Contaminant ta Assessment & Risk Evaluation

Transcription

1 The presence of Endosulfan Sulfate Residues in Water, Sediment and Biological Samples in South Florida: Potential Environmental Implications i South Florida CARE Contaminant ta Assessment & Risk Evaluation Piero Gardinali, Adolfo Fernandez, Gary Rand, John Carriger Tham Hoang and Joffre Castro National Park Service Cooperative Science GEER July 14, 21

2 Contaminants in South Florida: the old picture Publications Miles & Pfeuffer (1997) Miller & McPherson (21) Scott et al. (22) Key et al. (23) Caccia et al. (23) Fulton et al. (24) Monitoring Programs SFWMD USGS NOAA DERM USDA-ARS FIU

3 DDT, DDD and DDE: environmental legacy Paul Hermann Müller won the 1948 Nobel Prize in Physiology or Medicine for his 1939 discovery of DDT as an insecticide useful in the control of malaria, yellow fever and many other insect-vector diseases. DDT SOIL SEDIMENT ORGANISMS p,p -DDT + o,p-ddt H DDE DDD DDMU, DDA, DBP Rappolt, RT (1973). "Use of oral DDT in three human barbiturate intoxications: hepatic enzyme induction by reciprocal detoxicants". in Toxicol 6 (2):

4 Endosulfan: The Last Chlorinated Pesticide? O O S O Endosulfan (Thiodan) is a commercial mixture of two active isomers O O S O Controls wide range of insect pests Residual effects Used on white flies, army worms and caterpillars in South Florida tomato regions (3 lb/acre) Used on non-food crops (cotton, tobacco, ornamentals) and food crops (vegetables, fruits, cereals)

5 Endosulfan: The Last Chlorinated Pesticide? O O S O Onlyremaining organochlorine insecticide registered under USEPA FIFRA In use since 195 s but not produced in US since 1982 assified as a persistent organic pollutant (POP) Persistence Accumulation Long-range transport Scheduled for inclusion in the Stockholm Convention Canada ada (27) under consideration sde ato for phase-out Phased out in EU in 27 (18 month grace period)

6 Endosulfan: The Last Chlorinated Pesticide? O O S O Will likely be replaced by organophosphates and pyrethroids Still clear advantages will NOT develop pest resistant Endosulfan is volatile Endosulfan is more persistent Endosulfan sulfate is the main metabolite Endosulfan sulfate is the only compound present in fish Fish are the most sensitive non-target organisms

7 GEER 28: Endosulfan in Organisms FIU-ENP (Fish) and NOAA MW (Oysters) Map provided by Max Feken

8 What criteria is available for management? Available Environmental Criteria i Florida Section Table: Criteria for Surface Water Quality assifications (Effective July 27, 25) ass I ass II ass III Freshwater ass III Marine.56 g/l.87 g/l.56 g/l.87 g/l Hawaii (1999) Freshwater Wildlife Acute.22 g/l Chronic.56 g/l Hawaii Saltwater Wildlife Acute Chronic (1999).34 g/l.87 g/l Colorado (1999) Freshwater Wildlife Acute.11 g/l Chronic.56 g/l This guidelines apply only to Endosulfan or but not to Endosulfan Sulfate

9 Surface Waters: SFWMD Data ENDOSULFAN AT S CO ONCENTRAT TION, ug/l ug/l ES. E(I+II) FDEP CRITERION

10 What has changed since then: The endosulfan residues of toxicological i l concern are: α-endosulfan, d β-endosulfan, and endosulfan sulfate. For purposes of conducting the endosulfan risk assessment, the Agency (EPA) assumed that the 3 residues of toxicological concern are approximately equal in toxicity due to their similar structures and physicochemical properties. (EPA-HQ-OPP )

11 What has changed since then: The chronic toxicity of endosulfan to freshwater fish is estimated as low as.2323 μg/l (estimated NOAEC), which is about half of EPA s freshwater chronic water quality criterion of.56 μg/l. Chronic toxicity of freshwater invertebrates is estimated as low as.11 μg/l (estimated NOAEC). Chronic effects associated with NOAECs used to derive these toxicity reference values include impacts on survival, growth and reproduction.. (EPA-HQ-OPP )

12 EPA Risk Assessment 21 (EPA-HQ-OPP )

13 EPA Risk Assessment 21 (EPA-HQ-OPP )

14 EPA Risk Assessment 21 (EPA-HQ-OPP )

15 How toxic is the metabolite? Sensitivity Rank Fish Arthropods Rainbow Trout Tilapia Golden Perch Stripped Bass Daphnia Gammarus f. Gammarus l. Mosquitofish Fathead Silver Perch Stonefly Harlequinfish Rainbowfish Catla Carp SSD 1th Centile=.11 µg/l Bream Common Carp Not all species behave the same way Total Endosulfan (µg/l) DATA ARE FOR ENDOSULFAN ONLY NOT THE METABOLITE

16 How toxic is the metabolite? Sensitivity Rank Fish Arthropods Rainbow Trout Tilapia Golden Perch Stripped Bass Daphnia Gammarus f. Gammarus l. Mosquitofish Fathead Silver Perch Stonefly Harlequinfish Rainbowfish Catla Carp SSD 1th Centile=.11 µg/l Bream Common Carp Not all species behave the same way Total Endosulfan (µg/l) DATA ARE FOR ENDOSULFAN ONLY NOT THE METABOLITE

17 Is the metabolite as toxic and the parent compounds? Bluegill sunfish LC g/l (EPA 27) * * Fathead Minnow LC g/l (FIU) Mosquitofish LC g/l (FIU) 1% Mortality hours S ug/L *Data generated at FIU Carriger at al., (21) Arch Environ Contam Toxicol 58:

18 Bioconcentration in Fish? Only ES present in tissue 1 8 Uptake by Mugil cephalus ENDOSULFAN SULFATE Ct t 56.8(1.36 ) wet basis Tissue concen ntration in ng/g ENDOSULFAN I ENDOSULFAN II BCF = 1622 MDL MDL Schimmel et al 1977 Mullet (25 mm) Mugil cephalus Uptake and depuration from water at.35 g/l for 28 days Commercial formulation (Thiodan) Only ES accumulated Edible ~Whole tissue Modeled BCF 1622 Rapid elimination <48h Time (days) MDL

19 Depuration fast but data scarce tion (ng/g DW) Tissue Concnetra y = e.626x r 2 =.9437 Uptake phase Depuration phase Model prediction Sub-lethal exposure 9 th centile.1 ug/l Endosulfan sulfate 4 35 days Time (days) T½=11 days >>> 48 hours Hoang et al., (21) In preparation. 19 * Modeled after Schimmel et al. 1977

20 Worst case scenario: Loveland Slough Intensive Water Sediment Fish Benthic Endosulfan

21 Surface water concentrations at S-178: Localized? 18 Endo osulfan concn netration (ng/l L) ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I S178 S Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9)

22 Surface 18 water concentrations 18 ation (ng/l) Endosulfan concnetra ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I 332B ation (ng/l) Endosulfan concnetra ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I S-176E Endosulfan concnetra ation (ng/l) ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I C Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9) 2 Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9) 2 Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9) (ng/l) ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I C concnetration (ng/l) ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I S-176S Endosulfan concnetration Endosulfan 6 4 Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9) 2 Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9) ncnetration (ng/l) Endosulfan co ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I S-18C (ng/l) Endosulfan concnetration ENDOSULFAN SULFATE ENDOSULFAN II ENDOSULFAN I S-178 Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9) 2 Nov(8) Dec(8) Jan(9) Feb(9) Mar(9) Apr(9) May(9)

23 Residues in whole fish: Endosulfan sulfate ONLY ENDOSULFAN SULFATE IN FISH TISSUE ENDOSULFAN SULFATE IN FISH TISSUE Endosulfan Sulfate (ng/g dry wt t.) East Boundary C-111 Tamiami Shark Slough FL Bay Loveland East Boundary C-111 Tamiami Taylor Slough Shark Slough Florida Bay West Boundary

24 Distribution of fish concentrations

25 Other organisms? 1 NOAA's Mussel Watch Joe Bay (FBJB) S-178 CLAM S-178 MUSS ight) tion (ng/g dry we Concentrat EI EII 8 ES

26 Endosulfan Fate and Transport SPRAY AND DUST DRIFT 9 pg/m3 VOLATILIZATION?? RAIN <7ng/L?? ADSORPTION???? RUNOFF LEACHING 35 ng/g CHEMICAL DEGRADATION BIOLOGICAL DEGRADATION.45 ug/l GROUND WATER?? 188 ng/g 14 ng/g g 12 ng/g CANAL 6 ng/g MARSH

27 A little conclusion slide EPA Moves to Terminate All Uses of Insecticide Endosulfan to Protect Health of Farmworkers and Wildlife Release date: 6/9/21 Contact Information: Dale Kemery WASHINGTON The U.S. Environmental Protection Agency (EPA) is taking action to end all uses of the insecticide endosulfan in the United States. Endosulfan, which is used on vegetables, fruits, and cotton, can pose unacceptable neurological and reproductive risks to farmworkers and wildlife and can persist in the environment For more information: * Modeled after Schimmel et al

28 Another conclusion slide 28 * Modeled after Schimmel et al. 1977

29 But we have to be patient Ban decree June 14, 1972 Enacted December 31, 1972 Last used in the US in June 1979 Produced until 1985 abroad DDE still present in biota today 29 * Modeled after Schimmel et al. 1977