1
1 10 100 1000 10000 Sum 14 PBDEs in Blubber (ng/g lw) HS GS RS US Sweden Iceland Greenland abc abc abb 1 10 100 Sum 7 Dechloranes in Blubber (ng/g lw) HS GS RS abb a ab b 1 10 100 1000 Sum Other BFRs in Blubber (ng/g lw) HS GS RS ab c aa b a c b Susan D. Shaw 1 , Michelle L. Berger 1 , Da Chen 2 , Aqqalu Rosing-Asvid 3 , Sandra Magdalena Granquist 4 , Anna Roos 3,5 1 Shaw Institute, 55 Main Street, Blue Hill, ME 04614; 2 Southern Illinois University Carbondale, 1263 Lincoln Drive, Carbondale, IL 62901; 3 Greenland Institute of Natural Resources, Box 570 3900 Nuuk, Greenland; 4 The Icelandic Seal Center, Brekkugata 2, 530 Hvammstangi, Iceland; 5 Swedish Museum of Natural History, Frescativägen 52, 114 18 Stockholm, Sweden Marine mammals (whales, dolphins, seals) are confronted with complex stresses including ocean pollution and climate change, and an estimated 40% of their species face extinction by 2050. 1 As top predators, marine mammals bioaccumulate a wide range of pollutants including banned industrial chemicals (PCBs), pesticides (DDT), as well as flame retardants, heavy metals, petroleum, and highly fluorinated compounds. 2-6 These chemicals are linked with serious health effects in marine mammals, such as endocrine disruption, immune suppression, and decreased survival. 7-9 Climate change is an increasing stress for marine mammals, particularly for those from northern latitudes with rapid warming rates. 10 Global warming is causing a reduction in ice cover, critical breeding grounds for several species, as well as radical shifts in prey availability. 11 Climate change also affects the distribution and toxicity of chemical pollutants in the marine environment in complex ways. 10 This study reports on the occurrence, distribution, and time trends of legacy (banned) and novel flame retardants in nine species of marine mammals inhabiting the coasts of the eastern US, Sweden, Iceland, and Greenland. These data, combined with climate change data, will help predict the health and survival of these populations and inform policy to sustain life in the oceans. Methods Flame retardants in seals from different regions Flame retardant concentrations in US marine mammals Patterns of flame retardant chemicals in US species Time trends in US and Sweden harbor seals Toothed whales (dolphins, porpoises, pilot whales) had higher contaminant concentrations than the seals or baleen whales (minke, humpback), reflecting their higher position on the food web. Compared to other regions, US Atlantic harbor seals had the highest concentrations of PBDEs, Dechloranes, and other BFRs including HBBZ, BB-101, and Firemaster 550 components. In US species, PBDEs were the predominant flame retardants reflecting their higher volume use in the US than in Europe. PBDEs and other BFRs were decreasing in Swedish harbor seals, but not in US harbor seals between 2000-2016. Schipper, JJS et al. 2008. Science 322:225-230; 2. Shaw, SD and Kannan, K 2009 Rev Environ Health 24:157-229; 3. Houde, MAO et al. 2011 Environ Sci Technol 45:7962-7973; 4. Law, RJ 2014 Mar Pollut Bull:82:7-10; 5. Shaw, SD et al. 2014 Sci Total Environ 490:477-487; 6. Letcher, RJ et al. 2018 Sci Total Environ 610:121-136; 7. Desforges, JP et al. 2017 Environ Sci Technol 51:11431-11439; 8. Jenssen, BM 2006 Environ Health Persp 114:76-80; 9. Hall, AJ et al. 2009 Environ Sci Technol 43:6364-6369 10. Noyes, PD et al. 2009 Environ Int 35:971-986; 11. Kovacs, KM and Lydersen, C 2008 Sci Progress 91:117-150. 12. Shaw, SD et al. 2010 Rev Environ Health 25:261-305; 13. Feo, ML et al. 2012 Anal Bioanal Chem 404:2625-2637. 14. Covaci, A et al. 2011 Environ Int 37:532-556.; 15. PubChem https://pubchem.ncbi.nlm.nih.gov; 16. Alaee, M et al. 2003 Environ Int 29:683-689. Species US Sweden Iceland Greenland Harbor Seal 72 85 11 Grey Seal 8 11 10 Ringed Seal 10 2 21 White-sided Dolphin 9 White-beaked Dolphin 15 Harbor Porpoise 9 Long-finned Pilot Whale 4 9 Minke Whale 2 6 Humpback Whale 1 13 Figure 2. Box plots of concentrations of sum PBDEs, sum Dechloranes, and sum other BFRs in harbor seals (HS), grey seals (GS), and ringed seals (RS) from the US, Sweden, Iceland, and Greenland. Letters above the bars indicate significant differences among countries by Kruskal-Wallis and post hoc Mann-Whitney U tests (p<0.05). 1 10 100 Sum 7 Dechloranes in Blubber (ng/g lw) HS GS WsD HP PW MW HW 1 10 100 1000 10000 Sum 14 PBDEs in Blubber (ng/g lw) HS GS WsD HP PW MW HW b c a b ab Figure 3. Box plots of concentrations of sum PBDEs, sum Dechloranes, and sum other BFRs in harbor seals (HS), grey seals (GS), white-sided dolphins (WsD), harbor porpoises (HP), pilot whales (PW), minke whales (MW), and a humpback whale (HW) from the US. Letters above the bars indicate significant differences among species by Kruskal-Wallis and post hoc Mann-Whitney U tests (p<0.05). 1 10 100 1000 10000 Sum Other BFRs in Blubber (ng/g lw) HS GS WsD HP PW MW HW c d a bc ab Figure 4. Average composition of sum PBDEs, sum Dechloranes and sum other BFRs in blubber of US harbor seals (HS), grey seals (GS), white-sided dolphins (WsD), harbor porpoises (HP), pilot whales (PW), minke whales (MW), and a humpback whale (HW). 1 10 100 Sum 7 Dechloranes in Blubber (ng/g lw) 2000 2005 2010 2015 Strand Year 1 10 100 1000 10000 Sum 14 PBDEs in Blubber (ng/g lw) 2000 2005 2010 2015 Strand Year Sweden: R2=0.25, F1,83=27.2, p<0.001 US Sweden Figure 5. Time trends of PBDEs, Dechloranes and other BFRs in harbor seal blubber from the US and Sweden between 1998- 2016. 1 10 100 Sum Other BFRs in Blubber (ng/g lw) 2000 2005 2010 2015 Strand Year Sweden: R2=0.09, F1,83=7.99, p=0.006 Map? NW Atlantic (US) Arctic (Iceland, Greenland) Baltic (Sweden) The authors would like to thank Allied Whale/College of the Atlantic, New England Aquarium, International Fund for Animal Welfare, Mystic Aquarium, and New York Marine Rescue Center for providing the US samples for this project. Samples from Greenland, Iceland, and Sweden were imported under National Marine Fisheries Service permit No. 22272. 30 YEARS OF ENVIRONMENTAL IMPACT RESEARCH Compound Uses PBDEs BDE-17 2,2',4-Tribromodiphenyl Ether Constituents of PentaBDE commercial mixture. Mainly used as additive flame retardants (FR) in flexible polyurethane foam and fabrics. Banned in Europe and withdrawn from US commerce in 2004. 12 BDE-28 2,4,4'-Tribromodiphenyl Ether BDE-47 2,2',4,4'-Tetrabromodiphenyl Ether BDE-49 2,2',4,5'-Tetrabromodiphenyl Ether BDE-66 2,3',4,4'-Tetrabromodiphenyl Ether BDE-99 2,2',4,4',5-Pentabromodiphenyl Ether BDE-100 2,2',4,4',6-Pentabromodiphenyl Ether BDE-153 2,2',4,4',5,5'-Hexabromodiphenyl Ether BDE-154 2,2',4,4',5,6'-Hexabromodiphenyl Ether BDE-183 2,2',3,4,4',5',6-Heptabromodiphenyl Ether Constituents of OctaBDE commercial mixture. Mainly used as additive FR in hard plastics and thermoplastic resins. Banned in Europe and withdrawn from US commerce in 2004. 12 BDE-201 2,2',3,3',4,5',6,6'-Octabromodiphenyl Ether BDE-202 2,2',3,3',5,5',6,6'-Octabromodiphenyl Ether BDE-196 2,2',3,3',4,4',5,6'-Octabromodiphenyl Ether BDE-197 2,2',3,3',4,4',6,6'-Octabromodiphenyl Ether Dechloranes Syn-DP Syn-Dechlorane Plus Constituents of commercial Dechlorane Plus. Additive FR in wire coatings, plastic roofing, computer parts 13 Anti-DP Anti-Dechlorane Plus DEC-602 Dechlorane 602 FR use information very limited. Also found as impurities in pesticides 13 DEC-603 Dechlorane 603 DEC-604 Dechlorane 604 Cplus Chlordene Plus CL11-DP Mono-dechlorinated Dechlorane Plus Breakdown product of Dechlorane Plus 13 Other BFRs ATE 2,4,6-tribromophenyl allyl ether Additive FR in expandable polystyrene and foam 14 TBPX 2,3,5,6-tetrabromo-p-xylene Additive FR in paints, textiles, plastics 15 TBOCT Tetrabromo-o-chlorotoluene Additive FR, Use information very limited 15 PBT Pentabromotoluene Used in plastics, polystyrene, rubbers and textiles 14 PBEB Pentabromoethylbenzene Additive in polyester resins for electronics, textiles and foam 14 HBBZ Hexabromobenzene Additive to paper, wood, textiles, and electronics mostly in Japan 14 BB-101 2,2',4,5,5'-pentabromobiphenyl Legacy flame retardant. PBBs banned in US in 1974 16 BTBPE 1,2-bis-(2,4,6-tribromophenoxy)ethane Replacement for OctaBDE. Additive FR in plastics, resins, coatings 14 EHTBB 2-ethylhexyl-2,3,4,5-tetrabromobenzoate Constituents of Firemaster 550. Replacement for PentaBDE in polyurethane foam 14 BEHTBP Bis(2-ethyl-1-hexyl)tetrabromophthalate Table 2. Compounds analyzed in marine mammal tissues and their commercial uses. Table 1. Sample numbers for species per region. Figure 1. Map of sampling regions. Assessing Global Threats of Pollution and Climate Change to Marine Mammals Across Three Oceans Results Introduction Conclusions References Acknowledgements 0 20 40 60 80 100 GS HS WsD HP PW MW HW % of Total PBDEs in Blubber PBDE Composition - US BDE-28 BDE-47 BDE-49 BDE-99 BDE-100 BDE-153 BDE-154 BDE-183 Other 0 20 40 60 80 100 GS HS WsD HP PW MW HW % of Total Other BFRs in Blubber Other BFR Composition - US HBBZ EHTBB BEHTBP BB-101 ATE TBPX TBOCT PBT PBEB BTBPE 0 20 40 60 80 100 GS HS WsD HP PW MW HW % of Total Dechloranes in Blubber Dechlorane Composition - US DEC-602 DEC-603 DEC-604 Cplus Syn-DP Anti-DP CL11-DP

Marinemammals(whales,dolphins,seals ... · in harbor seals (HS), grey seals (GS), white-sided dolphins (WsD), harbor porpoises (HP), pilot whales (PW), minke whales (MW), and a humpback

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Page 1: Marinemammals(whales,dolphins,seals ... · in harbor seals (HS), grey seals (GS), white-sided dolphins (WsD), harbor porpoises (HP), pilot whales (PW), minke whales (MW), and a humpback

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Susan D. Shaw1, Michelle L. Berger1, Da Chen2, Aqqalu Rosing-Asvid3, Sandra Magdalena Granquist4, Anna Roos3,5

1 Shaw Institute, 55 Main Street, Blue Hill, ME 04614; 2 Southern Illinois University Carbondale, 1263 Lincoln Drive, Carbondale, IL 62901; 3 Greenland Instituteof Natural Resources, Box 570 3900 Nuuk, Greenland; 4 The Icelandic Seal Center, Brekkugata 2, 530 Hvammstangi, Iceland; 5 Swedish Museum of NaturalHistory, Frescativägen 52, 114 18 Stockholm, Sweden

Marine mammals (whales, dolphins, seals) are confronted with complex stressesincluding ocean pollution and climate change, and an estimated 40% of their speciesface extinction by 2050.1 As top predators, marine mammals bioaccumulate a widerange of pollutants including banned industrial chemicals (PCBs), pesticides (DDT), aswell as flame retardants, heavy metals, petroleum, and highly fluorinatedcompounds.2-6 These chemicals are linked with serious health effects in marinemammals, such as endocrine disruption, immune suppression, and decreasedsurvival.7-9

Climate change is an increasing stress for marine mammals, particularly for thosefrom northern latitudes with rapid warming rates.10 Global warming is causing areduction in ice cover, critical breeding grounds for several species, as well as radicalshifts in prey availability.11 Climate change also affects the distribution and toxicityof chemical pollutants in the marine environment in complex ways.10

This study reports on the occurrence, distribution, and time trends of legacy(banned) and novel flame retardants in nine species of marine mammals inhabitingthe coasts of the eastern US, Sweden, Iceland, and Greenland. These data, combinedwith climate change data, will help predict the health and survival of thesepopulations and inform policy to sustain life in the oceans.

Methods

Flame retardants in seals from different regions Flame retardant concentrations in US marine mammals

Patterns of flame retardant chemicals in US species Time trends in US and Sweden harbor seals

• Toothed whales (dolphins, porpoises, pilot whales) had higher

contaminant concentrations than the seals or baleen whales (minke,

humpback), reflecting their higher position on the food web.

• Compared to other regions, US Atlantic harbor seals had the highest

concentrations of PBDEs, Dechloranes, and other BFRs including HBBZ,

BB-101, and Firemaster 550 components.

• In US species, PBDEs were the predominant flame retardants reflecting

their higher volume use in the US than in Europe.

• PBDEs and other BFRs were decreasing in Swedish harbor seals, but not in

US harbor seals between 2000-2016.

Schipper, JJS et al. 2008. Science 322:225-230; 2. Shaw, SD and Kannan, K 2009 Rev Environ Health24:157-229; 3. Houde, MAO et al. 2011 Environ Sci Technol 45:7962-7973; 4. Law, RJ 2014 Mar Pollut

Bull:82:7-10; 5. Shaw, SD et al. 2014 Sci Total Environ 490:477-487; 6. Letcher, RJ et al. 2018 Sci TotalEnviron 610:121-136; 7. Desforges, JP et al. 2017 Environ Sci Technol 51:11431-11439; 8. Jenssen, BM

2006 Environ Health Persp 114:76-80; 9. Hall, AJ et al. 2009 Environ Sci Technol 43:6364-6369 10. Noyes,

PD et al. 2009 Environ Int 35:971-986; 11. Kovacs, KM and Lydersen, C 2008 Sci Progress 91:117-150. 12.

Shaw, SD et al. 2010 Rev Environ Health 25:261-305; 13. Feo, ML et al. 2012 Anal Bioanal Chem404:2625-2637. 14. Covaci, A et al. 2011 Environ Int 37:532-556.; 15. PubChem

https://pubchem.ncbi.nlm.nih.gov; 16. Alaee, M et al. 2003 Environ Int 29:683-689.

Species US Sweden Iceland Greenland

Harbor Seal 72 85 11

Grey Seal 8 11 10

Ringed Seal 10 2 21

White-sided Dolphin 9

White-beaked Dolphin 15

Harbor Porpoise 9

Long-finned Pilot Whale 4 9

Minke Whale 2 6

Humpback Whale 1 13

Figure 2. Box plots of concentrations of sum PBDEs, sum Dechloranes, and sum other BFRs

in harbor seals (HS), grey seals (GS), and ringed seals (RS) from the US, Sweden, Iceland,

and Greenland. Letters above the bars indicate significant differences among countries by

Kruskal-Wallis and post hoc Mann-Whitney U tests (p<0.05).

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b c a b ab

Figure 3. Box plots of concentrations of sum PBDEs, sum Dechloranes, and sum other BFRs

in harbor seals (HS), grey seals (GS), white-sided dolphins (WsD), harbor porpoises (HP),

pilot whales (PW), minke whales (MW), and a humpback whale (HW) from the US. Letters

above the bars indicate significant differences among species by Kruskal-Wallis and post

hoc Mann-Whitney U tests (p<0.05).

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c d a bc ab

Figure 4. Average composition of sum PBDEs, sum Dechloranes and sum other BFRs in

blubber of US harbor seals (HS), grey seals (GS), white-sided dolphins (WsD), harbor

porpoises (HP), pilot whales (PW), minke whales (MW), and a humpback whale (HW). 1

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Sweden: R2=0.25, F1,83=27.2, p<0.001

US

Sweden

Figure 5. Time trends of PBDEs,

Dechloranes and other BFRs in harbor

seal blubber from the US and Sweden

between 1998- 2016.

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Sweden: R2=0.09, F1,83=7.99, p=0.006

Map?

NW Atlantic (US)

Arctic (Iceland, Greenland)

Baltic (Sweden)

The authors would like to thank Allied Whale/College of the Atlantic, New England Aquarium,

International Fund for Animal Welfare, Mystic Aquarium, and New York Marine Rescue Center for

providing the US samples for this project. Samples from Greenland, Iceland, and Sweden were imported

under National Marine Fisheries Service permit No. 22272.

30 YEARS OF ENVIRONMENTAL IMPACT RESEARCH

Compound Uses

PB

DE

s

BDE-17 2,2',4-Tribromodiphenyl Ether

Constituents of PentaBDE commercial mixture. Mainly

used as additive flame retardants (FR) in flexible

polyurethane foam and fabrics. Banned in Europe and

withdrawn from US commerce in 2004. 12

BDE-28 2,4,4'-Tribromodiphenyl Ether

BDE-47 2,2',4,4'-Tetrabromodiphenyl Ether

BDE-49 2,2',4,5'-Tetrabromodiphenyl Ether

BDE-66 2,3',4,4'-Tetrabromodiphenyl Ether

BDE-99 2,2',4,4',5-Pentabromodiphenyl Ether

BDE-100 2,2',4,4',6-Pentabromodiphenyl Ether

BDE-153 2,2',4,4',5,5'-Hexabromodiphenyl Ether

BDE-154 2,2',4,4',5,6'-Hexabromodiphenyl Ether

BDE-183 2,2',3,4,4',5',6-Heptabromodiphenyl EtherConstituents of OctaBDE commercial mixture. Mainly

used as additive FR in hard plastics and thermoplastic

resins. Banned in Europe and withdrawn from US

commerce in 2004. 12

BDE-201 2,2',3,3',4,5',6,6'-Octabromodiphenyl Ether

BDE-202 2,2',3,3',5,5',6,6'-Octabromodiphenyl Ether

BDE-196 2,2',3,3',4,4',5,6'-Octabromodiphenyl Ether

BDE-197 2,2',3,3',4,4',6,6'-Octabromodiphenyl Ether

De

chlo

ran

es

Syn-DP Syn-Dechlorane Plus Constituents of commercial Dechlorane Plus. Additive

FR in wire coatings, plastic roofing, computer parts 13Anti-DP Anti-Dechlorane Plus

DEC-602 Dechlorane 602

FR use information very limited. Also found as

impurities in pesticides 13

DEC-603 Dechlorane 603

DEC-604 Dechlorane 604

Cplus Chlordene Plus

CL11-DP Mono-dechlorinated Dechlorane Plus Breakdown product of Dechlorane Plus 13

Oth

er

BFR

s

ATE 2,4,6-tribromophenyl allyl ether Additive FR in expandable polystyrene and foam 14

TBPX 2,3,5,6-tetrabromo-p-xylene Additive FR in paints, textiles, plastics 15

TBOCT Tetrabromo-o-chlorotoluene Additive FR, Use information very limited 15

PBT Pentabromotoluene Used in plastics, polystyrene, rubbers and textiles 14

PBEB PentabromoethylbenzeneAdditive in polyester resins for electronics, textiles and

foam 14

HBBZ HexabromobenzeneAdditive to paper, wood, textiles, and electronics

mostly in Japan 14

BB-101 2,2',4,5,5'-pentabromobiphenyl Legacy flame retardant. PBBs banned in US in 1974 16

BTBPE 1,2-bis-(2,4,6-tribromophenoxy)ethaneReplacement for OctaBDE. Additive FR in plastics,

resins, coatings 14

EHTBB 2-ethylhexyl-2,3,4,5-tetrabromobenzoateConstituents of Firemaster 550. Replacement for

PentaBDE in polyurethane foam 14BEHTBP Bis(2-ethyl-1-hexyl)tetrabromophthalate

Table 2. Compounds analyzed in marine mammal tissues and their commercial

uses.

Table 1. Sample numbers for species per region.

Figure 1. Map of sampling regions.

Assessing Global Threats of Pollution and Climate Change to Marine Mammals Across Three Oceans

Results

Introduction

Conclusions References

Acknowledgements

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BDE-28 BDE-47 BDE-49 BDE-99 BDE-100

BDE-153 BDE-154 BDE-183 Other

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DEC-602 DEC-603 DEC-604 Cplus

Syn-DP Anti-DP CL11-DP