Genesis of porphyry Mo deposits linked to gradually dehydrating subcontinental lithospheric mantle metasomatised by previous subduction in northeastern China

Lithos 336–337 (2019) 143–150

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Genesis of porphyry Mo deposits linked to gradually dehydrating subcontinental lithospheric mantle metasomatised by previous subduction in northeastern China Yifei Liu a,⁎, Leon Bagas a,b, Sihong Jiang a a b

MNR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China Centre for Exploration Targeting, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia

a r t i c l e

i n f o

Article history: Received 15 November 2018 Accepted 31 March 2019 Available online 3 April 2019 Keywords: Hydrated SCLM Gradually dehydrating SCLM Mafic, alkali magma Northeastern China Porphyry Mo mineralisation

a b s t r a c t Many Mesozoic Mo-bearing granites, present along the northern margin of the Precambrian North China Block (NCB) and Phanerozoic Xing'an-Mongolian Belt (XMB) within the Central Asian Orogen (CAO) have hydrated sources. These granites are temporally and spatially related to biotite-rich mafic, alkali syenitic plutons, are highly evolved, have an arc-like trace element geochemical pattern, and were emplaced between ca. 245–129 Ma bracketed by A2- and A1-type granites. This conflicts temporally with the current model involving the westward subduction of the Pacific oceanic plate. We use Sm/Nd and Th/Yb ratios of Mesozoic nepheline-bearing pyroxene-biotite syenites (biotite-syenites), mantle-peridotite xenoliths from Palaeozoic diamondiferous kimberlites, and Mesozoic to Cenozoic alkali basalts to define a hydrous melt-extraction trend. The results indicate a Palaeozoic mantle-peridotite source that is more metasomatised than the lower continental crust and the source of the Mesozoic (b129 Ma) to Cenozoic mantle-peridotite xenoliths (Th/Yb b 1). This indicates that the sub-continental lithospheric mantle (SCLM) beneath northeast China has been gradually dehydrating since the Palaeozoic, and the lower continental crust and Cenozoic SCLM in northern NCB are too depleted to be the magmatic source for the Mo-bearing granites. The results of the study also indicate that the Palaeozoic SCLM beneath the northern margin of the NCB was more metasomatised than beneath its central zone. The development of Mo-bearing granites in both the Precambrian northern margin of NCB and Phanerozoic XMB indicate that the presence of an ancient SCLM is not necessary for the genesis of Mo mineralisation. From these observations, it is proposed that the genesis of Mo mineralisation in the region is attributed to a hydrated SCLM metasomatised by the subduction of the Paleo-Asian oceanic plate rather than the younger Pacific oceanic plate. © 2019 Elsevier B.V. All rights reserved.

1. Introduction Porphyry deposits represent an important Cu and Mo source commonly linked to a contemporary subduction setting, where hydrous magma is generated in a metasomatised mantle wedge above a subducting oceanic plate (Richards, 2003). Some porphyry deposits, however, are associated with rift-related magmatism in extensional tectonic settings, such as Mo deposits in the Rio Grande of USA and the Oslo rifts in Norway (White et al., 1981). The deposits have long been thought to be associated with magmas derived from the lower continental crust during partial melting (e.g. Stein and Crock, 1990), and have been recently attributed to large volumes of mafic, alkali magmatism sourced from an ancient metasomatised sub-continental lithospheric mantle (SCLM; Audétat, 2010; Pettke et al., 2010). However, an ancient SCLM will gradually deplete in its basaltic component ⁎ Corresponding author. E-mail address: [email protected] (Y. Liu).

https://doi.org/10.1016/j.lithos.2019.03.035 0024-4937/© 2019 Elsevier B.V. All rights reserved.

through geological time (Griffin et al., 2009). It is thus not clear how an ancient SCLM, or lower continental crust dominated by high-grade (granulite-facies) rocks, can provide a hydrous magma enriched in large ion lithophile elements (LILE) and metals for the genesis of porphyry deposits in an extensional setting without subduction of an oceanic plate. Mesozoic Mo deposits in northeastern China are related to highly evolved granites generated in an extensional setting along the northern margin of the Precambrian North China Block (NCB) and Phanerozoic Xing'an-Mongolian Belt (XMB) to the north within the Central Asian Orogen (CAO) (Fig. 1; Wang et al., 2011). The region has at least 20 large-scale Mesozoic (ca. 245 to 129 Ma) deposits with resources exceeding 0.1 Mt Mo for a combined resource of over 9 Mt Mo. Mo mineralisation in the northern margin of NCB and XMB share similar characteristics in their temporal distribution (Fig. 2). Their genesis is attributed by some authors to partial melting of the lower continental crust or Mo-rich sedimentary rocks during the subduction of the Pacific oceanic plate (e.g. Pirajno and Zhou, 2015; Sun et al., 2016).

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Fig. 1. Maps of the northern margin of the North China Block (NCB) and Xing'an-Mongolian Belt (XMB) showing: (a) distribution of Mo deposits present in the study area are parallel to the Palaeozoic subduction zone and around the Songliao Basin; (b) Mesozoic highly evolved mafic, alkali, biotite-syenites, and highly evolved ferroan granites, including ferroan I-type, peralkaline and metaluminous A1- and A2-type granites, distributed in the same region as the two Mo belts (after Wu et al., 2002; Yan et al., 2007); and (c) Cenozoic alkali basalt distributed in the same region as the two Mo belts (after Wang et al., 2015). The Mo deposits in the NCB constitute the Southern molybdenite belt, and Mo deposits in the XMB constitute the Northern molybdenite belt (ages for the Mo deposits were dated by molybdenite Re-Os and zircon La-ICP-MS or SHRIMP U-Pb methods, there are 16 ages for Mo deposits in the northern margin of NCB, 26 ages for Mo deposits in XMB, and 5 ages for porphyry Cu deposits have been shown. The ages have been reviewed by and from Zeng et al., 2012; Chen et al., 2017; Liu and Jiang, 2017).

The juvenile XMB A 2 -type granites

A 1 -type granites

Zhangguangcai Range Alkali basalts Mo mineralization

Xing'an Range

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Mafic, alkali biotite-syenites Mo mineralization

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Beginning of the subduction of the Pacific oceanic plate

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Age (Ma) Fig. 2. Temporal relationship between different types of highly evolved igneous rocks in the refractory northern margin of Precambrian NCB and Phanerozoic XMB, indicative of temporal developing sequence of highly evolved rocks. The ages for the mafic, alkali biotite-syenites are reviewed by and from Yan et al. (2007), most of them are dated with zircon La-ICP-MS or SHRIMP U-Pb methods, some of them were dated with Rb-Sr isochrones method. Ages for A-type granite are from Wu et al. (2002), Kovalenko et al. (2006) and Yang et al. (2006, 2008a), which were dated with zircon La-ICP-MS or SHRIMP U-Pb methods.

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We use Th/Yb and Sm/Nd ratios to compare metasomatised and hydrated degree of the Palaeozoic to Cenozoic SCLM, and lower continental crust to determine the source of Mesozoic hydrous Mo-bearing granites, and define the extraction trend of hydrous melts from an enriched SCLM. Our evidence indicates that a large number of porphyry Mo deposits in extensional tectonic setting can be sourced from hydrous melt extractions from hydrated SCLM metasomatised by previous subduction.

to high 87Sr/86Sr(i) and negative εNd(t) signatures in northern NCB (Zhou et al., 2001). The isotopic signatures also show that the SCLM beneath the central part of NCB is less extensively modified than its northern margin (Zhang et al., 2003). These characteristics indicate that the SCLM beneath the northern part of NCB was significantly modified during the subduction of the Paleo-Asian oceanic plate.

2. Geological evolution history and geodynamics in the study area

The geological evolution of XMB involved growth of a Phanerozoic continent in the period between ca. 500 to 120 Ma. Igneous rocks emplaced during this period have TNd-DM model ages between 1300 and 500 Ma and positive εNd(t) values (Jahn et al., 2000; Wu et al., 2000, 2011; Zhou et al., 2009). Re-depletion (TRD) and TNd-DM model ages of mantle xenoliths interpreted as being derived from the SCLM under XMB indicate that the SCLM is approximately the same age as the overlying continental crust (Wu et al., 2003). Northern NCB includes high-grade Archean to Early Palaeoproterozoic rocks unconformable overlain by Late Palaeoproterozoic to Mesozoic rocks and Cenozoic cover (Jiang et al., 2013; Zhai and Santosh, 2011; Zhao et al., 2012). The U-Pb zircon dates from the region show that protolith ages for most of the granulite-facies rocks are ca. 2600 to 2450 Ma with metamorphism taking place during 1900–1800 Ma, with 87Sr/86Sr(i) values of 0.705 to 0.716 and εNd(t) values of −10 to −28 are reported for the lower continental crust at ca. 130 Ma (Jiang et al., 2013). Tatsumoto et al. (1992) propose that multiple metasomatic events affected the continental lithosphere with one before the Neoproterozoic when an enriched mantle (EM1) signature was present, and one after the Neoproterozoic when an EM2 was generated. The Mesozoic SCLM beneath northern NCB is also proposed to have a component with a Sr-Nd isotopic EM-1 signature (Zhang et al., 2004; Wu et al., 2006; Xu et al., 2008). Furthermore, the SCLM is younger than the crust, meaning that the Archean SCLM was replaced by a Sr-Nd isotopic depleted SCLM, although relics of Archean lithospheric mantle have survived beneath the western and central parts of NCB (Zheng et al., 2001; Gao et al., 2002; Wu et al., 2003c; Wu et al., 2006; Rudnick et al., 2004; Xu et al., 2008). It is worth noting that the occurrence of Palaeozoic diamondiferous kimberlites implies the existence of thick (~200 km) SCLM at the time of volcanism. However, the Cenozoic basalt-hosted mantle xenoliths are spinel-facies, which indicates the present SCLM is much thinner (60–120 km). This also indicates that over 100 km of the SCLM beneath NCB have been removed since the Palaeozoic (Fan et al., 2000; Gao et al., 2002; Zhang, 2005).

The study area is divided into the northeastern part of NCB and XMB in eastern CAO by the Ondor Sum–Yongji Suture (Fig. 1). The northern margin of NCB and XMB extend eastward across the Inner Mongolia, Heilongjiang and Jilin provinces, and north of the Hebei and Liaoning provinces (Fig. 1). There are various theories proposed for the evolution of CAO including the generation of most of the crust during the Palaeozoic to Mesozoic (Han et al., 2006; Jahn et al., 2000). It is now posited that the evolution of the orogen began at least in the Mesoproterozoic with the development of island-arcs (Gordienko et al., 2009; Rytsk et al., 2007). This shows that the Paleo-Asian oceanic plate existed during the Mesoproterozoic and was long-lived with subduction and accretion throughout the Neoproterozoic into the Late Palaeozoic (Kröner et al., 2014; Rytsk et al., 2007). Xiao et al. (2003) interpret XMB as representing a series of Palaeozoic accretionary wedges formed by the northwest- and southdirected subduction of the Paleo-Asian oceanic plate. The southward migration of the plate beneath NCB is currently thought to have formed a Palaeozoic continental arc accretionary zone (Chen et al., 2000; Xiao et al., 2003; Windley et al., 2007; Zhang et al., 2007a, 2007b; Xu et al., 2015). The subduction culminated the collision of CAO with NCB during the Permian along the Solonker Suture, which represents the location of the final closure of the Paleo-Asian Ocean (Xiao et al., 2003; Windley et al., 2007; Chen et al., 2009; Xu et al., 2015). The geodynamics for the Late Palaeozoic to Mesozoic tectonic events in the region are still in debate. Northern NCB experienced significant tectonic changes from the N-S orientated subduction during the Palaeozoic to N-S orientated extension during the Mesozoic (Davis et al., 2001; Jahn et al., 2000; Meng, 2003; Pirajno and Zhou, 2015; Tomurtogoo et al., 2005). It is commonly thought that XMB and the northern NCB were under a post-collisional setting related to the closure of various Paleo-Asian oceanic arms during the Permian or Triassic (Xiao et al., 2003; Yang et al., 2012; Zhang et al., 2014; Zhao et al., 2016). Zhang et al. (2010) and Pirajno and Zhou (2015) propose that the region was affected by widespread and multiple tectono-thermal events along much of the eastern margin of mainland Asia and extended inland into Mongolia during the Mesozoic. These Mesozoic events lead to formation of alternating northward and southward tectonic vergence of major faults, and collisional tectonics in the Yinshan–Yanshan Belt along the northern margin of NCB, and the development of rift basins in the interior of NCB and XMB (e.g. Davis et al., 2001; Meng, 2003; Wang et al., 2017). It has also been suggested that the Mesozoic tectonic events involved the subduction and closure of the Mongol–Okhotsk Ocean in the northwestern part of XMB, northwestward subduction of the Paleo-Pacific oceanic plate, a stagnant Paleo-Pacific oceanic plate beneath the eastern part of XMB, or lithospheric delamination in eastern China (Van der Voo et al., 1999; Tomurtogoo et al., 2005; Wu et al., 2005; Zhang et al., 2010; Kuritani et al., 2013; Chen et al., 2015; Tang et al., 2014; Wang et al., 2015). A large volume of Phanerozoic igneous rocks in XMB have positive εNd(t) values between ~0 and +5.4, and TDM model ages of ca. 1300 to 500 Ma, indicative of derivation from a juvenile source that was separated from a depleted mantle (Jahn et al., 2000; Wu et al., 2000; Ying et al., 2010; Zhou et al., 2001). Isotopic (Sr-Nd-Pb) systematics indicate that the Mesozoic volcanism across the XMB and NCB boundary is gradually zoned with low 87Sr/86Sr(i) and positive εNd(t) signatures in XMB

3. Nature of lithosphere beneath the study area

4. Developing patterns of Mo-bearing granites and other highly evolved magmatic rocks The XMB and northern NCB are characterised by widespread Late Palaeozoic to Mesozoic highly evolved magmatic rocks, including Iand A-types granites and mafic, alkali syenites (Wu et al., 2002, 2003; Yan et al., 2007; Zhang et al., 2014). These highly evolved rocks constitute a continuous alkali-rich plutonic belt along XMB and the northern margin of NCB (Fig. 1). The alkali-rich pluton belt in XMB extends from the Khan Bogd District of Mongolia through the Erenhot and East Ujimqin banners to the northern part of the Great Xing'an, Lesser Xing'an, and Zhangguangcai ranges (Fig. 1, Wu et al., 2002, 2003; Kovalenko et al., 2006; Zhao et al., 2016). The alkali-rich pluton belt in the northern margin of NCB extends from the western part of Inner Mongolia to the Liaoning and Jilin provinces (Zhang et al., 2014). The alkali-rich pluton belts in XMB and the northern margin of NCB are connected with each other at the Zhangguangcai Range in Jilin Province. Mo deposits are widespread in the alkali-rich pluton belts in XMB and the northern margin of NCB (Fig. 1). The highly evolved magmatic rocks in the study area were initially water-poor, N250 Ma, A2-type granites and progressed through water-

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5. Arc-like magmas formed by dehydration melting from metasomatised sources Studies of melt-inclusions in granites show that most primary Mobearing melts related to Mo mineralisation are water rich (N5%), and have low Mo contents averaging ~6 ppm (Audétat, 2015; Audétat et al., 2011; Mercer et al., 2015). Large volumes of water derived from magma chambers are necessary for the formation of Mo deposits, such as the Questa porphyry deposit in New Mexico, USA (Klemm et al., 2008). The genesis of this deposit requires a rhyolitic magma with a volume of ~30–100 km3 containing enough water to generate a deposit containing N0.4 Mt Mo (Audétat, 2010; Mercer et al., 2015). The extensive Mesozoic Mo mineralisation along the northern margin of NCB and XMB is characteristic of a significant emplacement of water-rich Mo-bearing magma into the upper crust from sources enriched in water and Mo. Examples are the Mo-bearing granites at the Chalukou and Diyanqin'amu deposits in XMB, and the Chaganhua and Caosiyao deposits in northern NCB. The deposits have similar trace element geochemistry as porphyry Cu-related granites, with significant negative Nb, Ta and Ti high field-strength elements (HFSEs) anomalies, and positive LILE and Pb anomalies (Fig. 3a). The traceelement geochemistry is also similar to the Mesozoic mafic, alkali biotite-syenites spatially related to the Mo-bearing granites (Yang et al., 2012; Wu et al., 2003; Fig. 3b). Dehydration melting of a mantle-wedge fluxed with fluids released from a subducting oceanic plate will result in hydrous magmas significantly enriched in light rare earth elements (LREEs), Pb, Th and U, and depleted in HFSEs (e.g. Nb, Ta and Ti). These HFSEs are relatively fluidinactive and retained in rutile-bearing eclogites due to their geochemical behaviour during dehydration partial melting (Kessel et al., 2005; Klemme et al., 2005). Although negative Nb, Ta and Ti anomalies are characteristic of the Precambrian continental crust and Phanerozoic arc-magmatism, positive Th and U anomalies would be evident in the trace element patterns during dehydration melting based on their geochemistry (Foley et al., 2000, 2002; Kessel et al., 2005). Lower continental crust xenoliths with negative Th and U anomalies are commonly observed in the northern margin of NCB (Fig. 3c), and are significantly different from the Mo-bearing granites in the area (Liu et al., 2001). The granulite xenoliths from the Cenozoic Hannuoba alkali basalts

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Oyu Tologoi Porphyry Cu (4 data) Mo-bearing granites from the XMOB (63 data) Mo-bearing granites from the nor thern NCB (75 data)

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Evolved granite A 1 -type granite (ca.126 Ma) A 2 -type granite (ca.196-190 Ma)

Triassic mafic syenite (21 data)

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rich, ca. 250–129 Ma Mo-bearing granites and mafic alkali biotitesyenites to water-poor, b129 Ma, A1-type granites. This was followed by Cenozoic alkali volcanism without hydrothermal mineralisation (Fig. 2). The Mo mineralisation in XMB and the northern margin of NCB was formed during the Triassic (ca. 243–223 Ma), Early and Middle Jurassic (ca. 187–160 Ma) and Late Jurassic to Early Cretaceous (ca. 156– 129 Ma). The Triassic mineralisation migrated from the western to the eastern parts of the two Mo belts during the Early Jurassic, and then migrated back to their western parts during the Late Jurassic to Early Cretaceous. The Mo-bearing granites have average values of 75.7 wt% SiO2 and 7.7 wt% Na2O + K2O, a differentiation index (DI) of 91, and are commonly biotite-rich (N5%), similar to the Climax Mo-bearing granites in the USA (Liu and Jiang, 2017; White et al., 1981). The mafic alkali biotite-syenite plutons in the study area are characterised by nepheline, clinopyroxene, and up to 15% biotite (eg. Niu et al., 2016; Yang et al., 2012), that is indicative of a hydrous magmatic source. Some of the mafic alkali biotite-syenite plutons host coeval sub-economic Mo mineralisation, such as the Hekanzi syenitic pluton at 40°38′N and 119°11′ E (Liu et al., 2012a, 2012b). It is worth noting that the study area hosts no Mo mineralisation younger than 120 Ma, although the Cretaceous A-type granites and Cenozoic basalts are alkali-rich and the westward subduction of the Pacific oceanic plate has been active since its inception during the Early to Middle Mesozoic (Fig. 1).

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Average of lower crust of the NCB Paleozoic SCLM xenoliths, Mengying, central NCB (5 data) Paleozoic SCLM xenoliths, Tieling, nor thern NCB (7 data) Cenzoic SCLM xenoliths, Hanhuoba, nor thern NCB (14 data)

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Th Nb K Ce Sr Nd Hf Eu Gd Y Lu Ba U Ta La Pb P Zr Sm Ti Tb Yb

Fig. 3. Primitive mantle normalised trace element patterns for: (a) Palaeozoic Cu-bearing rocks at the Ouyu Tolgoi deposit and Mesozoic Mo-bearing granites at the Chalukou, Diyanqin'amu, Chaganhua and Caosiyao deposits showing that the Mo-bearing granites have arc-like trace element patterns (Wainwright et al., 2011; Dolgopolova et al., 2013; Liu et al., 2012a, 2012b, Liu et al., 2015; Li et al., 2014; Liu and Jiang, 2017); (b) Triassic mafic, biotite-syenites in the Baotoudong and Hekanzi syenites, and highly evolved granites (Niu et al., 2016; Wu et al., 2002, 2003; Yang et al., 2012); (c) the lower crust beneath the North China Block, peridotites xenoliths from the Palaeozoic diamondiferous Kimberlites and the Cenozoic Hannuoba alkali basalts (Liu et al., 2001; Xia et al., 2004; Zhang et al., 2008; Wu et al., 2006); and (d) Cenozoic Hannuoba alkali basalt showing an Ocean Island Basalt (OIB) affinity (Zhi et al., 1990).

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6. Hydrous melts extraction from a hydrated SCLM The REEs Sm and Nd have very similar atomic weights, are incompatible, and their ratios will not appreciably change during fractional crystallisation. However, there is a small difference in the liquid/mineral 0.6

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Melt extraction trend

Sm/Nd

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AverageTh/Yb ratio of Philippine mantle xenoliths

partition coefficient (Dfluid/solid) between Sm and Nd at pressures of 4– 6 GPa (Kessel et al., 2005). Under these conditions, Sm/Nd ratios of source rocks will change after a large volume of hydrous melt has been removed during small degrees of partial melting. In contrast, Th will significantly partition into hydrous melts, and Yb will partition into solid phases during dehydration partial melting (Kessel et al., 2005). Mantle xenoliths with elevated Th/Yb and low Sm/Nd ratios that were metasomatised during subduction have been observed in the Philippines and Italy (Maury et al., 1992; Schiavi et al., 2012). Therefore, the Sm/Nd and Th/Yb ratios can be used as indicators for the degree of metasomatism by hydrous melts from deeper levels in the mantle, and for decompression-induced dehydration partial melting in the SCLM and lower continental crust. Using these criteria, metasomatism and removal of hydrous melts from SCLM and the lower continental crust in NCB and XMB are indicated by variations in Sm/Nd and Th/Yb ratios of peridotite and granulite xenoliths, which are present in Palaeozoic diamondiferous kimberlites and Mesozoic to Cenozoic alkali basalts. Xenoliths of Palaeozoic lithospheric mantle peridotites in kimberlites from beneath NCB have very high Th/Yb ratios of N1 and low Sm/ Nd ratios of b0.2, characteristic of LILE-fertile Palaeozoic SCLM (Fig. 4; Wu et al., 2006). Mesozoic to Cenozoic (b120 Ma) mantle and granulite xenoliths from the lower continental crust beneath northern NCB have Th/Yb ratios of b1 (except for 3 of 42 peridotite samples), and Sm/Nd ratios of N0.2 (e.g. Song and Frey, 1989; Xu et al., 1998; Fan et al., 2000; Rudnick et al., 2004; Zhang, 2005; Wu et al., 2006, Fig. 4). This shows that the b120 Ma SCLM and lower continental crust were less hydrated

have an estimated water content of 100 to 1000 ppm (Yang et al., 2008b). If Mo-bearing granites are derived from the lower continental crust, a melt with a volume of 20 km3 containing 5% water is needed for the formation of deposits containing N0.1 Mt Mo. If half of the water is released during dehydration melting in the lower crust, a magma with a volume of around 4000 km3 containing ~500 ppm H2O is needed for partial melting during the genesis of a Mo-bearing magma. However, most of granulite xenoliths from the Cenozoic alkali basalts and granulites in northern NCB are distributed along a ca. 2600 Ma Sm-Nd isotopic reference line, and a ca. 1900 Ma Rb-Sr isotopic reference line (Jiang et al., 2013). This shows that a large volume of melt has not been extracted from the lower continental crust since ca. 1900 Ma, otherwise the Sm-Nd and Rb-Sr isotopic system would be perturbed. The water-rich nature and arc-like trace element patterns of Mobearing granites, and their close spatial relationship with the Mesozoic hydrous mafic, alkali biotite-syenites show that the key factor for the generation of Mo-bearing magmas in the study area is dehydration melting of hydrated sources. This also demonstrates that the lower continental crust along northern NCB is too depleted in LILE and water to be the source for Mo magmas.

DM

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Average Sm/Nd ratio of Italy mantle inclusions

De dry plet aft sou ed a ex er m rce nd tra el cti t on En so rich by urce ed a me hyd met nd w lts rou aso et s ma tis e

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Th/Yb Cenzoic alkali basalt (52 data)

Mo granites from the XMOB (75 data)

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Mo granites in the northern NCB (85data)

Cenozoic SCLM xenolith, Hebi, central NCB (5 data)

Mafic, alkali biotite-syenite (20 data)

Mesozoic SCLM xenolith, Fuxin, northern NCB (12 data)

Evolved granite (4 data)

Paleozoic SCLM xenolith, Tieling, northern NCB (7 data)

A-type granite (18 data)

Paleozoic SCLM xenolith, Mengyin, central NCB (5 data) DM: depleted mantle Granulite xenolith, lower crust (34 data)

PM: primitive mantle

Fig. 4. Sm/Nd vs Th/Yb diagram showing the SCLM has been gradually depleted in LILEs and water by hydrous melts extraction since the Palaeozoic. Data are from Zhi et al. (1990), Liu et al. (2001), Zhou et al. (2002), Wu et al. (2002, 2003, 2006); Xia et al. (2004), Zheng et al. (2005), Zheng et al. (2007), Yang et al. (2006, 2012), Xu et al. (2008), Niu et al. (2016), and Liu and Jiang (2017).

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than the Palaeozoic SCLM, and thus could not be the source of Mo mineralisation. Xenolith of Palaeozoic mantle peridotites from beneath northern NCB are characterised by their 100 times higher LILE content than the xenoliths of Cenozoic mantle peridotites in the region (Fig. 3c). Thus, large volumes of alkali and water-rich melts were gradually emplaced into the upper crust during the thinning of the LILE-fertile Late Palaeozoic lithosphere. The melts are represented by the Mesozoic mafic, alkali biotite-syenites and Mo-bearing granites with elevated Th/Yb and low Sm/Nd ratios, and are commonly interpreted as being sourced from a metasomatised and enriched SCLM (e.g. Yang et al., 2012). The consequence is the SCLM has been depleted gradually in LILEs and water since the Late Palaeozoic, and the Sm/Nd and Th/Yb ratios of the biotite-syenites and mantle peridotites from the study area define an extraction trend of hydrous melts from an enriched and hydrated SCLM (Fig. 4). Mantle xenoliths in Palaeozoic kimberlites from the SCLM beneath northern NCB, such as at Tieling, have a higher Th/Yb ratio than those from central NCB, such as at Mengyin (Wu et al., 2006; Zhang et al., 2008). The xenoliths have higher Th/Yb ratios than the Hebi mantle xenoliths in the Cenozoic basalts from central NCB, which represents shallow relics of an Archean SCLM (Zheng et al., 2005; Fig. 4). This reveals that the SCLM beneath northern NCB is more extensively metasomatised than beneath its central part, which is consistent with the gradual zonation from enriched Sr-Pb-Nd isotopes in the volcanic units in northern NCB to depleted Sr-Pb-Nd isotopes in XMB (Zhou et al., 2001; Zhang et al., 2003).

7. Implication It was proposed that ancient, metasomatised SCLM plays a very important role in the formation of the Climax-type Mo deposits based on Pb isotope studies (Pettke et al., 2010). However, both the refractory NCB and juvenile XMB contain Mo-bearing granites with similar emplacement histories (Figs. 1 and 2). The Mo-bearing granites in XMB, however, have positive εNd(t) values in contrast to those in northern NCB with negative εNd(t) values (e.g. Li et al., 2014; Wu et al., 2017). The distinct Nd isotopic characteristics of the Mo-bearing granites show that Archean SCLM sources have been metasomatised during ancient events are not required for the generation of water- and LILEfertile Mo-bearing magmas in both regions. It also indicates that the water- and LILE-fertile features of the sources for the Mo-bearing granites are related to Palaeozoic metasomatism. Although subduction of the Pacific oceanic plate is continuing today, no Mo deposits younger than ca. 129 Ma are present in the coastal region of northeastern China. Cenozoic alkali basalts present have ocean island basalt affinities (Zhi et al., 1990), which is significantly different from arc-like Mo-bearing granites (Fig. 3d). Furthermore, the variation of Sm/Nd and Th/Yb ratios of mantle peridotites through geological time indicates that the SCLM beneath northern NCB and XMB has been gradually depleted in LILEs and water. The low water content of the Cenozoic SCLM in the region is consistent with an estimated water content of b155 ppm for the peridotite xenoliths from the Cenozoic Hannuoba alkali basalts (Yang et al., 2008b). Together with the nature of mantle peridotites from northern NCB being more enriched in LILEs and water than those from centre NCB means that the Palaeozoic to Early Cretaceous (N120 Ma) SCLM was metasomatised during previous subduction of the Paleo-Asian oceanic plate, rather than the contemporary subduction of the Pacific oceanic plate. Based on the evidence presented in this paper, it is concluded that a large number of porphyry Mo deposits can be produced during riftrelated magmatism from the extraction of hydrous melts from a hydrated SCLM, which was metasomatised by previous subduction of an oceanic plate.

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