Chemical Contaminants in fish Richard A. Snyder & Natalie Karouna-Renier Center for Environmental Diagnostics and Bioremediation rsnyder@uwf.edu http://uwf.edu/cedb/ Acknowledgments US NAVY, Pre-reefing study of ex-Oriskany site, William Patterson and Richard Snyder http://www.uwf.edu/rsnyder/reports/Oriskrpt.pdf Centers for Disease Control and Prevention (CDC) Project Director, K. Ranga Rao http://uwf.edu/cedb/PERCH_CDC_Final_Report_2007.pdf US EPA cooperative agreement X-97455002 Project Director, K. Ranga Rao. he contents of this report are the sole responsibility of the authors and do not represent the views of the US EPA.Σ While the authors take responsibility for the contents, we cannot take full credit for the work. Florida Fish and Wildlife Conservation Commission (FWCC) special activity license for the collections, Holt Hatchery personnel (Gray Bass, John Knight et al.) We are grateful for the advice, cooperation, and assistance of local commercial and recreational fishermen. The work could not have been accomplished without a small army of students and staff at the UWF, including Suzanne Gibson, Matthew Wagner, Jeffrey Allison, and Alexander Ren. National Fish Consumption Advisories 2002 32.9% of the nation’s lake acreage 15.3% of the total river miles 100% of the Great Lakes and their connecting water bodies 71% of coastal waters including 100% of the Gulf Coast 39 chemicals responsible for advisories mercury, PCBs, chlordane, dioxins, and DDT = 96% Study Goal To assess the body burdens of toxic materials in shellfish and fish in the Pensacola Region as a vector for human exposure to regional contaminants. State-wide: limited consumption of freshwater fish based on Hg 2006 Escambia River, Perdido River, Blackwater River, Woodbine Springs Lake, and Yellow River No consumption statewide of king mackerel (>39”) and shark (>43”) for Hg Several “no consumption” advisories on all fish due to Hg Shadow bass in Blackwater river largemouth bass, bowfin, gar, redear sunfish in Woodbine Springs lake No Consumption for Organics Fenholloway River - any fish due to dioxins Wagner Creek –Checkered Puffer or Striped Mojarra due to dioxins Lake Apopka - brown bullhead catfish due to pesticides http://www.doh.state.fl.us/floridafishadvice/fish_consumption_guide.htm “Since there is no acceptable data that show PCB contamination in Florida Waters, the Bureau of Environmental Epidemiology has not established criteria and has not determined the human health risk for these non-dioxin like PCBs. If accepted data becomes available that show PCBs contamination of fish in Florida waters, the department will establish a criteria to address potential health risks.” State of Florida Dept of Health, May 2002 HSE 34 R 1970. Bulletin of Environmental Contamination & Toxicology 5:171-180. DeBusk, Poyer & Herzfeld 2002 Compiled EPA sediment data from 1993 (top) and 1996 (bottom) Persistent Organic Pollutants 1 9 1 9 O 2 8 3 7 2 8 3 7 O O 4 6 4 6 polychlorinated dibenzo-p-dioxins 75 congeners 3’ polychlorinated dibenzofurans 135 congeners 2’ 2 3 4’ 4 5’ 6’ 6 5 polychlorinated biphenyls (PCBs) 209 congeners Potential Sources of Dioxins/Furans Combustion Sources waste incineration, fuel combustion, cement kilns, forest fires, building fires, open burning of wastes. Metals Smelting, Refining and Processing Chemical Manufacturing: by-products from the manufacture of chlorine bleached wood pulp, chlorinated organics:PCP, PCBs, phenoxy herbicides (2,4,5T), TCE, DCE, vinyl chloride, etc PCBs PCBs were manufactured in the U.S. in large quantities from 1929 until 1977 Insulating fluids in electrical transformers Plasticizers, lubricants, fluids in vacuum pumps and compressors, hydraulic fluids 1960s spill of Arochlor 1254 in Escambia River Sediment contamination in urbanized bayous Bioaccumulation Age/size Trophic Status 1.2 Toxin in Body Tissue 1 0.8 0.6 0.4 0.2 0 300 350 400 450 500 Length (mm) 550 600 650 Screening Values U.S. EPA Screening Values (SV) • threshold concentration of the chemical in food that is of potential public health concern 70 kg weight (~156 lbs), 70 year lifetime, risk level 10-5 Risk based on different consumption rates (uncooked weight) Recreational fishers (17.5 g.day-1 = 4.3 oz .week-1) Mean fish and shellfish consumption in Florida (46 g.day-1 = 11.4 oz .week-1) Subsistence fishers (142.4 g.day-1 = 35.2 oz .week-1) Compound Mercury (Hg) Total PCBs TEQDFP Recreational Fishers 0.40 ppm 20 ppb 0.256 ppt Subsistence Fishers 0.049 ppm 2.45 ppb 0.14 ppt Dioxin/Furan and PCB TEQs TEQ= Toxic Equivalent Concentration 1998 World Health Organization Toxic Equivalency Factors (TEFs) weighing factors that compare the toxicity of a congener to 2,3,7,8-TCDD TEFs also for dioxin-like PCBs Updated in 2005 Non-detects: 0, 1/2DL, DL Blue Crab and Oysters as indicators Squares = crab sampling stations Triangles = oyster sampling stations WHO TEQs in Oysters Oyster TEQs by location Green Line = US EPA Recreational fisher SV Purple Line = FDA US market survey average Red line = Southern Mississippi market average Bayou Grande Bayou Chico Bayfront Auditorium Bayou Texar P'cola Bay Bridge N P'cola Bay Bridge Mid P'cola Bay Bridge S Gaberonne Esc. I-10 Bridge Mid Escambia Bay #7 Escambia Bay #1 Escambia Bay #5 Escambia bay # 8 Garcon Point Bridge N Garcon Point Bridge Mid Garcon Point Bridge S East Bay #13 East Bay #2 East Bay #3 East Bay #5 East Bay #8 East Bay #9 Bob Sykes Bridge Mid TEQDFP pg/g 6 5 4 3 2 1 0 WHO TEQs in Oysters 6.0 TEQ (ppt) 5.0 4.0 3.0 2.0 1.0 0.0 Urban Bayous Recreational SV Bridges ND=DL/2 Oyster Beds ND=0 0 Perdido-11 Mil e Creek Perdido B ay U pper Perdido B ay Lill ian B ridge Perdido B ay Bayou Grande Upper Bayou Grande Bayou Chico upper Bayou Chico Bridge Bayou Chico mouth Bayou Texar Upper Bayou Texar Mid Bayou Texar Mouth Escambi a Bay NW Mackey Cove Escambi a Channel Escambi a Bay NE Gaberonne Devils Poi nt Mulat Bayou Indi an Bayou Trout Bayou Escambi a Bay SE Garcon Point Redfish Point East River Yel low River Bl ackwater Bay Hoffman Bayou TEQ ng/Kg Blue Crab TEQs by location 0.8 0.6 0.4 0.2 WHO TEQs in Crab Muscle 1.00 0.90 0.80 TEQ (ppt) 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 Recreational SV ND=DL/2 ND=0 Blue Crab TEQs muscle and hepatopancreas y = 6.688 + 25.734x R= 0.71785 Hepatopancreas TEQ DFP ng/kg 40 35 30 25 20 15 10 5 0 0 0.2 0.4 0.6 Muscle tissue TEQ DFP 0.8 ng/kg 1 Upper Escambia Lower Escambia NE Escambia Bay Upper Perdido Lower Perdido 11-Mile Creek Lower Yellow River Lower Blackwater Upper Blackwater Upper Yellow River Shoal River SW Escambia Bay Bayou Texar East Bay Hoffmann Bayou Bayou Chico Bayou Grande Recreational SV Sum of PCBs g/Kg 60 50 Bass Mullet 40 30 20 10 0 A Lower Escambia River and Upper Bay y = -149.38 + 78.298log(x) R= 0.8094 Upper Escambia River 90 80 Total PCBs g/Kg 70 60 50 40 30 20 10 100 200 300 400 500 600 700 800 900 Mean Fish weight (g) in composite Fish Skin contribution to POP and Hg exposure Sample n Mean L (mm) Mullet Fillet only 4 314 Mullet Fillet w/Skin Mean W (g) Mean Age 305.81 2.00 ΣPCBs ug/kg TEQDF TEQp Hg ng/Kg ng/Kg mg/kg 24.10 0.710 0.930 0.010 54.70 0.310 1.758 0.011 Red Drum Sciaenops ocelatus 1.2 1.2 1 1 Total Hg mg/Kg Total Hg mg/Kg Spotted Sea Trout Cynoscion nebulosus 0.8 0.6 0.4 0.2 0 300 0.8 0.6 0.4 0.2 350 400 450 500 Length (mm) 550 600 650 0 300 400 500 600 700 Length (mm) 800 900 Spotted Sea Trout Cynoscion nebulosus Red Drum Sciaenops ocelatus 70 25 60 20 Total CB (g/Kg) Total CB (g/Kg) 50 15 10 40 30 20 5 10 0 200 0 400 600 800 1000 1200 1400 1600 W eight (g) 0 1000 2000 3000 4000 5000 6000 7000 W eight (g) DATE 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 9/14/07 ZONE Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge Esc. I-10 Bridge SPECIES Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Cynoscion arenarius Cynoscion arenarius Cynoscion arenarius Cynoscion arenarius Cynoscion nebulosus Cynoscion nebulosus Micropogonias undulatus Micropogonias undulatus Micropogonias undulatus Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Common Name LENGTH mm WEIGHT g Sheepshead 245 280 Sheepshead 255 340 Sheepshead 310 610 Sheepshead 312 550 Sheepshead 345 700 Sheepshead 420 1350 Sheepshead 440 1580 Sheepshead 455 1770 White Trout 296 238 White Trout 335 330 White Trout 350 440 White Trout 360 460 Spotted Sea Trout 354 350 Spotted Sea Trout 455 820 Croaker 202 100 Croaker 223 130 Croaker 265 245 Mullet 408 750 Mullet 424 750 Mullet 450 930 Mullet 470 1010 Total PCBs ug/kg 41 54 173 88 84 74 192 165 336 192 71 105 27 26 303 174 274 678 1010 284 1580 Sheepshead Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus 200 0.4 0.35 Total Mercury mg/Kg Total PCBs g/Kg 150 100 50 0.3 0.25 0.2 0.15 0.1 0.05 0 200 250 300 350 400 450 Mean Length (mm) 500 550 0 200 250 300 350 400 450 Mean Length (mm) 500 550 mono di tri tetra penta hexa hepta octa nona mono di tri tetra penta hexa hepta octa nona Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Micropogenias undulatus Micropogenias undulatus Micropogenias undulatus Cynoscion nebulosus Cynoscion nebulosus Cynoscion arenarius Cynoscion arenarius Cynoscion arenarius Cynoscion arenarius Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus Archosargus probatocephalus 1260 1254 1248 1242 Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Micropterus salmoides Micropterus salmoides Micropterus salmoides Ictalurus punctatus Micropterus salmoides Micropterus salmoides Micropterus salmoides Sciaenops ocellatus Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Mullet Fillet only Mullet Fillet w/Skin Cynoscion arenarius Cynoscion arenarius Sciaenops ocellatus Cynoscion nebulosus Mugil cephalus Mugil cephalus Mugil cephalus Paralichthys sp. Cynoscion nebulosus Mugil cephalus Mugil cephalus Mugil cephalus 1260 1254 1248 1242 0 0.2 0.4 0.6 0.8 Proportion of Total PCB 1 Before Ivan and I-10 Construction 0 0.2 0.4 0.6 0.8 Proportion of Total PCB After Ivan and I-10 Construction 1 1 Scomb er om or us ca valla Scomb er om or us ma cula tus 2.5 To tal Mercu ry m g/Kg To tal Mercu ry m g/Kg 0.8 2 1.5 1 0.4 0.2 0.5 0 600 0.6 800 1000 1200 1400 Me an Leng th (m m ) 1600 0 500 520 540 560 580 600 Me an Leng th (m m ) 620 640 350 50 Scomb er om or us ca valla Scomb er om or us ma cula tus 300 250 To tal PCBs g/Kg To tal PCBs g/Kg 40 200 150 100 30 20 10 50 0 600 800 1000 1200 1400 Me an Leng th (m m ) 1600 0 500 520 540 560 580 600 Me an Leng th (m m ) 620 640 25 Total PCBs g/kg Total PCBs g/kg 25 20 15 10 5 0 300 400 500 600 Length (mm) 700 800 20 15 10 5 0 100 200 300 400 500 600 Length (mm) 700 800 Sample ID mono di tri tetra penta hexa hepta octa RoundSc ad-1 Li zardfi sh-2 Li zardfi sh-1 Amberjac k-1 Amberjac k-2 KingMack -1 Redfis h-1 VerSnapper-3 VerSnapper-4 VerSnapper-1 VerSnapper-2 RedPorgy-1 RedPorgy-3 RedPorgy-2 Sc amp-3 Sc amp-1 Sc amp-2 Gag-4 Gag-1 Gag-2 Gag-3 Atl Croaker-1 GraySnapper-1 GraySnapper-2 RedSnapper-11 RedSnapper-12 RedSnapper-17 RedSnapper-16 RedSnapper-1 RedSnapper-5 RedSnapper-2 RedSnapper-10 RedSnapper-3 RedSnapper-15 RedSnapper-9 RedSnapper-7 RedSnapper-6 RedSnapper-4 RedSnapper-14 RedSnapper-13 RedSnapper-8 Squid-1 Squid-2 Spot-1 Pinfis h-1 Tomtate-2 Tomtate-1 RedGrouper-2 RedGrouper-1 RedGrouper-3 SandDoll ar-1 Sandperch-1 SandSeatrout-1 Bank SeaBass -2 Bank SeaBass -1 WhBPorgy-1 GrayTrig-5 GrayTrig-2 GrayTrig-3 GrayTrig-4 GrayTrig-1 Sc all op-1 1260 1254 Aroc hlors 1248 1242 1232 nona total deca mono di tri tetra penta hexa hepta octa nona Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Micropterus salmoides Micropterus salmoides Micropterus salmoides Ictalurus punctatus Micropterus salmoides Micropterus salmoides Micropterus salmoides Sciaenops ocellatus Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Mugil cephalus Mullet Fillet only Mullet Fillet w/Skin Cynoscion arenarius Cynoscion arenarius Sciaenops ocellatus Cynoscion nebulosus Mugil cephalus Mugil cephalus Mugil cephalus Paralichthys sp. Cynoscion nebulosus Mugil cephalus Mugil cephalus Mugil cephalus 1260 1254 1248 1242 0 0.2 0.4 0.6 0.8 Proportion of Total PCB Estuarine Offshore 1 The PERCH Fish Atlas Combined Studies EPA CDC Navy 46 species http://uwf.edu/cedb Fish Atlas http://uwf.edu/cedb Fish Atlas http://uwf.edu/cedb Fish Atlas http://uwf.edu/cedb Should you eat the fish? YES!