299

Geochemical Journal, Vol. 44, pp. 299 to 313, 2010

*Corresponding author (e-mail: xsxu@nju.edu.cn)

Copyright © 2010 by The Geochemical Society of Japan.

Geochronology, petrogenesis and metallogeny of Piaotang granitoidsin the tungsten deposit region of South China

ZHENYU HE,1 XISHENG XU,1* HAIBO ZOU,2 XUDONG WANG1 and YAO YU1

1State Key Laboratory for Mineral Deposits Research, Department of Earth Sciences, Nanjing University, Nanjing 210093, China2Department of Geology and Geography, Auburn University, Auburn, AL 36849, U.S.A.

(Received August 31, 2009; Accepted December 23, 2009)

The tungsten deposit region of South China is well known as the world’s leading tungsten (W) producer. The Piaotangtungsten deposit in the region is such a representative large-scale quartz vein type tungsten polymetallic deposit that isclosely associated with granitoids. In the present study we present precise LA-ICP-MS zircon U–Pb dating and LA-MC-ICPMS zircon Hf isotopic data for the samples from exposed quartz diorite body and buried granite stock in the Piaotangtungsten deposit area. Zircon U–Pb dating results indicate that the quartz diorite body was formed in Early Paleozoic timeat 439 ± 2 Ma, whereas the granite body was emplaced in Early Yanshanian time at 158 ± 3 Ma. Both the quartz diorite andgranite have negative εHf(t) values, with similar two-stage zircon Hf model ages ranging from 1.8 to 2.1 Ga. Throughintegration of our new data with the isotope data of Precambrian basement rocks in western Cathaysia, we suggest that thePaleoproterozoic Hf model ages (1.8–2.1 Ga) might be an average age which resulted from mixing of continental materi-als of different ages. Both the Piaotang Early Paleozoic quartz diorite and Early Yanshanian granite are produced byreworking of the heterogeneous Neoproterozoic crust. Our zircon ages, together with the geochemical data and geologicalfeatures and ore-forming ages of this tungsten deposit, indicate that the buried Early Yanshanian granite, rather than theexposed quartz diorite, is genetically associated with tungsten mineralization.

The distinct metallogeny difference between the Piaotang Early Paleozoic quartz diorite and Early Yanshanian granitecan be ascribed to the different degrees of magma differentiation. The Early Yanshanian granite is highly differentiatedrock and similar to the other W–Sn deposits generating granitoids in South China. The extents of magma differentiationdepend on the tectonic setting and the mechanism of magma generation. On the basis of the relationship between twodifferent stages of magmatism and W mineralization in the Piaotang tungsten deposit, and the similarities with othergranite related W–Sn deposits in the same region, it is proposed that the regional tectonic setting and lithosphere dynam-ics are the key factors controlling the metallogenic capacity of granitoids in South China.

Keywords: granitoids, tungsten metallogeny, U–Pb dating, Hf isotope, South China

ment of granitoid intrusions. The magmatic activities growstronger with time, reaching the climax in LateYanshanian; (3) Composite granitoid complexes are quitecommon in South China, which are formed by multi-stagemagma emplacements. Repeated intracrustal reprocess-ing by partial melting and magma differentiation has un-doubtedly contributed to important mineralization in theupper crust; (4) Significant compositional overlaps aremarked between the granitoids of various magmatismcycles, though they may have different petrogenetic types.

Large-scale tungsten-polymetallic mineralization isassociated with multi-stage granitoid magmatism in SouthChina (Hsu, 1943; Xu et al., 1984). The South Chinatungsten-polymetallic mineralization region is known tobe the world’s leading producer of tungsten and antimony,with subordinate Sn, Mo, Bi, Nb, Ta, Hg, As, Be, Pb, Zn,REE, etc. (Tanelli, 1982). The attention of the geologicalresearch has long been paid to the metallogenic epoch,source of the ore-forming elements, fluid types, hydro-

INTRODUCTION

The granitoids of South China, characterized by com-plex geological setting and the close relationship withendogenic metal mineralization, have drawn wide inter-ests of geologists over the last several decades. The fea-tures of these granitoids can be briefly summarized asfollows (Jahn et al., 1990; Zhou, 2003; Wang and Shen,2003; Zhou et al., 2006; Li and Li, 2007; Xu, 2008): (1)Vast granitoids are widely distributed throughout SouthChina, and Mesozoic granitoids have the largest outcropareas, covering a total area about 135,300 km2; (2) Thegranitoid magmatic activities have been operative forabout 1 billion years since Neoproterozoic time. Episodictectonic events were accompanied by repeated emplace-

300 Z. He et al.

thermal alteration and granitoid affiliation. Accurateknowledge of temporal and spatial distribution of gran-ites is critical to the research of regional mineralization.

The southern Jiangxi Province is the host of the mostimportant tungsten district of South China. All the tung-sten deposits are restricted in a 17 km long and 3~5 kmwide NNE tungsten-tin polymetallic mineralization belt,i.e., Xihuashan–Zongshukeng mineralization belt (Mei,1985; Wu et al., 1987). The Piaotang tungsten deposit isa representative large-scale quartz vein type tungstenpolymetallic deposit in this belt. The granitoids in thismining area include exposed quartz diorite body and bur-ied stock-like granite body. Previous isotopic dating re-sults indicated that the quartz diorite body and granitebody might have different ages. Shan (1976) reported aK–Ar method age of 274 Ma for the quartz diorite; Wu etal. (1987) obtained a K–Ar age of 155.7 ± 1.8 Ma for thegranite; and a new study by Zhang et al. (2009) provideda TIMS U–Pb zircon age of 161.8 ± 1.0 Ma for the gran-ite. However, Shan (1976) and Wu et al. (1987) did notprovide detailed isotope data for careful evaluation, eventhere was no age error presented in the result of Shan(1976). The K–Ar ages might be affected by later stagethermal disturbance, precise and accurate dating is there-fore still needed for the Piaotang quartz diorite and gran-ite. In addition, it is not clear whether quartz diorite orlater granite activity is directly associated with tungstenmineralization. Another unanswered question is whetheror not there is any genetic relationship between these twomagmatisms. Solving these problems is also beneficial

to tungsten polymetallic deposit exploration. We thusconducted detailed zircon U–Pb, Hf isotopic and wholerock geochemical studies on the quartz diorite and gran-ite from the Piaotang tungsten deposit area, in order todetermine their crystallization ages and to gain moreinsights into their magma sources and the relationshipbetween magmatic processes and tungsten mineralization.Meanwhile, the geochemical data of nearby tungsten min-eralized Dajishan granite (151.7 ± 1.6 Ma, Zhang et al.,2006) and metallogeny barren Wuliting granite (237.5 ±4.8 Ma, Qiu et al., 2004) are integrated for comparison.

GEOLOGICAL SETTING

Most of the tungsten deposits of South China are lo-cated in the adjacent area of Jiangxi, Hunan andGuangdong Provinces, in particular in the Nanling region(Xu et al., 1984). The deposit types include quartz veintype, granite type, greisen type, skarn type, strata bound-disseminated type, and fracture zone type (Tanelli, 1982).The Piaotang tungsten deposit is located in Zuoba Townof Dayu County in southern Jiangxi Province, which is inthe northern section of Xihuashan–Zongshukeng NNEtungsten-tin polymetallic mineralization belt. It is a large-scale quartz vein type tungsten polymetallic deposit, com-posed mainly of wolframite and cassiterite. Valuable quan-tities of Mo, Bi, Cu, Pb, Zn are also discovered in themine. The exposed strata of the mining area consist mainlyof Middle–Upper Cambrian metamorphic rock seriesmade up of low-grade metamorphic sandstone, slate and

Fig. 1. (a) Sketched geological map showing the major tectonic scheme of South China and the location of studied area (afterChen and Jahn, 1998). Also shown are the locations of two metamorphic basements exposed in vicinity of the study area, theTanxi gneiss and Xunwu gneiss. (b) Simplified geological map of the Piaotang tungsten deposit (modified after Shan, 1976).

Zircon U–Pb dating and Hf isotopes of Piaotang granitoids 301

a small amount of siliceous slate, with minor sporadically-distributed Devonian sandy gravel (Fig. 1) (Jiangxi,1984). The Piaotang tungsten deposit is composed of hun-dreds of ore-bearing quartz veins densely distributed inthe low-grade metamorphic wall rocks, and extend down-ward into the buried granite body (Mei, 1985). The tec-tonic history is complex. A strong fold belt was formedin Early Paleozoic, and then the fault structures werehighly developed during early Yanshanian stage, mainlyconsisting of the apparent EW trending faults and NEtrending faults.

Igneous rocks in this mining area include exposedquartz diorite body and buried stock-like granite bodywhich is hidden below 300 meters level (Shan, 1976).The quartz diorite body is situated in the north part of themining area, forming a tumor-like intrusion with expo-sure area of ~3 km2. The south part of the quartz dioritebody intrudes the Cambrian strata, and the north partshows fault contact with the Devonian Tiaomajian For-mation. Metamorphism has not developed in the contactzones. The grain size increases towards the center of thebody from fine-grained to medium-grained, along withdecreasing quartz content. The buried granite body in-trudes the low metamorphic Cambrian pelitic and sandyrocks. The boundary between granite and wall rocks issharp, and contact metamorphism is well developed.Hornfels is widespread in wall rocks. The granite body ismainly composed of two transitional rock types (Mei,1985): fine-grained porphyritic monzogranite and me-dium-grained porphyritic K-feldspar granite.

Samples of this study were all collected from the minetunnels. The quartz diorite sample was collected from the15th exploration line 556 meter elevation. They are grey-green in colour, medium-grained, and rarely porphyritic.The dominant minerals are feldspars, with some K-feldspar grains showing Carlsbad law twin. The volume

content of quartz is 10% and forms interstitial grains. Themafic minerals are about 25%, mainly consisting of biotiteand hornblende. Accessory minerals are Fe–Ti oxides,apatite, titanite and rare zircon. The rocks have under-gone extensive hydrothermal alterations. Feldspar waspartly replaced by sericites and chlorites. Hornblende wasaltered by biotitization and chloritization (Fig. 2a). Thegranite samples were collected from the 7th explorationline at elevation 268 meters between the III2 ore belt andIII1 ore belt, and the rock type is medium-grainedporphyritic K-feldspar granite. It is grey in colour,porphyritic in texture. The phenocrysts are mainly com-posed of orthoclase and quartz. The matrix is medium-grained and mainly consists of quartz (~35%), orthoclase(~45%), muscovite (~15%) and plagioclase (~3%; An =20) (Fig. 2b).

ANALYTICAL METHODS

Zircons were separated using standard density andmagnetic separation techniques. Random zircon grainswere hand-picked under a binocular stereomicroscope andwere mounted in epoxy in 1.4 cm diameter circular grainmount. The mount was then polished to section the crys-tals in half for analysis. In order to characterize the inter-nal structures of the zircons and to choose potential tar-get sites for U–Pb dating and Hf analyses, back scatteredelectron (BSE) and Cathodoluminescence (CL) imageshave been obtained using a JEOL JXA-8100 microprobeat the State Key Laboratory of Mineral Deposits Research,Nanjing University. The operating conditions were: 15kV accelerating voltage, 20 nA beam current.

Zircon U–Pb analyses were carried out on an Agilent7500a ICP-MS equipped with New Wave Research 213nm laser ablation system at the State Key Laboratory ofMineral Deposits Research, Nanjing University. The la-

Fig. 2. Photomicrographs of representative samples (Crossed nicols). (a) Quartz diorite (PT18), 1, Plagioclase alterated tosericites and chlorites; 2, hornblende alterated to biotites and chlorites; (b) Major mineral components of K-feldspar granite(PT06). Qtz, Quartz; Pl, plagioclase; Kfs, K-feldspar; Ms, muscovite.

302 Z. He et al.

ser system delivers a beam of 213 nm UV light from afrequency-quintupled Nd:YAG laser. The ablated mate-rial is transported in a He carrier gas through 3 mm i.d.PVC tubing and then combined with Ar in a 30 cm3 mix-ing chamber prior to entering the ICP-MS for isotopicquantification. Analyses were carried out with a beamdiameter of 30–40 µm, 5 Hz repetition rate, and energyof 10–20 J/cm2. Data acquisition for each analysis took100 s (40 s on background, 60 s on signal).

Raw count rates for 206Pb, 207Pb, 208Pb, 232Th and 238Uwere collected for age determination, and the dwell timeof per isotope are 15, 30, 10, 10, 15 ms, respectively. Datawere acquired on five isotopes using the instrument’stime-resolved analysis data acquisition software. Massdiscrimination of the mass spectrometer and residual el-emental fractionation were corrected by calibrationagainst a homogeneous zircon standard, GEMOC/GJ-1(609 Ma; Jackson et al., 2004), which was used as a pri-mary standard. The raw ICP-MS data were exported inASCII format and processed using GLITTER (VanAchterbergh et al., 2001), an in-house data reduction pro-gram. GLITTER calculates the relevant isotopic ratios,ages and errors. Errors in isotopic ratios include contri-butions from the uncertainties in background and signalfor unknowns and standards and an assumed 1% error(1σ) is assigned to the given values of the isotope ratiosfor the standard and propagated through the error analy-sis. Detailed analytical procedures are similar to thosedescribed by Jackson et al. (2004). Samples are analyzedin “runs” of ca. 18 analyses, which include 10–12 un-knowns, bracketed by two to four analyses of the stand-ard. The “unknowns” include 2 analyses of well-charac-terized zircon, Mud Tank (TIMS age = 732 ± 5 Ma; Blackand Gulson, 1978) which was analyzed frequently as anindependent control on reproducibility and instrumentstability. Eight analyses of Mud Tank during this studyyielded a 206Pb/238U age of 732 ± 19 Ma (mean ± 2 S.D.).

Common Pb was corrected according to the methodproposed by Andersen (2002). The analyses presentedhere have been corrected assuming recent lead-loss. Theage calculations and plotting of Concordia diagrams weremade using Isoplot (ver. 2.49) (Ludwig, 2001). The con-centrations of U and Th in each analytical spot were de-rived by comparison of background-corrected count rateswith mean count rates on the GJ-1 standard, which hasmean U and Th contents of 330 and 8 ppm, respectively.

Zircon Hf isotope analyses were carried out in situ bya New Wave Research 213 nm laser-ablation system plusa Nu Plasma MC-ICPMS at the State Key Laboratory ofEnvironmental Geochemistry, Institute of Geochemistry,Chinese Academy of Sciences in Guiyang. The detailedprocedure has been reported by Tang et al. (2008) and abrief description was presented here. The Nu Plasma MC-ICP-MS features a unique geometry with a fixed detector

array of 12 Faraday cups and 3 ion counters; for this workwe analyzed masses 171 and 173–179 simultaneously inFaraday cups. A 10 Hz repetition rate, beam diameter of60 µm, and pulse energy density of ~4.40–5.27 J/cm2 wereused. Data were collected by using time-resolved analy-sis (TRA) method, and the ablation times were about 60s after 30 s blank measurements. The measurement inte-gration time was 0.2 s. The ablated materials were trans-ported first by carrier gas He (0.60–0.85 L/min) from thelaser ablation cell, then mixed Ar (1.10–1.15 L/min) viaa Y connection to the MC-ICP-MS torch.

The instrumental mass bias for Hf was corrected bynormalizing 179Hf/177Hf to 0.7325 using the exponentiallaw. The isobaric interference of 176Lu on 176Hf was cor-rected by measured intensity of 175Lu and a recommended176Lu/175Lu ratio of 0.026549 (Chu et al., 2002), and βLu= βHf (Iizuka and Hirata, 2005) to calculate 176Lu inten-sity and 176Lu/177Hf ratio. The intensity of 176Yb was cal-culated by measured intensity of 173Yb and a recom-mended 176Yb/173Yb ratio of 0.78696 (Thirlwall andAnczkiewicz, 2004) and βYb, which was calculated fromthe measured 173Yb/171Yb ratio for each data point and arecommended 173Yb/171Yb ratio of 1.12346 (Thirlwall andAnczkiewicz, 2004). The 176Yb/177Hf ratio was calculatedfollowing the method reported by Iizuka and Hirata(2005). During the course of data acquisition in this study,

Fig. 3. (a) Cathodoluminescence images of representative zir-cons from Piaotang quartz diorite; (b) back scattered electronimages of representative zircons from Piaotang K-feldspar gran-ite. Circles with enclosed data indicate the location of Hf analy-ses, whereas circles without data indicate the location of U–Pbanalyses.

Zircon U–Pb dating and Hf isotopes of Piaotang granitoids 303

replicates of the standard zircon 91500 gave a mean valueof 176Hf/177Hf = 0.282304 ± 28 (2 S.D., n = 27). Analyseson zircon standard TEMORA have been carried out byTang H. F., yielded a mean 176Hf/177Hf ratio of 0.282678± 29 (2 S.D., n = 6), which is in good agreement with theanalytical results in other laboratories, e.g., analyses byWoodhead et al. (2004) gave 176Hf/177Hf value of0.282686 ± 7 (2 S.D.) using the solution technique and0.282680 ± 24 (2 S.D.) for laser MC-ICPMS analyses;analyses by Wu et al. (2006) gave 176Hf/177Hf value of0.282680 ± 31 (2 S.D.) for laser MC-ICPMS analyses.

The measured 176Lu/177Hf ratios and the 176Lu decayconstant of 1.865 × 10–11 yr–1 reported by Scherer et al.(2001) were used to calculate initial 176Hf/177Hf ratios.The chondritic values of 176Lu/177Hf = 0.0336 and 176Hf/177Hf = 0.282785 reported by Bouvier et al. (2008) wereused for the calculation of εHf values. The depleted man-tle Hf model ages (TDM) were calculated using the mea-sured 176Lu/177Hf ratios of zircon based on an assump-tion that the depleted mantle reservoir has a linear iso-topic growth from 176Hf/177Hf = 0.279718 at 4.55 Ga to0.283250 at present, with 176Lu/177Hf = 0.0384 (Griffinet al., 2000). We also present a two-stage model age(TDM2) for each zircon, which assumes that its parentalmagma was produced from an average continental crust(176Lu/177Hf = 0.015) that originally was derived fromthe Depleted Mantle (Griffin et al., 2002).

Whole rock major elements were analyzed using anARL9800XP+ X-ray fluorescence spectrometer (XRF) atthe Centre of Modern Analysis, Nanjing University, fol-lowing the procedures described by Franzini et al. (1972).The analytical precision is generally less than 2%. Theglass discs were prepared by fusion of a mixture of 0.6 gsample powder and 6.6 g lithium borate. Trace elementconcentrations were determined with an ELAN 6000 ICP-MS at the Institute of Geochemistry, Chinese Academyof Sciences in Guiyang, following procedures described

by Qi et al. (2000). The precision was generally betterthan 5% for most trace elements. Analyses of internationalstandards OU-6 and GBPG-1 are in agreement with rec-ommended values (Thompson et al., 2000; Potts andKane, 2005).

RESULTS

Zircon U–Pb geochronologyZircons separated from quartz diorite (PT18) are trans-

parent, light yellow in color, and 80–120 µm in size, withsome oscillatory zoning and no inherited cores (Fig. 3a).Analyses of 17 zircon grains from quartz diorite wereobtained. Their Th/U ratios mostly range from 1.09 to1.99 (Table 1), indicating an igneous origin (Hoskin andSchaltegger, 2003). All the analyses are plotted on ornearby the concordia curve as a coherent group. Theyyield 206Pb/238U ages between 437–441 Ma, with a mean206Pb/238U age of 439 ± 2 Ma (2 S.D.) (Fig. 4a), which istaken as the crystallization age. Therefore, the Piaotangquartz diorite was formed in Early Paleozoic time, ratherthan previously reported Late Paleozoic time (274 Ma)(Shan, 1976). The new age is consistent with the intru-sive ages of the Doushui granite (432–474 Ma), situatingonly ~30 km to the north of the present study area (Maoet al., 2008).

Zircons separated from K-feldspar granite sample(PT06) are euhedral and light brown in color, typically150–230 µm long and 80–120 µm wide, with concentricoscillatory zoning, lacking inherited cores (Fig. 3b). TheirTh/U ratios are high and in the range of 0.36 to 1.00 (Ta-ble 1). The 18 analyses are tightly grouped and concord-ant, defining a mean 206Pb/238U age of 158 ± 3 Ma (2S.D.) (Fig. 4b), which is interpreted as the crystallizationage for the Piaotang granite. This age is in agreement withthe whole rock K–Ar age of 155.7 ± 1.8 Ma reported byWu et al. (1987) and the TIMS U–Pb zircon age of 161.8

Fig. 4. Zircon U–Pb concordia diagrams for the Piaotang quartz diorite (a) and K-feldspar granite (b).

304 Z. He et al.

Ana

lysi

sT

hU

Th/

UIs

otop

ic r

atio

Age

(M

a)

(ppm

)(p

pm)

207 P

b/20

6 Pb

± 1 σ

207 P

b/23

5 U ±

1σ

206 P

b/23

8 U ±

1σ

208 P

b/23

2 Th

± 1σ

207 P

b/20

6 Pb

± 1σ

207 P

b/23

5 U ±

1σ

206 P

b/23

8 U ±

1σ

208 P

b/23

2 Th

± 1σ

PT

18: q

uart

z di

orit

ePT

18-1

1233

922

1.34

0.05

88 ±

0.0

0088

0.57

101

± 0.

0091

60.

0704

4 ±

0.00

089

0.02

459

± 0.

0015

556

0 ±

1645

9 ±

643

9 ±

549

1 ±

31

PT18

-211

9868

61.

750.

0555

2 ±

0.00

104

0.53

766

± 0.

0102

50.

0702

4 ±

0.00

090.

0222

1 ±

0.00

191

433

± 21

437

± 7

438

± 5

444

± 38

PT18

-329

121

71.

340.

0555

1 ±

0.00

137

0.53

884

± 0.

0131

60.

0704

2 ±

0.00

097

0.02

219

± 0.

0019

743

3 ±

3143

8 ±

943

9 ±

644

4 ±

39

PT18

-412

1965

91.

850.

0557

9 ±

0.00

136

0.54

091

± 0.

0130

60.

0703

3 ±

0.00

098

0.02

083

± 0.

0024

544

4 ±

3043

9 ±

943

8 ±

641

7 ±

49

PT18

-615

2383

51.

820.

0572

5 ±

0.00

095

0.55

708

± 0.

0096

70.

0705

9 ±

0.00

090.

0231

± 0

.001

8750

1 ±

1845

0 ±

644

0 ±

546

2 ±

37

PT18

-715

5884

91.

840.

0561

± 0

.001

60.

5448

5 ±

0.01

550.

0704

4 ±

0.00

109

0.02

036

± 0.

0027

645

6 ±

3644

2 ±

1043

9 ±

740

7 ±

55

PT18

-897

649

11.

990.

0571

± 0

.001

280.

5549

3 ±

0.01

237

0.07

051

± 0.

0009

50.

0244

3 ±

0.00

279

495

± 26

448

± 8

439

± 6

488

± 55

PT18

-10

689

460

1.50

0.05

537

± 0.

0015

10.

5382

2 ±

0.01

447

0.07

051

± 0.

0010

10.

0257

3 ±

0.00

373

427

± 35

437

± 10

439

± 6

513

± 74

PT18

-510

4267

91.

540.

0570

9 ±

0.00

111

0.55

584

± 0.

0111

60.

0706

3 ±

0.00

094

0.02

319

± 0.

0024

349

5 ±

2244

9 ±

744

0 ±

646

3 ±

48

PT18

-11

800

736

1.09

0.05

771

± 0.

0012

10.

5598

3 ±

0.01

223

0.07

037

± 0.

0010

20.

0212

5 ±

0.00

1651

9 ±

2445

1 ±

843

8 ±

642

5 ±

32

PT18

-13

951

687

1.39

0.05

576

± 0.

0017

80.

5426

3 ±

0.01

692

0.07

062

± 0.

0011

0.02

329

± 0.

0037

443

± 42

440

± 11

440

± 7

465

± 73

PT18

-14

647

430

1.50

0.05

732

± 0.

0012

20.

5549

± 0

.012

160.

0702

2 ±

0.00

099

0.02

436

± 0.

0020

950

4 ±

2544

8 ±

843

7 ±

648

6 ±

41

PT18

-15

576

396

1.45

0.05

637

± 0.

0012

80.

5465

9 ±

0.01

243

0.07

033

± 0.

0009

50.

0241

9 ±

0.00

276

467

± 27

443

± 8

438

± 6

483

± 54

PT18

-17

1188

700

1.70

0.05

927

± 0.

0014

10.

5759

7 ±

0.01

387

0.07

05 ±

0.0

0101

0.02

581

± 0.

0031

157

7 ±

2846

2 ±

943

9 ±

651

5 ±

61

PT18

-18

1244

739

1.68

0.05

811

± 0.

0011

70.

5671

± 0

.011

810.

0707

9 ±

0.00

097

0.02

602

± 0.

0028

953

4 ±

2345

6 ±

844

1 ±

651

9 ±

57

PT18

-19

515

384

1.34

0.05

635

± 0.

0015

50.

5476

1 ±

0.01

506

0.07

049

± 0.

0010

50.

0269

6 ±

0.00

379

466

± 35

443

± 10

439

± 6

538

± 75

PT18

-20

949

754

1.26

0.05

967

± 0.

0016

0.58

156

± 0.

0156

30.

0707

± 0

.001

050.

0280

8 ±

0.00

438

592

± 33

465

± 10

440

± 6

560

± 86

PT

06:

K-f

elds

par

gran

ite

PT06

-117

725

60.

690.

0490

5 ±

0.00

195

0.16

922

± 0.

0066

20.

0250

2 ±

0.00

039

0.00

925

± 0.

0009

615

0 ±

6215

9 ±

615

9 ±

218

6 ±

19

PT06

-361

611

670.

530.

0517

8 ±

0.00

213

0.17

716

± 0.

0070

70.

0248

2 ±

0.00

042

0.00

812

± 0.

0016

427

6 ±

6016

6 ±

615

8 ±

316

3 ±

33

PT06

-455

810

080.

550.

0460

5 ±

0.00

217

0.15

779

± 0.

0071

40.

0248

5 ±

0.00

033

0.00

87 ±

0.0

0083

325

± 10

114

9 ±

615

8 ±

217

5 ±

17

PT06

-262

112

510.

500.

0518

5 ±

0.00

151

0.17

753

± 0.

0050

60.

0248

3 ±

0.00

036

0.00

91 ±

0.0

0129

279

± 39

166

± 4

158

± 2

183

± 26

PT06

-653

811

960.

450.

0497

4 ±

0.00

126

0.17

028

± 0.

0042

70.

0248

4 ±

0.00

035

0.00

85 ±

0.0

0105

183

± 33

160

± 4

158

± 2

171

± 21

PT06

-856

282

40.

680.

0503

± 0

.001

720.

1721

7 ±

0.00

573

0.02

484

± 0.

0003

90.

0087

2 ±

0.00

125

209

± 48

161

± 5

158

± 2

175

± 25

PT06

-918

018

01.

000.

0505

1 ±

0.00

229

0.17

358

± 0.

0076

80.

0249

3 ±

0.00

042

0.00

861

± 0.

0010

121

9 ±

7116

3 ±

715

9 ±

317

3 ±

20

PT06

-11

240

414

0.58

0.04

621

± 0.

0030

30.

1571

± 0

.010

020.

0246

6 ±

0.00

037

0.00

786

± 0.

0004

58

± 14

414

8 ±

915

7 ±

215

8 ±

9

PT06

-12

484

1342

0.36

0.05

247

± 0.

0014

0.18

191

± 0.

0047

80.

0251

7 ±

0.00

035

0.00

934

± 0.

0009

430

6 ±

3517

0 ±

416

0 ±

218

8 ±

19

PT06

-13

465

937

0.50

0.04

605

± 0.

0032

30.

1556

2 ±

0.01

066

0.02

451

± 0.

0003

70.

0082

9 ±

0.00

088

447

± 15

514

7 ±

915

6 ±

216

7 ±

18

PT06

-14

169

212

0.79

0.05

233

± 0.

0031

80.

1782

6 ±

0.01

047

0.02

471

± 0.

0005

10.

0079

± 0

.000

9130

0 ±

9616

7 ±

915

7 ±

315

9 ±

18

PT06

-16

530

1469

0.36

0.04

866

± 0.

0060

60.

1626

1 ±

0.02

006

0.02

423

± 0.

0004

20.

0076

8 ±

0.00

107

132

± 25

815

3 ±

1815

4 ±

315

5 ±

21

PT06

-17

213

379

0.56

0.05

099

± 0.

0028

10.

1765

± 0

.009

370.

0251

1 ±

0.00

050.

0070

1 ±

0.00

101

240

± 86

165

± 8

160

± 3

141

± 20

PT06

-18

231

344

0.67

0.05

254

± 0.

0018

0.17

991

± 0.

0060

20.

0248

3 ±

0.00

038

0.00

844

± 0.

0007

930

9 ±

4816

8 ±

515

8 ±

217

0 ±

16

PT06

-19

369

922

0.40

0.04

907

± 0.

0015

30.

1688

9 ±

0.00

524

0.02

497

± 0.

0003

90.

0075

3 ±

0.00

081

151

± 44

158

± 5

159

± 2

152

± 16

PT06

-20

371

818

0.45

0.04

915

± 0.

0012

30.

1684

9 ±

0.00

422

0.02

486

± 0.

0003

40.

0084

1 ±

0.00

0815

5 ±

3415

8 ±

415

8 ±

216

9 ±

16

PT06

-21

433

1000

0.43

0.04

919

± 0.

0012

10.

1714

6 ±

0.00

422

0.02

528

± 0.

0003

50.

0096

7 ±

0.00

102

157

± 32

161

± 4

161

± 2

195

± 20

PT06

-23

487

1244

0.39

0.04

964

± 0.

0013

50.

1714

9 ±

0.00

461

0.02

506

± 0.

0003

60.

0100

7 ±

0.00

134

178

± 36

161

± 4

160

± 2

203

± 27

Tabl

e 1.

L

A-I

CP

-MS

zirc

on U

–Pb

isot

opic

ana

lyse

s of

the

Pia

otan

g qu

artz

dio

rite

and

K-f

elds

par

gran

ite

Zircon U–Pb dating and Hf isotopes of Piaotang granitoids 305

± 1.0 Ma by Zhang et al. (2009). Our zircon ages thusfurther reveal that although the Piaotang granite and thequartz diorite occur in close association, they are not theproducts of contemporary magma activities.

Zircon Hf isotopesBecause zircon has high hafnium concentrations and

low Lu/Hf ratios, correction for in situ radiogenic growthin zircons, in particular in young zircons, is negligible.In addition, the Lu–Hf isotopic system can elucidate thenature of magma sources and the magma mixing proc-esses (Griffin et al., 2002; Yang et al., 2007). Fourteenzircons from quartz diorite sample (PT18) have beenanalyzed for Hf isotopic compositions, yielding a narrowrange of initial 176Hf/177Hf ratios between 0.282243 and0.282343, and εHf(t) values between –9.4 and –5.8 (Table2; Figs. 5 and 6). The εHf(t) values show unimodal distri-

bution (Fig. 5) in spite of a little wide variation range.Their TDM model ages are between 1.28 and 1.44 Ga, andTDM2 model ages vary from 1.78 to 2.00 Ga (Fig. 7).

Thirteen spots of Hf isotopic analyses were carriedout for zircons from K-feldspar granite sample (PT06).They have initial 176Hf/177Hf ratios between 0.282280 and0.282332, yielding εHf(t) values between –14.4 and –12.5(Figs. 5 and 6). They show unimodal distributions andreveal a symmetrical bell curve in the frequency distri-bution diagram (Fig. 5). This corresponds to TDM agesbetween 1.29 Ga and 1.42 Ga, similar to the TDM ages forquartz diorite. Their calculated TDM2 model ages rangebetween 1.97 and 2.09 Ga, which are almost identical withthose of the quartz diorite (Fig. 7).

Major and trace elementsMajor and trace element compositions of the Piaotang

Spot Age (Ma) 176Hf/177Hf 2 S.E. 176Lu/177Hf 176Yb/177Hf (176Hf/177Hf)i εHf(t) 2 S.E. TDM (Ga) TDM2 (Ga)

PT18: quartz dioritePT18-01 439 0.282306 0.000028 0.001447 0.050252 0.282294 −7.6 1.0 1.35 1.89

PT18-03 439 0.282322 0.000026 0.000940 0.037933 0.282314 −6.9 0.9 1.31 1.84

PT18-04 438 0.282347 0.000040 0.001506 0.062024 0.282335 −6.2 1.4 1.30 1.80

PT18-05 440 0.282339 0.000030 0.001361 0.056513 0.282328 −6.4 1.1 1.30 1.81

PT18-06 440 0.282343 0.000034 0.002259 0.081528 0.282324 −6.5 1.2 1.33 1.82

PT18-08 439 0.282258 0.000024 0.001867 0.075640 0.282243 −9.4 0.8 1.44 2.00

PT18-10 439 0.282328 0.000050 0.001207 0.051401 0.282318 −6.8 1.8 1.31 1.84

PT18-11 438 0.282298 0.000036 0.000958 0.034672 0.282290 −7.8 1.3 1.35 1.90

PT18-13 440 0.282355 0.000032 0.001419 0.052024 0.282343 −5.8 1.1 1.28 1.78

PT18-15 438 0.282346 0.000038 0.001914 0.065815 0.282330 −6.3 1.3 1.31 1.81

PT18-17 439 0.282315 0.000028 0.002102 0.084371 0.282298 −7.5 1.0 1.36 1.88

PT18-18 441 0.282326 0.000034 0.002079 0.081195 0.282309 −7.0 1.2 1.35 1.85

PT18-19 439 0.282322 0.000024 0.001159 0.045568 0.282312 −6.9 0.8 1.32 1.85

PT18-20 440 0.282333 0.000040 0.001571 0.051510 0.282320 −6.7 1.4 1.32 1.83

PT06: K-feldspar granitePT06-03 158 0.282334 0.000032 0.001429 0.055389 0.282330 −12.6 1.1 1.31 1.98

PT06-04 158 0.282314 0.000026 0.000820 0.031485 0.282312 −13.2 0.9 1.32 2.02

PT06-06 158 0.282294 0.000022 0.001276 0.051105 0.282290 −14.0 0.8 1.36 2.07

PT06-09 159 0.282314 0.000019 0.001145 0.040238 0.282311 −13.3 0.7 1.33 2.02

PT06-11 157 0.282284 0.000028 0.001404 0.057783 0.282280 −14.4 1.0 1.38 2.09

PT06-12 160 0.282301 0.000024 0.001474 0.057771 0.282297 −13.7 0.8 1.36 2.05

PT06-14 157 0.282334 0.000032 0.000698 0.027242 0.282332 −12.5 1.1 1.29 1.97

PT06-16 154 0.282296 0.000020 0.001415 0.055833 0.282292 −14.0 0.7 1.37 2.06

PT06-17 160 0.282304 0.000015 0.001031 0.040881 0.282301 −13.6 0.5 1.34 2.04

PT06-18 158 0.282309 0.000020 0.000900 0.035330 0.282306 −13.4 0.7 1.33 2.03

PT06-19 159 0.282303 0.000040 0.003235 0.111864 0.282293 −13.9 1.4 1.42 2.06

PT06-20 158 0.282304 0.000024 0.000828 0.031800 0.282302 −13.6 0.8 1.33 2.04

PT06-23 160 0.282314 0.000020 0.001119 0.044957 0.282311 −13.2 0.7 1.33 2.02

Table 2. Zircon Hf isotope compositions of the Piaotang quartz diorite and K-feldspar granite

Note: εHf(t) = 10000 {[(176Hf/177Hf)S – (176Lu/177Hf)S × (eλt – 1)]/[(176Hf/177Hf)CHUR,0 – (176Lu/177Hf)CHUR × (eλt – 1)] – 1}; TDM = 1/λ × ln{1 +[(176Hf/177Hf)S – (176Hf/177Hf)DM]/[(176Lu/177Hf)S – (176Lu/177Hf)DM]}; TDM2 = 1/λ × ln{1 + [(176Hf/177Hf)S,t – (176Hf/177Hf)DM]/[(176Lu/177Hf)C –(176Lu/177Hf)DM]} + t.

306 Z. He et al.

quartz diorite and granite are given in Tables 3 and 4 andFigs. 8, 9 and 10. In general, the Piaotang K-feldspar gran-ite and monzogranite have similar geochemical charac-teristics. Both the granites show high SiO2 contents be-tween 72.78 wt.% and 76.96 wt.%, they have high alkalicontents with (K2O + Na2O) contents of 6.15–9.09 wt.%.All samples have higher K2O than Na2O contents. In addi-tion, the Piaotang K-feldspar granite and monzogranitehave very low Fe2O3, MgO, CaO, and P2O5 contents, sug-gesting their crystallization from highly evolved magmas,which are very similar to the major element compositionof Dajishan granite (Fig. 8). Compared with the granites,Piaotang quartz diorite have lower SiO2, but higher Al2O3,Fe2O3, MgO, CaO and P2O5 contents (Table 3), and thecomposition of the most silicic one is similar to that ofWuliting granite (Fig. 8). In the chemical variation dia-grams, most of the major element oxides vs. silica varia-tion show negative correlation for the Piaotang quartzdiorite and granite (Fig. 8 shows SiO2 vs. CaO, Fe2O3,

Al2O3, and P2O5 variations), suggesting a close geneticrelation between the Piaotang quartz diorite and granite.

The Piaotang K-feldspar granite and monzogranite arehigh in LREE and HREE abundance. They are character-ized by nearly flat to moderately HREE-enriched patterns(Fig. 9a), with clear tetrad effect and pronounced Eu nega-tive anomalies (Eu/Eu* = 0.01–0.06). The TE1,3 value thatcharacterizes degrees of the tetrad effect (Irber, 1999)ranges from 1.02 to 1.10 (Table 4). The spidergrams ofthe granites show strongly enriched in Rb, Th, U andHREE and extremely depleted in Ba, Sr, P, Eu and Ti (Fig.9b). In contrast, Piaotang quartz diorite is characterizedby higher REE concentrations (∑REE = 143 ppm), en-richment of LREE and depletion of HREE, with (La/Yb)N

Hf Hf

2 2

25

23

23

Fig. 5. Histogram of εHf(t) values for zircons for the Piaotangquartz diorite (a) and K-feldspar granite (b).

Fig. 6. Diagram of εHf(t) versus age of zircons for the Piaotangquartz diorite and K-feldspar granite. The dashed lines ofcrustal extraction are calculated by using the 176Lu/177Hf ratioof 0.015 for the average continental crust (Griffin et al., 2002).The date of Tanxi gneiss and Xunwu gneiss are from Yu et al.(2007) and Wang et al. (2008) respectively.

Fig. 7. Histograms of Hf model ages for zircons from thePiaotang quartz diorite (a and b) and K-feldspar granite (cand d).

Fig. 8. Major element oxides vs. SiO2 plots for the Piaotangquartz diorite and granite. Also illustrated for comparison arethe fields of Wuliting granite and Dajishan granite in theDajishan tungsten mine (Qiu et al., 2004).

Zircon U–Pb dating and Hf isotopes of Piaotang granitoids 307

ratio of 9.55. Its chondrite-normalized REE pattern (Fig.9a) show relative steep slope with an insignificant nega-tive Eu anomalies (Eu/Eu* = 0.79), which is similar tothe REE pattern of Wuliting granite. Although character-ized by enrichment in Rb, Th, U, K and depletion in Ba,Sr, Ti, the spidergram of the Piaotang quartz diorite isdifferent from that of Piaotang granite but similar to thatof Wuliting granite (Fig. 9b).

DISCUSSION

Crustal components of the Cathaysia Block and the na-ture of magma sources

The South China Block has a complex tectonic his-tory, and is composed of two major Precambrian conti-nental blocks: the Yangtze Block to the northwest, andthe Cathaysia Block to the southeast, divided by theJiangshan–Shaoxing (in Zhejiang) and Pingxiang–Yushan(in Jiangxi) fracture zones (Fig. 1a, Chen and Jahn, 1998).The Mesozoic volcanic-intrusive rocks are mainly dis-tributed in the Cathaysia Block (Zhou et al., 2006). TheCathaysia Block can be further divided into the interiorparts of Cathaysia (western Cathaysia) and the coastalareas (eastern Cathaysia). The boundary between east andwest Cathaysia is roughly along the Zhenghe–Dapu faultas defined by Chen and Jahn (1998). Recently, Xu et al.(2007) suggest that the eastern and western CathaysiaBlock may have different crustal evolution history, on thebasis of U–Pb dating and Hf isotope data of detrital zir-cons separated from sand samples from the Oujiang River(in Zhejiang Province) and the North River (in GuangdongProvince). The basement of eastern Cathaysia is domi-nantly Paleoproterozoic in age (1850–2400 Ma), whereasthe crust of western Cathaysia was mainly generated dur-ing Neoproterozoic time, although it contains some mi-nor Archean to Mesoproterozoic components (Xu et al.,

Sample PT18 SC01a SC02a SC03a SC04a SC05a PT03 PT06 PT11 PM01b PM02b PM03b PM04b PM05b

Rock type quartz diorite K-feldspar granite monzogranite

SiO2 55.87 64.23 64.27 55.32 55.46 56.43 73.97 72.78 74.57 76.61 76.63 76.96 76.55 75.38TiO2 1.08 0.65 0.63 0.89 0.99 0.72 0.08 0.09 0.08 0.11 0.12 0.12 0.10 0.09Al2O3 14.12 14.61 16.38 14.61 14.01 17.94 13.87 14.49 13.40 12.36 12.38 12.37 12.60 12.87Fe2O3 10.25 4.66 4.74 8.25 8.88 5.01 1.09 2.67 1.24 1.05 1.28 1.09 0.93 0.74MnO 0.29 0.17 0.13 0.28 0.21 0.34 0.14 0.56 0.16 0.17 0.08 0.07 0.10 0.10MgO 6.85 2.85 2.59 6.69 5.77 3.22 0.01 0.04 0.06 0.00 0.07 0.05 0.02 0.07CaO 2.90 3.16 3.36 4.71 6.59 4.86 0.72 1.13 0.87 0.65 0.72 0.75 0.63 0.61Na2O 0.90 2.82 5.08 2.06 2.04 5.45 4.19 2.05 3.29 3.15 3.43 3.33 3.57 3.81K2O 3.79 4.9 3.35 4.54 3.85 3.62 4.90 4.10 4.90 4.88 4.26 4.64 4.59 4.46P2O5 0.46 0.25 0.17 0.4 0.16 0.27 0.02 0.03 0.03 0.02 0.02 0.02 0.02 0.02LOI 3.83 1.61 2.47 1.28 2.21 1.52 1.11 2.02 1.45 0.87 0.84 0.55 0.50 0.82Total 100.34 99.96 100.25 99.2 100.34 99.33 100.09 99.95 100.05 99.90 99.86 99.98 99.62 99.75

Table 3. Major element compositions (wt.%) of the Piaotang quartz diorite and granite

Note: LOI: loss on ignition.Data from aWu et al. (1987); bHua et al. (2003), other samples are from this study.

2007).With respect to the Precambrian metamorphic base-

ment rocks distributed in western Cathaysia, such asLongchuan gneiss in northeast of Guangdong, Lanhegneiss and Tanxi gneiss in northern Guangdong,Zengcheng gneiss in central Guangdong, and Xunwugneiss in southern Jiangxi, their protoliths are allNeoproterozoic sedimentary rocks (Xu et al., 2005; Yu etal., 2006, 2007; Wang et al., 2008). As for the granulite-facies metamorphic rocks distributed in southwesternFujian Province and the Yunkai areas which may repre-sent lower crustal component are all parametamorphites,their protoliths are also Neoproterozoic sedimentary rocks(Yu et al., 2006). Therefore, the ancient Archean toMesoproterozoic crust which may ever exist in westernCathaysia was completely obliterated through multi-stagecrustal recycling and reworking in the evolution process(Zheng and Zhang, 2007), and even the Neoproterozoicjuvenile crust have been efficiently reworked into latercontinental crust. The major components of middle-lowercrust beneath the western Cathaysia are these lateNeoproterozoic sedimentary rocks (Yu et al., 2007).

In the present study, the Early Paleozoic quartz dioriteand Early Yanshanian granite have very consistentsingle-stage zircon Hf model ages in spite of a slight dif-ference in the two-stage zircon Hf model ages (Fig. 7).Their two-stage Hf model ages of zircons were 1.78–2.00Ga and 1.97–2.09 Ga respectively, and exhibit a narrowrange from 1.78 to 2.09 Ga as a whole (Table 2). Becausethey have negative εHf(t) values, two-stage Hf model agesof zircons can reflect the age of their source materialsbetter (Zheng et al., 2007; Wu et al., 2007). This leads usto favor a direct involvement of a Paleoproterozoic crustin derivation of these rocks. However, the study area islocated in western Cathaysia Block, and the protoliths ofthe metamorphic basement exposed in vicinity of the study

308 Z. He et al.

Furthermore, the age spectrum of detrital zircons fromNorth River which lies entirely within western Cathaysiaalso lacks the distribution of Paleoproterozoic ages of2400–1850 Ma (Xu et al . , 2007). The foregoingPaleoproterozoic rocks are merely distributed in the east-ern Cathaysia block (Xu et al., 2007). Therefore, thePiaotang Early Paleozoic quartz diorite and EarlyYanshanian granite are likely to be produced by rework-ing of Neoproterozoic crust, rather than Paleoproterozoic.

As shown in U–Pb zircon age versus εHf(t) diagram(Fig. 6), zircons from the Piaotang Early Paleozoic quartzdiorite and Early Yanshanian granite are all located be-tween two crustal evolution lines determined from Tanxi

Sample PT18 PT03 PT06 PT11 PM01a PM02a PM03a PM04a PM05a

Rock type quartz diorite K-feldspar granite monzogranite

Li 435 48.2 1270 109 128 125 121 93.9 80.7Cr 263 34.5 2.86 4.25 3.17 3.49 5.38 14.7 3.44Ni 64.5 13.1 0.52 0.88 1.86 2.23 2.93 5.70 1.08Ga 18 20.3 14.7 17.1 19.5 20.2 17.5 17.2 18.9Rb 739 602 1010 522 691 676 559 595 589Sr 139 14.2 7.46 23 11.2 20.3 23.2 12.9 10.0Y 21.2 149 74.8 131 109 82.8 104 91.1 132Zr 170 64.4 82.7 83 89.0 78.2 85.8 69.8 64.0Nb 18.5 36.5 18.8 38.7 31.6 27.1 33.3 36.4 30.0Sn 141 29.6 187 20.2 26.5 18.9 13.7 15.1 13.3Ba 568 30.5 20.8 77.6 21.2 33.7 33.5 17.1 24.1Hf 5.04 4.68 4.99 5.65 6.27 4.96 4.57 4.73 5.04Ta 1.33 9.77 4.01 9.32 11.5 11.5 8.58 12.6 11.7W 208 4.84 9.22 4.51 211 161 3.82 17.9 3.3Pb 225 99.9 95.8 92.2 378 71.1 79.9 73.8 98.2Th 12.5 24.5 29.9 34.9 30.2 32.2 30.9 23.5 14.6U 3.58 30.7 26.0 32.5 26.4 23.6 26.5 25.9 26.9La 29.4 7.72 14.8 10.4 8.35 13.1 12.9 10.3 6.79Ce 57.9 21 35.8 25.6 22.5 31.6 30.9 25.8 17.4Pr 6.82 3.41 4.7 3.61 3.14 3.99 4.37 3.42 2.54Nd 26.5 17.6 19.9 15.6 13.8 15.7 19.4 14.4 12.5Sm 5.42 11.6 7.58 8.1 7.19 6.22 9.46 6.53 7.55Eu 1.41 0.14 0.14 0.16 0.08 0.13 0.15 0.09 0.04Gd 5.40 18.4 9.86 13.9 8.51 7.33 10.76 7.70 10.4Tb 0.79 3.5 1.78 2.71 1.89 1.54 2.29 1.71 2.48Dy 4.15 22.8 11.6 18.8 14.2 11.1 16.4 12.8 18.6Ho 0.89 4.77 2.59 4.48 3.08 2.31 3.33 2.76 4.14Er 2.24 13.4 7.34 12.8 9.87 6.92 10.0 8.54 12.9Tm 0.32 2.09 1.12 2.06 1.71 1.13 1.71 1.45 2.34Yb 2.08 13.5 7.24 14.1 12.72 7.34 11.2 10.1 16.6Lu 0.33 1.99 1.05 2.1 2.00 1.03 1.59 1.50 2.48Eu/Eu* 0.79 0.03 0.05 0.05 0.03 0.06 0.04 0.04 0.01(La/Yb)N 9.55 0.39 1.38 0.50 0.44 1.20 0.78 0.68 0.28∑REE 143.64 141.95 125.50 134.44 109.03 109.37 134.44 107.08 116.79

TE1,3 0.95 1.03 1.02 1.02 1.10 1.10 1.07 1.10 1.07Rb/Sr 5.32 42.39 135.39 22.70 61.71 33.28 24.07 46.08 58.80Nb/Ta 13.91 3.74 4.69 4.15 2.75 2.35 3.88 2.89 2.56

Table 4. Trace element concentrations (ppm) of the Piaotang quartz diorite and granite

Note: Eu/Eu* = 2 × EuN/(SmN + GdN); aData from Hua et al. (2003), other samples are from this study.Degree of the tetrad effect: TE1,3 = (t1 × t3)1/2 (Irber, 1999), where, t1 = (Ce/Cet × Pr/Prt)1/2 and t3 = (Tb/Tbt × Dy/Dyt)1/2, with Ce/Cet = CeN/(LaN

2/3 × NdN1/3), Pr/Prt = PrN/(LaN

1/3 × NdN2/3), Tb/Tbt = TbN/(GdN

2/3 × HoN1/3) and Dy/Dyt = DyN/(GdN

1/3 × HoN2/3).

area are considered to be Neoproterozoic sedimentaryrocks, including Tanxi gneiss in Nanxiong region andXunwu gneiss in Dingnan–Xunwu region (Fig. 1a). Inparticular, zircon U–Pb age and Hf isotope studies showthat these sedimentary rocks are mainly composed ofGrenville and Neoarchean clastic materials and also con-tain a number of Mesoproterozoic and small amount oflate Neoproterozoic and Mesoarchaean components (Yuet al., 2007; Wang et al., 2008). These materials are mainlyproduced by reworking of ancient crust with minor in-puts from juvenile crust (Fig. 6; Yu et al., 2007; Wang etal., 2008), and no Paleoproterozoic crustal basement hasbeen found in the western Cathaysia (Yu et al., 2008).

Zircon U–Pb dating and Hf isotopes of Piaotang granitoids 309

gneiss and Xunwu gneiss. This implies that Piaotangquartz diorite and granite were generated from similarsource rocks, their geochemical differences could becaused by fractional crystallization process. Consideringthe big time gap of ~280 Ma between the emplacementof Piaotang quartz diorite and granite, we therefore sug-gest that the Piaotang quartz diorite and granite were gen-erated by partial melting of the similar Neoproterozoiccrustal source at different time. The Paleoproterozoic Hfmodel ages (1.8–2.1 Ga) of the samples might be an av-erage age which resulted from mixing of continental ma-terial of different ages.

Tungsten mineralization and its relationship to graniticmagmatism

It is generally accepted that W and Sn mineralizationsare associated with anatectic granitoids with predominantS-type character, although many S-type granitoids arebarren and some I-type are associated in particular withW mineralizations (Tanelli, 1982). South China is a typi-cal area of peraluminous granitoid activity associated withW–Sn–Nb–Ta mineralization (Xu et al., 1984). Severalgeologic features as follows can genetically link Piaotangtungsten mineralization to the buried Early Yanshaniangranitic intrusion, and support that the ore-forming ma-terials and fluids are mainly produced by the differentia-tion of Early Yanshanian granitic magma at the late stageof evolution (Shan, 1976; Mei, 1985; Zhang, 1991). Thedeposits veins are distributed almost exclusively in theouter contact zone of the Early Yanshanian granite, andore-rich site is controlled by the spatial shape of granitebody. Major minerals of the deposit veins also occur inthe Early Yanshanian granite as accessory minerals. Fine-grained granitic veins may gradually transform to ore-bearing quartz veins. Oxygen isotope analysis showed that

the Early Yanshanian granite and the ore-bearing quartzveins had consistent δ18O values, which of 12.43‰ and12.18‰, respectively (Mei, 1985). Therefore, thePiaotang tungsten mineralization bears a close geneticrelation to the Early Yanshanian granitic activity.

The issue on the metallogeny age of Piaotang tung-sten deposits has been well constrained by a number ofgeochronological studies. Mu (1990) determined a K–Arage of 156.8 Ma for tungsten deposit veins; Li et al. (1993)obtained a Rb–Sr age of 150.2 ± 1.4 Ma from fluid inclu-sions in quartz; Liu et al. (2008) dated the muscovite fromquartz veins and yielded an 40Ar/39Ar age of 158.9 ± 1.4Ma; and Zhang et al. (2009) reported a 40Ar/39Ar age of152 ± 1.9 Ma for the muscovite from ores and a Re–Osage of 151.1 ± 8.5 Ma for molybdenite from ores. These

Fig. 9. Chondrite-normalized REE patterns (a) and Primitive mantle-normalized trace element diagrams (b) for the Piaotangquartz diorite and granite. The chondrite values are from Taylor and McLennan (1985), the primitive mantle values are fromMcDonough and Sun (1995). Data for the Early Mesozoic Wuliting granite are also shown for comparison (Qiu et al., 2004).

Fig. 10. Rb/Ba vs. Rb/Sr plot for the Piaotang quartz dioriteand granite. Also illustrated are the fields of the Wuliting graniteand Dajishan granite (original data are from Hua et al. (2003)and Qiu et al. (2004)). Symbols are same as in Fig. 8.

310 Z. He et al.

available ages indicate that the mineralization age wasapproximately in the range of 150–159 Ma, and the maxi-mum mineralization age is close to the age of buried gran-ite body determined in this study (158 ± 3 Ma). This pro-vides further evidence for the close relationship betweenthe tungsten mineralization and the buried EarlyYanshanian granite.

The most distinct feature of the Early Yanshanian gran-ite is highly differentiated. The extreme evolved natureis well reflected by the high Si, low Ti, Mg, Fe, Ca, Sr,Ba (Figs. 8 and 9), and very high Rb/Sr ratio ranging fromabout 23 to 135, which is similar to the tungsten miner-alization associated Dajishan granite situated in vicinityof the studied area (Fig. 10). Furthermore, their REE pat-terns display with pronounced tetrad effect (Fig. 9), indi-cating that they are highly fractionated with interactionof magma and fluids (Bau, 1996; Irber, 1999; Jahn et al.,2001). As emphasized by Jahn et al. (2001), the REE tet-rad effect is most visible in late stage of magma evolu-tion with strong hydrothermal interactions, and occurstypically in highly evolved magmatic systems which arerich in H2O, CO2 and elements such as Li, B and F and/orCl. Their atypical low Nb/Ta ratios (2.35–4.69) (Table 4)also demonstrate fluid-magma interaction (Green, 1995).Studies on the fluid inclusions in the wolframite-bearingquartz veins from the major mineralizing stage of Piaotangtungsten deposit also indicated that the ore-forming flu-ids consist of dominate magmatic water and minorgroundwater (Wang et al., 2008). So, it seems reasonablethat the tungsten mineralization in Piaotang is related tothe late hydrothermal stage of granite magma evolution,which is consistent with the previous suggestions on othertypical W–Sn deposit (Breiter et al., 1999; Qiu et al.,2004; Mao et al., 2009).

In contrast to buried Early Yanshanian granite, thePiaotang Early Paleozoic quartz diorite is barren in min-eralization of economic significance. Several observationssupport this idea, for example, W-bearing quartz veinsare merely located exclusively to the south of the body.Ore veins can be observed cutting through the body, show-ing clear chronological order. In addition, the majority ofveins are lower than the outcrop of quartz diorite in el-evation (Shan, 1976; Mei, 1985; Zhang, 1991). Our zir-con U–Pb dating of quartz diorite reveals a big time gapof ~280 Ma between its emplacement and the tungstenmineralization, which indicates that W mineralization wasnot associated to the quartz diorite, although the depositsveins occur in the vicinity of this intrusion. Furthermore,the Piaotang Early Paleozoic quartz diorite is an interme-diate-acidic igneous rock, and is characterized by lowconcentration of SiO2, total alkalis but high Rb/Sr ratioand high content of Al2O3, Fe2O3, MgO, CaO and P2O5,without the geochemical signatures of highly differenti-ated granite. It is geochemically similar to the Early

Mesozoic Wuliting granite that is also not related to themineralization of the Dajishan tungsten Mine (Figs. 8, 9and 10; Qiu et al., 2004). This might explain why theEarly Paleozoic quartz diorite is barren in mineralization,although zircon Hf isotopic data suggest that the quartzdiorite and Early Yanshanian granite may have the simi-lar magma source.

The role of intraplate tectonism in the metallogeny of thePiaotang Tungsten deposit

Why did the Early Paleozoic quartz diorite undergoonly low degree fractionations? An important foldorogeny in Early Paleozoic in South China resulted inthe formation of granitoids that are mainly distributed inthe areas of southern Jiangxi Province and Wuyi Moun-tain. They are usually in situ to semi-in situ rocks, andwere generated by decompressing melting of tectonicallyover-thickened crust in deep and closed non-extensionalenvironment (Zhou, 2003; Wang and Shen, 2003; Zenget al., 2008). By contrast, it is well constrained that thetectonic setting of South China in Early Yanshanian is anintraplate extensional regime (Zhou et al., 2006; Li et al.,2007; Chen et al., 2008). The Early Yanshanian granitoidsare mainly distributed in hinterland, extending northeast-erly discretely, with an exception that EW-trending in theNanling region. Minor amounts of Early Yanshaniansyenites, gabbros, and bimodal volcanic rocks are asso-ciated with the EW-trending granitoid belts (Zhou et al.,2006). All these exhibit distinct geodynamic regime ofcrustal melting controlled by asthenosphere upwelling (Heet al., 2007; Li et al., 2007).

Middle–Late Jurassic t ime is the importantmetallogenic period in SE China. The metallogeny mainlyencompasses two styles of ore systems, i.e., W–Snpolymetallic deposits; skarn and porphyry copper depos-its (Mao et al., 2009). These W–Sn polymetallic depositsare all associated with highly fractionated granitoids.Some of the granites have high Ga/Al values and Zr, Nb,Ce and Y concentrations, similar to the A-type granitoids(Zhu et al., 2008; Jiang et al., 2008). The skarn and por-phyry copper deposits associated with porphyries mainlyoccur in the northeastern Jiangxi Province. The famousDexing large-scale porphyry copper deposit is such a rep-resentative of them which is closely associated with EarlyYanshanian adakitic porphyries (Wang et al., 2006). Boththe two styles of ore systems are associated with theintraplate magmatic events, upwelling asthenosphericmantle played the dominant role in magma generation andrelated metallogeny (Wang et al., 2006; Zhu et al., 2008;Jiang et al., 2008; Pirajno et al., 2009).

As mentioned above, the spatially accompaniedPiaotang Early Paleozoic quartz diorite and EarlyYanshanian granite were produced by reworking of theNeoproterozoic crust, and they shared the same country

Zircon U–Pb dating and Hf isotopes of Piaotang granitoids 311

rocks of Cambrian strata. Thus the protolith compositionsand country rocks could not be the critical factors for theirdistinct metallogenic capacity. Their contrastingmetallogenic endowments can be ascribed to the differ-ent degrees of magma differentiation, and the extent ofmagmatic differentiation is ultimately constrained by thetectonic setting and the mechanism of magma generation.The Early Paleozoic quartz diorite was generated by de-compressing melting of over-thickened crust, while theEarly Yanshanian granite was generated by partial melt-ing of the similar crustal component induced by intra- orunderplating of mafic magmas under extensional regime.The upwelling asthenosphere provided sufficient heat forpartial melting of the crust through the intra- orunderplating of mafic magmas, and enhanced thegeothermal gradients. Thus the granitic magmas couldundergo significant differentiation to form the related Wmineralization (e.g., Breiter et al., 1999; Pirajno et al.,2009). Therefore by comparing the relationship betweentwo different stages of granitoid magmatism and W min-eralization in Piaotang deposit area, it is recognized thatthe regional tectonic setting and lithosphere dynamicsmight be the key factors in metallogenic capacity of SouthChina granite. In the future it is worthwhile to investi-gate whether or not there is plagioclase-rich accumula-tion differentiated from the early Yanshanian granitemagma in the deeper crust. The three-dimensional distri-bution of the buried granite is a critical factor in prospec-tive regional mineral exploration.

CONCLUSIONS

The crystallization age of the Piaotang quartz dioriteis 439 ± 2 Ma, which indicates that it was formed in theEarly Paleozoic rather than previously reported LatePaleozoic time. The age of buried granite is 158 ± 3 Ma.The Early Paleozoic quartz diorite and Early Yanshaniangranite have similar Paleoproterozoic zircon Hf modelages, and both of them were derived from Neoproterozoiccrust which contains ancient recycled materials. Throughintegration of the geological characteristics of Piaotangtungsten deposit and the information of ore-forming ages,this study provides further evidence for the close geneticrelationship between tungsten mineralization and buriedEarly Yanshanian granite. The Early Paleozoic quartzdiorite is not related to the mineralization. The contrast-ing features in metallogenic endowments can be ascribedto the different degrees of magma evolution. The EarlyYanshanian granite is highly differentiated and showsmany aspects of the features of tungsten-tin polymetallicdeposits related granitoids in South China. The extentsof magmatic evolution are controlled by the tectonic set-ting and the genetic mechanism of granitoid magma. Inessence, the regional tectonic setting and lithosphere dy-

namics might be the key factors in the mineralization ca-pacity of granitoids in South China.

Acknowledgments—We are thankful to the staff of geologicalsurvey department of Piaotang Mine in Jiangxi Province forfield-work assistance, and to Tang, H. F. for his assistance withzircon Hf isotope analysis. Dr. Tsuyoshi Iizuka, Dr. Wang Qiangand editor Dr. Katsuhiko Suzuki are thanked for their carefulreview which improved the paper. This work was supported byNSF of China Grant (40730313), China Geological SurveyProject (1212010632100) and Jiangsu Innovation Project forPhD Candidates (CX08B_022Z).

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