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 65Cu 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 65Cu 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 65Cu 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

-3

SiO2 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 65Cu 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 3YY-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

Location Sample No. Type Cu 65Cu 2SD nOrogenic 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 3RBZ-4 Non-metasomatized 1.93 0.05 0.02 3RBZ-5 Non-metasomatized 1.12 -0.15 0.05 3RBZ-6 Non-metasomatized 1.83 -0.19 0.03 3RBZ-7 Non-metasomatized 2.40 0.15 0.03 3RBZ-8 Non-metasomatized 5.01 0.05 0.05 3RBZ-9 Non-metasomatized 4.10 -0.03 0.06 3RBZ-10 Non-metasomatized 6.23 0.08 0.02 3YBZ3 Metasomatized 6.29 0.46 0.02 3

Zimafang, Dabie-Sulu 13ZMF-1 Metasomatized 11.25 0.35 0.02 313ZMF-2 Metasomatized 4.45 0.51 0.05 3Repeat Metasomatized 0.48 0.03 313ZMF-3 Metasomatized 2.51 -0.34 0.05 3RBZ-2 Non-metasomatized 4.32 -0.11 0.02 3

Xugou, Dabie-Sulu 99XG-1C(XJ-1I) Metasomatized 5.30 0.05 0.03 398XG-410(XJ-4D) Metasomatized 64.69 0.10 0.06 399XG-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.

Sample no. Rock type Location SiO2wt.%

MgOwt.

%

TiO2 wt.%

Cu (ppm) 65Cu 2sd

07-FC-1 Continental basalt Fangcheng - - - 26.7 0.06 0.03 07-FC-2 Continental basalt Fangcheng - - - 26.8 0.04 0.05 07-FC-4 Continental basalt Fangcheng - - - 13.9 0.30 0.05

Repeat - - - - 0.32 0.0513AFS-4 Continental basalt Anfengshan 42.36 8.36 2.49 47.5 -0.18 0.04

Repeat -0.15 0.0210FS-6 Continental basalt Taihang 46.56 9.72 2.12 54.8 0.25 0.07 FS-1 Continental basalt Taihang 44.07 8.81 2.79 45.4 0.01 0.04 FS-3 Continental basalt Taihang 47.06 7.43 2.28 50.3 0.14 0.10 FS-30 Continental basalt Taihang 43.53 9.93 2.63 44.5 0.35 0.07

Repeat 0.39 0.06FS-36 Continental basalt Taihang 46.31 8.47 2.21 64.0 0.15 0.05 HHL-2 Continental basalt Taihang 45.73 8.26 2.49 43.2 0.19 0.07 ZQ-1 Continental basalt Taihang 49.8 7.17 2.22 41.7 0.21 0.06 JX-1 Continental basalt Taihang 47.4 6.72 2.91 34.8 0.18 0.06

MAS-1 Continental basalt Taihang 47.21 6.47 2.74 32.5 0.12 0.03JD-1 Continental basalt Taihang 47.03 6.48 2.74 34.8 0.15 0.05GB-2 Continental basalt Taihang 47.31 6.72 2.89 41.3 0.14 0.03

HBJ4-1 Continental basalt Liaoxi 54.83 6.45 0.86 54.3 0.05 0.03 HBJ4-2 Continental basalt Liaoxi 53.16 6.23 0.90 50.3 0.17 0.03 HBJ4-3 Continental basalt Liaoxi 52.84 7.03 0.89 77.9 0.18 0.04

Repeat 0.21 0.05SHT-3 Continental basalt Liaoxi 56.67 5.92 0.74 32.5 -0.12 0.09 SHT-14 Continental basalt Liaoxi 55.78 5.21 1.1 44.3 -0.07 0.01 JG-01 Continental basalt Liaoxi 44.84 8.31 2.92 58.2 0.03 0.02 JG-02 Continental basalt Liaoxi 45.48 8.25 2.89 56.4 0.02 0.05 JG-03 Continental basalt Liaoxi 44.82 8.38 2.93 58.3 0.05 0.07 JG-05 Continental basalt Liaoxi 45.01 8.3 2.95 55.6 0.18 0.04 JG-07 Continental basalt Liaoxi 43.4 8.39 2.95 58.0 0.02 0.03 JG-09 Continental basalt Liaoxi 44.82 8.30 2.93 61.4 0.07 0.04 Ferrar Cont. Flood basalt Antarctica 49.67 7.38 0.44 85.0 0.03 0.06

ZCZ1-1 Andesite Liaoxi 60.19 3.30 0.77 28.1 0.05 0.08 ZCZ1-3 Andesite Liaoxi 61.67 3.77 0.74 29.5 0.01 0.08

PAN-05-011 Accreted OIB Panama Azuero 48.3 6.80 2.80 102.8 0.18 0.08 PAN-05-019 Accreted OIB Panama Azuero 39.9 30.91 0.76 48.5 0.04 0.05 PAN-05-021 Accreted OIB Panama Azuero 44.9 16.48 1.94 81.9 0.18 0.05 PAN-05-024 Accreted OIB Panama Azuero 45.2 3.57 3.36 83.6 0.15 0.07PAN-05-028 Accreted OIB Panama Azuero 42.0 26.30 1.27 59.4 0.17 0.07

REU 140822-31 OIB, La Reunion Indian Ocean 44.6 20.58 1.69 84.3 0.12 0.05 REU 140822-32 OIB, La Reunion Indian Ocean 44.2 21.53 1.65 68.1 -0.02 0.05 REU 140825-38 OIB, La Reunion Indian Ocean 46.7 6.79 2.96 67.4 0.10 0.02 REU 140825-41 OIB, La Reunion Indian Ocean 44.8 9.22 2.75 66.1 0.09 0.02 REU 140825-45 OIB, La Reunion Indian Ocean 46.4 9.88 2.61 69.5 -0.07 0.06 REU 140829-71 OIB, La Reunion Indian Ocean 46.4 9.85 2.62 89.5 0.13 0.03 REU 140911-77 OIB, La Reunion Indian Ocean 46.6 9.47 2.62 71.4 0.03 0.03 La Palma 1971 OIB, Canary Isl. Atlantic Ocean 43.0 7.73 3.72 88.5 0.12 0.07

Manuna Ulu 1974 OIB, Hawaii Pacific Ocean 49.6 8.06 2.37 106.2 0.06 0.05 CR01-1 MORB Carlsberg Ridge 48.6 8.42 1.32 84 0.07 0.07 CR02-1 MORB Carlsberg Ridge 49.1 7.58 1.58 68 0.10 0.08 CR03-3 MORB Carlsberg Ridge 48.5 9.24 1.18 76 0.11 0.06 CR04-1 MORB Carlsberg Ridge 47.5 8.39 1.42 258 0.05 0.03 AR04-1 MORB North Atlantic 49.0 8.25 1.55 69 0.14 0.04 AR05-1 MORB North Atlantic 46.5 6.66 1.29 109 0.04 0.07 BRI-21 Back arc basalt Costa Rica 47.29 6.32 1.44 76.1 0.15 0.07 BRI-23 Back arc basalt Costa Rica 47.18 6.37 1.58 103.0 0.19 0.03 BRI-25 Back arc basalt Costa Rica 46.35 5.42 1.73 111.7 0.11 0.05 PAS-74 Forearc bas..andesite Costa Rica 55.79 3.26 0.73 132.7 0.23 0.07 PAS-75 Forearc basalt Costa Rica 48.30 3.94 0.86 239.1 0.15 0.07 PAS-78 Forearc basalt Costa Rica 50.32 4.46 0.67 148.7 0.10 0.02 INA-067 Arc dacite Costa Rica 65.85 1.08 0.43 39.7 0.07 0.05 INA-087 Arc andesite Costa Rica 56.80 2.17 0.69 74.5 0.28 0.07

Repeat 0.26 0.04TAL-79 Calc-alk. arc andesite Costa Rica 59.20 2.75 0.67 96.4 0.07 0.06 ALT-02 Tholeiitic arc basalt Costa Rica 47.38 6.73 1.07 46.7 0.03 0.03

GAM-07 (200) Arc basalt Kamchatka EVF 51.6 5.35 0.85 17.0 0.26 0.08GAM-14 (200) Arc andesite Kamchatka EVF 55.8 3.62 0.86 15.6 0.17 0.02 GAM-26 (200) Arc basalt Kamchatka EVF 50.6 4.94 1.00 51.6 0.12 0.02 GAM-28 (200) Arc basalt Kamchatka EVF 49.8 6.24 0.83 64.4 0.07 0.02 KIZ-01 (230) Arc dacite Kamchatka EVF 63.6 2.44 0.58 20.3 -0.14 0.04

Repeat -0.15 0.04

Note: EVF: Kamchatka Eastern Volcanic Front; CKD: Central Kamchatka, Depression; SR: Kamchatka Sredinny Ridge back arc; NCKD: North Central Kamchatka Depression. The numbers bracketed in the sample no. of arc basalts, andesites and dacites represent the distance to the trench (km). *The three andesites have adakitic geochemical signature. Major element compositions of the continental basalt from Antarctica and OIB from Reunion, LaPalma and Hawaii were measured by wet-chemistry methods in this study with an analytical uncertainty of better than 2%. Cu concentrations of these samples were measured in this study by solution ICP-MS with an uncertainty of better than ±10%.

References cited in the supplementary materials: Liu, J.-G., Rudnick, R. L., Walker, R. J., Gao, S., Wu, F. Y., Piccoli, P. M., 2010. Processes

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Liu, J.-G., Rudnick, R. L., Walker, R. J., Gao, S., Wu, F.-Y., Piccoli, P. M., Yuan, H., Xu, W.-L., Xu, Y.-G., 2011. Mapping lithospheric boundaries using Os isotopes of mantle xenoliths: An example from the North China Craton. Geochim. Cosmochim. Acta 75, 3881-3902.

Rudnick, R. L., Gao, S., Ling, W. L., Liu, Y. S., Mcdonough, W. F., 2004. Petrology and geochemistry of spinel peridotite xenoliths from Hannuoba and Qixia, North China Craton. Lithos 77, 609-637.

Sun, S., Mcdonough, W., 1989. Chemical and isotopic systematics of oceanic basalts: implications for mantle composition and processes. Geological Society London Special Publications 42, 313.