1. Survey of the New York City Watershed for the Presence of Pharmaceuticals 1 Center for Environmental Health, NYS Department of Health, Troy, NY 2 Wadsworth Center for Laboratories and Research, NYS Department of Health, Albany, NY Lloyd Wilson 1, Patrick O’Keefe 2, Patrick Palmer 1, Robert Sheridan 2, Robert Briggs 2, and Thomas King 2

2. Project Goals  Determine if detectable levels of selected pharmaceutical analytes are present in the NYC Watershed Why? To address concerns in recent scientific and popular literature regarding the potential for contamination of surface waters by hormones and human-use pharmaceuticals

3. Media Headlines  Rx-Drug H 2 WOE New York Post, 8/23/04  Stay calm everyone, there’s Prozac in the drinking water London Observer, 8/8/04  Household supplies appear in water: Drugs, disinfectants worry state panel The Arizona Republic, 7/23/04  Eat, drink and be wary: Chemicals often linger in water after treatment Poughkeepsie Journal (NY), 1/18/04  Fish off Arctic city get drug cocktail from sewers Reuters, 11/24/03  Frogs, fish, and pharmaceuticals a troubling brew… CNN, 11/14/03  Drugs in your drinking water? Take a valium The Globe and Mail (Canada), 2/12/03

4. Project Goals (continued)  characterize input to watershed from effluent of four WWTPs (day-of-week, seasonality, variability within and between plants)  monitor major inputs and output of key reservoirs  monitor terminal reservoirs to determine if any analytes are detectable prior to distribution

5. Project Goals (continued) What are we looking for (and why)? Basic compoundsAcid/neutral compounds amoxicillin (antibiotic) 17  -ethinylestradiol (steroid) atenolol (beta-blocker) 17  -estradiol (steroid) caffeine (stimulant) estrone (steroid) cephalexin* (antibiotic) ibuprofen (analgesic) sulfamethoxazole (antibiotic) valproic acid* (antiepileptic) trimethoprim (antibiotic) *to our knowledge, these compounds have not been previously investigated

6. Methodology  Four-liter grab samples (pharmaceuticals) (406 total samples to be collected, including duplicates) Samples are extracted within 48 hours  Analysis via Agilent 1100 HPLC and ThermoQuest LCQ Ion Trap LC/MS with ESI (electrospray ionization) - SIM for all analytes, except amoxicillin and cephalexin (MS/MS) Methodology developed by Dr. Patrick O’Keefe, NYSDOH WCLR; Method Detection Limit (MDL) study approved by US EPA

7. Methodology  Detection limits (from MDL study) Basic cmpds ng/L Env. Conc. Acid/neutral cmpds ng/L Env. Conc. amoxicillin 367 n/a  -ethinylestradiol 39 42 atenolol 9 3-241 17  -estradiol 40 64 caffeine 80 9-14000 estrone 30 2-70 cephalexin* 502 n/a ibuprofen 20 8-81 sulfamethoxazole 111 400 valproic acid* 199 n/a trimethoprim 4 2-240 *to our knowledge, these compounds have not been previously investigated - Environmental concentrations are those found in surface waters or WWTP effluents in the literature

8. Project Description  Pilot Study 3 consecutive days samples collected at each site for pharmaceuticals, VOCs, & SVOCs  4 seasonal sampling events 7 consecutive days of pharmaceutical samples; VOCs & SVOCs at the WWTPs for 3 days  EOH (2 WWTPs + 6 surface water locations) WOH (2 WWTPs + 4 surface water locations)

10. Pilot Study- Results  WWTPs: - atenolol was found in every sample - trimethoprim was found in all samples from Yorktown, Carmel, and Margaretville - caffeine was found in all samples from Yorktown and Carmel, one sample from Margaretville - ibuprofen detected at all sites - estrone and 17  -estradiol detected once, only at Carmel - no detections of amoxicillin, cephalexin, sulfamethoxazole, valproic acid, or 17  -ethinylestradiol

11. WWTP results - preliminary data

12. Pilot Study (cont’d)  Reservoir keypoints - caffeine was detected in a sample from CROGH - trimethoprim was detected in a sample from CATLEFF and one from Neversink - ibuprofen was detected in one sample from CATLEFF, CROGH, and WDA Some of these detections were in higher concentrations than a number of the WWTP effluent concentrations. These results were NOT verified in the corresponding duplicates.

13. EOH results - preliminary data

14. Conclusions and Findings  variability in concentrations between WWTPs  daily concentrations at individual WWTPs were similar over the three sampling days  very few detections in reservoir samples (and not in dupes)  several detected compounds supported by recent USGS data: - DOH target analytes: caffeine, ibuprofen, trimethoprim - DOH non-target analytes: acetaminophen, carbamazepine, carisoprodol, DEET, valium

15. Project Status Completed work: June ’03: Preliminary sampling/pilot study (70 samples) Mar 04 Pilot Report finalized May 04 Sampling completed (340 samples total over 4 seasons) June 05Final Data from Laboratory Planned work: November 05 Interagency draft report Final report January 06 ( Follow-up proposal already developed)

16. Acknowledgements We would like to thank the following people for their assistance in the design and implementation of this project: Ken Markussen, NYS Department of Environmental Conservation Patrick Phillips, US Geological Survey Charles Cutietta-Olson, NYC Department of Environmental Protection Dennis McChesney, US Environmental Protection Agency This work was funded by the US EPA under a New York City Watershed Protection Grant from the Safe Drinking Water Act. This grant was administered by the NYS DEC.

17. The End.