Carbonatite-Metasomatism Signatures Hidden in Silicate-Metasomatized

Received: 10 November 2016 Revised: 21 January 2017 Accepted: 16 February 2017 DOI: 10.1002/gj.2920

RESEARCH ARTICLE

Carbonatite‐metasomatism signatures hidden in silicate‐ metasomatized mantle xenoliths from NE China

Ben‐Xun Su1 | Xin‐Hua Zhou1 | Yang Sun1 | Ji‐Feng Ying1 | Patrick Asamoah Sakyi2

1 State Key Laboratory of Lithospheric Evolution, Institute of Geology and Lithium isotopes measured in situ in minerals from typical silicate‐metasomatized mantle xeno- Geophysics, Chinese Academy of Sciences, liths from NE China show that olivine has higher Li abundances of 1.2–4.0 ppm and higher δ7Li Beijing, China values of −0.12–15.46‰ than those in orthopyroxene (Li = 0.56–3.0 ppm; δ7Li = −11.84– 2 Department of Earth Science, University of 7.31‰) and clinopyroxene (Li = 0.21–2.1 ppm; δ7Li = −9.81–14.75‰). The Li distributions Ghana, Legon‐Accra, Ghana between these coexisting minerals show a prominent signature of carbonatite metasomatism. Correspondence δ7 Ben‐Xun Su and Xin‐Hua Zhou, State Key The correlation of Li with Li abundance in orthopyroxene is in accordance with petrological Laboratory of Lithospheric Evolution, Institute expectation of preferential reaction of orthopyroxene with carbonatite melt. The carbonatite of Geology and Geophysics, Chinese Academy metasomatic agent inferred from the Li isotope systematics is compatible with petrological and of Sciences, P.O. Box 9825, Beijing 100029, geochemical features such as the presence of apatite, appearance of wehrlite, and presence of China. Email: [email protected]; high‐Mg# minerals and low Ti/Eu in clinopyroxene. The complicated Li isotope composition of [email protected] olivine implies that carbonatite metasomatism occurred after silicate metasomatism. These features indicate that the predominant silicate metasomatism is extensively recorded by petrology, Funding information mineralogy, and geochemistry, whereas Li isotope systematics is more sensitive to subordinate National Natural Science Foundation of China, carbonatite metasomatism. The metasomatic melts are inferred to be relatively enriched in 6Li Grant/Award Number: 41173045, 41522203, 41173011; Youth Innovation Promotion and thus suggests that they were probably derived from a highly dehydrated slab. Association, Chinese Academy of Sciences, Grant/Award Number: 2016067 KEYWORDS

Handling editor: Y. Liu Li isotopes, lithospheric mantle, mantle metasomatism, mantle xenoliths

1 | INTRODUCTION melts makes their discriminations more blurred (Dalton & Presnall, 1998; Dawson, Pinkerton, Pyle, & Nyamweru, 1994; Moore & Metasomatism is a universal phenomenon in the Earth’s mantle and Wood, 1998; Xiao et al., 2010). plays a significant role in modifying the physical and chemical proper- Nonetheless, newly developed Li isotope systematics have been ties of the mantle (Menzies & Hawkesworth, 1987). Two types of employed to discriminate different mantle metasomatic agents mantle metasomatic melts, namely, silicate and carbonatite melts, have (Krmíček, Romer, Ulrych, Glodny, & Prelević, 2016; Seitz & Woodland, been recognized. Due to distinct compositional natures, their impacts on 2000; Su et al., 2014a; Woodland, Seitz, & Yaxley, 2004). An apparent the mantle are quite different; that is, involvement of carbonatite melts disequilibrium Li distribution between olivine and clinopyroxene would elevate electrical conductivity of the mantle three orders of commonly results from mantle metasomatism. Lithium concentrations magnitude higher than silicate melts (Gaillard, Malki, Iacono‐Marziano, would be elevated in mantle minerals in metasomatism, with preferen- Pichavant, & Scaillet, 2008). Hence, it is important to distinguish these tial incorporation into olivine relative to clinopyroxene during two metasomatic agents in order to better understand mantle heteroge- carbonatite metasomatism, whereas the opposite is true in silicate neity and the genesis of diverse magmatism. Although many geochemi- metasomatism (Seitz & Woodland, 2000; Woodland et al., 2004). cal indicators have been established for distinguishing metasomatic Isotopically, carbonatite‐metasomatized olivine grains are character- agents, more empirical and experimental observations show that the ized by lower δ7Li values than normal mantle value, whereas silicate‐ mantle affected by carbonatite or silicate melt metasomatism would metasomatized olivine has elevated δ7Li (Su et al., 2014a). These present qualitatively similar patterns or signatures (Laurora et al., elemental and isotopic discriminators of Li have been successfully 2001; Su et al., 2012; Sweeney, Prozesky, & Przybylowicz, 1995; applied so far in many case studies (Li, Xia, & Deloule, 2012; Rudnick Zhang, Suddaby, O’Reilly, Norman, & Qiu, 2000). Furthermore, & Ionov, 2007; Su, Zhang, Deloule, Vigier, & Sakyi, 2014b; Su, Zhou, commonly mutual immiscibility between carbonatite and silicate & Robinson, 2016; Tang, Zhang, Nakamura, & Ying, 2011; Zhang,

Deloule, Tang, & Ying, 2010). Additionally, there are also vast differ- volcanic rocks represented by the Changbaishan volcano, which ences in Li abundances and heterogeneity in δ7Li values for various erupted in 1120 B.C. and 1050, 1413, 1597, 1668, and 1702 A.D. in types of carbonatites (Halama, McDonough, Rudnick, & Bell, 2008; the east, are mostly alkaline basalts (Zou et al., 2003). Their genesis Harmer, Lee, & Eglington, 1998), which may account for variable has been linked to mantle upwelling induced by a slab window during compositions in carbonatite metasomatism. the Pacific subduction (Tang et al., 2014). The Wudalianchi‐Keluo vol- In this study, we examined Li distribution and isotopic composi- canic field in the west (Figure 1) consists of around 20 volcanic cones tions of major constituent minerals of mantle xenoliths from the and is dominated by potassic to ultrapotassic rocks. They erupted dur- Dayishan volcanic rocks in the Keluo area, NE China, to track metaso- ing the Late Miocene–Pleistocene (10–0.11 Ma) and more recently matic signatures. Typical silicate metasomatic features in these (1719–1721 A.D.). The major rocks are leucitite, basanite, and tephrite xenoliths have been investigated with respect to petrology, mineral (Liu, 1987; Zhang et al., 2012). These potassic rocks display a typical chemistry, and geochemistry (Zhang, Liu, Ge, Wu, & Chu, 2011; Zhang enriched mantle I signature, and their origin is still controversial, that et al., 2000), whereas carbonatite metasomatic signatures remain is, whether they are from metasomatized lithospheric mantle, astheno- ambiguous. Zhang et al. (2000) suggested that a combination of spheric mantle, delaminated lower crust, or mantle transition zone petrologic and geochemical characteristics from the Keluo xenoliths (Zhang, Suddaby, Thompson, Thirlwall, & Menzies, 1995; Zou et al., is more consistent with potassic silicate melts as the agents of metaso- 2003; Chen, Zhang, Graham, Su, & Deng, 2007; Chu et al., 2013; matism. Studies by Zhang, Shao, Xu, Wang, and Chen (2007) and Kuritani, Kimura, Ohtani, Miyamoto, & Furuyama, 2013; Sun et al., Zhang et al. (2011) discovered some additional features pointing to 2014; Sun, Ying, Su, Zhou, & Shao, 2015; Zhao, Fan, Zou, & Li, 2014; localized carbonatite metasomatism. In this study, the Li data obtained Sheng, Liao, & Gerya, 2016). The Dayishan volcano, with an age of from the Keluo xenoliths shed more light on carbonatite metasoma- 0.13 Ma, is one of the eruptive centers in the Wudalianchi‐Keluo area tism preserved in these typical silicate‐metasomatized xenoliths and (Zhang et al., 2012; Figure 1) and contains abundant mantle xenoliths. are therefore used to constrain the nature and origin of such a metaso- The xenoliths vary from 1 to 6 cm in size and are mainly spinel‐facies matic agent. peridotite and websterite. Samples selected for Li isotope analysis in this study were collected from the Dayishan volcano. They consist of two lherzolites, three harzburgites, two wehrlites, and two websterites 2 | REGIONAL GEOLOGY AND SAMPLE (Table 1). DESCRIPTIONS

2.1 | Harzburgite The Cenozoic volcanic field in NE China forms an important part of the West Pacific volcanic zone (Liu, Masuda, & Xie, 1994). These volcanic The harzburgites are commonly coarse grained and display curved rocks are mainly distributed in the boundary between the margin of grain boundaries (Figure 2a). Olivine is 3 to 7 mm in diameter and the Songliao Basin and its surrounding orogenic belts (Figure 1). The displays kink band texture. Orthopyroxene is highly variable in size,

FIGURE 1 Distribution of Cenozoic basaltic volcanic rocks in NE China and xenolith location in this study [Colour figure can be viewed at wileyonlinelibrary.com] 684 SU ET AL.

TABLE 1 Li abundances and isotopic compositions of olivine (Ol), orthopyroxene (Opx), and clinopyroxene (Cpx) in the Dayishan xenoliths from NE China

Sample Ol Li δ7Li 2σ Opx Li δ7Li 2σ Cpx Li δ7Li 2σ

Harzburgite 12DYS‐04 Rim 1.68 10.15 1.14 Rim 0.75 −3.53 1.36 Rim 0.43 −7.00 1.41 Mantle 1.61 8.75 1.19 Core 1.63 7.71 1.25 Core 0.73 −0.30 1.37 Core 0.21 −0.88 1.77

12DYS‐16 Rim 2.01 9.35 1.12 Rim 0.56 7.31 1.49 Rim 0.26 11.80 1.66 Core 2.01 11.14 1.16 Core 0.72 5.12 1.37 Core 0.37 5.45 1.44

12DYS‐05 Rim 2.64 4.95 1.08 Rim 1.00 2.46 1.26 Core 2.50 4.99 1.07 Core 1.18 3.83 1.21 Lherzolite 12DYS‐11 Rim 1.31 6.35 1.20 Rim 0.73 1.86 1.37 Rim 0.25 11.21 1.65 Mantle 1.21 8.08 1.29 Mantle 0.66 4.13 1.47 Mantle 0.26 9.69 1.75 Core 1.23 10.51 1.24 Core 0.69 3.42 1.39 Core 0.30 10.17 1.55

12DYS‐02 Rim 3.43 4.10 1.03 Rim 2.92 −11.84 1.08 Rim 2.02 −8.58 1.02 Mantle 3.21 4.63 1.04 Mantle 2.05 −9.81 1.03 Core 3.18 3.62 1.05 Core 3.03 −10.94 1.03 Core 1.98 −8.45 1.01 Wehrlite 12DYS‐06 Rim 1.23 15.46 1.22 Rim 1.50 −8.97 1.03 Core 1.40 8.11 1.25 Core 1.20 −6.74 1.10

12DYS‐17 Rim 3.78 −0.12 1.03 Rim 0.44 1.36 1.37 Mantle 3.05 4.47 1.04 Mantle 0.56 14.75 1.27 Core 2.84 2.37 1.05 Core 0.47 9.35 1.34 Websterite 12DYS‐20 Rim 1.83 1.31 1.13 Rim 1.20 −4.79 1.21 Rim 0.78 −2.41 1.17 Mantle 1.17 −3.56 1.21 Mantle 0.69 −2.13 1.21 Core 1.74 3.74 1.20 Core 1.16 −3.71 1.28 Core 0.69 −3.07 1.21

12DYS‐15 Rim 4.04 5.95 1.02 Rim 2.29 −8.69 1.07 Rim 0.65 −1.59 1.22 Mantle 3.88 6.25 1.01 Mantle 2.14 −8.97 1.08 Mantle 0.58 −0.60 1.30 Mantle 3.73 6.19 1.03 Mantle 2.29 −6.85 1.09 Mantle 0.57 −0.22 1.27 Core 3.61 5.48 1.05 Core 2.33 −3.68 1.06 Core 0.54 1.25 1.29 ranging from 0.5 to 8 mm, and shows denticulate or curved contact 2.3 | Wehrlite with grains. Some coarse‐grained orthopyroxene grains contain tiny The wehrlites are characterized by inequigranular texture and are clinopyroxene lamellae. Spinel is commonly rounded in shape and made up of olivine and clinopyroxene with minor or no orthopyroxene poikilitic among silicate minerals and occasionally occurs as inclusions and spinel. Phlogopite is abundant in sample 12DYS‐17 (Figure 2c) and within olivine and orthopyroxene. All the harzburgites in this study is also reported in Zhang et al. (2011). Orthopyroxene + spinel exsolu- and in previous studies (e.g., Zhang et al., 2011) contain interstitial tion lamellae in clinopyroxene show subperpendicular distributions fine‐grained clinopyroxene (mostly <1 mm). A melt pocket observed similar to those in lherzolites. in sample 12DYS‐05 (Figure 2a) is composed of clinopyroxene, olivine, spinel, and/or glass. 2.4 | Websterite

Websterite in this study is a new xenolith type found in the Dayishan | 2.2 Lherzolite locality. They display a mosaic texture and are dominated by The lherzolites consist of olivine, orthopyroxene, clinopyroxene, and orthopyroxene and clinopyroxene with accessory olivine and spinel spinel with occasional occurrence of glass, phlogopite, and rutile as (Figure 2d). Olivine is rounded in shape and displays kink bands. Exso- reported by Zhang et al. (2011). They display equigranular textures lution is commonly observed in orthopyroxene and clinopyroxene. and well‐defined grain boundaries. Triple junctions are common among Melt pocket is also observed in these websterites. the neoblasts (Figure 2b). Olivine is 2 to 4 mm in diameter and shows smooth contact with adjacent grains. Exsolution lamellae are common 3 | ANALYTICAL METHODS in orthopyroxene and clinopyroxene. The orthopyroxene has clinopyroxene lamellae along crystallographic controlled directions; In situ Li contents and isotopic compositions were measured on gold‐ whereas, the clinopyroxene contains orthopyroxene + spinel exsolu- coated thin sections using a Cameca IMS‐1280 SIMS at the Institute tion lamellae, with subperpendicular distributions with respect to each of Geology and Geophysics, Chinese Academy of Sciences, Beijing, other. China, following established methods (Decitre et al., 2002). The O− SU ET AL. 685

FIGURE 2 Photomicrographs of the Dayishan mantle xenoliths from NE China. (a) Harzburgite 12DYS‐05 contains melt pockets (MP) associated with secondary clinopyroxene (Cpx); (b) lherzolite 12DYS‐02 shows triple junction texture between major minerals; (c) wehrlite 12DYS‐17 contains phlogopite (Phl) as metasomatic product; (d) websterite 12DYS‐15 displays mosaic texture. Ol = olivine; Opx = orthopyroxene; Sp = spinel [Colour figure can be viewed at wileyonlinelibrary.com]

primary ion beam was accelerated at 13 kV, with an intensity of about spinel (39–56); and low Al2O3 contents in orthopyroxene 15 to 30 nA. The elliptical spot was approximately 20 × 30 μm in size. (1.85–2.79 wt.%) and clinopyroxene (2.62–4.87 wt.%; Table S1), which Positive secondary ions were measured on an ion multiplier in pulse‐ can be ascribed to 3–13% melt extraction as estimated by Zhang et al. counting mode, with a mass resolution (M/DM) of 1,500 and an energy (2000, 2011). Two lherzolite samples show distinct compositions; slit open at 40 eV without any energy offset. A 180‐s presputtering sample 12DYS‐02 has mineral chemistry similar to the harzburgites, without raster was applied before analysis. The secondary ion beam whereas sample 12DYS‐11 is relatively fertile with respect to Mg# in position in the contrast aperture, as well as the magnetic field and olivine (90.4), orthopyroxene (90.4), and clinopyroxene (91.7) and Cr# the energy offset, was automatically centered before each measure- in spinel (11) and Al2O3 content in clinopyroxene (5.71 wt.%; Table ment. Thirty cycles were measured with counting times of 12, 4, and S1). Major elemental compositions of minerals in the wehrlites and 4 s for 6Li, background at the 6.5 mass, and 7Li, respectively. Olivine websterites have much in common with those in the lherzolite sample sample 06JY29Ol with Mg# of 91.2, orthopyroxene sample 12DYS‐11. Additionally, wehrlite sample 12DYS‐06 has slightly lower 06JY34Opx with Mg# of 92.1, and clinopyroxene sample 06JY29Cpx Mg# in olivine and pyroxenes than those in sample 12DYS‐17, and with Mg# of 91.9 (Su et al., 2015) were used as standards. The the same occurs between websterite samples 12DYS‐15 and 7 7 7 6 7 6 measured δ Li values are given as δ Li, [( Li/ Li)sample/( Li/ Li)L‐ 12DYS‐20 (Table S1).

SVEC − 1] × 1,000, relative to the standard NIST SRM 8545 (L‐SVEC; Clinopyroxene is characterized by light rare earth element enrich- Flesch, Anderson, & Svec, 1973). The instrumental mass fractionation ment relative to heavy rare earth element (except lherzolite sample 7 7 7 is expressed in δ Li units: Δi = δ LiSIMS − δ LiMC‐ICPMS. Eighteen 12DYS‐11) and negative Nb, Ta, and Ti anomalies in spider diagrams analyses on the olivine standard in this study yielded homogeneous (Figure 3). Clinopyroxene in the websterites differs from those of other Li isotopic composition with Δi = 24.7 Æ 1.6‰ (2SD); 18 analyses on rock types by displaying prominent large ion lithophile element enrich- the orthopyroxene standard yielded homogeneous Li isotopic compo- ment. The (La/Yb)N ratios of clinopyroxene in the xenoliths are highly sition with Δi = 39.5 Æ 1.6‰ (2SD); and 31 analyses on the variable and mostly high, corresponding to variable and low Ti/Eu clinopyroxene standard yielded homogeneous Li isotopic composition ratios (Figure 4; Table S2). These trace element features together with with Δi = 37.3 Æ 1.5‰ (2SD). major elemental compositions suggest that the mantle xenoliths had been significantly metasomatized after partial melting. The Li concentration and isotopic data are reported in Table 1. In 4 | ANALYTICAL RESULTS general, Li abundance in the minerals in the Dayishan xenoliths is variable from 0.21 to 4.0 ppm but is homogenously distributed within Compositionally, minerals in the harzburgites are characterized by individual grains, whereas Li isotopic compositions are highly variable refractory components, that is, high Mg# in olivine (~92), with δ7Li ranging from −11.84‰ to 15.46‰ at intersample and orthopyroxene (~92), and clinopyroxene (91.7 and 93.4); high Cr# in intermineral scales and have large difference up to 13‰ of δ7Li in 686 SU ET AL.

FIGURE 3 Chondrite‐normalized rare earth element and primitive mantle‐normalized trace element patterns for clinopyroxene of the Dayishan mantle xenoliths from NE China. The chondrite and primitive mantle values are from Anders and Grevesse (1989) and Sun and McDonough (1989), respectively [Colour figure can be viewed at wileyonlinelibrary.com]

rim–mantle–core profile (Table 1). Olivine has higher Li abundances of 1.21–4.0 ppm and higher δ7Li values of −0.12–15.46‰ than those in orthopyroxene (Li = 0.56–3.0 ppm; δ7Li = −11.84–7.31‰) and clinopyroxene (Li = 0.21–2.1 ppm; δ7Li = −9.81–14.75‰; Table 1; Figure 5). The two harzburgites and one lherzolite sample (12DYS‐11) show lower Li abundances in minerals than their counterparts in lherzolite sample 12DYS‐02, wehrlites, and websterites (Figure 6). The δ7Li values are well correlated with Li abundances in orthopyroxene and clinopyroxene but are very complex in olivine in the various rock types (Figure 7).

5 | DISCUSSION

Petrological and geochemical features of the mantle xenoliths in the Wudalianchi‐Keluo volcanic rocks in this study and the literature FIGURE 4 Plot of Ti/Eu versus (La/Yb)N for clinopyroxene of the Dayishan mantle xenoliths from NE China. Fields of worldwide reveal significant metasomatism in the lithospheric mantle beneath this 7 carbonatite and silicate metasomatism are after Coltorti et al. (1999) region. The Li distribution and enrichment and large δ Li variations of [Colour figure can be viewed at wileyonlinelibrary.com] the minerals established in this study further confirm the occurrence SU ET AL. 687

FIGURE 5 Histogram of Li contents and δ7Li values of olivine, orthopyroxene, and clinopyroxene of the Dayishan mantle xenoliths from NE China. δ7Li of MORB is inferred from relatively pristine olivine and fresh MORB (Jeffcoate et al., 2007; Magna et al., 2006; Seitz, Brey, Lahaye, Durali, & Weyer, 2004; Tomascak et al., 2008) [Colour figure can be viewed at wileyonlinelibrary.com]

locality (Figure 2) are evidence of modal silicate metasomatism, as silicatemelt–peridotiteinteraction isa processresponsible for producing pyroxenes at the expense of olivine and transforming harzburgite and lherzolite to pyroxenite (Su et al., 2012). Clinopyroxene in the Dayishan

mantle xenoliths mostly has low (La/Yb)N (chondrite‐normalized) and highly variable Ti/Eu ratios, which are consistent with metasomatism by silicate melts (Figure 4; Coltorti, Bonadiman, Hinton, Siena, & Upton, 1999; Zhang et al., 2000, 2011). Zhang et al. (2000) ruled out carbonatite melts as responsible for the metasomatism due to a lack of petrographic evidence for mantle carbonates, replacement of orthopyroxenes by clinopyroxene and/or wehrlite products as observed from carbonate‐bearing peridotites and wehrlites elsewhere (Ionov, O’Reilly, Genshaft, & Kopylova, 1996; Neumann, Wulff‐ Pedersen, Pearson, & Spencer, 2002; Su et al., 2012; Yaxley, Green, & Kamenetsky, 1998). They, however, observed high Ca/Al ratios in these xenoliths and high field strength element depletion and low Ti/Eu in the constituent clinopyroxene, which have been widely interpreted as key signatures of carbonatite metasomatism (Harmer et al., 1998; Klemme, van der Laan, Foley, & Gunther, 1995; Laurora et al., 2001; Rudnick, McDonough, & Chappell, 1993; Yaxley et al., 1998). Zhang et al. (2007) found apatite in some xenoliths and a

wehrlite sample, while Zhang et al. (2011) discovered high (La/Yb)N

and CaO/Al2O3 ratios in some samples, all pointing to local carbonatite metasomatism. Our study indicates that such carbonatite metasomatism is well recorded by Li isotope systematics. Below, we first discuss relatively minor carbonatite metasomatism compared to the predominant silicate metasomatism in the Dayishan mantle xenoliths and then use Li isotopes to constrain the origin of metasomatic melts.

5.1 | Carbonatite metasomatism FIGURE 6 Li–Li diagrams showing Li abundances in coexisting orthopyroxene and clinopyroxene and olivine and clinopyroxene of As carbonatite melt is Si undersaturated and alkaline in nature (Chen, the Dayishan mantle xenoliths from NE China. Equilibrium partitioning Kamenetsky, & Simonetti, 2013; Harmer et al., 1998), carbonatite melt fields are from Woodland et al. (2004). Average values of mantle reacts first with orthopyroxene to form clinopyroxene, converting olivine, orthopyroxene, and clinopyroxene are from Su et al. (2014a) harzburgite or clinopyroxene‐poor lherzolite to clinopyroxene‐rich [Colour figure can be viewed at wileyonlinelibrary.com] lherzolite or wehrlite (Wallace & Green, 1988; Yaxley, Crawford, & of metasomatism (Figures 6 and 7), inferred to have been caused by Green, 1991; Laurora et al., 2001). Mineral products of carbonatite typical potassic silicate metasomatic agents (Zhang et al., 2000). The metasomatism also include olivine, amphibole, feldspar, apatite, rutile, silicate melt pockets, phlogopites, and websterites in the Dayishan and sulphide with rare phlogopite (Ionov et al., 1996; Rudnick et al., 688 SU ET AL.

1993; Su et al., 2010; Yaxley et al., 1991). The appearance of wehrlite grains (Figures 3 and 4), suggests a petrographic linkage with carbonatite (Figure 2c) and apatite in some of the Keluo xenoliths (Zhang et al., metasomatism. Generally high Mg# of the minerals in the websterites

2007, 2011), together with high (La/Yb)N ratios in some clinopyroxene and wehrlites (Table S1) also reflect a genetic relation with carbonatite metasomatism. The reaction between carbonatite melt and peridotite causes orthopyroxene to preferentially incorporate Li (Figure 6a). As a conse- quence, the δ7Li value of orthopyroxene significantly decreases and shows good correlations with Li abundance (Figure 7b) as light isotopes diffuse faster than heavy ones (Parkinson, Hammond, James, & Rogers, 2007; Richter, Davis, DePaolo, & Watson, 2003). Clinopyroxene in harzburgites and lherzolites has lower Li concentration than average value of mantle clinopyroxene due to melt extraction (Figure 6). Nonetheless, Li isotopes of the clinopyroxene may have been re‐equilibrated with the metasomatic melts as evident by the slight Li enrichment and significant δ7Li decrease in the rim relative to the core of clinopyroxene except sample 12DYS‐04 (Figure 7c). In addition, clinopyroxene in lherzolite sample 12DYS‐02, with the highest Li abundance, plots within or close to the equilibrium partitioning field (Figure 6; Woodland et al., 2004) and displays homogeneous Li abundance and isotopic compositions similar to its coexisting olivine and orthopyroxene, which are compatible with equilibrium texture (Figure 2b). Higher Li abundance in olivine than the coexisting orthopyroxene and clinopyroxene in individual samples is in accordance with carbonatite metasomatism (Figure 6) that commonly partitions more Li into olivine than silicate metasomatism (Su et al., 2014a, 2014b; Woodland et al., 2004). Such Li elemental distribution appears as a prominent signature of carbonatite metasomatism; however, taking into account the Li isotopic composition, it is most likely that the observed features and effects were caused by a combination of both carbonatite and silicate metasomatism. The olivine grains with Li abundance of average mantle olivine show higher δ7Li values than the average value of mantle olivine, reflecting silicate‐metasomatic signature (Figure 7a; Su et al., 2014a, 2014b). The olivine grains enriched in Li (>2.5 ppm) have average mantle δ7Li values or even lower, which is probably correlated with carbonatite metasomatism (Figure 7a). Fur- thermore, these olivine grains are mostly characterized by higher‐Li and lower‐δ7Li rims than their cores and display poor correlations between Li abundance and δ7Li value relative to the pyroxene. Studies have shown that some reverse rim–core profiles might be generated by interdiffusive modifications (Dohmen, Kasemann, Coogan, & Chakraborty, 2010; Wunder et al., 2007). The complex and restricted zoning of Li abundance and δ7Li in olivine relative to orthopyroxene and clinopyroxene (Figure 7) are probably due to faster diffusion of Li in pyroxene than in olivine (Dohmen et al., 2010; Parkinson et al., 2007; Richter, Watson, Chaussidon, Mendybaev, & Ruscitto, 2014; Rudnick & Ionov, 2007). Additionally, websterite is generally thought to be products of silicate metasomatism and expected to be rich in heavy Li isotopes (Su et al., 2014a). The websterites in this study have FIGURE 7 Li‐δ7Li diagrams showing generally negative correlations lower δ7Li values of the constituent minerals (olivine = 1.31–6.25‰; δ7 between Li abundance and Li value in major minerals of the orthopyroxene = −8.97‰ to −3.56‰; clinopyroxene: −3.07–1.25‰) Dayishan mantle xenoliths from NE China. The dashed lines link the than expected, thus reflecting compositional influence of carbonatite core and rim of each mineral grain. The grey bars indicate average values of mantle minerals (Su et al., 2014a). The trends of silicate and metasomatism. Notably, the signatures of carbonatite metasomatism carbonatite metasomatism agents are defined by Su et al. (2014a) are mostly recorded in the rims of the studied minerals, whereas sili- [Colour figure can be viewed at wileyonlinelibrary.com] cate metasomatism is mostly present in the cores, suggesting that SU ET AL. 689 carbonatite metasomatism occurred after silicate metasomatism. We low‐δ7Li metasomatic melts. Alternatively, Marschall, Pogge von further conclude that predominant silicate metasomatism is Strandmann, Seitz, Elliott, and Niu (2007) proposed kinetic redistribu- extensively recorded by petrology, mineralogy, and geochemistry, tion and addition of Li from ambient country rocks for large Li isotopic whereas Li isotope systematics is more sensitive to subordinate fractionation and high Li content in orogenic eclogites. Of course, carbonatite metasomatism. kinetic effects may ultimately generate the feedstock for light‐Li melts through processes occurring in the sources of such rocks, but the prob- lem is that we may not be able to distinguish their compositional signa- 5.2 | Constraints on the origin of metasomatic melts tures that were derived from the sources rather than processes The inferred potassic silicate melts acting as metasomatic agents in the occurring during exhumation and emplacement (Tomascak et al., Wudalianchi‐Keluo lithospheric mantle were interpreted to have 2016). Thus, the highly dehydrated slab is presumed to have originally originated from deep asthenospheric mantle but not conclusively contained much lower Li concentrations and δ7Li values under mantle discerning the role of subducted materials (Zhang et al., 2000, 2007). conditions and is responsible for the unusual Li characteristics in the Local carbonatite metasomatism was referred in the study of Zhang mantle. et al. (2011), but neither the composition nor the origin of the carbonatite melts was constrained. The silicate and carbonatite melts 6 | CONCLUSIONS probably share, although difficult to test, a common source, as the occurrence of the potassic volcanic rocks has close affinity to that of The investigations of Li elemental and isotopic compositions in the the carbonatites (e.g., Castorina, Stoppa, Cundari, & Barbieri, 2000; mineral constituents of the Dayishan mantle xenoliths indicate Dawson et al., 1994; Harmer et al., 1998; Stoppa, Cundari, Rosatelli, disequilibrated Li distributions between coexisting minerals and & Woolley, 2003). If so, they might have been derived from a mantle heterogeneous Li isotopic compositions. These features, together with source with subducted components and were likely differentiated dur- petrological observations and mineral chemistry results, reveal that ing percolation in the mantle through wall–rock interaction, fraction- these rocks have undergone carbonatite metasomatism following ation, and immiscibility (Brooker & Kjarsgaard, 2011; Dasgupta, silicate metasomatism. The metasomatic melts are inferred to have Hirschmann, & Stalker, 2006; Moore & Wood, 1998; O’Reilly & Griffin, been derived from a highly dehydrated slab with low Li content and 2013; Su et al., 2012), which are consistent with the local and variable δ7Li value. compositional features observed in the studied spinel‐facies xenoliths. The minerals studied here mostly have normal mantle or lower Li ACKNOWLEDGEMENTS abundance, significantly lower than their counterparts in This study was financially supported by the National Natural Science metasomatized mantle nodules worldwide (Su et al., 2014a; Tomascak, Foundation of China (Grants 41173045, 41522203, and 41173011) Magna, & Dohmen, 2016). Even the websterites and wehrlites that and Youth Innovation Promotion Association, Chinese Academy of formed during metasomatism contain <4 ppm Li in minerals (Table 1). Sciences (Grant 2016067). This low‐Li feature implies that the metasomatic melts were significantly depleted in Li relative to oceanic island basalts (OIBs), arc lavas, REFERENCES continental volcanic rocks, and carbonatites (see summary inTomascak Anders, E., & Grevesse, N. (1989). Abundances of the elements: Meteoritic et al., 2016). Hence, the source rocks of the melts probably suffered and solar. 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