1. New York City Department of Environmental Protection Bureau of Water Supply Water Quality New York City Department of Environmental Protection Bureau of Water Supply Water Quality Pharmaceutical and Personal Care Products in the NYC Watershed David Lipsky, Ph.D., Q.E.P. Timothy Martin, M.P.A. Ian Hurley, Ph.D. Carla Glaser, M.E.M. Carla Glaser, M.E.M.

2. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Introduction Sampling and Analytical Approach Preliminary Conclusions Objectives

3. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Introduction PPCPs (pharmaceutical and personal care products) represent a subclass of organic compounds that have been detected in surface waters, groundwater, wastewaters and drinking water throughout world. Term “PPCP” is used loosely and is ill-defined; can include endocrine disrupting chemicals, xenobiotics, hormonally active chemicals, pesticides and newly emerging contaminants. Sources include wastewater, runoff from agricultural fields, biosolids, urban runoff, air, and other sources.

4. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Not a new issue, but a result of advances in analytical capabilities These advances now allow research scientists to reliably detect an increasing number of organic constituents at the ng/L (part per trillion) range However, there are only a few contract laboratories or water utility laboratories with such demonstrated capabilities No widely available standard methods Introduction (con’t)

5. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Different studies looked at different analytes with different methods No common assessment program defining procedures to follow for collecting samples and the specific PPCPs that should be targeted Introduction (con’t)

6. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Introduction (con’t) A recent study published in ES&T by Benotti, et.al., found PPCPs in the tap water of 19 U.S. water utilities The 11 most frequently detected compounds, all found at low levels included: atenolol, atrazine, carbamazepine, estrone, gemfibrozil, meprobamate, naproxen, phenytoin, sulfamethoxazole, TCEP, and trimethoprim

7. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Approach Utilize two contract labs to perform analyses Samples collected quarterly at source water keypoints (pre-chlorination) High degree of field and laboratory QA/QC

8. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Approach (con’t) 10 samples analyzed per quarter “Clean Hands” sampling technique QAPP USGS collects side by side samples for independent analysis

9. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Approach (con’t) Site CodeSite DescriptionReason for Site Selection CROGHCroton Gatehouse, untreated effluent from New Croton Reservoir Keypoint sampling location. Pre-chlorination. DEL18Delaware Aqueduct, Shaft 18 untreated effluent from Kensico Reservoir CATLEFFCatskill Aqueduct, lower effluent chamber, untreated Kensico Reservoir effluent PPCP Monitoring Sites

10. New York City Department of Environmental Protection Bureau of Water Supply Water Quality PPCP Monitoring Locations CROGH CATLEFF DEL18

11. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Approach (con’t) LocationSample Sample Dup Trip Blank Field Blank LFMLFMD CROGH XXX&X& X&X& X&X& X&X& DEL18 XX CATLEFF XX &: Taken at alternating locations for each sampling event Samples collected

12. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Selected PPCP Laboratory Analysis Methods Suite of PPCP compounds analyzed Appx. # of compounds in suite Description of compounds Phenolic Endocrine Disrupting Chemicals 10 Chemicals which may block or mimic natural hormones, thereby disrupting normal functioning of organs. Estrogens and other hormones10 Estrogens and other hormones which may affect the reproductive physiology of fish communities, and may pose a public health concern. Pharmaceutically Active Compounds (Positive/Negative) 40 Pharmaceutically active compounds such as pain relievers, antibiotics, anticonvulsants, antidepressants, replacement hormones, and chemicals related to coffee and tobacco. Pharmaceutically Active Compounds (Positive/Negative) 20 Same as above – using an alternative screening method.

13. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Laboratory Minimum Reporting Limits (MRLs) MRLs are the lowest reportable concentration for an analyte. Normally, an MRL will be above the amount found in a blank. Each lab must verify accuracy and precision of their results at MRLs. Lab regulators suggest ± 50 percent of the expected value as a reasonable goal at an MRL.

14. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Representative MRLs CompoundMRL (ng/L) Acetominophen1 Bis Phenol A (BPA)10 Caffeine3 Carbamazepine5 Cotinine1 DEET5 Diazepam1 Estradiol1 Estrone0.5 Ethinyl Estradiol - 17 alpha5 Fluoxetine5 Gemfibrozil1 Ibuprofen1 Iopromide5 Nicotine5 Perfluoro octanesulfonate-PFOS0.2 Progesterone0.1 Sulfamethoxazole1 Testosterone1 Triclosan5 Trimethoprim1

15. New York City Department of Environmental Protection Bureau of Water Supply Water Quality PPCP “clean hands” sampling technique “Dirty hands” assisting “clean hands” in removing sample bottle from inner/outer bag.

16. New York City Department of Environmental Protection Bureau of Water Supply Water Quality PPCP “clean hands” sampling technique “Clean hands” taking a field blank.

17. New York City Department of Environmental Protection Bureau of Water Supply Water Quality “Dirty hands” assisting “clean hands” with placing filled sample bottle back into inner/outer bag. CRO1T SAMPLING TAP PPCP “clean hands” sampling technique

18. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Laboratory QC Test-Specific Controls: “Blanks” – negative controls – 1 per batch of 20 samples or less Checks for target chemical picked up during lab processing of samples Must be “non-detected”

19. New York City Department of Environmental Protection Bureau of Water Supply Water Quality “LFB” – positive controls – 1 per batch of 20 samples or less All target compounds, at ng/L levels Checks for target chemical lost during processing Must be 70 – 130 percent of expected levels Test-Specific Controls: Laboratory QC

20. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Laboratory QC “Spikes” - known amounts of target compounds added to sample Checks for masking of target compounds by interferences in samples Check amount recovered after background is subtracted 70 - 130 percent of expected levels Sample-Specific Controls:

21. New York City Department of Environmental Protection Bureau of Water Supply Water Quality “Duplicates” – 2 samples or 2 “spikes” Compare amounts of target compounds found in matched pairs Checks for reproducibility Less than 30 percent difference Sample-Specific Controls: Laboratory QC

22. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Laboratory QC “Internal standard” Compound NOT found in samples Added just before analysis Controls for short-term changes in instrument performance Added to all samples and QC:

23. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Laboratory QC “Surrogate” Compound NOT found in samples and chemically similar to target compounds Added before sample QC processing Controls for losses of target compounds during processing Added to all samples and QC:

24. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Decreasing as labs get more experience, modify methods QC Problems Date Number of QC problems LAB ALAB B January-091684 April-09743 July-09429

25. New York City Department of Environmental Protection Bureau of Water Supply Water Quality QC Problems Low recoveries of “surrogate” from samples (testosterone-d3, ibuprofen-d3, acetaminophen-d4) Low recoveries of target compounds from spikes (sulfamethoxazole, chlorotetracycline) Possible cause: background interference (with internal standards?) Common QC problems:

26. New York City Department of Environmental Protection Bureau of Water Supply Water Quality QC Problems Low recoveries of target compounds from “LFB” (fluoxetine, bacitracin) Possibly cause: loss during extraction from reagent water Less common QC problems:

27. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Program appears to be providing credible results –Good agreement among duplicates –Few detects in blanks –Clean hands technique more time consuming but advisable to reduce cross-contamination as a possible source of error –Good agreement between laboratories Conclusion

28. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Need detailed expert review of contract lab results Continues to require high degree of interaction between DEP and contract lab personnel to address QA/QC issues Need additional scientific/QA review before publishing results Conclusion (con’t)

29. New York City Department of Environmental Protection Bureau of Water Supply Water Quality Questions? Thank You