Contaminants of Emerging Concern in the Tidal Delaware River a Pilot Monitoring Survey 2007-2009 A. Ronald MacGillivray, Ph.D. DRBC Delaware County Environmental Summit February 16, 2013 1
Contaminants of Emerging Concern Pharmaceuticals and Personal Care Products (PPCP) Hormones Stain repellants/nonstick surfaces [PFAS] Flame Retardants [PBDE] Detergents [NP] Plasticizers [bis-phenol A] 2
Map of Delaware River Basin Land Use from USGS National Land Cover Database CEC survey was conducted in the tidal Delaware River (outlined in black) urbanized and industrialized area Over 6 million residents live in contributing watersheds 3
Pharmaceutical Source Map for the Delaware River Basin 4
Delaware River Basin Ambient Water Sampling Zones 2 and 3 use public water supply 5
Ambient Water Surveys in the Tidal Main Stem Delaware River 2007 # of analytes / # detected 2008 # of analytes / # detected 2009 # of analytes / # detected 13/11 13/11 13/11 54/21 72/49 119/46 Sterols and Hormones 24/6 27/11 17/2 NP and NPE 3/2 4/1 4/2 Not monitored 1/0 1/0 46/24 Not monitored Not monitored PFAS stain repellants/nonstick surfaces PPCP EPA Method 1694 plus extended list of analytes - pharma and personal care prod. nonyl phenols hormones only detergents bis-phenol-a plasticizers PBDE EPA Method 1614 flame retardants 6
Criteria for Prioritization of PPCP Environmental occurrence Aquatic toxicity Potential human health effects (sensitive populations) Analytical feasibility (EPA Method 1694) Results are based on filtered surface water samples prior to additional treatment for drinking water. Human health risk assessment methodologies differ from ecological assessments and may identify other priorities. 7
Fifteen Priority PPCP in Tidal Delaware River 3500 Codeine Metformin 3000 Thiabendazole 2-Hydroxy-ibuprofen 2500 Triclocarban mean ng/l metformin Fluoxetine 2000 Dehydronifedipine Acetaminophen 1500 codeine Clarithromycin > RM 95 = Source Water Lincomycin Ibuprofen 1000 Gemfibrozil Sulfamethoxazole 500 Erythromycin-H2O Carbamazepine 0 mouth of bay 50 68 80 88 river mile 105 131 head of tide 8
Summary PPCP Similar contaminants and concentrations reported in other fresh and estuarine surface waters with exception of codeine and metformin. Recommend monitoring all parameters feasible. Fifteen priority PPCP proposed for focused study in Delaware Estuary out of 57 PPCP detected. 9
Hormones Natural and synthetic hormones were detected in low ng/l levels at limited locations (e.g, estrone, norethindrone, 17-αethynylestradiol, desogestrel and testosterone). Concentration for environmental safety are not available for hormones. Some hormones are included in SDWA Contaminant Candidate List 3 and Unregulated Contaminants Monitoring Rule 3. Hormones warrant further study in the Delaware River Basin. 10
Brominated Flame Retardants polybrominated diphenyl ethers (PBDE) used in electronics, textiles and polymers 11
Polybrominated Diphenyl Ethers (PBDE) Flame Retardants In Ambient Waters Of The Tidal Delaware River Grouped by Homologs 10000 9000 8000 7000 DeBDE NoBDE Four congeners on UCMR2 list 6000 OcBDE pg/l HpBDE > RM 95 = Source Water Sites 5000 HxBDE PeBDE TetraBDE 4000 TriBDE DiBDE 3000 2000 1000 0 50 mouth of bay 68 80 88 River Miles 105 131 head of tide 12
Mean PBDE in DE Estuary Fish vs. Fish Elsewhere 2500 Data Sources: DE Est: This presentation. SF Bay: Lunder and Sharp. 2003. Tainted Catch. N. Amer and Europe: Hites. 2004. ES&T, 38(4). Taiwan: Peng, et.al. 2007. Chemosphere, 66. Total PBDE, (ng/g lipid) 2000 1500 1000 500 0 DE Est SF Bay N. Amer from presentation by Dr. Rick Greene, DNREC Europe Taiwan
Perfluoroalkyl and Polyfluoroalkyl Substances 14
Perfluoroalkyl Carboxylic Acids (PFCAs) In Ambient Waters Of The Tidal Delaware River 2009 600.0 PFNA C9 500.0 ng/l 400.0 300.0 200.0 100.0 0.0 50 68 80 88 105 131 River Miles mouth of bay head of tide 15
PFOA (C8) In Ambient Water Of The Tidal Delaware River 80 70 60 ng/l 50 40 EPA Provisional Health Advisory Short-term Value = 400 ng/l NJDEP Preliminary Health-based Guidance Chronic Exposure = 40 ng/l 30 Source Water > RM 95 20 10 0 RM 50 Liston Point RM 68 S of Del Mem Br RM 80 Marcus Hook RM 88 @ Schuylkill R RM 105 @Pennsauken Cr RM 131 Biles Channel 16
Perfluorooctane sulfonate (PFOS) In Ambient Water Of TheTidal Delaware River 14 EPA Provisional Health Advisory 200 ng/l > RM 95 Aquatic Life Chronic Benchmark 5,100 ng/l (Giesy et al., 2010) Avian Wildlife Benchmark 47 ng/l (Giesy et al., 2010) 12 n g /L 10 8 6 4 2 0 RM 50 RM 68 RM 80 RM 88 RM 105 RM 131 17
PFUnA C11 18
Summary PFASs PFASs detected at ng/l (pptr) levels in water PFNA (C9) highest PFAS concentrations in water Concentrations in water appear to be going down PFASs in Delaware River fish fillets at ng/g (ppb) levels PFUnA(C11) > PFOS(C8) > PFNA(C9) > PFDoA(C12) > PFDA(C10) Additional ecotoxicology information needed especially on the bioaccumulative and persistent longer chain and sulfonated compounds 19
Summation Current assessment and regulatory approaches are inadequate for many compounds detected in waters of the estuary. Fifteen PPCP are prioritized for focused study. Some CEC may require regulation under the SDWA. Additional ecotoxicology information is needed for assessment of aquatic life and wildlife protection. 20
Next Step Pennsylvania Water Resources Research Center And Pennsylvania Sea Grant Funded Project Occurrence Survey for Emerging Contaminants of Concern in Pennsylvania Tributaries of the Delaware River Temple University and DRBC in 2013 21
Disposal of Unused Pharmaceuticals The Drug Enforcement Administration (DEA) NATIONAL TAKE-BACK INITIATIVE Upcoming Take-Back Day April 27, 2013 http://www.deadiversion.usdoj.gov/drug_ disposal/takeback/ 22
Acknowlegements Tom Fikslin and DRBC MMA staff for support and advice throughout the project Greg Cavallo, DRBC for data management support AXYS Analytical staff for analytical support Final report is available online Contaminants of Emerging Concern in the Tidal Delaware River Pilot Monitoring Survey 20072009, DRBC, July 2012 http://www.state.nj.us/drbc/quality/reports/emerging/ Contact Information: Ronald.MacGillivray@drbc.state.nj.us 23