Perfluorinated compounds in marine surface waters: data from the Baltic Sea and methodological challenges for future studies
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1 Accessory publication Perfluorinated compounds in marine surface waters: data from the Baltic Sea and methodological challenges for future studies Torben Kirchgeorg, A,B Ingo Weinberg, A Annekatrin Dreyer A and Ralf Ebinghaus A A GKSS Research Centre, Max-Planck-Strasse 1, D Geesthacht, Germany B Corresponding author. torben.kirchgeorg@gkss.de Sample information... 5 Blanks... 7 Detection limits... 8 PFC concentrations... 9 PFC composition Spatial distribution Information on analytes Page 1 of 15
2 Information on the Baltic Sea Fig. A1. Subdivision of the Baltic Sea. The basins mostly have specific water exchange characteristics. The map was downloaded from the Helcom website (HELCOM, 2010). [2] Page 2 of 15
3 Fig. A2. Main currents in the Baltic Sea. The map was downloaded from the website of the European Environment Agency [1] (EEA, 2007). Page 3 of 15
4 Fig. A3. Population density in the catchment of the Baltic Sea (UNEP/GRID-Arendal, 2001). [3] Page 4 of 15
5 Sample information Table A1. Sample information Sample ID Sample name Date Time (hour) Latitude Longitude Salinity (psu) Temperature ( C) 1 Alkor320-AB 1 1 June Alkor320-AB 2 1 June Alkor320-AB 3 1 June Alkor320-AB 4 1 June Alkor320-AB 5 1 June Alkor320-AB 6 1 June Alkor320-AB 7 1 June Alkor320-BB 3 1 June Alkor320-BB 5 1 June Alkor320-BB 7 1 June Alkor320-BB 8 1 June Alkor320-BB 11 2 June Alkor320-BB 12 2 June Alkor320-BB 20 2 June Alkor320-BB 24 2 June Alkor320-BB 26 3 June Alkor320-SF 54 3 June Alkor320-SF 47 3 June Alkor320-BB 27 3 June Alkor320-BB 31 3 June Alkor320-BB 42 3 June Alkor320-BB 44 4 June Alkor320-BB 34 4 June Alkor320-BB 38 4 June Alkor320-BB 36 4 June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ June MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July Page 5 of 15
6 Sample ID Sample name Date Time (hour) Latitude Longitude Salinity (psu) 50 MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July MSM08/ July Temperature ( C) Page 6 of 15
7 Blanks Table A2. Average concentrations (ng L 1 ) observed in blank samples during the two sampling campaigns Alkor 320 MSM08/3 PFBS 0.15 n.d. PFPS n.d. n.d. PFHxS PFHpS n.d. n.d. PFOS PFNS n.d. n.d. PFDS n.d. n.d. TH-PFOS n.d PFHxSi n.d. n.d. PFOSi PFDSi n.d. n.d. PFBA n.d PFPA PFHxA PFHpA n.d PFOA PFNA PFDA PFUnDA PFDoDA PFTriDA n.d PFTeDA n.d PFPeDA n.d. n.d. PFHxDA n.d PFHpDA n.d. n.d. PFOcDA n.d Me2PFOA n.d. n.d. FOSA NMeFOSA n.d. n.d. NEtFOSA n.d. n.d. NMeFOSE n.d NEtFOSE n.d. n.d. MeFBSA n.d MeFBSE FHEA (6:2 FTCA) n.d. n.d. FOEA (8:2 FTCA) n.d. n.d. FDEA (10:2 FTCA) n.d. n.d. FHUEA (6:2 FTUCA) n.d FOUEA (8:2 FTUCA) 0.05 n.d. FDUEA (10:2 FTUCA) n.d. n.d. Page 7 of 15
8 Detection limits Table A3. Average instrumental limits of detection (IDL, in pg, n=3) and method detection limits (MDL,in ng L-1, n=6) on the basis of signal to noise ratios of 3 (Ahrens et al. pers. comm.). Analyte IDL (pg) MDL (ng L 1 ) Dissolved phase Particle phase PFBS PFHxS PFHpS n.d. PFOS PFDS n.d. n.d. TH-PFOS n.d. PFHxSi n.d. PFOSi PFDSi n.d. n.d. PFBA n.d. PFPA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTriDA n.d. n.d. PFTeDA n.d. n.d. PFHxDA n.d. n.d. PFOcDA n.d. n.d. Me2PFOA n.d. MeFBSA n.d. n.d. PFOSA MeFOSA n.d. n.d. EtFOSA n.d. n.d. MeFBSE n.d. n.d. MeFOSE n.d. n.d. EtFOSE n.d FHEA n.d. n.d. FOEA n.d. n.d. FDEA n.d. n.d. FHUEA n.d. n.d. FOUEA n.d. n.d. FDUEA n.d. n.d. Page 8 of 15
9 PFC concentrations Table A4. Concentrations (ng L 1 ) of PFC quantified in Baltic Sea surface water <Blk, below the blank value; n.d., not detected; n.q.: not quantified Sample ID Sample name 1 Alkor320-AB 1 <Blk n.d n.d. 2 Alkor320-AB n.d. n.d n.d. n.q. n.d. 3 Alkor320-AB 3 <Blk n.d n.q. n.d. 4 Alkor320-AB 4 <Blk n.d n.d. n.d. 5 Alkor320-AB 5 <Blk n.d. n.d n.d. n.d. 6 Alkor320-AB n.q. n.d. 7 Alkor320-AB 7 <Blk n.d n.d. n.d. 8 Alkor320-BB n.d n.q. n.d. n.d. 9 Alkor320-BB 5 <Blk n.d. n.d n.q. n.d. n.d. 10 Alkor320-BB 7 <Blk n.d n.d n.q. n.d. n.d. 11 Alkor320-BB 8 <Blk n.d n.d. n.d. 12 Alkor320-BB 11 <Blk n.d n.q. n.q Alkor320-BB 12 n.d n.d. n.d n.q. n.d. n.d. 14 Alkor320-BB 20 n.d n.d n.d. n.d. 15 Alkor320-BB 24 <Blk n.d n.d. n.d. 16 Alkor320-BB 26 <Blk n.d n.d. n.d. 17 Alkor320-SF 54 <Blk n.d n.d. n.d. 18 Alkor320-SF 47 <Blk n.d n.d. n.d. 19 Alkor320-BB 27 <Blk n.d n.d. n.d. 20 Alkor320-BB n.d n.d n.d. n.d. n.d. 21 Alkor320-BB 42 <Blk n.d n.q. n.d. n.d. 22 Alkor320-BB 44 n.d. n.d n.d n.q. n.d. n.d. 23 Alkor320-BB 34 <Blk n.d n.q. n.d Alkor320-BB n.d n.q. n.d Alkor320-BB 36 <Blk n.d n.d n.q. n.d. n.d. 26 MSM08/ n.q. n.d MSM08/ n.q. n.q MSM08/ n.q MSM08/3-4 n.d <Blk MSM08/3-5 n.d n.d n.q MSM08/ n.q MSM08/ n.d n.q MSM08/ n.d n.q MSM08/ n.d n.q MSM08/3-10 n.d n.q MSM08/3-11 n.d n.d n.q MSM08/3-12 n.d n.q MSM08/3-13 n.d n.q MSM08/ n.d n.d MSM08/ <Blk n.d MSM08/3-16 n.d n.d n.q MSM08/ n.d n.d n.d MSM08/ n.q MSM08/ n.q. n.d PFBS PFHxS PFOS PFBA PFPA PFHxA PFHpA PFOA PFNA PFDA PFDoDA FOSA Page 9 of 15
10 Sample ID Sample name 45 MSM08/3-20 n.q n.d n.q MSM08/ n.d. n.d n.q MSM08/ n.d. n.d MSM08/ n.d n.q MSM08/ n.d n.d MSM08/ n.q MSM08/ n.d MSM08/3-27 n.d n.q MSM08/3-28 n.d n.d. n.d n.q. n.d MSM08/3-29 n.q n.d. n.d MSM08/ n.q MSM08/ n.q. n.d MSM08/3-32 n.d n.d n.d. n.d MSM08/3-33 n.d n.d n.q. n.d. n.d. 59 MSM08/3-34 n.d n.d n.q. n.d MSM08/3-35 n.d n.d n.d MSM08/3-36 n.d n.q. n.d MSM08/3-37 n.d n.d n.d MSM08/ n.d n.q. n.d. n.d. 64 MSM08/ n.d n.q. n.d. n.d. 65 MSM08/ n.d MSM08/ n.d MSM08/ n.q. n.d. n.d. 68 MSM08/ n.d. n.d. 69 MSM08/ n.q. n.d. n.d. 70 MSM08/ n.d MSM08/ n.d n.d. 72 MSM08/ n.q. n.d. n.d. 73 MSM08/ n.q. n.d. n.d. 74 MSM08/ n.q. n.d. n.d. PFBS PFHxS PFOS PFBA PFPA PFHxA PFHpA PFOA PFNA PFDA PFDoDA FOSA Page 10 of 15
11 PFC composition Fig. A4. PFC composition in Baltic Sea water samples. PFBA and FOSA were not included since absolute values of concentrations were uncertain. Note that there were blank Problems for PFBS in Alkor 320 samples (ID 1-25). Page 11 of 15
12 Spatial distribution Salinity PFHxS PFHxA PFHpA PFNA PFDA Fig. A5. Spatial distribution of salinity and various PFC in surface water of the Baltic Sea. Page 12 of 15
13 Information on analytes Table A5. Analytes, acronyms, formula, supplier, purity, precursor and product ions for the MS/MS detection Well. Lab., Wellington Laboratories; Lanc. Syn., Lancaster Synthesis. n.a., not available Analyte Abbreviation Formula Supplier (purity) Precursor, product ion (m/z) Perfluorobutane sulfonate PFBS C 4 F 9 SO 2 O Fluka (97%) , 79.8 Perfluoropentane sulfonate PFPS C 5 F 11 SO 2 O n.a , 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. (>98%) , 79.3 Perfluorooctane sulfonate PFOS C 8 F 17 SO 2 O Well. Lab. (>98%) , 79.7 Perfluorononane sulfonate PFNS C 9 F 19 SO 2 O n.a , 79.8 Perfluorodecane sulfonate PFDS C 10 F 21 SO 2 O Well. Lab. (>98%) , :2 fluorotelomer sulfonate 6:2 FTS C 6 F 13 C 2 H 4 SO 3 ABCR (98%) , Perfluoro-1-hexane sulfinate PFHxSi C 6 F 13 SO 2 Well. Lab. (>98%) , Perfluoro-1-octane sulfinate PFOSi C 8 F 17 SO 2 Well. Lab. (>98%) , Perfluoro-1-decane sulfinate PFDSi C 10 F 21 SO 2 Well. Lab. (>98%) , 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. (98%) , Perfluorooctanoic acid PFOA C 7 F 15 COOH Lanc. Syn. (95%) , Perfluorononanoic acid PFNA C 8 F 17 COOH Lanc. Syn. (97%) , Perfluorodecanoic acid PFDA C 9 F 19 COOH Lanc. Syn. (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. (>98%) , Perfluorotetradecanoic acid PFTeDA C 13 F 27 COOH Alfa Aesar (96%) , Perfluorotridecanoic acid PFPDA C 14 F 29 COOH n.a , Perfluorohexadecanoic acid PFHxDA C 15 F 31 COOH Alfa Aesar (95%) , Perfluoroheptadecanoic acid PFHpDA C 16 F 33 COOH n.a , Perfluorooctadecanoic acid PFOcDA C 17 F 35 COOH Alfa Aesar (97%) , ,7-dimethylperfluorooctanoic acid Me 2 PFOA C 9 F 19 COOH Alfa Aesar (97%) , 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 Page 13 of 15
14 Analyte Abbreviation Formula Supplier (purity) Precursor, product ion (m/z) N-methyl perfluorooctane sulfonamide MeFOSA C 8 F 17 SO 2 NH(CH 3 ) 3M (n.a.) , N-ethyl perfluorooctane 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 perfluorooctane sulfonamidoethanol MeFOSE C 8 F 17 SO 2 N(CH 3 )C 2 H 4 OH 3M (n.a.) , 58.9 N-ethyl perflurooctane sulfonamidoethanol EtFOSE C 8 F 17 SO 2 N(C 2 H 5 )C 2 H 4 OH 3M (n.a.) , Perfluorohexyl ethanoic acid FHEA C 6 F 13 CH 2 COOH Well. Lab. (>98%) , Perfluorooctyl ethanoic acid FOEA C 8 F 17 CH 2 COOH Well. Lab. (>98%) , Perfluorodecyl ethanoic acid FDEA C 10 F 21 CH 2 COOH Well. Lab. (>98%) , H-Perfluoro-2-octenoic acid FHUEA C 6 F 12 CHCOOH Well. Lab. (>98%) , H-Perfluoro-2-decenoic acid FOUEA C 8 F 16 CHCOOH Well. Lab. (>98%) , H-Perfluoro-2-dodecenoic acid FDUEA C 10 F 20 CHCOOH Well. Lab. (>98%) , Perfluoro-1-hexane[ 18 O 2 ]sulfonate [ 18 O 2 ]-PFHxS C 6 F 13 S[ 18 O 2 ]O Well. Lab. (>98%) , 83.9 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. (>98%) , 79.5 Perfluoro-1-[1,2,3,4-13 C 4 ]octanesulfinate [ 13 C 4 ]-PFOSi C 4 F 9 [1,2,3,4-13 C 4 ]F 8 SO 2 Well. Lab. (>90%) , 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. (>98%) , 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. (>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. (>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. (>98%) , Perfluoro-n-[1,2-13 C 2 ]decanoic acid [ 13 C 2 ]-PFDA C 8 F CF 13 2 COOH Well. Lab. (>98%) , Perfluoro-n-[1,2-13 C 2 ]undecanoic acid [ 13 C 2 ]-PFUnDA C 9 F CF 13 2 COOH Well. Lab. (>98%) , Perfluoro-n-[1,2-13 C 2 ]dodecanoic acid [ 13 C 2 ]-PFDoDA C 10 F CF 13 2 COOH Well. Lab. (>98%) , N-methyl-d 3 -perfluoro-1-octanesulfonamide d 3 -N-MeFOSA C 9 D 3 HF 17 NO 2 S Well. Lab. (>98%) , N-ethyl-d 5 -perfluoro-1-octanesulfonamide d 5 -N-EtFOSA C 10 D 5 HF 17 NO 2 S Well. Lab. (>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. (>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. (>98%) , Perfluorohexyl-[1,2-13 C 2 ]ethanoic acid [ 13 C 2 ]-FHEA C 6 F CH 13 2 COOH Well. Lab. (>98%) , Perfluorooctyl-[1,2-13 C 2 ]ethanoic acid [ 13 C 2 ]-FOEA C 8 F CH 13 2 COOH Well. Lab. (>98%) , Perfluorodecyl-[1,2-13 C 2 ]ethanoic acid [ 13 C 2 ]-FDEA C 10 F CH 13 2 COOH Well. Lab. (>98%) , H-Perfluoro-[1,2-13 C 2 ]-2-octenoic acid [ 13 C 2 ]-FHUEA C 6 F CH 13 COOH Well. Lab. (>98%) , H-Perfluoro-[1,2-13 C 2 ]-2-decenoic acid [ 13 C 2 ]-FOUEA C 8 F CH 13 COOH Well. Lab. (>98%) , H-Perfluoro-[1,2-13 C 2 ]-2-dodecenoic acid [ 13 C 2 ]-FDUEA C 10 F CH 13 COOH Well. Lab. (>98%) , 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. (>98%) , Page 14 of 15
15 References [1] EEA, Baltic Sea physiography (depth distribution and main currents) 2007 (European Environmental Agency). Available at [Verified 18 March 2010]. [2] HELCOM, The nature of the Baltic Sea 2010 (Helsinki Commission). Available at [Verified 18 March 2010]. [3] UNEP/GRID-Arendal, Population density in the Baltic Sea drainage basin 2001 (UNEP/GRID-Arendal Maps and Graphics Library). Available at baltic_sea_drainage_basin [Verified 18 March 2010]. Page 15 of 15
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