SUPPLEMENTARY INFORMATION Acceleration of modern acidification in the South China Sea driven by anthropogenic CO2 Yi Liu1,2*, Zicheng Peng1, Renjun Zhou1,3, Shaohua Song2, Weiguo Liu2, Chen-Feng You4*, Yen-Po Lin4, Kefu Yu5, Chung-Che Wu6, Gangjian Wei7, Luhua Xie7, George S. Burr6 & Chuan-Chou Shen6* 1. CAS Key Laboratory of Crust-Mantle Material and Environment, School of Earth and Space Science, University of Science and Technology of China, Hefei 230026, China 2. State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences, Xi’an 710075, China 3. CAS Key Laboratory of Geospace Environment, School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026, China 4. Earth Dynamic System Research Center (EDSRC), National Cheng Kung University, Tainan 701, Taiwan 5. South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou 510301, China 6. High-Precision Mass Spectrometry and Environment Change Laboratory (HISPEC), Department of Geosciences, National Taiwan University, Taipei 10617, Taiwan 7. State Key Laboratory of Isotope Geochronology and Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China *Correspondence and requests for materials should be addressed to Y.L. (gee@ustc.edu.cn), C-F. Y. (cfy20@mail.ncku.edu.tw) or C-C. S. (river@ntu.edu.tw). Local setting The South China Sea (SCS) covers an area of 3.5 × 106 km2, which is the largest marginal sea in the world. This region is strongly dominated by a seasonal Asian Monsoon1. Abundant coral reefs are distributed all over the SCS, which cover a latitudinal range of 16o, providing excellent material for coral-based climate research2-6. Our modern and fossil corals were drilled from Xiaodonghai Reef, off south Hainan located in the northern SCS. At our sample site, for the period 2002-2011, the monthly chlorophyll a concentration (Chl), varies from 0.02 mg/m3 to 2 mg/m3 with prominent peaks occurring in winter (Supplementary Fig. 1d), reflecting a Chl annual cycle in the South China Sea7. In parallel, the monthly mean wind speed (Supplementary Fig. 1c), varying between 0.4 m/s and 11 m/s, also shows strong winter peaks. Contrary to the pattern of annual cycles of Chl and wind speed, most precipitation falls in in the summer (Supplementary Fig. 1b). Like the precipitation, the sea surface temperature (SST) shows a maximum value (~30 °C) in the summer and a minimum value (~22 °C) in the winter (Supplementary Fig. 1a). Supplementary Figures 32 SST (oC) (a) 28 24 precipitation (mm) 20 800 600 (b) 400 200 0 12 wind (m/s) (c) 9 6 3 0 Chl (mg/m3) 2.5 2.0 (d) 1.5 1.0 0.5 0.0 1994 1996 1998 2000 2002 2004 2006 2008 2010 Supplementary Figure 1. Variations of monthly mean values of environmental variables within the study area. (a) Sea surface temperature (SST). (b) Precipitation. (c) Surface wind speed. (d) Sea surface chlorophyll a concentration (Chl). Monthly SST data (17-19°N, 115-117°E) with 1° resolution from 1994 to 2011 were from the Optimum Interpolation Sea Surface Temperature, Version 2, provided by NOAA: (http://www.esrl.noaa.gov/psd/data/gridded/data.noaa.oisst.v2.html). Wind data (17-19°N, 115-117°E) with a 0.25° resolution were from the Blended Sea Winds provided by the National Climate Data Center of NOAA: http://www.ncdc.noaa.gov/oa/rsad/air-sea/seawinds.html. Precipitation data (17-19°N, 115-117°E) were from the Global Precipitation Climatology Centre (GPCC) with a 1° resolution (http://www.esrl.noaa.gov/psd/data/gridded/data.gpcc.html). Sea surface Chl data (17.9-18.3°N, 109.3-109.7°E) from 2002 to 2011 were from MODIS (Moderate Resolution Imaging Spectroradiometer) Level 3 with a spatial resolution of 4 km. 2.5 a R2 = 0.38, n =105, p < 0.0001 Chl (mg/m3) 2.0 1.5 1.0 0.5 0.0 0 2 4 6 8 10 12 wind (m/s) 2.5 b R2 = 0.0042, n = 105, p = 0.514 Chl (mg/m3) 2.0 1.5 1.0 0.5 0.0 0 200 400 600 800 1000 precipitation (mm) Supplementary Figure 2. Correlations (Pearson) between (a) Chl and wind speed and (b) Chl and precipitation from AD 2002-2011. B ( o/oo ) 23 a d δ 24 11 25 22 1050 1100 1850 1900 1950 2000 1850 1900 1950 2000 1850 1900 1950 2000 8.6 b pHcf e 8.4 1050 pHsw 8.2 1100 f c 8.0 7.8 1050 1100 Year (A.D.) Supplementary Figure 3. Time series of measured δ11B and reconstructed pHcf and pHsw. a-c, Data for fossil Porites coral Dong-5 from AD 1048-1079. d-f, Data for modern Porites coral Song-5 during AD 1839-2001. Vertical red bars denote the 2σ uncertainty. 8.4 a. Flinders Reef pHsw 8.2 8.0 b. Arlington Reef 7.8 8.4 7.6 c. St. ALOHA (Hawaii) 8.2 -0.0018 pH year-1 pHsw 8.2 8.0 8.0 d. Xiaodonghai Reef 7.8 -0.0015 pH year-1 7.8 7.6 1750 7.6 1800 1850 1900 1950 2000 Year (A.D.) Supplementary Figure 4. Time series of modern observational and reconstructed pHsw. Reconstructed pHsw of (a) Frinders Reef13 (cyan) and (b) Arlington Reef14 (blue) from the Great Barrier Reef (GBR). (c) Observational pHsw at Station ALOHA, Hawaii15 (pink). (d) Reconstructed Xiaodonghai Reef pHsw in the South China Sea (SCS) (this study, red). Solid black lines show the decreasing trends of pHsw in Hawaii and the SCS. pHsw 8.4 pHsw 8.2 a 8.0 7.8 -2.0 -2.8 δ 13 C ( o/oo ) b -2.4 -3.2 -3.6 -5.0 c Col 1 vs Col 2 -5.2 δ 18 O ( o/oo ) -4.8 -5.4 1850 1900 1950 2000 Year (A.D.) Supplementary Figure 5. Time series of (a) reconstructed pHsw, (b) measured δ13C, and (c) measured δ18O of the modern Porites coral Song-5 during AD 1839-2001. 2000 pHsw 8.2 1600 Col 35 vs Col 36 8.0 R2 = 0.011, p = 0.613 1200 precipiataion (mm) 8.4 7.8 1850 1900 1950 2000 Year (A.D.) Supplementary Figure 6. Comparison between pHsw and precipitation. Green line denotes precipitation variation and red line coral-inferred pHsw in Xiaodonghai Reef. Precipitation data are from the GPCC as in Supplementary Fig. 2b. Supplementary Figure 7. Local instrumental seawater pH in AD 2009 and 2010. This pH record is characterized with higher pH in winter and lower in summer. pH was measured with an Orion pH glass electrode (ROSS Combination pH/model 81-02)and a Corning pH meter (Model pH/ion analyzer 350) with a precision of 0.005 pH units16. SST is also shown. Supplementary Tables Supplementary Table 1. U-Th isotopic compositions and 230Th date of the first annual banding of the 32 yr-section coral Porites fossil Dong-5 Sample No. Dong-5-4 2σ 238 232 Th ppt δ234U measureda 2543 ± 7.1 817.8 ± 3.7 144.3 ± 3.6 U ppb 230 Th/238U activityc 0.010137 ±0.000051 230 Th/232Th ppmd 520.6 ± 3.2 Age (y) uncorrected Age (y) correctedc,e δ234U correctedb 971.4 ± 5.7 964.0 ± 6.8 144.7 ± 3.6 Chemistry8 and instrumental analysis9 was performed in 2012. Analytical errors are 2σ of the mean. a 234 δ U = ([234U/238U]activity - 1) x 1000. b 234 δ Uinitial corrected was calculated based on 230Th age (T), i.e., δ234Uinitial = δ234Umeasured X eλ234*T, and T is corrected age. c 230 Th/238Uactivity = 1 - e-λ234*T + (δ234Umeasured/1000)[λ230/(λ230-λ234)](1 - e-(λ230 -λ234) T ), where T is the age. Decay constants are 9.1705 x 10-6 yr-1 for 230Th, 2.8221 x 10-6 yr-1 for 234U (ref.10), and 1.55125 x 10-10 yr-1 for 238U (ref.11). d The degree of detrital 230Th contamination is indicated by the 230Th/232Th atomic ratio instead of the activity ratio. e Age corrections were calculated using an estimated atomic 230Th/232Th ratio of 4 (±2) ppm (ref. 12). Supplementary Table 2. The dataset of the modern coral Song-5 from AD 1838-2001 Years (A.D.) δ11B pHcf pHsw δ13C δ18O 1998-2001 1994-1997 1990-1993 1986-1989 1982-1985 1978-1981 1974-1977 1970-1973 1966-1969 1962-1965 1958-1961 1954-1957 1950-1953 1946-1949 1942-1945 1938-1941 1934-1937 1930-1933 1926-1929 1922-1925 1918-1921 1914-1917 1910-1913 1906-1909 1902-1905 1898-1901 1894-1897 1890-1893 1886-1889 1882-1885 1878-1881 1874-1877 1870-1873 1866-1869 1862-1865 1858-1861 1854-1857 1850-1853 1846-1849 1842-1845 1838-1841 23.03 23.28 22.16 22.39 23.27 23.47 23.54 23.13 23.41 22.75 23.10 23.96 24.18 24.10 24.23 23.67 23.53 24.11 23.86 23.66 23.50 24.14 24.37 23.80 24.23 23.77 23.57 24.79 24.49 23.90 23.66 24.56 24.42 24.91 24.69 24.88 24.68 24.43 24.32 24.67 24.21 8.43 8.45 8.37 8.39 8.45 8.46 8.46 8.44 8.46 8.41 8.43 8.49 8.51 8.50 8.51 8.47 8.46 8.50 8.48 8.47 8.46 8.50 8.52 8.48 8.51 8.48 8.47 8.54 8.52 8.49 8.47 8.53 8.52 8.55 8.54 8.55 8.54 8.52 8.51 8.54 8.51 7.95 7.98 7.82 7.86 7.98 8.01 8.02 7.96 8.00 7.91 7.96 8.08 8.11 8.09 8.11 8.04 8.02 8.10 8.06 8.03 8.01 8.10 8.13 8.05 8.11 8.05 8.02 8.19 8.15 8.07 8.03 8.16 8.14 8.21 8.18 8.20 8.17 8.14 8.13 8.17 8.11 -3.12 -3.29 -3.33 -3.14 -3.25 -3.43 -2.87 -3.18 -3.22 -2.82 -2.64 -2.84 -2.34 -2.65 -2.64 -2.69 -3.06 -3.26 -3.07 -2.58 -2.89 -2.80 -2.32 -2.51 -3.15 -2.73 -2.33 -2.36 -3.11 -2.70 -2.25 -2.40 -2.10 -2.38 -2.45 -2.96 -3.25 -2.67 -2.50 -2.74 -2.88 -5.22 -5.11 -5.10 -5.14 -5.38 -5.09 -5.10 -4.95 -5.29 -5.00 -4.92 -5.28 -5.11 -5.08 -5.02 -5.20 -5.19 -5.19 -5.31 -5.18 -5.20 -5.19 -5.14 -5.16 -5.20 -5.04 -5.16 -4.96 -5.12 -5.01 -4.92 -5.12 -5.08 -5.07 -4.87 -5.14 -4.86 -5.00 -4.96 -5.03 -5.01 Supplementary Table 3. Biweekly geochemistry dataset of the modern coral Song-5 in AD 2000 Sample No. Song-2000-1 Song-2000-2 Song-2000-3 Song-2000-4 Song-2000-5 Song-2000-6 Song-2000-7 Song-2000-8 Song-2000-9 Song-2000-10 Song-2000-11 Song-2000-12 Song-2000-13 Song-2000-14 Song-2000-15 Song-2000-16 Song-2000-17 Song-2000-18 Song-2000-19 Song-2000-20 Song-2000-21 Song-2000-22 Song-2000-23 Song-2000-24 Song-2000-25 Song-2000-26 Song-2000-27 Song-2000-28 Song-2000-29 Song-2000-30 δ11B 23.21 22.71 22.67 22.69 22.31 21.70 22.34 22.18 22.84 22.77 21.93 22.68 22.50 22.10 22.06 22.19 22.47 22.60 23.12 23.34 23.11 23.09 23.30 pHcf pHsw 8.46 8.01 8.39 7.87 8.37 7.83 8.37 7.82 8.34 7.75 8.27 7.60 8.33 7.74 8.35 7.78 8.42 7.93 8.38 7.85 8.34 7.75 8.40 7.89 8.39 7.85 8.37 7.83 8.34 7.75 8.36 7.81 8.36 7.80 8.38 7.84 8.41 7.90 8.43 7.94 8.43 7.94 8.46 8.01 8.49 8.08 δ13C δ18O -3.16 -3.17 -3.67 -3.32 -3.74 -3.75 -3.54 -3.57 -3.21 -3.16 -3.47 -3.48 -3.17 -2.75 -3.01 -3.25 -3.72 -3.49 -3.42 -3.30 -2.79 -2.75 -2.88 -3.01 -3.14 -3.07 -3.46 -3.21 -3.58 -3.39 -5.07 -4.84 -5.21 -5.04 -5.43 -5.65 -5.68 -5.79 -6.12 -5.87 -5.51 -5.21 -5.61 -5.45 -5.30 -5.38 -5.18 -5.57 -5.38 -5.62 -5.50 -5.60 -5.57 -5.35 -4.95 -4.73 -4.97 -4.68 -4.86 -4.97 Supplementary Table 4. The dataset of the fossil coral Dong-5 4-year intervals δ11B pHcf pHsw 1 2 3 4 5 6 7 8 24.56 24.40 24.63 24.89 24.71 24.55 25.24 24.22 8.53 8.52 8.53 8.55 8.54 8.53 8.57 8.51 8.16 8.14 8.17 8.20 8.18 8.16 8.25 8.12 References for Supplementary Information (SI): 1. 2. 3. 4. 5. 6. 7. 8. 9. Yu, K., Zhao, J., Wei, G., Cheng, X. & Wang, P. Mid–late Holocene monsoon climate retrieved from seasonal Sr/Ca and δ18O records of Porites lutea corals at Leizhou Peninsula, northern coast of South China Sea. Global Planet. Change 47, 301-306 (2005). Wei, G. et al. Mg/Ca, Sr/Ca and U/Ca ratios of a Porites coral from Sanya Bay, Hainan Island, South China Sea and their relationships to sea surface temperature. Palaeogeogr. Palaeoclimat. Palaeoecol. 162, 59–748 (2000). Sun, D, et al. Seasonal and interannual variability of the Middle Holocene East Asian monsoon in coral δ18O records from the South China Sea. Earth Planet. Sci. Lett. 237, 69–84 (2005). Shen, C.-C. et al. 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