Validation of a Framework for Evaluating the Potential Effects and Risks of Trace Organic Compounds (TOrCs) to Aquatic Life Carrie Turner, John Wolfe and Jen Daley, LimnoTech Allen Burton, University of Michigan Drew McAvoy, University of Cincinnati WEFTEC Water Environment Federation Annual Conference – New Orleans, LA Session 417 – September 27, 2016 Background • Elevated fish intersex observed below WWTP outfalls – – – Due to exposures to endocrine disrupting compounds (EDCs) (e.g. estrogen) Exposures occur simultaneously with many other stressors (e.g. nutrients, metals, pesticides, PAHs, TDS, temperature, altered habitat, flow) A complex puzzle…… Intersex sturgeon tissue - Diana Papoulias, USGS •3-Year Project for Water Environment & Reuse Foundation (WE&RF) – CEC6R12: Testing and Refinement of the Trace Organics Screening Tool – Refining and validating a screening tool developed in a 1st Phase of WERF research (2010) for evaluating the effects of trace organics (TOrCs) downstream of utilities. © 2011 Electric Power Research Institute, Inc. All rights reserved. 2 WE&RF’s Research on TOrCs • Research Areas – Treatability – Aquatic Ecological Effects – Risk Communications • Project Summary – 50 TOrC-related funded projects • Objective – Help facility and industry managers make decisions https://www.werf.org/c/KnowledgeAreas/TraceOrganics/Trace_Organics_Research_a t_a_Glance.aspx © 2011 Electric Power Research Institute, Inc. All rights reserved. 3 WE&RF Project CEC6R12: Testing and Refining Site Screening Tools (Phase 2) Vision for Screening Tools – Must be useful and usable by utilities • Good fit for existing utility data • Easy to interpret results – Support sound decisions by utilities • Targeted data gathering • Effective source control and treatment – Promote clearer understanding of complex issues • Assist communication with stakeholders & regulators © 2011 Electric Power Research Institute, Inc. All rights reserved. 4 Three Step Framework for Screening Sites for Potential TOrC Risk 1. Determine if biological community is impaired 2. Use existing data to construct lines of evidence for an overall weight-ofevidence assessment of the role of TOrCs in impairment (Level 1 WoE) 3. If warranted, design and conduct a sampling program to generate contemporary datasets for a more detailed weight-of-evidence assessment (Level 2 WoE) © 2011 Electric Power Research Institute, Inc. All rights reserved. 5 1. Assess biological community 2. Qualitative WoE (Existing Data) 3. Semi-Quantitative WoE (New Data) First Level of Screening: Bio Assessment and Level 1 Weight of Evidence • Use existing site data to: – – Characterize level of impairment Evaluate the roles of TOrCs and other stressors • Assign site to a risk level: – – – “High”, “Moderate”, “Low” or “Possible” Concern So management response can be consistent with risk Accounting for uncertainty • Applied to five case study sites with resulting potential risk level of “Moderate” and “Possible” Concern © 2011 Electric Power Research Institute, Inc. All rights reserved. 6 Tools to Assist Use of the Site Screening Risk Framework • Smaller, cost-effective list of TOrCs to monitor • Suggested list of biomarkers to evaluate TOrC effects • Risk Calculator model comparing TOrC exposures to TOrC effect levels • Level 1 WoE site screening assessment and “scoring” tool • Level 2 WoE scoring examples © 2011 Electric Power Research Institute, Inc. All rights reserved. 7 WERF Indicator TOrCs High Treatability No Compound CAS # TOrC Class Priority Indicator Recommended Indicator TOrCs (use all compounds in assessments and as many as possible in monitoring) Ubiquitous Presence/ Absence Indicator Y Y Y Y Y 1 N,N-diethyltoluamide (DEET) 134-62-3 Personal care product 2 Triclosan 3380-34-5 Personal care product 3 Carbamazepine 298-46-4 Pharmaceutical Y Y Y 4 Fluoxetine 54910-89-3 Pharmaceutical Y Y Y 5 Gemfibrozil 25812-30-0 Pharmaceutical Y Y Y 6 Ibuprofen 15687-27-1 Pharmaceutical Y Y Y 7 Meprobamate 57-53-4 Pharmaceutical Y Y Y 8 Sulfamethoxazole 723-46-6 Pharmaceutical Y Y Y 9 Trimethoprim 738-70-5 Pharmaceutical Y Y Y 10 Bisphenol A 80-05-7 Other Y Y Y 11 Caffeine 58-08-2 Other Y Y Y 12 Androstenedione 63-05-8 Hormone Y NA Y 13 17β-Estradiol (E2) 50-28-2 Hormone Y NA Y NA Y NA Y Y Y 14 Estrone 53-16-7 Hormone Nonpoint Source Indicator TOrCs (select 1-2 compounds for assessment and monitoring) Y 15 Fluoranthene1 206-44-0 PAH Y 16 Atrazine 1912-24-9 Pesticide 17 Bifenthrin1 82657-04-3 Pesticide Ya NA 18 Chlorpyrifos1 2921-88-2 Pesticide Y NA 19 Pentachlorophenol1 87-86-5 Pesticide Y NA © 2011 Electric Power Research Institute, Inc. All rights reserved. Y NA 8 Y TOrC Risk Calculator • Predicts the risk of effluent TOrCs in receiving waters to aquatic life – – Exposure based on either measured or predicted effluent TOrC concentrations and in-stream dilution Effects based on either laboratory measured or QSAR predicted acute and chronic toxicity • Already tabulated in Risk Calculator – Risk based on comparing the Predicted Exposure Concentration (PEC) to the Predicted No Effect Concentration (PNEC) using Risk Quotient (RQ) method • RQ = [PEC]/[PNEC] • RQ > 1 indicates potential risk • Benefits – – – – Site specific model Easy to use for utility staff Requires only data for a single site Easily updated with new information/data © 2011 Electric Power Research Institute, Inc. All rights reserved. 9 Risk Calculator Example PNEC RQ = PEC / PNEC = 0.081 / 0.02 PEC © 2011 Electric Power Research Institute, Inc. All rights reserved. 10 Case Study Example, Level 1 Weight of Evidence Tier of Concern: © 2011 Electric Power Research Institute, Inc. All rights reserved. Moderate Concern 11 Level One WoE Scoring (Qualitative) Level 1 WoE Element TOrC Effects TOrC Exposure TOrC Site Factors High WoE Factor Score Multiple surveys show biomarker or other effects Risk quotient for more than one indicator compound is greater than 1 using site-specific measured effluent data and 7Q10 flow Effluent discharge comprises more than 70% of the total stream flow, OR Moderate WoE Factor Score Individual survey shows biomarker or other effects Risk quotient for one indicator compound is greater than 1 using site-specific measured effluent data and 7Q10 flow Effluent discharge comprises between 1% and 70% of the total stream flow, OR WRRF level of treatment is Primary, OR WRRF level of treatment is Secondary or Advanced Secondary, OR Treatment effectiveness is poor, based on sludge residence time and effluent concentrations of TSS, BOD and NH3 Other Stressors Habitat is adversely impacted, OR DO exceeds WQS, OR NH3 exceeds WQS, OR at least 3 parameters are identified as potential stressors © 2011 Electric Power Research Institute, Inc. All rights reserved. Possible WoE Factor Score Evidence of physical deformities, tumors, and lesions Risk quotient for one indicator compound is greater than 1 using literature effluent data and 7Q10 flow Incomplete data WRRF level of treatment is Tertiary, OR Treatment effectiveness is good, OR Treatment effectiveness is moderate, OR At least half of the other risk factors score “High” At least 2 parameters are identified as potential stressors 12 Low WoE Factor Score Individual survey shows NO biomarker or other effects Risk quotient for all indicator compounds is less than 1 using measured or literature effluent data and 7Q10 flow Effluent discharge comprises less than 1% of the total stream flow, OR At least half of the other risk factors score “Moderate” or “Low” One parameter is identified as potential stressor No parameters are identified as potential stressors Second Level of Analysis: More Complete Weight of Evidence (SemiQuantitative) • Where screening indicates at least a Moderate Level of Concern: – – – • Fill in gaps in site chemistry/community/habitat data Additional biomonitoring, upstream and downstream Characterize relationships between TOrCs, other stressors, and aquatic life impairment Two case study sites where initial screening indicated Moderate or Possible Level of Concern – – Validate tools and Level 1 WoE results Advance science of TOrC-related biomarker analysis © 2011 Electric Power Research Institute, Inc. All rights reserved. 13 Sampling to Support Multiple Lines of Evidence • Chemical loadings (in-stream, WWTP) – – TOrCs Conventional: nutrients, metals, solids, BOD5, alkalinity, hardness • Exposure effects – – Caged minnows In-situ caged invertebrates • In situ toxicity identification evaluation • Biological community assessments • Stream physical conditions – – – Habitat Dissolved oxygen, temperature, pH, conductivity via sonde Flow (in-stream and at WWTP) © 2011 Electric Power Research Institute, Inc. All rights reserved. 14 TOrC Exposure Levels and Potential Risk •Potential Risk TorC Compound 4-Nonylphenol Androstenedione (ADS) 25 compounds Atrazine analyzed by Bisphenol A EPA-Cincinnati Caffeine (CFN) Carbamazepine (CBZ) Dihydrotestosterone DNORG (17-Desacetyl Norgestimate) DROS (Drospirenone) Bold compounds = EDA (Ethynodiol Diacetate) Indicator TOrC Estradiol (E2) Estriol Estrone (E1) Ethinyl estradiol (EE2) Levonorgestrel Medroxyprogesterone Acetate MEGA (Megestrol Acetate) Nonylphenol Diethoxylate Nonylphenol Mono Ethoxylate Norethindrone NORG (Norgestimate) Progesterone Testosterone (TST) Triclocarban Triclosan (TCC) – Estimated Risk Quotient (RQ) as PEC/PNEC for indicator TOrCs. RQ >1 identified as potential risk • Site 1: 1/10 indicator TOrCs have RQ > 1 • Site 2: 0/10 indicator TOrCs have RQ > 1 © 2011 Electric Power Research Institute, Inc. All rights reserved. 15 Cas No. 25154-52-3 63-05-8 1912-24-9 80-05-7 58-08-2 298-46-4 521-18-6 53016-31-2 67392-87-4 297-76-7 50-28-2 50-27-1 53-16-7 57-63-6 797-63-7 71-58-9 3562-63-8 20427-84-3 27986-36-3 68-22-4 35189-28-7 57-83-0 58-22-0 101-20-2 3380-34-5 Vitellogenin (Vtg) in Liver Samples from Fathead Minnow Males - qPCR Site 1 Site 2 Biales, et al. 2007. Environ. Toxicol. Chem. 26: 287-296 © 2011 Electric Power Research Institute, Inc. All rights reserved. 16 Vtg in Plasma Samples from Fathead Minnow Males-ELISA Site 1 Statistically significant differences but measured concentrations are close to or below detection limits US Environmental Protection Agency, 2002. EPA/600/R-01/067. Duluth, MN © 2011 Electric Power Research Institute, Inc. All rights reserved. Site 2 Statistically significant differences but measured concentrations are close to or below detection limits 17 Level 2 Weight-of-Evidence Approach and Semi-Quantative Results • Approach – – Compare downstream to upstream Semi-quantitative scoring using minus signs correlated to: • “Low” effect (0) • “Moderate” effect (-) – – “Possible” effect (- -) “High” effect (- - -) Overall Level of TOrC concern determined Intended as examples that can be adjusted for site-specific conditions • Results Level of TOrC Concern1 Biological Indices TOrC Exposure TOrC Effects Other Stressors Site 1 Low --- 0 - -- Site 2 Possible -- 0 -- -- © 2011 Electric Power Research Institute, Inc. All rights reserved. 18 Conclusions Impacted stream likely due to non-TOrC stressors. Continued monitoring suggested Potential wastewater effluent effects. Continued monitoring with special studies suggested Conclusions • Assessment Framework – – – – – Set of useful tools, within logical risk-based framework Adaptable to site-specific considerations Requires regulatory driver: biological impairment Recognizes potentially confounding role of non-TOrC stressors WoE consistent with evolving science • Tools/protocols are – – – – Flexible enough to begin with available data Iterative, for smart data gathering and reduction in key uncertainties Holistic, recognizing potential effects of other stressors on health of aquatic ecosystem Designed to be easy for wastewater utilities to use • Final report to be published later this year © 2011 Electric Power Research Institute, Inc. All rights reserved. 19 Questions Carrie Turner Senior Project Engineer LimnoTech (734) 332-1200 [email protected] © 2011 Electric Power Research Institute, Inc. All rights reserved. Lola Olabode Program Director WE&RF (571) 384-2109 [email protected] 20
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