In cooperation with the Ohio Water Development Authority; National Park Service; Cities of Aurora, Bedford, Bedford Heights, Solon, and Twinsburg; Portage and Summit Counties; and in collaboration with the Ohio Environmental Protection Agency Occurrence of Organic Wastewater Compounds in the Tinkers Creek Watershed and Two Other Tributaries to the Cuyahoga River, Northeast Ohio Scientific Investigations Report 2008–5173 U.S. Department of the Interior U.S. Geological Survey Cover image: View of Tinkers Creek near Dunham Road, Cuyahoga County, Ohio (photograph by John S. Tertuliani, U.S. Geological Survey). Occurrence of Organic Wastewater Compounds in the Tinkers Creek Watershed and Two Other Tributaries to the Cuyahoga River, Northeast Ohio By J.S. Tertuliani, D.A. Alvarez, E.T. Furlong, M.T. Meyer, S.D. Zaugg, and G.F. Koltun In cooperation with the Ohio Water Development Authority; National Park Service; Cities of Aurora, Bedford, Bedford Heights, Solon, and Twinsburg; Portage and Summit Counties; and in collaboration with the Ohio Environmental Protection Agency Scientific Investigations Report 2008–5173 U.S. Department of the Interior U.S. Geological Survey U.S. Department of the Interior DIRK KEMPTHORNE, Secretary U.S. Geological Survey Mark D. Myers, Director U.S. Geological Survey, Reston, Virginia: 2008 For product and ordering information: World Wide Web: http://www.usgs.gov/pubprod Telephone: 1-888-ASK-USGS For more information on the USGS—the Federal source for science about the Earth, its natural and living resources, natural hazards, and the environment: World Wide Web: http://www.usgs.gov Telephone: 1-888-ASK-USGS Any use of trade, product, or firm names is for descriptive purposes only and does not imply endorsement by the U.S. Government. 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Suggested citation: Tertuliani, J.S., Alvarez, D.A., Furlong, E.T., Meyer, M.T, Zaugg, S.D., and Koltun, G.F., 2008, Occurrence of organic wastewater compounds in the Tinkers Creek watershed and two other tributaries to the Cuyahoga River, Northeast Ohio: U.S. Geological Survey Scientific Investigations Report 2008–5173, 60 p. iii Contents Abstract ...........................................................................................................................................................1 Introduction.....................................................................................................................................................2 Purpose and Scope ..............................................................................................................................2 Study Area..............................................................................................................................................5 Methods...........................................................................................................................................................5 Passive Sampling Technology ............................................................................................................5 Polar Organic Chemical Integrative Samplers (POCIS) ........................................................7 Semipermeable Membrane Devices (SPMDs) .......................................................................8 Sampling-Site Selection and Sampler Deployment ........................................................................8 Streambed-Sediment Sampling .......................................................................................................10 Laboratory Analyses....................................................................................................................................11 Reporting of Data .........................................................................................................................................11 Quality Control ..............................................................................................................................................12 Trip Blanks ............................................................................................................................................12 Field Replicates ...................................................................................................................................13 Reagent and Matrix Spikes ...............................................................................................................13 Method Blanks and Surrogate and Internal Standards ...............................................................14 Results ...........................................................................................................................................................14 Compounds in Water ..........................................................................................................................15 Antibiotic Compounds ...............................................................................................................15 Pharmaceutical Compounds ....................................................................................................16 Wastewater Compounds ..........................................................................................................16 Hydrophobic Compounds .........................................................................................................16 Compounds in Streambed Sediments .............................................................................................18 Pharmaceutical Compounds ....................................................................................................18 Wastewater Compounds ..........................................................................................................19 Summary and Conclusions .........................................................................................................................20 References Cited..........................................................................................................................................21 Appendix A. Detailed Analytical Methods and Passive Sampling Theory ........................................24 POCIS and SPMD Media Preparation and Extraction ..................................................................24 Chemical Analysis of POCIS and SPMD Extracts .........................................................................24 Chemical Analysis of Streambed Sediments .................................................................................25 Passive Sampling Theory ..................................................................................................................26 Estimation of Ambient Water Concentrations .......................................................................26 References Cited.................................................................................................................................27 Appendix B. Organic Wastewater Compound Analytes and Reporting Levels, by Sample Media and Analytical Method. .....................................................................................................28 References Cited.................................................................................................................................36 Appendix C. Quality-Control Data ............................................................................................................37 Appendix D. Organic Wastewater Compounds in Polar Organic Chemical Integrative Sampler (POCIS) Extracts .............................................................................................................43 Appendix E. Organic Wastewater Compounds in Semipermeable Membrane Device (SPMD) Extracts .............................................................................................................................51 Appendix F. Organic Wastewater Compounds in Streambed Sediments .........................................54 iv Figures 1–3. Maps Showing— 1. Locations of sampling sites within the Tinkers Creek watershed ...............................3 2. Locations of reference sampling sites relative to the Tinkers Creek watershed .....4 3. Land cover in the Tinkers Creek watershed....................................................................6 4. Photographs of passive-sampler canister in stream and with polar organic integrative sampler (POCIS) disks removed .............................................................................7 5. Component view of a POCIS disk ...............................................................................................7 6. Photograph of lipid-filled polyethylene membrane tube from a semipermeable membrane device (SPMD) ..........................................................................................................8 7. Schematic of sampling-site locations near the Bedford Heights wastewater- treatment-plant outfall ...............................................................................................................10 8. Graph showing numbers of detections of antibiotic, pharmaceutical, wastewater, and hydrophobic compounds in water (as determined by analysis of POCIS and SPMD media) upstream and downstream from wastewater treatment plants in the Tinkers Creek watershed. ..........................................................................................................15