Susan D. Shaw, DrPH Director, Marine Environmental Research Institute Professor, School of Public Health, Environmental Health Sciences, SUNY, Albany

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1 Susan D. Shaw, DrPH Director, Marine Environmental Research Institute Professor, School of Public Health, Environmental Health Sciences, SUNY, Albany Green Science Policy Symposium San Francisco, CA April 12, 2013

2 HFRs Are Global Contaminants Harbor seal (Phoca vitulina ) Shaw et al. 2008, 2009, 2011, Meng et al. 2009, Law et al Sea lion (Zalophus californianus) Meng et al. 2009, Stapleton et al Polar bears Kannan et al. ES&T 2005, Muir et al. ES&T 2006 Ringed seal (Pusa hispida ) Riget et al. 2006, Johansen et al No. elephant seal (M. angustirostris) Meng et al Killer whales Krahn et al. Mar Poll Bull 2007, Rayne et al. ES&T 2004

3 Marine Mammals As Sentinels Assessing POPs in NW Atlantic Harbor Seals and Fish Characterizing regional trends Sources & exposure pathways Legacy & emerging pollutants replacement HFRs Toxic thresholds & mortalities Policy implications Marine Environmental Research Institute

4 High Exposure, Mass Mortalities Hazardous Waste (US EPA) PCBs ppm in fat (Shaw et al. 2013) PBDEs 4-10 ppm fat

5 PBDE Levels in Pinnipeds Asia Europe No. Fur Seal, Japan coast Harbor Seal, Wadden Sea ng/g lipid Blubber Canada Gray Seal Baltic Ringed Seal Baltic Harbor Seal, St Lawrence Estuary Canada US Greenland Ringed Seal Harbor Seal, SF Bay, CA Harbor Seal (3700 ng/g) NW Atlantic CA Sea Lion (55000 ng/g) CA Sea Lion (5800 ng/g) Sum PBDE (ng/g lw)

6 PBDEs in North American Pinnipeds California sea lion (range ) Ringed seal Greenland 5800 California sea lion 3700 NW Atlantic harbor seal Pacific harbor seal Hooded seal Gray seal So. California sea lion Pacific harbor seal No. elephant seal PBDE levels in California sea lions (mean ng/g ppm lipid wt lipid) highest reported in wildlife to date

7 PBDE Levels in Cetaceans Asia Humpback Dolphin, Hong Kong ng/g lipid Blubber Europe Australia Canada US Brazil (liver) Harbor porpoise, UK Beluga Whale, St. Lawrence Estuary Killer Whale, Alaska Bottlenose dolphin, Florida Bottlenose dolphin, Texas Gulf of Mexico Bottlenose Dolphin UK (7700 ng/g) Killer Whale, CA coast (13000 ng/g) Killer Whale, Puget Sd (6800 ng/g) Bottlenose Dolphin SC (6800 ng/g) Sum PBDE (ng/g lw)

8 PBDE Levels in North American Cetaceans Residents Killer whales Killer whale Offshore Harbor porpoise Transients Residents 3100 (CA 2000 ng/g coast) lipid wt due to diet of sea lions 6800 High PBDE levels in transient killer whales Beluga whale Bottlenose dolphin White-sided dolphin

9 Harb o r Seal- U S Harb o r Seal- U S Harb o r Seal- N o rway Harb o r Seal- N o rway Po lar B ear- Svalb ard C o mmo n T ern- N o rway A rct ic T ern- N o rway A rct ic T ern- N o rway Glauco us Gull- N o rway Slat y- b reast ed rail- C o mmo n snip e- C hina Hard head cat f ish- U S A t lant ic st ing ray- U S Sp iny d o g f ish- U S A t l. sharp no se shark- U S B ull shark- U S F lo und er- Jap an Sea B ass- Jap an Po lar co d - N o rway A m. Plaice- U S W hit e hake- U S A t l. M ackerel- U S Ho rse mussel- C anad a Ho rse mussel- C anad a Ho rse mussel- C anad a Ho rse mussel- C anad a BDE-209 Levels in Marine Biota Blubber (Shaw et al. 2008) NW Atlantic Florida coast W. Canada, waste outflow Liver (Shaw et al. 2009) plasma (ng/g lipid) blubber eggs ~ ~ ~ ~ PRD, China muscle (405) (530) whole body (514) (780)

10 Sum PBDE (ng/g lw).. Time Trends in North America Penta BDEs Doubling ~2-5 years Leveling after 2005? dungeness crab whitefish bull shark cormorant great blue heron beluga whale bottlenose dolphin harbor seal-ca harbor seal-canada harbor seal-ne US human-us

11 Cetaceans Pinnipeds HBCD Levels Increasing in US Harbor seal Harbor seal Harbor seal Harbor seal Ringed seal Grey seal Northern fur seal California sea lion Bottlenose dolphin Bottlenose dolphin Bottlenose dolphin Melon-headed whale Melon-headed whale Finless porpoise Finless porpoise Striped dolphin Indo-Pacific humpback dolphin Indo-Pacific humpback dolphin Finless porpoise Finless porpoise Finless porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Harbor porpoise Common dolphin Common dolphin Common dolphin Norway Baltic Sea Japan U.S. (This study) China US Japan ng/g lw Blubber Europe

12 Penta-BDE Replacements: Firemaster 550 (TBB, TBPH) (2,3,4,5-tetrabromobenzoate & tetrabromophthalate) Harbor seals, NW Atlantic (Shaw et al 2011) Peregrine falcons, Canadian Gr Lakes (Fernie et al Dioxin 2011) Franciscana dolphins, Brazil coast (Torre et al Dioxin 2011) Dolphins, So. China Sea (Lam et al. 2009)

13 BTBPE: Octa-BDE Replacement (Octabromodiphenyl ethane) Northwest Atlantic harbor seals (Shaw et al 2012) Shellfish and fish from e waste regions of China (Ismail et al 2009, Shi et al, 2009, Wu et al 2010) Lake trout from Lake Ontario, Canada (Fernie et al 2010)

14 DBDPE: Deca-BDE Replacement (Decabromodiphenyl ethane) Herring gull eggs from the Great Lakes ( ) ng/g lw (Gauthier et al ES&T 2009). Gull eggs up to 2880 ng/g lw (2005) > BDE-209 Waterbirds (Chinese pond heron) from the Pearl River Delta, South China median ng/g lw in muscle (Luo et al 2008) Chinese giant pandas DBDPE ng/g lw. Red pandas ng/g lw (Hu et al 2008)

15 Health Effects in Marine Biota (PBDEs) Seals: Thyroid hormone alterations, reduced first year survival, disruption of in vitro immune responses, recurring die-offs (UMEs) Mink: Complete reproductive failure, thyroid alterations Raptors: Reproductive impairment, eggshell thinning, infertility, thyroid alterations Zhang et al. Env Tox Chem 2008, Martin et al. Env Tox Chem 2007, Frouin et al. 2010, Fernie et al. ES&T 2009, McKernan et al. Env Toxicol Chem 2009, Johnansson et al. Environ Toxicol Chem 2009, Hall et al. Env Poll 2003, Hall and Thomas Env Tox Chem 2007, Hall et al. EST 2009

16 From Science to Policy Deca Ban in Maine 2007 Kids Safe Products Act 2008

17 Firefighters: Sentinel Species? High exposure Testicular cancer Prostate cancer Bladder cancer (transitional cell carcinoma) Multiple myeloma Non-Hodgkin s lymphoma Breast cancer

18 Firefighter Exposure Multiple toxic chemicals (metals, gases, HFRs, PFCs, combustion by-products) Burning of BFR-treated materials (foam furniture, plastics, electronics) produces large amounts of brominated dioxins/ furans To date, brominated dioxins not studied in firefighters

19 Flame Retardants (PBDEs) Clothing, textiles, mattresses, upholstery, TVs, computers, plastics, electronics, building materials: dust (80%) food (20%) Endocrine disruptors, developmental neurotoxins, cancer

20 Perfluorinated Chemicals (PFCs) Food wrappers, stain-resistant fabrics, Scotchgard, Gortex, non-stick pans (Teflon), fire-fighting foams, drinking water Endocrine disruptors, liver, heart disease, cancer (PFOA)

21 Pilot Study 12 Veteran San Francisco Firefighters Firefighters 5 years Responded to 20 fires in last 5 years Had not worked in industries with known chemical emissions Blood sampled (100 ml) within 24 hrs. after fire event Chemical Analysis (SUNY Lab/ Kannan) High resolution gas chromatography high resolution mass spectrometry (HRGC-HRMS) High-performance liquid chromatography tandem mass spectrometry (HPLC- MS/MS)

22

23 ΣPBDD/F Brominated dioxins and furans in firefighter blood PBDD/Fs pg/g TEQ lw ΣPBDD US ΣPBDF CA Firefighters CA Firefighters Serum ΣPBDD/F CA Firefighters (104) Europe German Extruder Operators (2) German Maintinence Mechanics (2) German Production Employees (2) Blood (116) German R+D Personnel (2) Sweden General Population (3) Adipose Various Population (4) Milk References 1. This study 3. Jogsten et al Zober et al Kotz et al 2005

24 Chlorinated dioxins and furans in firefighter blood US Europe Russia CA Firefighters NY WTC responders ME (2) NY WTC responders LE (2) MI Population (3) Population (4) German Pregnant women (5) Firefighters (6) Firefighters (6) Firefighters (7) Mothers (8) Japan Population (9) PCDD/Fs pg/g TEQ lw Asia Japan Population (10) Taiwan Firefighters/ Investigators (11) Taiwan Population (12) References 1 This study 4 Schecter et al Chernyak et al Uemura et al Horii et al Wittsiepe et al Humblet et al Hsu et al Hong et al Chernyak et al Iida et al Hsu et al 2009

25 PBDE levels (ng/g lw) in firefighter serum US Europe CA Firefighters CA Population (2) CA Carpet layers (3) MA (+ CA) Foam recyclers (3) MA Population (4) US - CA Population (2) US Population (5) Sweden Rubber mixers (6) Korea Incinerator workers (7) 135 China, Guiyu E-waste recyclers (8) Asia (580) China, Haojiang residents (8)

26 Deca-BDE (BDE-209) Dominates PBDE Patterns in Firefighter Blood

27 % of total PBDE. BDE-209 in E-Waste Recyclers Guiyu, South China BDE % 68% 30 Guiyu 25 Haojiang Human blood Ongoing 20 exposure to BDE-209 in burning plastics? BDE Congener Data: Bi et al 2007

28 Ongoing Exposure to Burning Plastics Guiyu South China

29 Perfluorochemicals in firefighter blood PFCs ng/g lw PFHxSa PFOA PFNA PFOS CA Firefighters NY WTC responders(2) US Population (3) China Population (4) Australia Population (5)

30 Summary High levels of brominated dioxins/ furans in firefighter blood High levels and patterns of PBDD/Fs, PBDEs, PFCs imply occupational exposure Study helps explain high rates of cancer and health problems in firefighters Large-scale studies needed

31 From Science to Policy: Safe Chemicals Act US Senate July

32 For information, contact Marine Environmental Research Institute

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