1 Evaluation of Water Contamination from Consumer Product Uses Rick Reiss SOT DC Spring Symposium April 15, 2010 2 Introduction Many consumer products are disposed of down residential drains Transported into sewer systems and potentially released into the environment Contaminate waterways leading to risk to aquatic species Potentially make its way into drinking water Sorb to sludge in sewage treatment plants Some sludge is used as biosolids for agricultural amendment Potential for terrestrial exposures 3 Factors Affecting Potential Risks Quantities used Methods of disposal Dilution into waterway Physicochemical properties Binding to organic matter Aquatic degradation Toxicity to aquatic organisms 4 Summary of Reconnaissance Studies USGS has performed surveys in streams, surface water sources of drinking water, and groundwater Found a variety of antimicrobials, fragrances, flavoring chemicals, pesticides, plasticizers, cosmetics, etc. However, the low levels of most detections raises questions about whether there is a risk Many potential chemicals have not been measured 5 CASE STUDY #1 – TRICLOSAN AQUATIC EXPOSURES 6 Approach Triclosan (2,4,4’-trichloro-2’-hydroxydiphenyl ether) is a broad spectrum bactericide Generally low human toxicity, but high toxicity to algae Recent studies address estrogenic activity Used soaps, detergents, surface cleansers, disinfectants, cosmetics, pharmaceuticals, and oral hygiene products. Most (~95%) of the uses are disposed of down residential drains 7 Purpose of the Study Estimation of the distribution of triclosan concentrations in reaches following WWTP discharge. Based on: Characteristics of reaches Discharge mass from WTTP Physicochemical properties Estimation of risk to aquatic organisms based on most sensitive species in phylogenic groups. 8 Significant Factor Affecting Loading: Dilution at Outfall 9 Factors Affecting Triclosan Loading into Rivers Triclosan loading into river Influent concentration Removal efficiency in WWTP Physical properties of river Dilution pH Suspended sediment concentration Organic carbon content of sediment Physicochemical properties 10 Development of an Aquatic Exposure Model Steady-state model accounting for ionization, sorption with suspended sediment, and complexation with dissolved organic carbon (DOC). Downstream dissipation modeled from results of dieaway studies. Probabilistic inputs developed for effluent concentration, pH, stream velocity, suspended sediment concentration (including organic carbon content), and DOC concentration 11 Characteristics of Reaches EPA’s Clean Water Needs Survey contains extensive data for WWTP facilities. Mean flow, low flow, velocity, pH, and discharge volume Of the 16,024 WWTPs in 1996, sufficient data were available for 11,010 facilities. 12 Mean Flow Dilution at WWTPs 100,000,000 10,000,000 Mean Flow Dilution 1,000,000 100,000 10,000 1,000 100 10 1 0 20 40 60 Cumulative Frequency 80 100 13 Low Flow Dilution (One in 10 years) 10,000,000 1,000,000 Low Flow Dilution 100,000 10,000 1,000 100 10 1 0 20 40 60 Cumulative Frequency 80 100 14 Triclosan Removal in Wastewater Treatment Plants Slough Meltham Crofton Chertsey West Union - II Effluent Influent West Union - I Glendale Loveland Columbus 0 5 10 15 20 25 15 Wastewater Treatment Removal Significant removal due to high sorption to sludge Removal rates: Activated sludge: 94 to 96 percent (4 plants) Trickling filter: 58 to 96 percent (4 plants) Distribution of U.S. treatment plants: (1) activated sludge: 86%, (2) trickling filter: 12%, and (3) primary treatment: 2%. 16 Physicochemical Properties of Triclosan Property Value Molecular Weight 289.6 Water Solubility 12 mg/L Dissociation constant (pKa) 8.14 at 20oC Vapor pressure 7x10-4 Pa at 25oC Partition coefficient (log Kow) 4.8 Aerobic biodegradation in soil 17.4-35.2 day half-life Aqueous photolysis 41-min half-life at pH of 7 and 25oC Adsorption to suspended solids (Koc) 47,454 mg/g 17 Correlation Between Suspended Sediment and Organic Carbon Content Percentage Organic Carbon 100 10 1 0 0 1 10 100 1,000 Suspended Sediment Concentration (mg/L) 10,000 18 Triclosan Die-Away Studies Triclosan dissipation in an 8 kilometer stretch of Cibalo Creek in south central Texas (Morrall et al.): Half-life, dilution-corrected, was 12.8 hours. Half-life, including dilution, was 5 hours Measured triclosan dissipation in the River Aire in the U.K. (Sabaliunus et al.): Half-life, including dilution, was 3.3 hours 19 Summary of Probabilistic Analysis Data on stream characteristics for 11,010 reaches obtained from Needs survey for both mean and low flow dilutions. Suspended sediment and DOC concentration from USGS data, and organic carbon content from correlation. Environmental fate properties of triclosan (e.g., sorption). Die-away rate 20 Estimated Concentrations at Discharge Point 600 Triclosan Conc (ppt) 500 400 Mean Flow 300 Low Flow 200 100 0 5th 10th 25th 50th 75th Percentile 90th 95th 21 Lowest NOECs Across Species Class Species NOEC (ppb) Acute fish (bluegill sunfish, fathead minnow) 100 Acute aquatic invertebrates (Ceriodaphnia dubia) 50 Algae (Scenedesmus subspicatus) 0.67 Aquatic plants (Lemna gibba) 62.5 Chronic fish (rainbow trout) 34 Chronic aquatic invertebrates (Daphnia magna) 40 22 Margins of Safety at Outfall (Low Flow) 10000 1000 50th 100 90th 10 95th 1 23 Margins of Safety 5 Miles Downstream, Low Dissipation (Low Flow) 100000 10000 1000 50th 100 90th 10 95th 1 24 Margins of Safety 5 Miles Downstream, High Dissipation (Low Flow) 1000000 100000 10000 1000 100 10 1 50th 90th 95th 25 Summary of Case Study There should be no direct effects to fish, plants or invertebrates due to triclosan exposures from WWTPs There may be some effects to algae for reaches where the dilution is low (or when the dilution is low) Uncertainties exist regarding degradates of triclosan in water, particularly due to photolysis 26 CASE STUDY #2 – TRICLOSAN TERRESTRIAL EXPOSURES 27 Introduction Triclosan has a high potential to sorb with organic matter Sludge is wastewater treatment plants is very rich in organic matter Some wastewater sludge is used as soil amendments in agriculture 28 Exposure Pathways Direct exposure Earthworms Soil microorganisms Terrestrial plants Secondary exposures Consumption of earthworms (birds and mammals) Fish exposed in water from wastewater effluent (birds and mammals) 29 Triclosan Concentrations in Sludge 18 16 Concentration (ug/g) 14 Max Value Used for 12 10 8 6 4 2 0 Primary Secondary Primary Sludge Sludge Sludge Columbus, OH Digested Sludge Glendale, OH Primary Sludge Digested Sludge Primary Secondary Digested Sludge Sludge Sludge West Union, OH Location and Type of Sludge Primary Secondary Sludge Sludge Loveland, OH 1McAvoy et al. (2002) 30 Endpoint Values for Risk Assessment Species Value Birds, acute (bobwhite quail) LD50 = 862 mg/kg Birds, subchronic (bobwhite quail) LD50 = 577 mg/kg/day Mammals, acute (rats) LD50 = 3700 mg/kg Mammals, chronic (hamsters) NOEL = 75 mg/kg/day Earthworms NOEL >1026 mg/kg Microorganisms HA50 = 236 mg/L Soil respiration and nitrification NOEL = 1 mg/kg Cucumbers NOEC = 1 mg/kg (pre-emergent study in relevant soil) ED50 = 0.74 mg/kg (shoot dry weight in sand) 31 Key Factors in the Exposure Assessment Assumed soil amendment rates 0.5-2.0 kg/m2/year Soil degradation rate 35 day half-life Bioconcentration factors in fish and earthworms 32 Predicted Environmental Concentrations 0.25 Concentration (mg/kg) 0.2 0.15 0.1 0.05 0 soil earthworm EU Default cucumber weight soil earthworm cucumber weight US Ag-land Typical soil earthworm US Ag-land Upper-Bound 33 Margins of Safety for Secondary Fish Exposure 10,000,000 1,000,000 Margin of Safety (log-scale) 100,000 10,000 1,000 100 10 1 Osprey Belted EU FishKingfisher Eating Bird Typical Scenario Mink EU FishEating Mammal Osprey Belted EU FishKingfisher Eating Bird Mink Upper-Bound Scenario EU FishEating Mammal 34 Margins of Safety for Secondary Exposure from Earthworms 100,000,000 10,000,000 1,000,000 Margin of Safety (log-scale) 100,000 10,000 1,000 100 10 1 Short-tailed EU Worm- Herring Gull American EU Worm- Short-tailed EU Worm- Herring Gull American EU WormShrew Eating Woodcock Eating Bird Shrew Eating Woodcock Eating Bird Mammal Mammal Typical Scenario Upper-Bound Scenario 35 Margins of Safety for Terrestrial Plants 1,000 Margin of Safety (log-scale) 100 10 1 Typical Application Upper-Bound Application 36 Conclusions Everything must go somewhere! Especially things that don’t degrade quickly and/or stick to organic matter Risk assessment methods can be applied to address potential exposures in aquatic and terrestrial environments Can be used to differentiate real risks from mere exposures