A screening study investigating the presence of Emerging Contaminants within the Ohio River Basin The Ohio River Valley Water Sanitation Commission (ORSANCO) and United States Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory ORSANCO Page 1 of 279 A screening study investigating the presence of Emerging Contaminants within the Ohio River Basin Prepared by: Erich Emery, Manager of Research and Biological Programs John Spaeth, Aquatic Biologist The Ohio River Valley Water Sanitation Commission 5735 Kellogg Ave Cincinnati, Ohio 45230 and Marc Mills, Ph.D. Shoji Nakayama, Ph.D. Jamin Frommel U.S. Environmental Protection Agency National Risk Management Research Laboratory 26 West Martin Luther King Drive, MS 190 Cincinnati, Ohio 45268 May 25, 2010 ORSANCO Page 2 of 279 Executive Summary Background: Recent improvements in analytical detection capabilities and the availability of these methods to researchers via commercial labs have now enabled water resource managers to conduct studies such as this on broader spatial scales and on a wider range of compounds. Analytes are now being detected and quantified in the part per trillion (ng/L) range. In 2002, ORSANCO’s Research Committee identified Contaminants of Emerging Concern (CECs) as a top research priority. Research has demonstrated there are many sources of CECs to the environment, including wastewater treatment plants (WWTPs), confined animal feeding operations (CAFOs), industrial discharges, etc. It has been shown that WWTPs are not currently designed to remove these chemicals to the very low levels, nor are they required by regulatory agencies to do so. Therefore, we anticipated finding detectable levels of CECs in the Ohio River at locations below possible sources and potentially at background areas. To date, little information is available regarding possible human health risk, however, it is more generally accepted that risks have been demonstrated for aquatic species exposed to these compounds. Understanding possible ecological risks was considered a primary purpose for the Commission’s research efforts on CECs. In 2005, ORSANCO collaborated with USEPA to conduct a pilot study on the Ohio River. This study targeted a limited list of endocrine disrupting chemicals which included steroid hormones and alkylphenolic compounds. Methods employed during the pilot study enabled researchers to detect the presence of steroid hormones, but quantification was not possible. It was determined that future efforts should include a broader list of chemicals and provide reportable quantities. Study Overview: In September and October, 2009, single grab samples were collected from 22 locations on the mainstem Ohio River and the lower reaches of tributaries. Target analytes included 158 compounds considered to be contaminants of emerging concern or emerging contaminants. o 118 ‐ Pharmaceutical and Personal Care Products (PPCPs) o 27 ‐ Hormones and Sterols o 13 ‐ Perfluorinated Compounds (PFCs) This study was designed to generate data as preliminary survey by the Commission and results would be used to guide future actions. Practical Limitations of Study: Though this study utilized the state of the art analytical approaches, practical limitations to the study could restrict the data utility and conclusions that can be drawn. The analytical laboratory methods employed are research or draft EPA methods. For PFCs, no EPA standard ORSANCO Page 3 of 279 method for surface waters is currently available. However, draft EPA methods 1694 (PPCPs) and 1698 (Hormones and Steroids) have been released to the public as single‐laboratory validated methods. It should be noted that the lab that worked with EPA to develop the draft methods (1694 and 1698), the single lab that has been validated, and the lab utilized for this study are one and the same. Due to the spatial and temporal limits of the study approach, it may not be possible to quantify loadings, identify or characterize sources, or characterize downstream fate and transport. The collection of single grab samples does not allow for temporal characterizations or statistical analysis at individual sites. Data Use: This report will be used by ORSANCO Committees, Sub‐Committees, Advisory Committees and Workgroups. These groups will provide advice and guidance to the Commission regarding warranted future studies or actions. Additionally, ORSANCO and EPA staff will collaborate on a more thorough data summary/evaluation and report. ORSANCO Page 4 of 279 Table of Contents Executive Summary ......................................................................................................................... 2 List of Figures ................................................................................................................................... 5 List of Tables .................................................................................................................................... 6 1.0 Introduction ..................................................................................................................................... 7 2.0 Methods .......................................................................................................................................... 8 2.1 Study Design ....................................................................................................................... 8 2.2 Sample Collection ............................................................................................................. 11 2.3 Target Analytes ................................................................................................................. 12 2.4 Analytical Methods ........................................................................................................... 19 3.0 Data Validation .............................................................................................................................. 19 3.1 Quality Assurance Review ................................................................................................. 19 3.1.1 USEPA Memo .................................................................................................................... 19 3.1.2 ORSANCO Memo .............................................................................................................. 25 3.2 Lab Validation ................................................................................................................... 26 3.3 Target Analyte Concentration ........................................................................................... 26 3.4 QA/QC by Analyte Group .................................................................................................. 26 3.4.1 Perfluorinated Compounds (PFCs) .................................................................................... 26 3.4.2 Pharmaceuticals and Personal Care Products (PPCPs) ..................................................... 26 3.4.3 Hormones and Sterols ...................................................................................................... 26 4.0 Results ........................................................................................................................................... 87 5.0 Next Steps .................................................................................................................................... 101 6.0 References ................................................................................................................................... 102 Appendix 1 Method Summaries ................................................................................................ 103 Appendix 2 Case Narratives – AXYS Analytical Services, Ltd. ................................................... 135 ORSANCO Page 5 of 279 List of Figures Figure 1. Map showing sampling locations Figure 2. Picture of sampling device Figure 3. Picture of sample transfer ORSANCO Page 6 of 279 List of Tables Table 1. Sample numbers and general location information. Table 2. Analytes targeted for Ohio River emerging contaminants screening study. Table 3.1. Concentration and surrogate recovery of perfluorinated compounds (PFCs) Table 3.2. Calibration range and minimum reporting limit (MRL) for PFCs Table 3.3. Ongoing precision and recovery (OPR) for PFCs Table 3.4. Concentration and surrogate recovery of pharmaceutical and personal care products (PPCPs) Table 3.5. Calibration range and minimum reporting limit (MRL) for PPCPs Table 3.6. Ongoing precision and recovery (OPR) for PPCPs Table 3.7. Concentration and surrogate recovery of hormones Table 3.8. Concentration and surrogate recovery of sterols Table 3.9. Calibration range and minimum reporting limit (MRL) for hormones and sterols Table 3.10. Ongoing precision and recovery (OPR) for hormones and sterols Table 4. Concentrations of perfluoroalkyl compounds (PFCs), pharmaceuticals and personal care products (PPCPs), and hormones/sterols in the Ohio River and its tributaries ORSANCO Page 7 of 279 1.0 Introduction Marked improvements in analytical detection capabilities over the last 15 years has led to the quantitative and qualitative characterization of a variety of organic chemicals occurring at trace levels in surface waters, treated wastewater effluents, drinking water supplies, and fish tissue (Boyd and Furlong 2002; Kolpin et al. 2002; Galloway et al. 2005; Zimmerman 2005; Benotti et al. 2006; Lower Columbia River Estuary Partnership 2007).