Contaminants of Emerging Concern in the Delaware River Estuary

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1 Contaminants of Emerging Concern in the Delaware River Estuary National Estuary Program Meeting Thomas J. Fikslin, Ph.D. Delaware River Basin Commission February 24, 2010

2 Background DRBC Interstate commission created in Charged with protecting the water resources of the basin. Has water quality criteria and extensive monitoring programs for ambient water, sediment and fish. Control of Toxic Pollutants: key element in Delaware Estuary CCMP. Goals: collect ambient water and fish data on contaminants of emerging concern

3 Basin Facts Largest un-dammed river east of the Mississippi 330 miles 13,539 square mile drainage 17 million water users 216 tributaries Three reaches included in National Wild and Scenic River System One of the world s largest freshwater tidal estuaries Delaware Bay- 782 sq. miles

4 What are contaminants of emerging concern? Increased interest by scientists, the public, and regulators in substances and toxic effects not historically monitored or assessed. Improved analytical methods to detect compounds. Fate and transport not well understood. Growing body of information on adverse effects, but consensus has not been reached concerning the toxicity of many compounds.

5 Map of Delaware River Basin Land Use USGS National Land Cover Database Ambient water survey was conducted in the tidal Delaware River (outlined in black) Urbanized and industrialized area Over 6 million residents live in contributing watersheds

6 Map of Pharmaceutical Sources in the Delaware River Basin

7 Ambient Water Sampling Locations

8 Emerging Contaminants Surveys Delaware Estuary PFC LC/MS/MS PPCP LC/MS/MS Hormones GC/LRMS NP and NPE GC/MS bisphenol-a LC/MS/MS # of analytes / # of analytes / # of analytes / # detected # detected # detected 13/11 13/11 13/NA 54/21 72/49 119/NA 24/6 27/11 17/NA 3/2 3/1 3/NA 1/0 1/NA

9 ng/l codeine PPCP in Tidal Delaware River mouth of bay RM head of tide Caffeine Triclocarban Diphenhydramine Naproxen Ibuprofen Codeine Carbamazapine Diltiazem Dehydronifedipine Gemfibrozil Trimethoprim Sulfanilamide Sulfamethoxazole Sulfadimethoxine Sulfadiazine Ofloxacin Norfloxacin Erythromycin-H2O Clarithromycin Azithromycin Over the counter prescription antibiotics

10 Summary PPCP Analyzed for 72 compounds. Detected 21 compounds. Concentrations in the ng/l (ppb) range Individual compound conc. max. - Codeine at 169 ng/l at RM 68 Combined pharmaceuticals conc. max ng/l at RM 68 Similar contaminants present in surface waters near other urban areas.

11 Aquatic ecotoxicity data, primarily based on individual compounds and single species tests, are readily available for only 16 out of the 21 PPCP analytes detected limiting assessment of risk to aquatic life. Tier One screening for prioritization of future assessment and characterization Risk Index = PEC/PNEC Risk Index > 1.0 (clarithromycin effect on algal growth) Risk Index > 0.1 (carbamazapine effect on Ceriodaphnia dubia, ibuprofen effect on Hydra, erythromycin effect on Pseudokirchneriella subcapitata, sulfamethoxazole effect on cyanobacteria)

12 Perfluorochemicals Possess unique properties that make them ideal for use in products that resist heat, oil, stains, grease and water. They are commonly used in nonstick cookware, stain-resistant carpet and fabrics, fire-fighting foam and other industrial applications. Their chemical structure make them extremely resistant to degradation in the environment.

13 PFC In Ambient Waters Of TheTidal Delaware River 1, ng/l River Miles PFOSA PFOS PFHxS PFBS PFDoA PFUnA PFDA PFNA PFOA PFHpA PFHxA PFPeA PFBA

14 PFOA In Ambient Water Of TheTidal Delaware River 80 S. Del. Mem. Br Liston Point MPCA fcc = 1,620 ng/l MPCA dfcc = 610 ng/l PFOA ng/l Marcus Hook Creek 20 Schuylkill R. 10 Pennsauken R. Biles Channel River Miles

15 PFOS In Ambient Waters Of TheTidal Delaware River 9 Schuylkill R. 8 7 Liston Point S. Del. Mem. Br. Marcus Hook Creek Pennsauken R. MPCA human health based surface water criteria 6 ng/l 6 PFOS ng/l Biles Channel River Miles

16 PFNA In Ambient Waters Of The Tidal Delaware River 1,200 1,000 Marcus Hook Creek S. Del. Mem. Br. PFNA ng/l Liston Point Schuylkill R. 200 Pennsauken R. Biles Channel River Miles

17 Perfluorinated Alkyl Sulfonate Results for Pelagic Species Delaware River ,000 45,000 Mean Values 40,000 Picograms per Gram (ppt) 35,000 30,000 25,000 20,000 15,000 10,000 5, River Mile (RM) PFBS PFHxS PFOS PFOSA

18 Perfluorinated Carboxylate Results for Pelagic Species Delaware River ,000 70,000 Mean Values Picograms per Gram (ppt) 60,000 50,000 40,000 30,000 20,000 10, River Mile (RM) PBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA

19 Summary PFCs PFC detected at ng/l levels PFNA highest PFC concentrations PFOA levels do not exceed MN surface water criteria of 610 ng/l PFOS levels exceed MN surface water criteria of 6 ng/l Additional information needed especially on longer chain and sulfonated compounds.

20 Brominated Flame Retardants Penta-BDE: used in foam products such as seat cushions and other household upholstered furniture; rigid insulation Octa-BDE: used in high-impact plastic products (e.g., computers, automobile trim). Deca-BDE: plastics (e.g., wire and cable insulation, adhesives, coatings and textile coatings) & fabric/carpet/drapery treatment

21 PBDE In Ambient Waters Of TheTidal Delaware River PBDEs in the Ambient Waters of the Delaware Estuary pg/l mouth of bay River Miles DiBDE TriBDE TeBDE NBDE OBDE HpBDE HxBDE PeBDE DBDE head of tide

22 Total PBDE, (ng/g lipid) Mean PBDE in DE Estuary Fish vs. Fish Elsewhere Data Sources: DE Est: This presentation. SF Bay: Lunder and Sharp Tainted Catch. N. Amer and Europe: Hites ES&T, 38(4). Taiwan: Peng, et.al Chemosphere, DE Est SF Bay N. Amer Europe Taiwan from presentation by Rick Greene, DNREC

23 Summary PBDE Total PBDE detected at concentrations between 246 to 9,376 pg/l. DecaBDE predominant homolog at three sites (2,090 to 7,630 pg/l). NonaBDE, PeBDE and TeBDE each predominant at different sites (29 to 161 pg/l). PeBDE and OBDE have low potential for direct toxicity, can bioaccumulate. DecaBDE concern is persistence and potential for transformation to bioaccumulative forms.

24 Next Steps DRBC plans to continue the assessment of sources, fate and effect of emerging contaminants in the Delaware Estuary through: Periodic ambient water and fish tissue surveys in mainstem of Delaware River. Limited POTW effluent sampling. Ambient surveys in tributaries for PFC. Collaborative studies on the effects: Continue comparisons to effects levels need to develop criteria for priority chemicals. Exploring the use of alternative bioassays and other measures of impacts on aquatic health.

25 Contact Information (609) (609) DRBC Website: