Supplementary materials
Liu, S.-A., et al., Copper isotopic composition of the silicate Earth
Contents:
Fig. S1: Micrograph of orogenic peridotites analyzed in this study
Fig. S2: Result of long-term Cu isotope analysis of in-house Cu standard
Fig. S3: Correlation of Cu with S concentration for cartonic peridotites
Fig. S4: Correlation of Al2O3 and Cu with MgO for cratonic peridotites
Fig. S5: Correlation of d65Cu with MgO and Cu concentration for cratonic peridotites
Table S1: Analytical methods and data of major and trace elements of orogenic peridotites
Table S2 Copper isotopic compositions of cratonic and orogenic peridotites
Table S3 Copper isotopic compositions of basalts, andesites and dacites
References: cited in the supplementary materials.
Fig. S1 Micrograph of orogenic peridotites analyzed in this study, showing the presence or lacking of metasomatized minerals such as phlogopite. Ol: olivine; Grt: garnet; Opx: orthopyroxene; Serp: serpentine; ZMF: Zimafang, Dabie-Sulu orogen; RBZ: Dabie-Sulu orogen.
Figure S2 Long-term analysis of in-house Cu standard (YS-Cu) against NIST 976 from August, 2012 to August, 2014, yielding an average d65Cu value of 0.53‰ with two standard deviations of ±0.03‰ (N = 69).
Figure S3 Correlation of Cu with S concentration for cartonic peridotite xenoliths from Damaping, the North China Craton. The positive correlation indicates that Cu in the peridotites is mainly hosted by sulfides.
Figure S4 Correlation of Al2O3 and Cu concentrations with MgO for peridotites studied. The data are from Rudnick et al. (2004) and Liu J. et al. (2010; 2011). The star represents the primitive mantle (PM) with MgO = 38.8 wt.%, Al2O3 = 4.4 wt.%, and Cu = ~28 ppm (Sun and McDonough, 1989).
Figure S5 Correlation of Cu isotopic compositions with MgO and Cu concentrations for peridotites reported in this study. The data from Fansi (NCC), in which all peridotites were metasomatized, are separately plotted in the lower diagram. Except for sample FS2-09, the peridotites from Fansi display positive correlation between d65Cu and Cu concentration.
Table S1 Major and trace elements of orogenic peridotites reported in this study.
Sample no. / RBZ-1 / RBZ-2 / RBZ-3 / RBZ-4 / RBZ-5 / RBZ-6 / RBZ-7 / RBZ-8 / RBZ-9 / RBZ-10 / 13ZMF-1 / 13ZMF-2 / 13ZMF-3SiO2 / 41.50 / 41.39 / 41.32 / 41.02 / 40.73 / 40.82 / 42.26 / 42.24 / 42.38 / 42.18 / 42.3 / 39.9 / 44.6
TiO2 / 0.01 / 0.02 / 0.02 / 0.01 / 0.01 / 0.01 / 0.02 / 0.03 / 0.01 / 0.01 / 0.03 / 0.02 / <0.01
Al2O3 / 0.08 / 0.18 / 0.10 / 0.10 / 0.10 / 0.12 / 0.79 / 0.71 / 0.59 / 0.61 / 3.53 / 2.64 / 2.73
TFe2O3 / 7.36 / 7.33 / 7.22 / 7.35 / 7.44 / 7.38 / 7.53 / 7.88 / 7.65 / 7.73 / 8.21 / 7.56 / 7.41
MnO / 0.11 / 0.11 / 0.11 / 0.11 / 0.11 / 0.09 / 0.12 / 0.12 / 0.12 / 0.12 / 0.12 / 0.11 / 0.12
MgO / 48.64 / 47.53 / 48.15 / 48.38 / 49.16 / 49.32 / 43.36 / 44.82 / 43.29 / 43.31 / 38.0 / 38.4 / 40.6
CaO / 0.01 / 1.12 / 0.01 / 0.5 / 0.02 / 0.07 / 1.09 / 0.44 / 0.56 / 0.27 / 2.53 / 1.98 / 1.35
Na2O / 0.03 / 0.03 / 0.03 / 0.029 / 0.03 / 0.03 / 0.05 / 0.04 / 0.04 / 0.03 / 0.26 / 0.14 / 0.11
K2O / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.20 / 0.19 / 0.07
P2O5 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.03 / 0.01 / 0.05 / <0.01
Li / 1.72 / 1.78 / 1.72 / 1.64 / 1.51 / 1.48 / 0.88 / 0.87 / 0.90 / 0.97 / 1.34 / 1.03 / 0.45
Be / 0.03 / 0.04 / 0.01 / 0.03 / 0.03 / 0.03 / 0.05 / 0.04 / 0.01 / 0.05 / 0.17 / 0.09 / 0.1
Sc / 2.61 / 2.60 / 2.62 / 2.30 / 2.36 / 2.33 / 5.44 / 4.31 / 4.39 / 4.69 / 13.79 / 11.59 / 11.29
V / 7.4 / 12.6 / 5.8 / 7.1 / 8.9 / 7.7 / 24.8 / 19.4 / 17.4 / 19.1 / 32.8 / 28.7 / 20.2
Cr / 1064 / 2227 / 448 / 943 / 1596 / 1332 / 2472 / 1876 / 1781 / 1874 / 2790 / 2583 / 3764
Co / 165.2 / 179.2 / 194.7 / 176.2 / 93.3 / 95.4 / 122.9 / 128.6 / 114.5 / 199.0 / 98.18 / 97.58 / 94.58
Ni / 1613 / 1486 / 1547 / 1501 / 1543 / 1555 / 1261 / 1275 / 1285 / 1390 / 1875 / 1931 / 1889
Cu / 1.42 / 4.32 / 1.27 / 1.93 / 1.12 / 1.83 / 2.40 / 5.01 / 4.10 / 6.23 / 11.25 / 4.45 / 2.51
Zn / 26.8 / 31.9 / 26.1 / 25.2 / 26.8 / 26.1 / 30.8 / 26.4 / 26.8 / 28.7 / 45.8 / 42.0 / 42.4
Ga / 0.167 / 0.254 / 0.150 / 0.178 / 0.201 / 0.198 / 0.493 / 0.395 / 0.348 / 0.384 / 2.39 / 1.52 / 1.21
Rb / 0.123 / 0.406 / 0.144 / 0.134 / 0.129 / 0.137 / 0.175 / 0.245 / 0.163 / 0.186 / 7.78 / 5.57 / 2
Sr / 1.35 / 1.55 / 0.92 / 1.24 / 2.49 / 2.71 / 5.77 / 4.76 / 4.88 / 4.41 / 56.95 / 69.55 / 42.35
Y / 0.02 / 0.07 / 0.02 / 0.02 / 0.03 / 0.04 / 0.05 / 0.05 / 0.04 / 0.05 / 3.63 / 2.24 / 0.76
Zr / 0.136 / 0.488 / 0.150 / 0.145 / 0.965 / 0.329 / 0.451 / 0.402 / 0.211 / 0.285 / 1.91 / 0.9 / 0.47
Nb / 0.042 / 0.066 / 0.045 / 0.040 / 0.058 / 0.059 / 0.061 / 0.050 / 0.054 / 0.074 / 0.25 / 0.21 / 0.24
Cs / 0.014 / 0.034 / 0.020 / 0.014 / 0.009 / 0.013 / 0.009 / 0.020 / 0.013 / 0.016 / 0.38 / 0.48 / 0.14
Ba / 1.506 / 6.359 / 1.985 / 1.099 / 0.882 / 1.007 / 1.685 / 7.440 / 1.792 / 4.420 / 191.73 / 229.73 / 175.73
La / 0.031 / 0.323 / 0.040 / 0.095 / 0.040 / 0.059 / 0.077 / 0.065 / 0.123 / 0.126 / 1.34 / 1.13 / 0.77
Ce / 0.060 / 0.683 / 0.063 / 0.204 / 0.090 / 0.124 / 0.159 / 0.132 / 0.249 / 0.253 / 1.7 / 2.43 / 1.36
Pr / 0.008 / 0.065 / 0.009 / 0.022 / 0.014 / 0.018 / 0.021 / 0.018 / 0.029 / 0.029 / 0.16 / 0.29 / 0.13
Nd / 0.039 / 0.166 / 0.036 / 0.062 / 0.065 / 0.077 / 0.086 / 0.070 / 0.117 / 0.110 / 0.62 / 1.33 / 0.48
Sm / 0.022 / 0.045 / 0.028 / 0.028 / 0.029 / 0.030 / 0.035 / 0.035 / 0.040 / 0.035 / 0.14 / 0.29 / 0.05
Eu / 0.001 / 0.004 / 0.001 / 0.002 / 0.002 / 0.003 / 0.005 / 0.003 / 0.005 / 0.006 / 0.08 / 0.11 / 0.05
Gd / 0.005 / 0.026 / 0.004 / 0.008 / 0.011 / 0.012 / 0.015 / 0.010 / 0.015 / 0.018 / 0.27 / 0.26 / 0.01
Tb / 0.000 / 0.002 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.002 / 0.002 / 0.06 / 0.04 / 0
Dy / 0.003 / 0.011 / 0.003 / 0.003 / 0.005 / 0.006 / 0.009 / 0.009 / 0.007 / 0.009 / 0.46 / 0.3 / 0.07
Ho / 0.000 / 0.002 / 0.001 / 0.001 / 0.001 / 0.001 / 0.002 / 0.002 / 0.001 / 0.002 / 0.12 / 0.07 / 0.01
Er / 0.002 / 0.006 / 0.002 / 0.003 / 0.003 / 0.005 / 0.006 / 0.005 / 0.003 / 0.005 / 0.37 / 0.24 / 0.09
Tm / 0.000 / 0.001 / 0.001 / 0.000 / 0.000 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.06 / 0.03 / 0.01
Yb / 0.003 / 0.006 / 0.004 / 0.003 / 0.003 / 0.006 / 0.006 / 0.007 / 0.005 / 0.007 / 0.44 / 0.26 / 0.14
Lu / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.001 / 0.07 / 0.05 / 0.03
Hf / 1.097 / 1.346 / 1.747 / 1.238 / 0.768 / 0.593 / 0.613 / 0.649 / 0.572 / 1.884 / 0.06 / 0.03 / 0.01
Ta / 0.014 / 0.017 / 0.019 / 0.015 / 0.016 / 0.013 / 0.009 / 0.010 / 0.008 / 0.047 / 0.02 / 0.01 / 0.01
Pb / 0.185 / 0.244 / 0.506 / 0.132 / 0.073 / 0.102 / 0.180 / 0.154 / 0.122 / 0.119 / 10.74 / 9.07 / 6.29
Th / 0.008 / 0.051 / 0.008 / 0.013 / 0.006 / 0.012 / 0.010 / 0.020 / 0.015 / 0.018 / 1.87 / 1.06 / 0.36
U / 0.011 / 0.033 / 0.013 / 0.014 / 0.007 / 0.013 / 0.012 / 0.018 / 0.013 / 0.015 / 0.33 / 0.19 / 0.06
Analytical Methods: Major elements were analyzed by wet-chemistry methods at the China University of Geoscience, Beijing, China. Analytical uncertainties for the majority of major elements were better than 1%. For trace element determination, whole-rock powder (~50 mg) was dissolved in a mixture of HF + HNO3 at 190°C using Parr bombs for ~ 72 hrs. Dissolved samples were diluted to 50 ml using 1% HNO3 before analyses. Analyses were accomplished using an inductively coupled plasma mass spectrometer (ICP-MS) at the University of Science and Technology of China. Reproducibility was better than 5% for elements with concentrations >10 ppm and less than 10% for those <10 ppm.
Table S2 Copper isotopic compositions of mantle peridotites reported in this study.
Sample No. / SiO2 / Al2O3 / MgO / Mg# / S / ƒo2 / Cu / d65Cu / 2SD / nCratonic peridotites
FS-01 (M) / 43.0 / 1.94 / 42.4 / 89.6 / - / 25.1 / 0.14 / 0.07 / 5
FS-18 (M) / 45.7 / 2.00 / 40.9 / 91.0 / - / 10.5 / 0.15 / 0.03 / 5
FS-36 (M) / 44.4 / 3.46 / 38.3 / 89.2 / - / 43.9 / 0.30 / 0.03 / 5
FS-44 (M) / 43.9 / 2.16 / 41.2 / 90.0 / - / 14.6 / 0.25 / 0.04 / 5
FS-45 (M) / 43.9 / 2.54 / 38.5 / 89.5 / - / 46.7 / 0.22 / 0.07 / 6
FS-50 (M) / 42.9 / 2.59 / 39.7 / 88.7 / - / 25.8 / 0.49 / 0.05 / 5
FS-64 (M) / 42.8 / 2.01 / 43.0 / 89.3 / - / 45.0 / 0.68 / 0.04 / 5
FS-68 (M) / 42.4 / 1.12 / 45.0 / 90.6 / - / 11.9 / -0.21 / 0.05 / 6
FS2-04 (M) / 43.9 / 1.53 / 43.5 / 90.4 / - / 14.9 / -0.10 / 0.03 / 5
FS2-09 (M) / 44.5 / 3.93 / 37.4 / 89.3 / - / 41.5 / -0.64 / 0.04 / 5
FS2-10 (M) / 42.9 / 2.67 / 39.7 / 87.6 / - / 21.6 / -0.13 / 0.02 / 5
YY-04 (N) / 43.88 / 1.63 / 44.39 / 91.7 / <22 / -0.7 / 7.4 / 0.15 / 0.09 / 4
YY-08 (M) / 44.38 / 2.97 / 39.9 / 90.0 / <22 / 0.0 / 25.9 / -0.09 / 0.04 / 5
YY-09 (M) / 44.44 / 3.04 / 40.77 / 90.6 / <22 / -0.1 / 8.6 / 0.13 / 0.02 / 5
YY-11 (M) / 42.45 / 1.77 / 44.79 / 90.6 / <22 / -0.4 / 5.1 / 0.06 / 0.07 / 5
YY-13 (M) / 43.76 / 2.44 / 41.87 / 90.5 / <22 / 0.1 / 8.7 / 0.02 / 0.05 / 5
YY-22 (M) / 43.96 / 2.45 / 42.26 / 91.0 / <22 / -0.5 / 13.8 / -0.04 / 0.05 / 6
YY-26 (N) / 43.39 / 3.08 / 41.65 / 90.4 / 24 / -0.5 / 22.0 / -0.24 / 0.05 / 5
Repeat / -0.15 / 0.09 / 3
YY-27 (M) / 42.77 / 2.87 / 41.16 / 89.6 / <22 / -0.1 / 11.6 / -0.03 / 0.04 / 5
YY-51(M) / 41.34 / 1.12 / 46.02 / 91.4 / <22 / 0.2 / 3.9 / 0.27 / 0.04 / 4
YY-52 (M) / 43.67 / 2.7 / 41.5 / 90.6 / <22 / 0.2 / 11.0 / 0.20 / 0.08 / 5
YY-60 (M) / 42.52 / 1.26 / 44.85 / 90.9 / <22 / 0.0 / 6.4 / 0.30 / 0.06 / 6
DMP-04 (N) / 44.40 / 2.29 / 42.05 / 91.1 / 73 / -0.7 / 17 / 0.16 / 0.05 / 6
DMP-19 (N) / 44.83 / 1.91 / 40.74 / 91.1 / 91 / -1.0 / 10 / 0.13 / 0.07 / 6
DMP-25 (M) / 44.39 / 1.61 / 43.88 / 91.7 / 20 / -0.4 / 10 / -0.09 / 0.07 / 6
DMP-41 (M) / 44.75 / 2.76 / 40.15 / 90.2 / 110 / -3.6 / 15 / 0.06 / 0.08 / 6
DMP-51 (N) / 44.83 / 1.96 / 41.97 / 91.0 / 130 / -1.3 / 14.7 / 0.19 / 0.06 / 6
DMP-56 (N) / 44.79 / 3.49 / 38.15 / 89.5 / 260 / -1.3 / 27.3 / -0.07 / 0.09 / 6
DMP-58 (N) / 44.87 / 3.16 / 38.82 / 89.7 / 230 / -1.3 / 20.5 / 0.05 / 0.07 / 6
DMP-60 (M) / 46.34 / 3.67 / 36.68 / 89.7 / 320 / -2.8 / 22.4 / 0.21 / 0.08 / 6
Note: Major elements and ƒo2 values of peridotites are from Rudnick et al. (2004) and Liu J. et al. (2010, 2011). Major element compositions of the garnet peridotite sample (Alps-01) were measured by wet-chemistry methods in this study with an analytical uncertainty of better than 2%. Cu concentrations were measured in this study by solution ICP-MS with an uncertainty of better than ±10%. M and N behind sample number indicate metasomatized and non-metasomatized, respectively.
Table S2 Continued
Orogenic peridotites /
Alps orogenic belt / Alps-01 / Metasomatized / 48.8 / -0.10 / 0.05 / 3 /
Raobazhai, Dabie-Sulu / RBZ-1 / Non-metasomatized / 1.42 / -0.12 / 0.05 / 3 /
/ RBZ-3 / Non-metasomatized / 1.27 / -0.01 / 0.05 / 3 /
/ RBZ-4 / Non-metasomatized / 1.93 / 0.05 / 0.02 / 3 /
/ RBZ-5 / Non-metasomatized / 1.12 / -0.15 / 0.05 / 3 /
/ RBZ-6 / Non-metasomatized / 1.83 / -0.19 / 0.03 / 3 /
/ RBZ-7 / Non-metasomatized / 2.40 / 0.15 / 0.03 / 3 /
/ RBZ-8 / Non-metasomatized / 5.01 / 0.05 / 0.05 / 3 /
/ RBZ-9 / Non-metasomatized / 4.10 / -0.03 / 0.06 / 3 /
/ RBZ-10 / Non-metasomatized / 6.23 / 0.08 / 0.02 / 3 /
/ YBZ3 / Metasomatized / 6.29 / 0.46 / 0.02 / 3 /
Zimafang, Dabie-Sulu / 13ZMF-1 / Metasomatized / 11.25 / 0.35 / 0.02 / 3 /
/ 13ZMF-2 / Metasomatized / 4.45 / 0.51 / 0.05 / 3 /
/ Repeat / Metasomatized / 0.48 / 0.03 / 3 /
/ 13ZMF-3 / Metasomatized / 2.51 / -0.34 / 0.05 / 3 /
/ RBZ-2 / Non-metasomatized / 4.32 / -0.11 / 0.02 / 3 /
Xugou, Dabie-Sulu / 99XG-1C(XJ-1I) / Metasomatized / 5.30 / 0.05 / 0.03 / 3 /
/ 98XG-410(XJ-4D) / Metasomatized / 64.69 / 0.10 / 0.06 / 3 /
/ 99XG-1A / Metasomatized / 48.02 / -0.20 / 0.02 / 3 /
Rongcheng, Dabie-Sulu / RC-1J / Metasomatized / 2.41 / 1.82 / 0.04 / 3 /
Table S3 Copper isotopic compositions of basalts, andesites and dacites reported in this study.