Survey of the New York City Survey of the New York City Watershed for the Presence of Watershed for the Presence of PharmaceuticalsPharmaceuticals

11Center for Environmental Health, NYS Department of Health, Troy, NYCenter for Environmental Health, NYS Department of Health, Troy, NY

22Wadsworth Center for Laboratories and Research, NYS Department of Health, Albany, NYWadsworth Center for Laboratories and Research, NYS Department of Health, Albany, NY

Lloyd WilsonLloyd Wilson11, Patrick O’Keefe, Patrick O’Keefe22, Patrick Palmer, Patrick Palmer11, , Robert SheridanRobert Sheridan22, Robert Briggs, Robert Briggs22, and Thomas King, and Thomas King22

Project GoalsProject 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

Media HeadlinesMedia Headlines Rx-Drug H2WOE 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

Project Goals Project Goals (continued)(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

Project Goals Project Goals (continued)(continued)

What are we looking for (and why)?

Basic compounds Acid/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

MethodologyMethodology

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

MethodologyMethodology

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

Project DescriptionProject 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)

Pilot Study- Pilot Study- ResultsResults

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

WWTP results - preliminary data

Pilot Study Pilot Study (cont’d)(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.

EOH results - preliminary data

Conclusions and FindingsConclusions 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

Project StatusProject 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 05 Final Data from Laboratory

Planned work:

November 05 Interagency draft report

Final report January 06 (Follow-up proposal already developed)

AcknowledgementsAcknowledgements

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.

The End.The End.