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National Kxposure Research Laboratory
Research Abstract
Government Performance Results Act (GPRA) Goal #2
Annual Performance Measure #20
Significant Research Findings:
Polar Organic Chemical Integrative Sampling (POCIS) and Liquid
Chromatography-Electrospray Ion Trap Mass Spectrometry (LC-
ES/ITMS) for Assessing Selected Prescription and Illicit Drugs in
Treated Sewage Effluents
Scientific	Improvements in detection technology over the past decade have revealed that raw
Problem and	sewage and treated wastewater can contain ng/L to |ig/L [part-per-trillion (ppt) to
Policy Issues	part-per-billion (ppb)] concentrations of numerous pharmaceuticals and personal
care products (PPCPs), including not just drugs and their metabolites, but also
synthetic fragrances and detergents, all of which can find their way into the natural
environment after excretion or disposal by end-users. Once present in raw sewage,
these substances have the potential to enter surface or ground waters through
straight-piping, from sewage treatment plant effluent, wet-weather runoff, seepage
from landfills, recharging of aquifers with treated sewage effluent, or
drainage/deep-percolation from fields irrigated with sewage effluent. Many of
these compounds are more polar than pollutants of historic concern and are not
readily sorbed to the subsoil, thereby increasing their potential to enter surface or
ground waters. The purpose of the research presented in this paper is twofold: (1)
demonstrate the advantageous coupling of two state-of-the-art techniques: a time-
weighted polar organic chemical integrative sampler (POCIS) and liquid
chromatography-electrospray ion trap mass spectrometry (LC-ES/ITMS); and (2)
assess these methodologies at three water treatment sites to determine the presence
of six polar drugs [e.g., azithromycin, fluoxetine, omeprazole, levothyroxine,
methamphetamine, and MDMA (Ecstasy)] in wastewater discharges.
Most conventional environmental pollutant screening techniques for water
matrices use grab sampling. However, a limitation to grab sampling, compared
with continuous samplers, is that grab sampling gives an incomplete picture of
overall concentrations of pollutants over a temporal basis. For example, a study
by Williams el al.1 showed that daily grab samples of waters taken from a river
had a wide variance in daily estrone concentrations. Once the water sample is
collected, it is usually subjected to some type of extraction method [e.g., solid
phase extraction (SPE) or liquid-liquid extraction (LLE)] before analysis can
occur. A drawback to SPE and LLE is their limited capacity (sample volume sizes
are usually 1- to 2-L) thereby limiting the detection limit. Two of the strengths of
the POCIS are its capacity to handle large volumes of water [millions of
gallons/day (mgd)] over a period of several days or weeks, thereby giving time
weighted average (TWA) concentrations and its ability to detect episodic changes
in environmental contaminant concentrations which are often missed with
Research
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conventional grab samples. POCIS is capable of concentrating polar analytes (such
as the pharmaceuticals of interest in this study), and the membrane design allows
for the selective sampling of the residues from the dissolved (bioavailable) phase,
allowing POCIS to be deployed in nearly all aqueous environments regardless of
water quality. One drawback to this approach is that for accurate concentrations to
be calculated, calibration studies need to be conducted on the analytes of interest.
For the purpose of this pilot study, the POCIS sampling technique was evaluated
during 30-day deployments at three geographically distinct sites with diverse
population densities: Nevada, Utah, and South Carolina.
1. Williams RJ, Johnson AC, Smith JJL, Kanda Rakesh. (2003). "Steroid Estrogens Profiles Along
River Stretches Arising from Sewage Treatment Works Discharges." Environ Sci Technol 37:1744-
1750.
Results and	This pilot study showed for the first time the practicality of using a TWA sampler
Impact	to better understand the broader presence of drugs being released into the
environment. We believe this data represents the first time that two illicit drugs
(namely, methamphetamines and MDMA) have been confirmed and quantified in
wastewater effluents, and reported in the peer-reviewed literature (Archives
Environ Contam Toxicol, 47(4), 427-439, 2004). Finding the antibiotic
azithromycin at all the wastewater treatment plant (WWTP) sites may lead to risk
assessments and consideration of policy and management practices to reduce
loadings into receiving waters.
This research effort involved the collaboration of an ORD scientist (Tammy Jones-
Lepp) with scientists responsible for developing POCIS (Dr. David Alvarez and
Dr. Jim Petty, U.S. Geological Survey-Columbia Environmental Research Center
(USGS-CERC), Columbia, MO). This effort also involved the participation and
collaboration of three wastewater treatment plants (Nevada, Utah, and South
Carolina), as well as one state entity (State of South Carolina). A number of
presentations as well as two publications resulted from this research:
Jones-Lepp TL, Alvarez D, Petty J, Huggins J "Polar Organic Chemical Integrative
Sampling (POCIS) and LC-ES/ITMS for Assessing Selected Prescription and Illicit Drugs in Treated
Sewage Effluents," Archives Environ Contam Toxicol, 47(4), 427-439, 2004.
Alvarez DA, Petty JD, Huckins JN, Jones-Lepp TL, Getting DT, Manahan SE
"Development of a Passive, in situ, Integrative Sampler for Hydrophilic Organic Contaminants in
Aquatic Environments," Environ Toxicol Chem, Vol. 23(7), 1640-1648, 2004.
Future Research Future collaboration between USGS-CERC and ORD/NERL-ESD will entail a
temporal/longitudinal study of macrolide antibiotics in drinking water and an
urban drinking/recreational water source.
The methodologies developed for this research project will be applied toward
understanding the fate of macrolide antibiotics from wastewater into biosolids
produced by WWTPs.
Questions and inquiries regarding this research can be directed to:
Tammy Jones-Lepp
U.S. EPA, Office of Research and Development
National Exposure Research Laboratory
944 East Harmon Ave.
Las Vegas, NV 89119
Phone: 702/798-2144
E-mail: jones-lepp.tammy@epa.gov
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Funding for this project was through the U.S. EPA's Office of Research and
Development, National Exposure Research Laboratory, and the work was
conducted by the Environmental Sciences Division in collaboration with the
USGS-CERC (interagency agreement #DW14900401).

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