Supporting Information for

Transcription

1 Supporting Information for Accumulation of perfluoroalkyl compounds in Tibetan mountain snow: temporal patterns from 1980 to 2010 Xiaoping Wang 1 *, Crispin Halsall 2 **, Garry Codling 2, Zhiyong Xie 3, Baiqing Xu 1, Zhen Zhao 3, Yonggang Xue 1, Ralf Ebinghaus 3, Kevin C. Jones 2 Summary of the number of pages, figures, and tables Figure SI-1 Detail positions of the sampling sites Page S3 Table SI-1 Details about the snow cores Page S4-5 Table SI-2 Details about fresh snow samples collected at Namco Page S6 Figure SI-2 Dating results of the snow cores Page S7 Text SI-1 Dating uncertainties Page S9 Table SI-3 Recoovery standard mix and injection standard used Page S10 for HPLC-MS-MS detection Table SI-4 Target analyst of this study Page S11 Table SI-5 Statistics of the recoveries of water samples and Page S12 matrix spike check Table SI-6 Values of target compounds in lab blanks and Page S13 ground water blanks (pg/l) Table SI-7 Data of melted deep snow water blank concentration Page S14 and method detection limits (pg/l) Table SI-8 Concentration of the PFCs (pg/l) in snow core of the Page S15 Mt. Zuoqiupu glacier Table SI-9 Concentration of the PFCs (pg/l) in snow core of the Page S16 Mt. Muztagata glacier Table SI-10 Concentration of the PFCs (pg/l) in surface snow of Page S17 the Namco Table SI-11 Concentration of the PFCs (pg/l) in duplicate melted snow core samples of the Mt. Zuoqiupu glacier Page S18 Table SI-12 Concentration of the PFCs (pg/l) in duplicate melted Page S19 1

2 snow core samples of the Mt. Zuoqiupu glacier Table SI-13 RSD% between duplicate samples of Mt. Zuoqiupu Page S20 glacier Table SI-14 RSD% between duplicate samples of Mt. Muztagata Page S21 glacier Figure SI-3 Concentration increase of PFOS and PFOA during Page S22 the period from 1980 to 1999 as recorded by Mt. Muztagata glacier Table SI-15 Comparison of PFCs deposition fluxes (fg cm-2 yr-1) Page S23 Table SI-16 Correlation (r) of individual compounds among Mt. Page S25 Muztagata samples Table SI-17 Correlation (r) of individual compounds among Mt. Zuoqiupu samples Page S26 2

3 Figure SI-1 Detail positions of the sampling sites. 1. Mt.Muztagata (snow core), 2. Namco (surface snow), 3. Mt.Zuoqiupu (snow core) 3

4 Table SI-1 Details about the snow cores. label year Core length Weight (kg) Density Accumulation Number of Particle Length of melted (m) (g/cm3) flux (kg/m2/y) samples* matter (g/l) layers (cm) Mt. Muztagata snow core (22.4m) M-IC M-IC M-IC M-IC M-IC =9 M-IC , =5 M-IC =8 M-IC M-IC M-IC Mt. Zuoqiupu snow core (30m) Z-IC =11 Z-IC =16 Z-IC Z-IC =21 Z-IC =4 Z-IC =11 Z-IC =9 Z-IC =22 Z-IC (whole ice) 4

5 Z-IC (whole ice) Z-IC =7 Z-IC =9 * Sample number =1 means only one sample was loaded and the volume equals to 2 litters. Sample number =2 means duplicates were prepared and 2 litters of water were extracted for each duplicate. 5

6 Table SI-2 Details about fresh snow samples collected at Namco Episode Snow depth Snow density SWE (m) Particles (g/l) (cm) Dec/10, Nov/24, Nov/05,

7 Figure SI-2 Dating result for two glaciers according to δ 18 O seasonal variations Stable isotopes in ice cores have been widely used as a paleothermometer in the Tibetan Plateau. However, moisture sources and water vapor recycling differ between the northern and southern TP (Tian et al., 2001a), resulting in spatially variable isotope-temperature relationships. The main moisture in the northern TP is dominated by strong continental recycling with high evaporation and mainly convective precipitation. Moisture in the southern TP is mainly provided by the Indian monsoon, with humid oceanic origins such as the Bay of Bengal (Tian et al., 2001b; Vuille et al., 2005). Therefore, in west and north TP, the most depleted isotope ratios are associated with accumulation during the coldest temperatures (winter).the southern TP exhibits the opposite relationship; monsoon moisture (with a depleted isotopic signature) arrives during the warm season (summer) resulting in a negative isotope-temperature correlation (Joswiak et al., 2010). 7

8 References: Joswiak, D. R., Yao,T., Wu,G., Xu, B., and Zheng W. (2010) A 70-yr record of oxygen-18 variability in an ice core from the Tanggula Mountains, central Tibetan Plateau Climate of Past, 6, Tian, L., Yao, T., Sun, W., Stievenard, M., and Jouzel, J. (2001a) Relationship between δd an δ18o in precipitation on north and south of the Tibetan Plateau and moisture recycling, Science of China Ser. D, 44(9), Tian, L., Yao, T., Numaguti, A., and Sun, W. (2001b) Stable isotope variations in monsoon precipitation on the Tibetan Plateau, Journal of Meteorological Society of Japan. 79(5), Vuille, M., Werner, M., Bradley, R. S., and Keimig, F. (2005) Stable isotopes in precipitation in the Asian monsoon region, Journal of Geophysics Research. 110, D23108, doi: /2005jd006022, 8

9 Text SI-1 Dating uncertainties We must remain alert to the processes that can lead to uncertainty for age dating. These include erosion and replacement of snow layers by wind and temporal fluctuations of δ 18 O even within the same season. For Mt. Muztagata glacier, the very high elevation and low temperatures prevent surface snow melting year-round. However, in situ observations found that strong winds could remove some of the fresh snow possibly disrupting annual accumulation layers. The Mt. Zuoqiupu glacier is the most southerly sample site in this study. Due to the relatively lower elevation and warmer climate, evidence of melting was apparent in the core taken from this site which may result in dating uncertainties. We estimate that the dating uncertainty is around 1-2 years. 9

10 Table SI-3 Recovery standard (RS) mix and injection standard used for the HPLC-MS/MS Detection analyte acronym formula supplier (purity) precursor/ Perfluoro-n-(1,2,3,4-1 3 C 4 )butanoic acid Perfluoro-1-hexane[ 18 O 2 ]sulfonate Perfluoro-1-[1,2,3,4-1 3 C 4 ]octanesulfonate Perfluoro-n-(1,2-13 C 2 )hexanoic acid Perfluoro-n-[1,2,3,4-1 3 C 4 ]octanoic acid Perfluoro-n-[1,2,3,4,5-13 C 5 ]nonanoic acid Perfluoro-n-[1,2-13 C 2 ]decanoic acid Perfluoro-n-[1,2-13 C 2 ]undecanoic acid Perfluoro-n-[1,2-13 C 2 ]dodecanoic acid 2Hperfluoro-[1,2-13 C2]- 2-decenoic acid product ion [m/z] [ 13 C 4 ]-PFBA [2,3,4-13 C 3 ]F 13 7 COOH Well. Lab. (>98%) 216.8/171.8 [ 18 O 2 ]-PFHxS C 6 F 13 S[ 18 O 2 ]O - Well. Lab (>98%) 402.9/ 83.9 [ 13 C 4 ]-PFOS C 4 F 9 [1,2,3,4-13 C 4 ]F 8 SO 2 O - Well. Lab.(>98%) 502.9/ 79.5 [ 13 C 2 ]-PFHxA C 4 F 9 [2-13 C]F 2 13 COOH Well. Lab. (>98%) 314.9/ [ 13 C 4 ]-PFOA C 4 F 9 [2,3,4-13 C 3 ]F 6 13 COOH Well. Lab. (>98%) 416.9/ [ 13 C 5 ]-PFNA C 4 F 9 [2,3,4,5-3 C 4 ]F 8 13 COOH Well. Lab. (>98%) 467.9/ [ 13 C 2 ]-PFDA C 8 F CF 2 13 COOH Well. Lab. (>98%) 514.9/ [ 13 C 2 ]-PFUnDA C 9 F CF 2 13 COOH Well. Lab. (>98%) 564.9/ [ 13 C 2 ]-PFDoDA C 10 F CF 2 13 COOH Well. Lab. (>98%) 614.9/ MFOUEA Injection standard CF 3 (CF 2 ) 6 CF= 13 CH 13 COOH Well. Lab. (>98%) / Well. Lab., Wellington Laboratories 10

11 Table SI-4 Target analysts of this study analyte acronym formula supplier (purity) Perfluorobutane sulfonic acid Perfluorohexane sulfonic acid Perfluoroheptane sulfonic acid Perfluorooctane sulfonic acid Perfluorodecane sulfonic acid Perfluorobutanoic acid Perfluoropentanoic acid Perfluorohexanoic acid Perfluoroheptanoic acid Perfluorooctanoic acid Perfluorononanoic acid Perfluorodecanoic acid Perfluoroundecanoic acid Perfluorododecanoic acid Perfluorotridecanoic acid Perfluorotetradecanoi c acid precursor/ product ion [m/z] PFBS C 4 F 9 SO 2 O - Fluka (97%) 298.9/ 79.8 PFHxS C 6 F 13 SO 2 O - Fluka (98%) 398.9/ 79.8 PFHpS C 7 F 15 SO 2 O - Well. Lab. a 449.0/ 79.3 (>98%) PFOS C 8 F 17 SO 2 O - Well. Lab. a 498.9/ 79.7 (>98%) PFDS C 10 F 21 SO 2 O - Well. Lab. a 598.9/ 79.5 (>98%) PFBA C 3 F 7 COOH ABCR (99%) 112.9/ PFPA C 4 F 9 COOH Alfa Aesar 262.8/ (98%) PFHxA C 5 F 11 COOH Fluka (97%) 312.9/ PFHpA C 6 F 13 COOH Lanc. Syn. b 362.9/ (98%) PFOA C 7 F 15 COOH Lanc. Syn. b 412.9/ (95%) PFNA C 8 F 17 COOH Lanc. Syn. b 462.9/ (97%) PFDA C 9 F 19 COOH Lanc. Syn. b 512.9/ (97%) PFUnDA C 10 F 21 COOH ABCR (96%) 562.9/ PFDoDA C 11 F 23 COOH Alfa Aesar (96%) PFTriDA C 12 F 25 COOH Well. Lab. a (>98%) PFTeDA C 13 F 27 COOH Alfa Aesar (96%) 612.9/ / / a:well. Lab.. Wellington Laboratories. b: Lanc. Syn.. Lancaster Synthesis. 11

12 Table SI-5. Statistics of the recoveries of water samples and matrix spike check Mass labelled Water Samples Matrix spike compounds max min Mean SD mean SD [ 13 C 4 ]-PFBA 150% 36% 102% 32% 98% 12% [ 13 C 2 ]-PFHxA 145% 38% 101% 29% 72% 15% [ 18 O 2 ]-PFHxS 125% 39% 57% 22% 58% 12% [ 13 C 4 ]-PFOA 91% 30% 50% 19% 56% 11% [ 13 C 4 ]-PFOS 155% 38% 61% 25% 57% 18% [ 13 C 5 ]-PFNA 136% 52% 98% 23% 66% 10% [ 13 C 2 ]-PFDA 142% 32% 95% 34% 88% 19% [ 13 C 2 ]-PFUnDA 136% 48% 99% 26% 92% 28% [ 13 C 8 ]-FOSA 109% 36% 65% 21% 78% 17% [ 13 C 2 ]-PFDoDA 99% 29% 62% 23% 73% 24% 12

13 Table SI- 6 Values of target compounds in lab blanks and ground water blanks (pg/l) Lab Blank (LB) Ground water blank (GB) LB1 LB2 LB3 LB4 LB5 LB6 Average GB1 GB2 GB3 Average PFBS ND ND ND ND ND ND ND ND ND PFHxS ND ND ND ND ND ND ND ND ND PFHpS ND ND ND ND ND ND ND ND ND PFOS ND ND ND ND ND ND ND ND ND PFDS ND ND ND ND ND ND ND ND ND PFBA ND ND ND ND ND ND 11.9 ND PFPA ND ND ND ND ND ND ND ND ND PFHxA ND ND ND ND ND ND ND ND ND PFHpA ND ND ND ND ND ND ND ND ND PFOA PFNA ND ND ND ND ND ND ND ND ND PFDA ND ND ND ND ND ND ND ND ND PFUnDA ND ND ND ND ND ND ND ND ND PFDoDA ND ND ND ND ND ND ND ND ND PFTriDA ND ND ND ND ND ND ND ND ND PFTeDA ND ND ND ND ND ND ND ND ND ND means chemical was not detected in blank. Only PFOA was detected in lab blanks. 13

14 Table SI-7 Melted deep-snow water (DSW) blank concentrations and limits of detection (LOD, pg/l) DSW1 DSW 2 DSW 3 DSW 4 DSW 5 DSW 6 Average 3*std S/N=10 PFBS ND ND ND ND ND ND 20 PFHxS ND ND ND ND ND ND 20 PFHpS ND ND ND ND ND ND 20 PFOS PFDS ND ND ND ND ND ND 20 PFBA PFPA PFHxA ND ND ND ND ND ND 20 PFHpA ND ND ND ND ND ND 20 PFOA PFNA ND ND ND ND ND ND 10 PFDA ND ND ND ND ND ND 20 PFUnDA ND ND ND ND ND ND 5 PFDoDA ND ND ND ND ND ND 10 PFTriDA ND ND ND ND ND ND 20 PFTeDA ND ND ND ND ND ND 20 Limits of detection (LODs) were defined as three times the standard deviation of the average blank. When a target compound was not detected in the blanks, the the LOD was calculated as a S/N ratio of 10 based on a sample volume of 2 L. LOD 14

15 Table SI-8 Concentration of the PFAs (pg/l) in the snow core of the Mt. Zuoqiupu glacier Z-IC1 Z-IC2 Z-IC3 Z-IC4 Z-IC5 Z-IC6 Z-IC7 Z-IC8 Z-IC9 Z-IC10 Z-IC11 Z-IC12 Time PFBS ND ND ND ND ND ND ND ND ND ND ND ND PFHxS ND ND ND ND ND ND ND ND ND ND ND ND PFHpS ND ND ND ND ND ND ND ND ND ND ND ND PFOS BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFDS ND ND ND ND ND ND ND ND ND ND ND ND PFBA BDL 28.3 BDL BDL BDL BDL BDL PFPA BDL BDL BDL BDL BDL BDL BDL BDL PFHxA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFHpA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFOA PFNA BDL BDL BDL BDL BDL BDL 16.4 BDL BDL BDL PFDA BDL BDL BDL BDL BDL BDL BDL BDL PFUnDA ND ND ND ND ND ND ND ND ND ND ND ND PFDoDA ND ND ND ND ND ND ND ND ND ND ND ND PFTriDA ND ND ND ND ND ND ND ND ND ND ND ND PFTeDA ND ND ND ND ND ND ND ND ND ND ND ND sum All the reported values are blank corrected. 15

16 Table SI-9 Concentration of the PFAs (pg/l) in the snow core of the Mt. Muztagata glacier M-IC1 M-IC2 M-IC3 M-IC4 M-IC5 M-IC6 M-IC7 M-IC8 M-IC9 M-IC10 time PFBS ND ND ND ND ND ND ND ND ND ND PFHxS ND ND ND ND ND ND ND ND ND ND PFHpS ND ND ND ND ND ND ND ND ND ND PFOS PFDS ND ND ND ND ND ND ND ND ND ND PFBA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFPA PFHxA BDL BDL PFHpA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFOA PFNA BDL BDL BDL BDL PFDA BDL BDL BDL PFUnDA BDL BDL BDL BDL BDL PFDoDA BDL BDL BDL BDL PFTriDA ND ND ND ND ND ND ND ND ND ND PFTeDA ND ND ND ND ND ND ND ND ND ND sum All the reported values are blank corrected. 16

17 Table SI-10 Concentrations of the PFAs (pg/l) in surface snow collected near Lake Namco Episode 1 Episode 2 Episode 3 Snow Snow Snow Average ± RSD% Snow Snow Snow Snow Average ± RSD% Snow 3 1a 1b 1c std 2a 2b 2c 2d std PFBS BDL BDL BDL BDL BDL BDL BDL BDL PFHxS ND ND ND ND ND ND ND ND PFHpS ND ND ND ND ND ND ND ND PFOS ±19 44% ±20 42% 25 PFDS ND ND ND ND ND ND ND ND PFBA ±139 5% ±198 12% 913 PFPA ±56 21% ±65 22% 94.5 PFHxA ±10 8% ± % 63.5 PFHpA ±305 47% ±160 42% PFOA ±26 17% ±25 15% 68.1 PFNA ±6.5 8% ±9.6 13% 49.2 PFDA ±4.7 15% ±4.4 19% 9.2 PFUnDA ± ±8.6 BDL PFDoDA ±5.0 BDL BDL 18.6 BDL 13.4±7.4 BDL PFTriDA ND ND ND ND ND ND ND ND PFTeDA ND ND ND ND ND ND ND ND sum ± ± All the reported values are blank corrected. 17

18 Table SI-11 Concentration of PFAs (pg/l) in duplicate melted snow core samples of Mt. Zuoqiupu Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC Z-IC 1A 1B 4A 4B 5A 5B 7A 7B 8A 8B 9A 9B 10A 10B 11A 11B 12A 12B PFBS ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFHxS ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFHpS ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFOS BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFDS ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFBA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFPA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFHxA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFHpA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFOA PFNA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFDA BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL PFUnDA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFDoDA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFTriDA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND PFTeDA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 18

19 Table SI-12 Concentration of PFAs (pg/l) in duplicate melted snow core samples of Mt. Muztagata M-IC7A M-IC7B M-IC8A M-IC8B M-IC9A M-IC9B M-IC10A M-IC10B PFBS ND ND ND ND ND ND ND ND PFHxS ND ND ND ND ND ND ND ND PFHpS ND ND ND ND ND ND ND ND PFOS PFDS ND ND ND ND ND ND ND ND PFBA BDL BDL BDL BDL BDL BDL BDL BDL PFPA PFHxA BDL BDL BDL BDL BDL PFHpA BDL BDL BDL BDL BDL BDL BDL BDL PFOA PFNA BDL BDL BDL BDL BDL BDL BDL BDL PFDA BDL BDL BDL BDL BDL BDL PFUnDA BDL BDL BDL BDL BDL BDL BDL BDL PFDoDA BDL BDL BDL BDL BDL BDL BDL BDL PFTriDA ND ND ND ND ND ND ND ND PFTeDA ND ND ND ND ND ND ND ND 19

20 Table SI-13 % RSD determined for duplicate samples of the Mt. Zuoqiupu glacier Z-IC1 Z-IC4 Z-IC5 Z-IC7 Z-IC8 Z-IC9 Z-IC10 Z-IC11 Z-IC12 PFBS PFHxS PFHpS PFOS PFDS PFBA 33% 15% 22% 10% PFPA 22% 53% 8% PFHxA 21% 9% 18% PFHPA 18% PFOA 10% 12% 3% 14% 5% 8% 37% 31% 17% PFNA 15% 28% 40% 22% PFDA 10% 12% PFUnDA PFDoDA PFTriDA PFTeDA 20

21 Table SI-14 % RSD determined for duplicate samples of Mt. Muztagata glacier M-IC7 M-IC8 M-IC9 M-IC10 PFBS PFHxS PFHpS PFOS 17% 42% 20% 17% PFDS PFBA PFPA 4% 44% 16% 37% PFHxA 16% PFHPA PFOA 30% 48% 28% 26% PFNA PFDA PFUnDA PFDoDA PFTriDA PFTeDA 21

22 Figure SI-3 Concentration increase of PFOS and PFOA during the period from 1980 to 1999 as recorded by Mt. Muztagata glacier 22

23 Table SI-15 Comparison of PFC depositional fluxes (fg cm -2 yr -1 ). time site Mt. Muztagata snow core Mt. Zuoqiupu snow core Devon Island icecap (Canada Colle Gnifetti snow (Swiss/Italian Precipitation, Remote Canada (ON, NS) Precipitation, Continental US (rural) Precipitation, Kawaguchi, Japana (industrial) Arctic) Alps) PFOS PFBA PFPA PFHxA PFOA PFNA PFDA PFUnDA PFDoDA sum Referenc This study (1) (2) (3) (3) (4) References (1) Young, C. J.; Furdui, V. I.; Franklin, J.; Koerner, R. M.; Muir, D. C. G.; Mabury, S. A., Perfluorinated Acids in Arctic Snow: New Evidence for Atmospheric Formation. Environmental Science & Technology 2007, 41, (10), (2) Kirchgeorg, T.; Dreyer, A.; Gabrieli, J.; Kehrwald, N.; Sigl, M.; Schwikowski, M.; Boutron, C.; Gambaro, A.; Barbante, C.; Ebinghaus, R., 23

24 Temporal variations of perfluoroalkyl substances and polybrominated diphenyl ethers in alpine snow. Environmental Pollution 2013, 178, (0), (3) Scott, B. F.; Spencer, C.; Mabury, S. A.; Muir, D. C. G., Poly and perfluorinated carboxylates in North American precipitation. Environmental Science & Technology 2006, 40, (4) Kwok, K. Y.; Taniyasu, S.; Yeung, L. W. Y.; Murphy, M. B.; Lam, P. K. S.; Horii, Y.; Kannan, K.; Petrick, G.; Sinha, R. K.; Yamashita, N., Flux of Perfluorinated Chemicals through Wet Deposition in Japan, the United States, And Several Other Countries. Environmental Science & Technology 2010, 44, (18),

25 Table SI-16 Pearson correlation (r) matrix of PFAs for the Mt. Muztagata snow core samples PFOS PFPA PFHxA PFOA PFNA PFDA PFUnA PFDoA PFOS *.743 *.866 ** PFPA **.945 ** ** PFHxA ** ** * PFOA ** * PFNA PFDA * PFUnA * PFDoA 1 * and ** are significant at p < 0.05 and p < 0.01, respectively. 25

26 Table SI-17 Pearson correlation matrix (r) of PFAs in the Mt. Zuoqiupu snow core samples PFBA PFPA PFHxA PFOA PFNA PFDA PFBA *.845 **.840 ** PFPA * PFHxA * PFOA * PFNA ** PFDA 1 * and ** are significant at p < 0.05 and p < 0.01, respectively. 26

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