Occurrence of perfluoroalkyl compounds in surface waters from the North Pacific to the Arctic Ocean

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1 Supporting Information Occurrence of perfluoroalkyl compounds in surface waters from the North Pacific to the Arctic Ocean Minghong Cai 1, 2,* Zhen Zhao 3, Zhigao Yin 2, Lutz Ahrens 3,4, Peng Huang 5, Minggang Cai 5, Haizhen Yang 2, Jianfeng He 1, Renate Sturm 3, Ralf Ebinghaus 3, Zhiyong Xie 3 ** 1 SOA Key Laboratory for Polar Science, Polar Research Institute of China, Shanghai , China 2 College of environmental science and engineering, Tongji University, Shanghai , China 3 Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research GmbH, Institute of Coastal Research, Max-Planck Straße. 1, D Geesthacht, Germany 4 Current address: Air Quality Research Division, Science and Technology Branch, Environment Canada, 4905 Dufferin Street, Downsview, Ontario M3H 5T4 Canada 5 College of Oceanography and Environmental Science, Xiamen University, Xiamen , China *Corresponding author. Tel.: ; fax: address: caiminghong@pric.gov.cn (M. Cai) **Corresponding author. Tel.: ; fax: zhiyong.xie@hzg.de

2 Table of contents: Table S1. Analytes, Acronyms, Formula, Supplier, Purity, Precursor and Product Ions for the HPLC-MS/MS Detection Table S2. Station information about sampling date, time and position Table S3. Station information about Temperature ( C), Salinity (S ), Chlorophyll (mg L -1 ), and Colored dissolved organic matter (CDOM, mg L -1 ) Table S4 The values of instrument detect limit (IDL) (pg L -1 ), method quantification limit (MQL) (pg L -1 ) and the concentrations in the field blank (pg L -1 ). Table S5 Statistics of the recoveries of water samples and matrix spike check Table S6 Concentrations of ionic PFCs in the sea waters from Arctic Ocean (pg L -1 ) Table S7 Concentrations of ionic PFCs in the sea waters between Northwest Pacific Ocean and Bering Sea (pg L -1 ) Table S8 Concentrations of ionic PFCs in the snow and ice column from Arctic Ocean (pg L -1 ) Figure S1. Correlations between PFOA and PFNA in ice core samples (I1-I3)

3 Table S1. Analytes, Acronyms, Formula, Supplier, Purity, Precursor and Product Ions for the HPLC-MS/MS Detection Analyte Acronym Formula Supplier (purity) Precursor/ product ion [m/z] Perfluorobutane sulfonate PFBS C 4 F 9 SO 2 O - Fluka (97%) / 79.8 Perfluorohexane sulfonate PFHxS C 6 F 13 SO 2 O - Fluka (98%) / 79.8 Perfluoroheptane sulfonate PFHpS C 7 F 15 SO 2 O - Well. Lab. a (>98%) / 79.3 Perfluorooctane sulfonate PFOS C 8 F 17 SO 2 O - Well. Lab. a (>98%) / 79.7 Perfluorodecane sulfonate PFDS C 10 F 21 SO 2 O - Well. Lab. a (>98%) / 79.5 Perfluorobutanoic acid PFBA C 3 F 7 COOH ABCR (99%) / Perfluoropentanoic acid PFPA C 4 F 9 COOH Alfa Aesar (98%) / Perfluorohexanoic acid PFHxA C 5 F 11 COOH Fluka (97%) / Perfluoroheptanoic acid PFHpA C 6 F 13 COOH Lanc. Syn. b (98%) / Perfluorooctanoic acid PFOA C 7 F 15 COOH Lanc. Syn. b (95%) / Perfluorononanoic acid PFNA C 8 F 17 COOH Lanc. Syn. b (97%) / Perfluorodecanoic acid PFDA C 9 F 19 COOH Lanc. Syn. b (97%) / Perfluoroundecanoic acid PFUnDA C 10 F 21 COOH ABCR (96%) / Perfluorododecanoic acid PFDoDA C 11 F 23 COOH Alfa Aesar (96%) / Perfluorotridecanoic acid PFTriDA C 12 F 25 COOH Well. Lab. a (>98%) / Perfluorotetradecanoic acid PFTeDA C 13 F 27 COOH Alfa Aesar (96%) / Perfluorohexadecanoic acid PFHxDA C 15 F 31 COOH Alfa Aesar (95%) / N-methylperfluorobutane sulfonamide MeFBSA C 4 F 9 SO 2 NH(CH 3 ) 3M (n.a.) / Perfluorooctane sulfonamide FOSA C 8 F 17 SO 2 NH 2 ABCR (97%) / 77.9 N-methyl perfluoroctane sulfonamide MeFOSA C 8 F 17 SO 2 NH(CH 3 ) 3M (n.a.) / N-ethyl perfluoroctane sulfonamide EtFOSA C 8 F 17 SO 2 NH(C 2 H 5 ) ABCR (95%) / N-methylperfluorobutane sulfonamidoethanol MeFBSE C 4 F 9 SO 2 N(CH 3 )C 2 H 4 OH 3M (n.a.) / 59.0 N-methyl perfluoroctane sulfonamidoethanol MeFOSE C 8 F 17 SO 2 N(CH 3 )C 2 H 4 OH 3M (n.a.) / 58.9 N-ethyl perfluroctane sulfonamidoethanol EtFOSE C 8 F 17 SO 2 N(C 2 H 5 )C 2 H 4 OH 3M (n.a.) / 58.8 Perfluoro-n-(1,2,3,4-13 C 4 )butanoic acid [ 13 C 4 ]-PFBA [2,3,4-13 C 3 ]F 13 7 COOH Well. Lab. a (>98%) /171.8 Perfluoro-1-hexane[ 18 O 2 ]sulfonate [ 18 O 2 ]-PFHxS C 6 F 13 S[ 18 O 2 ]O - Well. Lab. a (>98%) / 83.9 Perfluoro-1-[ 13 C 8 ]octanesulfonamide [ 13 C 8 ]-FOSA [1,2,3,4,5,6,7, C 8 ]F 17 SO 2 NH 2 Well. Lab. a (>98%) /77.8 Perfluoro-1-[1,2,3,4-13 C 4 ]octanesulfonate [ 13 C 4 ]-PFOS C 4 F 9 [1,2,3,4-13 C 4 ]F 8 SO 2 O - Well. Lab. a (>98%) / 79.5 Perfluoro-n-(1,2-13 C 2 )hexanoic acid [ 13 C 2 ]-PFHxA C 4 F 9 [2-13 C]F 13 2 COOH Well. Lab. a (>98%) / Perfluoro-n-[1,2,3,4-13 C 4 ]octanoic acid [ 13 C 4 ]-PFOA C 4 F 9 [2,3,4-13 C 3 ]F 13 6 COOH Well. Lab. a (>98%) / Perfluoro-n-[1,2,3,4,5-13 C 5 ]nonanoic acid [ 13 C 5 ]-PFNA C 4 F 9 [2,3,4,5-3 C 4 ]F 13 8 COOH Well. Lab. a (>98%) / Perfluoro-n-[1,2-13 C 2 ]decanoic acid [ 13 C 2 ]-PFDA C 8 F CF 13 2 COOH Well. Lab. a (>98%) / Perfluoro-n-[1,2-13 C 2 ]undecanoic acid [ 13 C 2 ]-PFUnDA C 9 F CF 13 2 COOH Well. Lab. a (>98%) / Perfluoro-n-[1,2-13 C 2 ]dodecanoic acid [ 13 C 2 ]-PFDoDA C 10 F CF 13 2 COOH Well. Lab. a (>98%) / N-methyl-d 3 -perfluoro-1-octanesulfonamide d 3 -N-MeFOSA C 9 D 3 HF 17 NO 2 S Well. Lab. a (>98%) / N-ethyl-d 5 -perfluoro-1-octanesulfonamide d 5 -N-EtFOSA C 10 D 5 HF 17 NO 2 S Well. Lab. a (>98%) / (N-deuteriomethylperfluoro-1-octanesulfoneamido)- 1,1,2,2-tetradeuterioethanol d 7 -N-MeFOSE C 8 F 17 SO 2 N(CD 3 )C 2 D 4 OH Well. Lab. a (>98%) / (N-deuterioethylperfluoro-1-octanesulfoneamido)-1, 1,2,2-tetradeuterioethanol d 9 -N-EtFOSE C 8 F 17 SO 2 N(C 2 D 5 )C 2 D 4 OH Well. Lab. a (>98%) / 58.9 N-deuterioethylperfluoro-1-octanesulfonamidoacetic acid d 5 -EtFOSAA C 8 F 17 SO 2 N(C 2 D 2 C 2 D 3 )C 2 H 2 CO 2 H Well. Lab. a (>98%) / a Well. Lab., Wellington Laboratories; b Lanc. Syn., Lancaster Synthesis; n.a., not available

4 Table S2 Station information about sampling date, time and position Station Original Station Date (mon/day/yy) Time (hh:mm) Longitude_east Latitude_north A1 B05 7/12/2010 6: A2 B08 7/14/ : A3 BS05 7/19/ : B1 R01 7/20/ : B2 C02 7/21/ : B3 R07 7/22/2010 6: B4 C05 7/24/2010 1: B5 C09 7/25/2010 9: B6 S23 7/26/ : B7 S24 7/26/ : B8 S26 7/27/ : B9 MS02 7/28/ : B10 MS03 7/29/2010 3: B11 Mor01 7/29/ : B12 Mor02 7/29/ : B13 BN01 7/30/ : C /4/ : C /5/ : C /6/ : C /8/ : C /9/ : C /10/ : I1 IS1 7/31/2010 4: I2 IS2 8/2/2010 8: I3 IS3 8/9/2010 9:

5 Table S3 Station information about Temperature ( C), Salinity (S ), Chlorophyll (mg L -1 ), and Colored dissolved organic matter (CDOM, mg L -1 ) Station Temperature Salinity Chlorophyll CDOM A A A B B B B B B B B B B B B B C C C C C C I I I

6 Table S4. The values of instrument detect limit (IDL) (pg L -1 ), method quantification limit (MQL) (pg L -1 ) and the concentrations in the field blank (pg L -1 ). Compounds IDL MQL Field blank PFBA <130 PFPA <20 PFBS PFHxA <27 PFHxS <66 PFHpA 7 11 <11 PFHpS PFOA MeFBSA <70 MeFBSE <100 PFOS <21 PFNA <22 PFDA <35 PFDS 4 6 <6.3 PFUnDA <21 FOSA <81 PFDoDA 5 9 <8.6 PFTriDA <25 MeFOSA <92 MeFOSE <27 EtFOSA <24 EtFOSE <23 PFTeDA 5 9 <8.8 PFHxDA 9 15 <15 6

7 Table S5. 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 196% 36% 102% 39% 54% 53% [ 13 C 2 ]-PFHxA 165% 72% 101% 24% 44% 61% [ 18 O 2 ]-PFHxS 86% 36% 57% 11% 100% 84% [ 13 C 4 ]-PFOA 212% 75% 117% 33% 49% 47% [ 13 C 4 ]-PFOS 157% 60% 103% 25% 82% 64% [ 13 C 5 ]-PFNA 187% 78% 112% 29% 56% 54% [ 13 C 2 ]-PFDA 177% 51% 98% 32% 65% 57% [ 13 C 2 ]-PFUnDA 138% 30% 76% 33% 47% 64% [ 13 C 8 ]-FOSA 152% 51% 90% 27% 69% 66% [ 13 C 2 ]-PFDoDA 176% 23% 72% 44% 35% 55% d 3 -N-MeFOSA 194% 28% 75% 43% 54% 52% d 7 -N-MeFOSE 211% 25% 84% 52% 45% 47% d 5 -N-EtFOSA 212% 1% 69% 57% 42% 47% d 9 -N-EtFOSE 229% 18% 86% 57% 38% 44% 7

8 Table S6 Concentrations of ionic PFCs in the sea waters from Arctic Ocean (pg L -1 ) MQL B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 Min Max PFBS 17 <17 <17 53 <17 <17 78 <17 36 < <17 <17 <17 78 PFHxS 66 <66 <66 <66 <66 <66 <66 <66 <66 <66 <66 <66 <66 < PFHpS 19 <19 <19 < < PFOS <21 53 PFDS <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 < PFBA 130 <130 <130 <130 < < < < PFPA PFHxA 27 <27 <27 <27 <27 <27 <27 28 <27 <27 <27 <27 <27 <27 <27 28 PFHpA < <11 < < < <11 < PFOA < <20 67 PFNA < <22 51 PFDA 35 <35 <35 <35 <35 <35 <35 <35 <35 <35 <35 <35 <35 < PFUnDA <21 <21 <21 <21 <21 <21 <21 <21 <21 <21 <21 <21 <21 24 PFDoDA 8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 < PFTriDA 25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 < PFTeDA 8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 < PFHxDA 15 <15 <15 <15 <15 <15 <15 <15 <15 <15 <15 <15 <15 < MeFBSA 70 <70 <70 <70 <70 <70 <70 <70 <70 <70 <70 <70 <70 <70 MeFBSE 100 <100 <100 <100 <100 <100 <100 <100 <100 <100 <100 <100 <100 <100 FOSA <81 <81 <81 <81 <81 <81 <81 <81 <81 <81 <81 <81 < MeFOSA 92 <92 <72 <72 <72 <72 <72 <72 <72 <72 <72 <72 <72 < EtFOSA 24 <24 <24 <24 <24 <24 <24 <24 <24 <24 <24 <24 <24 < MeFOSE <27 <27 <27 <27 <27 <27 <27 <27 <27 <27 <27 <27 <27 31 EtFOSE 23 <23 <23 <23 <23 <23 <23 <23 <23 <23 <23 <23 <23 < Ionic PFC

9 Table S7 Concentrations of ionic PFCs in the sea waters between Northwest Pacific Ocean and Bering Sea (pg L -1 ) Compounds MQL A1 A2 A3 C1 C2 C3 C4 C5 C6 Min Max PFBS 17 <17 26 <17 <17 <17 <17 < < PFHxS 66 <66 <66 <66 <66 <66 <66 <66 <66 < PFHpS 19 <19 <19 <19 <19 <19 <19 <19 <19 < PFOS 21 < <21 35 <21 <21 <21 <21 <21 60 PFDS 6.3 <6.3 < < <6.3 <6.3 < PFBA 130 <130 <130 <130 <130 < <130 <130 <130 < PFPA <20 < < PFHxA 27 <27 <27 <27 <27 <27 <27 <27 <27 < PFHpA 11 <11 < < PFOA 20 <20 < < PFNA < < <22 70 PFDA 35 <35 <35 37 <35 <35 <35 <35 <35 <35 <35 37 PFUnDA 21 <21 <21 25 <21 23 <21 <21 <21 <21 <21 25 PFDoDA 8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 < PFTriDA 25 <25 <25 <25 <25 <25 <25 <25 <25 < PFTeDA 8.8 <8.8 <8.8 <8.8 <8.8 < <8.8 <8.8 < PFHxDA 15 <15 <15 <15 <15 <15 <15 <15 <15 < MeFBSA 70 <70 <70 <70 <70 <70 <70 <70 <70 < MeFBSE 100 <100 <100 <100 <100 <100 <100 <100 <100 < FOSA 81 <81 <81 90 < <81 <81 < MeFOSA 92 <92 <92 <92 <92 <92 <92 <92 <92 < EtFOSA <24 24 < MeFOSE <27 30 EtFOSE <23 23 < ionic PFC

10 Table S8 Concentrations of ionic PFCs in the snow and ice column from Arctic Ocean (pg L -1 ) Analyte MQL IS1_Snow IS1_S IS1_M IS1_B IS2_Snow IS2_S IS2_M IS2_B IS3_Snow IS3_S IS3_M IS3_B Min Max PFBS 17 <17 <17 <17 < <17 < < PFHxS 66 <66 <66 <66 <66 <66 <66 <66 <66 <66 <66 <66 < PFHpS 19 <19 <19 <19 <19 <19 <19 <19 <19 <19 <19 <19 < PFOS 21 < <21 < <21 <21 37 <21 <21 <21 44 PFDS 6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 < PFBA <130 <130 <130 <130 <130 <130 < <130 <130 < PFPA 20 <20 <20 <20 < < <20 66 PFHxA 27 <27 30 <27 <27 <27 <27 <27 <27 <27 61 <27 <27 <27 61 PFHpA <11 <11 <11 61 <11 <11 41 <11 99 PFOA PFNA PFDA < < PFUnDA <21 26 <21 < <21 < PFDoDA 8.6 < <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6 < PFTriDA <25 <25 <25 <25 <25 <25 <25 <25 < PFTeDA 8.8 <8.8 < <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 <8.8 < PFHxDA 15 <15 <15 <15 26 <15 <15 <15 <15 <15 <15 <15 <15 <15 26 MeFBSA 70 <70 <70 <70 <70 <70 <70 <70 <70 <70 <70 <70 < MeFBSE 100 <103 <100 <100 <100 <100 <100 < <100 <100 <100 <100 < FOSA 81 < <81 <81 <81 <81 <81 <81 <81 <81 <81 <81 < MeFOSA 92 <92 <92 <92 <92 <92 <92 <92 <92 <92 <92 <92 < EtFOSA 24 <24 <24 <24 <24 <24 <24 <24 <24 <24 <24 <24 < MeFOSE 27 <27 <27 <27 <27 <27 <27 <27 <27 <27 <27 <27 < EtFOSE 23 <23 <23 <23 <23 <23 <23 <23 <23 <23 <23 <23 < ionic PFC

11 Figure S1. Correlations between PFOA and PFNA in ice core samples (I1-I3) 11

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