Supporting Information

Occurrence of Substituted Diphenylamine Antioxidants and

Benzotriazole UV Stabilizers in Arctic Seabirds and Seals

Zhe Lu,a* Amila O. De Silva,b* Jennifer F. Provencher,c Mark L. Mallory,d Jane L. Kirk,b Magali

Houde,e Connor Stewart, b Birgit M. Braune,f Stephanie Avery-Gomm,f,g Derek C.G. Muirb

a Institut des Sciences de la Mer de Rimouski, Université du Québec à Rimouski, Rimouski,

Québec G5L 3A1, Canada

b Aquatic Contaminants Research Division, Environment and Climate Change Canada,

Burlington, Ontario L7S 1A1, Canada

c Canadian Wildlife Service, Environment and Climate Change Canada, Gatineau, Québec, J8Y

3Z5, Canada

d Department of Biology, Acadia University, Wolfville, Nova Scotia B4P 2R6, Canada

e Aquatic Contaminants Research Division, Environment and Climate Change Canada, Montréal,

Québec H2Y 2E7, Canada

f National Wildlife Research Centre, Environment and Climate Change Canada, Carleton

University, Ottawa, Ontario K1A 0H3, Canada

g School of Biological Sciences, University of Queensland, St. Lucia, Queensland 4072,

Australia

Tables: 5

Figures: 8

Pages: 15

List of Tables and Figures

S1

Table S1. Predicted physicochemical, persistence and long-range transport potential parameters

of target SDPAs and BZT-UVs.

Table S2. Biological parameters of Arctic seabird and ringed seal samples.

Figure S1. Structures of target SDPAs and BZT-UVs.

Table S3. UPLC-MS/MS experimental parameters and QA/QC results.

Figure S2. UPLC-MS/MS MRM chromatograms of SDPAs and BZT-UVs standards.

Figure S3. UPLC-MS/MS MRM chromatograms of C8MS-1, C8C8, UV329 and UV350 in

standard, seabird, seal and blank samples.

Table S4. Concentrations of SDPAs and BZT-UVs in wildlife samples from Arctic and sub-

Arctic sites.

Table S5. Partition of C8MS-1 and total SDPAs between the paired female liver and egg.

Figure S4. Concentrations of C8MS-1, C8C8, total SDPAs and UV350 in seabird eggs from

Prince Leopold Island.

Figure S5. Concentrations of C8C8, C8MS-1 and total SDPAs in seabird livers from Prince

Leopold Island.

Figure S6. Concentrations of C8MS-1, C8C8, and total SDPAs in fulmar livers from Prince

Leopold Island and Labrador Sea.

Figure S7. Concentrations of C4, C8, diAMS, C8MS-1, total SDPAs, UV329, UV350 and total

BZT-UVs in the livers of ringed seals from Resolute Bay, Arviat, Sachs Harbour, and Lake

Melville.

Figure S8. Composition profiles of BZT-UVs in individual seal liver sample from Resolute Bay,

Arviat, Sachs Harbour and fulmar eggs from Prince Leopold Island.

S2

Table S1. Predicted physicochemical (log Kaw, log Kow, half-lives (t1/2) in air, water, soil, sediment and fish), persistence and long-range

transport potential parameters of targeted SDPAs and BZT-UVs.

Chemicals

Molecular

Weight(g/mol)

Estimated physicochemical propertiesa Predicted total persistent and transport potentialc

Log Kaw Log Kow

t1/2

air(days)

t1/2

water(days)

t1/2

soil(days)

t1/2

sediment(days)

Povd

(days)CTDe

(km)

C4 225.34 -3.96 5.20 0.05 38 75 338 108 90C4C4 281.44 -3.54 7.11 0.05 60 120 540 173 106

C8 281.44 -3.46 7.05 0.05 60 120 540 173 107C4C8 337.55 -3.05 8.96 0.05 180 360 1620 519 234C8C8 393.66 -2.56 10.8 0.05 180 360 1620 519 1833

C9 295.47 -3.34 7.55 0.05 38 75 338 108 67C9C9 421.72 -2.31 11.8 0.05 60 120 540 173 2578

diAMS 405.59 -5.98 8.51 0.05 60 120 542 173 2743MS 273.38 -5.30 5.45 0.05 38 75 338 108 93

C8MS 385.60 -4.39 9.21 0.05 180 360 1621 519 2159C8C8MS 497.81 -3.49 13.0 0.05 180 360 1621 519 2860UV234 447.58 -13.3 7.67 0.49 60 120 542 173 2838UV326 315.81 -11.3 5.55 0.72 60 120 542 173 1377UV327 357.89 -10.9 6.91 0.81 60 120 542 173 2732UV328 351.50 -10.6 7.25 0.68 60 120 542 173 2801UV329 323.44 -10.7 6.21 0.33 60 120 542 173 2315UV350 323.44 -10.8 6.31 0.60 38 75 338 108 2410

a Predicted by EPI suite V4.1; bdata are normalized to 10 g fish at 15°C; cPredicted by OECD Pov-LRTP Tool; dPov: Overall

persistence; eCTD: characteristic travel distance.

S3

Table S2. Biological parameters (meanstandard error) of Arctic seabird and ringed seal samples. NA: not available.

Species Abbreviations Location Time N Sex Sample Length Age

Black-legged kittiwake BLKI Prince Leopold Island August 2013 5 5F Liver NA NA

Black-legged kittiwake BLKI Prince Leopold Island August 2013 6 NA Egg NA NA

Northern fulmar NOFU Prince Leopold Island August 2013 9 5F,4M Liver NA NA

Northern fulmar NOFU Prince Leopold Island August 2013 5 NA Egg NA NA

Northern fulmar NOFU Labrador Sea July 2015 10 10F Liver NA NA

Ringed seal Seal Resolute Bay April-August 2017 3 2F,1

M Liver 11712 85

Ringed seal Seal Sachs Harbour July 2017 3 2F,1M Liver 1097 62

Ringed seal Seal Arviat October 2017 3 3F Liver 12416

169

Ringed seal Seal Lake Melville April-May 2016 5 3F,2M Liver 876 11

S4

Figure S1. Chemical structures of targeted SDPAs and BZT-UVs. The structures for C4, C4C4, C8, C4C8, C8C8, C9, C9C9, MS,

C8MS and C8C8MS are the most representative and comprise the major proportions within the technical mixture. (Reference:

Environment and Climate Change Canada and Health Canada, 2017. Screening assessment for substituted diphenylamines.

S5

https://www.canada.ca/en/environment-climate-change/services/evaluating-existing-substances/screening-assessment-substituted-

diphenylamines.html; Accessed in May 2018.)

Table S3. UPLC-MS/MS experimental parameters and QA/QC results. aDeclustering potential (V). bCollision energy (eV).cCollision

Cell Exit Potential (V). dSurrogate standard spike. e pg g-1 (ww). N/A: not applicable. MQLs in red: MQLs were estimated based on the

S6

Compound

Precursor ion (m/z)

Production (m/z) forquantificatio

n

Production (m/z)

for qualificatio

n

DPa

(V)

CEb

(eV)

Retention time(min)

Recovery%(Eggs; n = 4)

Recovery%(Bird liver; n = 3 )

Recovery%(Seal liver; n = 2 )

MQLe

Birdegg

MQLe

Bird liver

MQLe

Seal liver

C4 226 134 106 106 43 4.43 715 604 927 2.0 4.0 4.0

C4C4 282 134 106 126 49 5.67 735 542 7814 7.0 15 14

C8 282 134 106 126 49 5.78 746 563 7912 4.0 8.0 60

C9 296 134 210 106 47 6.18 725 543 7610 4.0 10 10

C4C8 338 134 106 131 53 6.58 751 5315 7218 30 20 10

C8C8 394 134 106 146 63 7.55 673 619 6410 5.0 10 40

C9C9 422 134 336 131 61 8.49 633 588 629 24 70 60

diAMS 406 196 119 156 55 6.05 745 557 6320 20 10 10

MS-1 274 182 105 96 41 4.46 685 7611 1007 16 56 24

MS-2 274 180 105 96 57 4.72 705 8112 1146 2.0 4.0 2.0

C8MS-1 386 134 180 76 51 6.49 723 5711 6616 2.0 7.0 3.0

C8MS-2 386 57 180 76 57 6.61 713 6910 639 60 210 90

C8MS-3 386 57 180 76 57 6.71 715 6810 637 32 70 30

C8C8MS 498 57 105 111 89 8.78 695 518 629 12 42 18

UV234 448 370 119 91 31 6.63 675 507 5814 730 230 110

UV326 316 260 107 61 29 6.53 788 6719 8724 1600 4300 4100

UV327 358 302 246 46 33 7.12 737 8822 6514 2400 4800 5000

UV328 352 282 212 96 33 7.30 683 635 6518 450 990 900

UV329 324 212 253 106 35 6.35 723 666 7017 390 640 580

UV350 324 268 212 86 31 6.63 735 642 799 130 350 310

UV234-d4 452 374 N/A 86 35 6.61 644 503 6324 N/A N/A N/A

UV328-d4 356 286 N/A 51 37 7.26 682 6612 7626 N/A N/A N/A

UV329-d4 328 216 N/A 81 39 6.33 697 697 7313 N/A N/A N/A

mean concentration of blanks plus 10 times of standard deviation of the blanks.

S7

Figure S2. UPLC–MS/MS MRM chromatograms of SDPAs and BZT-UVs standards.

S8

S9

Figure S3. UPLC–MS/MS MRM chromatogram

examples of (A) C8MS-1 (MRM 386.3>134.0), (B)

C8C8 (MRM 394.4>134.1), (C) UV350 (MRM

324.2>268.1), and (D) UV329 (MRM 324.2>212.0)

in standard, seabird, seal and blank samples. Please

note that the scale of y-axis (signal intensity) in each

graph is different.

Table S4. Detection frequency (in red color) and concentrations (pg g -1; median and range) of SDPAs and BZT-UVs in bird eggs, bird

livers and seal livers from arctic and sub-arctic regions.

Species Location Time Tissue n lipid % C4 C4C4 C8 C9 C4C8 C8C8 C9C9 diAMS

BLKI PLI 2013 Egg 6 12.1±0.4 0%<2

0%<7

0%<4

17%<4-5

0%<30

83%10 (<5-11)

0%<24

0%<20

BLKI PLI 2013 Liver 5 3.7±0.2 0%<4

0%<15

0%<8

20%<10-139

0%<20

40%<10-17

0%<70

0%<10

NOFU PLI 2013 Egg 5 13.9±0.9 20%<2-5

0%<7

20%<4-25

20%<4-6

0%<30

100%9 (5-32)

0%<24

0%<20

NOFU PLI 2013 Liver 9 3.0±0.1 0%<4

0%<15

11%<8-20

11%<10-49

0%<20

56%17 (<10-52)

0%<70

0%<10

NOFU LS 2015 Liver 10 3.9±0.1 0%<4

40%<15-371

0%<8

0%<10

40%<20-403

50%17 (<10-221)

20%<70-1215

20%<10-15

Seal RB 2017 Liver 3 3.1±0.9 33%<4-6

0%<14

0%<60

0%<10

0%<10

33%<40-45

0%<60

67%14 (<10-49)

Seal SH 2017 Liver 3 2.5±0.4 0%<4

0%<MQL14

0%<60

0%<10

0%<10

0%<40

0%<60

0%<10

Seal AR 2017 Liver 3 2.1±0.4 0%<4

0%<14

0%<60

0%<10

0%<10

0%<40

0%<60

0%<10

Seal LM 2016 Liver 5 2.8±0.5 100%12 (7-40)

20%<14-30

60%60 (<60-190)

0%<10

0%<10

0%<40

0%<60

20%<10-27

Species Location Time Tissue n lipid % C8MS-1 Total SDPAs UV234 UV326 UV328 UV329 UV350 Total BZT-UVs

BLKI PLI 2013 Egg 6 12.1±0.4 100%10 (3-30) 22 (11-30) 0%

<7300%

<16000%

<4500%

<39033%

<130-433 <MQL-433

BLKI PLI 2013 Liver 5 3.7±0.2 100%277 (177-627) 328 (247-697) 0%

<2300%

<43000%

<9900%

<6400%

<350 <MQL

NOFU PLI 2013 Egg 5 13.9±0.9 100%3 (2-46) 28 (12-60) 0%

<7300%

<16000%

<4500%

<39060%

280 (<130-3035) 280 (<MQL-3035)

NOFU PLI 2013 Liver 9 3.0±0.1 100%343 (136-724) 376 (136-724) 0%

<2300%

<430011%

<990-38410%

<6400%

<350 <MQL-3841

NOFU LS 2015 Liver 10 3.9±0.1 100%169 (124-531) 326 (131-2266) 10%

<230-5590%

<43000%

<9900%

<6400%

<350 <MQL-559

Seal RB 2017 Liver 3 3.1±0.9 100%13 (8-55) 55 (27-108) 0%

<11033%

<4100-55670%

<900100%

1678 (1609-9411)33%

<310-1660 1648 (1609-16638)

Seal SH 2017 Liver 3 2.5±0.4 100%37 (20-39) 37 (20-39) 0%

<11033%

<4100-56600%

<900100%

3395 (2696-8509)0%

<310 8356 (3395-8509)

Seal AR 2017 Liver 3 2.1±0.4 100%18 (15-64) 18 (15-64) 0%

<11033%

<4100-66210%

<90033%

<580-1879100%

11978 (1195-12324) 7816 (6077-12324)

Seal LM 2016 Liver 5 2.8±0.5 100%18 (10-22) 92 (23-279) 0%

<1100%

<41000%

<9000%

<58020%

<310-383 <MQL-383

Note:The target compounds UV327, MS-1, MS-2, C8MS-2, C8MS-3 and C8C8MS were not detected in any samples. Abbreviation: BLKI-Black-Legged Kittiwakes; NOFU- Northern Fulmars; PLI- Prince Leopold Island; LS- Labrador Sea; RB- Resolute Bay; SH- Sachs Harbour; AR-Arviat; LM- Lake Melville; MQL- method quantification limit.

S10

Table S5. Partition coefficients (log10 (concentration in liver/concentration in egg)) of C8MS-1

and total SDPAs between the paired female liver and egg. NA: data is not available because

C8C8 concentration was <MQL in liver or egg.

Sample

BLKI Sample

NOFUC8MS-1 C8C8 Total SDPAs C8MS-1 C8C8 Total SDPAs

1 1.32 NA 1.08 1 1.67 NA 0.992 1.42 0.19 1.05 2 0.81 0.66 0.763 1.65 NA 0.96 3 2.52 NA 1.064 1.44 NA 0.94 4 1.07 NA 1.005 1.10 0.23 1.16 5 2.42 NA 1.43

S11

Figure S4. Concentrations of C8MS-1, C8C8, total SDPAs and UV350 in the eggs of black-

legged kittiwakes (BLKI) and northern fulmars (NOFU) from Prince Leopold Island (PLI).

Boxplots are defined as follows: center line, median; boxplot edges, 25th and 75th percentile;

whiskers, 5th and 95th percentile of distribution. Unpaired t test with Welch’s correction was

used to make comparison between two bird species. NA: statistics are not available due to low

detection frequency (<50%). The results of other target compounds are not shown here because

of the low detection frequency (<50%) in the two bird species.

S12

Figure S5. Concentrations of C8C8, C8MS-1 and total SDPAs in the livers of black-legged

kittiwakes (BLKI) and northern fulmars (NOFU) from Prince Leopold Island (PLI). Boxplots are

defined as follows: center line, median; boxplot edges, 25th and 75th percentile; whiskers, 5th

and 95th percentile of distribution. Unpaired t test with Welch’s correction was used to make

comparison between two bird species. NA: statistics are not available due to low detection

frequency (<50%). The results of other target compounds are not shown here because of the low

detection frequency (<50%) in the two bird species.

S13

Figure S6. Concentrations of C8MS-1, C8C8, and total SDPAs in the livers of northern fulmars

(NOFU) from Prince Leopold Island (PLI) and Labrador Sea (LS). Boxplots are defined as

follows: center line, median; boxplot edges, 25th and 75th percentile; whiskers, 5th and 95th

percentile of distribution. Unpaired t test with Welch’s correction was used to make comparison

between two groups. The results of other target compounds are not shown here because of the

low detection frequency (<50%) in both sampling sites.

S14

Figure S7. Concentration (mean ± standard error bar) of C4, C8, diAMS, C8MS-1, total SDPAs, UV329, UV350 and total BZT-UVs

in the livers of ringed seals from Resolute Bay (RB), Sachs Harbour (SH), Arviat (AR) and Lake Melville (LM). NA: statistics are not

available due to low detection frequency (<50%). The results of other target compounds are not shown here because of the low

detection frequency (<50%) in all sampling sites.

S15

Figure S8. Composition profiles of BZT-UVs in individual seal liver sample from Resolute Bay

(RB), Sachs Harbour (SH) and Arviat (AR) and the eggs of northern fulmars (NOFU) from

Prince Leopold Island (PLI).

S16