SUSAN KLOSTERHAUS, SAN FRANCISCO ESTUARY INSTITUTE By Susan Klosterhaus
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1 SUSAN KLOSTERHAUS, SAN FRANCISCO ESTUARY INSTITUTE By Susan Klosterhaus
2 Emerging Contaminants Workgroup What CECs have the potential to adversely impact beneficial uses in the Bay? Chemical Screening Pilot Study Status and Trends Annual Monitoring
3 RMP CEC Studies Screening of Bay Samples for Previously Unknown Organic Contaminants (2003) South Bay Pharmaceutical Study ( ) Perfluorinated Compounds ( ) Chlorinated Paraffins (2008) Triclosan (2008) Current Use Flame Retardants ( ) Brominated Dioxins, Furans (2010) PPCPs, PFCs, Alkylphenol Ethoxylates (2010) NOAA Mussel Watch CEC California Pilot Study (2010) Broadscan Screening of Bay Wildlife ( )
4 AXYS/CEC Mussel Pilot Study Water, sediment, benthic 5 margin sites 104 PPCPs, alkylphenol ethoxylates, PFCs Support NOAA Mussel Watch CEC CA Pilot Study Proof of concept for method development Ribbed horsemussel (Geukensia demissa)
5 12 PPCPs Detected in Water at All Sites Compound Use Max ng/l Mean Valsartan antihypertensive Sulfamethoxazole antibiotic Carbamazepine anticonvulsant Caffeine stimulant Gemfibrozil antilipidemic Atenolol beta blocker Meprobamate antianxiety Diethyl-3-methyl-benzamide, N,N- (DEET) insect repellent Erythromycin-H20 erythromycin metabolite 12 4 Triamterine antihypertensive 10 4 Benzoylecgonine cocaine metabolite; analgesic 7 5 Diltiazem antianginal 3 1
6 19 Other PPCPs Detected in Water ng/l Compound (# sites detected) Use Max Mean Ibuprofen (1) antiinflammatory 38 8 Metoprolol (3) antianginal 26 6 Cotinine (4) nicotine metabolite Clarithromycin (2) antibiotic 18 5 Sulphamethizole (1) antibiotic 16 3 Amphetamine (2) stimulant 10 4 Naproxen (1) antiinflammatory 8 2 Hydrocodone (1) analgesic 7 1 Trimethoprim (2) antibiotic 4 1 Thiabendazole (1) fungicide Cocaine (4) stimulant 2 1 Diphenhydramine (4) antihistamine 2 1 Desmethyldiltiazem (2) diltiazem metabolite Dehydronifedipine (4) antianginal Albuterol (1) antiasthmatic Propoxyphene (2) analgesic Amitryptiline (2) antidepressant Diazepam (1) antianxiety hydroxy-amitriptyline (2) amitriptyline metabolite
7 11 PPCPs Detected in Sediment Compound (# sites detected) Ciprofloxacin (2) Caffeine (3) Triclocarban (3) Trimethoprim (1) Triamterene (5) Thiabendazole (2) Diethyl-3-methyl-benzamide, N,N- (DEET) (2) Erythromycin-H20 (1) Amphetamine (2) Sulphamethoxazole (1) Cocaine (1) Use antibiotic stimulant antimicrobial antibiotic antihypertensive fungicide 9 2 insect repellent 3 1 erythromycin metabolite stimulant antibiotic stimulant ng/g dry wt Max Mean 33 compounds not reported by lab due to poor surrogate recoveries High MDLs for triclosan (60 ng/g), others
8 17 PPCPs Detected in Mussels ng/g wet wt Compound (# sites detected) Use Max Mean Diethyl-3-methyl-benzamide, N,N- (DEET) (5) insect repellent 14 7 Digoxigenin (3) cardiac drug metabolite 10 5 Carbamazepine (5) anticonvulsant 5 3 Amphetamine (3) stimulant 4 1 Triclocarban (2) antimicrobial Sertraline (5) antidepressant Dehydronifedipine (5) antianginal Triamterine (3) antihypertensive Ranitidine (3) antacid Diphenhydramine (3) antihistamine Atenolol (1) beta blocker Cocaine (2) stimulant Amitryptiline (2) antidepressant Sulphamethizole (1) antibiotic Erythromycin-H20 (4) erythromycin metabolite Enalapril (2) antihypertensive Diltiazem (2) antianginal
9 PPCPs in SF Bay Comparison to 2006 South Bay Study Results comparable Higher frequency of detection in 2010 (30%) Spatial Trend Highest in South Bay, lowest in Central Bay, but several exceptions Potential Impacts? Concentrations much lower than available toxicity thresholds Effects of long-term exposure to low concentrations unknown
10 Alkylphenol Ethoxylates Nonionic surfactants in detergents, emulsifiers, pesticide formulations 80% nonylphenol ethoxylates, 20% octylphenol ethoxylates C 9 H 19 O(CH 2 CH 2 O) n H Nonylphenol polyethoxylate Degrade to mono-, di-ethoxylates, nonylphenol, octylphenol Endocrine disrupting chemicals C 9 H 19 OCH 2 CH 2 OH Nonylphenol monoethoxylate Phased out/restricted in Europe, Canada Monitored in RMP 2002 Pilot Study C 9 H 19 OH Nonylphenol
11 Alkylphenol Ethoxylates Water NP max 73 ng/l Sediment NP max 86 ng/g Mussels NP max 95 ng/g
12 NOAA Mussel Watch CEC California Pilot Study Increase focus on CECs 2010 effort as CA Pilot Study Multi-agency collaboration - Chemical analysis $$ from NOAA - Partners leveraged resources, provided field support Study Goals Develop list of high priority CECs for national program Investigate alternative methods (passive samplers)
13 NOAA Mussel Watch CEC California Pilot Study Winter sampling at existing MW sites (n=69) Stratified by land use 4 sites in SF Bay Historic analyte list on subset Summer sampling, targeted new sites (n~10) Large POTWs Stormwater discharge Dry season ag runoff Caged bivalves, PSDs 5 sites in SF Bay Summer Target Sites
14 NOAA Mussel Watch CEC California Pilot Study Target CECs PBDEs, polybrominated biphenyls (PBBs) ~120 PPCPs PFCs Alkylphenols Current use pesticides Current use flame retardants Nanoparticles (single walled carbon nanotubes) Timeline Sample collection completed (Sept) Data by early 2011 Report in Summer 2011
15 Broadscan Screening of Bay Wildlife Targeted Analysis extract clean-up GC-MS Chem X??? Broadscan Analysis extract ID, quantify w/standards Minimal clean-up GC X GC TOF MS ID large peaks ID unknowns w/ MS libraries Quantify w/standards
16 Broadscan Screening of Bay Wildlife (w/nist) Year 1 (2010) Harbor seal, mussel sample collection Method development, analysis of seal samples (blubber and liver) Year 2 (2011) Method development, analysis of mussel samples Partnerships The Marine Mammal Center SCCWRP/San Diego State Univ.
17 State CEC Advisory Panels Two Panels: - Recycled Water - Coastal and Marine Ecosystems Incorporate current knowledge into regulatory process Recommend strategies for monitoring, managing CECs Reports available to management community - Recycled Water: June Ecosystems: Summer 2011
18 CEC Profiles Providing information to water/air quality managers, public Antimicrobials, alkylphenols, carbamazepine Fact sheets on website Work with BACWA and Regional Board
19 Next Steps CEC synthesis report, theme for Pulse of the Estuary, Annual Meeting Identify, strengthen partnerships with other science organizations to address critical issues
20 Acknowledgements Richard Grace, Candice Navaroli, AXYS Analytical Paul Salop, Jay Johnson, Applied Marine Sciences Denise Greig, The Marine Mammal Center John Kucklick, NIST RMP Data Management Team RMP Emerging Contaminant Workgroup Meg Sedlak, Jay Davis, Jamie Kass, Rachel Allen, Don Yee, SFEI
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