Supporting information

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Supporting information

A Novel Finding of Widespread Occurrence and Accumulation of Bisphenol A

Diglycidyl Ethers (BADGEs) and Novolac Glycidyl Ethers (NOGEs) in

Marine Mammals from the United States Coastal Waters

Jingchuan Xue

1

, Kurunthachalam Kannan

1,2,*

1

Wadsworth Center, New York State Department of Health, and Department of Environmental

Health Sciences, School of Public Health, State University of New York at Albany, Albany, NY

12201, United States

2

Biochemistry Department, Faculty of Science and Experimental Biochemistry Unit, King Fahd

Medical Research Center, King Abdulaziz University, Jeddah, Saudi Arabia

*Corresponding author:

K. Kannan

Wadsworth Center

Empire State Plaza, P.O. Box 509

Albany, NY 12201-0509

Tel: +1-518-474-0015

Fax: +1-518-473-2895

E-mail:

[email protected]

Submission to: ES&T

Pages: 22

Tables: 8

Figures: 9

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Molecular structures Chemicals Precursor ions

[M+NH4]+ (m/z) Product ions (m/z) Declustering potential (V) Entrance potential (V) Collision energy (V) Collision cell exit potential (V) BADGE 358 191 20 10 23 8 BADGE•H2O 376 209 30 12 20 5 BADGE•HCl 394.3 227.1 30 10 25 5 BADGE•2H2O 394 209 30 10 24 8

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S3 BADGE•H2O•HCl 412 227 15 12 30 9 D6-BADGE 364 197 20 10 23 8 BADGE•2HCl 430.3 227.1 20 10 20 5 BFDGE 330 163.2 15 10 17 5 BFDGE•2HCl 402.2 199 13 10 19 4

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S4 BFDGE•2H2O 366.5 181.2 10 2 20 5 O O O O O O 3R-NOGE 492 163 18 12 30 10 O O O O O O O O 4R-NOGE 654 163 14 12 35 10

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Table S2. Method Performance of BADGEs and NOGEs in various species and tissues analyzed in this study

Analyte

Sea Otter Liver Sea Otter Kidney Sea Otter Brain Recovery (%) MLOQ ( ng·g-1) Recovery (%) MLOQ ( ng·g-1) Recovery (%) MLOQ ( ng·g-1) Absolute Relative Absolute Relative Absolute Relative

BADGE 91±5.49 102±8.89 16.4 40±9.08 104±8.91 16.4 66±15.1 96±1.13 8.21 BADGE•HCl 96±6.40 108±18.4 82.1 59±33.1 150±59.1 82.1 73±17.2 106±1.20 41.1 BADGE•2HCl 117±4.72 131±9.05 82.1 74±49.0 81±6.96 41.1 98±5.71 146±7.76 41.1 BADGE•H2O 80±6.37 91±15.8 82.1 41±4.23 111±25.2 41.1 89±14.2 131±12.5 41.1 BADGE•2H2O 85±5.46 96±7.44 41.1 53±25.1 136±40.7 8.21 87±9.97 130±16.2 8.21 BADGE•HCl•H2O 80±6.23 90±6.42 41.1 52±15.2 138±33.8 41.1 80±6.41 118±16.3 41.1 BFDGE 89±18.8 101±30.7 8.21 51±7.40 134±17.2 41.1 74±6.17 111±23.1 164 BFDGE•2HCl 121±0.38 136±14.6 82.1 47±7.03 125±12.0 41.1 85±24.3 124±4.78 41.1 BFDGE•2H2O 76±4.34 85±13.0 82.1 70±14.0 166±16.5 82.1 84±19.1 126±41.4 41.1 3R-NOGE 93±3.63 105±15.2 41.1 64±12.8 169±15.7 16.4 80±40.6 113±29.2 16.4 4R-NOGE 89±6.26 100±17.4 41.1 49±1.16 132±18.9 16.4 83±19.4 122±4.00 16.4

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Dolphin Liver Dolphin Blubber Whale Liver Polar Bear Liver Recovery (%) _MLOQ ( ng·g-1) Recovery (%) _MLOQ ( ng·g-1) Recovery (%) _MLOQ ( ng·g-1) Recovery (%) MLOQ ( ng·g-1) Absolute Relative Absolute Relative Absolute Relative Absolute Relative

88±21.9 94±2.84 41.1 47±22.2 87±7.90 41.1 55±8.50 130±11.4 16.4 59±21.6 106±2.07 16.4 99±1.47 110±25.5 82.1 45±24.3 80±15.4 41.1 66±19.6 98±45.6 16.4 55±17.6 101±18.2 41.1 114±62.9 129±44.2 82.1 55±6.94 82±5.28 41.1 84±24.7 135±70.3 41.1 50±16.5 93±22.5 82.1 107±9.60 117±21.3 82.1 65±42.4 119±33.9 8.21 _58±2.36 139±1.63 41.1 _56±13.1 108±33.9 82.1 111±15.8 123±38.9 82.1 92±73.6 166±77.5 41.1 56±12.0 134±22.6 41.1 67±12.1 127±24.1 41.1 120±24.9 135±56.1 82.1 65±42.7 121±41.9 16.4 45±5.36 108±5.48 82.1 47±9.18 95±36.9 16.4 69±19.4 75±8.37 41.1 48±21.4 94±4.46 8.21 25±3.78 74±6.23 41.1 26±3.65 46±9.23 82.1 105±14.5 115±23.1 16.4 51±32.7 89±27.3 16.4 71±31.2 100±32.4 41.1 45±20.1 80±15.2 164 100±16.9 113±46.4 82.1 44±13.8 87±15.8 82.1 46±0.02 110±5.71 82.1 33±6.84 61±10.1 164 93±16.1 101±14.6 41.1 47±23.3 88±10.1 41.1 50±22.3 118±47.4 41.1 51±17.2 95±21.3 41.1 85±1.09 94±21.1 41.1 47±22.0 89±12.2 41.1 65±10.2 124±548 41.1 65±8.84 125±34.9 41.1

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Table S3. Limit of quantitation (LOQ) and Blank concentrations of the major target analytes

Instrumental LOQ (ng/ml) BLK (ng/mL) BADGE 0.1 < LOQ BADGE•HCl 0.2 < LOQ BADGE•2HCl 5 < LOQ BADGE•H2O 0.5 < LOQ BADGE•2H2O 0.1 0.69 BADGE•HCl•H2O 0.5 < LOQ BFDGE 1 < LOQ BFDGE•2HCl 0.5 < LOQ BFDGE•2H2O 1 < LOQ 3R-NOGE 0.2 < LOQ 4R-NOGE 0.5 < LOQ

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Table S4. Concentrations (ng/g, wet weight) of BADGEs and NOGEs detected in livers of cetaceans found stranded along Florida

coastal waters

species sex age length (cm) date stranded water body liver

BADGE·2HCl BFDGE·2H2O

Bottlenose Dolphin _F _n.d. ₂₄₅ _5/26/2001 _{Gulf of Mexico} _{< 82.1} ₁₈₇

M n.d. 260 10/23/2000 Gulf of Mexico 133 < 82.1

F 50+ 251 1/5/1994 Gulf of Mexico 227 < 82.1

F n.d. 234 11/22/1999 Sarasota Bay 347 < 82.1

M n.d. 283 3/4/2000 Gulf of Mexico 643 < 82.1

F <20 241 2/26/1999 Anna Maria Sound < 82.1 < 82.1

F 44 250 8/9/1996 Sarasota Bay 318 < 82.1

F 23+ 239 8/27/1995 Sarasota Bay < 82.1 < 82.1

F 25 245 7/16/1997 Palma Sola Bay 919 < 82.1

F 22+ 236 7/25/1998 Palma Sola Bay 190 < 82.1

Stenella Coeruleoalba

Dolphin M 15 225 9/23/1994 Venice Inlet 360 < 82.1

M 13-16 208 7/3/1997 Gulf of Mexico 574 < 82.1

Steno Bredanensis

Doplohin F 15 243 11/27/1995 Anna Maria Sound 169 < 82.1

F 7 218 12/3/1995 Tampa Bay 402 < 82.1

Stenella Clymene

Dolphin F 4 154 6/15/1995 Gulf of Mexico 1400 < 82.1

F >18 183 6/15/1995 Gulf of Mexico 501 < 82.1

F 3 161 6/15/1995 Gulf of Mexico 968 < 82.1

Pygmy Sperm Whale _M _n.d. ₂₉₃ _8/23/2000 _{Atlantic ocean} ₂₁₅ _{< 82.1}

M >20 290 8/16/1994 Anclote River 55.2 < 82.1

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Table S5. Concentrations (ng/g, wet weight) of BADGEs and NOGEs detected in livers, brains and kidneys of Sea Otters collected

from the California coastal waters

tissue sample ID county collection

date sex sex

body condition

postmortem

state BADGE·2HCl BADGE BADGE·2H2O liver _13008-001 _{San Luis Obispo} _8/19/1994 _M _Immature _Poor _Poor ₇₀₅ _{< 16.4} _{< 41.1}

13013-001 Monterey 8/23/1994 M Subadult Good Fair 1730 < 16.4 < 41.1

13043-001 Monterey 9/6/1994 F Immature Fair Good 360 < 16.4 < 41.1

13105-001 Santa Cruz 9/30/1994 M Adult Fair Good 838 < 16.4 < 41.1

13127-001 San Luis Obispo 10/12/1994 M Adult Good Fair 502 < 16.4 < 41.1

13203-001 San Luis Obispo 11/18/1994 M Adult Emaciated Good 271 < 16.4 < 41.1

13220-001 Monterey 11/28/1994 F Immature Poor Poor 146 < 16.4 < 41.1

13326-001 Santa Cruz 1/14/1995 M Adult Poor Good 274 < 16.4 < 41.1

13409-001 Monterey 2/11/1995 M Suckling Fair Good 321 < 16.4 < 41.1

13454-001 Santa Cruz 2/23/1995 F Adult Poor Good 919 < 16.4 < 41.1

13479-001 San Luis Obispo 3/20/1995 F Adult Emaciated Fair 437 < 16.4 < 41.1

13800-001 San Luis Obispo 8/1/1995 M Immature Good Good 888 < 16.4 < 41.1

13815-001 Monterey 8/8/1995 F Adult Emaciated Good 322 19.6 < 41.1

13847-001 Monterey 8/23/1995 M Adult Emaciated Good 585 < 16.4 < 41.1

13853-001 San Luis Obispo 8/13/1995 F Immature Poor Good 433 < 16.4 < 41.1

13866-001 San Luis Obispo 7/4/1995 F Adult Good Fair 707 < 16.4 < 41.1

13884-001 Monterey 9/14/1995 M Adult Good Good 837 < 16.4 < 41.1

13900-001 Santa Cruz 9/23/1995 M Adult Poor Fair 366 < 16.4 < 41.1

13925-001 Santa Cruz 10/9/1995 M Subadult Good Good 266 < 16.4 < 41.1

13947-001 Monterey 9/30/1995 M Adult Fair Fair 1570 < 16.4 < 41.1

13958-001 San Luis Obispo 11/2/1995 F Immature Poor Good 294 < 16.4 < 41.1

13971-001 Monterey 11/12/1995 M Immature Poor Good 561 < 16.4 < 41.1

13985-001 Monterey 11/27/1995 F Adult Emaciated Good 392 < 16.4 < 41.1

13986-001 Monterey 11/27/1995 M Subadult Excellent Good 1970 < 16.4 < 41.1

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13105-001 Santa Cruz 9/30/1994 M Adult Fair Good 510 < 8.21 < 8.21

13220-001 Monterey 11/28/1994 F Immature Poor Poor 54.5 < 8.21 < 8.21

13800-001 San Luis Obispo 8/1/1995 M Immature Good Good 404 < 8.21 15.8

13815-001 Monterey 8/8/1995 F Adult Emaciated Good 1010 < 8.21 16.9

kidney _13105-001 _{Santa Cruz} _9/30/1994 _M _Adult _Fair _Good ₃₅₁ _{< 16.4} _{< 8.21}

13220-001 Monterey 11/28/1994 F Immature Poor Poor < 41.1 < 16.4 < 8.21

13479-001 San Luis Obispo 3/20/1995 F Adult Emaciated Fair 477 < 16.4 < 8.21

13800-001 San Luis Obispo 8/1/1995 M Immature Good Good 550 < 16.4 < 8.21

13815-001 Monterey 8/8/1995 F Adult Emaciated Good 186 < 16.4 < 8.21

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Table S6. Concentrations (ng/g, wet weight) of BADGEs and NOGEs in livers of Sea Otters from the Washington coastal waters

sample ID location stranding date sex age class BADGE·2HCl

19057 Alaskan sea, WA 5/5/2004 M subadult (adolescent) 288

16961-1 Alaskan sea, WA 7/3/2000 F adult 430

18124(FOIL) Alaskan sea, WA 4/3/2002 M adult 1430

18208 Alaskan sea, WA 6/11/2002 M adult 522

16961-2 Alaskan sea, WA 7/17/2000 M subadult 776

18316(FOIL) Alaskan sea, WA 8/23/2002 M adult 1600

19030 Alaskan sea, WA 4/12/2004 F adult 83.5

18338 Alaskan sea, WA 8/11/2002 F adult 549

16961-3 Alaskan sea, WA 8/5/2000 F adult < 82.1

17315 Alaskan sea, WA 7/22/2001 F adult 1650

16904 Alaskan sea, WA 7/16/2000 M adult 86.4

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Table S7. Concentrations (ng/g, wet weight) of BADGEs and NOGEs in livers of Sea Otters from the Alaska coastal waters

location stranding date sex age class cause of death BADGE·2HCl

Pws, Valdez 8/12/1998 M adult hunted 239

Pow Island, High Water Island 10/14/1996 M old adult hunted 276

Pws, Valdez Arm, Shoup Bay 9/7/1997 M adult hunted 480

PWS, ORCA INLET, WHITSHED 2/1/1998 M old adult hunted < 82.1

KACHEMAK BAY, BISHOP BEACH 2003 M pup stranded 206

n.d. n.d. n.d. n.d. n.d. 218

Alaskan sea, AK 4/11/1996 M subadult n.d. 2220

KACHEMAK BAY, HOMER 1/27/2003 M adult stranded 257

KACHEMAK BAY, BISHOP BEACH 5/1/2002 M pup stranded 2950

KACHEMAK BAY 2/22/2003 M adult hunted 139

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Table S8. Concentrations of BADGEs and NOGEs in livers of Polar Bears from the Beaufort and Chukchi Seas

Sample ID FAT % village date collected age age class sex waterbody BADGE·2HCl

950086BL 5.6 GAMB 1/26/1995 4 sub-adult M Chuckchi sea 236

990652LC 4.6 GAMB 05/30/99 3 sub-adult M Chuckchi sea 86.6

2629LD 11.2 SAVO 06/03/02 18 adult M Chuckchi sea 432

2372LB 8.2 DIOM 12/04/00 <2.3 cub F Chuckchi sea < 82.1

990083LD 5.3 BARR 11/21/99 5 adult M Beaufort sea 127

980565LB 9.0 DIOM 05/12/99 3 sub-adult F Chuckchi sea 149

970012LB 7.0 BARR 12/03/97 16 adult M Beaufort sea < 82.1

950089AL 9.3 GAMB 01/26/95 4 sub-adult F Chuckchi sea 83.5

000245LE 4.9 DIOM 01/04/00 4 sub-adult M Chuckchi sea 290

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Figure S1. LC-MS/MS chromatograms of BADGE·2HCl (430.3 > 227.1) in post-matrix spiked

(50 ng) samples of all the tissues analyzed. (a) whale liver; (b) polar bear blubber; (c) sea otter

liver; (d) sea otter kidney; (e) sea otter brain; (f) dolphin liver; (g) dolphin blubber. Numbers

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Figure S2. GC-MS total ion chromatogram (TIC; left side) and mass spectrum of BADGE·2HCl

(right side) in tissue samples analyzed and standard solution. (a) sea otter brain; (b) sea otter

kidney; (c) sea otter liver; (d) polar bear liver; (e) dolphin liver; (f) BADGE·2HCl standard

solution. In the left side, numbers at the top of peaks represent retention times; in the right side,

numbers at the top of peaks represent the mass of ions.

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Figure S3. Four LC-MS/MS chromatograms transitions of BADGE·2HCl (430>227; 430>135; 430>167; 430>185) in samples of the

tissues analyzed and the standard solution. (a) sea otter liver; (b) sea otter brain; (c) sea otter kidney; (d) polar bear liver; (e) dolphin

liver; (f) BADGE·2HCl standard solution. Numbers in the right of the peak represent the retention times.

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Figure S4. Correlation between hepatic BADGE·2HCl

concentrations in bottlenose dolphins from

Florida coastal waters and the age. Note: only those samples with measurable levels of chemicals are

presented.

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Figure S5. Concentrations (mean±SD) of BADGE·2HCl in livers of dolphins from near-shore

Florida coastal waters and the Gulf of Mexico. Numbers next to the error bar with parentheses

represent the number of samples in this group.

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Figure S6. Concentrations (mean±SD) of BADGE·2HCl in livers of various categories of sea

otters from California coastal waters. (a) Age: immature vs sub-adult vs adult; (b) Body

condition: emaciated vs poor vs fair vs good vs excellent; (c) Postmortem state: poor vs fair vs

good. Numbers next to the error bar with parentheses represent the number of samples in this

group.

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Figure S7. Concentrations (mean±SD) of BADGE·2HCl in kidneys of various categories of sea

otters from California coastal waters. (a) Sex: male vs female; (b) Age: sub-adult vs adult; (c)

Body condition: emaciated vs poor vs fair vs good; (d) Postmortem state: fair vs good. Numbers

next to or above the error bar with parentheses represent the number of samples in this group.

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Figure S8. Concentrations (mean±SD) of BADGE·2HCl in brains of various categories of sea

otters from California coastal waters. (a) Sex: male vs female; (b) Age: immature vs sub-adult vs

adult; (c) Body condition: emaciated vs poor vs fair vs good; (d) Postmortem state: poor vs fair

vs good. Numbers next to or above the error bar with parentheses represent the number of

samples in this group.

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Supporting information