Chemical Geology 253 (2008) 205221

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Chemical Geology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c h e m g e o

Upper crustal abundances of trace elements: A revision and update

Zhaochu Hu a,b, Shan Gao a,b,
a b

State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Sciences, China University of Geosciences, Wuhan, 430074, PR China State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi'an, 710069, PR China

A R T I C L E

I N F O

A B S T R A C T
We report new estimates of abundances of rarely analyzed elements (As, B, Be, Bi, Cd, Ge, In, Mo, Sb, Sn, Te, Tl, W) in the upper continental crust based on precise ICP-MS analyses of well-characterized upper crustal samples (shales, pelites, loess, graywackes, granitoids and their composites) from Australia, China, Europe, New Zealand and North American. Obtaining a better understanding of the upper crustal abundance and associated uncertainties of these elements is important in placing better constraints on bulk crust composition and, from that, whole Earth models of element cycling and crust generation. We also present revised abundance estimates of some more commonly analyzed trace elements (Li, Cr, Ni, and Tm) that vary by N 20% compared to previous estimates. The new estimates are mainly based on signicant (r2 N 0.6) interelement correlations observed in clastic sediments and sedimentary rocks, which yield upper continental crust elemental ratios that are used in conjunction with well-determined abundances for certain key elements to place constraints on the concentrations of the rarely analyzed elements. Using the wellestablished upper crustal abundances of La (31 ppm), Th (10.5 ppm), Al2O3 (15.40%), K2O (2.80%) and Fe2O3 (5.92%), these ratios lead to revised upper crustal abundances of B = 47 ppm, Bi = 0.23 ppm, Cr = 73 ppm, Li = 41 ppm, Ni = 34 ppm, Sb = 0.075, Te = 0.027 ppm, Tl = 0.53 ppm and W = 1.4 ppm. No signicant correlations exist between Mo and Cd and other elements in the clastic sediments and sedimentary rocks, probably due to their enrichment in organic carbon. We thus calculate abundances of these elements by assuming the upper continental crust consists of 65% granitoid rocks plus 35% clastic sedimentary rocks. The validity of this approach is supported by the similarity of SiO2, Al2O3, La and Th abundances calculated in this way with their upper crustal abundances given in Rudnick and Gao [Rudnick, R., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L. (Ed.), The Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, vol. 3. ElsevierPergamon, Oxford, pp. 164.]. The upper crustal abundances thus obtained are Mo = 0.6 ppm and Cd = 0.06 ppm. Our data also suggest a 20% increase of the Tm, Yb and Lu abundances reported in Rudnick and Gao [Rudnick, R., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L. (Ed.), The Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, vol. 3. ElsevierPergamon, Oxford, pp. 164.]. 2008 Elsevier B.V. All rights reserved.

Article history: Received 24 December 2007 Received in revised form 19 May 2008 Accepted 21 May 2008 Editor: R.L. Rudnick Keywords: Geochemistry Composition of the upper continental crust Trace elements

1. Introduction The upper continental crust is the Earth's major repository of incompatible elements (2070%, depending on element and model considered; Rudnick and Fountain, 1995). Knowledge of the chemical composition of the upper crust is thus important for understanding formation and evolution of the continental crust and, ultimately, the Earth, geochemical mass balance calculations for the crust and the whole earth, and quantifying other geochemical processes (Rudnick and Gao, 2003; Hawkesworth and Kemp, 2006a,b). For these reasons, determining the chemical composition of the upper continental crust (UCC) has been an aim of geochemists since the rst analyses of rocks were undertaken (Clarke, 1889). Two approaches have generally been
Corresponding author. State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi'an, 710069, PR China. E-mail address: sgao@263.net (S. Gao). 0009-2541/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.chemgeo.2008.05.010

used to determine the UCC composition (see Rudnick and Gao, 2003, for review). One is to establish weighted averages of the compositions of rocks exposed at the surface by large-scale sampling campaigns (Clarke, 1889; Clarke and Washington, 1924; Shaw et al., 1967, 1976, 1986; Eade and Fahrig, 1971, 1973; Ronov and Yaroshevsky, 1967, 1976; Gao et al., 1992, 1998; Condie, 1993; Borodin, 1998). All major-element determinations of upper crust composition rely upon this method. The other approach is to determine the average concentrations of insoluble elements in ne-grained clastic sediments and sedimentary rocks (e.g., shale, mudstone, graywacke, siltstone, loess, and tillite) and use these to infer the average composition of their source regions (Goldschmidt, 1933; McLennan et al., 1980; McLennan, 2001; Taylor et al., 1983; Taylor and McLennan, 1985, 1995; Sims et al., 1990; Gao and Zhang, 1991a; McDonough et al., 1992; Condie, 1993; Plank and Langmuir, 1998; Gallet et al., 1998; Barth et al., 2000; PeuckerEhrenbrink and Jahn, 2001; Hattori et al., 2003; Teng et al., 2004; Kamber et al., 2005). The latter method is based on the concept that

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the process of sedimentation averages wide areas of the exposed crust. This method was originally employed by Goldschmidt (1933) and his Norwegian colleagues in their analyses of glacial sediments to derive average composition of the crystalline rocks of the Baltic shield. For the most part, estimates of upper crustal abundances from sedimentary rocks have been intentionally restricted to insoluble trace elements (e.g., REE, Th, Sc, Co) that are least fractionated by various sedimentary processes, such as chemical and physical weathering, mineral sorting during transport, and diagenesis (McLennan et al., 1980). In contrast, elements with high solubilities in natural waters (e.g., alkali and alkaline-earth elements, B, Re, Mo, and U) have greater potential to be fractionated by sedimentary processes. Thus, their concentrations in ne-grained sedimentary rocks may not be representative of their source region. Soluble elements may not be as fractionated in wind-blow loess deposits, as reected by the fact that trace element abundances in loess are similar to those of the upper crust, and no correlation with element solubility and mobility are observed (Taylor et al., 1983). Recently, this general approach has been applied to other trace elements with relatively high solubility such as As, Cs, Cr, Li, Mo, Sb, U, V and W or elements that might be strongly affected by sedimentary sorting, such as Nb and Ta (e.g., Sims et al., 1990; McDonough et al., 1992; Plank and Langmuir, 1998; Barth et al., 2000; McLennan, 2001; Teng et al., 2004; Rudnick and Gao, 2003). It is also likely that some of the heavy metals are concentrated in ore bodies (W, In, Sn, Cu, etc.) and hence may be very heterogeneously distributed in the crust. Loess, shales and sandstones

may or may not even tap these ore bodies, and thus may represent a biased sampling of the UCC. Kesler and Wilkinson (2008) used a timespace model for the tectonic migration of porphyry copper deposits vertically through the crust to calculate Earth's endowment of copper in mineral deposits. Their results indicate that 3 1011 tonnes (t) of copper resides in ore bodies at all levels in the Earth's crust. For a crustal mass of 1.52 1019 t (Lodders and Fegley, 1998) and an average copper content of 27 ppm (Rudnick and Gao, 2003), the continental crust contains 4.0 1014 t of copper. Kesler and Wilkinson's estimate of 3 1011 t of copper in deposits in the crust accounts for only 0.08% of this amount. Thus, the effect of ore deposits on the estimated upper crustal abundance is probably negligible. Rudnick and Gao (2003) review the present-day composition of the continental crust, the methods employed to derive these estimates, and the implications of the continental crust composition for the formation of the continents, earth differentiation, and its geochemical inventories. They show that the major-element composition of the UCC is very consistent between studies, with most major-element averages falling within 10% of Eade and Fahrig's (1973) Canadian Shield average. However, trace elements abundance estimates show signicantly larger variations than major elements from study to study and for some trace elements, only single estimates are available. These differences are likely due to a combination of inadequate sampling, analytical difculties, and real regional variation in upper crustal abundances. Elements whose estimated UCC abundances vary

Table 1 Analyzed upper crustal samples Sample AO-10 AO-12 PL-1 PL-6 PW-4 PW-5 SC-1 SC-2 SC-4 SC-5 SC-8 MI-4 MI-1 SCO-1 CY-4a-A CY-4a-B BP-1 BP-5 BP-3 1 CH Hungar P Comp D059 D060 D062 D075 D100 D104 D111 D119 D122 D124 D355 D276 D284 D308 D312 D314 T1 T2 T3 Locality Amadeus Basin Amadeus Basin Canning Basin Canning Basin Perth Basin Perth Basin State Circle State Circle State Circle State Circle State Circle Mt. Isa Group Mt. Isa Group North America Kansas Kansas Banks Penn., New Zealand Banks Penn., New Zealand Banks Penn., New Zealand Kaiserstuhl China Hungary The North Qinling Belt The North Qinling Belt The North Qinling Belt The Yangtze craton The South Qinling Belt The South Qinling Belt The South Qinling Belt The Yangtze craton The Yangtze craton The Yangtze craton The South Qinling Belt The North Qinling Belt The South Qinling Belt The Yangtze craton The Yangtze craton The Yangtze craton Tibet Tibet Tibet Rock type Shale Shale Shale Shale Shale Shale Shale Shale Shale Shale Shale Shale Shale Shale Loess Loess Loess Loess Loess Loess Loess Loess Graywacke (n = 82) Graywacke(n = 36) Graywacke(n = 5) Graywacke(n = 16) Pelite(n = 16) Pelite(n = 2) Pelite(n = 24) Pelite(n = 15) Pelite(n = 25) Pelite(n = 7) Pelite(n = 172) Granodiorite (n = 23) Diorite (n = 21) Granodiorite (n = 12) Granite (n = 12) Granite (n = 15) Granodiorite (n = 3) Leucogranite (n = 4) Leucogranite (n = 5) Age Upper Proterozoic Upper Proterozoic Permian Carboniferous Triassic Triassic Silurian Silurian Silurian Silurian Silurian Middle Proterozoic Middle Proterozoic Upper Cretaceous CIA 72 66 80 77 80 75 75 75 75 75 73 69 85 59 59 59 57 61 65 Source Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 Nance and Taylor, 1976 USGS Taylor et al., 1983 Taylor et al., 1983 Taylor et al., 1983 Taylor et al., 1983 Taylor et al., 1983 Taylor et al., 1983 Teng et al., 2004 Teng et al., 2004 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Gao et al., 1998 Zhang et al., 2004 Zhang et al., 2004 Zhang et al., 2004

Paleoproterozoic Mesoproterozoic Paleoproterozoic Neoproterozoic Devonian Carboniferous Silurian Neoproterozoic Silurian Jurassic Devonian Cretaceous Neoproterozoic Neoproterozoic Neoproterozoic Neoproterozoic

55 64 55 56 60 80 72 66 72 79 77

n is number of individual samples to make the composite. CIA is the Chemical Index of Alteration (Nesbitt and Young, 1982).

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by more than 50% between studies or for which only a few estimates are available include As, B, Be, Bi, Cd, Co, Cr, Cs, Cu, Er, Ga, Ge, In, Li, Lu, Mo, Nb, Ni, Rb, Sb, Sc, Sn, Ta, Te, Tl, Tm, U, V, W, Yb and Zn. Most of these elements are siderophile and chalcophile. Some of them like As, Bi, In, Mo, Sb, Sn, Tl and W have particularly interesting geochemical properties because they are fractionated by both core and crust formation. During these processes, their doubly incompatible geochemical properties cause them to be partitioned into metal/ sulde as well as into silicate liquids (Jochum et al., 1993). Thus, the siderophile/chalcophile character accounts for their partitioning into the core and corresponding bulk depletion in the silicate portion of the earth (Jochum et al., 1993). Due to their incompatibility, these elements are also enriched in the crust, which is formed by the segregation of silicate liquids. In this paper, the relationships between concentrations of these elements in sediments and the UCC are evaluated. For elements that show good correlations with other elements in sediments (e.g., La and Nb), we use the observed element ratio (La/Nb) and the wellestablished UCC concentration of one element (La) to derive the concentration of the other element (Nb). For elements that show no or only a poor correlation with other elements in sediments, we use both granitoid rocks and sedimentary rock compositions to derive their concentration in the UCC, by analogy to the method used to derive the UCC major-element composition. 2. Samples of the upper continental crust Upper crustal samples used in this study come from those previously well-characterized by major and many of the trace element compositions (Table 1). They include (1) the suite of Post-Archean Shales (PAAS) which Taylor and his co-workers originally used to constrain the rare earth element (REE) contents of the upper crust (Nance and Taylor, 1976; Taylor and McLennan, 1985; Barth et al., 2000; Teng et al., 2004); (2) SCO-1, a shale standard reference material from the USGS; (3) worldwide loess (Taylor et al., 1983; Barth et al., 2000; Teng et al., 2004); and (4) upper crustal composites from China that include graywackes, shales and granites (Gao et al., 1991b, 1992, 1998; Zhang et al., 2004; Teng et al., 2004). Table 1 provides brief descriptions of these samples. 3. Analytical methods 3.1. Instrumentation Forty-eight trace elements were analyzed by using a PerkinElmer SCIEX ELAN 6100DRC ICP-MS. The outer and intermediate ICP gas ow rates were xed at 14 and 1.2 l/min, respectively. A glass microconcentric nebulizer (MCN) and a cyclonic spray chamber comprised the sample introduction system, with a typical sample uptake rate of 0.20 ml/min. The RF power was xed at 1350 W. The auto lens voltages were set by optimizing a solution of 10 ng/ml Mg, Co, Rh, Ce, Pb and U. For data acquisition, peak hopping (one point per peak) was used with a dwell time of 0.15 s. There were three sweeps per reading and three reading per replicate. The nebulizer gas ow rate was optimized to obtain maximum signal intensities for Mg, Co, Rh, Ce, Pb and U, while keeping the CeO+/Ce+ and Ce2+/Ce+ ratios below 2.5%. The isotope interferences of 114,115Sn+ on 114Cd+ and 115In+ were calibrated through the measurement of 118Sn+. Drift was minimized by ushing through a rock solution for 30 min before tuning the instrument for a run. Drift corrections are carried out using Rh as an internal standard and by repeatedly analyzing a calibration solution as a drift monitor over the duration of a run. Memory effect was avoided by manual analyses in which care was taken to completely wash-out B and Ta signals between samples using a 5% HNO3 + 0.1% HF alternated with 3% HNO3. The addition of HF and K+ solution was found to be more suitable for suppression of the volatilization and for the stabilization of B than

normally used mannitol and glycerol (Kozono et al., 1998). Potassium is a major element in our rock samples. This probably explains why B is not lost during the evaporation of the digested geological sample solutions. Direct determination of arsenic and tellurium in geological samples by ICP-MS is often complicated by the interferences of Nd2+, Sm2+, Eu2+ and ArCl+ on As+ and Xe+ on Te+. The high rst ionization potentials of As (9.81 eV) and Te (9.01 eV) also results in relatively low analytical sensitivity in ICP-MS. It is shown that both problems can be overcome by a combination of a 4% ethanol matrix modier with nebulizer gas ow rate adjustment. Detailed ICP-MS analytical protocols and mechanisms for As, Bi, Sb and Te have been reported in Hu et al. (2004, 2005, 2006, 2007). 3.2. Reagents Multi-element mixed external standard solutions were prepared from 1.0 mg/ml of single element standard solutions (National Center for Analysis and Testing of Steel Materials, China). Ultra-pure water with a resistivity of 18.0 M/cm was obtained from a Milli-Q water purication system (Millipore, USA). Ultra-pure nitric acids were prepared by sub-boiling distillation in a commercial available quartz still, while hydrouoric acid and ethanol were doubly distilled in a home-made sub-boiling distillation device. The conventional subboiling purication procedure is not effective in the reduction of As impurity in HF. This could be related to the presence of volatile As species like AsF3 (boiling point 63 C). To remove this volatile As species, a boiling procedure for hydrouoric acid was adopted before using the conventional sub-boiling purication procedure.

Fig. 1. Comparison of determined (a) Zr and (b) Nb concentrations in various geological samples (n = 555) by using XRF and ICP-MS.

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3.3. Sample digestion Sample digestion and analysis were carried out at the State Key Laboratory of Continental Dynamics, Northwest University, Xi'an. The sample solutions were maintained under clean room conditions during the entire procedure. Procedures of sample decomposition were as follows: (1) Fifty milligrams of sample powder were placed in a home-made PTFE-lined stainless steel bomb to which were added 1 ml of HNO3 and 1 ml of HF. The sealed bomb was then placed in an electric oven and heated to 190 C for 48 h; (2) After cooling, the bomb was opened and placed on a hot-plate, and evaporated to incipient dryness on the hot-plate (but not baked); (3) 1 ml of HNO3 was added, evaporated to dryness and followed by a second addition of HNO3 and evaporation to dryness; (4) The residue was then dissolved by adding 1.5 ml of HNO3 and 2.5 ml of 18 M/cm ultra-pure water; The bomb was then capped and placed in an electric oven overnight (at 150 C); (5) The nal solution was

made up to 50 ml by addition of ultra-pure water and 0.50 ml of 1.0 g/ml Rh internal standard solution. This pressurized acid sample digestion method has been widely used for analysis of trace elements in geological samples by ICP-MS (Jenner et al., 1990; Qi et al., 2000; Hu et al., 2005, 2006, 2007). This technique is generally much more efcient than conventional wet digestions in open systems: the loss of volatile elements is prevented, the quantity of reagent is reduced and the decomposition of insoluble minerals is more efcient. To examine the completeness of our sample digestion, we compare the Zr and Nb concentrations of 555 rock samples determined by both ICP-MS and X-ray uorescence (XRF) (using powdered pellets) during a period of four years obtained at our laboratory. As shown in Fig. 1, most of the ICP-MS and XRF data agree within 10% relative, which indicates the complete digestion of accessory minerals such as zircon. For the determination of As and Te, 4.80 ml each of sample solutions were taken and 0.20 ml of ethanol solvent added (Hu et al., 2005, 2006).

Table 2 Analyses of forty-eight trace elements in ve international rock standards (ppm) and blanks (ppb) Ppm AGV-1 (andesite) Ref Li Be B Sc V Cr Co Ni Cu Zn Ga Ge As Rb Sr Y Zr Nb Mo Cd In Sn Sb Te Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Tl Pb Bi Th U 10.7 2.1 8.1 12.3 119 9.4 15.2 15.5 58 87 20.2 1.25 0.88 66.6 660 19 231 14.6 2.1 0.061 0.042 4.9 4.2 0.0016 1.26 1200 38.2 67.6 8.3 31.7 5.72 1.58 4.7 0.69 3.55 0.68 1.82 0.28 1.63 0.244 5.1 0.87 0.52 0.35 37.4 0.05 6.4 1.93 n=6 11.0 2.22 8.07 12.2 123 9.81 15.8 16.4 60.5 89.3 20.6 1.24 1.08 69.9 671 20.5 227 14.7 2.17 0.062 0.047 4.83 4.45 0.0034 1.31 1230 38.7 68.8 8.58 33.3 5.96 1.69 4.94 0.70 3.69 0.70 1.76 0.27 1.72 0.27 5.06 0.92 0.57 0.33 39.6 0.051 6.38 1.98 RSD% 4.44 3.78 6.96 4.68 7.17 6.41 4.76 2.85 5.71 2.62 4.22 2.78 4.19 3.07 1.60 4.37 2.55 1.19 3.35 6.11 9.37 4.33 3.17 20.3 3.33 2.64 1.51 2.51 3.65 2.96 2.20 3.50 4.63 3.26 2.43 4.97 3.14 5.39 6.47 5.27 3.41 2.19 7.96 5.74 5.10 5.98 4.24 2.56 BHVO-1 (basalt) Ref 4.6 1.1 2.5 31 318 287 45 118 137 106 21 1.6 0.5 9.19 396 26 174 18.6 1 0.094 (0.18 2.1 0.15 0.0064 0.101 133 15.5 38.1 5.42 24.7 6.12 2.09 6.33 0.96 5.31 0.98 2.55 0.33 2 0.27 4.46 1.21 0.21 0.044 2.4 0.016 1.23 0.409 n=5 5.13 0.97 3.58 31.0 318 296 44.1 124 137 106 21.0 1.67 0.66 10.0 402 27.4 166 19.0 1.18 0.10 0.095 2.01 0.17 0.0080 0.11 140 16.0 39.4 5.72 26.1 6.36 2.09 6.28 1.00 5.51 1.05 2.53 0.35 2.15 0.31 4.53 1.29 0.24 0.045 2.13 0.012 1.25 0.44 RSD% 2.78 4.53 15.2 4.79 3.20 3.70 2.72 4.07 4.08 4.58 4.31 1.81 4.09 3.16 3.90 3.91 3.96 2.69 5.10 10.9 10.6 4.02 6.02 6.44 6.95 2.99 1.38 4.68 1.72 2.82 2.23 4.11 2.18 4.08 1.84 3.17 4.41 4.83 3.46 3.42 3.33 2.48 4.72 6.19 5.17 10.4 3.27 5.10 G-2 (granite) Ref 34 2.5 2.4 3.5 36 8.7 4.6 (5 11 86 23 1.14 0.25 170 478 11 309 12 (1.1 0.016 0.032 (1.8 0.07 (.005 1.34 1882 89 160 18 55 7.2 1.4 4.3 0.48 2.4 0.4 0.92 (.18 0.8 0.11 7.9 0.88 (.2 0.91 30 0.037 24.7 2.07 n=7 33.1 2.60 2.49 3.89 36.6 8.20 4.50 2.31 11.1 82.9 23.1 1.16 0.28 168 475 10.1 319 12.4 0.28 0.014 0.028 1.73 0.063 0.0081 1.37 1885 86.4 158 17.1 54.8 7.27 1.47 4.68 0.52 2.39 0.37 0.96 0.13 0.76 0.11 8.05 0.87 0.11 0.92 31.6 0.037 25.0 2.02 RSD% 6.15 5.77 24.3 5.47 3.96 5.88 2.52 7.67 4.65 2.11 3.16 3.01 9.74 4.49 1.12 1.67 5.27 1.86 6.67 17.3 5.50 5.69 6.88 6.80 3.19 2.95 3.65 3.20 4.37 4.01 2.44 3.39 2.97 3.68 3.83 2.68 3.60 4.58 3.65 3.11 2.89 3.90 16.0 2.95 4.15 3.10 2.53 4.87 SCO-1 (shale) Ref 45 1.84 72 10.8 131 68 10.5 27 28.7 103 15 (1 12.4 112 174 26 160 11 1.37 0.14 (.11 3.7 2.5 (.077 7.8 570 29.5 62 6.6 26 5.3 1.19 4.6 0.7 4.2 0.97 2.5 0.42 2.27 0.34 4.6 0.92 1.4 0.72 31 0.37 9.7 3 n=4 48.4 1.91 76.0 11.8 132 72.5 11.2 27.5 28.9 97.1 16.3 1.72 12.2 110 165 24.3 159 12.0 1.27 0.16 0.062 3.34 2.29 0.076 7.91 580 29.5 55.9 7.04 26.8 5.15 1.10 4.37 0.71 4.12 0.84 2.26 0.37 2.39 0.37 4.65 0.90 1.55 0.74 31.5 0.40 9.44 3.02 RSD% 4.79 3.44 6.99 3.32 3.05 4.26 4.42 5.98 5.11 1.54 2.64 1.57 4.00 1.95 1.26 1.12 3.65 1.06 6.06 6.19 4.64 2.84 3.92 3.13 2.53 1.91 2.47 3.15 5.24 3.64 2.68 3.57 4.27 1.75 3.62 3.16 3.78 4.83 2.81 2.87 3.78 2.70 4.93 3.09 4.71 2.96 1.79 2.01 GSR-5 (shale) Ref 44 3.0 154 18.5 87 99 21 36.8 42 55 25.6 3.1 1.4 205 90 26 96 14.3 0.35 0.033 0.082 2.0 0.17 0.022 14 450 62 109 13.6 48 8.4 1.7 6.7 1.02 5.1 0.98 2.7 0.43 2.6 0.41 2.9 1.0 0.79 0.71 8.7 0.23 12.8 1.5 n=4 55.0 3.16 159 19.2 91.4 109 22.0 40.8 44.2 54.0 25.4 3.55 1.54 207 91.3 28.3 95.7 13.5 0.42 0.0034 0.077 2.25 0.19 0.014 14.8 441 58.9 107 13.8 49.9 8.51 1.68 6.88 1.00 5.37 1.04 2.74 0.42 2.71 0.42 2.92 0.94 1.10 0.68 8.16 0.23 12.9 1.60 RSD% 3.77 3.25 5.21 5.54 4.03 2.51 4.64 4.16 2.49 2.16 2.88 1.35 2.19 4.08 2.01 2.37 1.07 0.44 5.64 42.3 2.96 2.13 6.30 7.97 2.73 3.11 3.01 3.49 4.48 3.15 2.30 2.30 3.26 3.64 0.54 1.25 2.27 2.05 2.79 2.98 4.16 3.16 6.20 4.65 3.14 2.09 2.60 2.48 Blank n=5 0.036 0.00091 0.39 0.033 0.50 0.53 0.0046 0.065 0.072 0.80 0.0037 0.0081 0.021 0.11 0.018 0.0018 0.0030 0.0012 0.035 0.0026 0.00016 0.0083 0.010 0.00097 0.00060 0.075 0.0025 0.0028 0.00056 0.0019 0.00079 0.00023 0.00063 0.00013 0.00058 0.00013 0.00027 0.00011 0.00043 0.00015 0.0010 0.00017 0.023 0.0026 0.043 0.00049 0.00062 0.00027 STD 0.028 0.00049 0.26 0.011 0.38 0.16 0.0032 0.037 0.022 0.56 0.0020 0.0040 0.009 0.05 0.018 0.0017 0.0015 0.0012 0.030 0.0015 0.00004 0.0016 0.006 0.00014 0.00034 0.063 0.0020 0.0016 0.00042 0.0017 0.00036 0.00014 0.00054 0.00005 0.00038 0.00008 0.00020 0.00003 0.00025 0.00007 0.0012 0.00009 0.010 0.0009 0.020 0.00028 0.00050 0.00025

The RSD is the relative standard deviation in percent. The reference values (Ref) of AGV-1 and BHVO-1 are taken from the preferred values in GeoRem (http://georem.mpch-mainz.gwdg.de/). The reference values of G-2, GSR-5 and SCO-1 are taken from Govindaraju (1994). Data underlined are recommended values. Other values are proposed except those preceded by a ( which are information values.

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3.4. Accuracy and precision Five USGS and IGGE rock standards: AGV-1 (andesite), BHVO-1 (basalt), G-2 (granite), GSR-5 (shale) and SCO-1 (shale) were used to monitor analytical accuracy and precision. As shown in Table 2, analytical precision of most of trace elements (RSD) is usually b 8% except for In (9.4%) and Te (20.3%) in AGV-1, B (15.2%), Cd (10.9%) and In (10.6%) in BHVO-1, As (9.7%), B (24.3%), Cd (17.3%) and W (16.0%) in G-2, and Cd (42.3%) in GSR-5, which are mainly caused by the low analyte concentrations in these samples. Accuracy is similar to the precision. This is demonstrated in Table 2 where our measured values for international reference materials are compared with the reference values from GeoReM (http://georem.mpch-mainz.gwdg.de/) and Govindaraju (1994). The agreement between our data and the reference values is better than 8% for most of the elements in these geological reference samples. For rarely analyzed elements such as Mo, Cd, In, Sn, Sb, W, Tl, Bi, As and Te, the validity of this analytical method were further evaluated by analyzing another eighteen international geological reference samples (Table 3). These rocks cover the whole compositional spectrum of igneous rock, ranging from ultramac (peridotite JP-1; dunite DTS-1) to mac (basalts BHVO-2, BIR-1, JB-3, GSR-3; dolerite DNC-1; diabase W-2) to intermediate (andesites AGV-2, BCR-2, JA-3, GSR-2; granodiorite JG-3) and nally to acidic (granites GSR-1; rhyolite RGM-1). They also include the most common sedimentary rocks of sandstone (GSR-4), shale (SGR-1) and limestone

(GSR-6). Most of the results were found to be in reasonable agreement with the reference values in Govindaraju (1994) and GeoReM and no systematic differences are apparent. Table 4 lists the major and trace element data for shale, loess and Chinese composite samples. The major-element data are taken from previously published works (Nance and Taylor, 1976; Taylor et al., 1983; Gladney and Roelandts, 1988; Gao et al., 1991b, 1998). 4. Discussion 4.1. Nb, Ta, Zr and Hf It is well-established that the continental crust is depleted in Nb and Ta relative to other highly incompatible elements such as La (Taylor and McLennan, 1985; Plank and Langmuir, 1998; Barth et al., 2000). The depletion of Nb or Ta relative to light REE, as seen in the crust, is suggestive of dominant crustal growth at convergent margins rather than intraplate settings, but determining the proportions of these two end members is critically dependent on dening the LaNb or LaTa ratio of the crust (Rudnick, 1995; Barth et al., 2000; Hawkesworth and Kemp, 2006b). In addition, it has been shown that both the continental crust and depleted upper mantle have subchondritic Nb/Ta and superchondritic La/Nb ratios, producing a mass balance problem for these elements in the Earth (McDonough, 1991; Rudnick et al., 2000; Kamber and Collerson, 2000). Therefore,

Table 3 Analyses of trace elements (ppm) in eighteen international rock standards Lithology AGV-2 BCR-2 BHVO-2 BIR-1 DNC-1 DTS-1 RGM-1 SGR-1 W-2 JA-3 JB-3 JG-3 JP-1 GSR-1 GSR-2 GSR-3 GSR-4 GSR-6 Andesite Basalt Basalt Basalt Dolerite Dunite Rhyolite Shale Diabase Andesite Basalt Granodiorite Peridotite Granite Andesite Basalt Sandstone Limestone Lithology AGV-2 BCR-2 BHVO-2 BIR-1 DNC-1 DTS-1 RGM-1 SGR-1 W-2 JA-3 JB-3 JG-3 JP-1 GSR-1 GSR-2 GSR-3 GSR-4 GSR-6 Andesite Basalt Basalt Basalt Dolerite Dunite Rhyolite Shale Diabase Andesite Basalt Granodiorite Peridotite Granite Andesite Basalt Sandstone Limestone As 0.70 1.03 0.92 0.068 0.18 0.05 3.1 62.5 1.18 4.35 1.77 0.45 0.31 2.28 2.24 0.65 9.21 4.6 Sb 0.50 0.306 0.084 0.47 0.88 0.43 1.35 3.34 0.712 0.37 0.18 0.082 0.044 0.30 0.20 0.10 0.76 0.62 Ref Mo 2.08 262 3.80 0.13 0.19 0.12 2.46 34.4 0.61 1.64 1.09 0.45 0.15 3.55 0.64 2.9 1.39 0.44 W 0.56 0.56 0.25 0.023 0.056 0.024 1.42 2.47 0.31 8.86 1.46 14.5 1.10 8.75 0.42 0.43 1.35 0.91 Ref 250 4 0.07 (.7 (.14 2.3 35.1 0.44 1.6 1.1 0.44 3.5 0.54 2.6 0.76 0.38 Ref Cd 0.082 0.75 0.095 0.095 0.085 0.011 0.066 1.14 0.091 0.091 0.079 0.046 0.009 0.061 0.065 0.054 0.061 Tl 0.32 0.34 0.026 0.0021 0.025 0.00090 0.88 0.65 0.12 0.21 0.047 0.4 0.0021 2.01 0.13 0.031 0.31 0.34 Ref In 0.048 0.096 0.088 0.060 0.048 0.0027 0.034 0.037 0.062 0.045 0.068 0.029 0.003 0.018 0.034 0.072 0.011 0.034 Bi 0.056 0.070 0.018 0.0054 0.011 0.0049 0.28 0.88 0.036 0.052 0.018 0.062 0.003 0.6 0.069 0.0076 0.19 0.16 Ref Sn 2.08 2.20 1.80 0.69 1.47 0.5 4.07 1.72 1.67 1.02 1.05 1.02 0.038 12.86 0.8 2.18 1.13 1.26 Te 0.0029 0.0048 0.017 0.0067 0.022 0.0012 0.0015 0.26 0.0027 0.0042 0.0022 0.0021 0.0014 0.0071 0.0024 0.0032 0.032 0.016 Ref 2.3 1.7 0.6 0.55 4.1 1.9 2 0.86 0.9 1 0.05 12.5 0.79 2 1.1 0.98 Ref

(0.44 (0.2 0.034 3 67 1.1 4.5 1.66 0.37 0.34 2.1 2.1 0.79 9.1 4.7 Ref

0.06 0.097 (.182 (0.01 0.065 0.93 0.077 0.09 0.082 0.06 0.032 0.061 0.067 0.06 0.069 Ref 0.27

0.055 0.0024 (0.15 (.096 0.0605 0.0622

0.02 0.033 0.063 0.026 0.042 Ref

0.13 0.46 0.96 0.5 1.26 3.4 0.77 0.34 0.15 0.07 0.21 0.12 0.083 0.6 0.43

0.21 (0.07 (.2 0.02 1.5 2.57 (0.3 0.9

(0.005 (0.026 (0.002 0.93 (.33 0.132 0.21 0.05 0.41 1.93 0.16 0.12 0.36 0.36

0.004 (0.02 0.006 0.274 0.94 (0.03 0.02

0.0057 0.003 (.248 0.00184 (0.003 (0.002 (0.002 (0.001 0.021 0.017 0.022 0.038 0.023

8.4 0.47 0.44 1.16 0.67

0.53 0.081 0.045 0.18 0.16

The reference values (Ref) of AGV-2, BCR-2, BHVO-2, BIR-1 and W-2 are taken from preferred values in GeoRem (http://georem.mpch-mainz.gwdg.de/). The reference values of other rock standard materials are taken from Govindaraju (1994). Data underlined are recommended values. Other values are proposed except those preceded by a ( which are information values.

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Table 4 Major (%) and trace element (ppm) compositions of analyzed upper crustal samples Shale SCO-1 SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 LOI Total Li Be B Sc V Cr Co Ni Cu Zn Ga Ge As Rb Sr Y Zr Nb Mo Cd In Sn Sb Te Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Tl Pb Bi Th U 62.78 0.63 13.67 5.14 0.05 2.72 2.62 0.90 2.77 0.21 AO-10 62.97 0.8 15.84 7.08 0.08 1.92 0.25 0.94 4.16 0.11 5.57 99.72 67.0 3.46 180 17.9 134 85.2 14.0 32.0 20.8 125 21.6 3.55 9.51 198 83.8 29.1 196 16.5 0.76 0.042 0.095 4.68 0.96 0.025 13.8 299 43.3 83.3 9.85 35.7 6.80 1.34 5.78 0.87 5.01 1.02 2.88 0.45 2.85 0.43 5.28 1.40 3.16 1.44 26.2 0.53 17.9 3.00 AO-12 56.56 0.79 20.66 5.75 0.02 3.13 0.13 0.82 8.41 0.05 3.86 100.18 86.6 4.97 248 19.8 130 111 18.1 46.3 43.6 58.3 26.4 3.31 2.31 250 67.0 30.0 163 16.1 0.43 0.010 0.107 4.82 0.35 0.040 21.1 383 45.1 80.9 10.5 38.2 6.36 1.15 5.36 0.90 5.48 1.14 3.18 0.50 3.17 0.49 4.90 1.40 3.27 1.28 7.74 0.91 19.4 2.33 PL-1 63.57 0.73 18.76 5.81 0.04 1.53 0.37 0.17 4.09 0.08 4.34 99.43 103 4.46 71.1 15.8 160 70.1 13.6 28.7 21.0 105 24.3 1.85 29.4 168 62.5 37.7 238 19.7 1.47 0.12 0.097 5.06 0.48 0.056 11.3 554 44.7 93.1 10.5 38.3 7.62 1.37 6.67 1.09 6.65 1.41 4.08 0.63 4.30 0.65 6.79 1.58 3.32 0.94 31.6 0.70 23.5 3.38 PL-6 61.08 0.68 15.67 4.93 0.05 1.86 4.73 0.43 3.47 0.1 7.31 100.31 56.4 2.81 91.3 13.2 75.1 53.0 13.0 22.7 33.0 69.4 19.8 1.87 3.43 186 258 33.4 204 16.9 0.27 0.063 0.077 4.22 0.51 0.033 11.0 323 46.9 89.2 10.5 38.7 7.16 1.18 6.01 1.01 5.59 1.15 3.17 0.54 3.34 0.53 5.91 1.54 2.65 1.01 24.1 0.53 19.8 3.68 PW-4 57.86 0.99 22.46 7.89 0.08 1.8 0.4 0.9 3.99 0.19 4.05 100.61 98.2 4.15 37.2 19.1 112 104 22.3 45.6 38.0 122 28.8 2.37 11.8 215 151 46.6 226 28.5 0.58 0.015 0.107 4.49 0.30 0.035 8.88 740 73.8 136 16.1 60.4 10.8 1.96 8.94 1.46 8.10 1.64 4.50 0.73 4.63 0.71 6.48 2.14 2.32 1.15 35.7 0.47 25.8 4.34 PW-5 55.34 0.96 22.08 8.82 0.15 1.68 0.53 0.88 3.2 0.21 5.5 99.35 114 4.18 48.4 16.4 113 97.7 25.5 49.8 40.1 121 27.2 2.68 17.9 170 113 40.5 175 26.5 0.63 0.013 0.11 4.85 0.33 0.042 9.28 606 64.8 118 14.9 53.3 9.96 1.88 8.48 1.31 7.54 1.50 4.04 0.63 3.99 0.61 5.02 1.94 2.77 1.05 29.0 0.51 21.2 3.25 SC-1 65.07 0.7 16.34 6.55 0.41 2.77 0.24 0.46 4.01 0.14 3.20 99.89 32.0 3.26 92.0 15.1 109 90.9 17.1 41.0 38.4 81.6 21.5 2.24 3.79 177 29.4 30.5 142 15.1 0.49 0.002 0.077 4.40 0.76 0.055 9.72 458 44.9 87.8 9.96 37.9 7.01 1.24 5.71 0.94 5.19 1.05 2.90 0.47 2.94 0.46 4.07 1.30 2.56 0.91 16.9 0.51 17.4 2.90 SC-2 65.34 0.71 16.5 6.25 0.25 2.63 0.23 0.36 4.23 0.15 3.18 99.83 27.0 3.34 91.7 12.7 105 88.8 18.6 40.7 46.3 63.6 21.3 2.32 3.65 185 26.8 30.8 142 15.3 0.23 0.004 0.083 4.56 0.81 0.051 10.1 486 46.2 89.7 10.3 39.1 7.32 1.33 6.02 0.98 5.37 1.06 2.92 0.47 2.99 0.46 4.03 1.30 2.61 0.99 10.1 0.49 17.5 2.88 SC-4 64.55 0.7 16.52 6.52 0.4 2.81 0.24 0.3 4.16 0.16 3.28 99.74 28.6 3.14 90.1 15.0 108 94.7 18.3 44.3 27.8 62.8 21.6 2.28 2.94 188 25.6 32.0 135 15.0 0.40 0.005 0.078 4.45 0.83 0.052 10.2 489 46.9 91.1 10.4 39.4 7.40 1.26 6.13 1.00 5.49 1.12 3.03 0.49 3.07 0.47 3.89 1.28 2.72 1.00 15.4 0.38 17.7 2.87 SC-5 65.34 0.72 17 5.99 0.25 2.68 0.22 0.25 4.45 0.15 3.26 100.31 29.1 3.46 109 15.5 110 90.2 16.7 39.1 18.6 52.5 22.4 2.20 4.41 198 24.5 30.8 139 15.7 0.17 0.005 0.077 4.61 0.93 0.058 10.6 499 48.6 93.3 10.9 40.8 7.51 1.34 6.07 0.98 5.28 1.07 2.92 0.48 2.97 0.46 3.97 1.35 2.57 1.03 7.63 0.50 18.6 2.96 Shales SC-8 65.58 0.72 16.51 6.32 0.22 2.63 0.21 0.64 4.09 0.14 3.12 100.18 27.7 3.20 80.3 16.7 111 85.7 16.3 39.0 116 62.3 20.5 2.07 9.89 173 31.0 30.0 138 13.6 0.15 0.020 0.073 4.03 0.75 0.036 9.00 423 40.8 83.9 9.52 35.2 6.59 1.19 5.58 0.86 5.08 1.05 2.95 0.47 2.85 0.43 3.70 1.19 2.50 0.87 6.02 0.23 17.1 2.80 MI-4 65.86 0.75 14.7 6.51 0.04 2.46 0.48 0.4 3.69 0.3 4.29 99.48 37.4 3.63 122 11.1 105 48.5 7.36 24.4 21.1 66.4 16.2 1.80 2.64 162 65.5 25.0 132 12.6 7.82 0.21 0.045 2.96 1.03 0.096 8.26 549 39.4 72.3 8.51 31.2 5.57 0.90 4.57 0.75 4.18 0.86 2.34 0.38 2.39 0.38 3.78 1.09 2.29 1.46 25.0 0.43 14.3 9.35 MI-1 70.97 0.45 13.84 4.2 0.04 2.46 0.34 1.17 3.6 0.21 3.38 100.66 38.4 3.51 103 12.7 73.8 95.4 7.53 23.8 18.8 22.8 17.5 2.29 5.84 178 25.8 18.6 95.4 10.3 2.47 0.11 0.061 2.76 1.71 0.086 6.32 472 28.1 49.6 5.90 22.1 4.06 0.73 3.36 0.56 3.14 0.65 1.78 0.30 1.90 0.30 2.83 0.87 1.89 1.27 7.49 0.40 12.3 2.97 Graywacke D059 63.84 0.92 14.50 6.90 0.16 2.63 3.28 2.20 2.89 0.18 2.92 100.01 54.5 2.22 14.2 18.2 124 86.4 18.2 36.3 41.7 89.0 20.3 2.02 17.8 157 159 37.6 276 16.4 0.58 0.15 0.082 3.75 1.52 0.038 8.68 762 40.1 85.5 9.88 36.8 7.33 1.40 6.46 1.05 6.44 1.34 3.72 0.60 3.82 0.59 7.53 1.19 1.68 1.09 26.5 0.32 18.3 2.88 D060 65.46 0.77 13.84 6.12 0.09 2.72 2.06 1.57 3.13 0.17 3.56 99.08 35.2 2.61 51.5 15.7 111 85.9 17.3 38.3 36.4 88.6 18.7 1.75 1.69 119 131 32.3 233 13.9 0.45 0.21 0.072 3.32 0.31 0.057 5.51 652 37.9 76.5 8.99 33.6 6.50 1.28 5.68 0.92 5.64 1.16 3.25 0.52 3.33 0.50 6.38 1.09 2.40 0.71 31.3 0.37 15.4 2.70 D062 67.54 0.77 14.33 5.60 0.08 1.50 2.50 2.75 2.66 0.13 1.70 99.06 67.6 2.96 4.11 13.3 70.6 40.0 12.3 14.1 19.7 88.3 19.7 1.86 0.39 187 135 29.6 255 20.3 0.35 0.11 0.074 4.80 0.10 0.012 12.5 625 46.4 96.3 11.3 41.4 7.97 1.24 6.71 1.01 5.72 1.09 2.84 0.42 2.66 0.41 7.18 1.40 0.81 1.22 111 0.16 22.0 2.67 D075 64.71 0.77 14.76 5.55 0.11 2.03 2.37 3.70 2.66 0.23 2.87 99.49 19.4 1.92 5.48 12.1 92.1 39.4 10.8 21.9 24.7 74.5 18.1 1.56 1.39 68.6 389 26.6 190 8.39 0.41 0.049 0.065 1.99 0.13 0.066 3.45 541 22.2 48.6 5.83 23.1 4.89 1.16 4.28 0.72 4.52 0.95 2.70 0.45 2.92 0.45 5.16 0.59 1.16 0.27 16.7 0.24 7.19 1.29 Pelite D100 60.87 0.92 14.96 7.08 0.08 3.55 2.97 1.58 3.97 0.19 3.57 99.35 61.6 2.76 71.8 17.6 128 92.9 19.2 45.0 32.5 83.9 20.9 1.99 2.57 155 163 30.1 200 17.0 0.37 0.071 0.074 3.26 0.70 0.025 8.93 760 40.3 79.2 9.52 35.1 6.72 1.38 5.64 0.89 5.29 1.08 2.97 0.47 3.02 0.46 5.44 1.25 2.15 0.84 29.7 0.25 14.8 2.54 D104 59.79 0.91 20.80 6.71 0.01 0.95 0.36 0.93 3.05 0.15 5.82 99.22 93.0 2.98 149 19.8 262 193 9.28 58.4 36.0 85.8 23.8 2.41 23.5 162 321 30.3 153 14.8 0.66 0.052 0.090 3.71 1.64 0.15 8.57 435 44.0 78.7 9.96 37.1 6.81 1.23 5.61 0.91 5.55 1.14 3.17 0.50 3.25 0.50 4.54 1.20 3.28 0.84 24.9 0.62 15.9 2.53

46.5 1.89 65.7 11.6 128 68.8 10.7 25.7 27.0 96.1 16.0 1.68 12.6 112 167 24.7 163 11.9 1.20 0.15 0.063 3.20 2.23 0.078 7.72 587 28.6 57.0 6.83 26.2 5.14 1.13 4.51 0.70 4.14 0.86 2.42 0.39 2.40 0.37 4.46 0.88 1.62 0.75 29.7 0.39 9.57 3.08

The data of major elements are taken from Nancy and Taylor (1976), Taylor et al. (1983) and Gao et al. (1998).

precise determination of the concentrations of Nb and Ta in the continental crust is important for establishing the style of crustal growth and geochemical mass balance in the Earth. Previously reported UCC La/Nb and La/Ta ratios fall in a range of 2.52.9 and 21.547.0, respectively [excluding the values of Shaw et al. (1967, 1976), which are signicantly lower (Condie, 1993; Taylor and McLenann, 1995; Wedopohl, 1995; Gao et al., 1998; McLenann, 2001; Barth et al., 2000)]. Lanthanum is strongly positively correlated with Nb (r2 = 0.76) and Ta (r2 = 0.86) in 33 sedimentary samples from this

study (SFig. 1), and the La/Nb and La/Ta ratios are essentially constant at 2.68 0.12 s and 33.7 1.2, respectively. The quoted uncertainty p xi x 2 =n, x = n . Unless otherwise indicated, all the reects 2 x i1 uncertainties mentioned below represent 2x. When the uncertainties in these ratios are taken into account, these ratios compare favorably with the UCC values determined by McLennan (2001), Plank and Langmuir (1998) and Barth et al. (2000). Since the UCC abundance of La is well-established (31 ppm, Taylor and McLennan, 1985; McLennan, 2001; Rudnick and Gao, 2003), these elemental ratios
n

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211

Pelite D111 65.43 0.95 14.26 6.03 0.10 2.09 1.26 1.39 3.23 0.15 5.42 99.90 54.4 2.58 57.0 15.3 124 82.9 14.6 36.4 34.1 109 19.9 2.07 3.56 144 112 23.6 198 18.0 1.23 0.21 0.072 2.99 0.43 0.039 7.89 821 29.2 65.1 6.99 25.7 4.97 1.02 4.11 0.66 4.06 0.85 2.49 0.42 2.82 0.45 5.45 1.29 2.05 0.70 19.3 0.29 13.8 2.63 D119 62.42 0.79 16.78 5.81 0.06 2.47 0.76 1.97 4.12 0.14 4.67 99.74 48.5 2.21 64.1 16.2 113 66.1 13.9 28.9 23.8 74.4 20.8 1.75 6.37 95.2 88.8 29.0 206 11.0 0.91 0.040 0.066 2.02 0.55 0.034 3.90 687 30.6 59.8 7.55 28.9 5.76 1.31 4.97 0.82 4.99 1.05 2.97 0.48 3.14 0.49 5.70 0.80 1.04 0.42 20.5 0.25 8.64 2.07

Pelite D122 66.15 0.77 15.40 6.15 0.07 1.98 0.46 1.00 3.77 0.13 5.06 100.60 51.5 3.03 85.9 14.4 133 91.3 15.6 47.2 29.2 96.2 20.5 2.14 6.67 164 54.1 30.1 191 15.5 1.13 0.12 0.073 3.34 0.91 0.060 9.27 705 40.5 77.8 9.48 35.0 6.66 1.27 5.62 0.90 5.38 1.12 3.09 0.49 3.22 0.49 5.51 1.21 2.22 1.02 19.9 0.44 14.9 3.54 D124 63.96 1.01 15.90 7.20 0.14 1.90 0.81 0.84 2.72 0.12 5.80 100.20 51.1 2.50 68.6 18.6 155 103 23.1 54.2 38.4 105 21.3 1.84 8.96 114 80.8 32.8 198 15.7 0.26 0.28 0.084 2.73 1.42 0.054 6.37 719 35.8 69.6 8.51 32.2 6.38 1.43 5.66 0.94 5.74 1.21 3.36 0.53 3.45 0.53 5.51 1.13 1.96 0.65 39.7 0.35 12.1 2.59 D355 61.31 0.71 16.02 6.31 0.09 2.93 3.12 1.00 3.24 0.16 5.30 99.77 47.7 2.83 71.7 16.1 110 99.9 16.4 44.3 36.2 71.2 19.5 1.94 17.7 157 107 27.2 183 14.5 0.19 0.061 0.075 3.32 1.33 0.039 9.05 597 35.5 71.0 8.37 31.2 6.00 1.18 5.16 0.81 4.80 0.99 2.78 0.44 2.86 0.45 5.20 1.14 2.83 0.81 62.7 0.43 14.3 2.34

Loess CY-4a-A 80.40 0.64 10.50 2.58 0.04 0.86 1.12 1.58 2.53 CY-4a-B 80.80 0.63 10.60 2.64 0.04 0.88 1.23 1.68 2.62 BP-1 72.70 0.57 15.80 3.30 0.05 0.95 1.56 3.27 2.39 BP-5 72.50 0.54 15.10 3.21 0.05 1.06 1.58 3.55 2.47 BP-3 72.5 0.69 15.2 3.94 0.054 0.88 1.27 3.13 2.26 CH 1 59.90 0.32 7.78 3.22 0.07 3.45 23.11 0.84 1.27 H

Leucogranite T3 73.15 0.29 14.79 1.91 0.026 0.85 1.35 3.86 2.74 0.10 T2 73.88 0.078 14.88 0.95 0.030 0.40 1.81 3.29 3.87 0.05

Diorite D284 56.82 1.27 15.82 8.46 0.15 4.07 4.75 3.99 2.00 0.30 2.78 99.81 24.4 1.97 13.9 27.1 133 77.9 22.4 32.2 18.2 101 19.1 1.56 2.97 39.9 353 36.3 315 15.0 0.80 0.094 0.083 2.08 0.58 0.013 2.23 508 23.2 57.0 6.90 29.1 6.77 2.04 6.41 1.05 6.29 1.30 3.42 0.56 3.46 0.53 6.90 0.99 0.97 0.26 13.4 0.17 5.18 1.48

Granodiorite T1 62.95 0.59 16.37 8.56 0.090 2.07 4.64 3.81 2.84 0.19 D308 58.92 0.62 16.79 6.94 0.11 3.15 6.29 3.76 1.17 0.18 2.04 99.51 16.8 0.98 3.02 17.6 138 28.9 19.7 19.7 26.5 64.4 18.0 1.22 0.19 33.9 490 19.1 121 6.71 0.24 0.042 0.042 0.76 0.046 0.0059 0.94 413 28.9 57.6 6.36 23.6 4.24 1.21 3.76 0.56 3.25 0.66 1.82 0.30 1.89 0.30 3.03 0.40 0.08 0.17 7.61 0.03 5.11 0.66 D276 64.70 0.50 16.57 3.94 0.081 1.37 3.71 4.14 3.07 0.23 1.45 99.54 14.5 2.58 4.04 6.78 56.0 7.89 6.67 4.29 8.58 61.3 19.0 1.33 0.23 88.7 865 21.0 200 20.0 0.076 0.035 1.65 0.064 0.0061 2.45 2342 55.5 100 10.8 36.1 5.98 1.63 4.92 0.68 3.80 0.74 1.95 0.32 1.91 0.29 5.03 1.53 0.22 0.51 20.9 0.07 12.2 2.04

Granite D312 68.45 0.25 16.38 2.05 0.049 0.71 2.59 5.38 2.03 0.10 1.34 99.21 21.4 1.39 6.17 2.80 22.8 2.99 3.30 2.32 7.36 42.7 15.2 1.01 0.19 46.7 633 8.82 136 4.94 0.18 0.028 0.018 0.75 0.051 0.0030 0.95 805 18.8 36.6 4.09 14.9 2.57 0.73 2.01 0.27 1.52 0.30 0.82 0.14 0.87 0.14 3.31 0.39 0.03 0.17 32.7 0.03 3.19 0.57 D314 74.66 0.22 12.62 1.59 0.042 0.32 0.55 4.04 4.56 0.04 0.89 99.43 5.33 1.97 7.78 3.18 8.68 1.91 1.13 1.15 3.62 47.3 14.9 1.55 0.72 90.3 64.5 27.4 243 9.16 0.60 0.037 0.065 1.78 0.11 0.0055 1.22 585 31.4 68.8 7.93 30.9 6.10 0.83 5.32 0.84 5.06 1.05 2.85 0.48 2.97 0.46 6.82 0.65 0.26 0.35 47.2 0.08 7.30 1.38

13.18 4.70

100.0 15.7 1.65 42.5 6.89 60.0 42.8 5.77 14.0 12.0 40.1 11.3 1.43 3.87 82.1 204 35.0 589 14.6 0.82 0.17 0.032 1.40 0.73 0.025 2.95 679 39.7 78.7 9.48 35.3 6.56 1.27 5.66 0.90 5.49 1.19 3.50 0.58 3.66 0.58 14.9 1.01 1.26 0.60 15.3 0.16 13.4 3.27

100.7 17.9 1.66 40.3 6.78 61.2 42.9 5.97 15.0 12.3 40.9 11.5 1.40 3.74 83.5 207 29.8 573 15.0 0.94 0.17 0.032 1.43 0.76 0.024 3.05 692 35.2 69.3 8.37 31.3 5.92 1.23 5.13 0.80 4.85 1.02 2.98 0.50 3.19 0.51 14.4 1.05 1.32 0.61 16.2 0.16 11.8 3.10

100.2 32.1 2.85 30.4 8.40 67.0 35.9 11.3 15.3 14.0 67.9 14.5 1.44 4.11 95.7 314 23.7 342 10.8 0.34 0.023 0.042 2.18 0.34 0.013 4.48 548 35.3 72.9 8.58 32.2 6.13 1.33 5.05 0.74 4.20 0.85 2.39 0.38 2.40 0.38 8.85 0.89 1.41 0.64 15.7 0.19 11.0 2.86

99.7 38.8 2.44 38.8 8.29 65.1 34.2 7.98 15.3 13.2 47.5 14.3 1.39 4.26 96.8 323 21.2 375 10.7 0.40 0.026 0.040 2.27 0.33 0.015 4.40 551 34.4 73.1 8.08 30.1 5.54 1.19 4.55 0.67 3.80 0.76 2.14 0.34 2.09 0.33 9.74 0.89 1.51 0.66 15.8 0.19 11.7 3.10

99.5 26.94 2.43 34.9 10.8 66.5 35.4 8.80 12.3 14.2 51.3 15.6 1.51 4.21 84.4 318 30.8 512 17.4 0.48 0.026 0.050 2.29 0.29 0.012 3.89 566 41.6 81.6 10.1 39.3 7.61 1.54 6.09 1.00 5.37 1.08 2.95 0.48 3.10 0.48 13.6 1.31 1.27 0.58 16.2 0.17 11.7 3.42

39.2 2.19 71.4 12.6 85.2 70.1 12.6 35.5 25.0 64.2 14.7 1.52 13.9 104 230 30.4 218 13.1 0.72 0.13 0.052 2.63 1.46 0.036 7.10 485 33.0 66.9 7.72 29.2 5.78 1.25 5.19 0.82 4.86 1.02 2.85 0.43 2.78 0.43 5.51 1.01 2.35 0.61 19.3 0.32 11.5 2.84

99.6 21.1 1.19 55.7 7.21 42.5 58.4 6.62 26.2 14.6 36.0 7.19 1.07 8.51 47.9 396 25.0 255 8.97 0.43 0.13 0.032 1.67 0.62 0.028 2.71 212 26.5 51.5 6.18 24.2 4.94 0.86 4.26 0.72 4.06 0.84 2.31 0.39 2.43 0.38 6.97 0.78 1.35 0.31 12.0 0.16 7.60 2.57

20.8 1.60 69.3 9.22 61.8 59.1 8.37 26.6 18.0 48.0 10.4 1.29 7.79 68.8 195 29.1 324 13.0 0.44 0.13 0.041 2.22 0.91 0.028 3.55 300 34.2 65.9 7.88 30.5 5.93 1.08 5.13 0.87 4.82 1.00 2.72 0.44 2.77 0.44 9.01 1.09 1.66 0.42 13.7 0.17 9.85 3.02

75.1 4.42 4.42 5.10 35.4 21.0 3.90 8.78 3.06 42.7 19.3 1.55 0.30 134 155 20.1 84.0 9.01 0.18 0.022 0.043 3.65 0.039 0.0019 6.10 435 23.5 48.2 5.84 21.4 4.71 0.92 4.14 0.65 3.81 0.73 1.87 0.29 1.93 0.28 2.94 1.24 0.85 0.74 39.1 0.07 13.0 2.51

106 5.69 6.19 4.01 9.60 8.65 1.29 4.65 2.57 23.5 17.3 2.05 0.48 252 96.4 38.7 55.3 10.9 0.09 0.041 0.024 2.26 0.19 0.0090 14.9 291 10.4 21.1 2.58 9.67 2.64 0.60 3.14 0.71 5.41 1.31 3.73 0.62 4.09 0.59 2.01 1.91 1.03 1.28 45.2 1.33 7.80 4.01

17.8 1.33 18.3 12.1 110 12.9 12.4 6.72 17.4 59.4 17.5 1.35 2.91 85.4 482 22.5 141 8.44 0.85 0.040 0.034 1.37 1.12 0.0041 5.74 710 25.9 55.9 6.83 24.4 4.70 1.19 4.23 0.60 3.63 0.77 2.13 0.34 2.32 0.35 3.76 0.84 2.07 0.38 19.8 0.08 9.17 3.02

can thus be used to obtain the upper crustal Nb and Ta abundances (Rudnick and Gao, 2003), which yields Nb = 11.6 0.5 ppm and Ta = 0.92 0.03 ppm (The quoted uncertainty reects 2 on that value, which derives from the uncertainty of the La/X ratio), a reduction by half of those of Taylor and McLennan (1985, 1995), conrming the estimates of Condie (1993), Plank and Langmuir (1998), Barth et al. (2000) and McLennan (2001). Nb in the 33 sedimentary samples is strongly correlated with Ta (r2 = 0.92) (SFig. 1c). These two elements are identical in ionic charge

and nearly identical in ionic radii and hence show strongly coherent geochemical behavior. Wedepohl (1995) and Gao et al. (1998) reported the UCC and bulk continental crust Nb/Ta ratio was 16.5 17.5, which is very close to the primitive mantle value of 17.617.8 (Hofmann, 1988; McDonough and Sun, 1995; Jochum et al., 1986), but signicantly higher than Taylor and McLennan's (1985, 1995) estimates at 11.011.4. Plank and Langmuir (1998) reported a Nb/Ta ratio of 14.2 1.8 on the basis of modern deep-sea sediments from a variety of tectonic and sedimentological regimes, which is very similar

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Table 5 Various estimates of trace element abundances (ppm) of the upper continental crust Element 1 Shaw et al. 2 Eade and 3 Condie 4 Gao et al. 5 Sims et al. 6 Plank and 7 Taylor and McLennan 8 McLennan 9 Wedepohl 10 Rudnick and Gao 11 This (1985, 1995) (2001) (1995) (2003) study (1967,1976) Fahrig (1973) (1993) (1998) (1990) Langmuir (1998) Li Be B Sc V Cr Co Ni Cu Zn Ga Ge As Rb Nb Mo Cd In Sn Sb Te Cs Er Tm Yb Lu Ta W Tl Bi U 22 1.3 9.2 7 53 35 12 19 14 52 14 20 1.95 28 15 98 80 17 38 32 70 18 1.34 4.4 82 12 0.78 0.079 1.73 0.3 3.55 20 3 15 11 60 35 10 20 25 71 17 1.6 1.5 112 25 1.5 0.098 0.05 5.5 0.2 3.7 2.3 0.33 2.2 0.32 2.2 2 0.75 0.13 2.8 (22) 3.1 17 (7) (53) (35) (12) (19) (14) (52) (14) 1.4 2 110 (26) 1.4 0.102 0.061 2.5 0.31 5.8 21 2.1 17 14.0 97 92 17.3 47 28 67 17.5 1.4 4.8 84 12 1.1 0.09 0.056 2.1 0.4 4.9 2.3 0.30 2.0 0.31 0.9 1.9 0.9 0.16 2.7 41 1.9 47 14 106 73 15 34 27 75 18.6 1.3 5.7 94 11.6 0.6 0.06 0.066 2.2 0.75 0.027 4.9 2.30 0.37 2.34 0.36 0.92 1.4 0.55 0.23 2.6

12 59 76 19 26 60

13.4 86 112 18 60

13.6 107 85 17 44

5.1 13.7 1.2

110 26 0.075

85

83 9.8

12

0.45 7.3

4.6

1.47 0.233 5.7 0.524 0.035 2.45

1.91 0.32 0.79

1.5

2.2

2.26 0.35 0.74 0.91 1.55 0.23 1.55

0.96 3.3

1.0

(1.5) (0.27) 1.5 1.4 0.75 0.123 (2.5)

Columns 14 represent averages of surface exposures. Columns 59 are estimates derived from ne-grain clastic sedimentary rocks and loess. Bracketed data in column 9 are values derived from Shaw et al. (1967, 1976).

to the estimate of Kamber et al. (2005) at 13.8 1.1 based on 30 alluvial sediments. On the other hand, Barth et al. (2000) suggested Nb/Ta ratios of 12.5 for the upper crustal and 11.4 for the bulk continental crust based on the analyses of the PAAS shales and worldwide loess. McLennan (2001) derived similar values of 12 and 10 for the two reservoirs. Our data, based on a wider variety of ne-grained clastic sediment and sedimentary rocks gives an upper crustal Nb/Ta = 12.6

from the correlations between La and Nb and Ta and a value of Nb/ Ta = 12.7 0.3 from the correlation between Nb and Ta (SFig. 1c). The two methods yield an identical Nb/Ta ratio, which is very similar to the above estimates of Barth et al. (2000) and McLennan (2001). Our data conrm the subchondritic Nb/Ta and superchondritic La/Nb and La/Ta ratios of the continental crust and reinforce the observation that the continental crust and the depleted mantle are not strictly complementary to one another (Barth et al., 2000; Rudnick et al., 2000; Kamber and Collerson, 2000; Xiao et al., 2006).

Fig. 2. Correlations between Ga and In in various ne-grained clastic sedimentary rocks and loess analyzed in this study. Lines represent linear t to data. r is correlation coefcient. Various upper crustal composition estimates are superimposed (Table 5). Estimates of In abundance given by Rudnick and Gao (2003) were calculated from averaging previous estimates of other workers and therefore are derivative and not shown.

Fig. 3. Correlations between Th and Sn in various ne-grained clastic sedimentary rocks and loess analyzed in this study.

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As expected, Zr and Hf show a very strong correlation (r2 = 0.99), with an average Zr/Hf ratio of 36.2 0.6 (SFig. 2). This is identical to the ratios determined by Condie (1993), Gao at al. (1998) and Kamber et al. (2005) at 37.2, 36.7, 36.4 and 36.9, respectively, but clearly higher than the UCC Zr/Hf of 32.8 given by Taylor and McLennan (1985, 1995) and the global subducted sediment average (32.0) of Plank and Langmuir (1998). As shown in SFig. 2, loess shows signicantly higher concentrations of Zr and Hf, which has been attributed to eolian concentration of zircon (Taylor et al., 1983). Thus, loess has elevated Zr/La and Hf/La ratios and cannot be used to derive upper crustal Zr and Hf concentrations, although their Zr/Hf ratio is identical to those of the other clastic sediments and the UCC. 4.2. Ga and In Gallium follows its expected geochemical behavior in showing a strong afnity to the same group IIIB elements Al2O3 (r2 = 0.83), with Al2O3/Ga = 8276 374 (SFig. 3). Taking the UCC Al2O3 value (15.4%) of Rudnick and Gao (2003), this ratio lead to UCC Ga = 18.6 0.8 ppm. Previously reported UCC abundances of Ga range from 14 to 20.9 ppm (Table 5). Our Ga abundance is identical to the estimate (18 ppm) of Gao et al. (1998) based on large-scale sampling and analysis of East China rocks. In contrast, few UCC estimates of In are available. Taylor and McLennan (1985, 1995) and Wedepohl (1995) gave values of 0.05 ppm and 0.061 ppm, respectively. The strong correlation (r2 = 0.91) between Ga and In in sedimentary rocks and loess yields an UCC In abundance of 0.066 0.003 ppm given the UCC Ga of 18.6 ppm (Fig. 2).

4.3. Sn The UCC Sn abundance is given at 5.5 ppm by Taylor and McLennan (1983, 1985, 1995) based on the study of sediments. This Sn value is factors of 3 and 2 higher, respectively, than the values given by Gao et al. (1998) and Wedepohl (1995), which were all calculated from rock averages. As shown in Fig. 3, Sn correlates well with Th in neclastic sedimentary rocks (r2 = 0.77), with the Th/Sn ratio of 4.7 0.4. Using the UCC Th abundance of 10.5 ppm (Rudnick and Gao, 2003), this ratio leads to a Sn abundance of 2.2 0.2 ppm. This value is within uncertainty of those estimated by Wedepohl (1995) and Rudnick and Gao (2003), but is signicantly lower than that estimated by Taylor and McLennan (1983, 1985, 1995). Taylor and McLennan (1983) calibrated their data using a theoretical calibration factor and recalibrated the literature data using their tin value for the G-1 standard rock (5.1 ppm). The Sn data for most of standard rocks (G-1, W-1, BCR-1, BHVO-1, MAG-1, SCO-1 and SGR-1) of Taylor and McLennan (1983) are systematically higher than reference values of Govindaraju (1994), Jochum et al. (1993) and the value obtained from this study by about a factor of 1.8. Therefore, we believe that the theoretically based recalibration in Taylor and McLennan (1983) is not justied, and consequently their UCC abundance of tin may be 80% lower. 4.4. Rb and Cs The upper crustal Rb abundance given by Taylor and McLennan (1985) is based on an assumed K2O/Rb ratio of 302. The average

Fig. 4. Correlations between (a) Rb/K2O and Rb, (b) Rb/Th and Rb, (c) Th and Rb and (d) Rb and Cs in various ne-grained clastic sedimentary rocks and loess analyzed in this study.

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K2O/Rb ratio determined in this study is 245 22. Using the UCC K2O abundance of 2.8% (Rudnick and Gao, 2003), this ratio leads to a Rb abundance of 115 10 ppm. As is illustrated in Fig. 4a, there is a signicant positive correlation between Rb/K2O and Rb in the sedimentary rocks and loess (r2 = 0.51), which indicates that Rb is more enriched relative to K2O during sedimentary processes. So we would over-estimate Rb concentrations in the upper continental crust if we use the correlation between K2O and Rb. In contrast, a much poorer positive correlation exists between Rb/Th and Rb ( r2 = 0.31) (Fig. 4b), and Rb correlates well with Th in the sedimentary rocks and loess (r2 = 0.69) (Fig. 4c), with a Th/Rb ratio of 0.11 0.01. Using this ratio and the UCC Th abundance of 10.5 ppm (Rudnick and Gao, 2003), a Rb concentration of 94 7 ppm is derived. This estimate may represent maximum concentrations for the UCC. Previously reported upper crustal abundances of Rb range from 82 to 112 ppm with an average of 93 12 ppm (Shaw et al., 1976; Eade and Fahrig, 1973; Condie, 1993; Gao et al., 1998; Taylor and McLennan, 1985; Rudnick and Gao, 2003), which is indistinguishable from this study when uncertainties in the latter are accounted for. As indicated in Fig. 4d, Rb is strongly correlated with Cs (r2 = 0.78) in the sedimentary rocks and loess, yielding a Rb/Cs ratio of 19.2 1.4. This ratio falls within the wide range of previous values (15.330) (Taylor and McLennan, 1985; Wedepohl, 1995; Rudnick and Fountain, 1995; Gao et al., 1998; Plank and Langmuir, 1998; McLennan, 2001; Rudnick and Gao, 2003), some of which are less well-constrained due to lack of reliable data for Cs. McDonough et al. (1992) suggest no

fractionation of Rb from Cs during sedimentary processing and deduced an average Rb/Cs of 19 11 for the upper crust based on analysis of 140 sediments and sedimentary rocks (including loess). This value is signicantly lower than the value of 30 in Taylor and McLennan's (1985) upper crust. Data for marine sediments compiled by Plank and Langmuir (1998) support a lower Rb/Cs ratio of the upper crust at 15.3. Using this ratio and a rubidium concentration of 112 ppm, they derived an upper crustal Cs concentration of 7.3 ppm. Although Cs data show only a poor correlation with La, the La/Cs ratio of sediments led McLennan (2001) to a revised Cs estimate of 4.6 ppm, which yields an Rb/Cs ratio of 24. Our Rb/Cs ratio (19.2 1.4) is identical to that found by McDonough et al. (1992), but with signicantly lower error, and conrms the coherent behavior of Rb and Cs during sedimentary processing. Rudnick and Fountain (1995) and Wedepohl (1995) adopt a Rb/Cs ratio of 20 and 19, respectively, similar to that found in this study. Using our Rb/Cs ratio (19.2) and a Rb abundance of 94 ppm, a UCC Cs abundance of 4.9 0.3 ppm is derived. This Cs concentration is in good agreement with recent estimates of Rudnick and Gao (2003) and McLennan (2001) at 4.9 ppm and 4.6 ppm, respectively. 4.5. Tl There is a signicant positive correlation between Tl/La and Tl in the sedimentary rocks and loess (r2 = 0.62) (Fig. 5a), which indicates that Tl is more enriched relative to La during sedimentary processes. So we would over-estimate Tl concentrations in the UCC if we use the

Fig. 5. Correlations between (a) Tl/La and Tl, (b) Tl/Rb and Tl, (c) Rb and Tl and (d) Th and Tl in various ne-grained clastic sedimentary rocks and loess analyzed in this study.

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and analysis of East China rocks, but are lower than previous estimates (33.1 ppm) of Taylor and McLennan (1985, 1995) and Wedepohl (1995). 4.7. Ge and W Germanium and tungsten also strongly correlate with Rb with r2 = 0.70 and 0.65 (excluding the greywacke sample D062), respectively (Fig. 7), and Rb/Ge = 72 5 and Rb/W = 66 5. Using an UCC Rb concentration of 94 ppm, these ratios lead to upper crustal Ge = 1.3 0.1 ppm and W = 1.4 0.1 ppm. The Ge abundance estimate is consistent with previous studies at 1.341.6 ppm (Taylor and McLennan, 1985, 1995; Wedepohl, 1995; Gao et al., 1998). In contrast, W shows factors of 23 of variation in previous studies (Table 5), with the Sims et al. (1990) estimate being highest. Sims et al. (1990) estimate is based on the observed constant W/Ba ratio (0.006 0.002) in shales and glacial loess samples and by assuming UCC abundance of Ba = 550 ppm. However, our data do not show any signicant correlations between W and Ba (r2 b 0.1). Our new W abundance is identical with estimate of Wedepohl (1995), which is calculated from rock averages compiled by Krauskopf (1970) in their derived proportions of major rock units. 4.8. Bi Bismuth correlates strongly with Be (r2 = 0.62) and W (r2 = 0.72) in sedimentary rocks (Fig. 8), with Be/Bi = 8.7 1.1 and W/Bi = 6.2 0.6. These ratios, combined with the Be and W values obtained above,

Fig. 6. Correlations between (a) Th and Be and (b) Rb and Be in various ne-grained clastic sedimentary rocks and loess analyzed in this study.

correlation between La and Tl. In contrast, no obvious correlation exists between Tl/Rb and Tl (r2 = 0.09) (Fig. 5b), and Rb correlates well with Tl in ne-clastic sedimentary rocks (r2 = 0.77) (Fig. 5c). The Rb/Tl ratio is constant at 171 10, which yields a UCC Tl abundance of 0.55 0.03 ppm given the UCC Rb abundance of 94 ppm. This thallium value is identical to that derived from surface sampling by Shaw et al. (1976), but is obviously lower than estimates at 0.75 1.55 ppm from other studies (Table 5). Kamber et al. (2005) found a constant Th/Tl ratio of 24 for 30 alluvial sediments. As shown in Fig. 5d, Tl is strongly correlated with Th (r2 = 0.91) in loess, pelites and graywackes (n = 19) with a Th/Tl of 20 1, but the correlation is much less signicant in shales with a Th/Tl ratio of 17 3 (n = 14). The reasons for the more scatted Tl correlations in shale are not clear. Using the Th/Tl ratio of 20 1and Th abundance of 10.5 ppm, a UCC Tl abundance of 0.53 0.04 is obtained, which is well within uncertainty of the value derived from the Rb/Tl ratio. 4.6. Be Fig. 6 illustrates the correlation between Be and Th (r2 = 0.59) and Rb (r2 = 0.74) in sedimentary rocks and loess. As indicated in Table 5, previous estimates of the Be concentration in the UCC range from 1.3 to 3.1 ppm. Our sedimentary data suggest upper crustal Th/Be = 5.4 0.4 and Rb/Be = 50 3, leading to an upper crustal Be content of 1.9 0.2 ppm or 1.9 0.1 ppm using the known Th and Rb abundances of the UCC. The two estimates agree within error and are consistent with the estimate (1.95 ppm) of Gao et al. (1998) based on large-scale sampling

Fig. 7. Correlations between Rb and Ge (a) and W (b) (excluding the graywacke sample D062) in various ne-grained clastic sedimentary rocks and loess analyzed in this study.

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4.10. Transition metals Sc, Co, V, Cr, Ni, Cu and Zn The UCC abundances of transition metals Sc, V, Cr, Co, Ni, Cu and Zn are less well-known compared to REE. For V, Cr, Co, and Ni, McLennan (2001) suggests an approximate factor of two increases in UCC abundances compared to those of Taylor and McLennan (1985) and Wedepohl (1995), which were taken from values of surface averages of the Canadian Shield (Shaw et al., 1967, 1976). As suggested by Gao et al. (1998), the Canadian Shield is not representative of the UCC transitional element abundances. This is because many of the mac volcanic rocks in the uppermost crust have been removed from this shield, which is now dominated by amphibolite-faces gneisses. In this regard, estimates from Eastern China are more representative, as the Eastern China estimates include samples from the North China and Yangtze cratons and Qinling orogenic belt. The latter preserves an almost complete section of the upper crust from unmetamorphosed to greenschist-faces volcanic and sedimentary rocks, as well as granitoids. It can be seen from Table 5 that transitional element estimates of McLennan (2001) are consistent with those of the Eastern China UCC (Gao et al., 1998). However, the correlations between La and transitional metals that form the basis of McLennan's (2001) estimates are not signicant. This is conrmed by our data (r2 b 0.3). In contrast, our data show good correlations between Fe2O3 (reported here as total Fe) and other transition metals (r2 = 0.510.85) (SFig. 5). Accordingly, the sedimentary data suggest an upper crustal Fe2O3/Sc = 4066 201, Fe2O3/Co = 4025 234, Fe2O3/V = 558 38, Fe2O3/Cr = 804 85, Fe2O3/ Ni = 1880 211, Fe2O3/Cu = 2177 187, and Fe2O3/Zn = 794 89. Given an upper crustal Fe2O3 abundance of 5.92% (Gao et al., 1998), these ratios lead to upper crustal estimates of Sc = 14 1 ppm, Co = 15 1 ppm, V = 106 7 ppm, Cr = 74 8 ppm, Ni = 32 4 ppm, Cu = 27 2 ppm and Zn = 75 9 ppm. As tabulated in Table 5, these new estimates of Sc, V, Cu and Zn are identical to those of Gao et al. (1998), McLennan (2001) and Rudnick and Gao (2003), but the values of Co, Ni and Cr are lower by about 20%, 40% and 20%, respectively. In order to reduce the effects of inadequate sampling, analytical differences and regional variation in upper crustal abundances on estimates, we calculate transition metal averages (Sc, V, Co, Cr and Ni) in various sediments (see Table 6 for data sources). There are excellent correlations between V and Sc (r2 = 0.87), V and Co (r2 = 0.82), Co and Cr (r2 = 0.63), Co and Ni (r2 = 0.68) and Cr and Ni (r2 = 0.94) in these averages (Fig. 10), with V/Sc = 7.6 0.5, V/Co = 7.0 0.4, Co/Cr = 0.20 0.03, Co/Ni = 0.43 0.07 and Ni/Cr = 0.46 0.04. Using our previously determined abundances of V = 106 ppm and Co = 15 ppm, these ratios lead to UCC abundances of Sc = 14 1 ppm (V/Sc), Co = 15 1 ppm (V/ Co), Cr = 73 10 ppm and Ni = 34 5 ppm, which are identical (within uncertainty) to the abundances derived from the correlations with

Fig. 8. Correlations between (a) Be and Bi and (b) W and Bi in various ne-grained clastic sedimentary rocks and loess analyzed in this study.

yield the UCC Bi abundances of 0.23 0.03 ppm (Be) and 0.23 0.02 ppm (W), respectively. This Bi abundance is identical to that of Gao et al. (1998) based on large-scale sampling and analysis of East China rocks, but is signicantly higher than the values given by Taylor and McLennan (1985, 1995) and Wedepohl (1995) (Table 5). Taylor and McLennan (1985, 1995) adopted Bi value (0.13 ppm) from Heinrichs et al. (1980). Wedepohl (1995) gave values of 0.123 ppm, which is also calculated from rock averages of Heinrichs et al. (1980), but is based on their derived proportions of major rock units. 4.9. U Uranium shows a weak correlation (r2 =0.38) with La in sedimentary rocks (excluding MI-4) (SFig. 4). The average La/U ratio is 14.01.1, and which leads to an upper crustal U content of 2.20.2 ppm. This value is within the range of previous estimates (1.52.8 ppm) (Table 5), and is identical to the values of Shaw et al. (1967, 1976) and Condie (1993) at 2.2 2.45 ppm. Since U is highly soluble and because loess [Cheimcal Index of Alteration (CIA)=5565; CIA=molar Al2O3 /(Al2O3 +CaO +Na2O+K2O), where CaO refers only to Ca that is not in carbonate and phosphate, Nesbitt and Young, 1982] is less weathered than shales and pelites (CIA=6685), loess may provide a more robust estimate of upper crustal abundance of U. This is supported by the considerably stronger correlation between La and U in loess samples (r2 =0.85) from Gallet et al. (1998) (n =25) and this study (n =8) (Fig. 9), with La/U=11.70.5. Using this ratio and given an UCC abundance of 31 ppm La, we derive a U concentration of 2.60.1 ppm, which is identical to the recent estimate (2.7 ppm) of Rudnick and Gao (2003).

Fig. 9. Correlations between La and U in loess from Gallet et al. (1998) and this study.

Z. Hu, S. Gao / Chemical Geology 253 (2008) 205221 Table 6 Averages of transition metals in various sediments and sedimentary rocks Clastic sediment averages (ppm) Rivera Loessb NASCc PAASd Russian shalee V Sc Co Cr Ni 147 18.3 18.9 129 62 77 7.8 10.6 56 20 140 16 20 100 60 132 19.5 21.5 105 57.5 Condief GLOSSg PM mudh 117 16 20 104 54 110 13.1 78.9 70.5 102 15.1 15.5 99 54 AM mudi 122 17.2 14.5 57 25 Alluvialj Loessk PAASk China pelitek 117 16.4 20.6 68.4 32.9 63.7 8.78 8.43 47.3 20 112 15.2 15.6 84.6 35.9 127 16.4 17.1 89.6 42.7 China Tillitel Condie graywackek sandm 99.3 14.8 14.7 62.9 27.7 91 10.7 10.7 82 36 15 2 2.5 30 8

217

Condie PM AM graywacken sando sandp 135 14 18 75 38 36 5.85 6.5 41 19 98 14.4 13.5 43 16

26 127 58

Many of the average values of sediments were calculated by McLennan (2001). a Average river suspended load from 19 major rivers of the world (Martin and Meybeck, 1979; Gaillardet et al., 1999). b Average loess based on eight regional averages (New Zealand, United States, Kaiserstuhl, Spitsbergen, Argentina, United Kingdom, France and China) (Taylor et al., 1983; Barth et al., 2000; Gallet et al., 1998; Jahn et al., 2001) (n = 52). c North American shale composite based on composite of 40 shales of mainly Phanerozoic ages (Gromet et al., 1984). d Post-Archean Average Australian Shale (n = 23) (Nance and Taylor, 1976; Taylor and McLennan, 1985). e Average of Phanerozoic (n = 34840) and late Proterozoic (n = 5940) shales mainly from the former Soviet Union (Ronov et al., 1988). f Average post-Archean cratonic shale (Condie, 1993)(n N 100). g Average global subducting sediment (Plank and Langmuir, 1998). h Average passive margin turbidite mud derived from trailing edge and continental collision basins (McLennan et al., 1990) (n = 9) and Paleozoic passive margin mud (Bhatia, 1981, 1985) (n = 10). i Average active margin turbidite mud derived from modern active margins (McLennan et al., 1990) (n = 18), Paleozoic oceanic island arcs (n = 9), continental arc (n = 12) and Andean-type margins (n = 2) (Bhatia, 1981, 1985). j Averages alluvial sediment (n = 28) collected from 25 rivers in Queensland, eastern Australia (Kamber et al., 2005). k This study. Loess (n = 8); PAAS shale (n = 13); China pelite (n = 261); China graywacke (n = 139). See Table 1 for details. l Average tillite derived from late Proterozoic Port Askaig tillite matrix (Panahi and Young, 1997) (n = 21) and Pleistocene till from central Canada (Yan et al., 2000) (n = 33). m Average Phanerozoic cratonic sandstone (Condie, 1993) (n N 100). n Average Phanerozoic greywacke, calculated from mean of Paleozoic (n N 100) and MesozoicCenozoic (n N 100) averages (Condie, 1993). o Average post-Archean sandstone from modern trailing edge and continental collision basins (McLennan et al., 1990) (n = 11) and Australian Paleozoic passive margin (Bhatia, 1981; Bhatia and Crook, 1986) (n = 15). p Average active margin turbidite sand from modern active margin basins (McLennan et al., 1993) (n = 25) and Paleozoic oceanic island arcs (n = 11), continental arcs (n = 32), and Andean-type margins (n = 10) (Bhatia, 1981; Bhatia and Crook, 1986).

Fe2O3. These sedimentary data suggest minor revisions of UCC abundances of Co [from 17.3 ppm (Rudnick and Gao, 2003) to 15 ppm], Cr (from 92 ppm to 73 ppm) and Ni (from 47 ppm to 34 ppm). As shown in Fig. 10e, our Ni and Cr estimates are consistent with those of Gao et al. (1998), which was based on large-scale sampling and analysis of Eastern China rocks. Although absolute estimates differ by about 2040%, our results conrm the suggestion of generally higher ferromagnesian trace elements in the UCC compared to the Canadian Shield (Gao et al., 1998; McLennan, 2001; Rudnick and Gao, 2003). 4.11. Li Teng et al. (2004) recently suggested an UCC lithium abundance of 35 11 ppm, based on MC-ICP-MS analyses of the same suite of shales and loess. Their estimate is signicantly higher than previous estimates of 2022 ppm (Table 5). As shown in Fig. 11a, lithium correlates positively with In (r2 = 0.62) in sedimentary rocks, with the ratios of In/Li = 0.0017 0.0002. Using this ratio and our derived UCC abundances of In (0.066 ppm), the Li abundance is 39 5 ppm. In contrast to loess and greywackes, pelites and shales are formed by more complicated processes (e.g., chemical and physical erosion, transportation, deposition and lithication) and generally subjected to a higher degree of weathering, as demonstrated by their generally higher CIA (Table 1). Accordingly, soluble Li is more readily separated from insoluble In in pelites and shales. This is supported by the stronger correlation between In and Li (r2 = 0.78) with In/Li = 0.0016 0.0002, if sedimentary samples with CIA N 72 are excluded (Fig. 11b). Using this ratio, we derive a Li concentration of 41 6 ppm, which is within uncertainty of the value proposed by Teng et al. (2004). 4.12. B The loess samples investigated here show a relatively restricted range of B concentrations from 30 ppm to 70 ppm, which is the result of physical mixing of glacially eroded sediments derived from a large

variety of upper crustal rocks. The population shows a distribution with an average value of 48 11 ppm. This value provides a rst-order estimate of the B concentration of UCC. Due to the weathering and sorption effects, the B contents of shales vary considerably from 35 to 250 ppm. To compensate for these effects, we examined the positive correlation between B and elements in sedimentary rocks and loess. Boron correlates positively (r2 N 0.4) with the following elements: (a) K2O, (b) Ge, (c) Rb, (d) Cs, (e) W and (f) Bi [excluding greywacke samples with extremely low B contents (D059, D062 and D075)], with K 2 O/B = 0.050 0.007, Ge/B = 0.029 0.004, Rb/B = 2.04 0.34, Cs/ B = 0.11 0.02, W/B = 0.031 0.004 and Bi/B = 0.0052 0.0008 (SFig. 6). Using these correlations and average upper crustal concentrations of these elements (Rudnick and Gao, 2003; this study), we determined a B concentration of the upper crust from each correlation (SFig. 6). The weighted mean of these results is 47 4 ppm. This value is signicantly higher than previous estimates at 9.228 ppm (Table 5). 4.13. Te Tellurium is present at very low concentrations in most geological materials. The analytical difculties in determining this element at nanogram levels accounts for the lack of crustal abundance data (Rudnick and Gao, 2003). Our Te data correlate positively with B (r2 = 0.67) in sedimentary rocks and loess, except for those samples with extremely low (D059, D062 and D075) or high (AO-10 and AO12) B concentration (Fig. 12). Excluding these samples, the B/Te ratio is constant at 1758 229. Using this ratio, and an upper crustal B abundance of 47 ppm, a Te abundance of 0.027 0.003 ppm is derived. 4.14. Sb and As Sims et al. (1990) suggest an As/Ce ratio of 0.08 0.03 in loess and shales, which led them to an As abundance of 5.1 1 ppm in the UCC. In a similar fashion they arrived at an upper crustal Sb abundance of 0.45 0.08 ppm. However, our data do not show any signicant

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Fig. 10. Correlations between (a) V and Sc, (b) V and Co, (c) Co and Cr, (d) Co and Ni, and (e) Cr and Ni [excluding the average of global subducting sediments (GLOSS)] in various average sediments and sedimentary rocks. See Table 6 for data sources. Large solid rectangle with error bars indicates upper crustal abundances with 2 errors from this study.

correlations between As and Sb and REE. In contrast, our data only show good correlations between Te and Sb (r2 = 0.86) in loess samples and between Sb and As (r2 = 0.80) in sedimentary samples (excluding samples with CIA N 72 and shale MI-1) (SFig. 7), with Te/Sb = 0.036 0.005 and Sb/As = 0.13 0.03. Using these ratios and our derived UCC abundances of Te (0.027 ppm), the Sb and As abundances are 0.75 0.11 ppm and 5.7 1.2 ppm, respectively. Our Sb abundance is higher than previous estimates at 0.20.45 ppm. The As abundance is within uncertainty of those of Sims et al. (1990), Gao et al. (1998) and Rudnick and Gao (2003) at 5.1 ppm, 4.4 ppm and 4.8 ppm, respectively, but is signicantly higher than estimates of Taylor and McLennan (1985, 1995) and Wedepohl (1995) at 1.52 ppm (Table 5).

4.15. Mo and Cd Our data do not show any signicant correlations between Cd and Mo and other elements. Thus, estimation of the UCC abundances of moderately soluble Cd and soluble Mo from sedimentary rocks is compromised. An alternative way to estimate upper crustal composition is by making weighted averages of upper crustal rock types: evolved igneous rocks (granites, granodiorites and diorite) and clastic sedimentary rocks and sediments (graywackes, pelites, loess, and shales). The weight ratio of granitoids (65%) to sedimentary rocks (35%) is determined using the well-constrained abundances of SiO2,

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219

sampling by Gao et al. (1998) at 0.78 ppm, but is lower than other author's estimates by factors of 2 to 3 (Table 5). Rare data on Cd are available for sedimentary rocks. Taylor and McLennan (1985) adopted Cd value from Heinrichs et al. (1980). Heinrichs et al. (1980) gave a value of 0.098 ppm, which is calculated from weighted sums of sedimentary rocks (10%), magmatic rocks (45%) and metamorphic rocks (45%). Wedepohl (1995) also adopted rock averages of Heinrichs et al. (1980) for the calculation of Cd abundance, but is based on their derived proportions of major rock units. Our new Cd abundance agrees with previous estimates at 0.0750.102 ppm when uncertainty is considered (Table 5). 4.16. Heavy rare earth elements Er, Tm, Yb and Lu REEs have very low solubility in water. Therefore, their concentrations in sedimentary rocks provide robust estimates of the average composition of their source region (Nance and Taylor, 1976; Taylor and McLennan, 1985). The REE patterns for post-Archean shales show striking similarities worldwide, which have led to the suggestion that the REE of shales reect that of the average upper continental crust (Nance and Taylor, 1976; Taylor and McLennan, 1985). Measurements of a variety of loess samples around the world also reveal that their REE patterns are remarkably constant and similar to those of average shales (Taylor et al., 1983; Gallet et al., 1998). As a result, all UCC REEs estimates, regardless of whether they are based on shales, loess, marine sediments, or surface sampling, agree to within 20% for the light REE (LREE). In contrast, the estimated heavy rare earth elements (HREEs) abundances show a variation of up to 50% (Rudnick and Gao, 2003). Fig. 13 compares various REE estimates of the upper continental crust, normalized to the results from this study (see below). Due to the presence of sedimentary rocks with low REE abundances (sandstones, carbonates, evaporates), the absolute upper crustal abundances are lower than those of shales by 1525% (Taylor and McLennan, 1985; Gao and Zhang, 1991a). The UCC REEs abundances of this study, Barth et al. (2000) and Kamber et al. (2005) are all calculated based on the abundances in ne-grained clastic sedimentary rocks by assuming an UCC La abundance of 31 ppm and then diluting the REE content of the sedimentary rock average by the appropriate amount to obtain this La abundance. As shown in Fig. 13, the REE estimates of Condie (1993), Taylor and McLennan (1985), Barth et al. (2000), Rudnick and Gao (2003) and this study agree to within 20%. Moreover, the estimates of Barth et al. (2000) and Rudnick and Gao (2003) agree to within 7% of this study except for the Tm, Yb and Lu values of Rudnick and Gao (2003), which

Fig. 11. Correlations between In and Li in (a) all ne-grained clastic sedimentary rocks and loess analyzed in this study and (b) in samples with CIA 72.

Al2O3, La and Th. Using this ratio and the average compositions of upper crustal granitoids and clastic sedimentary rocks (Table 4), the calculated upper crustal composition has 66.2% SiO2, 15.6% Al2O3, 31.7 ppm La, and 10.4 ppm Th, which are identical to the estimates of Rudnick and Gao (2003). We thus derive upper crustal abundances of 0.6 0.3 ppm Mo and 0.06 0.02 ppm Cd. The quoted uncertainty reects 2x on that value, which derives from the uncertainty of the averages. The Mo abundance is similar to that derived from surface

Fig. 12. Correlations between B and Te in various ne-grained clastic sedimentary rocks and loess analyzed in this study. Two shales (AO-10 and AO-12) and three graywackes (D059, D062 and D075) samples are excluded from the linear regression.

Fig. 13. Comparison of various REE estimates of the upper continental crust (Shaw et al., 1967, 1976; Condie, 1993; Taylor and McLennan, 1985, 1995; Wedepohl, 1995; Gao et al., 1998; Barth et al., 2000; Rudnick and Gao, 2003; Kamber et al., 2005). All values normalized to the REE compositions obtained in this study.

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are about 20%, 15% and 14% lower, respectively. Tm is the least constrained of all the REEs, because it is mono-isotopic (and therefore cannot be analysed by isotope dilution) and since many ICP-MS protocols use it as an internal standard (e.g., Eggins et al., 1997). Furthermore, Er and Tm abundances are provided only by Taylor and McLenann (1985) and Rudnick and Gao (2003). The Er value of Rudnick and Gao (2003) is directly taken from Taylor and McLennan (1985), and the Dy, Ho and Tm values are interpolated from the REE pattern. It is therefore difcult to ascertain whether the relative higher Tm (0.37 ppm), Yb (2.36 ppm) and Lu (0.36 ppm) values determined here are due to an over-estimate of Tm, Yb and Lu in our samples (Table 4) or a genuine feature of the UCC [note that the Er value (2.30 ppm) of this study is identical to that of Taylor and Mclenann (1985)]. There are strong correlations between Er and Tm, Yb, and Lu in our samples, loess from Gallet et al. (1998) and alluvial sediments from Kamber et al. (2005) (r2 0.93) (SFig. 8), with Er/Tm = 6.3 0.1, Er/ Yb = 0.99 0.01 and Er/Lu = 6.5 0.1. As we use the same suite of shale and loess samples as Barth et al. (2000), their data are not shown in SFig. 8. Using an upper crustal Er abundance of 2.30 ppm, these ratios lead to UCC abundances of Tm = 0.37 0.01 ppm, Yb = 2.34 0.03 ppm and Lu=0.36 0.01 ppm, which are within uncertainty of the values obtained above using the ratio of the given La abundance to the average La content in the ne-clastic sedimentary rocks. SFig. 9 compares REE patterns of the various estimates of the UCC, where chondrite values are taken from Palme and Jones (2003). The REE pattern of this study is very smooth. It is concluded from these lines of evidence that the higher Tm, Yb and Lu abundances of this study are not due to over-estimate of Tm, Yb and Lu in our samples. We thus suggest 20% increases of Tm, Yb and Lu abundances from values (0.3 ppm Tm, 2 ppm Yb, and 0.31 ppm Lu) of Rudnick and Gao (2003) to our preferred values (0.37 ppm Tm, 2.34 ppm Yb and 0.36 ppm Lu). 5. Conclusions We derived new estimates of UCC abundances for As, B, Be, Bi, Cd, Co, Cr, Cs, Cu, Er, Ga, Ge, In, Li, Lu, Mo, Nb, Ni, Rb, Sb, Sc, Sn, Ta, Te, Tl, Tm, U, V, W, Yb and Zn, mostly based on signicant (r2 N 0.6) interelement correlations observed in the clastic sediments and sedimentary rocks in conjunction with well-determined UCC abundances for certain key elements. We calculate abundances of Cd and Mo by assuming that the upper continental crust consists of 65% granitoid rocks plus 35% clastic sedimentary rocks. The validity of this assumption is supported by back-calculated upper crustal SiO2, Al2O3, La and Th abundances, which are identical to the values of Rudnick and Gao (2003). Suggested revisions and updates to the upper crustal abundances given by Rudnick and Gao (2003) are as follows (all in parts per million): B = 47, Bi = 0.23, Cr = 73, Li = 41, Lu = 0.36, Mo = 0.6, Ni = 34, Te = 0.027, Tl = 0.53, Tm = 0.37, W = 1.4 and Yb = 2.34. Acknowledgments This research is supported by the National Nature Science Foundation of China (Grants 90714010, 40703006, 40521001, 40373013, 40673019), Chinese Ministry of Education and State Administration of Foreign Expert Affairs (306021, IRT0441, B07039). We thank Roberta L. Rudnick, Ross Taylor and Hongfei Zhang for providing upper crustal samples. We also thank Roberta L. Rudnick, Bernhard Peucker-Ehrenbrink and one anonymous reviewer for their constructive comments on the early draft of the manuscript. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.chemgeo.2008.05.010.

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