regional case study of alkylphenol ethoxylates1

1. Regional Case Study of Alkylphenol Ethoxylates1 Region 5 US EPA Al Alwan, George Azevedo, John Dorkin, Dan Hopkins, Peter Howe, Bryan Nielsen, Mari Nord, Rob Pepin, Robert L. Thompson, Marc Tuchman, Dennis Wesolowski, Larry Zintek

3. Alkylphenolpolyethoxylates(APEs) Degradation products Extremely toxic to aquatic organisms Will probably be the regulatory end point Endocrine disruption to aquatic organisms To date water quality standards have not addressed this

4. Common Environmental Metabolites of Nonylphenol Ethoxylates (Adapted from Ahel et al., 1994; Naylor, 1992)

5. DAILY ENVIRONMENT

6. Canadian Environmental Protection Act (CEPA)Priority Substance List Assessment ReportNonylphenol and Its Ethoxylates It is proposed that NP and its ethoxylates be considered �toxic� as defined in Section 64 of the CEPA.

7. Brief APE Literature Review(�Slightly� Biased)

8. NP Bioconcentration Factors Bluegill 220 Fathead Minnow 271 Fathead Minnow 293

9. Depuration Half-Life (Hours) Gammerus pulex 38 Killifish 9 Mussels 7 Salmon 96

10. NP Aquatic Criteria Document (draft March 2003) Freshwater Chronic criterion : 5.9 ppb Acute criterion : 27.9 ppb Saltwater Chronic criterion : 1.4 ppb Acute criterion : 6.7 ppb

11. Canadian Risk Assessment Based on cumulative toxicity of all APEs Estimated toxicity of NP1EO and NP2EO at half that for NP Recognized endocrine disruption but was not the major regulatory end point �Apparently� APEs will be controlled through mandatory pollution prevention

12. Japanese killifish chart

13. Additional ORD / Region 5 Activities ORD provided funds for Region 5 Central Regional Laboratory to conduct acute toxicity testing on NP1EO and NP2EO to develop TEQ for aquatic toxicity QAPP under development

14. British Streams Summary(Johnson and Sumpter 2001) Hypothesized Endocrine Disruption Effects in Fish Outside Immediate Discharge Due Primarily to: 17 a-ethinylestradiol (EE2) Major Issue is How Far Downstream EE2 Persists Alkylphenols

15. Biomarkers for Endocrine Disruption (ED) in Fish Decrease or cessation of egg production Imposex Oocytes in testes Vitellogenin (VTG) - Egg yolk protein formed primarily in female fish Produced by liver in response to estrogen Males can produce if exposed to estrogen or estrogen mimics NP exposure known to cause all of these effects Relevance to population effects needs to be addressed

16. NP Endocrine Disruption in Fathead Minnows Miles-Richardson et al. (1999) NOAEL estimated from effects on endocrine disruption six fold less than standard chronic toxicity for early life stage of fathead minnow Question biological relevance of endocrine disruption to fish populations Acknowledged that risk assessment does not include APEs other than NP

17. Other Considerations Related to Endocrine Disruption in Effluent Dominated Streams Hormones are another major factor

18. Effects of Exposure to 17 �-estradiol Effects of Exposure to 17 �-estradiol (E2) to Male Fathead Minnows1 Threshold for histologic changes in testes = ~ 0.04 ppt Threshold for vitellogenin induction = ~ 0.04 ppt 1(Miles-Richardson et al., 1999) Effluent Concentrations2 17 �-estradiol effluent concentrations at four Michigan STPs Average = 1.5 ppt ( range = nd � 3.7 ppt ) 2(Snyder et al., 1999)

19. Relative Potencies of Steroidal Estrogens in Fish (Thorpe et al., 2003) VTG induction in 14 day exposure to juvenile female rainbow trout EE2 > E2 > E1 (Estrone)

20. Minneapolis Metro Plant Inconsistencies Male fish collected in effluent Carp VTG increase and testosterone decrease (Folmar et al., 1996) Walleye VTG increase and testosterone decrease (Folmar et al., 2000) Laboratory Study Goldfish, exposed to effluent samples for 10 weeks exhibited no change in testosterone. (Schoenfuss et al., 2002)

21. Metro Minneapolis Walleye APE Fish Tissue Concentrationsppm (�g/g wet weight) NP = 0.2 NP1EO = 2.0 NP2EO = 3.1 NP3EO = 0.8 NP4EO = 0.1 NP5EO = 0.0 Total = 6.2

22. Fox River (Wisconsin) 1995 APEConcentrations (�g/L)15 paper mill effluents ranked

23. Fox River (Wisconsin) 1995 APEConcentrations (�g/L)6 POTW�s ranked

24. Fox River APE Concentrations (�g/L)(Upstream Green Bay WWTP)

25. Alkylphenol Effluent Concentrations (�g/L) at 8 Large Region 5 POTW'sFebruary and March 1998 (Barber et al., 2000)

26. Environment Canada graph

27. Chicago Waterways

28. Major Chicago WTPs Flow

29. Estimated Percent of Daily Flow at Lockport Due to Combined Effluent Flow From MWRGDC WRP�s in 2002

30. Chicago Waterway 7 Day average Flows and Total Precipitation

31. Region 5 CRL APEs Method Initiative

32. Chicago Waterways

33. Chicago Waterways

34. North Branch Chicago River Alkylphenol Sediment Concentrations (PPM)

35. Average Concentration of NP and NPEs in Carp from North Branch Chicago River1

36. National Pollution Discharge Elimination System (NPDES) Permits Water Quality Based Effluent Limits (WQBEL) Controls traditional toxics Question whether WQBEL�s facilitate full recovery of large effluent dominated streams

37. MWRDGC and Region 5 Central Regional Laboratory Toxicity Testing Cooperative Whole Effluent Toxicity (WET) testing at 3 major WRP�s To date no chronic toxicity Region 5 Chicago Waterways toxicity testing at Lockport To date no chronic toxicity

38. MWRDGC Stream Quality graph

39. Other Contributing Factors Combined Sewer Overflows Contaminated sediments Barge traffic Habitat limitations

40. Conclusions Widespread APE occurrence in Region 5 water, sediment and fish tissue Appears that some effluents may exceed proposed water quality criteria for NP Region 5 Central Regional Laboratory has SOP for NP, NP1EO and NP2EO Region 5 developing TEQ for NP, NP1EO and NP2EO to account for the toxicity of ethoxylates Consideration should be given to phasing out APEs in US due to increased cost associated with removing from POTW effluents