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Chemie der Erde 76 (2016) 441–448

Contents lists available at ScienceDirect

Chemie der Erde

j o ur na l ho mepage: www.elsev ier .de /chemer

eochronology and magma oxygen fugacity of Ehu S-type graniticluton in Zhe-Gan-Wan region, SE China

un-Ting Qiua,b, Liang Qiua,∗

School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, ChinaNational Key Laboratory of Science and Technology on Remote Sensing Information and Image Analysis, Beijing Research Institute of Uranium Geology,hina National Nuclear Corporation, Beijing 100029, China

r t i c l e i n f o

rticle history:eceived 4 February 2016eceived in revised form 3 June 2016ccepted 14 June 2016ditorial handling - D. Upadhyay

eywords:

a b s t r a c t

In this paper, we determined the U-Pb isotopic and trace element compositions of zircons from the Ehu S-type granite in the Zhe-Gan-Wan region, SE China, using in-situ laser ablation (LA) ICP-MS. The weightedmean 206Pb/238U age of 132.0 ± 0.6 Ma for the Ehu granite indicates that the pluton was formed in theEarly Cretaceous and during the Late Mesozoic Cu-Mo mineralization quiescence in Zhe-Gan-Wan region.The calculated logarithmic magma oxygen fugacities for Ehu granite range from −19.19 to −11.43 with anaverage magma oxidation state of FMQ-0.29, which is much lower than those of Cu-Mo bearing granites

agma oxygen fugacityirconhu plutonu-Mo mineralizationhe-Gan-Wan region

in the Zhe-Gan-Wan region. Since Ehu granite was derived from partial melting of metasedimentarybasement without fractional crystallization and mantle-derived magma contamination, the low oxidationstate of this granite suggests that the assimilation of metasedimentary basement component may notsignificantly increase the oxidation state of reduced melts from asthenospheric mantle and could notgenerate oxidized magmas that are favorable for Cu-Mo mineralization.

. Introduction

The adjacent region of Zhejiang, Jiangxi, and Anhui ProvincesZhe-Gan-Wan region) in east China is located along the southeast-rn margin of the Yangtze Block (Wong et al., 2011). This regionas in a convergent plate boundary during the Yanshanian epoch

Jurassic-Cretaceous) (Zhou and Li, 2000; Zhou et al., 2006; Li andi, 2007; Wang et al., 2011; Wang et al., 2013b) where numerousorphyries (Zhou and Li, 2000; Li and Li, 2007) and characteristicccurrence of many deposits of copper, gold, molybdenum, lead andinc (Wang et al., 2003; Zeng et al., 2012; Qiu et al., 2013b). Previ-us studies suggested that the Mesozoic porphyry Cu, Mo, or Cu-Moeposits in the Zhe-Gan-Wan region are mostly related to Jurassicorphyry stocks (older than 150 Ma), while those formed duringhe Cretaceous era (younger than 150 Ma) are generally barren ofu and Mo. (Zeng et al., 2012; Qiu et al., 2013b, 2014b).

The magma oxygen fugacity has been demonstrated as one ofhe essential factors that control Cu-Mo-Au mineralization (e.g,

andela and Holland, 1986; Candela and Bouton, 1990; Blevin andhappell, 1992; Candela, 1992; Lynton et al., 1993; Hedenquistnd Lowenstern, 1994; Mengason et al., 2011). For example, clas-

∗ Corresponding author.E-mail addresses: midimyself@126.com (J.-T. Qiu), qiuliang@cugb.edu.cn,

iuliang2011@gmail.com (L. Qiu).

ttp://dx.doi.org/10.1016/j.chemer.2016.06.004009-2819/© 2016 Elsevier GmbH. All rights reserved.

© 2016 Elsevier GmbH. All rights reserved.

sical Cu-Mo porphyries or Cu-Mo-bearing granites are related tooxidized melt systems (e.g, Ballard et al., 2002; Mengason et al.,2011; Li et al., 2012). Qiu et al. (2013b) determined the magmaoxygen fugacities of several Mo bearing and barren porphyries inwest Zhejiang area, and proposed that the Late Mesozoic “Cu-Momineralization quiescence” in Zhe-Gan-Wan region may be relatedto the low oxygen fugacities of magmas during the Cretaceous era.This view point was supported by the widely distributed Creta-ceous reduced A-type granites in the Zhe-Gan-Wan region (Wonget al., 2009; Jiang et al., 2011; Yang et al., 2012; Qiu et al., 2013b).Petrogenetic studies suggest that some of these reduced A-typegranites were derived from the asthenospheric mantle with lim-ited assimilation from old crustal components (Wong et al., 2009),which may imply a relatively reduced mantle condition. However,as crustal components may also contribute to the formation of Cuor Mo bearing granites, the oxidation state of the magma that wasderived from this end member should be investigated before weget a better understanding of the Cretaceous Cu-Mo mineralizationquiescence in the Zhe-Gan-Wan region.

In this study, we determine the U-Pb isotopic and trace ele-ment compositions of zircons from the Ehu S-type granitic plutonin Jiangxi Province using Laser Ablation ICP-MS, in an attempt to

provide new constrains on oxidation states of magmas that werederived from crustal components in the Zhe-Gan-Wan region.

442 J.-T. Qiu, L. Qiu / Chemie der Erde 76 (2016) 441–448

Fig. 1. Geological sketch map of China with plate boundaries. (b) Distribution of Mesozoic granites in South China (revised after Qiu et al., 2014b). (c) Distribution of Mesozoicgranites in west Zhejiang and northeast Jiangxi with U-Pb ages (U-Pb ages are from Qiu et al., 2014b).

der Erde 76 (2016) 441–448 443

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J.-T. Qiu, L. Qiu / Chemie

. Geological background

The Zhe-Gan-Wan region located in the northeast of the Southhina Block (Fig. 1). The South China Block was formed by amalga-ation of the Yangtze and the Cathaysia blocks (Fig. 1a,b) during

arly Neoproterozoic, and subsequently experienced early Palaeo-oic and Meozoic tectonic events (e.g., Zhou and Li, 2000; Li andi, 2007; Yang et al., 2013; Qiu et al., 2014b, 2014c). Extensiveranites emplaced during these tectonic events, which formed theouth China Large Granitic Province (LGP). Granites of the Southhina LGP mainly intruded during the Mesozoic, and are dominatedy high-potassium calc-alkaline series granodiorite, quartz mon-onite, granite, biotite granite, and granite porphyry (Zhou et al.,006). More than 80 vol.% of granites of the province are peralumi-ous, and 40% vol.% are strongly peraluminous (A/CNK > 1.1; Zhout al., 2006; Huang et al., 2015). The granitoids include I-, and S- typeranites that are widely distributed and show a younging trendcean-towards (Zhou and Li, 2000), and the A-type granites thatere emplaced along the coastal region (Wong et al., 2009) and

hi-Hang belt (Jiang et al., 2011; Yang et al., 2012).The Ehu pluton (Fig. 1c), with an outcrop area of 160 km2 has

een investigated in this study. This pluton intruded into the Pre-ambrian metasedimentary rocks and was intruded by graniticykes. It consists of two-mica granites with an association ofonzogranite-syenogranite (Zhao et al., 2010). These rocks have

medium-grained granitic texture and comprise K-feldspar, pla-ioclase, quartz, muscovite and biotite (Jiang et al., 2011). Theccessory minerals are zircon, apatite, epidote and Fe-Ti oxidesZhao et al., 2010). The granitic rocks show minor alteration, i.e.,eldspars locally exhibit sericitization and argillation. Biotites areenerally euhedral to subhedral. The granite is characterized byigh alumina saturation index (ASI > 1.10), high K2O content (∼5%),nd low Na2O (<3.2%), showing S-type granite affinity. The lowut consistent Mg# values with pure crustal melts suggest thathe granitic magmas did not mix with mantle-derived melts (Jiangt al., 2011). The negative correlation between initial 87Sr/86Sralues and SiO2 content indicate the granitic magmas did not expe-ience crystal fractionation after partial melting (Jiang et al., 2011).

. Sampling and methods

The rock sample (D019) (Fig. 1c) used for zircon U-Pb and tracelement composition analysis was collected from a granitic outcropn the northeast of Ehu pluton (29◦31′22.50′′N; 117◦32′11.00′′E).

The sample (D019) was crushed to 0.27 mm grain size. Zir-on grains were separated by standard density and magneticechniques, and then further purified by hand picking using atereoscopic microscope at the Hebei Institute of Regional Geol-gy and Mineral Resources Survey, China. The zircon grains areuhedral columnar crystals with 0.05 mm to 0.3 mm width, lightrown-yellow to colorless, and mainly display {1 0 0} + {1 0 1}rystal faces and subordinately the {1 1 0} face. The grains wereounted in epoxy resin, carefully polished until their cores were

xposed, and photographed via transmitted light, reflected light,nd cathodoluminescence (CL). LA-ICP-MS zircon U-Pb isotopicnd trace element analyses were performed at Yanduzhongshieological Analysis Laboratories Ltd., using a Bruker aurora M90

CP-MS equipped with a New Wave213 deep-UV YAG Laser Abla-ion System. Helium was used as the carrier gas. The spot size was0 �m. The data acquisition time was 45s. GJ-1 was used as stan-ard sample in U-Pb isotopic analysis. SRM610 was employed as

xternal standard and Si as the internal standard in the trace ele-ent analysis. The raw data were first handled with ICPMSDataCal

.8.3 software (Liu et al., 2008), and then processed with Isoplot

.0 (Ludwig, 2003) and CGDK + ZOFIT software package (Qiu et al.,

Fig. 2. U-Pb concordia and weighted average plots of zircons from the Ehu graniticpluton with typical zircon CL image.

2013a; Qiu et al., 2014a; for more information about CGDK + ZOFITplease refer to Appendix A).

4. Results and discussion

4.1. Zircon U-Pb age

Most of the zircon grains from the Ehu granitic pluton are char-acterized by oscillatory zoning revealed by CL image with Th/Uratios greater than 0.1, indicating their magmatic origins. Fortyanalyses are within 10% discordance, suggesting no major Pb lossafter the zircon crystallization. These analyses yield 206Pb/238Uages in the range of 125.2 Ma to 138.7 Ma with a weighted mean206Pb/238U age of 132.0 ± 0.6 Ma (2�) (MSWD = 0.85). The isotopiccompositions, and U-Pb ages that were used for mean age calcu-lation are listed in Table 1 and are plotted on U-Pb concordia andweighted average diagrams (Fig. 2).

4.2. Zircon trace element composition

All forty analyses show trace element patterns depleted in LREEand enriched in HREE with variable positive Ce anomalies andapparent negative Eu anomalies. Two analyses (D019-47 and D019-111), due to the influence from mineral inclusions in zircon grains,show remarkable enrichment of LREE and were excluded from thedataset. One analyse (D019-42) was also excluded because its Ticontent (0.57 ppm) is below the detection limit. The rest 37 anal-yses yield �REE values in the range of 580.56–1735.96 ppm andTi content ranging from 3.64 to 16.04 ppm. The results of zircontrace-element composition were listed in Table 2 and plotted inFig. 3.

4.3. Ti-in-zircon temperature and magma oxygen fugacity of Ehupluton

The Ti-in-zircon and revised Ti-in-zircon thermoeters presentedby Watson and Harrison (2005); Watson et al. (2006) and Ferry andWatson (2007) have successfully used to compute temperatures

at which the zircon crystallized. In this study, due to the absenceof rutile, the titanium in the melt system is unsaturated, thus therevised Ti-in-zircon thermometer (Ferry and Watson, 2007) wasused for zircon crystallization temperature calculation. As quartz

444 J.-T. Qiu, L. Qiu / Chemie der Erde 76 (2016) 441–448

Table 1U-Pb isotopic compositions and ages of zircons from Ehu granitic pluton.

Spot Element composition(ppm) Isotopic element ratio Isotopic ages(Ma)

Th U Th/U 207Pb/235U 206Pb/238U 207Pb/235U 206Pb/238U

ratio 1� ratio 1� age 1� age 1�

D019-07 75.56 388.10 0.19 0.148516 0.007155 0.020650 0.000322 140.6 6.3 131.8 2.0D019-10 94.87 347.70 0.27 0.144847 0.007031 0.020796 0.000314 137.4 6.2 132.7 2.0D019-11 75.62 246.18 0.31 0.153145 0.010850 0.020644 0.000415 144.7 9.6 131.7 2.6D019-14 232.62 385.67 0.60 0.141924 0.007476 0.020882 0.000314 134.8 6.6 133.2 2.0D019-15 214.94 430.85 0.50 0.149743 0.007299 0.020798 0.000354 141.7 6.4 132.7 2.2D019-17 114.33 501.25 0.23 0.144393 0.008536 0.020626 0.000382 136.9 7.6 131.6 2.4D019-18 111.50 359.81 0.31 0.151914 0.008260 0.020432 0.000347 143.6 7.3 130.4 2.2D019-19 126.54 437.74 0.29 0.157491 0.010710 0.021045 0.000374 148.5 9.4 134.3 2.4D019-20 93.74 361.04 0.26 0.145809 0.008106 0.020546 0.000361 138.2 7.2 131.1 2.3D019-21 164.14 738.90 0.22 0.131964 0.005105 0.020926 0.000344 125.9 4.6 133.5 2.2D019-22 99.00 442.17 0.22 0.130984 0.006293 0.020760 0.000337 125.0 5.7 132.5 2.1D019-23 121.23 437.40 0.28 0.146950 0.007529 0.020721 0.000391 139.2 6.7 132.2 2.5D019-24 105.66 422.88 0.25 0.143585 0.007276 0.020671 0.000347 136.2 6.5 131.9 2.2D019-33 137.06 976.26 0.14 0.144389 0.005359 0.020582 0.000266 136.9 4.8 131.3 1.7D019-34 365.41 751.20 0.49 0.138401 0.005750 0.020671 0.000257 131.6 5.1 131.9 1.6D019-35 139.25 1374.28 0.10 0.142750 0.004369 0.020801 0.000260 135.5 3.9 132.7 1.6D019-41 114.67 427.49 0.27 0.138856 0.006774 0.021004 0.000304 132.0 6.0 134.0 1.9D019-42 169.19 718.96 0.24 0.137583 0.005022 0.020750 0.000257 130.9 4.5 132.4 1.6D019-43 102.59 450.28 0.23 0.144642 0.006621 0.020563 0.000294 137.2 5.9 131.2 1.9D019-44 202.32 603.56 0.34 0.138091 0.005376 0.020581 0.000277 131.3 4.8 131.3 1.7D019-45 127.36 542.90 0.23 0.150021 0.006137 0.020911 0.000279 141.9 5.4 133.4 1.8D019-46 144.36 567.21 0.25 0.146640 0.006507 0.020564 0.000255 138.9 5.8 131.2 1.6D019-47 161.78 820.90 0.20 0.140840 0.006193 0.020569 0.000232 133.8 5.5 131.3 1.5D019-48 106.59 888.95 0.12 0.142441 0.006101 0.020378 0.000210 135.2 5.4 130.0 1.3D019-49 126.02 677.72 0.19 0.137494 0.005344 0.020743 0.000257 130.8 4.8 132.3 1.6D019-50 71.44 560.54 0.13 0.146122 0.006944 0.020723 0.000328 138.5 6.2 132.2 2.1D019-51 90.75 444.51 0.20 0.148348 0.007452 0.020525 0.000324 140.5 6.6 131.0 2.0D019-55 135.44 692.15 0.20 0.140979 0.005807 0.020784 0.000316 133.9 5.2 132.6 2.0D019-60 365.41 838.52 0.44 0.141396 0.006103 0.021294 0.000412 134.3 5.4 135.8 2.6D019-62 233.40 763.56 0.31 0.161878 0.006495 0.021754 0.000586 152.3 5.7 138.7 3.7D019-63 168.80 465.71 0.36 0.148254 0.007490 0.020661 0.000353 140.4 6.6 131.8 2.2D019-83 102.44 503.69 0.20 0.159636 0.008649 0.021278 0.000397 150.4 7.6 135.7 2.5D019-86 138.47 1315.49 0.11 0.144024 0.005188 0.020602 0.000246 136.6 4.6 131.5 1.6D019-87 164.87 759.65 0.22 0.142271 0.006253 0.019610 0.000339 135.1 5.6 125.2 2.1D019-91 167.19 670.89 0.25 0.151988 0.007014 0.020133 0.000303 143.7 6.2 128.5 1.9D019-92 175.25 390.31 0.45 0.139110 0.007728 0.020553 0.000362 132.3 6.9 131.2 2.3D019-93 184.21 414.23 0.44 0.152578 0.007952 0.020717 0.000292 144.2 7.0 132.2 1.8D019-97 84.93 446.94 0.19 0.139068 0.007654 0.020974 0.000336 132.2 6.8 133.8 2.1D019-102 220.60 377.40 0.58 0.148236 0.007950 0.020761 0.000397 140.4 7.0 132.5 2.5D019-111 204.67 713.04 0.29 0.148324 0.006242

Note: discordances of all spots listed in Table 1 are less than 10%.

FsT

oooi

ig. 3. REE normalized patterns of zircons from the Ehu granitic pluton with twoignal plots showing influence on trace element analysis from mineral inclusion.he chondrite normalized values are from Boynton (1984).

ccurred both as phenocryst and matrix, the aSiO2 is set to 1 becausef silicon saturation in the melt system. Based on the occurrencef Fe-Ti minerals (Zhao et al., 2010) and calculated titanium activ-ty for similar phase assemblages (Ghent and Stout, 1984; Watson

0.021177 0.000297 140.4 5.5 135.1 1.9

et al., 2006; Hiess et al., 2008), the aTiO2 has been conservativelyestimated to be 0.6. The calculated temperatures using the revisedTi-in-zircon thermometer assuming aSiO2 = 1 and aTiO2 = 0.6 are inthe range of 976 K (703 ◦C) to 1120 K (847 ◦C) with an average of(1046 ± 31, 1�) K or (773 ± 31, 1�)◦C, which is similar to ∼757 ◦Cas reported by Jiang et al. (2011). The results are listed in Table 3.

The incorporate Ce4+, and thus Ce anomalies, in zircon providesqualitative estimations of magma oxidation states. A calibrationwas proposed by Trail et al. (2011, 2012) to determine the oxygenfugacity of magmatic melt, which can be expressed as follows:

ln(

ıCe)

= (0.1156 ± 0.0050) × ln(

fO2

)

+13860 ± 708T

− 6.125 ± 0.484

where fO2 is oxygen fugacity, T is absolute temperature, and ıCe isCe anomaly.

Usually, the determination of ıCe based on La-Pr interpolationis often influenced by the low La and Pr concentrations, large ana-lytical errors, and small LREE-rich mineral inclusions in zircons

(Qiu et al., 2014a). Alternatively, the lattice strain model, whichquantified the relationship between logarithms of partition coeffi-cients against ionic radii (Blundy and Wood, 1994), permites ıCe becomputed from more enriched Gd to Lu together with Nd and Sm,

J.-T. Qiu, L. Qiu / Chemie der Erde 76 (2016) 441–448 445

Table 2Trace element composition of zircons from Ehu granitic pluton.

Sample Element composition(ppm)

Ti La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

bulk rock 5.95 13.75 1.80 6.50 1.92 0.09 1.89 0.38 2.28 0.36 0.88 0.12 0.70 0.10D019-07 8.90 0.01 2.05 0.04 0.72 2.44 0.10 15.26 6.38 80.07 30.56 134.50 29.65 269.19 49.88D019-10 10.15 0.01 2.53 0.09 1.59 3.94 0.18 23.66 8.39 96.79 33.75 140.09 28.89 247.82 44.12D019-11 9.32 0.01 2.76 0.05 1.12 3.63 0.14 20.37 7.19 86.80 32.43 140.90 29.63 264.37 50.05D019-14 8.84 0.02 6.69 0.23 3.51 8.43 0.17 49.78 18.12 217.76 80.69 347.34 73.49 664.37 119.18D019-15 16.04 0.21 6.21 0.21 3.16 6.99 0.13 44.38 16.00 191.80 72.13 316.71 67.07 603.77 110.35D019-17 7.45 0.01 2.44 0.06 1.25 4.02 0.15 27.01 10.08 119.58 42.30 173.79 35.75 335.76 55.21D019-18 11.01 0.01 3.53 0.12 2.67 6.10 0.35 31.26 11.01 127.11 44.29 180.77 36.57 325.50 57.26D019-19 5.51 0.00 3.11 0.07 1.92 5.09 0.13 29.41 10.98 131.13 46.32 194.30 41.18 362.76 64.14D019-20 9.17 0.02 2.90 0.12 1.98 4.57 0.23 25.58 9.45 109.85 38.73 164.18 33.66 300.72 54.07D019-21 7.59 0.00 4.10 0.08 1.89 5.41 0.14 33.24 13.12 158.32 57.61 250.94 53.71 486.94 87.49D019-22 8.99 0.00 2.52 0.05 0.98 3.24 0.15 20.97 8.05 100.82 34.97 150.19 31.00 274.68 49.40D019-23 8.36 0.01 3.58 0.05 1.56 4.61 0.24 26.96 10.15 122.04 43.67 188.33 39.58 356.50 65.14D019-24 8.01 0.07 3.13 0.09 1.22 3.53 0.15 22.89 8.74 109.89 38.82 164.42 34.57 310.70 55.10D019-33 4.27 0.00 2.02 0.06 1.26 4.15 0.11 28.98 12.70 156.54 53.96 232.47 47.30 418.41 73.38D019-34 6.93 0.04 6.31 0.21 3.59 8.21 0.22 46.44 16.90 193.50 67.13 285.45 58.74 524.01 91.86D019-35 6.66 0.01 1.78 0.05 1.15 4.65 0.11 32.99 14.93 190.01 66.87 285.96 60.46 574.70 92.53D019-41 6.76 0.23 3.90 0.12 1.18 3.18 0.11 22.15 9.19 118.47 45.52 209.79 48.58 450.94 80.92D019-42 0.57 0.29 3.31 0.18 2.38 6.23 0.17 36.32 13.86 171.68 57.35 240.70 49.28 4434.06 775.63D019-43 9.14 0.00 2.37 0.09 1.03 4.15 0.12 25.67 10.45 129.19 47.60 209.29 44.62 17.27 5.08D019-44 6.86 0.79 5.20 0.41 4.43 7.55 0.24 38.37 14.07 169.39 58.35 249.59 51.55 450.29 79.14D019-45 6.59 0.00 2.68 0.05 1.36 4.13 0.13 26.48 10.89 130.14 46.30 199.39 41.75 376.94 68.54D019-46 5.50 0.67 5.09 0.51 2.78 5.01 0.17 29.45 11.28 140.45 50.89 223.30 48.78 452.04 80.37D019-47 16.63 3.19 11.13 1.16 6.77 7.25 0.29 36.64 13.25 158.32 53.40 212.38 41.12 347.85 59.25D019-48 6.49 0.00 1.67 0.04 0.92 2.87 0.06 20.45 8.97 107.70 36.35 142.88 28.29 227.05 37.23D019-49 7.93 0.00 2.85 0.05 1.06 4.10 0.08 25.70 10.45 131.63 48.10 207.63 44.33 401.22 70.74D019-50 5.95 0.01 2.41 0.09 1.61 3.24 0.19 20.03 7.63 92.02 32.27 135.32 28.03 253.80 44.95D019-51 6.53 0.08 2.97 0.15 2.41 4.22 0.20 24.82 8.75 106.28 37.92 161.31 33.74 306.56 55.94D019-55 3.73 0.00 2.51 0.07 1.40 4.17 0.16 29.50 10.68 130.12 44.71 183.45 37.72 344.60 59.70D019-60 11.17 0.04 5.15 0.33 6.27 12.95 0.39 64.38 22.69 258.87 91.11 377.92 79.03 698.27 118.56D019-62 6.96 1.01 8.52 0.60 4.12 6.09 0.29 32.85 11.75 141.42 50.48 218.86 48.06 441.79 82.64D019-63 9.66 0.97 6.46 0.47 3.39 6.07 0.25 34.72 12.28 147.65 52.16 227.20 49.01 432.94 78.56D019-83 5.61 0.01 2.68 0.06 1.10 3.50 0.15 23.12 8.88 119.79 41.93 187.06 39.52 353.81 69.17D019-86 9.12 0.14 2.35 0.22 2.26 5.95 0.16 37.20 16.44 202.67 69.18 285.63 55.26 462.36 83.17D019-87 15.01 0.14 4.43 0.35 3.58 7.70 0.32 33.79 13.74 160.13 52.19 218.73 43.09 370.05 69.26D019-91 10.90 0.05 3.15 0.17 2.38 6.76 0.21 39.64 14.87 173.12 61.06 265.40 53.68 474.95 88.29D019-92 4.58 0.01 16.55 0.04 0.98 2.94 0.10 19.19 6.79 81.75 31.89 140.58 29.16 259.86 49.52D019-93 3.64 0.00 17.75 0.06 1.10 2.77 0.04 18.69 6.92 85.40 34.02 145.11 30.45 269.68 51.20D019-97 6.22 0.00 1.84 0.03 0.85 2.77 0.13 17.14 6.71 83.78 29.76 129.79 26.74 236.92 44.10D019-102 10.55 0.00 5.48 0.14 2.62 6.86 0.26 40.72 15.00 176.23 65.16 286.28 60.21 529.00 95.99D019-111 10.19 13.04 29.81 3.16 13.34 8.51 0.17 41.47 15.83 202.48 77.37 355.13 77.88 712.01 129.90

N unpublished data.2.Bulk rock composition was treated as melt composition during zirconc

wf

g29wT−ti

4Z

seBBp(Ld

ote:1. bulk rock rare element compositions for the Ehu granitic pluton are authors’rystallized (Ballard et al., 2002).

hich offers more reliable estimates of Ce anomalies and oxygenugacities (Qiu et al., 2014a).

In this study, the lattice strain model was used for magma oxy-en fugacity determination (Blundy and Wood, 1994; Ballard et al.,002; Qiu et al., 2014a). Two zircon grains (D019-92 and D019-3) yield inconsistent high oxygen fugacity of −9.29 and −10.24,hich are statistical outliers and were excluded from the dataset.

he rest 35 grains yield oxygen fugacities ranging from −19.19 to11.43 with an average of −15.40. The calculated magma oxida-

ion state is FMQ-0.29. The results are listed in Table 3 and plotedn Fig. 4.

.4. Implication to Cu-Mo mineralization quiescence inhe-Gan-Wan region

The association between mineralization and magma oxidationtate has been demonstrated by extensive field observations andxperiments (e.g., Burnham and Ohmoto, 1980; Candela, 1992;levin and Chappell, 1992; Hedenquist and Lowenstern, 1994;allard et al., 2002; Mungall, 2002). Generally, Cu and Mo por-

hyries or Cu-Mo-bearing granites are related to oxidized granitese.g., Ballard et al., 2002; Sun et al., 2004; Mengason et al., 2011;i et al., 2012; Sun et al., 2013; Zhang et al., 2013), whereas W-Sneposits preferably occur in reduced granites(e.g., Lehmann, 1982;

Fig. 4. Zircon crystallization temperature and magma oxygen fugacity plots of theEhu granitic pluton. HM, FMQ, and IW buffers were referred to Myers and Eugster(1983), while NNO buffer was referred to O’Neill and Pownceby (1993).

446 J.-T. Qiu, L. Qiu / Chemie der Erde 76 (2016) 441–448

Table 3Crystallization temperatures and magma oxygen fugacities of zircons from the Ehu granitic plution.

Sample T(K) �Ce logfo2 �FMQ Corr. Comment

D019-07 1057.33 40.58 −12.32 2.5 −0.99939D019-10 1070.75 15.63 −15.29 −0.75 −0.99939D019-11 1062.05 27.27 −13.6 1.13 −0.999D019-14 1056.62 22.44 −14.58 0.26 −0.99868D019-15 1120.48 24.61 −11.43 2.1 −0.99832D019-17 1039.67 21.04 −15.63 −0.41 −0.99961D019-18 1079.33 12.15 −15.85 −1.49 −0.99902D019-19 1010.89 17.38 −17.77 −1.88 −0.99935D019-20 1060.36 15.33 −15.84 −1.08 −0.99901D019-21 1041.51 26.97 −14.61 0.57 −0.99933D019-22 1058.37 29.44 −13.48 1.32 −0.99974D019-23 1051 25.97 −14.3 0.67 −0.99936D019-24 1046.73 30.6 −13.88 1.18 −0.99958D019-33 987.85 19.98 −18.45 −2 −0.99984D019-34 1032.64 17.76 −16.6 −1.23 −0.99907D019-35 1028.79 20.89 −16.18 −0.72 −0.9998D019-41 1030.29 55.65 −12.43 3 −0.99854D019-42 837.14 14.57 −29.12 −8.22 −0.99962 (1)D019-43 1059.98 29.45 −13.4 1.36 −0.99959D019-44 1031.63 12.27 −18.04 −2.64 −0.99751D019-45 1027.84 24.1 −15.69 −0.2 −0.99968D019-46 1010.72 24.49 −16.49 −0.6 −0.9971D019-47 1124.58 15.47 −13 0.44 −0.99514 (2)D019-48 1026.38 18.82 −16.69 −1.17 −0.99921D019-49 1045.73 33.53 −13.59 1.5 −0.99968D019-50 1018.04 17.34 −17.42 −1.7 −0.99869D019-51 1026.92 14.28 −17.7 −2.19 −0.99749D019-55 976.12 19.4 −19.19 −2.44 −0.99962D019-60 1080.81 7.72 −17.49 −3.16 −0.99843D019-62 1033.01 25.25 −15.27 0.11 −0.99529D019-63 1065.64 22.02 −14.24 0.41 −0.99742D019-83 1012.7 32.77 −15.3 0.55 −0.9995D019-86 1059.75 11.66 −16.9 −2.12 −0.99965D019-87 1113 11.31 −14.66 −0.99 −0.99896D019-91 1078.21 14.13 −15.33 −0.95 −0.99945D019-92 994.12 209.37 −9.29 7.01 −0.99902 (3)D019-93 974.06 216.89 −10.24 6.57 −0.99877 (3)D019-97 1022.21 25.75 −15.72 −0.1 −0.99965D019-102 1074.79 24.09 −13.48 0.97 −0.99899D019-111 1071.21 35.41 −12.2 2.33 −0.98091 (2)Mean 1045.66 −0.29Dev. 30.64 1.53

Notes:1 The computation was performed by CGDK + ZOFIT software package (see Appendix A).2 Temperatures were calculated using revised Ti-in-zircon thermometer(Ferry and Watson, 2007), aSiO2 = 1, aTiO2 = 0.6.3 Ce anomalies were calculated using lattice strain model (Blundy and Wood, 1994).4 Oxygen fugacities ware calculated using the method proposed by Trail et al. (2011, 2012).5 FMQ buffer was referred to Myers and Eugster (1983).6 Ionic radii according to Shannon (1976).Comments:(((

LM

a+oFLsgG2aiatp

1) Ti content is bellow detection limit.2) Mineral inclusion influence.3) Statistical outlier.

ehmann and Mahawat, 1989; Lehmann and Harmanto, 1990;engason et al., 2011).The magma oxidation state of terrestrial igneous rocks are usu-

lly in the range between wüstite-magnetite (WM) buffer and NNO1, while those erupted in island arcs and non-arc settings havexidation states higher than NNO + 1 (∼FMQ + 2) and lower thanMQ-1, respectively (e.g., Christie et al., 1986; Carmichael, 1991;ee et al., 2005). During the Late Mesozoic, the upwelling astheno-phere played a significant role in the petrogenesis of the Mesozoicranitoids in SE China, and many A- type granites formed in the Zhe-an-Wan region (Wong et al., 2009; Jiang et al., 2011; Yang et al.,012). Qiu et al. (2013b) noticed that many A-type granites, suchs the Shangjieshou, Baijuhuajian, Tongshan, and Damaoshan gran-

tes, are characterized by the high FeOt/(FeOt + MgO) ratios (0.88–1)nd low Al2O3 contents (11.47–14.35 wt%), showing reduced A-ype granite affinity. Dall’Agnol and Carvalho de Oliveira (2007)roposed that the oxidation states of reduced A-type granites are

usually lower than NNO, which was confirmed by the oxidationstate of FMQ-1.1 for the Shangjieshou granite. Petrogenetic studyon the Baihuhuajian granite suggested that the granite was orig-inally sourced from the asthenospheric mantle and experiencedhigh degree of fractional crystallization and minor assimilationfrom old crustal components (Wong et al., 2009). The low oxidationstate of Baijuhuajian granite may imply a relatively reduced magmasource of asthenospheric mantle for the Zhe-Gan-Wan region dur-ing the Late Mesozoic.

Recent geochemical and isotopic studies (Liu et al., 2010;Wang et al., 2013a) reveal the positive correlation between zir-con Ce4+/Ce3+ (a proxy for fO2) and �18O of rock samples from theLower Yangtze River belt (LYRB), which suggests that assimilation

of components enriched in oxidized components may increase oxy-gen fugacity of magma. Since assimilation from metasedimentarybasement component are very common during magma upwelling,

der E

it

Wbmvmoigsms

Sip1aan

5

1

2

3

A

rB2I

A

t0

R

B

B

B

B

J.-T. Qiu, L. Qiu / Chemie

t is important to investigate if such process significantly increasedhe magma oxygen fugacity.

The Ehu granite, a typical S-type granitic pluton in the Zhe-Gan-an region, was formed by partial melting of metasedimentary

asement, with no fractional crystallization and mantle-derivedagma mixing during its evolution (Jiang et al., 2011), which pro-

ides a good opportunity to investigate the oxidation state of theelt generated from metasedimentary basement. The measured

xidation state of the Ehu granite in this study is FMQ-0.29, whichs only 0.81 log unit higher than that of ore-barren Shangjieshourantie in Zhejiang provice (Qiu et al., 2013b). Such low oxidationtate may imply that the assimilation of metasedimentary base-ent component may be unimportant to increase the oxidation

tate of melts from a reduced asthenospheric mantle source.Regardless of the low magma oxygen fugacities, the

hangjieshou and Ehu granites are devoid of Sn-W mineral-zation, which is contrary to the generalization that W-Sn depositsreferably occur in reduced granites (Burnham and Ohmoto,980; Lehmann, 1982; Lehmann and Mahawat, 1989; Lehmannnd Harmanto, 1990; Mengason et al., 2011). The mechanism ofbsence of Sn-W mineralization in the above two reduced graniteseeds further investigation.

. Conclusions

) U-Pb isotopic ages for the Ehu granitic pluton are in the rangeof 125.2 Ma–138.7 Ma with a weighted mean 206Pb/238U age of132.0 ± 0.6 Ma, suggesting the pluton was formed in the EarlyCretaceous period and during the so-called Late Mesozoic Cu-Momineralization quiescence in Zhe-Gan-Wan region.

) The calculated zircon crystallization temperatures and logarith-mic magma oxygen fugacities for Ehu pluton are in the rangesof 702.97 ◦C–847.33 ◦C, and −19.19 to −11.43, respectively. Themagma oxidation state relative to FMQ buffer is FMQ-0.29 forEhu plution, which is much lower than those of Mo-bearingTongcun and Cu-bearing Dexing granites.

) The low oxidation state of Ehu granite suggests that the assim-ilation of metasedimentary basement component may notsignificantly increase the oxidation state of melts derived fromreduced asthenospheric mantle.

cknowledgements

This study was financially supported by the National Natu-al Science Foundation of China (Grant No. 41502037), Nationalasic Research Program of China (973 Program, Granted No.014CB440903) and the Youth Foundation of Beijing Research

nstitute of Uranium Geology (DD1405-A).

ppendix A. Supplementary data

Supplementary data associated with this article can be found, inhe online version, at http://dx.doi.org/10.1016/j.chemer.2016.06.04.

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