a 14-year depositional ice record of perfluoroalkyl acids in the … · a 14-year depositional ice...

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A 14-year depositional ice record of perfluoroalkyl

acids in the High Arctic

John J. MacInnis†, Katherine French‡, Derek C.G. Muir‡, Christine Spencer‡, Alison

Criscitiello, Amila O. De Silva‡*, Cora J. Young†*

†Department of Chemistry, Memorial University, St. John’s, NL, Canada A1B 3X7 ‡Aquatic Contaminants Research Division, Environment and Climate Change Canada, Burlington, ON, Canada L7S 1A1 Department of Geography, University of Calgary, Calgary AB, Canada T2N 1N4

*Corresponding Authors [email protected], [email protected]

Text .......................................................................................................................... 3

S1.1. Sample preparation and analysis ................................................................................3

S1.2. Data analysis ...............................................................................................................4

S1.3. Even-even PFCA homologue trends ..........................................................................3

Tables ....................................................................................................................... 5

Table S1. Comparison of PFAA concentration in field, stay, and method blanks..............5

Table S2. Analyte and internal standards used for PFAA analysis .....................................6

Table S3. Recovery of internal standard in sample extracts ...............................................7

Table S4. Recovery of instrument performance standard ...................................................7

Electronic Supplementary Material (ESI) for Environmental Science: Processes & Impacts.This journal is © The Royal Society of Chemistry 2017

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Table S5. Summary of chromatographic conditions ...........................................................8

Table S6. Summary of inlet and mass spectrometric conditions ........................................8

Table S7. Summary of PFAA elution order, retention time, and ion transitions ................9

Table S8. Instrument limit of detection and quantification for PFAAs ..............................9

Table S9. PFAA concentrations on the Devon Ice Cap ...................................................10

Table S10. PFAA fluxes to the Devon Ice Cap .................................................................11

Table S11. Coefficients of determination and statistical significance of PFAA homologues ........................................................................................................................12

Table S12. First order elimination kinetics for PFOS flux, 1998-2004 using 2006 and 2008 data sets .....................................................................................................................13

Figures ........................................................................................................................................ 14

Figure S1. Depth profile of inorganic ions on the Devon Ice Cap ....................................14

Figure S2. Chromatogram of PFAAs in a low-level standard ..........................................15

Figure S3. Chromatogram of PFAAs in an extracted blank .............................................16

Figure S4. Chromatogram of PFSAs and internal standards in Devon Ice Cap extract ...17

Figure S5. Chromatogram of PFCAs and internal standards in Devon Ice Cap extract ...18

Figure S6. Comparison of PFCA concentrations from sampling campaigns at the Devon Ice Cap in 2006 and 2008 ..................................................................................................19

Figure S7. Relationship between PFDA and PFUnDA concentrations ............................20

Figure S8. Comparison of PFOS concentrations from sampling campaigns at the Devon Ice Cap in 2006 and 2008 ..................................................................................................21

Figure S9. Temporal flux trend for PFOA, PFNA, PFDA, PFUnDA, and PFOS calculated from samples collected in 2006 and 2008 ........................................................22

Figure S10. Comparison of PFOS flux using 2006 and 2008 sampling and first order elimination kinetics for PFOS flux from 1998-2004 using 2006 and 2008 data ...............23

Figure S11. Comparison of chloride-sodium molar ratios on the Devon Ice Cap to expected ocean ratios .........................................................................................................24

References .......................................................................................................................24

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S1.1 Sample preparation and analysis

Samples were defrosted the night before extraction, and 500 mL of melted sample was

used. Melted samples were spiked with 30 μL of a surrogate mixture (Table S2), which acted as

the internal standard to monitor recovery. Covered samples were shaken and sonicated for ten

minutes and were placed in the lab for 30 minutes to equilibrate at room temperature. Samples

were concentrated using an OASIS® weak anion exchange (WAX) solid phase extraction (SPE)

cartridge (6 cm3, 150 mg, 30 µm). Two elution fractions were collected: the first fraction was

eluted with 6 mL of methanol for FOSA, while the second fraction was eluted with 8 mL of

0.1% ammonia in methanol for PFAAs. Both fractions were evaporated to dryness using

nitrogen and reconstituted in 0.25 mL of water pre-cleaned using SPE and 0.25 mL methanol

(Fisher Brand HPLC Grade, ThermoFisher). Contamination was rarely observed in cartridge

blanks; however, where contamination was observed, it was generally lower than the LOQ.

Method recoveries for PFAAs ranged from 95 - 113 %, with the exception of PFOcDA ranging

from 35 - 70 %. Method recoveries demonstrate negative biases resulting from subsampling and

storage were not significant in this study. Recoveries for PFOcDA are reflective of the analytical

limitations of the method. Recovery of internal standards and instrument performance standards

in sample extracts are listed below (Tables S3 – S4). Due to the common presence of trace

PFAAs in purchased reagent water, water (Fisher Brand HPLC Grade, ThermoFisher) used in

the mobile phase was subjected to additional cleaning through OASIS WAX SPE.

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S1.2 Data Analysis

Years of deposition were based on snow density, ion chemistry, and annual snow

accumulation data as described in detail by Meyer et al.1 Net deposition fluxes for each analyte

were calculated by multiplying the ng L-1 concentration by the annual accumulation of water

equivalent (L cm-2 yr-1):

ngPFAALH2O

xLH2O

1000cmx

cmcm3

snowx25cmsnow

yearx10,000cm

m ngPFAAm year

S1.3 Even-even PFCA homologue trends

To further validate fluorotelomer precursor oxidation as a major source of PFCA

deposition at the Devon Ice Cap, even-even homologue relationships were determined for PFBA

to PFDoDA. A correlation between PFHxA and PFOA (R2 = 0.17, p = 0.0311) concentrations

was weak, moderate among PFHxA and PFBA (R2 = 0.32, p = 0.0016) and PFDA and PFDoDA

(R2 = 0.54, p<0.0001), and strong between PFOA and PFDA (R2 = 0.79, p<0.0001). Molar

PFCA flux ratios for even-even homologues were determined (Figure 2b). Unlike the even-odd

flux ratios, only 17% of the measurements were within a factor of two and only 56% of the

measurements were within a factor of 5. It is interesting that most flux ratios of PFOA: PFHxA,

and PFDA: PFOA, are within factors of 2 and 5, respectively. These observations are consistent

with our knowledge of the fugitive emissions of different FTOHs from fluoropolymer products.3

In the work of Dinglasan-Panlilio and Mabury, 8:2 FTOH was the dominant residual impurity in

marketed fluorinated products, followed by 6:2 and 10:2 FTOH.3 Elevated proportions of

residual volatile precursors in fluoropolymer products may suggest the presence of PFHxA,

PFOA, and PFDA on the Devon Ice Cap are partially derived from common fugitive emission

sources.

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Table S1. Comparison of PFAA concentration (ng L-1) in field, stay, and method blanks.

Perfluoroalkyl Substance

Stay Blank (500 mL HPLC grade water)

Field Blank A (500 mL HPLC grade water)

Field Blank B (500 mL HPLC grade water)

Method Blanks

PFBA <LOD <LOD <LOD 0.042-0.058 PFPeA <LOD <LOD <LOD <LOD PFHxA 0.476 0.265 0.255 <LOD PFHpA 0.037 0.046 0.045 <LOD PFOA 0.332 0.36 0.342 0.002-0.005 PFNA 0.061 0.063 0.061 <LOD PFDA 0.158 0.151 0.157 <LOD

PFUnDA 0.016 0.012 0.019 <LOD PFDoDA 0.028 0.026 0.030 <LOD PFTrDA <LOD <LOD <LOD <LOD PFTeDA <LOD <LOD <LOD <LOD PFHxDA <LOD <LOD <LOD <LOD PFOcDA <LOD <LOD <LOD <LOD PFECHS <LOD <LOD <LOD <LOD

PFBS 0.002 0.003 0.002 <LOD PFHxS <LOD <LOD <LOD <LOD PFHpS <LOD <LOD <LOD <LOD PFOS 0.018 0.014 0.018 <LOD PFDS <LOD <LOD <LOD <LOD FOSA <LOD <LOD <LOD 0.022-0.025

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Table S2. Analyte and internal standards used for PFAA analysis. Internal standards (IS) were used to evaluate recovery and matrix effects, while instrument performance (IP) standards were used to evaluate matrix effects only. Precursor ion/product ion transitions (m/z) are indicated in brackets.

Analyte Internal

Standard Instrument Performance

Standard PFBA 13C4 PFBA (217/172) 13C3 PFBA (216/172) PFPeA 13C5 PFPeA (268/223) 13C3 PFPeA (266/222) PFHxA 13C2 PFHxA (315/270) 13C5 PFHxA (318/273) PFHpA 13C4 PFHpA (367/322) PFOA 13C4 PFOA (417/372) 13C2 PFOA (415/370) PFNA 13C5 PFNA (468/423) 13C9 PFNA (472/427) PFDA 13C2 PFDA (515/470) 13C6 PFDA (519/474) PFUnDA 13C2 PFUnDA (565/520) 13C7 PFUnDA (570/525) PFDoDA 13C2 PFDoDA (615/570) PFTrDA 13C2 PFDoDA (615/570) PFTeDA 13C2 PFTeDA (715/670) PFHxDA 13C2 PFHxDA (815/770) PFOcDA 13C2 PFHxDA (815/770) PFBS 18O2 PFHxS (403/84) PFHxS 18O2 PFHxS (403/103) 13C3 PFHxS (402/99) PFHpS 18O2 PFHxS (403/84) PFOS 13C4 PFOS (503/80) 13C8 PFOS (507/99) PFDS 13C4 PFOS (503/80) PFECHS 18O2 PFHxS (403/84) FOSA 13C8 FOSA (506/78)

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Table S3. Recovery of IS in sample extracts. 500 mL of sample was spiked with 0.125 ng of internal standard prior to extraction. Recovery is based on peak area comparison to solvent standard. Mean (standard error) recovery reported for n=18 samples from the Devon Ice Cap.

IS Recovery (%) 13C4 PFBA 64 (3) 13C5 PFPeA 71 (4) 13C2 PFHxA 73 (3) 13C4 PFHpA 74 (3) 13C4 PFOA 89 (3) 13C5 PFNA 86 (3) 13C2 PFDA 83 (2) 13C7 PFUnDA 99 (1) 13C2 PFDoDA 74 (1) 13C2 PFTeDA 50 (3) 13C2 PFHxDA 98 (9) 13C4 PFOS 99 98 (1) 13C4 PFOS 80 97 (1) 18O2 PFHxS 103 102 (1) 18O2 PFHxS 84 103 (1)

Table S4. Recovery of IP standard in sample extracts. 500 mL of sample was spiked with 0.125 ng of performance standard after extraction. Recovery is based on peak area comparison to solvent standard. Mean (standard error) recovery reported for n=18 samples from the Devon Ice Cap.

IP Recovery (%)13C3 PFBA 98 (3) 13C3 PFPeA 98 (1) 13C5 PFHxA 100 (1) 13C2 PFOA 105 (1) 13C9 PFNA 97 (1) 13C6 PFDA 95 (1) 13C2 PFUnDA 86 (1) 13C8 PFOS 99 100 (1) 13C8 PFOS 80 101 (1) 13C3 PFHxS 99 104 (1)

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Table S5. Summary of chromatographic conditions.

Time (minutes)

Flow rate (mL min-1)

% H2O % MeOH

0 0.400 75 25

0.5 0.400 75 25

5.0 0.400 15 85

5.1 0.400 0 100

5.6 0.400 0 100

7.0 0.550 0 100

9.0 0.400 75 25

12.0 0.000 75 25

*Mobile phases buffered with 0.1 mM ammonium acetate.

Table S6. Summary of inlet and mass spectrometric conditions.

Capillary Voltage (kV) 0.5

Source Temperature (°C)

150

Desolvation Gas Temperature (°C)

450

Cone Gas Flow (L hr-1) 150

Desolvation Gas Flow (L hr-1)

650

Collision Gas Flow (mL min-1)

0.15

Nebulizer Pressure (bar) 7

Column Temperature (°C)

50

Injection Volume (μL) 9

Table S7. Summary of PFAA elution order, retention time, and ion transitions.

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Elution Order

PFAA Retention Time (min)

Quantifier Ion Transition (m/z)

Qualifier Ion Transition (m/z)

1 PFBA 0.91 213 > 169 2 PFPeA 2.11 263 > 219 3 PFBS 2.38 299 > 80 299 > 99 4 PFHxA 3.07 313 > 269 313 > 119 5 PFHpA 3.68 363 > 319 363 > 119,169 6 PFHxS 3.74 399 > 80 399 > 99 7 PFECHS 4.08 461 > 381 461 > 99 8 PFOA 4.12 413 > 369 413 > 169 9 PFHpS 4.16 449 > 80 449 > 99 10 PFNA 4.48 463 > 419 463 > 219 11 PFOS 4.50 499 > 80 499 > 99 12 PFDA 4.78 513 > 469 513 > 219 13 PFUnDA 5.03 563 > 519 563 > 319,269 14 PFDS 5.03 599 > 80 599 > 99 15 FOSA 5.13 498 > 78 16 PFDoDA 5.24 613 > 569 613 > 169 17 PFTrDA 5.42 663 > 619 663 > 169 18 PFTeDA 5.58 713 > 669 713 > 169 19 PFHxDA 5.82 813 > 769 813 > 169 20 PFOcDA 5.95 913 > 869 913 > 169 Table S8. Instrument limit of detection and quantitation for PFAAs.

Perfluoroalkyl Substance

LOD (pg L-1) LOQ (pg L-1)

PFBA 10 50 PFPeA 7 20 PFHxA 1 4 PFHpA 2 5 PFOA 2 6 PFNA 2 6 PFDA 1 4

PFUnDA 1 5 PFDoDA 1 4 PFTrDA 1 4 PFTeDA 2 5 PFHxDA 6 20 PFOcDA 10 40 PFECHS 0.3 1

PFBS 4 10 PFHxS 1 4 PFHpS 1 4 PFOS 1 4 PFDS 2 7 FOSA 1 3

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Table S9. Depth profile (cm) of PFAA concentrations (ng L-1) on the Devon Ice Cap. Values <LOQ are identified in blue.

LOD 0.010 0.007 0.001 0.002 0.002 0.002 0.001 0.001 0.001 0.001 0.002 0.004 0.001 0.002 0.0003 0.001 LOQ 0.050 0.020 0.004 0.005 0.006 0.006 0.004 0.005 0.004 0.004 0.005 0.010 0.004 0.007 0.001 0.003 Avg

Depth C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C4-S C8-S C10-S PFECHS FOSA 12.5 0.260 0.060 <LOD <LOD 0.079 0.035 0.013 0.014 0.011 <LOD <LOD 0.095 <LOD <LOD 0.020 <LOD 37.5 0.166 0.055 <LOD 0.052 0.069 0.112 0.017 0.027 <LOD <LOD <LOD 0.054 <LOD <LOD 0.019 <LOD 62.5 0.120 0.042 0.052 0.167 0.371 1.395 0.214 0.348 0.031 0.026 <LOD 0.065 0.014 <LOD 0.009 0.020 87.5 0.171 0.056 0.079 0.200 0.340 0.850 0.136 0.147 0.009 0.005 <LOD 0.086 0.017 <LOD 0.005 0.010 112.5 0.230 0.117 0.152 0.424 0.677 1.424 0.232 0.185 0.032 0.019 0.002 0.070 0.019 <LOD 0.007 0.013 137.5 0.467 0.245 0.183 0.505 0.505 0.878 0.143 0.121 0.017 0.006 <LOD 0.066 0.016 0.002 0.011 0.021 162.5 0.889 0.292 0.297 0.544 0.335 0.307 0.095 0.040 0.004 0.008 <LOD 0.105 0.016 <LOD 0.009 0.013 187.5 1.630 0.457 0.412 0.693 0.458 0.569 0.169 0.083 0.008 0.001 <LOD 0.120 0.013 <LOD 0.003 0.008 212.5 0.848 0.236 0.192 0.301 0.185 0.118 0.038 0.038 0.002 <LOD <LOD 0.196 0.013 <LOD <LOD 0.007 237.5 0.154 0.110 0.130 0.296 0.348 0.707 0.111 0.151 0.023 0.009 <LOD 0.152 0.017 <LOD 0.007 0.014 262.5 1.084 0.217 0.191 0.367 0.350 0.686 0.106 0.109 0.006 <LOD 0.002 0.132 0.002 <LOD 0.000 0.009 287.5 0.566 0.139 0.103 0.221 0.190 0.332 0.071 0.055 0.005 0.001 <LOD 0.088 0.009 <LOD 0.000 0.014 312.5 0.331 0.066 0.092 0.141 0.190 0.312 0.065 0.079 0.007 0.007 <LOD 0.113 0.010 <LOD 0.004 0.040 337.5 0.322 0.091 0.135 0.267 0.304 0.552 0.094 0.114 0.015 0.006 <LOD 0.092 0.010 <LOD 0.013 0.034 362.5 0.121 0.079 0.107 0.172 0.223 0.537 0.070 0.088 0.011 0.010 <LOD 0.103 0.014 <LOD 0.007 0.093 387.5 0.163 0.090 0.107 0.173 0.226 0.425 0.059 0.105 0.013 0.010 <LOD 0.109 0.015 <LOD 0.009 0.072 412.5 1.103 0.042 0.064 0.116 0.220 0.371 0.059 0.111 0.011 0.006 <LOD 0.089 0.011 <LOD 0.009 0.061 437.5 1.071 0.034 0.024 0.112 0.235 0.457 0.106 0.172 0.026 0.023 0.008 0.128 0.004 <LOD 0.009 0.082 462.5 0.138 0.065 0.071 0.154 0.437 0.541 0.121 0.104 0.007 0.012 0.003 0.177 0.016 <LOD 0.011 0.043 487.5 0.145 0.046 0.068 0.126 0.272 0.426 0.091 0.107 0.006 0.005 <LOD 0.175 0.019 <LOD 0.014 0.060 512.5 0.119 0.038 0.067 0.104 0.234 0.324 0.057 0.056 0.003 0.004 <LOD 0.141 0.016 <LOD 0.014 0.065 537.5 0.139 0.127 0.122 0.228 0.340 0.521 0.123 0.161 0.023 0.010 <LOD 0.159 0.017 0.009 0.012 0.129 562.5 0.366 0.152 0.171 0.257 0.211 0.211 0.045 0.055 <LOD 0.004 <LOD 0.216 0.016 <LOD 0.012 0.042 587.5 0.176 0.116 0.152 0.208 0.254 0.258 0.062 0.075 0.002 0.007 <LOD 0.226 0.015 <LOD 0.012 0.048 612.5 2.023 0.123 0.270 0.369 0.343 0.340 0.072 0.067 0.005 0.003 <LOD 0.154 0.015 <LOD 0.013 0.038 637.5 0.599 0.109 0.153 0.166 0.101 0.106 0.034 0.022 <LOD <LOD <LOD <LOD 0.017 <LOD 0.015 0.021 662.5 0.212 0.130 0.150 0.173 0.157 0.157 0.039 0.026 <LOD 0.001 <LOD <LOD 0.019 0.005 0.011 0.035 687.5 1.710 0.077 0.130 0.116 0.159 0.158 0.067 0.028 0.004 0.001 <LOD <LOD 0.027 0.007 0.015 0.036

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Table S10. PFAA flux to the Devon Ice Cap expressed in ng m-2 yr-1. Estimated PFAA flux (red) is calculated from homologue LOD.

Year C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C16 C18 C4-S C6-S C7-S C8-S C10-S PFECHS FOSA 2007 43.66 12.70 5.40 20.97 48.72 152.65 23.98 38.49 3.98 2.82 <0.50 <1.50 <2.49 17.57 <0.25 <0.25 1.53 <0.50 3.76 2.07 2006 38.97 16.61 22.22 59.77 97.66 219.58 35.57 32.37 3.86 2.20 0.39 <1.18 <1.97 15.39 <0.20 <0.20 3.53 <0.39 1.13 2.19 2005 127.91 50.19 45.13 97.82 77.56 108.23 21.98 14.72 1.92 1.33 <0.37 <1.12 <1.86 16.08 <0.19 <0.19 2.92 0.37 1.82 3.09 2004 243.87 68.28 59.87 98.89 64.15 70.48 21.18 11.93 0.98 0.19 <0.38 <1.13 <1.89 28.92 <0.19 <0.19 2.43 <0.38 0.39 1.42 2003 136.34 35.09 34.22 70.29 73.51 146.45 22.84 27.05 2.89 0.98 0.42 <1.26 <2.11 29.78 <0.21 <0.21 1.85 <0.42 0.73 2.45 2002 97.41 22.15 21.21 39.31 41.50 70.36 14.83 14.81 1.34 0.89 <0.44 <1.31 <2.19 22.07 <0.22 <0.22 2.06 <0.44 0.53 5.99 2001 48.37 19.63 27.69 49.46 60.02 126.72 18.71 23.14 2.98 1.89 <0.47 <1.40 <2.33 22.88 <0.23 <0.23 2.83 <0.47 2.24 15.74 2000 110.05 13.68 17.44 29.14 43.91 78.91 11.60 21.10 2.34 1.60 <0.39 <1.18 <1.96 19.69 <0.20 <0.20 2.67 <0.39 1.78 13.27 1999 139.81 11.13 10.74 30.14 75.87 113.28 25.71 31.58 3.84 4.07 1.23 <1.36 <2.27 34.61 <0.23 <0.23 2.19 <0.45 2.27 14.37 1998 29.49 9.34 15.05 25.59 56.56 83.73 16.55 18.30 1.03 1.07 <0.45 <1.34 <2.23 35.24 <0.22 <0.22 3.94 <0.45 3.11 13.94 1997 51.03 29.20 30.42 50.85 59.38 80.33 18.50 23.78 2.70 1.62 <0.42 <1.27 <2.11 38.98 <0.21 <0.21 3.47 1.19 2.58 18.86 1996 204.97 22.36 39.38 53.91 55.74 55.94 12.49 13.34 0.61 0.90 <0.37 <1.12 <1.87 35.58 <0.19 <0.19 2.77 <0.37 2.37 8.06 1995 42.66 7.79 10.89 11.84 7.22 7.53 2.44 1.58 <0.07 <0.07 <0.14 <0.43 <0.71 <0.28 <0.07 <0.07 1.23 <0.14 1.04 1.51 1994 14.71 9.01 10.41 12.04 10.93 10.93 2.73 1.80 <0.07 0.06 <0.14 <0.42 <0.69 <0.28 <0.07 <0.07 1.34 0.35 0.76 2.45 1993 153.28 6.93 11.63 10.39 14.25 14.13 6.01 2.55 0.32 0.08 <0.18 <0.54 <0.90 <0.36 <0.09 <0.09 2.39 0.64 1.31 3.19

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Table S11. Coefficients of determination (R2) and statistical significance (p) of PFAA homologues (n=28).

Na+ C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C4-S C8-S PFECHS C4 R2= 1.6e-03

p= 0.9553

C5 R2= 0.02 p= 0.4316

R2= 0.19 p= 0.0217

C6 R2= 0.03 p= 0.3444

R2= 0.32 p= 0.0016

R2= 0.79 p<0.0001

C7 R2= 0.07 p= 0.1874

R2= 0.16 p= 0.0345

R2= 0.79 p<0.0001

R2= 0.81 p<0.0001

C8 R2= 0.10 p= 0.1057

R2= 1.1e-03 p= 0.8627

R2= 0.13 p= 0.0625

R2= 0.17 p= 0.0311

R2= 0.46 p<0.0001

C9 R2= 0.06 p= 0.1935

R2= 0.04 p= 0.3056

R2= 2.3e-04 p= 0.9387

R2= 7.7e-04 p= 0.8882

R2= 0.12 p= 0.0667

R2=0.67 p<0.0001

C10 R2= 0.08 p= 0.1408

R2= 3.6e-04 p= 0.9235

R2= 0.05 p= 0.2537

R2= 0.05 p= 0.2331

R2= 0.27 p= 0.0048

R2= 0.79 p<0.0001

R2= 0.87 p<0.0001

C11 R2= 1.9e-03 p= 0.8232

R2= 0.05 p= 0.2454

R2= 0.04 p= 0.3138

R2= 0.03 p= 0.3423

R2= 5.9e-03 p= 0.6974

R2= 0.32 p= 0.0016

R2= 0.75 p<0.0001

R2=0.64 p<0.0001

C12 R2= 2.2e-04 p= 0.9407

R2= 0.04 p= 0.3356

R2= 0.03 p= 0.4025

R2= 0.04 p= 0.3168

R2= 0.01 p= 0.5853

R2= 0.33 p= 0.0013

R2= 0.61 p <0.0001

R2= 0.54 p<0.0001

R2= 0.71 p<0.0001

C13 R2= 0.02 p= 0.5222

R2= 0.07 p= 0.1875

R2= 0.09 p= 0.1132

R2= 0.07 p= 0.1749

R2=1.1e-03 p=0.8614

R2= 0.22 p= 0.0113

R2= 0.47 p<0.0001

R2= 0.43 p=0.0002

R2= 0.70 p<0.0001

R2=0.66 p<0.0001

C4-S R2= 2.8e-03 p= 0.7883

R2= 7.6e-03 p= 0.6587

R2= 0.01 p= 0.5940

R2= 0.01 p= 0.5371

R2= 0.01 p= 0.5689

R2= 0.02 p= 0.4254

R2= 5.3e-03 p= 0.7115

R2= 7.2e-04 p= 0.8925

R2= 2.6e-03 p= 0.7947

R2= 3.6e-03 p= 0.7607

R2=5.6e-03 p= 0.7044

C8-S R2= 0.03 p= 0.3675

R2= 4.9e-04 p= 0.9112

R2= 2.2e-03 p= 0.8145

R2= 0.09 p= 0.1269

R2= 0.04 p= 0.3298

R2= 0.09 p= 0.1233

R2= 0.03 p= 0.3970

R2= 0.06 p= 0.1942

R2= 4.2e-03 p= 0.7435

R2= 2.6e-06 p= 0.9935

R2= 6.6e-03 p= 0.6814

R2= 6.9e-03 p= 0.6749

PFECHS R2= 4.6e-03 p= 0.7314

R2= 0.03 p= 0.3987

R2= 0.19 p= 0.0205

R2= 0.14 p= 0.0531

R2= 0.21 p= 0.0142

R2= 0.11 p= 0.0863

R2= 0.11 p= 0.0905

R2= 0.12 p= 0.0682

R2= 0.05 p= 0.2383

R2= 0.01 p= 0.5490

R2= 6.3e-03 p= 0.6868

R2= 0.04 p= 0.3357

R2= 1.3e-03 p= 0.8566

FOSA R2= 9.1e-05 p= 0.9616

R2= 0.03 p= 0.3487

R2= 0.05 p= 0.2303

R2=0.03 p= 0.3620

R2= 0.05 p= 0.2723

R2= 6.1e-04 p= 0.9010

R2= 2.1e-03 p= 0.8152

R2= 7.8E-04 p= 0.8880

R2= 0.02 p= 0.4710

R2= 1.8e-04 p= 0.9460

R2= 0.01 p= 0.5976

R2= 0.15 p= 0.0406

R2= 0.01 p= 0.5886

R2= 1.3e-03 p= 0.8542

13

Table S12. First order elimination kinetics for PFOS flux, 1998-2004 using 2006 and 2008 data sets (corresponds to Fig S10)

2006 data 2008 data First order elimination rate, Ke (y-1) 0.3197±0.1333 0.0731±0.0400

p-value 0.0617 0.127 R2 on ln flux versus year regression 0.535 0.401

Degrees of freedom 5 5 Half life, T1/2 (y) based on ln2/ke 2.2 ± 5.2 9.5 ± 17

14

Figure S1. Depth profile of inorganic ions on the Devon Ice Cap.

15

Figure S2. Chromatogram of PFAAs in a low-level (~ 0.1 ng mL-1) standard. Chromatograms have not been smoothed. Precursor-product ion transition is shown in red for analytes. Peaks are annotated with retention time and standard concentration.

apr28 pfa L1

Time0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

May21_devon_PFA-4 22: MRM of 3 Channels ES-

713> 169 (PFTeDA) 2.14e4

5.57May21_devon_PFA-4 21: MRM of 2 Channels ES-

663 > 169 (PFTriDA) 1.55e45.42


613 > 169 (PFDoDA) 6.29e4


563 > 319 (PFUnDA)4.36e45.03


513 > 219 (PFDA) 9.25e4


463 > 219 (PFNA)1.02e54.48


413 > 169 (PFOA)1.63e54.12


363 > 119 (PFHpA)1.93e43.67

3.80


313 > 119 (PFHxA)1.00e43.07


263 > 219 (PFPeA)7.75e42.11


213 > 169 (PFBA)5.26e4

0.910.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

0.093 ng/ml

apr28 pfa L1

Time (min)0.60 1.00 1.40 1.80 2.20 2.60 3.00 3.40 3.80 4.20 4.60 5.00 5.40

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100


599 > 80 (PFDS)

1.19e55.03


498 > 78 (PFOS)

1.50e54.50


461> 99 (PFECHS)

1.56e54.08


449 > 80 (PFHpS)

1.01e54.16


399 > 80 (PFHxS)

1.63e53.74


299 > 80 (PFBS)

1.17e52.38

Abu

nda

nce

(%)

0.082 ng/ml

0.088 ng/ml

0.076 ng/ml

0.078 ng/ml

0.089 ng/ml

0.089 ng/ml

16

Figure S3. Chromatogram of PFAAs in extracted blank. Chromatograms have not been smoothed. Precursor-product ion transition is shown in red for analytes. Retention times are annotated for detected peaks.

may15 CB F2

Time0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100


713 > 169 (PFTeDA)8955.56

5.56

5.525.49

5.59

5.675.64

5.67


663 > 169 (PFTriDA)738

5.43

5.425.375.28

5.265.36

5.34

5.46

5.50

5.54


613 > 169 (PFDoDA)1.12e3

5.155.23

5.20

5.335.245.31


563 > 319 (PFUnDA)1.19e3

4.98

4.944.93

5.03

5.05

5.09 5.11


513 > 219 (PFDA)1.79e3

4.79

4.77

4.71

4.80

4.844.86


463 > 219 (PFNA)5.63e3

4.48

4.40

4.50

4.524.56


413 > 169 (PFOA)1.33e44.12


363 > 119 (PFHpA)4.91e3

3.643.63

3.593.57

3.56

3.733.643.79

3.83


313 > 119 (PFHxA)2.86e3

2.972.91 3.072.99

3.05

3.183.17

3.213.24


263 > 219 (PFPeA)1.28e4

1.86 2.041.93 2.03 2.242.10 2.17 2.30

2.33


213 > 169 (PFBA)4.32e40.90

may15 CB F2

Time (min)

2.40 2.60 2.80 3.00 3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00

%

0

100

2.25 2.30 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45 3.50 3.55 3.60 3.65 3.70 3.75 3.80 3.85 3.90 3.95 4.00 4.05 4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10

%

0

100

2.25 2.30 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45 3.50 3.55 3.60 3.65 3.70 3.75 3.80 3.85 3.90 3.95 4.00 4.05 4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10

%

0

100

2.25 2.30 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45 3.50 3.55 3.60 3.65 3.70 3.75 3.80 3.85 3.90 3.95 4.00 4.05 4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10

%

0

100

2.25 2.30 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45 3.50 3.55 3.60 3.65 3.70 3.75 3.80 3.85 3.90 3.95 4.00 4.05 4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10

%

0

100

2.25 2.30 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45 3.50 3.55 3.60 3.65 3.70 3.75 3.80 3.85 3.90 3.95 4.00 4.05 4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10

%

0

100


599 > 80 (PFDS)1.06e3

5.045.03

4.93

4.97 5.025.01 5.125.08

5.10


499 > 80 (PFOS)2.28e3

4.504.41

4.38

4.374.39 4.47

4.44

4.51

4.644.60

4.564.55

4.58

4.61


461 > 99 (PFECHS)3.55e3

4.08

3.96

3.94

3.92

3.88 3.90

3.96

4.043.97

4.024.00

4.09

4.104.14

4.124.20 4.27

4.224.27 4.28


449 > 80 (PFHpS)545

4.12

4.09

4.08

4.19

4.14

4.20

4.264.26

4.23


399 > 80 (PFHxS)2.70e3

3.66

3.68 3.75

3.73

3.71

3.76

3.773.78

3.85

3.83

3.87


299 > 80 (PFBS)1.87e3

2.38

2.372.21

2.222.25

2.302.28

2.35

2.38

2.39

2.412.592.492.42

2.46

2.462.47

2.52

2.562.54

0.059 ng/ml PFBA

0.005 ng/ml PFOA

Abu

ndan

ce (

%)

17

Figure S4. Chromatogram of PFSAs and internal standards in Devon Ice Cap extract. Chromatograms have not been smoothed. Precursor-product ion transition is shown in red for analytes and blue for internal standards. Retention times for detected peaks are in purple. This sample contained 0.105 ng L-1 PFBS, 0.016 ng L-1 PFOS, and 0.0088 ng L-1 PFECHS. PFHxS, PFHpS, PFDS, were < LOD.

May15-5 DEVON 150-175 F2

Time (min)0.60 1.00 1.40 1.80 2.20 2.60 3.00 3.40 3.80 4.20 4.60 5.00 5.40

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100


599 > 80 (PFDS)

1.72e3


503 > 80 (13C PFOS)

3.33e54.50


499 > 80 (PFOS)

2.20e44.50


461 > 99 (PFECHS)

1.86e44.09


449 > 80 (PFHpS)

4.02e3


403 > 84 (18O2 PFHxS)

3.98e53.73


399 > 80 (PFHxS)

4.97e3


299 > 80 (PFBS)

8.20e32.39

Abu

ndan

ce(%

)

18

Figure S5. Chromatogram of PFCAs and internal standards in Devon Ice Cap extract. Chromatograms have not been smoothed. Precursor-product ion transition is shown in red for analytes and blue for internal standards. Retention times for detected peaks are in purple. This sample contained 0.89 ng L-1 PFBA, 0.29 ng L-1 PFPeA, 0.30 ng L-1 PFHxA, 0.54 ng L-1 PFHpA, 0.34 ng L-1 PFOA, 0.31 ng L-1 PFNA, 0.095 ng L-1 PFDA, 0.040 ng L-1 PFUnDA, 0.044 ng L-1 PFDoDA, 0.0083 ng L-1 PFTrDA. PFTeDA was <LOD.

Time (min)

0.60 1.00 1.40 1.80 2.20 2.60 3.00 3.40 3.80 4.20 4.60 5.00 5.40

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100


468 > 423 (13C PFNA)1.01e64.48


463 > 219 (PFNA) 3.29e54.48


417 > 372 (13C-PFOA)7.63e54.12


413 > 169 (PFOA)4.92e54.12

4.00


367 > 322 (13 C PFHpA)8.68e53.68


363 > 119 (PFHpA)8.59e43.68


315 > 270 (13C2 PFHxA)7.15e53.07


313 > 119 (PFHxA)2.44e43.06


268 > 223 (M5PFPeA)2.63e52.10


263 > 219 (PFPeA) 2.40e52.09


217 > 172 (13C4 PFBA) 1.38e50.87


213 > 169 (PFBA) 5.68e50.89

May15-5 DEVON 150-175 F2

Time0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60

%

0

100

0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 5.00 5.10 5.20 5.30 5.40 5.50 5.60%

0

100


715 > 670 (MPFTEDA)4.67e5


713 > 169 (PFTeDA)1.42e3


663 > 169 (PFTriDA)2.59e3


615 > 570 (13C2 PFDoDA)2.86e5

5.24


613 > 169 (PFDoDA)1.00e4

5.25


565 > 520 (13C2 PFUnDA)7.89e5

5.03


563 > 319 (PFUnDA)1.99e4

5.03


515 > 470 (13C2 PFDA) 6.54e54.77


513 > 219 (PFDA) 9.11e44.77

Abu

ndan

ce(%

)

19

Figure S6. Comparison of PFCA concentrations from sampling campaigns at the Devon Ice Cap in 2006 (A) and 2008 (B).

20

Figure S7. Evaluation of volatile precursor oxidation as a source of PFAA deposition on the Devon Ice Cap using PFDA and PFUnDA concentrations.

21

Figure S8. Comparison of PFOS concentrations from sampling campaigns at the Devon Ice Cap in 2006 (A) and 2008 (B).

22

Figure S9. Temporal flux trend for PFOA (a), PFNA (b), PFDA (c), PFUnDA (d), and PFOS (e) calculated from samples collected in 2006 (blue) and 2008 (purple), along with three-year moving averages.

23

Figure S10. Comparison of a) PFOS flux using 2006 and 2008 sampling and b) first order elimination kinetics for PFOS flux from 1998-2004 using 2006 and 2008 data.

1998 1999 2000 2001 2002 2003 2004

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

ln P

FO

S f

lux

ln PFOS 2006 fluxln PFOS 2008 flux

1992 1994 1996 1998 2000 2002 2004 2006 2008

0

5

10

15

20

25

30

2006 sampling2008 sampling

year

PF

OS

flu

x (2

006)

ng

/m2

/y

1.0

1.5

2.0

2.5

3.0

3.5

4.0

PF

OS

flu

x (2

008)

ng

/m2/y

year

a)

b)

24

Figure S11. Comparison of chloride-sodium molar ratios on the Devon Ice Cap to expected ocean ratios. The gray dashed line corresponds to the average Cl-/Na+ ratio observed on the Devon Ice Cap, and the solid black line corresponds to the expected ocean ratio.4

References

(1) Meyer, T.; Muir, D. C. G.; Teixeira, C.; Wang, X.; Young, T.; Wania, F. Deposition of brominated flame retardants to the Devon Ice Cap, Nunavut, Canada. Environ. Sci. Technol. 2012, 46 (2), 826–833.

(2) 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. Environ. Sci. Technol. 2007, 41, 3455–3461.

(3) Dinglasan-Panlilio, M. J. A.; Mabury, S. A. Significant residual fluorinated alcohols present in various fluorinated materials. Environ. Sci. Technol. 2006, 40 (5), 1447–1453.

(4) Keene, W. C.; Pszenny, A. P.; Galloway, J. N.; Hawley, M. E. Sea-salt corrections and interpretation of constituent ratios in marine precipitation. J. Geophys. Res. 1986, 91 (D6), 6647.

a 14-year depositional ice record of perfluoroalkyl acids in the … · a 14-year depositional ice...

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