Canadian Journal of Earth Sciences

Zircon U-Pb and Molybdenite Re-Os Dating and Geological Implications of the Shimadong Porphyry Molybdenum Deposit in Eastern Yanbian, NE

Journal: Canadian Journal of Earth Sciences

Manuscript ID cjes-2019-0014.R2

Manuscript Type: Article

Date Submitted by the 29-May-2019 Author:

Complete List of Authors: Nie, Xi-Tao; University, College of Earth Sciences Sun, Jing-Gui; Jilin University, College of Earth Sciences; Sun, Feng-Yue; Jilin University, College of Earth Sciences Li, Bi-Le; JilinDraft University, College of Earth Sciences Zhang, Ya-Jing; Jilin University, College of Earth Sciences Liu, Wan-Zhen; Jilin Institute of Geological Survey

zircon U-Pb dating, molybdenite Re-Os dating, Geochemistry, Hf isotope, Keyword: Shimadong porphyry Mo deposit

Is the invited manuscript for consideration in a Special Not applicable (regular submission) Issue? :

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1 Zircon U-Pb and Molybdenite Re-Os Dating and Geological

2 Implications of the Shimadong Porphyry Molybdenum

3 Deposit in Eastern Yanbian, NE China

4 5 Xitao Nie1,2, Jinggui Sun1, Fengyue Sun1,*, Bile Li1, Yajing Zhang1, and Wanzhen 6 Liu2 7 8 1 College of Earth Sciences, Jilin University, 130061, China; 9 10 2 Jilin Institute of Geological Survey, Changchun 130061, China 11 12 * Corresponding author: Feng-Yue Sun, College of Earth Sciences, Jilin University, 13 No. 2166, Jianshe Street, Changchun 130061, China 14 15 E-mail: [email protected] 16 17 Tel.:+86 431 88502055 Draft 18

19 ABSTRACT

20 The Shimadong porphyry Mo deposit is located in eastern Yanbian, in the eastern part

21 of the north margin of the North China craton (NCC), NE China. Here, we present the

22 whole-rock major and trace elements, zircon U-Pb and Hf isotope data, and

23 molybdenite Re-Os data for the Shimadong deposit. The porphyry was emplaced at

24 163.7 ± 0.9 Ma and the mineralization at 163.1 ± 0.9 Ma, suggesting that the

25 mineralization was associated with the emplacement of the Shimadong porphyritic

26 monzogranite. The porphyritic monzogranite had high SiO2 (70.09–70.55 wt%) and

27 K2O + Na2O (7.98–8.27 wt%) contents and low MgO (0.51–0.53 wt%), TFeO

28 (2.4–2.47 wt%), CaO (2.19–2.26 wt%), and K2O/Na2O (0.8–0.82) contents. The

29 porphyry was rich in large ion lithophile elements Rb, Ba, K, and Sr, depleted in

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30 high-field strength elements Y, Nb, Ta, P, and Ti, without significant Eu anomaly

31 (δEu = 0.86-1.00), and depleted in heavy REE (HREEs) with LREE/HREE =

32 18.25–20.72 and (La/Yb)N =27.10–34.67. These features are similar to those of

33 adakitic rocks derived from a thickened lower crust. Zircon εHf(t) values for the

34 porphyritic monzogranite ranged from −19.2 to 6.3, and the two-stage Hf model ages

35 (TDM2) was 811–2421 Ma. These data indicate that the primary magma of the

36 Shimadong porphyritic monzogranite was mainly derived from partial melting of the

37 thickened lower crust consisting of juvenile crust and pre-existing crust. Combined

38 with the results of previous studies, our data suggest that the Shimadong porphyry Mo 39 deposit was emplaced along an activeDraft continental margin related to the westward 40 subduction of the paleo-Pacific Plate.

41 Keywords: Zircon U-Pb dating, Molybdenite Re-Os dating, Geochemistry, Hf isotope,

42 Shimadong porphyry Mo deposit, NE China.

43 1 Introduction

44 One of the largest molybdenum metallogenic belts in NE China, the east Xingmeng

45 orogenic belt (EXOB) is a segment of the east Central Asian orogenic belt (CAOB)

46 (Mao et al., 2011; Zeng et al., 2012a, 2013). The Paleozoic tectonic evolution of the

47 EXOB was dominated by the closure of the Paleo-Asian Ocean and consisted of

48 collisions of microcontinental blocks between the Siberian craton and the North China

49 craton (NCC). These blocks include the Khanka, Jiamusi, Songnen, Yanbian, Erguna,

50 Xing’an and Zhangguangcai massifs, all of which are separated from each other by

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51 major faults (Wu et al.,2000, 2001, 2004, 2007a, 2007b, 2011; Sun, 2001; Sun et al.,

52 2005a,b, 2013; Zhang et al., 2010; Meng et al., 2010, 2011; Zhou et al., 2010a,b,c;

53 Cao et al., 2012, 2013; Tang et al., 2013; Li et al., 2014; Wang et al., 2015a, 2015b;

54 Yang et al., 2017) (Fig. 1). The Mesozoic and Cenozoic tectonic evolutions were

55 caused by subduction of the paleo-Pacific plate beneath the East Asian continent,

56 superimposed on the EXOB and NCC (Li et al., 1999, 2009; Wu et al., 2007b, 2011;

57 Yu et al., 2012; Xu et al., 2013; Guo et al., 2015).

58 In the EXOB region, super-giant Mo deposits, such as the Chalukou, Luming and

59 Daheishan deposits, giant and medium scale Mo deposits, such as the Fuanpu, Jidetun,

60 Dongfeng, and Shimadong deposits,Draft and small-scale Mo deposits, such as the

61 Liushengdian and Sancha (Fig. 1) occur.

62 These Mo deposits are mainly porphyry type, followed by skarn or hydrothermal

63 vein types (Chen et al., 2012, 2017; Zhang, 2013b; Zhao, 2016; Zeng et al., 2018a). In

64 recent years, some studies have been conducted on molybdenum mines in the Jilin

65 Province, primarily focusing on three aspects of the system: (1) the mineralization

66 periods mainly concentrated between 163-195 Ma (Ge et al., 2007; Wang et al., 2009;

67 Wang, 2011; Di, 2011; Ju, 2012; Zhang, 2013a; Song, 2016; Guo et al., 2018; Zeng et

68 al., 2018; Zhou et al., 2018) and 110-128Ma (Sun et al., 2001; Zeng et al., 2010a,

69 2012b; Huang, 2014; Zhao, 2016), (2) the ore-forming materials derived from a

70 crustal source (Sun et al., 2001; Zhang, 2013a; Ju et al., 2012) or a mixed crustal and

71 mantle source (Sun et al., 2001; Li et al., 2009; Wang et al., 2009; Zhou et al., 2013;

72 Zhang, 2013a), and (3) magma originating in the ancient crust (Farmer and DePaolo,

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73 1984; Carten et al., 1993; Chen et al., 2000), partial melting of the lithospheric mantle

74 by percolated of subduction fluids (Westra and Keith, 1981; Pettke et al., 2010), and

75 partial melting of a thickened lower crust (Petford and Atherton, 1996; Kay and Kay,

76 2002; Hou et al., 2009; Chen et al., 2009; Guo et al., 2018). The Shimadong Mo

77 deposit is newly discovered medium scale deposit with 100,000 tons of ores at an

78 average grade of 0.08% Mo (Pei, 2012). However, the nature of the magma and the

79 mineralization constraints remain undetermined and the metallogenic tectonic

80 background is unknown. In order to solve the above problems, this paper presents the

81 zircon U-Pb ages, in-situ Hf isotopic, and whole-rock elemental compositions of the 82 porphyritic monzogranites as wellDraft as the molybdenite Re-Os ages in the Shimadong 83 Mo deposit.

84 2 Regional geologic setting

85 Composed of a basement and cover layer, the eastern Yanbian region is located in

86 the EXOB and NCC. The basement was formed by the late Archean Jiapigou Group

87 (2.5 Ga; Wu, 2017), granitic gneiss, and the Permian Qinglongcun Group (Jia, 1994;

88 Zhang, 2003; Qiu et al., 2004). The former two units are distributed on the NCC, and

89 the main lithologies are amphibole and amphibole plagioclase gneiss, metamorphic

90 hornblende diorite, metamorphic monzogranite, and other similar rock types. The

91 latter unit is distributed in the EXOB and includes marble of the Changren Formation

92 and griotte and gneiss from the Xindongcun Formation (274-250 Ma; Zhang et al.,

93 2007; Zhou et al., 2013b; Zhou, 2017). The cover layer consists of Mesozoic

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94 sedimentary rocks (Lei, 2015). The Mesozoic rift basin is mainly composed of the

95 Cretaceous Changcai Formation, Quanshuicun Formation, Dalazi Formation, and

96 Longjing Formation (Lei, 2015; Chen, 2017). The rocks in the rift basin constitute a

97 set of river-lake face clastic rocks and volcanic-volcaniclastic rocks. The distribution

98 of the rocks is fault controlled. The Cenozoic basalt of the Chuandishan Formation is

99 the youngest stratum exposed in the region and is found on the west side of the area.

100 Intrusive rocks in the region are widely distributed, and the shape and spatial

101 distribution of the rocks are observably controlled by the regional fault. The

102 distribution of the Archean tonalite and the Paleozoic complex rocks are limited and

103 scattered. The rocks have developedDraft schistosity, and the schistosity direction is

104 consistent with the regional tectonic line. A small number of mafic-ultramafic dikes

105 formed from 255–217 Ma are mainly related to copper nickel sulfide deposits (Wu et

106 al., 2004; Xie et al., 2007; Zhou, 2017; Wang, 2018). The Mesozoic granites that are

107 exposed over a large range, are mainly was divided into two periods: 166–195 Ma

108 (Sun, 2010; Zhang, 2013b; Zhang, 2014; Zhou et al., 2013; Zeng et al., 2018), and

109 111–128 Ma (Sun et al., 2012; Zhao, 2016). The exposed are monzogranite,

110 granodiorite, and granite lithologies along with a large number of porphyry Mo

111 deposits, are closely related to its genesis (Zhang, 2009; Sun, 2010; Tan et al., 2013;

112 Zhang, 2009; Yang et al., 2012; Zhou et al., 2013; Zhang, 2013b)

113 3 Deposit Geology

114 The Shimadong porphyry Mo deposit is located in the town of Nanping, east of

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115 Helong city. It is located at the southeast end of the Gudong River platinum

116 ultra-lithospheric fault zone.

117 The oldest exposed rock in the mining area is the Neo-Archean Formation

118 that is mainly composed of biotite amphibolite distributed as residues. The Jurassic

119 intrusive complex of the largest exposed area is divided into early Jurassic granitic

120 diorite (Lei, 2015), middle Jurassic porphyritic monzogranite, and fine-grained

121 monzogranite (Zhang et al., 2014) (Fig. 2a). The porphyritic monzogranite is closely

122 related to the Mo mineralization described below.

123 The orebodies mainly occur in the porphyritic monzogranite, and no obvious 124 boundary is present between theDraft orebodies and the wall rock. The shapes of the 125 orebodies are clintheriform or lenticular, and the topography follows the relief (Fig.

126 2b). The largest orebody with dip angles of 5°~35° is longer than 900 m, wider than

127 450 m, and has an average thickness of 10 m (Pei, 2012). The average grade of the

128 orebodies is 0.08% Mo.

129 Based on the field observation and the microscopic identification, this deposit can

130 be divided into three zones, from inside to outside: (1) an inner zone with a potassic

131 alteration and biotitization, as well as minor Mo mineralization, (2) a middle zone

132 comprising silicification and sericitization with abundant Mo mineralization, and (3)

133 an outer zone exhibiting carbonation, chloritization, and minor pyritization.

134 The commercial ore occurs as fine vein disseminated and fine vein (Fig. 3b). The

135 major ore mineral is molybdenite (Fig. 3b and f), and other metallic minerals

136 including pyrite (Fig. 3c), chalcopyrite (Fig. 3e), magnetite (Fig. 3d), and sphalerite

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137 (Fig. 3d and e). The gangue minerals include quartz, sericite (Fig. 3g), chlorite, biotite

138 (Fig. 3h), plagioclase, k-feldspar, calcite (Fig. 3i), and kaolin (Fig. 3g and h).

139 4 Samples and analytical methods

140 4.1 U-Pb zircon dating

141 Ore-bearing Shimadong porphyritic monzogranite samples (SMD-N1) (Fig. 3a) were

142 analyzed for zircon U-Pb dating and in-situ Hf isotope analysis. The sample was

143 extracted from the wall rock of the orebodies in the ZK024. The porphyritic

144 monzogranite was light red and exhibited porphyritic texture and massive structure.

145 The rocks contained 55-65% phenocrystsDraft with a grain size of 2-8 mm, and the

146 composition was plagioclase (20-25%), K-feldspar (20-25%), quartz (15-20%), and

147 minor biotite (~5%). The matrix was microcrystalline and was composed of quartz

148 and plagioclase. Minor accessory minerals, such as apatite, zircon, sphene, and

149 magnetite were also present and generally underwent chloritization, sericitization,

150 silicification, and kaolinization.

151 Typical cathodoluminescence (CL) images were obtained to identify the internal

152 structures and to choose potential target sites for the U-Pb and trace element analyses.

153 Zircon U-Pb dating and trace element analyses were performed using a Bruker Aurora

154 M90 inductively coupled plasma mass spectrometer (ICP-MS) combined with a New

155 Wave UP 213 laser ablation (LA) system at the Yanduzhongshi Geological

156 Analysis Laboratory. The beam diameter was 35 μm for all zircons, and each analysis

157 incorporated a background acquisition interval of 20-30 s (gas blank) followed by a

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158 30 s data acquisition interval. Two zircon standards, GJ-1 (610.0 ± 1.7 Ma; Elhlou et

159 al., 2006) and Plešovice (337.13 ± 0.13 Ma; Sláma et al., 2008) were used as external

160 standards to correct for mass fractionation. These standards were measured twice and

161 once, respectively, after every five sample analyses. A widely used protocol for

162 correction of the U-Pb dates (Liu et al., 2010a) was applied by analyzing the GJ-1 and

163 Plešovice standard zircons. The ANIST SRM610 standard silicate glass was used for

164 external standardization of the trace element analyses, and 29Si was used for internal

165 standardization. Offline selection and integration of the background and analytical

166 signals, time-drift correction, quantitative calibration for the trace element analyses, 167 and U-Pb dating were performed usingDraft the in-house software ICPMSDataCal (Liu et 168 al., 2010b). Common Pb was corrected following Andersen (2002). Concordia

169 diagrams and weighted mean calculations were processed using Isoplot (version 3.0;

170 Ludwig, 2003).

171 4.2 Molybdenite Re-Os dating

172 Molybdenite crystals were used to select pure molybdenite fine veins at the stage of

173 independent mineralization and fresh grains without oxidation and contamination. Six

174 ore samples were crushed, separated, and sieved to obtain molybdenites with a purity

175 of >99%. Re-Os isotope analyses of the arsenopyrite were performed in the Re-Os lab

176 at the National Research Center for Geoanalysis, Chinese Academy of Geological

177 Sciences. The chemical separation procedure is briefly described below (Du et al.,

178 1994, 2009; Qu et al., 2003; Li et al., 2009, 2010).

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179 The enriched 190Os and enriched 185Re were obtained from the Oak Ridge National

180 Laboratory. The weighed sample was loaded in a Carius tube through a thin-necked

181 long funnel. The mixed 190Os and 185Re spike solutions and 2 mL HCl and 4 mL

182 HNO4 were loaded while the bottom part of the tube was frozen at temperatures

183 ranging from −50 to −80 ℃ in an ethanol-liquid nitrogen slush, and the top was sealed

184 using an oxygen-propane torch. The tube was then placed in a stainless-steel jacket

185 and heated for 24 h at 230 ℃. Upon cooling, while keeping the bottom part of the tube

186 frozen, the neck of the tube was broken. The Os was separated by the method of direct

187 distillation from the Carius tube for 50 min and trapped in 3 mL of water that was 188 used for the multiple collector (MC)Draft ICP-MS (NEPTUNE-Plus) determination of the 189 Os isotope ratio. The residual Re-bearing solution was saved in a 150 mL Teflon

190 beaker for Re separation.

191 The residual Re-bearing solution was heated to near dryness. Five mL of 30%

192 NaOH was added to the residue, followed by Re extraction with 5 mL of acetone in a

193 50-mL centrifuge tube. The acetone phase was transferred to a 150 mL Teflon beaker

194 that contained 1 mL of water, evaporated to dryness and picked up in 2% HNO3 that

195 was used for the ICP-MS (X-Series) determination of the Re isotope ratio. The

196 average blanks for the method were ~3 pg Re and ~0.5 pg Os.

197 4.3 Whole-rock geochemistry determination

198 The samples were taken from the same borehole as the zircon U-Pb dating sample,

199 and fresh unaltered samples were selected for the major and trace element analysis.

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200 For the geochemical analysis, whole-rock samples, after removal of the altered

201 surfaces, were crushed in an agate mill to ~200 mesh. X-ray fluorescence (XRF;

202 PW1401/10) using fused glass disks and ICP-MS (Agilent 7500a with a shield torch)

203 were used to measure the major and trace element compositions, respectively, at the

204 Testing Center of Jilin University after acid digestion of the samples in Teflon bombs.

205 The analytical results for the BHVO-1 (basalt), BCR-2 (basalt), and AGV-1 (andesite)

206 standards indicated that the analytical precision for the major elements was better than

207 5%, and for the trace elements, generally better than 5% when the content was >10

208 ppm and better than 10% when <10 ppm. The analytical results for the major and 209 trace elements in the early MesozoicDraft granitic rocks are listed in Table 2.

210 4.4 Hf isotope analysis

211 The in-situ Lu-Hf isotope analyses of the zircon were undertaken using a

212 NewWave UP213 LA-MC-ICP-MS attached to a ThermoElectron Neptune-plus

213 MC-ICP-MS at the Beijing Yanduzhongshi Geological Analysis Laboratory. The test

214 procedure and calibration method were similar to those of Wu et al. (2006). The

215 zircon denudation used a repetition rate of 8 Hz, a laser energy density of 16 J/cm2, an

216 ablation time of 31 s, and 30 μm ablation pits. At the time of the test, due to the

217 extremely low 176Lu/177Hf ratio in the zircon (generally less than 0.002), the isotopic

218 interference of 176Lu on 176Hf was negligible. The average value of 173Yb/172Yb at

219 each test point was used to calculate the fractionation coefficient of Yb and then the

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220 interference of 176Yb on the 176Hf isotropic heterotopic elements was deducted. The

221 isotope ratio of 173Yb/172Yb was 1.35274.

222 5 Analytical results

223 5.1 U-Pb zircon ages

224 Zircons from the porphyritic monzogranite (samples SMD-N1) were automorphic,

225 100-200 μm long, and displayed typical magmatic oscillatory zoning in the CL

226 images (Fig. 4). These zircons had high Th/U ratios of 0.22-0.86 (Table 1). The

227 morphologic and chemical characteristics of the zircon grains in the intrusive rocks

228 clearly indicated a magmatic originDraft (Belousova et al., 2002). The results showed that

229 the ages ranged from 162 to 164 Ma and yielded a weighted mean age of 163.7 ± 0.9

230 Ma (1σ, MSWD = 0.15, n = 17; Fig. 5) that was interpreted as the crystallization age

231 of the porphyritic monzogranite.

232 5.2 Molybdenite Re-Os ages

233 Six molybdenite samples were analyzed for Re and Os isotope compositions and

234 these are listed in Table 2. The Re contents of the molybdenites ranged from 26.9 to

235 33.8 ppm, and the 187Os contents of the molybdenites ranged from 0.0461 to 0.0581

236 ppm, with model ages for the individual analyses ranging from 162.1 ± 2.5 to 163.8 ±

237 2.5 Ma. We obtained an isochron age of 169.0 ± 11 Ma (the initial 187Os of -1.7 ± 3.5

238 ng/g and MSWD = 0.21) (Fig. 6a) and a weighted mean model age of 163.1 ± 0.9 Ma

239 (n = 6, MSWD = 0.21) (Fig. 6b). The difference between the isochron age and the

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240 mean model age was due to a low degree of chemical fractionation and the narrow

241 ranges of the 187Re and 187Os values (Du et al., 2009). These results indicate that the

242 Mo mineralization occurred during the Middle Jurassic.

243 5.3 Major and trace elements

244 The Shimadong porphyritic monzogranite had compositions of SiO2 = 70.09-70.55

245 wt.%, Al2O3 = 15.00-15.41 wt.%, MgO = 0.51-0.53 wt.%, CaO = 2.19-2.26 wt.%,

246 Na2O = 4.41-4.59 wt.%, K2O = 3.57-3.68 wt.%, and Na2O/K2O = 1.22-1.24 (Table 3).

247 All samples plotted as granite in the TAS diagram (Fig. 7) belong to the high-K 248 calc-alkaline series (Fig. 8a) and areDraft classified as metaluminous-weakly peraluminous 249 in the A/NK vs. A/CNK diagram (Fig. 8b).

250 In terms of trace elements, the total amount of rare earth elements (REEs) in the

251 Shimadong porphyritic monzogranite was low (∑REE = 81.6 × 10-6~95.5 × 10-6)

252 (Table 3). Chondrite-normalized REE patterns for the Middle Jurassic intrusive rocks

253 from Shimadong were characterized by LREE/HREE fractionation (Fig. 9a),

254 enrichment in LREEs (∑ = 73.6 × 10-6~91.1 × 10-6), depletion in HREEs (∑ =

-6 -6 255 4.0×10 ~4.4×10 ), (La/Yb)N = 27.1~34.67, (Ce/Yb)N = 19.54~25.88, and with no

256 notable Eu anomalies (δEu = 0.86~1.00). A primitive mantle-normalized trace

257 element spidergram indicated that the Middle Jurassic granitoids were enriched in

258 large ion lithophile elements Rb, Ba, K, and Sr and depleted in the high field strength

259 elements Y, Nb, Ta, P, and Ti (Fig. 9b).

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260 5.4 Zircon Hf isotope compositions

261 Fifteen of twenty-four zircons from the Shimadong porphyritic monzogranite

262 sample SMD-N1 were analyzed for Hf isotope compositions at the site used for U-Pb

263 dating. The results of the zircon in-situ Lu-Hf isotope analysis and related calculations

264 are listed in Table 4. The initial 176Hf/177Hf ratios ranged from 0.282130 to 0.282848,

265 εHf(t) values ranged from −19.2 to 6.3, and the single-stage Hf model ages (TDM1)

266 and two-stage Hf model ages (TDM2) were 561-1562 Ma and 811-2421 Ma,

267 respectively.

268 6 Discussion Draft

269 6.1 Timing of magmatism and mineralization

270 In recent years, with the discovery of a series of Mo deposits in NE China, Mo

271 deposits have become the focus for some researchers. Significant chronologic data

272 suggest that the porphyry Mo mineralization in NE China can be divided into four

273 periods: early Paleozoic (475 Ma) (Zeng et al., 2014), Early Triassic (248-237 Ma)

274 (Zeng et al., 2010b), Early-Middle Jurassic (195-163 Ma) (Ge et al., 2007; Wang et al.,

275 2009; Wang, 2011; Di, 2011; Ju, 2012; Zhang, 2013a; Song, 2016), and Early

276 Cretaceous (142-110 Ma) (Sun et al., 2001; Zeng et al., 2010a, 2012b; Huang, 2014;

277 Zhao, 2016). Shao et al. (2016) obtained a Re-Os isochron age of 169.3 ± 1.9 Ma and

278 a weighted mean age of 165.6 ± 0.4 Ma. Our new data showed that six molybdenite

279 grains from the quartz-molybdenite fine veins yielded a Re-Os isochron age of 169.0

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280 ± 11 Ma and a weighted mean age of 163.1 ± 0.9 Ma that represents the

281 mineralization age as Middle Jurassic.

282 Previous studies have suggested that the porphyry stocks related to mineralization

283 in the Shimadong Mo deposit belong to the Gaoling rock mass (Shao et al., 2016).

284 The rock mass is a monzogranitic complex with an exposed area of approximately

285 350 km2 distributed along the periphery of the mining area. The obtained U-Pb ages

286 of the zircons were 172.2 ± 0.9 Ma and 170.9 ± 0.6 Ma (Zhang et al., 2014), however,

287 the sample locations were far away from the mining area (Fig 2c). Therefore, we

288 dated the ore-bearing surrounding rocks in the mining area, and obtained a U-Pb age

289 of 163.7 ± 0.9 Ma. This age suggestsDraft that Mo mineralization occurred during the

290 Middle Jurassic and that the porphyritic monzogranite is genetically related to the Mo

291 mineralization. Corresponding to the Early and Middle Jurassic is an important

292 large-scale molybdenum metallogenic period in NE China (Ge et al., 2007; Sun et al.,

293 2001; Chen et al., 2012; Zeng et al., 2012b; Shu et al., 2016).

294 6.2 Petrogenesis of the porphyritic monzogranite

295 The Middle Jurassic porphyritic monzogranite in Shimadong had high SiO2

296 (≥70.24%), high Al2O3 (≥15%), and low MgO (≤0.53%). It was rich in Sr

297 (≥465.7×10-6), poor in Y (≤6.565×10-6) and Yb (≤0.4661×10-6), had high Sr/Y ratios

298 (≥77.58×10-6) and La/Yb ratios (≥40.2×10-6), depleted HREEs, and unremarkable Eu

299 anomalies. These features are consistent with the geochemical characteristics of

300 adakite rocks (Defant and Drummond, 1990; Kay and Kay, 1993; Kay et al., 1993;

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301 Atherton and Petford, 1993; Castillo, 2012). All sample points plotted in the range of

302 adakite on the Sr/Y-Y and (La/Yb) N-YbN diagrams (Fig. 10). At present, there are

303 four main genetic mechanisms for adakite: (1) partial melting of subducted basaltic

304 oceanic crust (Defant and Drummond, 1990; Kelemen et al., 1995; Kay and Kay,

305 2002; Castillo, 2012); (2) crustal mixing and fractional crystallization of basaltic

306 magma (Feeley and Hacker, 1995; Wareham et al., 1997; Castillo et al., 1999; Rooney

307 et al., 2011); (3) magmatism related to the delamination of the lower crust (Kay and

308 Kay, 1993; Xu et al., 2002; Gao et al., 2004); and (4) partial melting of the thickened

309 lower crust (Petford and Atherton, 1996; Gao et al., 2004; Kay and Kay, 2002). 310 Different adakite rocks have differentDraft elemental characteristics. The high K 311 calc-alkaline and K element enrichment of the Shimadong porphyritic monzogranite

312 are different from adakitic rocks with low K and high Na2O/K2O ratios (≥12)

313 produced by typical subduction partial melting of oceanic crust. The crustal mixing

314 and differentiation of basaltic magma can produce a series of rocks from mafic to

315 felsic. The adakite area, considered the origin of this formation, produced a

316 basic-neutral-acidic rock series (Castillo et al., 1999; Macpherson et al., 2006; Li et al.,

317 2009). However, no mafic-ultramafic intrusive rocks from the same period have been

318 found in eastern Yanbian. Therefore, we assert that the Shimadong porphyritic

319 monzogranite was not formed by crustal mixing and differentiation of basaltic magma.

320 Adakites formed by partial melting of the subducted crust usually have high contents

321 of MgO (>3%) and high Mg# (>50), Cr, and Ni. These samples have low MgO, Mg#,

322 Cr, and Ni contents. Sr enrichment and no Eu anomaly indicate that plagioclase did

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323 not crystallize during the magma evolution process. The strong loss and low Yb and

324 Y characteristics of the HREEs indicate the presence of garnet and amphibole in the

325 residual phase in the source area. This feature indicates that the magma originated at a

326 depth greater than 50 km (Sen and Dunn, 1994; Rapp and Watson, 1995; Stern and

327 Kilian, 1996; Zhang et al., 2010). Losses of P and Ti indicate the presence of mineral

328 phase residues such as apatite, ilmenite, and biotite in the source area. Meanwhile,

329 losses of Nb and Ta indicate that Nb and Ta are dispersed in minerals containing Ti in

330 a homogeneous manner. In the discriminant diagrams for SiO2-MgO and SiO2-Mg#

331 (Fig. 11), samples plotted within the partial melting range of the thickened lower 332 crust. Draft

333 The Lu-Hf isotope system provides clues to the source of the Shimadong

334 porphyritic monzogranite. The εHf(t) values ranged from −19.2 to 6.3, and the

335 two-stage Hf model age (TDM2) ranged from 811-2421 Ma. These results indicate that

336 the magma evolved from a mixture of juvenile crust and pre-existing crust (Wu et al.,

337 2007c; Zeng et al., 2018), and the enrichment in Pb indicates the addition of mantle

338 magma. The Hf isotope compositions of most zircons were similar to that of the NCC

339 Proterozoic strata, and some zircons were similar to eastern CAOB late Proterozoic

340 rocks (Xie et al., 2012) (Fig. 12).

341 In summary, we suggest that the Shimadong porphyritic monzogranite exhibits

342 geochemical affinities with adakitic rocks and formed from the partial melting of

343 thickened lower crust consisting of juvenile crust and pre-existing crust.

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344 6.3 Metal source and magmatic constraints on ore formation

345 The rhenium content in the molybdenites varied greatly (Fleischer, 1960; Terada et

346 al., 1971). The variance of Re contents in the molybdenites indicates that the material

347 source was mainly mantle material (100 × 10-6~1000 × 10-6), crust-mantle mixed

348 material (10~100 × 10-6), and crust material (1~10 × 10-6) (Mao et al., 1999; Meng et

349 al., 2007). The Re content might reflect the source of the deposits (Zhou, 2011). Many

350 scholars discuss the metal source related the contents of Re (Li et al., 2009; Wang et

351 al., 2009; Chen et al., 2012; Sun et al., 2012; Zhang et al., 2015; Guo et al., 2018; Guo

352 et al., 2018). The Re contents of molybdenites in the Shimadong deposit ranged from

353 26.9 to 33.8 ppm and these valuesDraft suggest that the ore forming material may have

354 been derived from mixed crust and mantle (Fig. 13).

355 The geological, geochronological, elemental characteristics, and age of the

356 Shimadong porphyritic monzogranite suggest that the porphyritic monzogranite

357 exhibits adakitic features, and provides evidence of a magmatic control on the

358 porphyritic monzogranite in the Shimadong Mo deposit. Compared to normal felsic

359 magmas, adakitic magmas exhibit higher values of T, P, oxygen fugacity, and S

360 enrichment (Oyarzun et al., 2001). Under these conditions, sulfide magma is

361 unsaturated and Mo is concentrated in the magma as incompatible elements and

362 continues to become further enriched throughout the evolution of the magma

363 (Mungall, 2002; Wang, 2015). Cu, Au, Ag, and Mo are highly abundant in the mantle,

364 and adakitic magmas react with the mantle rock or lava during the rising stage, or

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365 magma mixing with the mantle may also lead to the enrichment of the adakite mass

366 and magmatic metallogenic metallic elements (Hou, 2003). During the formation of

367 adakite magma, amphibolite facies alter to eclogite facies under high temperature and

368 pressure. When the amphibolite decomposed a large amount of water was released

369 and a large amount of fluid was extracted that was very beneficial to the enrichment

370 of the metallic elements (Wang, 2003; Wang, 2015). According to the geochemical

371 behaviors of Sm, Yb, and Y in the lower crust, the low Y and Yb contents of adakite

372 indicate that there are more garnet mineral phase residues in the source region, while

373 the low Sm/Yb and high Zr/Sm ratios indicate that there are more hornblende residual 374 facies combinations in the sourceDraft region (Hou, 2005). For the same source rock (or 375 eclogite), a partial melting degree increase will lead to a large-scale transformation of

376 the residual phase from amphibole to garnet in the source region. Hence, the

377 water-rich adakite formed with a Sm/Yb value between 5 and 7 (kay et al., 2001). The

378 Sm/Yb values for the Daheishan, Fuanpu, and Shimadong Mo deposits were between

379 4.3-6.5 (Fig 14) with an average of 5.5 (n = 12). These values reflect the residual

380 phase of amphibole in the source region altering obviously to garnet during the

381 melting process releasing the large amount of fluid required by the porphyry copper

382 deposit, and it has the conditions for the formation of super-large and large-scale

383 deposits. However, the Sm/Yb value of the Xinhualong Mo deposit was between

384 4.2-4.5, reflecting that a small amount of hornblende decomposed during the melting

385 process in the source region. It is difficult to produce a large amount of fluid,

386 therefore, the scale of the deposit is relatively small.

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387 In summary, the adakitic magmatism in the Shimadong Mo deposit area played an

388 important role in the formation of the metallogenic system. In fact, the study found

389 adakitic magmas play an important role in an increasing number of porphyry

390 molybdenum deposits (Xi et al., 2018; Gu et al., 2018; Deng et al., 2019).

391 6.4 Geodynamic setting

392 According to the chronologic data, the Shimadong Mo mineralization occurred

393 during the Middle Jurassic (163.1 ± 0.9 Ma), and the slightly earlier porphyritic

394 monzogranite closely related to the mineralization crystallized at 163.7 ± 0.9 Ma. In 395 recent years, high-precision U-Pb Draftdating from zircons has shown that a large number 396 of Early-Middle Jurassic granites are distributed in NE China. For example, the

397 Daheishan, Chalukou, Fuanpu, Jidetun, Luming, Huojihe, Xingwen, and Yaojiagou

398 Mo Deposits have close spatiotemporal relations with Early-Middle Jurassic granites.

399 The paleo-Asian ocean was closed during the Late Permian-Early Triassic period in

400 NE China (Wu et al., 2007b; Zhang et al., 2009; Zhao et al., 2010; Peng et al., 2012;

401 Cao et al., 2012, 2013). The subduction of the paleo-Pacific Plate beneath the

402 Eurasian continent began during the Early-Middle Jurassic (Wu et al., 2007a; Zhou et

403 al., 2009; Pei et al., 2009; Yu et al., 2012; Xu et al., 2008, 2013; Zhou and Wilde,

404 2013). Voluminous Early-Middle Jurassic granitic magma in NE China were

405 emplaced under this condition accompanied by the formation of many porphyry

406 molybdenum deposits (Ge et al., 2007; Sun et al., 2012; Chen et al., 2012).

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407 The Middle Jurassic ore-related granitic magmatism in the Songnen block, Khanka

408 block, Yanbian block, and NCC belong to the high-K calc-alkaline series and are

409 geochemically metaluminous to slightly peraluminous, suggesting an active

410 continental margin setting (Wu et al., 2003, 2005; Chu et al., 2012). In addition,

411 various tectonic discrimination diagrams have been used to constrain the geodynamic

412 setting of the granitoids (Pearce et al., 1984). The samples of the Shimadong

413 porphyritic monzogranite and other Middle Jurassic ore-forming porphyries plot in

414 the fields of ‘VAG + syn-COLG’ and ‘VAG’ in the Nb-Y and Rb-(Y + Nb)

415 discrimination diagrams (Fig. 15) indicating that the relevant Mo deposit was 416 probably formed in an active continentalDraft margin.

417 In view of the above discussion, we suggest that the Middle Jurassic ore forming

418 intrusions of porphyry deposits in NE China occurred along an active continental

419 margin and were related to the westward subduction of the paleo-Pacific Plate (Fig.

420 16).

421 7 Conclusions

422 (1) LA-ICP-MS zircon U-Pb dating showed that the porphyritic monzogranite in the

423 Shimadong Mo deposit was emplaced at 163.7 ± 0.9 Ma. Molybdenite Re-Os dating

424 yielded a weighted mean model age of 163.1 ± 0.9 Ma. Therefore, this deposit formed

425 during the Middle Jurassic.

426 (2) Combining the petrology and Hf isotope characteristics demonstrated that the

427 Shimadong porphyritic monzogranite with adakitic affinities originated from the

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428 partial melting of thickened lower crust that favored porphyry Mo mineralization

429 owing to higher values of oxygen fugacity, S enrichment, and a large amount of

430 water.

431 (3) Based on the regional structure and large-scale Jurassic mineralization, we infer

432 that the Shimadong porphyry Mo deposit occurred against the tectonic background of

433 the westward subduction of the paleo-Pacific Plate beneath the Eurasian Plate.

434 Acknowledgements

435 This work was funded by the National Key R&D Program of China

436 (2017YFC0601304) and the NaturalDraft Science Foundation of Jilin Province of China

437 (20180101089JC). We greatly appreciate the contributions of colleagues from the

438 Jilin Institute of Geological Survey and the Jilin University who helped with

439 fieldwork and sample collection. Thanks are given to Yang Liu for language polishing

440 and constructive comments. We express our gratitude to Associate Editor Dr. Ali

441 Polat and two reviewers for their detailed comments and excellent suggestions that

442 improved this article.

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682 centro-eastern Jilin and its geological significance. Global Geology, 35(03): 683 717-728. (In Chinese with English abstract.)

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725 Wang, C.H., Song, Q.H., Wang, D.H., Li, L.X., Yu, C., Wang, Z.G., Qu, W.J., Du, 726 A.D., Ying, L.J. 2009. Re-Os isotopic dating of molybdenite from the Daheishan 727 molybdenum deposit of Jilin Province and its geological significance. Rock 728 Mineral. Anal, 28: 269-273. (In Chinese with English abstract.)

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754 Wareham, C.D., Millar, I.L., Vaughan, A.P.M. 1997. The Generation of Sodic Granite 755 Magmas, Western Palmer Land, Antarctic Peninsula. Contributions to 756 Mineralogy and Petrology, 128(1): 81-96.

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759 Wu, F.Y., Jahn, B.M., Wilde, S.A., Sun, D.Y. 2000. Phanerozoic crustal growth: 760 U-Pb and Sr-Nd isotopic evidence from the granites in northeastern China. 761 Tectonophysics, 328: 89-113.

762 Wu, F.Y., Wilde, S.A., Sun, D.Y. 2001. Zircon SHRIMP U-Pb ages of gneissic 763 granites in Jiamusi Massif, northeastern China. Acta Petrol. Sinica, 17: 443-452. 764 (In Chinese with English abstract.)

765 Wu, F.Y., Jahn, B.M., Wilde, S.A., Lo, C.H., Yui, T.F., Lin, Q., Ge, W.C., Sun, D.Y. 766 2003. Highly fractionated I-type granites in NE China (I): geochronology and 767 petrogenesis. Lithos, 66: 241-273.

768 Wu, F.Y., Wilde, S.A., Sun, D.Y., Zhang, G.L. 2004. Geochronology and 769 Petrogenesis of post-orogenic Cu, Ni-bearing mafic-ultramafic intrusions in Jilin, 770 NE China. Asian Earth Sci, 23: 791-797.

771 Wu, F.Y., Yang, J.H., Wilde, S.A., Zhang, X.O. 2005. Geochronology, petrogenesis 772 and tectonic implications of Jurassic granites in the Liaodong Peninsula, NE 773 China. Chem Geol, 221: 127-156.

774 Wu, F.Y., Yang, J.H., Lo, C.H., Wilde, S.A., Sun, D.Y., Jahn, B.M. 2007a. The 775 Heilongjiang Group: A Jurassic accretionary complex in the Jiamusi massif at the 776 western Pacific margin of northeasternDraft China. Island Arc, 16: 156-172.

777 Wu, F.Y., Zhao, G.C., Sun, D.Y., Wilde, S.A., Yang, J.H. 2007b. The Hulan group: 778 its role in the evolution of the central Asian orogenic belt of NE China. Asian 779 Earth Sci, 30: 542-556.

780 Wu, F.Y., Li, X.H., Zheng, Y.F., Gao, S. 2007c. Lu-Hf isotopic systematics and their 781 application in petrology. Acta Petrologica Sinica, 23: 185-220. (In Chinese with 782 English abstract.)

783 Wu, F.Y., Sun, D.Y., Ge, W.C., Zhang, Y.B., Grant, M.L., Wilde, S.A., Jahn, B.M. 784 2011. Geochronology of the Phanerozoic granitoids in northeastern China. Asian 785 Earth Sci, 41: 1-30.

786 Wu, P.F., Sun, D.Y., Wang, T.H., Gou, J., Li, R., Liu, W., Liu, X.M. 2013. 787 Chronology, Geochemical Characteristic and Petrogenesis Analysis of Diorite in 788 Helong of Yanbian Area, NE China. Geological Journal of China Universities, 789 19(04): 600-610. (In Chinese with English abstract.)

790 Wu, Q. 2017. Study on the Geological Characteristics and Enrichment Regularities of 791 Mineralization of Guandi Fe Deposit in Helong, Jilin Province. Jilin University, 792 Changchun, pp. 30-61. (In Chinese with English abstract.)

793 Xi, A.H., Ge, Y.H., Liu, Y., Xu, B.W., Li, B.L., Zhu, Y.D. 2018. Discovery of adakite 794 in Tieli Luming-molybdenum mine, Heilongjiang Province and its geological 795 implications. Acta Petrologica Sinica, 34(3): 719-732. (In Chinese with English 796 abstract.)

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797 Xie, H.Q., Zhang, F.Q., Miao, L.C., Li, T.S., Liu, D.Y. 2007. Char acter istics of the 798 Piaohechuan mafic-ultr amafic complex, central Jilin, Northeast China: 799 Constrains on the nature and evolution of the northeastern North China marginal 800 tectonic belt. Geological Bulletin of China, 26(7): 810-822.

801 Xie, J., Yang, S.L., Ding, Z.L. 2012. Methods and application of using detrital zircons 802 to trace the provenance of loess. Sci China Earth Sci, 55: 1837-1846.

803 Xu, W.L., Ge, W.C., Pei, F.P., Meng, E., Yu, Y., and Yang, D.B. 2008. 804 Geochronological frame of Mesozoic volcanism in NE China and its significance. 805 Bulletin of Mineralogy, Petrology and Geochemistry, 27: 286-287. (In Chinese 806 with English abstract.)

807 Xu, W.L., Pei, F.P., Wang, F., Meng, E., Ji, W.Q., Yang, D.B., Wang, W. 2013. 808 Spatial-temporal relationships of Mesozoic volcanic rocks in NE China: 809 constraints on tectonic overprinting and transformations between multiple 810 tectonic regimes. Journal of Asian Earth Sciences, 74: 167-193.

811 Xu, W.L., Wang, F., Pei, F.P., Meng, E., Tang, J., Xu, M.J., and Wang, W. 2013. 812 Mesozoic tectonic regimes and regional ore-forming background in NE China: 813 Constraints from spatial and temporal variations of Mesozoic volcanic rock 814 associations. Acta PetrologicaDraft Sinica, 29(2): 339-353. 815 Xu, J.F., Shinjo, R., Defant, M.J., Wang, Q., and Rapp, R.P. 2002. Origin of 816 Mesozoic adakitic intrusive rocks in the Ningzhen area of East China: Partial 817 melting of delaminated lower continental crust? Geology, 30(12): 111.

818 Yang, D.G., Sun, D.Y., Gou, J., Hou, X.G. 2017. U-pb ages of zircons from mesozoic 819 intrusive rocks in the yanbian area, jilin province, ne china: transition of the 820 paleo-asian oceanic regime to the circum-pacific tectonic regime. Journal of 821 Asian Earth Sciences, 143: 171-190.

822 Yang, J.H., Wu, F.Y., Shao, J.A. 2006. Constraints on the timing of uplift of the 823 Yanshan Fold and Thrust Belt, North China. Earth Planet Sci Lett, 246: 336-352.

824 Yang, Y.C., Han, S.J., Sun, D.Y., Guo, J., Zhang, S.J. 2012. Geological and 825 geochemical features and geochronology of porphyry molybdenum deposits in 826 the Lesser Xing’an Range-Zhangguangcai Range metallogenic belt. Acta 827 Petrologica Sinica, 28(2): 379-390. (In Chinese with English abstract.)

828 Yu, J.J., Wang, F., Xu, W.L., Gao, F.H. 2012. Early Jurassic mafic magmatism in the 829 Lesser Xing'an-Zhangguangcai Range, NE China and its tectonic implications: 830 constrains from zircon U-Pb chronology and geochemistry. Lithos, 142-143: 831 256-266.

832 Zeng, Q.D., Liu, J.M., Qin, F and Zhang, Z.L. 2010a. Geochronology of the 833 Xiaodonggou porphyry Mo deposit in northern margin of North China Craton. 834 Resource Geology, 60: 192-201.

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835 Zeng, Q.D., Liu, J.M., Zhang, Z.L., Chen, W.J., Zhang, W.Q. 2010b. Geology and 836 geochronology of the Xilamulun molybdenum metallogenic belt in eastern Inner 837 Mongolia, China. International Journal of Earth Sciences, 100: 1791-1809.

838 Zeng, Q.D., Liu, J.M., Xiao, W.J., Chu, S.X., Wang, Y.B., Duan, X.X., Sun, Y., Zhou, 839 L.L. 2012a. Mineralizing types, geological characteristics and geodynamic 840 background of Triassic molybenum deposits in the northern and southern margins 841 of North China Craton. Acta Petrol. Sin, 28: 357-371. (In Chinese with English 842 abstract.)

843 Zeng, Q.D., Liu, J.M., Chu, S.X., Wang, Y.B., Sun, Y., Duan, X.X., Zhou, L.L. 844 2012b. Mesozoic molybdenum deposits in the East Xingmeng orogenic belt, 845 northeast China: characteristics and tectonic setting. International Geology 846 Review, 54(16): 1843-1869.

847 Zeng, Q.D., Liu, J.M., Qin, K.Z., Fan, H.R., Chu, S.X., Wang, Y.B., Zhou, L.L. 2013. 848 Types, characteristics, and time-space distribution of molybdenum deposits in 849 China. Int. Geol. Rev, 55: 1311-1358.

850 Zeng, Q.D., Liu, J.M., Chu, S.X., Wang, Y.B., Sun, Y., Duan, X.X., Zhou, L.L., Qu, 851 W.J. 2014. Re-Os and U-Pb geochronology of the Duobaoshan porphyry 852 Cu-Mo-(Au) deposit, northeastDraft China, and its geological significance. J. Asian 853 Earth Sci, 79: 895-909.

854 Zeng, Q.D., Guo, W.K., He, H.Y., Zhou, L.L., Cheng, G.H., Su, F., Wang, Y.B., 855 Wang, R.L. 2018a. He, Ar, and S isotopic compositions and origin of giant 856 porphyry Mo deposits in the Lesser Xing’an Range-Zhangguangcai Range 857 metallogenic belt, northeast China. Journal of Asian Earth Sciences, 165: 858 228-240.

859 Zeng, Q.D., Wang, R.L., Cheng, G.H., Yang, Y.H. 2018b. Zircon U-Pb ages and Hf 860 isotope of the granitoids from the Xingwen porphyry molybdenum deposit in the 861 Xiaoxing'an Range-Zhangguangcai Range metallogenic belt, NE China. Geol. J, 862 53: 304-315.

863 Zhang, C., Guo, W., Xu, Z.Y., Liu, Z.H., Liu, Y.J., Lei, C.C. 2014. Study on 864 geochronology, petrogenesis and tectonic implications of monzogranite from the 865 Yanbian area, eastern Jilin Province. Acta Petrologica Sinica, 30(2): 512-526. (In 866 Chinese with English abstract.)

867 Zhang, C.Y. 2003. Petrology, Geochemistry and tectonic implication of QinglongCun 868 Group in Yanbian Area. Jilin University, Changchun, pp. 14-18 (In Chinese with 869 English abstract).

870 Zhang, C.Y., Zhang, X.Z., Qiu, D.M. 2007. Zircon U -Pb Isotopic Ages of Amphibol 871 ite of Qinglongcun Group in Yanbian Area and Its Geological Significance. 872 Journal of Jilin University (Earth Science Edition), 37(4): 672-677.

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873 Zhang, J., Zhao, Z.F., Zheng, Y.F. 2010. Postcollisional Magmatism: Geochemical 874 Constraints on the Petrogenesis of Mesozoic Granitoids in the Sulu Orogen, 875 China. Lithos, 119(3): 512-536.

876 Zhang, S.H., Zhao, Y., Song, B., Hu, J.M., Liu, S.W., Yang, Y.H., Chen, F.K., Liu, 877 X.M., Liu, J. 2009. Contrasting Late Carboniferous and Late Permian–Middle 878 Triassic intrusive suites fromthe northernmargin of theNorth China craton: 879 geochronology, petrogenesis and tectonic implications. Geological Society of 880 America Bulletin, 121: 181-200.

881 Zhang, X.J. 2009. Analysis on the prospecting potentiality andOre-forming geological 882 conditions in Tieli area Mo (Cu) Deposit, Heilongjiang Province. Jilin University, 883 Changchun, pp. 21-28 (In Chinese with English abstract).

884 Zhang, X.H., Zhang, H.F., Wilde, S.A., Yang, Y.H., Chen, H.H. 2010. Late Permian 885 to Early Triassicmafic to felsic intrusive rocks fromNorth , North China: 886 petrogenesis and implication for Phanerozoic continental growth. Lithos, 117: 887 283-306.

888 Zhang, Y.B., Wu, F.Y., Wilde, S.A., Zhai, M.G., Lu, X.P., Sun, D.Y. 2004. Zircon 889 U-Pb ages and tectonic implications of ‘Early Paleozoic’ granitoids at Yanbian, 890 Jilin Province, northeast China.Draft Island Arc, 13: 484-505. 891 Zhang, Y., Sun, J.G., Chen, Y.J., Zhao, K.Q., Gu, A.L. 2013a. Re-Os and U-Pb 892 geochronology of porphyry Mo deposits in central Jilin Province: Mo 893 ore-forming stages in NE China. Int. Geol. Rev, 55: 1763-1785.

894 Zhang, Y., 2013b. Research on Characteristics of Geology, Geochemistry and 895 Metallogenic Mechanism of the Jurassic Molybdenum Deposits in the Mid-East 896 Area of Jilin. Jilin University, Changchun, pp. 70-101 (In Chinese with English 897 abstract).

898 Zhang, Y., Sun, J.G., Xing, S.W., Zhao, K.Q., Ma, Y.B. 2015. Geochronology and 899 metallogenesis of porphyry Mo deposits in east-central Jilin province, China: 900 constraints from molybdenite Re-Os isotope systematics. Ore Geol. Rev, 71: 901 363-372.

902 Zhao, K.Q. 2016. Research on Magmatic-Fluid Process and Ore Forming of the 903 Mesozoic Porphyry Mo Metallogenic System in the Eastern of Xing-Meng 904 Orogenic Belt. Jilin University, Changchun, pp. 19-79 (In Chinese with English 905 abstract).

906 Zhao, Y., Chen, B., Zhang, S.H., Liu, J.M., Liu, J., Pei, J.L., 2010. Pre–Yanshanian 907 geological events in the northern margin of the North China Craton and its 908 adjacent areas. Geology in China, 37: 900-915. (In Chinese with English 909 abstract.)

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910 Zhou, J. 2017. Geochemical characteristics of ultrabasic rock and its tectonic 911 significance in Qinglongcun area, Jilin Province. Jilin University, Changchun, pp. 912 20-37 (In Chinese with English abstract).

913 Zhou, J.B., Wilde, S.A., Zhang, X.Z., Zhao, G.C., Zheng, C.Q., Wang, Y.J., Zhang, 914 X.H. 2009. The onset of Pacific margin accretion in NE China: evidence from the 915 Heilongjiang high-pressure metamorphic belt. Tectonophysics, 478: 230-246.

916 Zhou, J.B., Wilde, S.A., Zhao, G.C., Zhang, X.Z., Wang, H., Zeng, W.S. 2010a. Was 917 the easternmost segment of the Central Asian Orogenic Belt derived from 918 Gondwana or Siberia: an intriguing dilemma? Journal of Geodynamics, 50: 919 300-317.

920 Zhou, J.B., Wilde, S.A., Zhao, G.C., Zhang, X.Z., Zheng, C.Q., Wang, H., 2010b. 921 Pan-African metamorphic and magmatic rocks of the Khanka Massif, NE China: 922 further evidence regarding their affinity. Geological Magazine, 147(5): 737-749.

923 Zhou, J.B., Wilde, S.A., Zhao, G.C., Zhang, X.Z., Zheng, C.Q., Wang, H. 2010c. New 924 SHRIMP U-Pb zircon ages from the Heilongjiang Complex in NE China: 925 constraints on the Mesozoic evolution of NE China. American Journal of Science, 926 310: 1024-1053.

927 Zhou, J.B., Wilde, S.A. 2013a. TheDraft crustal accretion history and tectonic evolution of 928 the NE China segment of the Central Asian Orogenic Belt. Gondwana Res, 23: 929 1365-1377.

930 Zhou, J.B., Han, J., Wilde, S.A., Guo, X.D., Zeng, W.S., Cao, J.L. 2013b. A primary 931 study of the Jilin-Heilongjiang high- pressure metamorphic belt: Evidence and 932 tectonic implications. Acta Petrologica Sinica, 29(2): 386-398. (In Chinese with 933 English abstract.)

934 Zhou, L.L., Zeng, Q.D., Liu, J.M., Friis, H., Zhang, Z.L., Duan, X.X. 2013. 935 Geochronology of the Xingshan molybdenum deposit, Jilin Province, NE China, 936 and its Hf isotope significance. J. Asian Earth Sci, 75: 58-70.

937 Zhou, L.L., Zeng, Q.D., Liu, J.M., Friis, H., Zhang, Z.L., Duan, X.X., Lan, Y.G. 2014. 938 Geochronology of magmatism and mineralization of the Daheishan giant 939 porphyry molybdenum deposit, Jilin Province, Northeast China: constraints on 940 ore genesis and implications for geodynamic setting. International Geology 941 Review, 56(8): 929-953.

942 Zhou, L.L., Zeng, Q.D., Liu, J.M., Zhang, Z.L., Duan, X.X. 2018. What triggers 943 fertile porphyritic Mo magmas in subduction setting: A case study from the giant 944 Daheishan Mo deposit, NE China. Lithos, 316-317: 212-231.

945 Zhou, Q. 2011. Petrogenesis and Metallogeny for the Dexing Porphyry Copper 946 Deposits. University, pp. 1-99. (In Chinese with English abstract.)

947

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948 Figure and Supplementary Table Captions

949

950 Table 1 Zircon U-Pb data for the Shimadong porphyritic monzogranite.

951

952 Table 2 Re-Os isotope data of molybdenite from the Shimadong Mo deposit.

953

954 Table 3 Major element (wt.%) and trace element (ppm) compositions for the Shimadong 2+ 2+ 955 porphyritic monzogranite; Notes: TFeO = FeO + 0.8998 × Fe2O3. Mg# = 100 × mole Mg / (Mg 2+ 956 + Fe ). A/CNK = mole Al2O3/ (CaO + Na2O + K2O).

957

958 Table 4 Zircon Hf isotope compositions for the Shimadong porphyritic monzogranite.

959

960 Fig. 1. Geologicalmap showing the distribution of Mo deposits in NE China. The data sources are 961 listed in Supplementary Table 1. Draft

962

963 Fig. 2. (a) Geological map of the Shimadong porphyry Mo deposit; (b) Exploration section map in 964 the Shimadong Mo deposit showing that porphyry Mo mineralization is hosted in the 965 porphyritic monzogranite (modified after Shao (2016)), (c) Regional geographic location map 966 of the Shimadong porphyry Mo deposit (modified after Pei (2012)).

967

968 Fig. 3. Hand specimens and photomicrographs of porphyritic monzogranite from the Shimadong 969 porphyry Mo deposit. (a) Sample of porphyritic monzogranite. (b) Quartz-molybdenite fine 970 vein in porphyritic monzogranite. (c) Vein-like pyrite distributed between quartz fine vein. (d) 971 Magnetite and sphalerite distributed between quartz fine vein. (e) Chalcopyrite and sphalerite 972 irregularly distributed in the fissures of quartz fine vein. (f) molybdenite distributed between 973 quartz fine vein (g) Part of plagioclase replaced by kaolin and sericite. (h) Part of biotite 974 replaced by chlorite. (i) Fissures in quartz filled with later calcite veins. Mo: molybdenite, Py: 975 pyrite, Cp: chalcopyrite, Mt: magnetite, Sph: sphalerite, Qz: quartz; Pl: plagioclase; Bi: biotite; 976 Kf: K-feldspar; Ser: sericite; Chl: chlorite; Cal: calcite; Mo: molybdenite; Kl: kaolin.

977

978 Fig. 4. CL images of zircons from the Shimadong porphyritic monzogranite.

979

980 Fig. 5. (a) LA-ICP-MS zircon U-Pb Concordia diagram for the Shimadong porphyritic 981 monzogranite. (b) Plot of weighted mean 206Pb/238U dates.

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982

983 Fig. 6. (a) Re-Os isochron plot. (b) Weighted average of model ages.

984

985 Fig. 7 Total alkali-silica (TAS) diagram (Le Bas et al., 1986). The data for the Middle Jurassic Mo 986 deposits in the central and eastern region of Jilin are from Zhang (2013b). The same in 987 subsequent figures.

988

989 Fig. 8 (a) Geochemical characteristics of the Middle Jurassic granitoids associated with Mo

990 mineralization. A/NK versus A/CNK plot (after Maniar and Piccoli, 1989). (b) K2O versus

991 SiO2 diagram (after Rickwood, 1989).

992

993 Fig. 9 (a) Chondrite-normalized REE patterns and (b) primitive mantle-normalized trace element 994 patterns for the Middle Jurassic granitoids associated with Mo mineralization. Chondrite and 995 primitive mantle normalization values are from Nakamur (1974) and Sun and McDonough 996 (1989), respectively. 997 Draft

998 Fig. 10 (a) Sr/Y vs. Y and (b) LaN/YbN vs. YbN diagram for the Middle Jurassic granitoids 999 associated with Mo mineralization. The curves represent two models of partial melting of 1000 MORB with an amphibolite and eclogite restite: eclogite (garnet/clinopyroxene = 50/50), Sr = 1001 141 ppm, and Y = 21 ppm; garnet amphibolite (garnet/clinopyroxene = 10/90), Sr = 264 ppm, 1002 and Y = 38 ppm (Defant and Drummond, 1990).

1003

1004 Fig. 11 (a) MgO vs. SiO2 diagram and (b) Mg# vs. SiO2 diagram for the Shimadong porphyritic 1005 monzogranite. The field of metabasaltic and eclogite experimental melts (1.0–4.0 Pa) follows 1006 Rapp et al. (1999). The fields for delaminated lower crust, subducted oceanic crust, and 1007 thickened lower crust-derived adakitic rocks are after Wang et al. (2006).

1008

1009 Fig. 12 Compilation diagram of εHf (T) vs. U-Pb ages from the northeast NCC and eastern CAOB. 1010 Ranges are from Yang et al. (2006). The data for the Middle Jurassic Mo deposits is from 1011 Zhou et al. (2013, 2014); Zeng et al. (2018b).

1012

1013 Fig. 13 Discrimination diagram for molybdenite sources of the porphyry Mo deposits. The data for 1014 the Middle Jurassic Mo deposits is from Li et al. (2009); Wang et al. (2009, 2013); Zhang et 1015 al. (2013a, 2015); and Song et al. (2016).

1016

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1017 Fig. 14 Sm/Yb versus Y (Hou et al., 2005; Gu et al., 2018) for the Middle Jurassic granitoids 1018 associated with Mo mineralization.

1019

1020 Fig. 15. (a) Tectonic discrimination diagrams for the Middle Jurassic ore-forming intrusions of 1021 porphyry deposits in NE China. (a) Nb-Y and (b) Rb- (Y + Nb) diagrams modified after 1022 Pearce et al. (1984). VAG = volcanic arc granitoids, ORG = ocean ridge granitoids, WPG = 1023 within-plate granitoids, syn-COLG = syn-collisional granitoids.

1024 1025 Fig. 16. Sketch model of the Middle Jurassic geodynamic setting of the Shimadong porphyry Mo 1026 deposit. 1027

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Table 1 Zircon U-Pb data for the Shimadong porphyritic monzogranite. Isotope ratios Age (Ma) Spot no. Th(ppm) U(ppm) Th/U Pb207/ Pb207/ Pb206/ Pb207/ Pb206 1σ 1σ 1σ 1σ 1σ Pb206 U235 U238 U235 /U238 SMD-N1-01 92.2 386.8 0.24 0.05007 0.00113 0.17702 0.00411 0.02566 0.00030 165.5 3.55 163.3 1.86 SMD-N1-03 224.5 769.7 0.29 0.04946 0.00092 0.17560 0.00443 0.02576 0.00038 164.3 3.83 163.9 2.41 SMD-N1-04 1067.2 1785.6 0.60 0.04975 0.00056 0.17853 0.00421 0.02592 0.00047 166.8 3.63 165.0 2.94 SMD-N1-05 181.3 579.4 0.31 0.04891 0.00090 0.17271 0.00402 0.02561 0.00032 161.8 3.48 163.0 1.99 SMD-N1-06 185.4 543.0 0.34 0.04887 0.00116 0.17424 0.00454 0.02586 0.00026 163.1 3.93 164.6 1.64 SMD-N1-07 724.3 881.1 0.82 0.04969 0.00082 0.17694 0.00344 0.02588 0.00026 165.4 2.97 164.7 1.65 SMD-N1-08 271.2 803.2 0.34 0.04936 0.00089 0.17602 0.00378 0.02584 0.00023 164.6 3.26 164.4 1.44 SMD-N1-09 190.3 341.8 0.56 0.04962 0.00126 0.17552 0.00472 0.02571 0.00025 164.2 4.07 163.7 1.58 SMD-N1-11 83.9 364.2 0.23 0.04999 0.00140 0.17732 0.00488 0.02581 0.00032 165.8 4.21 164.3 2.03 SMD-N1-12 37.6 54.0 0.70 0.04975 0.00317 0.17228 0.01022 0.02568 0.00044 161.4 8.85 163.5 2.74 SMD-N1-16 43.6 191.2 0.23 0.04949 0.00116 0.17525 0.00441 0.02576 0.00030 164.0 3.81 164.0 1.89 SMD-N1-18 154.8 368.4 0.42 0.05047 0.00209 0.17758 0.00705 0.02559 0.00051 166.0 6.08 162.9 3.23 SMD-N1-21 238.7 464.1 0.51 0.04940 0.00066 0.17503 0.00257 0.02573 0.00029 163.8 2.22 163.8 1.81 SMD-N1-22 226.1 652.8 0.35 0.05384 0.00137Draft0.19027 0.00543 0.02566 0.00030 176.9 4.63 163.3 1.86 SMD-N1-23 71.0 151.0 0.47 0.04945 0.00157 0.17646 0.00633 0.02569 0.00035 165.0 5.46 163.5 2.21

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Table 2 Re-Os isotope data of molybdenite from the Shimadong Mo deposit.

Sample no. Weight(g) Re(ng/g) 2σ 187Re(ng/g) 2σ 187Os(ng/g) 2σ Model age (Ma) 2σ SMD-Re-Os-1 0.02058 28100 278 17662 175 47.77 0.31 162.1 2.5 SMD-Re-Os-2 0.03042 33851 339 21276 213 58.12 0.33 163.8 2.5 SMD-Re-Os-3 0.03057 26976 271 16955 170 46.13 0.33 163.1 2.6 SMD-Re-Os-4 0.03050 29181 225 18341 142 49.88 0.35 163.0 2.3 SMD-Re-Os-5 0.03025 30146 351 18947 220 51.70 0.30 163.6 2.7 SMD-Re-Os-6 0.03017 30002 264 18857 166 51.40 0.34 163.4 2.4

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Table 3 Major element (wt.%) and trace element (ppm) compositions for the Shimadong porphyritic monzogranite.

Sample no. SMD-Q1 SMD-Q2 SMD-Q3 SMD-Q4 SMD-Q5 SMD-Q6 Major elements (wt.%)

SiO2 70.24 70.42 70.30 70.09 70.37 70.55

Al2O3 15.41 15.29 15.23 15.00 15.14 15.13

Fe2O3 0.67 0.86 0.67 0.83 0.69 0.85

TFe2O3 2.68 2.67 2.68 2.74 2.67 2.68 FeO 1.81 1.63 1.81 1.72 1.78 1.65 TFeO 2.41 2.40 2.41 2.47 2.40 2.41 CaO 2.19 2.19 2.19 2.26 2.19 2.20 MgO 0.52 0.53 0.52 0.52 0.52 0.51

K2O 3.57 3.58 3.59 3.68 3.59 3.58

Na2O 4.41 4.43 4.40 4.59 4.41 4.41

TiO2 0.32 0.32 0.32 0.32 0.32 0.32

P2O5 0.09 0.09 0.09 0.09 0.09 0.09 MnO 0.11 0.10 0.11 0.11 0.11 0.11 LOI 0.52 0.43Draft0.50 0.42 0.46 0.44 TOTAL 99.86 99.89 99.73 99.65 99.66 99.84 Mg# 27.77 28.23 27.77 27.33 27.87 27.37

K2O+Na2O 7.98 8.01 7.99 8.27 8.00 7.99 A/NK 1.02 1.01 1.01 0.96 1.00 1.00 A/CNK 1.38 1.37 1.37 1.30 1.36 1.36 Trace elements (ppm) Li 44.74 29.99 36.94 49.15 50.93 36.34 Be 1.32 1.05 1.13 1.58 1.56 1.21 B 8.02 7.25 7.07 8.58 33.65 7.78 Sc 1.46 5.41 2.88 4.35 12.36 4.52 Ti 6770.00 5661.00 6085.00 6922.00 7444.00 6054.00 V 117.60 97.83 106.60 126.00 127.30 110.20 Cr 11.18 16.89 11.24 17.10 9.14 15.42 Mn 1042.00 1102.00 1056.00 1220.00 1268.00 1152.00 Co 16.22 13.03 13.79 16.61 17.82 13.98 Ni 6.63 8.26 5.45 10.58 7.80 8.13 Cu 36.62 14.45 9.06 6.91 4.54 11.27 Zn 91.23 75.18 86.29 92.26 106.70 83.90 Ga 19.50 18.30 18.02 23.02 26.75 19.36 Ge 6.59 5.77 5.64 6.83 8.63 6.20 As 0.79 1.00 0.66 1.16 1.12 0.92 Se 1.31 1.78 1.49 1.94 2.78 1.80

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Rb 6.49 15.26 9.96 19.24 29.10 14.42 Sr 547.80 580.70 509.10 662.80 940.00 579.50 Y 9.85 19.64 13.80 15.80 24.78 16.30 Zr 243.50 213.10 208.20 244.30 258.40 211.80 Nb 6.61 7.94 6.54 7.28 8.59 7.18 Mo 1.25 0.71 0.88 0.92 0.80 0.79 Cd 1.79 1.43 1.32 1.57 1.66 1.48 Sn 1.70 2.00 1.76 2.70 2.37 2.14 Sb 4.16 2.98 2.88 2.22 4.67 2.84 Cs 1.61 1.37 1.28 1.72 3.00 1.47 Ba 182.90 879.20 295.50 594.40 770.40 642.00 La 18.11 18.77 14.63 21.68 40.29 18.39 Ce 32.69 43.62 33.36 46.09 76.36 40.76 Pr 4.68 5.43 4.16 5.39 8.62 4.90 Nd 16.98 21.74 16.44 20.19 31.78 19.60 Sm 3.40 4.62 3.59 3.97 6.19 4.23 Eu 0.98 1.59 1.17 1.47 2.00 1.46 Gd 3.09 4.45Draft3.49 3.83 5.62 4.08 Tb 0.48 0.65 0.51 0.53 0.80 0.59 Dy 2.71 3.63 2.96 3.04 4.29 3.28 Ho 0.55 0.72 0.60 0.60 0.84 0.65 Er 1.61 2.04 1.63 1.72 2.34 1.82 Tm 0.23 0.29 0.23 0.25 0.32 0.25 Yb 1.45 1.88 1.50 1.63 2.10 1.65 Lu 0.23 0.29 0.22 0.26 0.33 0.27 Hf 7.39 6.61 6.45 7.67 7.98 7.00 Ta 0.69 0.81 0.49 0.70 0.81 0.66 W 0.27 0.28 0.25 0.32 0.33 0.29 Tl 0.33 0.32 0.33 0.45 0.57 0.34 Pb 9.58 13.12 11.20 13.64 15.63 12.65 Bi 0.11 0.09 0.09 0.08 0.09 0.09 Th 2.39 6.07 3.77 8.14 11.05 5.48 U 1.91 2.17 1.85 2.30 3.45 2.11 ΣREE 95.52 95.04 85.20 92.39 77.68 81.60 LREE 91.12 90.64 80.87 88.01 73.64 77.55 HREE 4.40 4.40 4.32 4.38 4.04 4.05 LREE/HREE 20.72 20.62 18.70 20.10 18.25 19.14

LaN/YbN 33.38 34.67 29.73 32.70 27.10 28.52 δEu 0.95 0.86 0.95 0.98 1.00 0.95 δCe 0.94 0.96 0.94 0.96 0.92 0.99

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2+ 2+ 2+ Notes: TFeO=FeO+0.8998×Fe2O3. Mg#=100×molar Mg /(Mg +Fe ). A/CNK=molar

Al2O3/(CaO+Na2O+K2O).

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Table 4 Zircon Hf isotope compositions for the Shimadong porphyritic monzogranite.

176 /177 176 177 176 177 t (Ma) Yb Hf Lu/ Hf Hf/ Hf 2σ εHf(0) εHf(t) TDM1 TDM2(average) fLu/Hf SMD-N1-01 163.3 0.010040 0.000462 0.282576 0.000027 -6.9 -3.4 943 1425 -0.99 SMD-N1-03 163.9 0.014808 0.000587 0.282522 0.000025 -8.8 -5.3 1021 1547 -0.98 SMD-N1-04 164.9 0.016205 0.000630 0.282538 0.000024 -8.3 -4.7 1000 1511 -0.98 SMD-N1-05 163.0 0.013872 0.000554 0.282572 0.000026 -7.1 -3.6 951 1436 -0.98 SMD-N1-06 164.5 0.014163 0.000595 0.282408 0.000022 -12.9 -9.3 1180 1803 -0.98 SMD-N1-07 164.7 0.017005 0.000685 0.282736 0.000022 -1.3 2.3 725 1067 -0.98 SMD-N1-08 164.4 0.010749 0.000450 0.282546 0.000025 -8.0 -4.4 984 1491 -0.99 SMD-N1-09 163.6 0.012373 0.000469 0.282802 0.000023 1.1 4.6 629 916 -0.99 SMD-N1-11 164.2 0.015523 0.000560 0.282130 0.000026 -22.7 -19.2 1562 2421 -0.98 SMD-N1-12 163.4 0.010385 0.000414 0.282572 0.000025 -7.1 -3.5 948 1435 -0.99 SMD-N1-16 163.9 0.005980 0.000230 0.282848 0.000021 2.7 6.3 561 811 -0.99 SMD-N1-18 162.9 0.033876 0.001149 0.282351 0.000023 -14.9 -11.4 1277 1934 -0.97 SMD-N1-21 163.7 0.017901 0.000610 0.282633 0.000021 -4.9 -1.4 867 1298 -0.98 SMD-N1-22 163.3 0.017758 0.000597Draft0.282664 0.000020 -3.8 -0.3 824 1229 -0.98 SMD-N1-23 163.4 0.018044 0.000625 0.282714 0.000023 -2.0 1.5 754 1116 -0.98

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Fig. 1. Geologicalmap showing the distribution of Mo deposits in NE China. The data sources are listed in Supplementary Table 1.

150x164mm (300 x 300 DPI)

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Fig. 2. (a) Geological map of the Shimadong porphyry Mo deposit; (b) Exploration section map in the Shimadong Mo deposit showing that porphyry Mo mineralization is hosted in the porphyritic monzogranite (modified after Shao (2016)), (c) Regional geographic location map of the Shimadong porphyry Mo deposit (modified after Pei (2012)).

472x312mm (300 x 300 DPI)

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Fig. 3. Hand specimens and photomicrographs of porphyritic monzogranite from the Shimadong porphyry Mo deposit. (a) Sample of porphyritic monzogranite. (b) Quartz-molybdenite fine vein in porphyritic monzogranite. (c) Vein-like pyrite distributed between quartz fine vein. (d) Magnetite and sphalerite distributed between quartz fine vein. (e) Chalcopyrite and sphalerite irregularly distributed in the fissures of quartz fine vein. (f) molybdenite distributed between quartz fine vein (g) Part of plagioclase replaced by kaolin and sericite. (h) Part of biotite replaced by chlorite. (i) Fissures in quartz filled with later calcite veins. Mo: molybdenite, Py: pyrite, Cp: chalcopyrite, Mt: magnetite, Sph: sphalerite, Qz: quartz; Pl: plagioclase; Bi: biotite; Kf: K-feldspar; Ser: sericite; Chl: chlorite; Cal: calcite; Mo: molybdenite; Kl: kaolin.

250x207mm (300 x 300 DPI)

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Fig. 4. CL images of zircons from the Shimadong porphyritic monzogranite.

349x87mm (600 x 600 DPI)

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Fig. 5. (a) LA-ICP-MS zircon U-Pb Concordia diagram for the Shimadong porphyritic monzogranite. (b) Plot of weighted mean 206Pb/238U dates.

341x127mm (300 x 300 DPI) Draft

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Fig. 6. (a) Re-Os isochron plot. (b) Weighted average of model ages.

352x139mm (300 x 300 DPI)

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Fig. 7 Total alkali-silica (TAS) diagram (Le Bas et al., 1986). The data for the Middle Jurassic Mo deposits in the central and eastern region of Jilin are from Zhang, 2013b. The same in subsequent figures.

122x108mm (300 x 300 DPI)

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Fig. 8 (a) Geochemical characteristics of the Middle Jurassic granitoids associated with Mo mineralization. A/NK versus A/CNK plot (after Maniar and Piccoli, 1989). (b) K2O versus SiO2 diagram (after Rickwood, 1989).

256x99mm (300 x 300 DPI) Draft

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Fig. 9 (a) Chondrite-normalized REE patterns and (b) primitive mantle-normalized trace element patterns for the Middle Jurassic granitoids associated with Mo mineralization. Chondrite and primitive mantle normalization values are from Nakamur (1974) and Sun and McDonough (1989), respectively.

371x146mm (300 x 300 DPI) Draft

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Fig. 10 (a) Sr/Y vs. Y and (b) LaN/YbN vs. YbN diagram for the Middle Jurassic granitoids associated with Mo mineralization. The curves represent two models of partial melting of MORB with an amphibolite and eclogite restite: eclogite (garnet/clinopyroxene = 50/50), Sr = 141 ppm, and Y = 21 ppm; garnet amphibolite (garnet/clinopyroxene = 10/90), Sr = 264 ppm, and Y = 38 ppm (Defant and Drummond, 1990).

245x98mm (300 x 300 DPI) Draft

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Fig. 11 (a) MgO vs. SiO2 diagram and (b) Mg# vs. SiO2 diagram for the Shimadong porphyritic monzogranite. The field of metabasaltic and eclogite experimental melts (1.0–4.0 Pa) follows Rapp et al. (1999). The fields for delaminated lower crust, subducted oceanic crust, and thickened lower crust-derived adakitic rocks are after Wang et al. (2006).

324x127mm (300 x 300 DPI) Draft

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Fig. 12 Compilation diagram of εHf (T) vs. U-Pb ages from the northeast NCC and eastern CAOB. Ranges are from Yang et al. (2006). The data for the Middle Jurassic Mo deposits are from Zhou et al. (2013, 2014); Zeng et al. (2018b).

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Fig. 13 Discrimination diagram for molybdenite sources of the porphyry Mo deposits. The data for the Middle Jurassic Mo deposits are from Li et al. (2009); Wang et al. (2009, 2013); Zhang et al. (2013a, 2015); and Song et al. (2016).

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Fig. 14 Sm/Yb versus Y (Hou et al., 2005; Gu et al., 2018) for the Middle Jurassic granitoids associated with Mo mineralization.

111x96mm (300 x 300 DPI)

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Fig. 15. (a) Tectonic discrimination diagrams for the Middle Jurassic ore-forming intrusions of porphyry deposits in NE China. (a) Nb-Y and (b) Rb- (Y + Nb) diagrams modified after Pearce et al. (1984). VAG = volcanic arc granitoids, ORG = ocean ridge granitoids, WPG = within-plate granitoids, syn-COLG = syn- collisional granitoids. 310x135mmDraft (300 x 300 DPI)

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Fig. 16. Sketch model of the Middle Jurassic geodynamic setting of the Shimadong porphyry Mo deposit. 137x69mmDraft (300 x 300 DPI)

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