Late Cenozoic intraplate volcanism in Changbai volcanic field, on the ...

2014-080

research-articleThematic Set Article: Asian TectonicsXXX10.1144/jgs2014-080M. Zhang et al.Intraplate volcanism in NE China

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Thematic set: Asian Tectonics Published online December 15, 2014

Journal of the Geological Society doi:10.1144/jgs2014-080 | Vol. 172 | 2015 | pp. 648–663

Late Cenozoic intraplate volcanism in Changbai volcanic field, on the border of China and North Korea: insights into deep subduction of the Pacific slab and intraplate volcanism Maoliang Zhang, Zhengfu Guo*, Zhihui Cheng, Lihong Zhang & Jiaqi Liu Key Laboratory of Cenozoic Geology and Environment, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China * Correspondence: [email protected]

Abstract: Late Cenozoic intraplate volcanism in the Changbai volcanic field straddles the border between China and North Korea, forming basic (alkali basalts and tholeiites) and intermediate–acidic (trachytes and peralkaline rhyolites) volcanic rocks with ages ranging from 19.9 Ma to the present. Major and trace elements and Sr–Nd–Pb isotopic compositions indicate that the basic magmas were formed by partial melting of the depleted mid-ocean ridge basalt-source mantle and contaminated by aqueous fluids with EM1-like isotopic signatures from the lower continental crust, whereas the intermediate–acidic magmas resulted from assimilation–fractional crystallization processes on the basic magmas. On the basis of petrological and geochemical studies, we propose that a magma underplating model could be used to explain the genesis of the Late Cenozoic intraplate volcanism. In this model, the mantle-derived basaltic magma was underplated at the base of the continental crust and contaminated by EM1-like aqueous fluids liberated from the lower crustal granulites. Geodynamic processes responsible for the magma underplating and subsequent eruption might be lithospheric extension and small-scale thermal upwelling, induced by episodic changes in convergence rates between the Eurasian and Pacific plates, indicating a genetic link between the intraplate volcanism and deep subduction of the Pacific slab. Received 1 July 2014; accepted 26 July 2014

The theory of plate tectonics, which successfully explains volcanism at mid-ocean ridges and subduction zones (Langmuir et al. 1992; Tatsumi & Eggins 1995), has long been considered inapplicable to study volcanism that occurs far from plate boundaries (Lee & Grand 2012). Intraplate volcanism is generally interpreted as the result of a mantle plume or ‘hotspot’ originating from the core–mantle boundary (Morgan 1971), especially when large igneous province (LIP) volcanism is involved (Campbell & Griffiths 1990). Nevertheless, a recent geodynamic model reveals that the formation of the Steens–Columbia River flood basalts about 17 Ma ago might have been triggered by rapid mantle upwelling associated with tearing of the subducting Farallon slab under the North American plate (Liu & Stegman 2012), indicating conceivable links between slab subduction and intraplate volcanism (Faccenna et al. 2010). This model might be illuminating for the genesis of Late Cenozoic intraplate volcanism in northeastern China, which remains a matter of heated debate (e.g. Basu et al. 1991; Deng et al. 1992; Choi et al. 2006; Zou et al. 2008; Kuritani et al. 2011). Intraplate volcanism in the Changbai volcanic field, located on the border of China and North Korea, first occurred in the Early Miocene and continued to the present (the last eruption was in AD 1903: Wei et al. 2013, and references therein) with several interruptions (Liu 1987, 1988), making it appropriate for investigation of the relationship between plate tectonics and intraplate volcanism because of its long-lived volcanic activity and volcanic rocks ranging from the basic to the intermediate–acidic series. Previous studies have attributed the Late Cenozoic intraplate volcanism in NE China to the following causes: (1) a mantle plume and sub-plume resulting from partial melting of the mantle in the presence of volatiles (Deng et al. 1992, 2004); (2) continental rifting associated with development of the Japan Sea (Liu et al. 2001); (3) asthenosphere upwelling owing to subduction of the Pacific plate or Kula–Pacific ridge (Basu et al. 1991; Zou et al. 2008); (4) hydrous plume upwelling from the mantle transition zone (MTZ; Zhao et al. 2009;

Kuritani et al. 2011). Despite much work, significant uncertainties still exist on the magma evolution and geodynamic processes responsible for the Late Cenozoic intraplate volcanism. It is uncertain whether deep-subducted materials (e.g. aqueous fluids or sediments) from the Pacific plate in the MTZ contribute to the basaltic magma (Zou et al. 2008; Kuritani et al. 2011). The origin of the EM1 component involved in magma evolution is equivocal (Basu et al. 1991; Choi et al. 2006; Kuritani et al. 2011), and, in particular, the geodynamic processes responsible for the Late Cenozoic intraplate volcanism need to be well constrained. In addition, Tianchi volcano, located in the central part of the Changbai volcanic field, is the most active and the only volcano with felsic magma eruptions in North China (Deng et al. 1992), differing from the adjacent active volcanoes in the Longgang and Jingbohu volcanic fields (Q.C. Fan et al. 1999, 2003). However, the genesis of felsic magma eruptions at Tianchi volcano is poorly understood. Recent volcanic observatory studies (e.g. Xu et al. 2012a) signal an increasing activity of the magma chamber beneath Tianchi volcano. However, the lack of detailed field sampling and of petrological and geochemical data has precluded further constraints on the genesis of the intraplate volcanism and assessment of the recent volcanic observatory results. In this study, we report new major and trace elements and Sr–Nd–Pb isotopic data for Late Cenozoic volcanic rocks in the Changbai volcanic field and explore magma evolution and associated geodynamic processes.

Geological setting The Changbai volcanic field, which straddles the border between China and North Korea, is located within the northeastern margin of the North China Craton (see Fig. 1a). The basement of the Eastern Block of the North China Craton consists primarily of Archaean tonalite–trondhjemite–granodiorite (TTG) gneisses, granitoids and supracrustal rocks, which are locally overlain by

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Intraplate volcanism in NE China

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Fig. 1. (a) Simplified map showing the distribution of Cenozoic volcanic rocks in northeastern China, including the Changbai, Longgang and Jingbohu volcanic fields (modified from Liu et al. 2001). NCC, North China Craton; DTGL, Daxinganling–Taihang Gravity Lineament. (b) Sketch map showing the distribution of Late Cenozoic volcanic rocks in the Changbai, Longgang and Jingbohu volcanic fields (modified from Fan et al. 2007).

Proterozoic–Palaeozoic strata composed of metasedimentary, bimodal volcanic rocks, clastic sedimentary rocks and thick carbonate deposits (Zhao et al. 2001). Voluminous A-type granites were emplaced in northeastern China during the Late Triassic to Early Jurassic and the Early Cretaceous (Jahn et al. 2000; Wu et al. 2002). Since the Late Cretaceous, the tectonic evolution of East Asia has been controlled by the successive subduction of the Kula and Pacific plates (Uyeda & Miyashiro 1974; Yin 2010), as well as the Indo-Asia collision about 55 Ma ago (Tapponnier et al. 2001). Late Cretaceous calc-alkaline volcanic rocks are dominantly distributed in extensional basins of various sizes associated with the rifting systems in eastern China (Ren et al. 2002; Zhang et al. 2002a; W.-M. Fan et al. 2003). Late Cenozoic intraplate volcanic rocks are widely distributed in eastern China (e.g. Zou et al. 2000; Chen et al. 2007), including the Changbai and the adjacent Longgang and Jingbohu volcanic fields (Fig. 1b). Minor basaltic magmas were erupted at some scattered volcanoes in the Changbai volcanic field during the Miocene to Pliocene (19.9–2.6 Ma; Liu 1987, 1988), whereas the predominant basaltic magmas were erupted by Tianchi volcano during the Early Pleistocene (2.34–1.48 Ma; Wei et al. 2013, and references therein) forming an extensive shield-like basaltic platform. The giant volcanic caldera of Tianchi volcano was formed by explosive eruptions of trachytic and peralkaline rhyolitic magmas since c. 1 Ma ago (Fan et al. 2007). Notably, the great Millennium eruption of Tianchi volcano with a Volcanic Explosivity Index (VEI) of seven, which occurred in AD 939–946 (Yin et al. 2012; Xu et al. 2013), gave rise to the huge ejection of about 100 km3 of peralkaline rhyolites and tephra (Zou et al. 2010). In contrast, only basaltic magmas were formed in the Longgang and Jingbohu volcanic fields (Fig. 1b). The basalts of Longgang were formed in the Quaternary and its last eruption occurred c. 1600 years ago (Fan et al. 2002), and basaltic magma eruptions occurred c. 5200–5500 years ago for Jingbohu active volcanoes (Q.C. Fan et al. 2003). In addition, some Late Miocene and Pleistocene basalts were also formed in the Jingbohu volcanic field (Liu et al. 1989).

Samples and analytical methods Mafic and felsic volcanic rocks were collected from the Changbai volcanic field (Table 1). According to previously published age

data (e.g. Liu 1987; Fan et al. 2006), our samples consist of Miocene–Pleistocene basaltic volcanic rocks, Late Pleistocene trachytes and Holocene peralkaline rhyolites. Most basaltic samples are aphyric with microphenocrysts of olivine, plagioclase and clinopyroxene. Trachytic samples are porphyritic, consisting of anorthoclase, plagioclase and rare Fe–Ti oxides. The peralkaline rhyolites are characterized by porphyritic texture, with phenocrysts of K-feldspar and a glass matrix. Whole-rock major element contents (wt%) were determined on fused glass discs by X-ray fluorescence (XRF) using an XRF-1500 sequential spectrometer (Shimadzu, Japan) at the Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing (IGGCAS), following the procedure reported by Guo et al. (2006). Precision is 1–3% RSD for elements present at >1 wt%, and about 10% RSD for elements present at 72) are close to the primary melts in the mantle source (Frey et al. 1978), which is consistent with the presence of spinel lherzolite xenoliths in these alkaline basalts (Wu et al. 1997). Similarly, mantle xenoliths and Ti-amphibole xenocrysts have also been discovered in the Longgang and Jingbohu basalts, respectively (Zhang et al. 2001; Tang et al. 2012). The rapid source-to-surface transportation of alkali basaltic magmas minimizes the influence of crustal contamination and low-pressure fractional crystallization on magma composition. On the other



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Table 1. (Continued) Sample no.: 0911 0912 0913 Locality: Zengfengshan Zengfengshan Zengfengshan Rock type: Basalt Basalt Basalt Age (Ma): 19.9 19.9 19.9 SiO2 TiO2 Al2O3 TFe2O3* MnO MgO CaO Na2O K2O P2O5 LOI Mg-no. La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Sc V Cr Co Ni Cu Zn Ga Rb Sr Y Zr Nb Ba Hf Ta Pb Th U

58.52 0.77 12.48 7.65 0.13 6.20 4.57 1.71 1.41 0.36 7.01 0.67 33.5 68.1 9.0 35.3 6.8 1.51 5.28 0.70 3.57 0.66 1.79 0.26 1.67 0.24 18.42 132.5 222.4 46.5 61.4 121.4 104.4 19.1 45.0 158 17.1 177.4 16.0 73 4.8 0.97 15.0 0.1 0.2

60.32 0.66 13.33 6.57 0.09 4.70 5.61 3.92 1.71 0.29 2.66 0.64 33.1 62.2 8.0 30.3 6.3 1.69 4.82 0.66 3.44 0.62 1.68 0.25 1.55 0.24 15.74 117.9 176.4 24.0 55.3 45.0 80.8 17.3 30.0 688 17.2 176.7 6.0 851 4.9 0.19 11.2 0.0 0.1

49.16 0.78 14.84 8.47 0.17 8.29 8.96 2.82 2.10 0.41 3.38 0.71 35.6 77.2 10.6 44.7 8.8 1.99 7.40 1.07 5.75 1.09 2.90 0.42 2.66 0.38 25.85 146.0 592.8 25.3 180.6 3.0 135.5 22.2 69.3 1469 29.5 112.9 7.3 1037 3.3 0.36 7.7 1.3 0.6

0914 Helong Basalt 2.6

0915 0916 0917 0918 Tumen River Junjianshan Junjianshan Junjianshan Basalt Basalt Basalt Basalt 2.6 2.6 1.57 2.6

58.49 0.90 17.16 6.49 0.11 2.50 5.64 3.94 2.40 0.23 1.96 0.49 25.5 51.0 6.4 24.8 5.5 1.36 4.69 0.75 4.20 0.84 2.37 0.36 2.35 0.36 15.57 131.2 26.6 17.6 12.3 17.1 73.1 19.6 57.8 423 23.4 181.4 7.5 552 5.2 0.51 13.0 6.6 1.6

52.36 1.71 17.53 8.89 0.11 5.90 9.03 3.26 0.85 0.23 0.26 0.62 26.1 51.9 7.0 31.2 7.8 3.79 7.50 1.08 5.74 1.07 2.50 0.35 2.03 0.29 20.09 132.9 86.1 31.0 66.8 31.5 127.5 23.5 34.7 424 25.9 189.6 21.0 1217 4.9 1.33 5.4 2.7 0.5

51.90 2.31 15.98 10.97 0.15 5.30 7.02 3.73 2.38 0.51 -0.24 0.54 35.1 65.1 8.3 32.9 7.2 2.93 6.65 0.98 5.12 0.95 2.34 0.32 1.91 0.28 18.81 160.5 103.8 35.6 95.1 31.2 119.3 23.1 33.5 577 23.6 177.5 29.4 1215 4.8 1.89 5.8 3.7 0.5

49.56 2.51 15.84 12.17 0.15 5.88 8.42 3.02 1.16 0.43 0.46 0.54 27.7 51.3 7.1 29.3 6.8 2.59 6.49 0.97 5.42 1.01 2.42 0.33 1.91 0.27 22.27 183.4 116.6 43.3 117.7 36.1 121.7 22.7 18.9 563 24.1 158.6 23.1 755 4.5 1.51 4.9 2.7 0.5

47.10 3.64 15.89 14.17 0.15 5.08 8.16 3.03 1.37 0.93 0.52 0.47 44.6 84.2 11.6 46.0 10.1 3.67 9.08 1.28 6.77 1.26 2.99 0.40 2.34 0.33 21.67 240.1 37.3 43.0 57.4 37.2 142.5 24.7 20.0 757 31.1 212.0 36.7 1188 5.9 2.53 5.4 4.2 0.7

0919 Junjianshan Basalt 2.98

0921 Guangping Basalt 1.48

52.77 2.38 15.02 11.33 0.14 4.81 7.34 3.26 1.77 0.51 0.38 0.51 29.2 60.0 8.3 36.2 9.3 2.73 8.19 1.20 6.12 1.12 2.83 0.38 2.26 0.33 19.20 160.5 90.1 36.3 81.0 37.5 130.1 22.2 30.4 504 27.4 236.1 19.1 518 6.2 1.25 6.0 2.7 0.5

52.86 2.32 14.62 12.14 0.16 4.16 6.28 3.42 2.76 0.78 -0.12 0.46 15.2 28.4 4.2 18.0 4.4 1.69 4.38 0.62 3.26 0.60 1.46 0.21 1.26 0.18 16.73 137.4 139.1 39.2 131.4 42.2 94.6 19.8 13.0 646 14.8 125.7 13.4 258 3.4 0.92 3.8 1.6 0.3

Major element oxide contents are normalized to 100 wt% on a volatile-free basis. Mg-number = Mg/(Mg + Fe2+), calculated assuming Fe2O3/(FeO + Fe2O3) = 0.20. Total iron is given as Fe2O3T. Age data are cited from Liu et al. (2001) and Fan et al. (2006). LOI, loss on ignition.

Table 2. Sr and Nd isotope compositions of the Changbai volcanic rocks in NE China Locality Tianwenfeng Tianwenfeng Qixiangzhan Qixiangzhan Waterfall Naitoushan Tumen River Junjianshan Junjianshan Guangping

Sample no. 0901 0902 0904 0905 0906 0908 0915 0917 0918 0921

87Rb/86Sr

43.71 179.61 213.34 263.72 366.81 0.2899 0.2365 0.0972 0.0764 0.0582

87Sr/86Sr ± 2σ

(87Sr/86Sr)i

εSr(i)

147Sm/144Nd

143Nd/144Nd ± 2σ

(143Nd/144Nd)i

εNd(i)

0.705441 ± 12 n.d. 0.705827 ± 23 n.d. 0.711002 ± 91 0.704779 ± 14 0.705109 ± 15 0.705158 ± 13 0.705020 ± 13 0.705043 ± 13

0.705441 n.d. 0.705554 n.d. 0.708919 0.704717 0.705100 0.705156 0.705017 0.705042

13.35 n.d. 14.97 n.d. 62.73 3.34 8.57 9.34 7.38 7.72

0.1170 0.1265 0.1123 0.1146 0.1099 0.1421 0.1516 0.1406 0.1331 0.1487

0.512588 ± 11 0.512606 ± 9 0.512596 ± 12 0.512575 ± 11 0.512564 ± 12 0.512748 ± 11 0.512558 ± 14 0.512496 ± 11 0.512554 ± 11 0.512554 ± 11

0.512588 0.512606 0.512596 0.512575 0.512564 0.512734 0.512555 0.512494 0.512551 0.512553

−0.98 −0.63 −0.82 −1.23 −1.44 3.34 −1.55 −2.76 −1.62 −1.62

Chondritic uniform reservoir (CHUR) at the present day ((87Rb/86Sr)CHUR = 0.0847 (McCulloch & Black 1984); (87Sr/86Sr)CHUR = 0.7045 (DePaolo 1988); (147Sm/144Nd)CHUR = 0.1967 (Jacobsen & Wasserburg 1980); (143Nd/144Nd)CHUR = 0.512638 (Goldstein et al. 1984)) was used for the calculations. λRb = 1.42 × 10−11 a−1 (Steiger & Jäger 1977); λSm = 6.54 × 10−12 a−1 (Lugmair & Marti 1978). Both εSr(i) and εNd(i) were obtained by using the average ages in the volcanic fields (Table 1).


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Table 3. Pb isotope compositions of the Changbai volcanic rocks in NE China Locality Tianwenfeng Tianwenfeng Tianwenfeng Qixiangzhan Qixiangzhan Waterfall Naitoushan Tumen River Junjianshan Junjianshan

Sample no.

206Pb/204Pb

207Pb/204Pb

208Pb/204Pb

238U/204Pb

235U/204Pb

232Th/204Pb

0901 0902 0903 0904 0905 0906 0908 0915 0917 0918

17.013 17.030 17.029 16.995 17.043 16.974 16.964 16.965 16.971 16.940

15.502 15.547 15.523 15.536 15.514 15.529 15.517 15.520 15.532 15.499

36.873 36.980 36.934 36.898 36.946 36.842 36.801 36.811 36.850 36.733

9.451 16.243 14.265 10.824 14.779 12.143 11.368 6.308 5.765 8.191

0.069 0.119 0.105 0.080 0.109 0.089 0.084 0.046 0.042 0.060

75.398 78.277 73.703 75.520 74.352 61.492 43.005 32.593 34.919 49.633

(206Pb/204Pb)i (207Pb/204Pb)i (208Pb/204Pb)i 17.013 17.030 17.029 16.995 17.042 16.973 16.938 16.962 16.969 16.937

15.502 15.547 15.523 15.536 15.514 15.529 15.516 15.520 15.532 15.499

36.873 36.980 36.934 36.898 36.946 36.841 36.769 36.807 36.847 36.727

λU238 = 0.155125 × 10−9 a−1, λU235 = 0.98485 × 10−9 a−1 and λTh232 = 0.049475 × 10−9 a−1 (Steiger & Jäger 1977). (207Pb/204Pb)NHRL = 0.1084 × (206Pb/204Pb)i + 13.491 (Hart 1984); (208Pb/204Pb)NHRL = 1.209 × (206Pb/204Pb)i + 15.627 (Hart 1984). Initial Pb isotope ratios were obtained by using the average ages of the volcanic fields (Table 1).

Fig. 2. Na2O + K2O v. SiO2 plot for the Late Cenozoic volcanic rocks at Changbai, Longgang and Jingbohu. All data plotted have been recalculated to 100 wt % on a volatile-free basis. Classification boundaries are from Le Bas et al. (1986) and Le Maitre et al. (1989). Filled symbols for Changbai samples represent data from this study; other symbols represent data of Xie et al. (1988), Liu et al. (1989, 1994, 1995), Basu et al. (1991), Fan et al. (1998, 1999, 2005, 2006), Hsu & Chen (1998), Hsu et al. (2000), Zhang et al. (2000), Chen et al. (2003, 2007, 2008), Shi et al. (2005), Wei et al. (2005), Wang et al. (2006), Yan et al. (2007, 2008), Zou et al. (2008) and Kuritani et al. (2009, 2011). Rock types: B, basalt, S1, trachybasalt; S2, basaltic trachyandesite; S3, trachyandesite; T, trachyte; U1, tephrite; U2, phonotephrite; U3, tephriphonolite; Ph, phonolite; O1, basaltic andesite; O2, andesite; O3, dacite; R, rhyolite.

hand, the Changbai intermediate–acidic rocks are highly differentiated, with SiO2 ranging from 63.88 to 77.57 wt%, plotted in the fields for trachytes and peralkaline rhyolites, indicating significant low-pressure fractional crystallization. The negative correlations between CaO, Al2O3, TiO2, P2O5 and SiO2 suggest removal of plagioclase, apatite and Fe–Ti oxides during magmatic differentiation (Fig. 3).

REE and other incompatible elements To constrain the partial melting process of the mantle source beneath the Changbai, Longgang and Jingbohu volcanic fields, we focus on samples with MgO >6 wt% in the discussion below, to minimize the influence of low-pressure fractional crystallization and crustal contamination on magma compositions (Plank & Langmuir 1993). The Changbai, Longgang and Jingbohu basalts display ocean island basalt (OIB)-like incompatible trace elements patterns (Figs 4 and 5), similar to other Late Cenozoic intraplate basalts in eastern China (e.g. Liu et al. 1994; Zou et al. 2000). Different degrees of enrichment in light rare earth elements (LREE) over heavy rare earth elements (HREE) could be observed (Fig. 4). The Changbai basalts have lower La/Yb (6.4–22.2) than the Longgang (5.3–36.8) and Jingbohu (13.0–59.1) basalts, which might be related to variations in mantle mineralogy and/or degrees of partial melting in the mantle source. The fractionation between LREE and HREE for the Changbai, Longgang and Jingbohu basalts decreases with decreasing alkali contents (Fig. 4), similar

to the Cenozoic Shuangliao basalts in northeastern China (Xu et al. 2012b). The Holocene Jingbohu basalts have higher La contents relative to the Miocene–Pleistocene Jingbohu basalts (Fig. 4), indicating decreasing degrees of partial melting in the mantle source from Miocene to Holocene or variations in composition of the mantle source. In addition, the Changbai, Longgang and Jingbohu basalts are enriched in large ion lithophile elements (LILE), especially Ba and Pb (Fig. 5), whereas no subductionrelated negative Ti–Nb–Ta anomalies are observed. The elevated LREE contents and distinctly negative Eu and Sr anomalies could be recognized from the Changbai trachytes and peralkaline rhyolites, suggesting significant low-pressure fractional crystallization of plagioclase (Figs 4 and 5). Furthermore, the removal of apatite and Fe–Ti oxides from trachytic and peralkaline rhyolitic magma gives rise to negative P and Ti anomalies, whereas the negative Ba and K anomalies of peralkaline rhyolites are associated with fractional crystallization of K-feldspar (Fig. 5).

Sr–Nd–Pb isotopes The Changbai, Longgang and Jingbohu basalts show discernible variations in Sr–Nd isotopic compositions. Specifically, the Changbai basalts with MgO >6 wt% have roughly the highest (87Sr/86Sr)i (0.704590–0.705203) and the lowest (143Nd/144Nd)i (0.512495–0.512743), whereas the Longgang and Jingbohu basalts plot to an endpoint with lower (87Sr/86Sr)i and higher



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Fig. 3. Plots of CaO (wt%), CaO/Al2O3 (wt%), FeOT (wt%) and Ni (ppm) v. MgO (wt%) for the Changbai, Longgang and Jingbohu basalts, and plots of CaO (wt%), Al2O3 (wt%), TiO2 (wt%) and P2O5 (wt%) v. SiO2 (wt%) for Changbai trachytes and peralkaline rhyolites. The symbols are as in Figure 2.

(143Nd/144Nd)i, forming a negatively correlated Sr–Nd isotopic trend (Fig. 6). The basaltic magma might result from the mixing of depleted mid-ocean ridge basalt (MORB)-source mantle (DMM) and enriched mantle (EM1), as stated by previous studies (e.g. Basu et al. 1991). Based on geochemical studies, we suggest that the EM1 component might be represented by aqueous fluids liberated from the lower continental crust (see the discussion below). Notably, the coexistence of radiogenic and less radiogenic Sr–Nd isotopic compositions indicates possible crustal contamination for the Changbai trachytes and peralkaline rhyolites, which might be differentiated from the basaltic magma (Fig. 6). The Pb isotopic compositions of most Changbai basalts display relatively wide variations, with (206Pb/204Pb)i, (207Pb/204Pb)i and (208Pb/204Pb)i in the range of 17.38–18.15, 15.27–15.60 and 36.72–38.65, respectively (Fig. 6). At a given (206Pb/204Pb)i, the Longgang basalts have the highest (207Pb/204Pb)i and (208Pb/204Pb)i. The Holocene Jingbohu basalts plot on the both sides of North Hemisphere Reference Line (NHRL; Hart 1984). The Changbai

trachytes and peralkaline rhyolites have Pb isotopic compositions comparable with those of the Changbai basalts.

Discussion Fractional crystallization and crustal contamination Before constraining the partial melting process in the mantle source, the effects of fractional crystallization and crustal contamination should be taken into consideration. Positive correlation between MgO and both CaO and CaO/Al2O3 reflects removal of clinopyroxene and olivine from primary melts, especially for the low-MgO (6 wt%) are also affected by fractional crystallization; for instance, of olivine and clinopyroxene. Decreasing Ni (6 wt % are plotted.

Fig. 5. Primitive mantle-normalized incompatible element diagrams for basalts, trachytes and peralkaline rhyolites from Changbai, Longgang and Jingbohu. The trace element compositions of OIB and primitive mantle normalization values are from Sun & McDonough (1989). To minimize the effect of magmatic differentiation and crustal contamination on the chondrite-normalized REE patterns, only primitive samples with MgO >6 wt % are plotted.



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Fig. 6. Plots of Sr–Nd–Pb isotopic compositions for basalts, trachytes and peralkaline rhyolites from Changbai, Longgang and Jingbohu. (a) (143Nd/144Nd)i v. (87Sr/86Sr)i. (b) Enlarged (143Nd/144Nd)i v. (87Sr/86Sr)i. (c) (143Nd/144Nd)i v. (206Pb/204Pb)i. (d) (87Sr/86Sr)i v. (206Pb/204Pb)i. (e) (207Pb/204Pb)i v. (206Pb/204Pb)i. (f) (208Pb/204Pb)i v. (206Pb/204Pb)i. For the basalts, only samples with MgO >6 wt % are plotted to minimize the effect of magmatic differentiation and crustal contamination. GLOSS represents the Global Subducting Sediment (Plank & Langmuir 1998). The NHRL (Northern Hemisphere Reference Line; Hart 1984), LCC (Lower Continental Crust; Liu et al. 2004) and UCC (Upper Continental Crust; Jahn et al. 1999), DMM and enriched mantle end-members (EM1 and EM2; Zindler & Hart 1986; Hofmann 1997; Zou et al. 2000), and MORB and OIB fields (Wilson 1989; Hofmann 1997) are shown for reference. The symbols are as in Figure 4.

The compositional variations of the Changbai, Longgang and Jingbohu basalts require processes additional to fractional crystallization (Kuritani et al. 2009), such as crustal contamination, although it might not be a primary cause of the petrogenetic variations of these basalts (Basu et al. 1991). Positive correlation between (87Sr/86Sr)i and SiO2 and negative correlation between (143Nd/144Nd)i and SiO2 could be observed in the Changbai, Longgang and Jingbohu basalts (Fig. 7), in apparent agreement with crustal contamination coupled with fractional crystallization. In addition, lower Ce/Pb relative to the ocean island basalts also indicates crustal contamination (Hofmann et al. 1986), especially

for the Changbai basalts (Fig. 7). As discussed below, we suggest that the upper continental crustal materials are not involved in contamination of the Changbai, Longgang and Jingbohu basalts, whereas aqueous fluids from the lower crust might act as the contaminant for underplated basaltic magma.

Variations in degree of partial melting in the mantle source Abundances of incompatible elements (e.g. LREE) and major elements (e.g. Na2O and TiO2) of basalts are primarily controlled


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Fig. 7. Plots of (87Sr/86Sr)i and (143Nd/144Nd)i v. SiO2 (wt%) and v. Ce/ Pb, to constrain the crustal contamination processes for the basalts with MgO >6 wt% from Changbai, Longgang and Jingbohu. The symbols are as in Figure 4.

by partial melting, crustal contamination and fractional crystallization processes, as well as the composition of the mantle source (Langmuir et al. 1992; Hirose & Kushiro 1993). Thus, we may use major and trace elements of basalts with MgO >6 wt% from Changbai, Longgang and Jingbohu to investigate the variations in degrees of partial melting in the mantle source. Because bulk partition coefficients of incompatible elements (e.g. La and Sm) are related to mineralogy as well as mineral proportions in the mantle source, the nearly straight line formed by La/Sm and La (Fig. 8) indicates a roughly homogeneous mantle source for the Changbai, Longgang and Jingbohu basalts (Allègre et al. 1977; Hofmann et al. 1986). However, some Holocene Jingbohu basalts slightly deviate from the line formed by other samples, suggesting variations in the composition of the mantle source. Although the basaltic magma underwent contamination by aqueous fluids from the lower continental crust, the influence of aqueous fluid on La/Sm could be neglected because the LILEenriched aqueous fluids would increase La/Sm ratios of contaminated magma, which is not observed in the basalts. For example, Changbai basalts with the highest contribution from aqueous fluid display the lowest La/Sm (Fig. 8). Therefore, we suggest that La/ Sm could be used to evaluate the degree of partial melting in the mantle source. Given that the removal of olivine and orthopyroxene would increase the Na2O content during magma ascent, the Na8.0 value (i.e. the calculated Na2O content at 8 wt% MgO) was proposed to calibrate the influence of low-pressure fractional crystallization on Na2O content (Michael & Bonatti 1985; Klein & Langmuir 1987). Under the pressure and temperature conditions of upper mantle melting, clinopyroxene is the primary host mineral for Na2O, which is strongly incompatible with most mantle minerals (e.g. olivine and orthopyroxene) and hence is moderately incompatible during partial melting (Jaques & Green 1980; Fujii & Scarfe 1985; Langmuir et al. 1992). Therefore, the corrected Na2O content (i.e. Na8.0 value) could be taken as a reliable indicator of relative degrees of partial melting in the mantle source. The Changbai basaltic rocks are characterized by relatively lower Na8.0 (2.1–3.6) and La/Sm (2.1–5.4), indicating that their source underwent a higher degree of partial melting than that of the Longgang and Jingbohu basalts. The Na8.0 and La/Sm of

Miocene–Pleistocene Jingbohu basalts are significantly lower than those of Holocene Jingbohu basalts. This could be interpreted as a decreasing degree of partial melting in the mantle source from Miocene to Holocene or changes in composition of the mantle source. The Quaternary Longgang basalts show relatively large variation in Na8.0 values and La/Sm, but most of the samples show signatures of a low degree of partial melting (Fig. 8). The variations in degree of partial melting are well correlated with the scales of basaltic magma eruptions in the Changbai, Longgang and Jingbohu volcanic fields. In detail, the Changbai basalts with the highest degree of partial melting give rise to the largest lava plateau, compared with those of the Longgang and Jingbohu basalts (Q.C. Fan et al. 2003, 2007). This might be related to the unique felsic magma eruption at Tianchi volcano, because magma with larger volume is more likely to stagnate in the crust, forming a crustal magma chamber in which mantle-derived basaltic magma could differentiate to felsic magma via crustal contamination and fractional crystallization processes.

Variations in contribution from aqueous fluids The enrichment of LILE (e.g. Ba, Sr and Pb) relative to high field strength elements (HFSE) and REE has long been interpreted as the result of addition of aqueous fluids during magma evolution, because (1) LILE are mobile in aqueous fluids, whereas HFSE and REE are relatively immobile (e.g. Hawkesworth et al. 1997; Turner et al. 2012), and (2) incompatible trace elements ratios (e.g. Ba/Th and Pb/U) do not fractionate significantly during partial melting and subsequent fractional crystallization if no contaminant is involved (Class et al. 2000). On the plots of Ba/Th, Sr/Th, Pb/U, Ba/La versus Th/Ce (Fig. 9), the Changbai, Longgang and Jingbohu basalts form similar negatively correlated trends, indicating contributions from aqueous fluids to the basaltic magma formation. It is noted that extents of contributions from aqueous fluids for the studied Late Cenozoic basalts display relative variations. Specifically, the Changbai basalts are characterized by higher Ba/Th, Sr/Th, Pb/U and Ba/La relative to those of the Longgang and Jingbohu basalts (Fig. 9), which might be associated with larger contributions from aqueous fluids relative to the Longgang and Jingbohu basalts. In contrast, the Jingbohu basalts have the lowest Ba/Th,



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Fig. 8. Plots of La/Sm v. Na8.0 (wt%), La/Sm v. La (ppm), Sr/Th v. La/Sm and Ba/Th v. La/Sm for the basalts with MgO>6 wt% from Changbai, Longgang and Jingbohu.

Sr/Th, Pb/U and Ba/La of the three groups. The contributions from aqueous fluids to the Longgang basalts fall between those for the Changbai and Jingbohu basalts, which is consistent with the spatial variations of Ba/Th and Pb/U of Late Cenozoic intraplate basalts from the Changbai and other volcanic fields in northeastern China (Kuritani et al. 2011). We suggest that the variations in contributions from aqueous fluids are associated with the extent of interaction between underplated basaltic magma and lower continental crustal granulites. Compared with the Longgang and Jingbohu basalts, the underplated basaltic magma with larger volume remained longer at the base of the continental crust, and had higher contributions from aqueous fluids, consistent with the higher extent of high-pressure fractional crystallization (Fig. 3).

Nature and origin of aqueous fluids Although the involvement of aqueous fluids in the Late Cenozoic basalts from northeastern China has been generally recognized (e.g. Kuritani et al. 2011), significant uncertainty on the nature and origin of these aqueous fluids still remains (Zou et al. 2003, 2008; Kuritani et al. 2011). In addition, the geochemical signatures observed in the Late Cenozoic basalts from northeastern China have been attributed to the involvement of components from DMM and EM1 by previous studies (e.g. Basu et al. 1991; Zhang et al. 1991; Choi et al. 2005), as indicated by the negatively correlated 87Sr/86Sr and 206Pb/204Pb, positively correlated 143Nd/144Nd and 206Pb/204Pb, and the unradiogenic Pb isotopic

compositions (Fig. 6). The DMM component is generally supposed to stem from asthenospheric mantle (Basu et al. 1991), whereas the origin of the EM1 component is still a matter of heated debate. It is noted that the aqueous fluids involved in magma evolution are characterized by low 143Nd/144Nd, high 87Sr/86Sr and low 206Pb/204Pb (Fig. 10), similar to the isotopic compositions of the EM1 endmember (Zindler & Hart 1986). Therefore, aqueous fluids would act as the EM1 component for the basaltic magma derived from depleted MORB-source mantle. Herein we evaluate the previously proposed possible origins of the aqueous fluids and argue that lower crustal granulite might be the origin of the EM1-like aqueous fluids. Sub-continental lithospheric mantle (SCLM) with low U/Pb ratios beneath eastern China has been considered as the reservoir for the EM1 component, which could be incorporated through interactions between upwelling asthenosphere and the SCLM (e.g. Basu et al. 1991; Tatsumoto et al. 1992). However, the time scale required for the formation of the EM1-like signature must be longer than 1 Ga for the SCLM (Rehkämper & Hofmann 1997), which explains why the EM1-like signatures are primarily restricted to Archaean lithosphere such as the Kaapvaal Craton (Walker et al. 1989). Although basalt-borne mantle xenoliths with EM1-like signatures (εNd 6 wt% from Changbai, Longgang and Jingbohu.

echanisms such as thermal erosion (e.g. Menzies et al. 1993) and m delamination (e.g. Deng et al. 1994) since the Mesozoic. Furthermore, Re–Os isotopic systematics of the Cenozoic basaltborne mantle xenoliths throughout the North China Craton show no Archaean TRD ages (Xu et al. 2008; Zhang et al. 2009) and the SCLM beneath northeastern China was primarily formed in Cenozoic times associated with lithospheric thinning (Griffin et al. 1998), and hence aqueous fluids from the SCLM would be unlikely to acquire EM1-like signatures. Choi et al. (2006) proposed that the Late Cenozoic intraplate basalts in northeastern China must have resulted from the mixing of two dominant asthenospheric mantle domains (i.e. the DMM and EM1). The EM1-like signatures of the shallow asthenosphere might be generated by the entrainment of EM1-rich cratonic mantle during lithospheric thinning of the North China Craton (Hoang et al. 1996; Flower et al. 1998). However, this mechanism is unable to explain the involvement of aqueous fluids in magma evolution, because the elevated Ba/Th and Pb/U ratios observed in the Changbai basalts indicate contributions from metasomatic components (e.g. aqueous fluids) other than partial melting and fractional crystallization processes (Class et al. 2000). Furthermore, whether or not the shallow asthenosphere with EM1-like signatures could remain isolation from the convecting mantle is still poorly constrained. The EM1-like signatures of aqueous fluids involved in the Changbai, Longgang and Jingbohu basalts have also been attributed to the stagnant subducted Pacific slab in the MTZ (Kuritani et al. 2011). However, this hypothesis must resolve the following

two challenges. First, formation of the EM1-like signatures requires the slab dehydration-induced metasomatized MTZ to be primarily isolated for long periods of time (>1 Ga), which might be an assumption too strict to be sufficiently valid because slab dehydration and melting of carbonated eclogite in the MTZ would reduce the viscosity of both the upper and lower mantle, leading to intensive interactions between the metasomatized MTZ and the circumjacent mantle (Hirth & Kohlstedt 1996; Dasgupta et al. 2004). Second, whether or not deep-subducted materials (e.g. fluid or sediment) in the MTZ are involved in the Late Cenozoic intraplate volcanism in northeastern China is still a matter of debate (Zou et al. 2008; Kuritani et al. 2011). Although water could be transported into the MTZ by high-pressure hydrous minerals or subduction-induced convection (Sano et al. 2004; Maruyama & Okamoto 2007), the fluid released from high-pressure hydrous minerals might be supercritical, because enriched components released from subducting oceanic crust at depths greater than 100 km have been identified as supercritical fluid rather than aqueous fluids and/or hydrous melts in subductionzone conditions (Mibe et al. 2011), not to mention the case of P–T conditions of the MTZ. This supercritical fluid is characterized by high mobility of almost all of the trace elements except for HREE, Y and Sc (Kessel et al. 2005). This means that if the stagnant Pacific slab-derived fluids represent the involved EM1 component the LILE (e.g. Ba, Pb and Sr) would not fractionate with LREE and HFSE, which is inconsistent with the geochemical signatures observed in the Changbai, Longgang and Jingbohu basalts. Therefore, we suggest that the slab dehydration processes



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Fig. 10. Plots of (87Sr/86Sr)i v. Ba/La, (143Nd/144Nd)i v. Ba/La and (206Pb/204Pb)i v. Pb/U for basalts with MgO >6 wt% from Changbai, Longgang and Jingbohu. Aqueous fluids are characterized by high Ba/La and Pb/U. Changbai basalts with higher (87Sr/86Sr)i and lower (143Nd/144Nd)i and (206Pb/204Pb)i, as well as higher Ba/La and Pb/U, are interpreted as the result of higher contributions from EM1-like aqueous fluids. The symbols are as in Figure 8.

in the MTZ with higher P–T conditions could hardly explain the geochemical characteristics of the Late Cenozoic intraplate volcanism in northeastern China. The lower continental crust with unradiogenic Pb isotopic composition has long been considered as a possible candidate for the EM1 component (Zindler & Hart 1986), owing to its low (U, Th)/ Pb ratios as exemplified by the high-grade Archaean metamorphic terranes (Moorbath et al. 1969; Chapman & Moorbath 1977). The lower crust of the North China Craton is dominated by rocks with Neoarchaean ages (e.g. Zheng et al. 2009; Zhang 2012; Jiang et al. 2013), which might have acquired EM1-like isotopic signatures with time. For example, Neoarchaean (c. 2.5 Ga) granulite xenoliths entrained in Late Cenozoic basalts from the North China Craton have remarkably unradiogenic Nd and Pb, and relatively radiogenic Sr isotopic compositions (Liu et al. 2004), verifying the existence of ancient lower crust with EM1-like isotopic signatures (Gao et al. 2003). Furthermore, nominally anhydrous minerals (such as clinopyroxene, orthopyroxene and plagioclase) from lower crustal granulite of the North China Craton are indeed hydrous, providing direct evidence for the potential water storage capacity of the lower continental crust (Xia et al. 2006), especially for the Precambrian (2.5–2.6 Ga, 1.8–1.9 Ga) lower continental crust (Yang et al. 2008). Therefore, it is possible that aqueous fluids could be liberated from the lower crustal granulites and imparted with EM1-like isotopic signatures, acting as the EM1 component involved in magma evolution. In addition, the strong fractionation of Ba, Pb and Sr relative to LREE (e.g. high Ba/La), as well as the unradiogenic Pb isotopes, suggests that the mantlederived magma might undergo contamination processes in the lower continental crust (Arculus & Johnson 1981; Arculus 1987), similar to the genesis of the Columbia River basalts (Carlson et al. 1981). We suggest that a possible mechanism responsible for the dehydration of lower crustal granulites might be magma underplating at the base of the lower continental crust, which could also explain the high-pressure fractional crystallization observed in the Changbai, Longgang and Jingbohu basalts.

Magma underplating and associated geodynamic processes Large-scale extensional movements, which are accompanied by widespread intraplate volcanism, have taken place in eastern China

since the Late Cretaceous (Ma & Wu 1987; Ren et al. 2002). Previous studies have attributed the extensional tectonics to the farfield effect of Indo-Asia collision about 55 Ma ago (Molnar & Tapponnier 1975; Tapponnier et al. 2001). However, Late Cretaceous and Palaeocene extensional faults in eastern China started earlier than the Indo-Asia collision, indicating that the IndoAsia collision is not the only driving mechanism for East Asia deformations (Ma & Wu 1987; Northrup et al. 1995; Schellart & Lister 2005). The successive subduction of the Kula and Pacific plate should also be taken into consideration (Uyeda & Miyashiro 1974; Yin 2010). The rate of Pacific–Eurasia convergence varied significantly during the Cenozoic (Northrup et al. 1995), and the major phases of overriding plate extension in East Asia occurred synchronously with a reduction in subduction velocity of the Pacific plate (Schellart 2005). Therefore, we suggest that magma underplating and eruption processes of the Late Cenozoic intraplate volcanism in northeastern China are associated with episodic changes in the convergence rates between the Eurasian and Pacific plates. The reduction of average convergence rate between the Eurasian and Pacific plates during the Early to Middle Miocene (19.5– 10.5 Ma; Northrup et al. 1995), which is consistent with the opening of the Japan Sea (Tatsumi et al. 1990), might have triggered back-arc extension and NE–SW-trending extensional faults, as well as basaltic magma underplating and eruption in northeastern China (Fig. 11a and b). Although the relative rate of Pacific– Eurasia convergence has been increasing since the Late Miocene (Northrup et al. 1995), the collision of the Ogasawara Plateau and Izu–Bonin and Mariana (IBM) arcs at 8 Ma might have led to a reduction in absolute velocity of the subducting Pacific slab and subsequent slab sinking and rollback (Schellart 2005; Miller et al. 2006). This is consistent with the significant trench retreat of the northwestern Pacific subduction zone since the Late Miocene (8– 0 Ma; Miller et al. 2006). We suggest that the post-8 Ma Eurasian lithospheric extension could account for mantle-derived magma underplating and eruptions in the Changbai, Longgang and Jingbohu volcanic fields (Fig. 11c and d). The lack of intraplate volcanism of ages ranging from 10.5 to 8 Ma in northeastern China could be well explained by the gap in lithospheric extension associated with the subduction kinetics of the Pacific plate. Therefore, the episodic changes in convergence rates between the Eurasian and Pacific plates during the Late Cenozoic (Northrup et al. 1995), as well as small-scale thermal upwellings induced by episodic


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Fig. 11. Geodynamic model for the genesis of Late Cenozoic intraplate volcanism in the Changbai, Longgang and Jingbohu volcanic fields.

plate motion and lithospheric extension (Buck 1986; Faccenna et al. 2010), could well explain the mantle-derived magma underplating at the base of the lower continental crust and subsequent intraplate volcanism in northeastern China.

Genesis of the felsic magma eruptions at Tianchi volcano The Tianchi active volcano is the only volcano that is characterized by felsic magma eruptions since c. 1 Ma (Deng et al. 1992; Fan et al. 2007), whereas the active volcanoes in the Longgang and Jingbohu volcanic fields have erupted only basaltic magma. At present, extensive bubbling hot springs and diffusive soil microseepage occur at Tianchi volcano, differing from the Longgang and Jingbohu volcanoes, which have little geothermal activity. In addition, the seismically detected low-velocity anomalies beneath Tianchi volcano have been considered to reflect magma chambers beneath it (Zhang et al. 2002b; Stone 2011), whereas no such low-velocity anomalies are present beneath the Longgang and Jingbohu volcanoes. Therefore, the genesis of the felsic magma eruptions at Tianchi volcano could be important for providing a signal from the chamber. During the Early to Middle Miocene, basaltic magmas in the Changbai and Jingbohu volcanic fields were erupted without retention in the upper crust (Fig. 11a and b), because the basaltic magmas were primarily alkaline and underwent rapid source-to-surface transportation, as indicated by the presence of mantle xenoliths (Wu et al. 1997). Since the Early Pleistocene (c. 2.34 Ma; Liu et al. 2001), the mantle source beneath Tianchi volcano underwent a higher degree of partial melting processes, giving rise to a large volume of tholeiitic magmas. These magmas were erupted by Tianchi volcano and formed an extensive shield-like basaltic platform. However, since the Late Pleistocene (c. 1 Ma; Fan et al. 2007), the tholeiitic magmas underwent retention in the upper crust owing to their large volume and subsequent decompression-induced

expansion during source-to-surface transportation, forming a seismically detected upper crustal magma chamber (e.g. Zhang et al. 2002b). During retention in the upper crust, the tholeiitic magmas were differentiated to trachytic and peralkaline rhyolitic magmas via low-pressure fractional crystallization and crustal contamination, leading to the felsic magma-dominated eruptions at Tianchi volcano (Fig. 11c and d). In contrast, the Longgang and Jingbohu basalts are characterized by a relatively lower degree of partial melting in the mantle source, and thus the alkali basaltic magma was erupted without retention in the upper crust, which is in agreement with the presence of mantle xenoliths and Ti-amphibole xenocrysts in the Longgang and Jingbohu basalts, respectively (Zhang et al. 2001; Tang et al. 2012). We suggest that a higher degree of partial melting in the mantle source, as well as the magma underplating and retention processes, could account for the unique felsic magma eruptions at Tianchi volcano.

Conclusions The Changbai basalts are characterized by lower Na8.0, lower La/Sm and stronger fractionation of LILE relative to HFSE and LREE (e.g. high Sr/Th, Ba/Th, Pb/U and Ba/La), compared with the Longgang and Jingbohu basalts, indicating a higher degree of partial melting in the mantle source and higher contributions from aqueous fluids, which could account for the unique felsic magma eruptions at Tianchi volcano. Some Changbai trachytes and peralkaline rhyolites have Sr–Nd isotopic compositions that are similar to those of the Changbai basalts, whereas other samples show signatures of crustal contamination, implying that the intermediate– acidic rocks resulted from assimilation and fractional crystallization (AFC) processes of the basaltic magma during retention in the upper crust. Based on the whole-rock major and trace elements and Sr–Nd–Pb isotopic data, we suggest that components from depleted MORB-source mantle (DMM) and enriched mantle (EM1) were


Intraplate volcanism in NE China both involved in the magma evolution of Late Cenozoic intraplate basalts from Changbai, Longgang and Jingbohu. We argue that aqueous fluids liberated from the hydrous Neoarchaean lower crustal granulite could acquire EM1-like isotopic signatures and act as the EM1 component during magma evolution. A magma underplating model is proposed to account for the genesis of the Late Cenozoic intraplate volcanism. The geodynamic processes responsible for magma underplating and eruption might be lithospheric extension associated with episodic changes in convergence rates between the Eurasian and Pacific plates during the Late Cenozoic, indicating a possible genetic link between deep subduction of the Pacific slab and intraplate volcanism in NE China.

Acknowledgements and Funding This study was financially supported by the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (Grant No. XDB03010600), and grants from the National Natural Science Foundation of China (NSFC) (Grants No. 41020124002 and 41130314). We are grateful to H. Li, X. Jin, C. Li, X. Li, W. Guo and G. Liu for their help in laboratory experiments and fieldwork.

Scientific editing by Xixi Zhao

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