class et al., 1998; Frey et al., 2000; Sen et al., 2005; Clague et al., 2006; Garcia et al., 2016). Both minerals have similar Table 2 Partition coefficients used in melting models. Ol Opx Cpx Spl Grt Amp Phl Zr 0.0005 KE a 0.0025 R 0.0003 FJ 0.01 P 0.014 KE 0.027 R 0.032 GR 0.0099 AGR 0.01 P 0.089 S 0.1234 HD 0.1280 J 0.164H 0.18 R 0.27 BL 0.001 R 0.07 KE 0.27 J 0.3 KE 2.12H 0.47 AGR 0.127 L 0.23 BR 0.18–0.33 A 0.017 L 0.13 A 0.23 BR 0.008 GR Hf 0.0028 R 0.001–0.004 D 0.0008 FJ 0.005 P 0.025 R 0.04 D 0.017 AGR 0.06 GR 0.01 P 0.10–0.20 T 0.179 S 0.19 F 0.23 J 0.256 HD 0.29H 0.3 R 0.34–0.38 W 0.36–0.46 D 0.55 BL 0.13 E 0.001 R 0.003 E 0.24 J 0.62 T 1.22H 0.32 P 0.33 L 0.45 BR 0.19 L 0.45 BR 0.091 GR Sm 0.0007 KE 0.0025 R 0.001 P 0.014 R 0.02 KE 0.011 AGR 0.015 GR 0.01 P 0.086–0.22 T 0.201 S 0.281 J 0.291 HD 0.33H 0.35 F 0.4 R 0.67 BL 0.31 E 0.21 GR 0.0006 KE 0.0006 R 0.23 T 0.25 J 0.5 KE 0.101 GR 0.217 P 0.66 BR 0.27 G 0.66 BR 0.017 GR La 7E-06 KE 4.5E-04 R 0.0005 D 0.0005 KE 0.0025 R 0.004 D 0.03 S 0.04–0.28 AG 0.0536 HD 0.06 R 0.089 BL 0.015 D 0.0001 R 0.0006 KE 0.001 KE 0.0016 J 0.007 L 0.055 L 0.06 G K 1E-09 KE 1E-05 KE 0.0072 HD 0 KE 1E-05 KE 0.58 L 3.67 L Ba 1E-09 KE * 5E-06 D 1E-05 KE 6E-06 D 0.00068 HD 4E-04 D 0 KE 1E-05 KE 7E-05 D 0.16 L 3.68 L Th 7E-06-1E-05 B 1.3E-04 R 5E-06 D 2E-05-3E-05 B 12.5E-05 R 1.5E-05 R 1.3E-032.1E-03 B 0.0070 T 0.0086 F 0.014H 1E-05 R 0.0014H 0.0036 T 2.1E −03 B 0.0039 L 0.017 BR 0.0014 L Nb 0.0001 KE 0.0017 R 0.0025 R 0.003 KE 0.003 S 0.0077 HD 0.008 R 0.020 BL 0.01 KE 0.07 R 0.0042 J 0.01 KE 0.159 L 0.20 BR 0.088 L Ti 0.015 KE 0.14 KE 0.273 S 0.347 J 0.35–0.43 D 0.384 HD 0.15 KE 0.28 J 0.6 KE 0.95 A 1.29 L 0.98 A 1.77 L Eu 9.5E-04 KE 0.0029 R 0.002 P 0.0185 R 0.03 KE 0.01 P 0.35 HD 0.38 BL 0.47 P 0.46 R 6E-04 KE 9E-04 R 1 KE 0.4 P 0.88 IF 0.029 IF Nd 0.00042 D 0.012 D 0.088 D 0.0006 ** 0.064 D Ce 0.0005 D 0.004 D 0.038 D 0.0006 ** 0.017 D Tb 0.006 D 0.0325 D 0.165 D 0.0015 ** 1.6 D Yb 0.03 D 0.08 D 0.25 D 0.0045 ** 4.0 D a Partition coefficients (K d =C imineral / C imelt ) between the main mantle minerals and basaltic or basanitic melts according to A - Adam et al. (1993); AG - Adam and Green (1994); AGR – Adam and Green (2006); B – Beattie (1993); BL - Blundy et al. (1998); BR - Brenan et al. (1995); D – Dunn (1987); E – Elkins et al. (2008); F - Falloon et al. (1988); FJ - Foley and Jenner (2004); GA – Gaetani et al. (2003); G – Green (1994); GR - Green et al. (2000); H - Hauri et al. (1994); HD - Hart and Dunn (1993); IFIrving and Frey (1984); J – Johnson (1994); KE - Kelemen et al. (1993); L - LaTourette et al. (1995); R – Remaidi (1993); S - Skulski et al. (1994); T – Takahashi (1986); W - Watson et al. (1987); D – Dixon et al. (2008) and P - Pilet (2015). Underlined values were used for the calculations. Ol, Opx, Cpx, Spl, Grt, Amph Phl denotes olivine, orthopyroxene, clinopyroxene, spinel, garnet, amphibole, phlogopite. * K dBa values for phlogopite are considered as equal to those of K dK . ** suggested values. A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 8 partition coefficients with basanitic melts (Green, 1994; LaTourette et al., 1995; Adam and Green, 2006). Specifically, Hf partition coefficients of Amp and Phl (K dHf =0.008–0.59) overlap those for Sm (0.017–0.66) and Zr (0.008–0.45) (Table 2; Adam et al., 1993, Green, 1994, LaTourette et al., 1995, and Adam and Green, 2006). A decrease in melting degree of an Ampand Phl-bearing mantle source results in similar Hf/Sm and Zr/Sm between melt and residue, and a slightly increasing Zr/Hf ratio in the melt (Fig. 3c, Fig. A3a). Partial melting in the presence of Amp and Phl are rather fingerprinted by enrichment in K, Nb, Ba and Ti relative to REE (Table 2; LaTourette et al., 1995; Brenan et al., 1995; Adam and Green, 2006). If Amp and Phl were responsible for the K and Ti depletion observed in Hawaiian rejuvenated-stage lavas, they would also exhibit Ba and Nb depletion (e.g., La Tourette et al., 1995) and Th enrichment, which are not observed. If residual Amp were present, for instance, during partial melting of lherzolites, Hf/Sm and Ba/K ratios of the partial melts would show positive correlations, while the opposite situation is observed. Amphibole and Phl also have much lower La partition coefficients than those of K (Table 2) so that Hf/Sm and La/K of partial melts are expected to be positively correlated in the presence of such residual phases (Fig. 3b; Fig. A3b). Strong contrast in Amp and Phl partitioning of K and Ba relative to that of Nb and Th (Table 2, e.g., LaTourette et al., 1995; Green, 1994; Adam and Green, 2006) also suggests that, if these phases are present during partial melting of a homogeneous mantle source, K/ Th and Ba/Th would vary at nearly constant Hf/Sm or Zr/Sm (Fig. 3e,g, Fig. A3c). Weakly negative correlations between Hf/Sm and Ti/Eu are also expected (Fig. 3a; Fig. A3d). In contrast, Hawaiian rejuvenatedstage lava series show clear negative correlations between (Hf/Sm) n and (La/K) n (Fig. 3b) and positive correlations of (Hf/Sm) n with (K/ Th) n , (Nb/Th) n , and (Ti/Eu) n (Fig. 3a,f,g), ruling out the involvement of Amp and Phl in their source. A different process is therefore needed to explain the coherent K and high-field strength elements (HFSE) depletion and relative Th, Ba and REE enrichment. Note that Niihau basaltic series is an exception devoid of pronounced K depletion relative to LREE (Fig. 4) and characterized by strong variations in (Nb/Th) n , (Ba/Th) n and (K/Th) n at nearly constant (Hf/Sm) n (Fig. 3f,g,h). The presence of hydrous phases in the mantle source of these lavas, as well as hydrous silicate fractionation, cannot be excluded, although the absence of pronounced K depletion relative La does not support this hypothesis. 3.2. Carbonatite metasomatism The trace-element variations observed in the Hawaiian rejuvenatedstage lavas, such as the range of Hf depletion relative to REE, point towards significant variability of their mantle source(s). The contrasting degrees of enrichment of fluid-mobile incompatible elements (LREE, Ba and Th) relative to the less mobile K, Hf, Zr, Ti and Nb specifically points towards metasomatic enrichment in the source of Hawaiian rejuvenated-stage lavas. We concur, in this regard, with Dupuy et al. (1992) who ascribed variations of Hf/Sm, Zr/Hf and Zr/Sm in oceanisland lavas to carbonatite metasomatism of their mantle source. This interpretation also corresponds to the scenario proposed by Dixon et al. (2008), invoking coupled carbonatite-silicate metasomatism in the source of the primitive Kiekie lavas on Niihau, Hawaii. To develop a robust model compatible with all available geochemical and petrologic data on the primitive lavas (and mantle xenoliths) of the Hawaiian series, we first envisage the geochemical consequences of carbonatite metasomatism from (1) the compositions of oceanic and continental carbonatite melts/glasses and lavas, (2) experimentally determined partition coefficients between mantle minerals and carbonatite melts, (3) the compositions of mantle peridotites and pyroxenites affected by carbonatite metasomatism. 3.2.1. Trace-element characteristics of carbonatites Differentiated carbonatite melts are characterized by high Ba, Th, Sr, LREE contents relative to Rb, K, Zr, Hf, Ti and heavy REE (HREE) (Nelson et al., 1988; Walter et al., 2008). These features may be explained by different extents of trace-element complexation with CO 32− as well as carbonatite melt equilibration with majoritic Grtbearing eclogite at high pressure (~ 25 GPa, Corgne and Wood, 2004). Carbonatites also exhibit variable Sr, Ta, Th, Nb and P contents, as well as significant Zr/Hf and Nb/Ta fractionation, potentially explained by fractional crystallization (Nelson et al., 1988; Eggler, 1989; Walter et al., 2008) and the appearance of Zrand Nb-rich phases. In particular, Zr/Hf range between 5 and 465,000 in continental and oceanic carbonatite series (Supplementary Data 2; Nelson et al., 1988, Gerlach et al., 1988, Woolley et al., 1991, Beccaluva et al., 1992 and Tayoda et al., 1994, Hoernle et al., 2002 and Bizimis et al., 2004) and vary widely in carbonated peridotites. For example, Zr/Hf in the carbonated Tanzanian mantle xenoliths vary from 20 to 100 (Rudnick et al., 1993). Since the Zr/Hf ratio in the PM is estimated to be 34–36 (Jochum et al., 1989; Weyer et al., 2002), the effect of carbonatite metasomatism (or melting of metasomatised peridotites) in the mantle lithosphere is expected to very significant, potentially resulting in either an increase or a decrease of Zr/Hf relative to the primitive mantle. Additionally, carbonatite melts are enriched in REE, Th and Ba relative to K, Zr, Hf and Ti. Indeed, carbonatite melts with CO 2 =17–45 wt% and SiO 2 <7 wt% are shown to have highly variable, and systematically lower than unity, (Ti/Eu) n =0.0004–0.27, (Zr/Sm) n =0.0006–1.1 and (Hf/Sm) n =0.0006–0.9, (K/Th) n =0.0003–0.9 (Nelson et al., 1988, Gerlach et al., 1988, Woolley et al., 1991, Beccaluva et al., 1992, Tayoda et al., 1994, Hoernle et al., 2002, Bizimis et al., 2004), contrasting with high (La/K) n (2.7–4300) and (Ba/K) n (5–3500) (Fig. 5) and highly variable (Ba/Th) n (0.02–266). In carbonatite melts with higher SiO 2 (7–22 wt%), these ratios are much more restricted: (Ti/Eu) n =0.2–0.3, (Zr/Sm) n =0.4–0.7, (Hf/Sm) n =0.6–0.9, (La/K) n =3–38 and (Ba/K) n = 4–34. 3.2.2. Partioning between mantle minerals and carbonatite melts Several experimental investigations have been performed to determine the partition coefficients between mantle minerals and carbonatite melts. Green and Wallace (1988) inferred that the reaction of primary carbonatite melt with spinel (Spl) lherzolite produces an increase in large-ion lithophile elements (LILE) without any significant decrease in Mg/(Mg +Fe). Brenan and Watson (1991) showed that interaction of carbonatite melt with a depleted lherzolite may markedly particularly raise the levels of LILE in Cpx. Based on experimentally determined trace-element partitioning between Cpx and carbonatite melt, Klemme et al. (1995) found that the most sensitive indicator of carbonatite metasomatism appeared to be low Ti/Eu in the metasomatised peridotite. Over a wider range of pressure conditions, Sweeney et al. (1995) and Dasgupta et al. (2009) concluded that carbonatite metasomatism results in Ti depletion and increase in LREE/HREE, LREE/Hf and LREE/ Ti in mantle minerals. Similarly, Dalou et al. (2009) investigated trace-element partitioning between majoritic Grt and carbonatite melt at 20 GPa, demonstrating that natural magnesioand calcio‑carbonatite melts are strongly depleted in Hf relative to Sm at high-pressure; however, no data for Ti were reported by these authors. 3.2.3. Metasomatized peridotites From all the available data on metasomatised peridotite xenoliths, we prefered to make use of high-quality ICP-MS data on trace element concentrations including Hf, Zr, REE, Th, Nb, Ta. Based on such data, Hauri et al. (1993) and Coltorti et al. (1999) showed that peridotite xenoliths from the islands of Savai'i, Tubuai and Grande Comore have been affected by carbonatite melts (Supplementary Dataset 2). These peridotite xenoliths show high REE abundances relative to Zr and Ti. Ionov et al. (1993) performed a detailed investigation of Spitsbergen peridotite xenoliths containing primary carbonate aggregates and quenched dolomite melts. These metasomatised peridotites showed marked enrichment in LREE, Sr, Ba and depletion in Zr, Hf, Nb and Ta. In A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 9 1 0.1 0.01 0.001 0.0001 (Hf/Sm)N (Rb/Sr)N 0.010.001 0.1 1 10 1 0.1 0.01 0.001 0.0001 (Hf/Sm)N (Ba/Th)N 0.01 0.1 1 10 100 1000 1 0.1 0.01 0.001 0.0001 (Hf/Sm)N Zr/Hf 550 500 0.001 0.01 0.1 1 (Hf/Sm)N (Sm/Nd)N 0.1 1 0.001 0.01 0.1 1 (Hf/Sm)N (Ba/K)N 1 10 100 1000 0.001 0.01 0.1 1 (Hf/Sm)N (K/Th)N 0.0001 0.001 0.01 0.1 1 0.001 0.01 0.1 1 (Hf/Sm)N 1 (La/K)N 10 100 1000 10000 0.0001 0.001 0.01 0.1 1 (Ti/Eu)N 0.001 0.01 0.1 1 (Hf/Sm)N Mantle xenoliths Continental carbonatites Oceanic carbonatite melts SLC pyroxenite xenoliths Hawaiian lavas and glasses World-wide carbonatites Fig. 5. Primitive-mantle-normalized trace-element ratios in mantle xenoliths and in carbonatite melt/magma: (Hf/Sm) n vs (Ti/Eu) n ; (La/K) n ; Zr/Hf; (K/Th) n ; (Ba/ K) n ; (Ba/Th) n ; (Sm/Nd) n ; (Rb/Sr) n . Composition of mantle xenoliths affected by carbonatite metasomatism; composition of continental carbonatites; oceanic carbonatite melts; pyroxenite xenoliths from SLC, Hawaiian Islands; rejuvenated-stage Hawaiian lavas and glasses; world-wide carbonatite composition are plotted. Compositions of mantle peridotites affected by carbonatite metasomatism are from Rudnick et al., 1993; Ionov et al., 1993; Yaxley et al., 1991. Extrusive carbonatite magma and melt compositions are from Nelson et al. (1988), Gerlach et al. (1988), Woolley et al. (1991), Beccaluva et al. (1992), Tayoda et al. (1994), Hoernle et al. (2002) and Bizimis et al. (2005). Compositions of pyroxenite xenoliths are from Frey (1980). The data sources are given in Supplementary Datasets 1, 2 and Table 1. Primitive-mantle composition after Sun and McDonough (1989). A.Y. Borisova and R. Tilhac Earth-Science Reviews 222 (2021) 103819 16 Anderson, K.R., Poland, M.P., 2017. Abundant carbon in the mantle beneath Hawai′i. Nat. 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