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Electronic Supplementary Material (ESI) for Environmental Science: Processes & Impacts This journal is © The Royal Society of Chemistry 2013

Atmospheric deposition of persistent organic pollutants and chemicals of emerging concern at two sites in northern Sweden Supplemental Information

Seth Newtona, Terry Bidlemanb, Magnus Bergknutb,c, Jacinthe Racined, Hjalmar Laudone, Reiner Gieslerf, Karin Wibergg a

Department of Applied Environmental Science (ITM), Stockholm University, SE-10691 Stockholm, Sweden

b

c

Department of Chemistry, Umeå University, SE-90187 Umeå, Sweden

Envix Nord AB, SE-90620, Umeå, Sweden

d

Air Quality Modelling Application, Canadian Meteorological Centre, 2121 Trans-Canada Highway, Dorval, QC,

Canada H9P 1J3 e

Department of Forest Ecology and Management, Swedish University of Agricultural Sciences (SLU), SE-90183

Umeå, Sweden f

Climate Impacts Research Centre, Department of Ecology and Environmental Science, Umeå University, SE-98107

Abisko, Sweden g

Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences (SLU), SE-75007

Uppsala, Sweden


Table S1 - Instrument Detection Limits (IDLs) and Method Detection Limits (MDLs). NA indicates that the compound was not detected in the blanks and a MDL could not be established.

α-TBECH β-TBECH DPTE EHTBB BTBPE HBB DP syn DP anti trifluralin chlorothalonil PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 α-HCH γ-HCH cis-chlordane trans-chlordane cis-nonachlor trans-nonachlor heptachlor heptachlor-exo-epoxide oxychlordane BDE-47 BDE-99 BDE-100 BDE-153 BDE-154

IDL (pg on column) 0.91 0.91 0.29 0.30 0.38 0.39 0.49 0.26 0.32 0.27 0.19 0.31 0.23 0.52 0.23 0.20 0.25 0.32 0.11 0.11 0.32 0.25 0.18 0.14 0.73 Not determined Not determined Not determined Not determined Not determined

MDL (pg per sample) NA NA NA NA 64 773 48 40 NA NA 142 285 278 52 195 262 98 203 19 11 NA 17 NA 21 99 255 206 45 319 86


Table S2 - Masses and retention times for all compounds.

Compound α-TBECH β-TBECH DPTE EHTBB BTBPE 13 C 12 BTBPE HBB 13 C 6 HBB DP syn DP anti trifluralin d 14 trifluralin

Mass 1 264.9228 264.9228 329.7891 420.6720 356.8124 362.8326 549.5059 555.5261 271.8102 271.8102 264.1087 267.0420

Mass 2 266.9208 266.9208 331.7870 422.6699 358.7928 364.8129 551.5039 557.5240 273.8072 273.8072 306.0702 315.1270

Retention Time 17.38 17.69 28.84 34.28 39.07 39.05 29.32 29.31 40.96 41.75 10.33 10.18

chlorothalonil PCB 28 13 C 12 PCB 28 PCB 52 13 C 12 PCB 52 PCB 101

263.8816 255.9613 268.0016 289.9224 301.9627 325.8804

265.8786 257.9584 269.9987 291.9194 303.9597 327.8775

13.20 14.43 14.42 16.09 16.08 20.68

13

C 12 PCB 101

337.9207 339.9178

20.67

PCB 118 13 C 12 PCB 118

325.8804 327.8775 337.9207 339.9178

24.20 24.17

PCB 138 13 C 12 PCB 138

359.8415 361.8385 371.8818 373.8788

27.08 27.06

PCB 153 C 12 PCB 153

359.8415 361.8385 371.8818 373.8788

25.52 25.51

PCB 180 13 C 12 PCB 180 13 C 12 PCB 97 13 C 12 PCB 188 α-HCH γ -HCH

393.8025 405.8428 337.9207 405.8428 180.9379 180.9379

395.7995 407.8398 339.9178 407.8398 182.9349 182.9349

30.71 30.69 21.82 25.06 10.72 11.96

13

C 6 lindane cis-chlordane trans-chlordane

186.9580 188.9550 372.8260 374.8230 372.8260 374.8230

11.95 20.92 20.08

cis-nonachlor

406.7870 408.7840

24.72

trans-nonachlor

406.7870 408.7840

21.21

13


13

C 10 trans-nonachlor heptachlor

416.8206 418.8176 271.8102 273.8072

21.19 15.06

heptachlor-exo-epoxide 13 C 10 heptachlor-exoepoxide oxychlordane BDE-47 13 C 12 BDE-47

352.8442 354.8413

18.79

362.8778 386.8052 483.7132 495.7357

364.8749 388.8023 485.7113 497.7513

18.76 18.85 15.62 15.62

BDE-99 C 12 BDE-99 BDE-100 13 C 12 BDE-100

403.7870 415.8273 403.7870 415.8273

405.7850 417.8429 405.7850 417.8429

17.60 17.60 17.16 17.16

13


Table S3a – Bulk deposition of compounds at the Abisko site in ng per sample, integrated over each two-month period. ND indicates that the compound was either not detected on the chromatogram or fell below the MDL/IDL before blank correction.

α-TBECH β-TBECH DP syn DP anti trifluralin chlorothalonil PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 α-HCH γ-HCH cis-chlordane trans-chlordane cis-nonachlor trans-nonachlor heptachlor heptachlor-exo-epoxide BDE-47 BDE-99 BDE-100

2009

2010

Oct-Nov ND ND 0.39 0.22 0.23 0.11 15 3.3 1.3 0.35 1.1 1.9 1.6 4.3 0.063 0.050 ND 0.055 0.038 0.076 0.57 ND ND

Dec-Jan ND ND 0.26 0.087 ND 0.040 3.4 1.7 0.94 0.18 0.50 0.73 0.72 2.2 0.058 0.051 ND ND ND 0.053 0.24 ND ND

2010 FebMar ND ND 3.6 1.0 ND ND 2.5 1.1 0.67 0.19 0.58 0.93 0.28 1.1 0.032 0.044 ND ND ND 0.030 0.64 0.25 0.14

2010 AprMay 0.27 0.23 0.56 0.26 0.061 ND 5.7 5.2 1.8 0.42 0.55 0.79 2.4 11 0.030 0.042 ND 0.032 0.068 0.061 0.32 ND ND

2010 JuneJuly 0.54 0.54 1.7 0.54 ND ND 14 26 8.1 1.2 1.9 3.0 6.9 41 0.18 0.23 ND ND 0.38 ND 0.69 0.30 0.073

2010 Aug-Sept 0.17 ND 0.44 0.10 0.030 0.044 6.2 5.5 1.6 0.29 0.54 0.84 2.1 9.1 0.041 0.052 ND 0.037 0.13 0.044 0.39 0.16 0.10

2010 OctNov 0.09 0.09 4.9 0.84 0.04 ND 3.3 2.6 0.92 0.16 0.33 0.47 1.0 6.1 0.02 0.03 ND ND 0.06 ND 0.31 0.33 0.097


Table S3b – Bulk deposition of compounds at the Krycklan site in ng per sample, integrated over each two-month period. ND indicates that the compound was either not detected on the chromatogram or fell below the MDL/IDL before blank correction.

α-TBECH β-TBECH DP syn DP anti trifluralin chlorothalonil PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 α-HCH γ-HCH cis-chlordane trans-chlordane cis-nonachlor trans-nonachlor heptachlor heptachlor-exo-epoxide BDE-47 BDE-99 BDE-100

2009

2010

Oct-Nov 0.032 ND ND ND 0.38 ND 0.53 0.27 0.57 0.12 0.35 0.49 0.25 0.57 0.044 0.054 ND 0.036 ND 0.16 1.8 ND ND

Dec-Jan 0.19 0.16 0.090 0.067 0.10 ND 5.7 1.6 1.3 0.21 0.57 0.72 0.20 1.5 0.027 ND 0.008 0.039 0.032 0.057 3.2 0.46 0.59

2010 FebMar 0.50 0.28 0.034 0.13 0.063 ND 9.3 2.2 1.4 0.22 0.65 0.87 0.074 0.97 0.044 0.029 0.008 0.045 0.039 0.082 1.1 ND ND

2010 AprilMay x x x x x x x x x x x x x x x x x x x x x x x

2010 JuneJuly 0.26 0.22 0.041 0.078 0.079 0.037 5.4 1.4 1.5 0.20 0.61 0.92 0.31 2.4 0.029 0.023 ND 0.027 0.025 0.085 1.4 ND ND

2010 AugSept ND ND ND ND 0.071 ND 0.66 0.56 0.70 0.067 0.26 0.39 0.10 0.30 ND 0.011 ND ND ND 0.031 0.96 ND ND


Table S4 - Temperature and precipitation data for the Abisko and Krycklan sites.

Abisko mean temperature, oC

2009

2009-10

2010

2010

2010

2010

2010

Oct. Nov.

Dec. Jan. -10.8

Feb. Mar. -11.5

Apr. May 1.8

June July 9.1

Aug. Sept. 7.6

Oct. – Nov. -2.7 32

-2.5

Abisko total precipitation (mm)

23

11

29

40

96

43

Krycklan mean temperature, oC

-0.2

-10.8

-9.7

5.4

13.8

9.9

Krycklan total precipitation (mm)

111

88

95

61

168

146


Details for calculating MDLs With two independent measurements of blanks, the probability that a sample value (Y) is greater than the geometric mean of the two blank values (X) by a factor of k can be calculated in the following way: Prob(Y/X >k) = Prob(Z > ln(k) / sqrt(3log(cv2+1)/2) where Z is a standard normal random variable and cv is the coefficient of variance. Using 1.645 for Z (to correspond to a 95% probability) and a CV of 1, k was calculated to be 5.351. This was multiplied by the geometric mean of the two blank levels to set the method detection limits. For compounds not found in the blank, a positive response was judged to be a peak with signal-to-noise ratio >3:1 (>IDL).


Figure S1 - Location of the two sampling sites


Figure S2 - A picture of the sampling sites Abisko (top) and Krycklan (bottom)


Figure S3a - Air parcel back trajectories at 10 m above ground level, computed 72 h backward from Abisko (top) and Krycklan (bottom). Trajectories were run at 0000, 0600, 1200 and 1800 UTC. The combined trajectories at 0600 and 1800 for twomonth sampling periods are displayed, with ratios of ΣHCHs/ΣPCBs in deposition.


Figure S3b - Air parcel back trajectories, as in Figure S1A.