Supporting Information for

An assessment of natural and anthropogenic trace elements in atmospheric deposition during 1776-2004 A.D. using the Miaoergou ice

core, eastern Tien Shan, China

Xiang Zoua, Shugui Houa,b,*, Shuangye Wua,c, Wangbin Zhanga, Ke Liua, Jinhai Yua,

Yaping Liud, Hongxi Panga

a School of Geographic and Oceanographic Sciences, Nanjing University, Nanjing, China.

b CAS Center for Excellence in Tibetan Plateau Earth Sciences, Beijing, China.

c Department of Geology, University of Dayton, Dayton, Ohio, USA.

d State Key Laboratory of Cryospheric Sciences, Northwest Institute of Eco-Environment

and Resources, Chinese Academy of Science, Lanzhou, China.

*Corresponding author: S. Hou (shugui@nju.edu.cn)

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Figure S1. Raw concentrations of Pb, Sn, Cu, Sb, As, Bi, Tl, and Rb during the period 1776-2004 A.D..

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Figure S2. (a) Spatial correlations between the Miaoergou Rb flux and antecedent annual precipitation (1901–2004 A.D.); (b) reconstructed scPDSI (1901–2004 A.D.). The monthly precipitation data with a 0.5° × 0.5° resolution (1901–2004 A.D.) were obtained from the Climate Research Unit at the University of East Anglia (CRU TS v. 3.24) (Harris et al., 2014). The scPDSI data with a 0.5° × 0.5° resolution (1901–2004 A.D.) are available at https://crudata.uea.ac.uk/cru/data/hrg/. The red star represents the location of Miaoergou. The solid cross indicates that correlation is significant at the 99% confidence level.

Table S1. Detection limit, procedure blank, and analytical results of Certified Reference Material SLRS‐4a (Liu et al., 2011).

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TEDetectio

nlimit

Procedure bankb

SLRS-4 (×1000)Found Certified Krachler et al.(2005)

V 2.7 4.8 ± 3.6 0.36 ± 0.004 0.32 ± 0.03Cr 21.4 74.4 ± 21.6 0.35 ± 0.02 0.33 ± 0.02Mn 1.5 20.3 ± 16.2 3.39 ± 0.03 3.37 ± 0.18Co 0.5 1.4 ± 0.6 0.041 ± 0.003 0.033 ± 0.08Ni 2.1 16.1 ± 13.9 0.78 ± 0.03 0.67 ± 0.08Cu 1.5 7.5 ± 4.8 1.83 ± 0.08 1.81 ± 0.08As 2.6 5.3 ± 1.6 0.72 ± 0.02 0.68 ± 0.06Rb 0.5 <D.L. 1.43 ± 0.05 —— 1.4 ± 0.07Sr 0.3 4.1 ± 1.2 28.3 ± 0.01 26.3 ± 3.2Mo 0.5 0.7 ± 0.3 0.20 ± 0.01 0.21 ± 0.02Cd 0.7 <D.L. 0.014 ± 0.001 0.012 ± 0.002Sn 1.2 3.8 ± 2.0 0.009 ± 0.001 ——Sb 0.5 <D.L. 0.24 ± 0.003 0.23 ± 0.04Ba 0.8 7.0 ± 3.1 12.3 ± 0.1 12.2 ± 0.6Tl 0.1 0.2 ± 0.0 0.007 ± 0.001 —— 0.0054 ± 0.0003Pb 0.3 34.0 ± 30.3 0.083 ± 0.002 0.086 ± 0.007Bi 0.1 <D.L. 0.002 ± 0.001 —— 0.0021 ± 0.0001Th 0.1 0.2 ± 0.1 0.02 ± 0.001 ——U 0.3 <D.L. 0.050 ± 0.001 0.050 ± 0.003

aUnit of measure is pg g−1.bD.L. is detection limit.

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Table S2. Statistical data for annual element excess concentration (Ex) (in ppb) for the three periods: 1776-1850 A.D., 1850-1950 A.D., 1950-2004 A.D. and ratio (Ex concentration as a percentage of total concentration in 1950-2004).

1776-1850 1850-1950 1950-2004Max Min Median Max Min Median Max Min Median Ratio(%)

V 1520.7 <0 <0 3915.9 <0 <0 4022.5 <0 73.3 9Mn 20870.

1<0 <0 98603.

9<0 <0 45640.

2<0 <0 <0

Co 537.4 <0 <0 2057.8 <0 <0 1857.1 <0 9.1 6Ni 1159.2 <0 <0 2874.3 <0 <0 4189.6 <0 27.6 7Cu 823.3 <0 2.9 2491.6 <0 <0 3600.8 <0 90.7 15As 263.7 <0 <0 99.1 <0 <0 500.6 <0 40.4 9Rb <0 <0 <0 <0 <0 <0 <0 <0 <0 <0Sr 95944.

5<0 <0 26249.

0<0 <0 18345.

2<0 <0 <0

Mo 196.0 <0 <0 39.3 <0 <0 58.3 <0 <0 <0Sn 66.7 <0 0.7 41.7 <0 0.0 215.8 <0 10.0 43Sb 16.5 <0 <0 12.5 <0 <0 85.3 <0 14.8 42Tl 18.7 <0 <0 34.4 <0 <0 59.1 <0 1.4 24Bi 8.5 <0 <0 18.3 <0 <0 111.2 <0 3.9 36Th 224.5 <0 1.6 203.7 <0 <0 410.0 <0 <0 <0U 153.9 <0 <0 51.1 <0 <0 43.7 <0 <0 <0Cr 885.6 <0 <0 1045.3 <0 <0 2152.4 <0 <0 <0Pb 2972.2 <0 2.1 3267.4 <0 30.1 19088.

5<0 629.5 57

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Table S3. Correlations between the Miaoergou TEs and dust concentrations (1810–2004 A.D.) from Zhang et al. (2017). All correlations are significant at the 99% confidence level.

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V 0.68Mn 0.66Co 0.67Ni 0.67Cu 0.63As 0.59Rb 0.70Sr 0.26Mo 0.28Sn 0.48Sb 0.40Ba 0.68Tl 0.55Bi 0.28Th 0.66U 0.66Cr 0.67Pb 0.26

Table S4. EOF analysis of Miaoergou TEs from the period 1950-2004 A.D..

TE EOF 1 EOF 2 EOF 3 EOF 4V 0.98 -0.08 -0.11 -0.09

Mn 0.97 -0.05 -0.17 -0.01 Co 0.98 -0.11 -0.16 -0.02 Ni 0.98 -0.09 -0.14 -0.02 Cu 0.99 -0.13 -0.04 -0.00 As 0.95 0.23 0.06 -0.00 Rb 0.97 -0.07 -0.12 -0.15 Sr 0.54 0.79 0.00 0.13 Mo 0.77 0.54 0.20 -0.07 Cd 0.85 -0.16 0.14 0.40 Sn 0.74 -0.11 0.54 -0.35 Sb 0.92 0.17 0.17 0.07 Ba 0.98 0.03 -0.13 -0.01 Tl 0.98 -0.07 -0.11 0.01 Bi 0.88 -0.20 0.10 0.27 Th 0.96 -0.06 -0.15 -0.09 U 0.97 0.12 -0.10 -0.02 Cr 0.98 -0.10 -0.12 -0.09 Pb 0.80 -0.28 0.42 0.11

Varience（%） 83.38 6.50 3.96 2.35

Cum.Variance（%） 83.38 89.88 93.84 96.18

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Table S5. EOF analysis of Miaoergou TEs from the period 1776-1950 A.D..

TE EOF 1 EOF 2 EOF 3 EOF 4V 0.99 -0.12 -0.02 -0.06

Mn 0.97 -0.12 0.02 -0.16Co 0.98 -0.13 0.01 -0.12Ni 0.99 -0.06 0.00 -0.09Cu 0.99 -0.11 -0.01 -0.08As 0.96 0.19 -0.07 0.14Rb 0.99 -0.10 -0.05 0.02Sr 0.32 0.91 0.10 -0.10Mo 0.61 0.72 0.02 0.03Cd 0.61 -0.15 0.76 0.15Sn 0.90 -0.10 -0.15 0.33Sb 0.94 0.09 -0.11 0.25Ba 0.98 0.09 0.01 -0.07Tl 0.98 -0.12 -0.02 -0.06Bi 0.97 -0.12 -0.04 0.02Th 0.96 -0.06 -0.11 0.11U 0.95 0.27 0.00 -0.02Cr 0.99 -0.12 -0.02 -0.06Pb 0.91 -0.14 0.02 -0.19

Varience（%） 82.88 8.65 3.39 1.80

Cum.Variance（%） 82.88 91.53 94.92 96.72

Reference:

Krachler, M., Zheng, J., Fisher, D., Shotyk, W., 2005. Analytical procedures for improved trace element detection limit in polar ice from Arctic Canada using ICP‐SMS. Anal. Chim. Acta 530, 291-298.

Liu, Y., Hou, S., Hong, S., Hur, S. D., Lee, K., Wang, Y., 2011. High-resolution trace element records of an ice core from the eastern Tien Shan, central Asia, since 1953 AD. J. Geophys. Res. Atmos 116(D12).

Zhang, W., Hou, S., Liu, Y. Wu, S., An, W., Pang, H., Wang, C., 2017. A high-resolution atmospheric dust record for 1810-2004 A.D. derived from an ice core in eastern Tien Shan, central Asia. J. Geophys. Res. Atmos 122(14), 7505-7518.

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