Journal of Asian Earth Sciences 115 (2016) 214–227
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Zircon U–Pb and Lu–Hf isotopic and geochemical constraints on the origin of the paragneisses from the Jiaobei terrane, North China Craton Houxiang Shan a,b,⇑, Mingguo Zhai a,c, Xiyan Zhu c, M. Santosh d, Tao Hong c, Songsheng Ge a,b a
State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China University of Chinese Academy of Sciences, Beijing 100049, China c Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China d China University of Geosciences (Beijing), Beijing 100083, China b
a r t i c l e
i n f o
Article history: Received 8 June 2015 Received in revised form 14 September 2015 Accepted 8 October 2015 Available online 8 October 2015 Keywords: Paragneisses Geochemistry Detrital zircon U–Pb–Hf isotopes Protolith Tectonic setting North China Craton
a b s t r a c t Clastic sedimentary rocks are important tracers to understand the evolution of the continental crust. Whole-rock major and trace element data, zircon U–Pb dating and Hf isotopic data for the paragneisses from the Jiaobei terrane are presented in this study in order to constrain their protoliths, provenance and tectonic setting. The paragneisses are characterized by enrichment in Al2O3 and TiO2, negative DF (DF = 10.44 0.21SiO2 0.32Fe2OT3 0.98MgO + 0.55CaO + 1.46Na2O + 0.54K2O) values and the presence of aluminum-rich metamorphic minerals (e.g., garnet and sillimanite). Together with the mineral assemblages and zircon features, it can be inferred that the protoliths of these rocks are of sedimentary origin. The K–A (A = Al2O3/(Al2O3 + CaO + Na2O + K2O), K = K2O/(Na2O + K2O)) and log(Fe2O3/K2O)–log (SiO2/Al2O3) diagrams indicate that they belong principally to clay–silty rocks with some contributions from graywacke. A series of geochemical indexes, such as the widely employed CIA (CIA = [Al2O3/ (Al2O3 + CaO⁄ + Na2O + K2O)] 100; molar proportions) and ICV (ICV = (Fe2O3 + MnO + MgO + CaO + Na2O + K2O + TiO2)/Al2O3) values, and the A–CN–K diagram for the paragneisses indicate relatively weak weathering in the source rocks and negligible post-depositional K-metasomatism. In addition, their REE patterns, low Cr/Zr (0.61–1.99), high Zr/Y (4.81–23.59) and Th/U (3.21–40.67) ratios, the low to moderate contents of Cr (197–362 ppm) and Ni (6.68–233 ppm), and source rock discrimination diagrams collectively suggest that the sediments of the protoliths of the paragneisses in the Jiaobei terrane were derived from the source with intermediate–acidic composition, probably granitic-to-tonalitic rocks. In combination with geochronological and isotopic studies on the paragneisses and the basement rocks in the Jiaobei terrane, it is suggested that the Archean–early Paleoproterozoic granitic rocks in the Jiaobei terrane possibly provided the most important source materials. In addition, the protoliths of the paragneisses might have been deposited during 2.47–2.42 Ga. High and heterogeneous ICV values of the paragneisses could imply a chemically immature source. A number of geochemical indicators and tectonic discrimination diagrams together indicate an island arc or active continent margin setting for the deposition of the protoliths of the paragneisses in the Jiaobei terrane. Together with the nearly contemporaneous igneous rocks, it can be inferred that the convergent margin setting was possibly operative during the Late Neoarchean–Early Paleoproterozoic transition in the Jiaobei terrane. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction Clastic sedimentary rocks have long been widely employed in previous investigations to understand the evolution of the
⇑ Corresponding author at: State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China. E-mail address:
[email protected] (H. Shan). http://dx.doi.org/10.1016/j.jseaes.2015.10.003 1367-9120/Ó 2015 Elsevier Ltd. All rights reserved.
continental crust (Mclennan and Taylor, 1983, 1991; Cox et al., 1995; Long et al., 2008; Liu et al., 2012). On one hand, they are common constituents of the Earth’s crust, the geochemistry of which can provide important information on the compositional evolution of continental crust (Fridman and Sanders, 1978; Taylor and McLennan, 1985; McLennan and Taylor, 1991; Condie, 1993; Gao et al., 1998; Reading, 2009; Chatterjee et al., 2013; Eriksson et al., 2013; Eriksson and Condie, 2014). On the other hand, clastic sedimentary rocks have been prevalent topics because their
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geochronology and geochemistry are powerful tools to constrain their potential provenance (Taylor and McLennan, 1985; Roser and Korsch, 1988; Griffin et al., 2004; Zhou et al., 2012) and reconstruct the tectonic settings of depositional basins (Bhatia, 1983, 1985; Bhatia and Crook, 1986; Roser and Korsch, 1986; Mclennan and Taylor, 1991; Wang et al., 2012). In addition, the Archean–Proterozoic transition (2.5 Ga), is an important period in the Earth’s evolution history and has witnessed many significant events or great changes globally (e.g., Belousova et al., 2010; Condie, 2013, 2014; Condie and Kröner, 2013 and references therein). However, the geodynamic settings of many terranes around the world at 2.5 Ga remain obscure. Therefore, detailed studies on the clastic sedimentary rocks during the Archean– Proterozoic transition can provide important clues to the crust evolution at 2.5 Ga. The Jiao-Liao-Ji Belt (JLJB), situated in the eastern margin of the North China Craton (NCC), has commonly been considered as the late Paleoproterozoic mobile belt that has unified the eastern NCC. However, its tectonic nature and formation process remain controversial, although extensive geochronological and geochemical studies on various rocks have been made within the belt (e.g., Li et al., 2003, 2006, 2011, 2012; Faure et al., 2004; Zhao et al., 2005, 2012; Li and Zhao, 2007; Tam et al., 2011; Shan et al., 2013, 2015a,b). In addition, the crustal evolution history from Neoarchean to early Paleoproterozoic is another major question closely related to the final formation of the JLJB. The provenance, metamorphic conditions and tectonic implications of the Neoarchean–Paleopro terozoic paragneisses, which constitute one of the dominant lithologies, can provide significant clues to address the topic (Shen et al., 1990; Qian and Li, 1999). Situated in the southwestern segment of the JLJB, the Jiaobei terrane preserves well-developed high-grade metamorphic basement rocks, including widespread paragneisses (Shandong Bureau of Geology and Mineral Resources, SBGMR, 1991), thus providing a very good opportunity to constrain the nature and evolution of the JLJB. Recently, detailed studies on the detrital zircon U–Pb dating and geochemistry of these rocks have been carried out to evaluate the provenance, geodynamic processes and crustal evolution (Wan et al., 2006; Li et al., 2007; Zhou et al., 2008a; Chu et al., 2011; Liu et al., 2013b), which mostly focused on the Paleo- to Neoproterozoic Jingshan, Fenzishan, Zhifu and Penglai groups. In contrast, the Archean–Paleoproterozoic paragneisses are poorly studied and only a limited number of data have been obtained. In this study, a detailed zircon U–Pb isotopic, zircon Hf isotopic and geochemical analyses of the Late Neoarchean–Early Paleoproterozoic paragneisses were carried out to interpret the nature of the protoliths, provenance and tectonic setting and thus to place important constraints on the tectonic history of the Jiao-Liao-Ji Belt. The results provide further insights into the Precambrian crustal evolution of the eastern margin of the NCC.
2. Geological setting The NCC has a complicated evolution history and witnessed multi-stage crustal growth events, recording nearly all the significant geological, tectonic and metallogenic events since ca. 3.8 Ga (Wu et al., 2008; Zhai and Santosh, 2011; Zhai, 2014 and references therein). The Jiaobei terrane, situated in the eastern NCC (Fig. 1a), is generally considered as the southwestern part of the Jiao-Liao-Ji belt (Zhao et al., 2005; Zhao and Zhai, 2013). To the northwest, it is bordered by the Tan-Lu Fault and to the southeast by the Wulian-Yantai Fault (Fig. 1b). The area consists dominantly of Precambrian metamorphic and deformed basement rocks, Mesozoic magmatic rocks and Mesozoic–Cenozoic sedimentary rocks (SBGMR, 1991). The Precambrian basement rocks are
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dominated by the Archean supracrustal rocks, granitic gneisses and minor mafic rocks, Paleoproterozoic Fenzishan and Jingshan groups, the low-grade metamorphic Zhifu Group, and Neoproterozoic low-grade metamorphic Penglai Group (Fig. 1b; e.g., SBGMR, 1991; Zhou et al., 2004; Tang et al., 2007; Jahn et al., 2008). Compared with the widely-distributed TTG (Tonalite–Trondhje mite–Granodiorite) gneisses in the Jiaobei terrane, the high-grade metamorphic supracrustal rocks are subordinate and exposed sparsely within TTG gneisses as enclaves or tectonic lenses. They consist mainly of amphibolites, biotite-plagioclase gneisses, felsic granulites and banded iron formations (BIFs) (SBGMR, 1991; Wang and Yan, 1992; Wan et al., 2006; Tang et al., 2007). Recently, zircon studies of these supracrustal rocks have revealed three episodes of magmatic ages at 2.9, 2.7 and 2.5 Ga and two metamorphic ages at 2.5 and 1.8–1.9 Ga (Zhang et al., 2003; Tang et al., 2007; Jahn et al., 2008; Zhou et al., 2008a; Wang et al., 2014a; Wu et al., 2014a,c; Shan et al., 2015a). The granitic (TTG and granite) gneisses, which underwent strong metamorphism and deformation processes, are exposed mainly in the Qixia area of the Jiaobei terrane (Fig.1b). Recent zircon U–Pb data obtained using LA-ICPMS and SHRIMP methods also yielded three phases of magmatic ages (2.9, 2.7 and 2.5 Ga; Tang et al., 2004, 2007; Jahn et al., 2008; Zhou et al., 2008a; Liu et al., 2011, 2013a; Xu et al., 2011; Wu et al., 2014a,c) and two clusters of metamorphic ages (2.5 and 1.85–1.95 Ga; e.g., Liu et al., 2011, 2013a; Wu et al., 2014a,c; Shan et al., 2015a,b). The TTG gneisses with different ages have distinct isotopic characteristics, indicating different origins (e.g., Jahn et al., 2008; Wu et al., 2014b). The minor mafic rocks are limitedly distributed and mainly occur as intrusions or enclaves within the granitic gneisses. Many of them record the 1.85–1.95 Ga high-pressure granulite-facies metamorphism that formed the mafic granulites (Liu et al., 2010, 2013c; Tam et al., 2011, 2012b). Unconformably overlying the TTG gneisses are the Paleoproterozoic Fenzishan and Jingshan groups. They are composed dominantly of high-Al biotite schists, granulites, marbles and graphite schists. Lying in southern and eastern part of the Jiaobei terrane (Fig. 1b), the Jingshan Group was subjected to upper amphibolite- to granulite-facies metamorphism, whereas metamorphism of much lower grade with only upper greenschist to amphibolite facies was reflected in the Fenzishan Group in the northern and western section of the area (Fig. 1b). The SHRIMP zircon dating revealed a major magmatic age population of 2.9– 2.2 Ga (Wan et al., 2006), and a metamorphic age population of 1.85–1.95 Ga (Zhou et al., 2004, 2008b; Wang et al., 2010; Tam et al., 2011, 2012a,b), indicating that the two groups might have been deposited during 2.2–1.9 Ga (Wan et al., 2006). The Zhifu Group, chiefly located on the Zhifu Island of the Jiaobei terrane (Fig. 1b), from the base to the top comprises the Laoyeshan, Bingying, and Dongkou formations. The rock types include K-feldspar quartzites, tourmaline quartzites, muscovite quartzites, muscovite-quartz schists and quartzite conglomerates, which were subjected to greenschist- to amphibolite-facies metamorphism (SBGMR, 1991). Whether the depositional age of the Zhifu Group is Paleoproterozoic (Yang et al., 2001; Liu et al., 2013b) or Mesoproterozoic (Wang et al., 2011) remains controversial. As the youngest part of the Precambrian basement in the Jiaobei terrane, the Neoproterozoic low-grade (greenschist facies) Penglai Group mainly includes crystalline limestones, slates and quartzites, which unconformably overlies the Jingshan and Fenzishan groups (Fig. 1b; SBGMR, 1991; Zhou et al., 2008a). Although the depositional and tectonic affinities of the Penglai Group remain ambiguous (Li et al., 2007; Zhou et al., 2008a; Chu et al., 2011), its deposition age is commonly taken as 1.1–0.8 Ga (Li et al., 2007; Chu et al., 2011).
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Fig. 1. (a) Tectonic subdivisions of the North China Craton (modified after Zhao et al., 2005). (b) Simplified geological map of the Jiaobei terrane (modified after Shandong Bureau of Geology and Mineral Resources (SBGMR), 1991; Zhou et al., 2008a,b, 2012). YB: Yinshan Block; KB: Khondalite Belt; OB; Ordos Block; WB: Western Block; TNCO: Trans-North China Orogen; EB: Eastern Block; JLJB: Jiao-Liao-Ji Belt.
3. Samples and analytical methods Rock samples selected for the present study are the paragneisses in the Archean–Paleoproterozoic supracrustal rocks, which were collected from the depth range of 50–700 m (Fig. 2) of the drill hole (Z2963) in Laizhou area in the Jiaobei terrane (Fig. 1b). They were subjected to upper amphibolite- to granulite-facies metamorphism and are composed mainly of plagioclase (35– 45%), quartz (20–25%), biotite (10–15%), garnet (5–15%) and in places minor K-feldspar (<5%) and sillimanite (<5%). Some garnet porphyroblasts contain biotite + quartz + feldspar inclusions and are corroded and replaced by the latter three mineral grains (Fig. 3). In some samples, the minerals are strongly foliated. The detailed analytical methods used in this study are as follows. 3.1. Major and trace elements Rock samples were first crushed and pulverized in an agate mill for geochemical analysis. The whole-rock major element compositions were determined by XRF-1500 X-ray fluorescence spectrometry using fused glass disks at the State Key Laboratory of Lithospheric Evolution in the Institute of Geology and Geophysics, Chinese Academy of Sciences (IGGCAS), Beijing, China. About 0.50 g rock
powder of each sample was firstly ignited at 1000 °C for about 1 h to determine the loss of ignition (LOI) and then fused with 3–4 drops of lithium tetraborate. The analytical accuracy was better than 5% as indicated by international rock standards (USGS) AGV-1. Trace elements (including rare earth elements) were determined by ICP-MS (Agilent 7500a) at IGGCAS after more than 5-days acid digestion of 50 mg rock powder of each sample in Teflon bombs. Analyses of rock standards indicate precision and accuracy better than 5% and further details can be found in Liu et al. (1996). 3.2. Zircon LA-ICP-MS U–Pb dating Zircons were first extracted by heavy liquid and magnetic separation techniques and then handpicked under a binocular microscope. The zircon grains were mounted in epoxy resin and polished until the grain centers were exposed. High definition cathodoluminescence (CL) images were taken by using a Gatan MonoCL3 cathode light emitters on JEOL JXA-8100 Electron Microprobe at IGGCAS. Zircon U–Pb dating were carried out at the State Key Laboratory of Lithospheric Evolution of the IGGCAS using an Agilent 7500a quadruple (Q)-ICPMS equipped with a 193 nm excimer ArF laserablation system (MicroLas, Germany). Either a 30 or 44 lm spot
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4. Results 4.1. Zircon U–Pb dating and Hf isotopes Detrital zircon U–Pb isotopic data and CL images of representative zircons for two paragneisses collected from the Jiaobei terrane are presented in Supplementary Table S1 and shown in Fig. 4, respectively. From these analyses, only the concordant or nearly concordant zircons with age discordance <15%, were employed to make plots in binned frequency histograms. Hf isotopic data are listed in Supplementary Table S2. Detrital zircons from the samples are rounded or subhedral short prisms with average grain sizes of 50–150 lm. Some zircons show relatively clear oscillatory zoning with or without rims indicating magmatic origin whereas the rest are rounded, structureless or with blurred irregular zoning structures indicating strong recrystallization (Fig. 4). Compared with the latter, the magmatic zircons are characterized by higher Th/U ratios (>0.1; Table S1), positive Ce anomalies, negative Eu anomalies and HREE enrichment. In addition, the metamorphic zircons generally show relatively brighter CL images (Fig. 4), possibly resulting from the loss of Th and U during the process of metamorphism.
Fig. 2. Simplified lithological profile of the upper segment (0–1000 m) of the drill hole (Z2963) in the Jiaobei terrane and the sample locations.
size was used. The detailed analytical procedures are described in Xie et al. (2008). Two standard zircon 91500 and one NIST610 measurements were made after every 10 sample analyses. All analyzed 207 Pb/206Pb, 206Pb/238U, 207Pb/235U and 208Pb/232Th ratios were calculated using the GLITTER 4.0 program (Macquarie University). Concordia diagrams and the age calculations were made using Isoplot 3.0 with 1r-error and 95% confidence levels (Ludwig, 2003).
3.3. Zircon Lu–Hf isotope analyses The in situ zircon Hf isotopic analyses were conducted at the State Key Laboratory of Lithospheric Evolution, IGGCAS. The detailed analytical technique was the same as described by Wu et al. (2006). The analyses were performed using a Neptune MCICPMS equipped with a GeoLas 200 M ArF excimer 193 nm laser ablation system with either a 44 lm or a 60 lm spot size. The domains for Hf isotopic analyses were the same as where the U–Pb dating analyses were carried out. During the analyses, the 176Hf/177Hf ratios of the standard zircon (GJ) were 0.282023 ± 0.000011 (2r, n = 30), a range consistent with the commonly accepted values obtained by the solution method and in situ studies (Woodhead and Hergt, 2005; Xie et al., 2008), after taking the analytical errors into account. The present day chondritic ratios of 176Hf/177Hf = 0.282785 and 176 Lu/177Hf = 0.0336 (Bouvier et al., 2008) with a decay constant for 176 Lu of 1.867 10 11 (Soderlund et al., 2004) were used to calculate the eHf(t) values. The depleted mantle line is defined by present-day 176Lu/177Hf ratio of 0.0384 and 176Hf/177Hf ratio of 0.28325 (Griffin et al., 2000), and a 176Lu/177Hf value of 0.015 for the average continental crust (Griffin et al., 2002) was used for calculation.
4.1.1. Sample Z2963-11 A total of 68 U–Pb analyses were conducted on 68 zircon grains. Spots 30 and 37 are reversely discordant (Fig. 5a), possibly due to uranium loss or redistribution of radiogenic Pb in the subsequent metamorphisms. Most of the other spots are concordant or nearly concordant (discordance within ±10%), yielding apparent 207 Pb/206Pb ages of 1848–2545 Ma (Fig. 5a and Table S1). Some spots have high Th/U ratios (most > 0.4) (Table S1) and relatively clear oscillatory zoning (Fig. 4), implying their magmatic origin. They show apparent 207Pb/206Pb ages of 2433–2545 Ma (Fig. 5a and Table S1), with a major peak at 2456–2499 Ma on the apparent 207 Pb/206Pb age histogram for concordant spots. The other analyses were performed on the metamorphic domains, which have low Th/U ratios (<0.1) (Table S1) and blurred irregular zoning structures or structureless (Fig. 4), and yielded apparent 207Pb/206Pb ages of 1848–2417 Ma (Fig. 5a and Table S1). The apparent 207 Pb/206Pb age histogram for concordant spots broadly shows a major age peak of 1805–1909 Ma and some minor peaks (Fig. 5a). Lu–Hf isotopic analyses were performed on 57 zircon domains of magmatic origin or metamorphic origin. The magmatic zircons from this sample have variable 176Lu/177Hf ratios of 0.000054– 0.000411 (average 0.000159) but relatively homogenous 176 Hf/177Hf ratios of 0.281315–0.281444 (average 0.281370) (Table S2). The eHf(t) values range from +2.59 to +8.16 (Fig. 6; Table S2), with TDM2 model age spectra varying from 2486 to 2784 Ma (Table S2). In comparison with the magmatic zircons, the metamorphic zircons from the sample have similar 176Lu/177Hf ratios (0.000054–0.000533, average 0.000159) but higher 176 Hf/177Hf ratios (0.281811–0.281306, average 0.281513), with their eHf(t) values and TDM2 model ages varying from 8.15 to +8.69 and 2065 to 3026 Ma, respectively (Table S2). 4.1.2. Sample Z2963-38 A total of 62 U–Pb analyses were performed on 62 zircon grains. These spots are distributed along a discordia line that intercepts the concordant curve at 2455 ± 9 Ma (MSWD = 7.8; Fig. 5b). Among them, 31 spots are concordant or nearly concordant (discordance within ±15%), yielding apparent 207Pb/206Pb ages of 2384–2517 Ma (Fig. 5b and Table S1). Except for 8 metamorphic domains ( 2, 3, 11, 18, 20, 32, 34 and 66), the others are all magmatic origin. In the binned frequency histogram (Fig. 5b), they display two peaks at 2442 and 2487 Ma. Taking
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Fig. 3. Photomicrogrpahs of the paragneisses from the Jiaobei terrane, showing the mineral assemblages of plagioclase + quartz + biotite + garnet ± sillimanite ± K-feldspar and the garnet porphyroblast corroded and replaced by other mineral grains. (a, b) – Z2963-03; (c, d) – Z2963-11; (e) – Z2963-38; (f) – Z2963-41. (+) and ( ) mean cross and plane polarized light, respectively. Mineral abbreviations: Pl – Plagioclase, Qtz – Quartz, Bt – Biotite, Grt – Garnet, Sil – Sillimanite, Fsp – Feldspar.
the analytical errors into consideration, the upper intercept age of 2455 Ma is broadly consistent with the younger peak of 2442 Ma. Lu–Hf isotopic analyses were made on the zircon domains that have been performed zircon U–Pb dating. The Lu–Hf analyses on detrital magmatic zircons from this sample have 176Lu/177Hf ratios from 0.000003 to 0.002111 (average 0.000097) and 176Hf/177Hf ratios from 0.281023 to 0.281524 (Table S2). The eHf(t) values range from negative to positive ( 0.34 to +8.38) (Fig. 6; Table S2) with TDM2 model ages of 2487–3012 Ma (Table S2), possibly indicating interaction between older continental crust and juvenile material. Compared with the magmatic zircons, the metamorphic zircons from the sample have lower 176Lu/177Hf ratios (0.000004– 0.000533, average 0.000037) but higher 176Hf/177Hf ratios (0.281129–0.282340) (Table S2). Their eHf(t) values vary from 8.15 to +8.69 with TDM2 model ages from 2065 to 3219 Ma (Table S2). 4.2. Geochemistry Geochemical compositions of the studied rocks are listed in Supplementary Tables S3 and S4. The samples have variable SiO2 (47.06–67.32 wt.%), Fe2OT3 (4.36–16.39 wt.%), MgO (1.28–7.34 wt. %), CaO (1.39–6.10 wt.%), Na2O (1.60–3.13 wt.%), K2O (0.68– 3.50 wt.%) and relatively high TiO2 (0.47–1.39 wt.%) contents. They have broadly similar SiO2/Al2O3 (3.04–5.03) but highly variable Fe2OT3/K2O ratios (1.54–10.21) (Fig. 7; Table S3). SiO2,
TiO2 and MnO contents in most analyzed samples are similar to those of the AUCA (Archean Upper Crust Average; Taylor and McLennan, 1985), however, there are systematic negative anomalies at Al2O3, CaO, MgO and Na2O and variable gains of Fe2OT3 and K2O. The rare earth element (REE) patterns of the paragneisses are plotted in Fig. 8a with the values of AUCA also shown for comparison and the corresponding REE data are given in Supplementary Table S4. Although they show various contents of La (13.6– 106 ppm), Gd (3.17–9.23 ppm), Yb (1.27–6.35 ppm) and total REE concentrations (108–466 ppm), their moderate to strong enrichments in LREE ((La/Yb)N = 4.21–55.5), flat to moderate HREE patterns ((Gd/Yb)N = 1.01–5.57) and slightly to moderately negative Eu anomalies (Eu/Eu⁄ = 0.45–0.92) in the samples are similar to those of the AUCA (Fig. 8a; Taylor and McLennan, 1985). Concentrations of LILEs (Large ion lithophile elements) of the samples in the present study are variable (Table S4) but they show similar patterns with those of AUCA on the primitive-mantle normalized trace element diagram (Fig. 8b). However, it is not the case for the HSFEs (High field strength elements). The samples show different degrees of positive or negative anomalies in HFSEs, and almost all of them are slightly enriched in Y, Zr and Hf when compared with those of AUCA, possibly due to the enrichment of garnet and zircon in the samples (Fig. 8b; Dostal and Keppie, 2009). In addition, most of the samples have similar or higher contents of ferromagnesian elements (such as Cr, Co and Ni) in comparison
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Fig. 4. Representive cathodoluminescence (CL) images of detrital zircons from the paragneisses in the Jiaobei terrane. The circles show positions of U–Pb and Hf analytical spots with corresponding 207Pb/206Pb ages and eHf(t) values.
with those of the AUCA (Table S4; Taylor and McLennan, 1985). The exceptions are samples Z2963-03, Z2963-08 and Z2963-38 with relatively lower Co and Ni contents (Table S4), suggesting less inputs of mafic source than those in other samples, which is consistent with the relatively higher SiO2 contents in samples Z2963-03, Z2963-08 and Z2963-38 (Table S3). 5. Discussion Although the samples in the present study were subjected to upper amphibolite- to granulite-facies metamorphism and mobile components such as K2O and Na2O might have undergone redistribution during the process of metamorphism, their contents and the ratios of them to other elements can indeed provide significant information on the protolith, provenance and tectonic setting (e.g., Shaw, 1972; Roser and Korsch, 1986). Therefore, we mainly use the immobile elements in the following discussion, with some useful plots and functions containing the mobile elements and their ratios employed as a reference. 5.1. Nature of the protolith The rocks in the present study are characterized by enrichment in Al2O3 and TiO2, depletion in CaO, and the presence of aluminumrich metamorphic minerals (e.g., garnet and sillimanite). These features are consistent with a sedimentary origin (Fig. 9a). The mineral assemblages in the samples are similar to those of the supracrustal rocks collected from other supracrustal belts (e.g., Dong et al., 2014). Some commonly used index calculation and discrimination diagrams also indicate that these rocks show the affinity to sedimentary rocks in protolith. DF function (DF = 10.44– 0.21SiO2 0.32Fe2OT3 0.98MgO + 0.55CaO + 1.46Na2O + 0.54K2O) has been proved to be valid to discriminate between the protolith of orthogneisses and paragneisses (Shaw, 1972). For the samples in this study, the DF values are mostly negative (average 2.23) (Table S3), showing the affinity of paragneisses. Furthermore, in
various elemental discrimination diagrams, such as the K–A diagram (A = Al2O3/(Al2O3 + CaO + Na2O + K2O), K = K2O/(Na2O + K2O); Fig. 9b), the samples occupy the field of sedimentary rocks. Therefore, all these lines of evidence suggest that the samples in the present study are of sedimentary origin. Herron (1988) proposed that Fe2O3/K2O and SiO2/Al2O3 ratios are helpful discriminators in identifying different types of sedimentary rocks. In the log(Fe2O3/K2O)–log(SiO2/Al2O3) diagram, the studied rocks mainly plot in the domain of Fe-rich shale with a few in the wacke area (Fig. 7), suggesting that these rocks were derived principally from clay–silty rocks with some contributions from graywacke.
5.2. Source weathering history As clastic sedimentary rocks generally experience a long geological process since the formation of sediments, their chemical composition is easily changed by such geological factors as source rock composition, the intensity of weathering and sorting during transportation and deposition, and finally post-depositional weathering (McLennan, 1989; Cullers et al., 1997; Roddaz et al., 2006). Therefore, an evaluation of the effects of these processes needs to be made before using their geochemistry to infer the nature of source rocks and tectonic setting of the deposition basin. The most widely used chemical index to quantitatively measure the intensity of source-area weathering is the Chemical Index of Alteration (CIA; Nesbitt and Young, 1982; Taylor and McLennan, 1985; Nesbitt et al., 1996). The CIA index is used to quantify the degree of feldspar degradation to clay minerals relative to unaltered protolith and is expressed as: CIA = [Al2O3/(Al2O3 + CaO⁄ + Na2O + K2O)] 100 (molar proportions), where CaO⁄ represents the CaO content in the silicate fraction. As in this study CO2 data are not available resulting in the impossibility to obtain CaO⁄, we have regarded the values of CaO as CaO⁄ if CaO < Na2O and taken the contents of Na2O as CaO⁄ if CaO > Na2O (Roddaz et al., 2006). Generally, CIA values range from 50 (unaltered rocks) to 100
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+ Na2O + K2O + TiO2)/Al2O3. Clastic sedimentary rocks with higher proportion of clay minerals will have low ICV values (generally < 1.0) and could suggest a mature source, whereas those with high ICV values (generally > 1.0) possibly imply a chemically immature source in active margin settings (Fig. 11). The paragneisses from this study display a relatively large range of ICV values from 1.22 to 3.46 (Table S3), which reveals a chemically immature source and indicates that the protoliths of these rocks were deposited in an active margin setting (Fig. 11). These conclusions are further evidenced by their distribution trend in the bivariate plots of HFSE such as Th/Sc–Zr/Sc diagram (Fig. 10b), in which they display a trend of compositional variation rather than sediment recycling (McLennan et al., 1993). 5.3. Provenance
Fig. 5. Concordia diagrams for detrital zircon U–Pb dating of the paragneisses from the Jiaobei terrane (blue circles and red circles represent magmatic domains and metamorphic domains, respectively). The age histogram for the concordant detrital zircons ((a) – all the zircons; (b) – magmatic zircons) of each sample is also shown. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
(strongly weathered rocks), with unweathered basalts and granitoids characterized by CIA values of 30–45 and 45–55, respectively. The paragneisses in our study have CIA values varying between 51 and 65 (Table S3), suggesting relatively weak weathering in the source rocks (Figs. 10a and 11). The extent of chemical weathering can be further revealed by using the triangular A (Al2O3)–CN (CaO⁄ + Na2O)–K (K2O) diagram (Fig. 10a) produced with the molar ratios of the elements. In the diagram are also plotted several mineral compositions for reference (Nesbitt and Young, 1984). The paragneisses from the Jiaobei terrane do not show obvious parallelism with the A–CN boundary, indicating relatively weak plagioclase alteration (Fig. 10a). Similarly, they do not distribute along the arrow of K-metasomatism in the A–CN–K diagram, suggesting negligible post-depositional K-metasomatism (Fig. 10a). In addition, the A–CN–K diagram also suggests the source rocks with granitic-to-tonalitic composition for the paragneisses in this study (Fig. 10a). Maturity of the source material of clastic sedimentary rocks can be reflected by Index of Compositional Variability (ICV; Cox et al., 1995), which is expressed by ICV = (Fe2O3 + MnO + MgO + CaO
It is commonly considered that large ion lithophile elements (LILE), such as Cs, Ba, Rb, Sr, Na and Pb are mobile during alteration and metamorphism. By contrast, the major elements (Fe, Al and Ti), the HFSE (Nb, Ta, Zr and Hf), most of the REE (except Ce and Eu) and some transition metals (Cr, Ni, and Sc) are relatively immobile and can survive during alteration and metamorphism, and thus can better preserve the information on compositional characteristics of the source rocks (Taylor and Mclennan, 1985; Cullers et al., 1988; McLennan and Taylor, 1991). Therefore, we try to employ these immobile elements and their ratios to derive information about the provenance of the paragneisses in the present study. In the chondrite-normalized REE pattern diagram (Fig. 8a), these paragneisses mostly display moderate to strong enrichment in LREE ((La/Yb)N = 4.21–55.5), relatively flat HREE patterns ((Gd/ Yb)N = 1.97 on average) and slightly to moderately negative Eu anomalies (Eu/Eu⁄ = 0.45–0.92), showing close affinity to the composition of Archean upper crust. The samples also show a number of other similarities to ACUA (see Section 4.2), suggesting the presence of Archean upper crust material in the sediment source. Therefore, it can be inferred that they were derived from source rocks with felsic to intermediate composition (Slack and Stevens, 1994). Moreover, Cr and Zr contents represent the relative amounts of chromite and zircon, respectively, thus the Cr/Zr ratio can be linked to the relative proportion of contributions from mafic
Fig. 6. eHf(t) vs. 207Pb/206Pb age (Ma) for the magmatic (detrital) zircons from the paragneisses and Neoarchean–early Paleoproterozoic granitic rocks in the Jiaobei terrane. Data for Z2963-21 and Z2963-30-1 are from Shan et al. (submitted for publication).
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and Th/U (3.21–40.67) ratios are also distinct from those of Archean basalts, but are similar to the corresponding ratios from Archean TTGs and granites (Wronkiewicz and Condie, 1987, 1989; Condie and Wronkiewicz, 1990; Condie, 1993), indicating that the sediments of the protoliths of the paragneisses were derived mainly from an intermediate to silicic source. Moreover, the low to moderate contents of Cr (197–362 ppm) and Ni (6.68– 233 ppm) in the paragneisses are consistent with the dominance of intermediate to silicic rocks and minor mafic materials in the source region (Garver et al., 1996). These inferences mentioned above can be further supported by their high La/Sc (0.61–7.85, 2.15 on average) and La/Co (0.40–4.02) ratios (Cullers, 2000). On the source rock discrimination diagram based on major elements, the samples principally plot in the fields of intermediate–acidic igneous provenance (Fig. 12; Roser and Korsch, 1988). This is also ⁄ evidenced by the Al2O3–Fe2OT⁄ 3 2–MgO 2 diagram, in which the samples in the present study plot in or near the field of the Neoarchean–early Paleoproterozoic granitic rocks in the Jiaobei terrane (not shown). In addition, most of the magmatic detrital zircons have subhedral prismatic shapes and magmatic oscillatory Fig. 7. Classification diagram for the paragneisses from the Jiaobei terrane using log (Fe2O3/K2O) vs. log(SiO2/Al2O3) of Herron (1988).
and felsic source materials (Wronkiewicz and Condie, 1989). Low Cr/Zr (0.61–1.99) ratios lie between those of Archean TTG–granite and shale sources, and are far less than the values of basalt– komatiite sources (Condie, 1993). Besides, high Zr/Y (4.81–23.59)
Fig. 8. Chondrite-normalized REE patterns (a) and PM-normalized spidergram (b) for the paragneisses from the Jiaobei terrane. PM and chondrite values are from McDonough and Sun (1995).
Fig. 9. (a) TiO2 vs. SiO2 and (b) K2O/(K2O + Na2O) vs. Al2O3/(Al2O3 + CaO + K2O + Na2O) diagrams for the paragneisses from the Jiaobei terrane.
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Paleoproterozoic granitic gneisses in the Jiaobei terrane (Fig. 6; Table S2; Liu et al., 2013a; Wu et al., 2014c; Zhang et al., 2014; Shan et al., 2015b) further support the above inference. Therefore, given all the above source indicators from geochemistry, geochronology and isotopes, it can be concluded that the Neoarchean–early Paleoproterozoic basement rocks with intermediate– acidic composition in the Jiaobei terrane provided the major source materials for the studied paragneisses, which is consistent with the conclusions inferred from the A–CN–K diagram (Fig. 10a). In addition, the apparent 207Pb/206Pb age histograms for the concordant spots from the samples (Fig. 13) can help identifying the age peaks. The youngest age peak for the magmatic zircons at 2472 Ma and the oldest age peak for metamorphic zircons at 2422 Ma, collectively provide a rough constraint on the depositional time of the protoliths of the paragneisses from the Jiaobei terrane that they might have been deposited during 2.47–2.42 Ga. However, this needs further geochronological study to confirm. 5.4. Comparison with the sedimentary sequence of the Jiaodong Group
Fig. 10. Geochemical diagrams of major and trace elements for the paragneisses from the Jiaobei terrane. Mineral abbreviations: Ka – kaolinite, Gi – gibbsite, Chl – chlorite, Sm – smectite, Il – illite, Pl – plagioclase, K – sp-potassium plagioclase.
zoning (Fig. 4), which also show more affinity to those with an intermediate–acidic source. In summary, all these lines of evidence suggest that the sediments of the protoliths of the paragneisses in the Jiaobei terrane were mainly derived from the source with intermediate–acidic composition. Besides the geochemical features, the age spectra of detrital zircons are conventionally important indicators to determine the provenance of Precambrian clastic sedimentary rocks (e.g., Fedo et al., 2003 and references therein). The apparent 207Pb/206Pb ages of the concordant magmatic spots from the samples range from 2427 to 2623 Ma (Fig. 13a; Table S1), which is consistent with the zircon U–Pb ages of widespread Neoarchean–early Paleoproterozoic granitic (mainly TTG) gneisses in the Jiaobei terrane (e.g., Faure et al., 2003; Tang et al., 2007; Jahn et al., 2008; Zhou et al., 2008a; Liu et al., 2013a; Wang et al., 2014a; Wu et al., 2014a,c; Shan et al., 2015a,b), indicating that the Neoarchean– early Paleoproterozoic granitic rocks in the Jiaobei terrane possibly provided the most important source materials. Furthermore, the similarities between the detrital zircon Hf isotope compositions from the paragneisses and those from the Neoarchean–early
‘‘Comparison method” is commonly employed in the studies of paragneisses, which proves to be very effective (e.g., Williams et al., 2009; Wang et al., 2014b). This method is to find as many similarities as possible between the studied samples and the possible sedimentary sequence and build a possible link between them (e.g., Williams et al., 2009; Wang et al., 2014b). The results of the present study provide specific evidence for a possible link between the paragneisses in the Jiaobei terrane and the sedimentary sequence of the Jiaodong Group with the comparison method, which is listed as follows. (1) The age populations of detrital zircons from the paragneisses in our study area (Fig. 13) are similar to those of the sedimentary sequence of the Jiaodong Group (Wan et al., 2012a,b); (2) Our field study revealed that the paragneisses in the present study and the Jiaodong Group were subjected to similar metamorphism and deformation (Yang, 1986; Yu, 1987; An, 1990; SBGMR, 1991; Wu et al., 1991; Jahn et al., 2008); (3) The paragneisses in our study area are petrologically and mineralogically similar to the sedimentary sequence of the Jiaodong Group (Fig. 3; Yang, 1986; Yu, 1987; An, 1990; SBGMR, 1991; Wu et al., 1991; Jahn et al., 2008; Wan et al., 2012b). Therefore, based on the available evidence, we propose that the paragneisses in the present study belong to the sedimentary sequence
Fig. 11. ICV vs. CIA diagram for the paragneisses from the Jiaobei terrane.
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Fig. 12. Source rock discrimination diagram for the paragneisses from the Jiaobei terrane (after Roser and Korsch (1988)). Discriminant Function 1 = 1.773TiO2 + 0.607Al2O3 + 0.76 Fe2OT3 1.5MgO + 0.616CaO + 0.509Na2O 1.224K2O 9.09; Discriminant Function 2 = 0.445TiO2 + 0.07 Al2O3 0.25 Fe2OT3 1.142MgO + 0.438CaO + 1.475Na2O + 1.426 K2O 6.861.
Fig. 14. Tectonic discrimination diagrams of (a) K2O/Na2O vs. SiO2 and (b) SiO2/ Al2O3 vs. K2O/Na2O (Roser and Korsch, 1986) for the paragneisses from the Jiaobei terrane. PM – passive margin; ACM – active continental margin; ARC – oceanic island-arc; A1 – arc setting, basaltic and andesitic detritus; A2 – evolved arc setting, felsic-plutonic detritus.
of the Jiaodong Group, although more geological studies are required to recover the primary stratigraphic succession.
5.5. Tectonic setting
Fig. 13. Zircon U–Pb age spectra (t(Ma)) for the concordant detrital zircons ((a) – magmatic zircons; (b) – metamorphic zircons) from the paragneisses in the Jiaobei terrane. To give a better constraint on the provenance, the detrital zircon data from the same supracrustal rock series from the previous study (Shan et al., submitted for publication) have also been included in the figure.
Petrography, geochemistry and isotope composition have been long widely used in many studies to determine the tectonic conditions during the deposition of sediments (e.g., Roser and Korsch, 1986; McLennan et al., 1990, 1993). In the present study, high ICV values of the paragneisses suggest low maturity of the source rocks and may reveal an active margin setting (Fig. 11). Roser and Korsch (1986) have proved that the K2O/Na2O, SiO2/Al2O3 and SiO2 values can be employed to distinguish the tectonic settings of sandstone–mudstone suits. On the K2O/Na2O vs. SiO2 and SiO2/Al2O3 vs. K2O/Na2O plots (Fig. 14), the paragneisses from the Jiaobei terrane straddle the areas of island arc and active continent margin and show remarkable distinction from the features of passive continent margin. Moreover, the REE patterns of
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Fig. 15. Co–Th–Zr/10, Sc–Th–Zr/10 and La–Th–Sc diagrams (Bhatia and Crook, 1986) for the paragneisses from the Jiaobei terrane. OIA – oceanic island arc; CIA – continental island arc; ACM – active continental margin; and PM – passive continental margin.
metasedimentary rocks have been proved be a good tracer for various tectonic environments (e.g., Bhatia and Crook, 1986). The samples in this study are characterized by LREE enrichment, HREE depletion, with (La/Yb)N ratios of 4.21–55.5, and negative Eu anomalies (Eu/Eu⁄ = 0.45–0.92), which are consistent with those of island arc or active continent margin setting (Bhatia and Crook, 1986). Their relatively high La/Sc (0.61–7.85, average 2.15), La/Y (0.58–6.24, average 1.54), Ti/Zr (7.58–40.53, average 23.70) and low Sc/Cr ratios (0.04–0.15, average 0.07), also indicate that these metasedimentary rocks were deposited in an island arc or active continent margin setting (Bhatia and Crook, 1986). Furthermore, both their La and Ce contents show good consistency with those of island arc and active continent margin setting (Bhatia and Crook, 1986). Immobile trace elements such as Ti, the HFSE (Nb, Ta, Zr and Hf) and some transition metals (Cr, Ni, and Sc) and ratios of Zr/Hf, Ta/ Nb, La/Sc and Th/U can generally preserve the information of the rocks’ original composition during long processes of erosion and transportation, and thus can be more important tracers for unraveling tectonic settings for the sedimentary rocks than aforementioned elements (Bhatia, 1985; Bhatia and Crook, 1986; Crichton and Condie, 1993). Many workers have made much endeavor on this aspect through systematic studies of these immobile trace elements and provided a set of discrimination diagrams to show the differences between tectonic settings such as oceanic arcs, continental arcs, active continental margins and passive continental margins (Bhatia, 1983, 1985; Bhatia and Crook, 1986). It is noteworthy that two essential requirements should be met before applying these diagrams. The first is that the original compositions are not changed due to differentiation or mixing during transportation, which requires transport of the materials to the sedimentary basin must be straight forward; the second is that the formation of the deposits must be roughly synchronous or close with the development of the basin. Relative short-distance transportation of the protoliths of the paragneisses in the present study, which is indicated by the crystal morphology of magmatic detrital zircons (Fig. 4), may help them to preserve original compositions. Besides, the depositional time (2.47–2.42 Ga) of the samples do not differ substantially from the major formation time of their source materials (2.47–2.53 Ga; Fig. 13a). Therefore, our samples can meet both the two requirements. In addition, these diagrams are more suitable to greywacke, however, most of our samples belong to shale with only a few belonging to greywacke. Therefore, we try
to use these discrimination schemes to dig some reference information for the paragneisses in our study. It seems that two samples of them have relatively low Th contents, but we consider that the discrimination results would not be significantly affected by this. In the Th–La–Sc, Th–Co–Zr/10 and Th–Sc–Zr/10 diagrams, almost all of the samples plot within or near the fields of ocean island arc and continental island arc (Fig. 15), confirming the above inferences. In addition, the nearly contemporaneous igneous rocks, such as TTG gneisses and amphibolites in the study area, which were considered to have been generated in a continental arc setting (e.g., Tang et al., 2007; Liu et al., 2011; Shan et al., 2015a,b), provide further evidence for the above speculations on the tectonic setting. Therefore, it can be inferred that the convergent margin setting was possibly operative during the Late Neoarchean–Early Paleoproterozoic transition in the Jiaobei terrane.
6. Conclusions Geochronological and geochemical analyses and Lu–Hf isotopic data presented in the present study for the paragneisses from the Jiaobei terrane has led to the following conclusions: (1) The protoliths of the rocks in the present study are of sedimentary origin and belong principally to clay–silty rocks with some contributions from graywacke. (2) A series of geochemical indexes for the paragneisses indicate relatively weak weathering in the source rocks and negligible post-depositional K-metasomatism. (3) The whole-rock geochemistry of the paragneisses indicates that the sediments of the protoliths of the paragneisses in the Jiaobei terrane were mainly derived from the source with intermediate–acidic composition, probably graniticto-tonalitic rocks. In combination with geochronological and isotopic studies on the paragneisses and the basement rocks in the Jiaobei terrane, it is suggested that the Archean–early Paleoproterozoic granitic rocks in the Jiaobei terrane possibly provided the most important source materials. In addition, the protoliths of the paragneisses might have been deposited during 2.47–2.42 Ga. (4) High and heterogeneous ICV values of the paragneisses reveal a chemically immature source and indicate that these clastic sedimentary rocks were deposited in an active margin
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setting. Furthermore, a number of geochemical indicators and tectonic discrimination diagrams, collectively indicate an island arc or active continent margin setting for the deposition of the protoliths of the paragneisses in the Jiaobei terrane. Together with the nearly contemporaneous igneous rocks, it can be inferred that the convergent margin setting was possibly operative during the Late Neoarchean–Early Paleoproterozoic transition in the Jiaobei terrane.
Acknowledgements This work was funded by the 973 program (Grant No. 2012CB4166006) supported by State Ministry of Science and Technology, and research programs (Grant Nos. 41030316 and 41210003) supported by the National Nature Science Foundation of China. We would like to express our gratefulness to the journal editor and three anonymous reviewers for their thoughtful comments that have greatly improved the final version of the paper. We also thank Dingshuai Xue and Wenjun Li for their help with major and trace element analyses. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jseaes.2015.10. 003. References An, Y.H., 1990. A new division of the metamorphosed strata in the Jiaodong region: an account on the newly delimited Jiaodong Group and Jingshan Group. Geol. Shandong 6 (1), 97–103 (in Chinese with English abstract). Belousova, E.A., Kostitsyn, Y.A., Griffin, W.L., Begg, G.C., O’Reilly, S.Y., Pearson, N.J., 2010. The growth of the continental crust: constraints from zircon Hf-isotope data. Lithos 119, 457–466. Bhatia, M.R., 1983. Plate tectonics and geochemical composition of sandstones. J. Geol. 91, 611–627. Bhatia, M.R., 1985. Rare earth element geochemistry of Australian Paleozoic graywackes and mudrocks: provenance and tectonic control. Sed. Geol. 45, 97–113. Bhatia, M.R., Crook, K.A.W., 1986. Trace element characteristics of graywackes and tectonic setting discrimination of sedimentary basins. Contrib. Miner. Petrol. 92, 181–193. Bouvier, A., Vervoort, J.D., Patchett, P.J., 2008. The Lu–Hf and Sm–Nd isotopic composition of CHUR: constraints from unequilibrated chondrites and implications for the bulk composition of terrestrial planets. Earth Planet. Sci. Lett. 273 (1), 48–57. Chatterjee, P., De, S., Ranaivoson, M., Mazumder, R., Arima, M., 2013. A review of the 1600 Ma sedimentation, volcanism, and tectono-thermal events in the Singhbhum craton, Eastern India. Geosci. Front. 3, 277–287. Chu, H., Lu, S.N., Wang, H.C., Xiang, Z.Q., Liu, H., 2011. U–Pb age spectrum of detrital zircons from the Fuzikuang formation, Penglai Group in Changdao, Shandong Province. Acta Petrologica Sinica 27 (4), 1017–1028 (in Chinese with English abstract). Condie, K.C., 1993. Chemical composition and evolution of the upper continental crust: contrasting results from surface samples and shales. Chem. Geol. 104, 1– 37. Condie, K.C., 2013. Plate Tectonics & Crustal Evolution. Elsevier. Condie, K.C., 2014. How to make a continent: thirty-five years of TTG research. In: Evolution of Archean Crust and Early Life. Springer, Netherlands, pp. 179–193. Condie, K.C., Kröner, A., 2013. The building blocks of continental crust: evidence for a major change in the tectonic setting of continental growth at the end of the Archean. Gondwana Res. 23 (2), 394–402. Condie, K.C., Wronkiewicz, D.J., 1990. Evolution of the Kaapvaal Carton: the Cr/Th ratio in pelites as an index of craton maturation. Earth Planet. Sci. Lett. 97, 256– 267. Cox, R., Lowe, D.R., Cullers, R.L., 1995. The influence of sediment recycling and basement composition on evolution of mudrock chemistry in the southwestern United States. Geochim. Cosmochim. Acta 59, 2919–2940. Crichton, J.G., Condie, K.C., 1993. Trace elements as source indicators in cratonic sediments: a case study from the Early Proterozoic Libby Creek Group, southeastern Wyoming. J. Geol. 101, 319–332. Cullers, R.L., 2000. The geochemistry of shales, siltstones, and sandstones of Pennsylvanian–Permian age, Colorado, USA: implications for provenance and metamorphic studies. Lithos 51, 181–203.
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