2. Status of current USGS work in the Assabet River

3. Overview of our knowledge of endocrine disrupting chemicals in the environment

4. Monitoring Progress Toward Meeting the Assabet River Phosphorus TMDL In cooperation with MassDEP

5. Duckweed (light green) and algae (dark green) cover the surface of Ben Smith impoundment on the Assabet River

6. TMDL objectives investigated by USGS Reduced concentrations of total and dissolved phosphorus in Assabet impoundmentsReduced concentrations of total and dissolved phosphorus in Assabet impoundments 90% decrease in release of phosphorus from riverine and impoundment sediments90% decrease in release of phosphorus from riverine and impoundment sediments 50% reduction in the extent and biomass of aquatic plants, primarily Lemna (duckweed)50% reduction in the extent and biomass of aquatic plants, primarily Lemna (duckweed)

7. Endocrine Disruptors in the Environment, An Overview

9. Boston Globe 10 March 2008

10. Flame retardant PBDE found in Lake Michigan, adding to concerns (Wisc.) Test finds Boulder Creek is potpourri of chemicals (Col.) Drugs found in tap water (W. Va.) Frogs, fish and pharmaceuticals a troubling brew: Prozac, other drugs detected in streams and their inhabitants (Nat’l) Old water tests, new pollutants, worry scientists (Ala.) Septic systems grow dangerously close (Fla.) Drugs From Waste Water Found in River Drinking water may be at risk (Conn.) The bactericidal agent triclosan modulates thyroid hormone-associated gene expression and disrupts postembryonic anuran development Common Industrial Chemicals In Tiny Doses Raise Health Issue (WSJ) Premature births may be linked to seasonal levels of pesticides and nitrates in surface water (Ind.) Water is becoming a dangerous drug Gender-bending industrial chemicals are skewing the birth ratio in favor of baby girls. Could a world without men be a few short generations away? Intersex in Smallmouth Bass Coincident with Population and Agriculture in Potomac Watershed Other headlines you may have read Everyday chemicals gather in most people (Alaska)

11. Emerging Contaminants

12. Emerging Contaminants? PPCP’s EDC’s PhAC’s HAA’s OWC’s EPOCs AWI’s CEC’s CPC’s ES’s

13. Human Drugs Vet. Drugs Antibiotics Hormones Steroids Detergents Plastics Pathogens Antioxidants Fire retardants Disinfectants Fumigants Fragrances Insecticides/ Repellants Nanomaterials Emerging Contaminants? PPCP’s EDC’s PhAC’s HAA’s OWC’s EPOCs AWI’s CEC’s CPC’s ES’s

14. Endocrine Active Compound EAC Organochlorine pesticidesOrganochlorine pesticides Polychlorinated biphenyls (PCBs)Polychlorinated biphenyls (PCBs) Heavy metalsHeavy metals PharmaceuticalsPharmaceuticals SurfactantsSurfactants Flame retardants (PBDEs)Flame retardants (PBDEs) PlasticizersPlasticizers

15. Chemicals we use daily can enter the waste stream and, eventually, the environment. From our homes and workplaces To our water resources

16. WWTPWWTP CSOsCSOs Industrial DischargesIndustrial Discharges LandfillsLandfills Water Reuse/RechargeWater Reuse/Recharge Human Waste Pathways

17. Agricultural sources

19. Next, some history…

20. EDCs in the environment

21. Buser and others, 1998 “Occurrence of the [cholesterol- lowering] pharmaceutical drug clofibric acid and the [household] herbicide mecoprop in various Swiss Lakes and in the North Sea”“Occurrence of the [cholesterol- lowering] pharmaceutical drug clofibric acid and the [household] herbicide mecoprop in various Swiss Lakes and in the North Sea”

22. Jobling and others, 1998 “Widespread Sexual Disruption in Wild Fish”“Widespread Sexual Disruption in Wild Fish” –Related high incidence of intersex characteristics in fish to levels of hormonally active chemicals detected downstream from wastewater treatment plants

23. - Streams (1999-2000) - Ground Water (2000) - Sources of Drinking Water (2001) - Streambed Sediment (2002) Occurrence - National Reconnaissance Studies ES&T; March 15, 2002 v. 36, no. 6, p. 1202-1211

24. National Reconnaissance Surveys (USGS Toxic Substances Hydrology Program) http://toxics.usgs.gov/regional/emc.html

25. USGS Stream Reconnaissance 139 streams were sampled for 95 compounds.139 streams were sampled for 95 compounds. 82 compounds were detected at least once in 80% of the streams.82 compounds were detected at least once in 80% of the streams. As many as 38 compounds were detected in a single sample.As many as 38 compounds were detected in a single sample. 33 of the 95 target compounds were known or suspected endocrine disruptors. All 33 were detected.33 of the 95 target compounds were known or suspected endocrine disruptors. All 33 were detected. Concentrations of all compounds were generally low and rarely exceeded DW guidelines, health advisories, or aquatic-life criteria.Concentrations of all compounds were generally low and rarely exceeded DW guidelines, health advisories, or aquatic-life criteria. But, many of the compounds have no guidelines.But, many of the compounds have no guidelines.

26. Endocrine disruptor effects on fish Intersex in fishIntersex in fish –Presence of oocytes in male gonad –Presence of spermatocytes in female gonad Female-biased sex ratiosFemale-biased sex ratios Impaired testicular function (reduced sperm abundance)Impaired testicular function (reduced sperm abundance) Impaired ovarian function (asynchronous ovary development)Impaired ovarian function (asynchronous ovary development) Elevated vitellogenin (protein associated with eggs) levels in malesElevated vitellogenin (protein associated with eggs) levels in males

28. Rodgers-Gray and others, 2001 “Exposure of Juvenile Roach (Rutilus rutilus) to Treated Sewage Effluent Induces Dose-Dependent and Persistent Disruption in Gonadal Duct Development”“Exposure of Juvenile Roach (Rutilus rutilus) to Treated Sewage Effluent Induces Dose-Dependent and Persistent Disruption in Gonadal Duct Development”

29. Hinck and others, 2009 “Widespread occurrence of intersex in black basses (Micropterus spp.) from U.S. rivers, 1995-2004”“Widespread occurrence of intersex in black basses (Micropterus spp.) from U.S. rivers, 1995-2004” –Widespread incidence of intersex in 9 major U.S. river basins –Most common in black (largemouth and smallmouth) bass –Reinforced findings of Blazer and others (2007) from Potomac River –Size of basins makes it difficult to determine causality

30. Boulder Creek, Colorado, study Vaida and others (2008) “Reproductive Disruption Downstream from an Estrogenic Wastewater Effluent”“Reproductive Disruption Downstream from an Estrogenic Wastewater Effluent” –Of 22 PPCPs and 44 Organic Wastewater Chemicals looked for, 12 PPCPs and 32 OWCs were present, including a number of EDCs. –Native fish populations were found to exhibit endocrine disruption, including low male-to- female sex ratio and fish having both female and male reproductive organs.

31. Boulder Creek <0.8 ng/L 2.1 ng/L 1.4 ng/L 2.9 ng/L 1.2 ng/L 17b-Estradiol in stream water <0.8 ng/L 2.1 ng/L 1.4 ng/L 2.9 ng/L 1.2 ng/L

32. Iwanowicz and others, 2009 “Reproductive health of bass in the Potomac, USA, drainage: Part 1. Exploring the effects of proximity to wastewater treatment plant discharge”“Reproductive health of bass in the Potomac, USA, drainage: Part 1. Exploring the effects of proximity to wastewater treatment plant discharge” –Combinations of EDCs from WWTPs seem to have a substantial effect on reproductive health of fish and the effects observed are also more widespread due to other (agricultural, suburban, and urban runoff) sources.

33. Alvarez and others, 2009 “Reproductive health of bass in the Potomac, USA, drainage: Part 2. Seasonal occurrence of persistent and emerging organic contaminants”“Reproductive health of bass in the Potomac, USA, drainage: Part 2. Seasonal occurrence of persistent and emerging organic contaminants” –84 of 138 targeted organic wastewater indicators and agricultural pesticides were detected in the Potomac River. Ag chemical concentrations spiked in the spring; other target analyte concentrations did not change seasonally. –Screening tests indicated the presence of compounds capable of inducing estrogenic responses.

34. Do chronic, low-level exposures affect wild populations of fish?

35. Kidd and others, 2007 “Collapse of a fish population after exposure to a synthetic estrogen”“Collapse of a fish population after exposure to a synthetic estrogen” –A 7-year, whole-lake study in Canada’s Experimental Lakes Area in northwestern Ontario –For the first 3 years, scientists applied a synthetic estrogen (used in birth control pills) at concentrations seen in municipal wastewater receiving waters (5-6 parts per trillion) to observe effects on the fathead minnow. –During the remaining 4 years, the effects were studied.

36. Observed effects on the fathead minnow Males produced female proteinsMales produced female proteins Intersex (male and female tissues in individuals)Intersex (male and female tissues in individuals) Other gonadal tissue deformities in malesOther gonadal tissue deformities in males Delayed ovarian development in femalesDelayed ovarian development in females

37. Population effects After 2 years of application, the minnow population crashed almost to extinction in the lake.After 2 years of application, the minnow population crashed almost to extinction in the lake. Following 3 years of application, population limped along for 2 more years before starting to rebound.Following 3 years of application, population limped along for 2 more years before starting to rebound.

38. It’s not all just about fish.

39. KRAJNIAK (2005) “Annelid Endocrine Disruptors and a Survey of Invertebrate FMRFamide- Related Peptides”“Annelid Endocrine Disruptors and a Survey of Invertebrate FMRFamide- Related Peptides” –In annelids, EDCs cause decreases in growth and reproductive output, delay sexual maturation, and inhibit the immune system.

40. Fluoxetine (antidepressant): Found in fish tissue at significant concentrations (Brooks et al., 2005).Fluoxetine (antidepressant): Found in fish tissue at significant concentrations (Brooks et al., 2005). Carbamazepine (antiepileptic): Sediment exposure of benthic insect (Oetkin, et al., 2005).Carbamazepine (antiepileptic): Sediment exposure of benthic insect (Oetkin, et al., 2005). Triclosan (antimicrobial disinfectant): Effects thyroid in frogs (Veldhoen et al., 2006).Triclosan (antimicrobial disinfectant): Effects thyroid in frogs (Veldhoen et al., 2006). Diclofenac (non-steroidal anti-inflammatory): Consumption of diclofenac-treated meat caused renal failure in vultures (Oaks et al., 2004).Diclofenac (non-steroidal anti-inflammatory): Consumption of diclofenac-treated meat caused renal failure in vultures (Oaks et al., 2004). Additional studies demonstrating evidence of ecological effects of EDCs

41. Antibiotics: Reduced soil microbial activity at Environmental Concentrations (Costanzo et al., 2005; Thiele-Bruhn and Beck, 2005).Antibiotics: Reduced soil microbial activity at Environmental Concentrations (Costanzo et al., 2005; Thiele-Bruhn and Beck, 2005). Ciprofloxacin, triclosan, Tergitol NP 10: shifts in algal community structure (Wilson et al., 2003).Ciprofloxacin, triclosan, Tergitol NP 10: shifts in algal community structure (Wilson et al., 2003). Mixture of 5 EDCs: Total estrogenicity affected fathead minnow reproduction (Brian et al., 2007).Mixture of 5 EDCs: Total estrogenicity affected fathead minnow reproduction (Brian et al., 2007). Drug Mixtures: 13 drugs at environmental levels inhibited growth of human embryonic cells (Pomati et al., 2006).Drug Mixtures: 13 drugs at environmental levels inhibited growth of human embryonic cells (Pomati et al., 2006). Additional studies, continued

42. Local studies Draft report, in review: “A multi-metric assessment of environmental contaminant exposure and effects in an urbanized reach of the Charles River near Watertown, MA”Draft report, in review: “A multi-metric assessment of environmental contaminant exposure and effects in an urbanized reach of the Charles River near Watertown, MA” –“This data report provides results from the fish health analysis, biomarkers of exposure and effects (i.e., reproductive, carcinogenic, genotoxic, and immunologic), sediment chemistry, toxicity, and fish/invertebrate community structure.” On-going study: “Assessment of Endocrine Disruption in Smallmouth Bass (Micropterus dolomieu) and Largemouth Bass (M. salmoides) in Region 5 National Wildlife Refuges”, including Great Meadows NWROn-going study: “Assessment of Endocrine Disruption in Smallmouth Bass (Micropterus dolomieu) and Largemouth Bass (M. salmoides) in Region 5 National Wildlife Refuges”, including Great Meadows NWR

43. Tributaries to the lower Charles River

44. Faneuil Brook

45. Laundry Brook

46. Organic wastewater contaminants detected in lower Charles River basin Diazinon (pest.)Diazinon (pest.) Carbaryl (pest.)Carbaryl (pest.) OPEO1 (d.m.)OPEO1 (d.m.) NPEO1(d.m.)NPEO1(d.m.) NPEO2 (d.m.)NPEO2 (d.m.) Para-nonylphenol (d.m.)Para-nonylphenol (d.m.) Bisphenol A (plast.)Bisphenol A (plast.) Tris(2-butoxy-ethyl) phosphate (f.r.)Tris(2-butoxy-ethyl) phosphate (f.r.) Para-cresol (pres.)Para-cresol (pres.) Diethylphthalate (plast.)Diethylphthalate (plast.) Tetrachlorethylene (PCE)Tetrachlorethylene (PCE) Phthalic anhydridePhthalic anhydride DEETDEET PhenanthrenePhenanthrene FluoroantheneFluoroanthene Cis-chlordaneCis-chlordane PyrenePyrene BenzopyreneBenzopyrene CoprostanolCoprostanol ChloresterolChloresterol Suspected or known endocrine disruptors; other contaminants

47. PharmaceuticalsPharmaceuticals –Painkillers (acetaminophen, ibuprofen) –Antacid (cimetidine) Antibiotics (trimezoprim, erithromycin, lincomycin)Antibiotics (trimezoprim, erithromycin, lincomycin) Hormones and steroids (androsterone, estriol, estrone, ethynyl estradiol)Hormones and steroids (androsterone, estriol, estrone, ethynyl estradiol) Stimulant (caffeine)Stimulant (caffeine) PPCPs detected in the lower Charles River Basin

48. Merrimack and Blackstone River basins surface water and groundwater raw (untreated) water supplies, 2001

49. PPCPs detected in Merrimack and Blackstone basins raw drinking-water supplies: CaffeineCaffeine Trimethoprim (antibiotic)Trimethoprim (antibiotic) Carbamazepine (antidepressant)Carbamazepine (antidepressant) Cotinine (nicotine breakdown product)Cotinine (nicotine breakdown product) AcetaminophenAcetaminophen Triclosan (anti-bacterial in liquid soaps)Triclosan (anti-bacterial in liquid soaps) Diphenhydramine, a.k.a., benadryl (antihistamine)Diphenhydramine, a.k.a., benadryl (antihistamine)

50. Suspected or known EDCs detected in the Merrimack and Blackstone River basins raw drinking water supplies Tris(dichlorisopropyl)- phosphate (f.r.)Tris(dichlorisopropyl)- phosphate (f.r.) Tris(2- chloroethyl)phosphate (f.r.)Tris(2- chloroethyl)phosphate (f.r.) Tris(2-butoxy- ethyl)phosphate (f.r.)Tris(2-butoxy- ethyl)phosphate (f.r.) Benzopyrene (PAH)Benzopyrene (PAH) Diazinon (pest.)Diazinon (pest.) Triclosan (anti- microbial)Triclosan (anti- microbial) 17β estradiol (hormone)17β estradiol (hormone) 1,4-dichlorobenzene (deod.)1,4-dichlorobenzene (deod.) Benzophenone (frag.)Benzophenone (frag.) Para-nonylphenol (d.m.)Para-nonylphenol (d.m.) Pentachlorophenol (pres.)Pentachlorophenol (pres.) Bisphenol A (plast.)Bisphenol A (plast.) NPEO2 (d.m.)NPEO2 (d.m.) AHTN (frag.)AHTN (frag.) HHCB (frag.)HHCB (frag.)

51. Occurrence of Organic Wastewater Contaminants, Pharmaceuticals, and Personal Care Products in Selected Water Supplies, Cape Cod, Massachusetts, June 2004

52. Cape Cod Of 13 different PPCPs and OWCs (or their breakdown products) detected in samples from public, semipublic, and private water supply wells, 3 were suspected EDCs.Of 13 different PPCPs and OWCs (or their breakdown products) detected in samples from public, semipublic, and private water supply wells, 3 were suspected EDCs. Of the 21 PPCPs and OWCs detected in monitoring (not drinking-water) wells as far as 1 mile from a municipal wastewater treatment plant, 5 were suspected EDCs.Of the 21 PPCPs and OWCs detected in monitoring (not drinking-water) wells as far as 1 mile from a municipal wastewater treatment plant, 5 were suspected EDCs.

53. Standley and others, 2008 “Wastewater-contaminated groundwater as a source of endogenous hormones and pharmaceuticals to surface water ecosystems”“Wastewater-contaminated groundwater as a source of endogenous hormones and pharmaceuticals to surface water ecosystems” –Wastewater compounds discharged to groundwater were detected in surface water ponds on Cape Cod.

54. Promising methods for wastewater and drinking water treatment: Reverse osmosis Ozonation Activated charcoal Other absorbents Some good news

55. Removal of wastewater compounds Spring 2004, special issue of Ground Water Monitoring and Remediation, Volume 24 Number 2Spring 2004, special issue of Ground Water Monitoring and Remediation, Volume 24 Number 2 –Laboratory and field studies indicated that many, but not all, compounds were removed in part or to undetectable levels when wastewater was used for recharge. –Some compounds persist in groundwater, reach surface water and may enter water supplies.

56. Estrogen removal in wastewater treatment process (Servos and others, 2005) Some mixed results, but…Some mixed results, but… –High solid retention times in treatment plants or lagoons were effective at reducing hormone levels. –Effectively operating plants achieving nitrification also had relatively high hormone removal.

57. Barber and others (2007) “Reproductive responses of male fathead minnows exposed to wastewater treatment plant effluent, effluent treated with XAD8 resin, and an environmentally relevant mixture of alkylphenol compounds”“Reproductive responses of male fathead minnows exposed to wastewater treatment plant effluent, effluent treated with XAD8 resin, and an environmentally relevant mixture of alkylphenol compounds” –Reproductive responses were strongest from exposure to untreated effluent. Resin treatment resulted in weaker responses.

58. Phillips and others (2005), “A Multi-Disciplinary Approach to the Removal of Emerging Contaminants in Municipal Wastewater Treatment Plants in New York State (2003-2004)” Median percent reduction in all EC compounds EC removal was associated with increasing Sludge Retention Time (SRT)

59. Not all wastewater goes into wastewater treatment plants.

60. Operated by Barnstable County Department of Health and the Environment In cooperation with Massachusetts DEP New England Region EPA TEST CENTER

61. Testing of onsite systems Fewest PPCPs were detected following passage through standard Massachusetts Title 5 septic system (2’ aggregate on top of 5’ of sand).Fewest PPCPs were detected following passage through standard Massachusetts Title 5 septic system (2’ aggregate on top of 5’ of sand). Title 5 systems are primarily designed to remove solids, BOD, not to nitrify.

62. In summary EDCs enter waterways from waste disposal (point sources) and from agricultural and urban runoff (non-point sources).EDCs enter waterways from waste disposal (point sources) and from agricultural and urban runoff (non-point sources). Waste-disposal sources seem to have the most immediate and strongest effects.Waste-disposal sources seem to have the most immediate and strongest effects. EDCs are highly variable in their environmental persistence and ability to migrate in groundwater and surface water.EDCs are highly variable in their environmental persistence and ability to migrate in groundwater and surface water. Other contaminants serve to complicate the story of ecosystem impairment.Other contaminants serve to complicate the story of ecosystem impairment.

63. Summary, continued Traditional toxicity testing is probably not appropriate for determining environmental effects of EDCs that occur in extremely low concentrations; estrogenicity testing is one approach.Traditional toxicity testing is probably not appropriate for determining environmental effects of EDCs that occur in extremely low concentrations; estrogenicity testing is one approach. EDCs, at concentrations now detectable in the environment, affect the reproductive capacity of aquatic organisms and have the potential to drive isolated populations to extinction.EDCs, at concentrations now detectable in the environment, affect the reproductive capacity of aquatic organisms and have the potential to drive isolated populations to extinction.

64. Summary, continued WWTPs were not designed to remove emerging contaminants.WWTPs were not designed to remove emerging contaminants. However, many of the general improvements to WWTPs have resulted in greater removal of some emerging contaminants.However, many of the general improvements to WWTPs have resulted in greater removal of some emerging contaminants. Although we can measure removal, we don’t know the ultimate fate of many emerging contaminants.Although we can measure removal, we don’t know the ultimate fate of many emerging contaminants.

65. Research Plan for Endocrine Disruptors USEPA/600/R-98/087, February 1998

66. Some key questions have been answered in part, or are objects of current research, but many still remain: What are the major sources and environmental fates of EDCs?What are the major sources and environmental fates of EDCs? What are the chemical classes of interest and their potencies?What are the chemical classes of interest and their potencies? How and to what degree are human and wildlife populations exposed to EDCs?How and to what degree are human and wildlife populations exposed to EDCs? What EDC-related effects are occurring in exposed human and wildlife populations?What EDC-related effects are occurring in exposed human and wildlife populations? What are the effects of exposure to multiple EDCs, and will a toxicity equivalency factor (TEF) approach be applicable?What are the effects of exposure to multiple EDCs, and will a toxicity equivalency factor (TEF) approach be applicable? Do testing guidelines adequately evaluate potential endocrine- mediated effects?Do testing guidelines adequately evaluate potential endocrine- mediated effects? What are the dose-response characteristics in the low-dose region?What are the dose-response characteristics in the low-dose region? What extrapolation tools are needed?What extrapolation tools are needed? How can unreasonable risks be managed?How can unreasonable risks be managed?