U.S. Department of the Interior

U.S. Geological Survey

Scientific Investigations Report 2012–5106

Prepared in cooperation with the Pennsylvania Department of Environmental Protection

Occurrence of Pharmaceuticals, Hormones, and Organic 

Wastewater Compounds in Pennsylvania Waters, 2006–09
Cover. Susquehanna River at Harrisburg, Pa. Photo by J. Kent Crawford, U.S. Geological Survey.
Occurrence of Pharmaceuticals, Hormones, 

and Organic Wastewater Compounds in 

Pennsylvania Waters, 2006–09

By Andrew G. Reif, J. Kent Crawford, Connie A. Loper, Arianne Proctor, 

Rhonda Manning, and Robert Titler

Prepared in cooperation with the 

Pennsylvania Department of Environmental Protection

Scientific Investigations Report 2012–5106

U.S. Department of the Interior

U.S. Geological Survey
U.S. Department of the Interior

KEN SALAZAR, Secretary

U.S. Geological Survey

Marcia K. McNutt, Director

U.S. Geological Survey, Reston, Virginia: 2012

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Suggested citation:

Reif, A.G., Crawford, J.K., Loper, C.A., Proctor, Arianne, Manning, Rhonda, and Titler, Robert, 2012, Occurrence of 

pharmaceuticals, hormones, and organic wastewater compounds in Pennsylvania waters, 2006–09: U.S. Geological 

Survey Scientific Investigations Report 2012–5106, 99 p.
iii

Acknowledgements

Funding support from the Pennsylvania Department of Environmental Protection and the 

U.S. Environmental Protection Agency is gratefully acknowledged. USGS researchers Dana 

Kolpin, William Foreman, Edward Furlong, Michael Meyer, Steven Zaugg, Keith Loftin, 

and James Gray conducted laboratory analyses and provided valuable advice throughout the 

study; without them the study would not have been possible. John Clune, Justin Knudson, Leif 

Olson, Tom Noonan, Heather Eggleston, and Emily Eggler, played an important role in sample 

collection. Linda Zarr contributed her expertise to the data analysis. Scott Hoffman provided 

valuable graphics support. Kim Otto (retired) provided editorial support. USGS reviewer 

Kevin Breen provided a particularly insightful review of an early draft of the manuscript. Other 

USGS reviewers, Lisa Senior, Pat Philips, and Doug Chambers offered valuable suggestions 

for improving the manuscript. The interest and support of Pat Bowling of the PADEP is greatly 

appreciated. The authors also wish to extend thanks to the landowners and the wastewatertreatment-plant operators who graciously allowed access to the wells and streams. To all who 

assisted in any way, the authors convey sincere thanks.
iv

Contents

Acknowledgements......................................................................................................................................iii

Abstract...........................................................................................................................................................1

Introduction.....................................................................................................................................................2

Purpose and Scope ..............................................................................................................................2

Categories of Contaminants of Emerging Concern.........................................................................2

Potential Sources of Contaminants of Emerging Concern ..........................................................11

Agricultural Sources .................................................................................................................11

Wastewater Effluents................................................................................................................11

Other Potential Sources of Contaminants of Emerging Concern ......................................11

Pharmaceutical Manufacturing Facilities ....................................................................11

Land Application of Biosolids .........................................................................................11

Landfill Leachate...............................................................................................................11

Combined Sewer Overflows ...........................................................................................12

On-Site Wastewater Systems.........................................................................................12

Previous and Current Investigations ...............................................................................................12

Study Design.................................................................................................................................................13

Methods.........................................................................................................................................................13

Site Selection and Sampling Locations ..........................................................................................13

Wells in Agricultural Areas Used to Supply Livestock ........................................................13

Streams Draining Areas with Animal-Feeding Operations.................................................19

Streams Receiving Municipal Wastewater Effluents..........................................................19

Stream Sites near Drinking-Water Intakes ...........................................................................19

Stream Sites Used to Evaluate Fish Health ...........................................................................20

Streamflow Measurement and Water-Quality Characteristics ..................................................20

Collection and Processing of Water-Quality Samples..................................................................23

Streamwater...............................................................................................................................23

Groundwater...............................................................................................................................23

Streambed Sediments...............................................................................................................24

Laboratory Analyses...........................................................................................................................24

Streamwater Samples ..............................................................................................................26

Pharmaceutical Compounds...........................................................................................26

Antibiotics and Ibuprofen................................................................................................26

Hormones...........................................................................................................................26

Organic Wastewater Compounds..................................................................................26

Streambed-Sediment Samples................................................................................................26

Antibiotics and Ibuprofen................................................................................................26

Hormones...........................................................................................................................27

Organic Wastewater Compounds..................................................................................27

Data Analysis.......................................................................................................................................27

Quality Assurance and Quality Control ....................................................................................................28

Quality Control for Field Measurements .........................................................................................28

Quality Control for Streamwater and Streambed-Sediment Samples.......................................28
v

Blanks.. ........................................................................................................................................28

Duplicates ...................................................................................................................................29

Laboratory-Matrix Spikes ........................................................................................................29

Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters.....31

Compounds in Groundwater Used to Supply Livestock ...............................................................31

Compounds in Streamwaters Upstream and Downstream from Animal-Feeding 

Operations ..............................................................................................................................31

Compounds in Streamwater and Streambed Sediments Upstream and Downstream 

from Wastewater Discharges .............................................................................................31

2006 Sampling Upstream and Downstream from Wastewater-Effluent-Discharge 

Sites................................................................................................................................34

2007 to 2009 Sampling Downstream from Wastewater-Effluent Discharges .................40

Compounds in Streamwaters near Drinking-Water Intakes .......................................................47

Pharmaceutical Compounds....................................................................................................50

Hormones....................................................................................................................................50

Patterns of Contaminant Occurrence ....................................................................................54

Hydrologic Conditions......................................................................................................54

Number of Permitted Discharges ..................................................................................54

Land Use.............................................................................................................................56

Seasonal Variability..........................................................................................................58

Compounds in Streamwaters and Streambed Sediment at Fish-Health Sites.........................60

Compounds in Streamwater ....................................................................................................60

Compounds in Streambed Sediment ......................................................................................60

Implications of Contaminants of Emerging Concern in Pennsylvania Waters ..................................65

Implications for Ecosystem Health ..................................................................................................65

Implications for Contaminants in Source Waters for Public Drinking-Water Supplies..........66

Summary........................................................................................................................................................66

References Cited..........................................................................................................................................68

Appendix A. Summary of laboratory methods. ......................................................................................82

Appendix B. Summary of duplicate sample results ..............................................................................83

Appendix C. Reagent-spiked and laboratory-spiked sample results.................................................87

.
vi

Figures

1. Map showing locations of wells used to supply livestock, stream-sampling sites

near animal-feeding operations, and stream-sampling sites near municipal

wastewater-effluent-discharge sites, south-central Pennsylvania ..................................15

2. Map showing locations of stream-sampling sites located near drinking-water 

intakes and sampling sites for evaluation of fish health in Pennsylvania.........................16

3. Photograph showing U.S. Geological Survey hydrologist collecting a water 

sample for analysis of contaminants of emerging concern using a DH-81 sampler 

fitted with Teflon adapter, Teflon nozzle, and Teflon 1-L bottle ...........................................24

4. Photograph showing Teflon cylinder and Teflon wafer used to collect 

streambed-sediment samples ..................................................................................................25

5. Photograph showing U.S. Geological Survey and Pennsylvania Department 

of Environmental Protection scientists processing a streambed-sediment sample 

in the field.....................................................................................................................................25

6. Graph showing pharmaceutical compounds detected in 24 streamwater samples 

collected from paired stream sites located upstream and downstream from five 

animal-feeding operations in Pennsylvania, 2006.................................................................33

7. Graph showing number of detections of pharmaceutical compounds, excluding 

antibiotics, in 20 streamwater samples collected from paired stream sites 

located upstream and downstream from five municipal wastewater-effluentdischarge-sites in Pennsylvania, 2006 ....................................................................................36

8. Boxplot showing number of detections of antibiotic compounds at concentrations 

greater than the reporting level in 20 streamwater samples collected from paired 

stream sites located upstream and downstream from five municipal

wastewater-effluent-discharge sites in Pennsylvania, 2006...............................................37

9. Graph showing carbamazepine concentrations in streamwater samples collected 

from paired stream sites located upstream and downstream from five municipal

wastewater-effluent-discharge sites in Pennsylvania, 2006...............................................38

10. Boxplot showing sulfamethoxazole and ofloxacin concentrations detected 

in samples collected from Lititz Creek near Lititz, Pennsylvania, the upstream site, 

T12, 01576420 and Lititz Creek at Rothsville, Pennsylvania, the downstream site, 

T13, 01576422, in 2006.................................................................................................................39

11. Graph showing number of contaminants of emerging concern detected at 

concentrations greater than the reporting level in streamwater samples collected 

from sites downstream from municipal wastewater-effluent-discharge sites 

in Pennsylvania, 2007–09...........................................................................................................44

12. Graph showing number of contaminants of emerging concern detected at 

concentrations greater than the reporting level in streambed-sediment samples 

collected from the Clark Creek reference site and eight stream sites located 

downstream from municipal wastewater-effluent-discharge sites 

in Pennsylvania, 2007–09...........................................................................................................46

13. Graph showing detection frequency of selected contaminants of emerging 

concern detected at concentrations greater than the reporting level in streamwater 

and streambed-sediment samples collected from eight sites located downstream 

from municipal wastewater-effluent-discharge sites in Pennsylvania, 2007–09 ............48

14. Map showing locations of 27 streamwater-sampling sites near drinking-water 

intakes with the number of total detections at concentrations greater than the 

reporting level, by compound class, in Pennsylvania, 2007–09 ..........................................49
vii

15. Graph showing number of detections of pharmaceutical compounds in 

streamwater samples collected from 27 stream sites located near drinking-water 

intakes in Pennsylvania, 2007–09.............................................................................................52

16. Graph showing number of contaminants of emerging concern detected at 

concentrations greater than the reporting level in streamwater samples collected 

from 27 stream sites near drinking-water intakes in Pennsylvania, 2007–09...................53

17. Graph showing number of detections of hormone and animal sterol compounds 

in 270 streamwater samples collected from 27 stream sites near drinking-water 

intakes in Pennsylvania, 2007–09.............................................................................................54

18. Graph showing concentration of sulfamethoxazole in streamwater samples 

collected from the Schuylkill River at Philadelphia, Pennsylvania, in relation to 

streamflow, 2007–09 ...................................................................................................................55

19. Graph showing detection frequency of commonly detected contaminants of 

emerging concern in each of four flow categories for streamwater samples taken 

from 27 stream sites located near drinking-water intakes in Pennsylvania, 2007–09 ....55

20. Graph showing number of detections of contaminants of emerging concern at 

concentrations greater than the reporting level by permitted discharges 

categories—low, mid, and high—for 27 stream sites located near drinking-water 

intakes in Pennsylvania, 2007–09.............................................................................................55

21. Graph showing detection frequency of selected contaminants of emerging 

concern by permitted discharge category—low, mid, and high—for 27 stream sites 

located near drinking-water intakes in Pennsylvania, 2007–09..........................................56

22. Graph showing number of detections of contaminants of emerging concern at 

concentrations greater than the reporting level in samples collected from 27 stream 

sites near drinking-water intakes by percentage of forested land use 

in Pennsylvania, 2007–09...........................................................................................................58

23. Graph showing number of detections of contaminants of emerging concern at 

concentrations greater than the reporting level in streamwater samples collected 

from 27 stream sites near drinking-water intakes in Pennsylvania, 2007–09...................59

24. Graph showing detection frequency of contaminants of emerging concern, 

by season, in 297 streamwater samples collected from 27 stream sites near 

drinking-water intakes in Pennsylvania, 2007–09 .................................................................59

25. Graph showing detection frequency of sulfamethoxazole and acetaminophen, 

by season, in 297 streamwater samples collected from 27 stream sites near 

drinking-water intakes in Pennsylvania, 2007–09 .................................................................59

26. Map showing location of fish-health sites sampled with the number of total 

detections greater than the reporting level, by compound class, in Pennsylvania, 

2007 or 2008..................................................................................................................................61

27. Graph showing number of contaminants of emerging concern detected at 

concentrations greater than the reporting level in streamwater samples collected 

at 16 fish-health sites in Pennsylvania, 2007 or 2008 ............................................................62

28. Graph showing number of contaminants of emerging concern detected at 

concentrations greater than the reporting level in streambed-sediment samples 

from 16 fish-health sites sampled in Pennsylvania, 2007 or 2008 .......................................64
viii

Tables

1. Pharmaceutical compounds analyzed in streamwater and streambed-sediment

samples, medicinal uses, and reporting levels........................................................................4

2. Hormones and animal sterols analyzed in streamwater and streambed-sediment

samples, medicinal uses, and reporting levels........................................................................7

3. Organic wastewater compounds analyzed in streamwater and

streambed-sediment samples, uses or sources, and reporting levels................................8

4. Objective addressed, study component, duration of sampling, number of locations

sampled, sample medium, compounds analyzed, and number of samples collected

for reconnaissance sampling of waters in Pennsylvania, 2006–09....................................14

5. Description of well sites used to supply livestock, stream sites receiving runoff

from animal-feeding operations, and stream sites near municipal wastewatereffluent-discharge sites, in south-central Pennsylvania, 2006–09.....................................17

6. Characteristics of wastewater-treatment-plants discharging to study streams ............20

7. Description of sampling sites near selected drinking-water intakes in Pennsylvania...21

8. Description of sampling sites used for evaluations of fish health in Pennsylvania ........22

9. Description of field measurement with reporting units and instrument reporting

accuracies used in this study...................................................................................................23

10. Compounds detected in equipment and field-blank samples collected 

from 2006 to 2009.........................................................................................................................28

11. Statistical summary of relative percent differences for contaminants of emerging

concern in duplicate samples of streamwater and streambed sediment collected 

in Pennsylvania, 2007–09...........................................................................................................30

12. Statistical summary of recoveries of laboratory-matrix spike samples for selected

analytical methods used in this study .....................................................................................30

13. Pharmaceutical compounds detected in quarterly samples collected from 6 wells

in agricultural areas and 12 stream sites located upstream and downstream from

animal-feeding operations in Pennsylvania...........................................................................32

14. Pharmaceutical compounds detected in streamwater samples collected from

paired stream sites located upstream and downstream from five municipal

wastewater-effluent-discharge sites in Pennsylvania, 2006...............................................35

15. Description of sampling sites downstream from wastewater-effluent-discharge

sites, number of compounds detected, total number of detections, average flow

difference between upstream and downstream sampling sites, and drainage area

for streamwater samples collected in Pennsylvania, 2006 .................................................40

16. Pharmaceutical compounds detected in streamwater and streambed-sediment

samples collected from Clark Creek and eight stream sites downstream from

wastewater-effluent-discharge sites in Pennsylvania, 2007–09 ........................................42

17. Hormone and animal sterol compounds detected in streamwater and

streambed-sediment samples collected annually from Clark Creek and eight

stream sites located downstream from municipal wastewater-effluent-discharge

sites in Pennsylvania, 2007–09 .................................................................................................45

18. Organic wastewater compounds detected in annual streamwater or streambedsediment samples collected at Clark Creek and eight stream sites located 

downstream from municipal wastewater-effluent-discharge sites 

in Pennsylvania, 2007–09...........................................................................................................74

19. Pharmaceutical and hormone and animal sterol compounds detected in

streamwater samples collected from 27 stream sites located near drinking-water

intakes in Pennsylvania, 2007–09.............................................................................................51
ix

Conversion Factors and Datum

Multiply By To obtain

Length

centimeter (cm) 0.3937 inch (in.)

meter (m) 3.281 foot (ft) 

kilometer (km) 0.6214 mile (mi)

Area

square kilometer (km2) 0.3861 square mile (mi2)

Volume

liter (L) 33.82 ounce, fluid (fl. oz)

liter (L) 2.113 pint (pt)

liter (L) 1.057 quart (qt)

liter (L) 0.2642 gallon (gal)

Flow rate

meter per second (m/s) 3.281 foot per second (ft/s) 

cubic meter per second (m3/s) 35.31 cubic foot per second (ft3/s)

cubic meter per second (m3/s) 22.83 million gallons per day (Mgal/d) 

Mass

gram (g) 0.03527 ounce, avoirdupois (oz)

Pressure

megapascal (MPa) 145.037 pound per square inch (lb/in2) 

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows:

°F=(1.8×°C)+32

Temperature in degrees Fahrenheit (°F) may be converted to degrees Celsius (°C) as follows:

°C=(°F-32)/1.8

Horizontal coordinate information is referenced to the North American Datum of 1983 (NAD 83)

Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (μS/cm at 

25°C).

Concentrations of chemical constituents in water are given in nanograms per liter (ng/L).

Concentrations of chemical constituents in stream-bed sediment are given in micrograms per 

kilogram (μg/kg).

20. Land-use statistics for 27 stream sites near drinking-water intakes 

in Pennsylvania, 2007–09...........................................................................................................57

21. Contaminant of emerging concern compounds detected in streamwater and 

streambed-sediment samples collected from 16 fish-health sites 

in Pennsylvania, 2007–09...........................................................................................................78

22. Detection frequencies of selected compounds in samples collected from sites

downstream from wastewater-effluent-discharge sites, 2007–09; sites near drinkingwater intakes, 2007–09; and fish-health sites, 2007 and 2008, in Pennsylvania...............63
x

Abbreviations and Acronyms

AFO Animal feeding operation

AHTN 6-Acetyl-1,1,2,4,4,7-hexamethyltetraline

ASE Accelerated solvent extraction

BHA 3-tert-Butyl-4-hydroxyanisole 

CAS American Chemical Society’s chemical abstract service

CSO Combined sewer overflow

DCM/MeOH five percent methanol in dichloromethane

DEET N,N-diethyl-m-toluamide

ESI Electrospray ionization

GAC Granular activated carbon

GC/MS Gas chromatography/mass spectrometry

GFF Glass fiber filter

HHCB Hexahydrohexamethyl-cyclopentabenzopyran 

HPLC High-performance liquid chromatography

HPLC/MS High-performance liquid chromatography/mass spectrometry

IDS Isotope dilution standard

LC/MS/MS Liquid chromatography/tandem mass spectrometry

LMS Laboratory matrix spike

LRB Laboratory reagent blank

LRL Laboratory reporting limit

MRL Minimum reporting level

MRM Multiple reaction monitoring

NF/RO Nanofiltration/reverse osmosis

NP total, para-Nonylphenol 

NWIS National Water Information System

OPEO1 Octylphenol, monoethoxy

OPEO2 Octylphenol, diethoxy

PADEP Pennsylvania Department of Environmental Protection

PAH Polycyclic aromatic hydrocarbon

PA-WSC Pennsylvania Water Science Center

PDBE 47 2,2’,4,4’-Tetrabromo diphenylether

MDL Method detection limit

MSTFA N-methyl-N-(trimethylsilyl)- trifluoroacetamide

NPEO2 nonylphenol, diethoxy (total)

NWQL National Water Quality Laboratory

ORGL Organic Geochemistry Research Laboratory

OWC Organic Wastewater Compound

RNA Ribonucleic acid

RPD Relative percent difference

SPE Solid-phase extraction

USGS U.S. Geological Survey

WQN Water Quality Network
Occurrence of Pharmaceuticals, Hormones, and Organic 

Wastewater Compounds in Pennsylvania Waters, 2006–09

By Andrew G. Reif, J. Kent Crawford, Connie A. Loper, Arianne Proctor, Rhonda Manning, and Robert Titler

six paired stream sampling sites located upstream and downstream from animal-feeding operations. The highest reported 

concentration of these seven compounds was for the antibiotic 

sulfamethoxazole (157 ng/L), in a sample from the downstream site on Snitz Creek in Lancaster County, Pa.

Twenty-one pharmaceutical compounds were detected in 

streamwater samples collected in 2006 from five paired stream 

sampling sites located upstream or downstream from a municipal wastewater-effluent-discharge site. The most commonly 

detected compounds and maximum concentrations were the 

anticonvulsant carbamazepine, 276 ng/L; the antihistamine 

diphenhydramine, 135 ng/L; and the antibiotics ofloxacin, 

329 ng/L; sulfamethoxazole, 1,340 ng/L; and trimethoprim, 

256 ng/L.

A total of 51 different contaminants of emerging concern 

were detected in streamwater samples collected from 2007 

through 2009 at 13 stream sampling sites located downstream 

from a wastewater-effluent-discharge site. The concentrations 

and numbers of compounds detected were higher in stream 

sites downstream from a wastewater-effluent-discharge site 

than in stream sites upstream from a wastewater-effluentdischarge site. This finding indicates that wastewater-effluent 

discharges are a source of contaminants of emerging concern; these contaminants were present more frequently in the 

streambed-sediment samples than in streamwater samples. 

Antibiotic compounds were often present in both the streamwater and streambed-sediment samples, but many OWCs were 

present exclusively in the streambed-sediment samples. Compounds with endocrine disrupting potential including detergent 

metabolites, pesticides, and flame retardants, were present in 

the streamwater and streambed-sediment samples. Killinger 

Creek, a stream where wastewater-effluent discharges contribute a large percentage of the total flow, stands out as a stream 

with particularly high numbers of compounds detected and 

detected at the highest concentrations measured in the reconnaissance sampling.

Nineteen contaminants of emerging concern were 

detected in streamwater samples collected quarterly from 

2007 through 2009 at 27 stream sites within 5 miles of a 

drinking-water intake. The number of contaminants and the 

concentrations detected at the stream sites within 5 miles 

Abstract

Concern over the presence of contaminants of emerging concern, such as pharmaceutical compounds, hormones, 

and organic wastewater compounds (OWCs), in waters of the 

United States and elsewhere is growing. Laboratory techniques developed within the last decade or new techniques 

currently under development within the U.S. Geological Survey now allow these compounds to be measured at concentrations in nanograms per liter. These new laboratory techniques 

were used in a reconnaissance study conducted by the U.S. 

Geological Survey, in cooperation with the Pennsylvania 

Department of Environmental Protection, to determine the 

occurrence of contaminants of emerging concern in streams, 

streambed sediment, and groundwater of Pennsylvania. Compounds analyzed for in the study are pharmaceuticals (human 

and veterinary drugs), hormones (natural and synthetic), and 

OWCs (detergents, fragrances, pesticides, industrial compounds, disinfectants, polycyclic aromatic hydrocarbons, fire 

retardants and plasticizers). Reconnaissance sampling was 

conducted from 2006 to 2009 to identify contaminants of 

emerging concern in (1) groundwater from wells used to supply livestock, (2) streamwater upstream and downstream from 

animal feeding operations, (3) streamwater upstream from 

and streamwater and streambed sediment downstream from 

municipal wastewater effluent discharges, (4) streamwater 

from sites within 5 miles of drinking-water intakes, and (5) 

streamwater and streambed sediment where fish health assessments were conducted.

Of the 44 pharmaceutical compounds analyzed in 

groundwater samples collected in 2006 from six wells used 

to supply livestock, only cotinine (a nicotine metabolite) and 

the antibiotics tylosin and sulfamethoxazole were detected. 

The maximum concentration of any contaminant of emerging concern was 24 nanograms per liter (ng/L) for cotinine, 

and was detected in a groundwater sample from a Lebanon 

County, Pa., well.

Seven pharmaceutical compounds including acetaminophen, caffeine, carbamazepine, and the four antibiotics tylosin, 

sulfadimethoxine, sulfamethoxazole, and oxytetracycline 

were detected in streamwater samples collected in 2006 from 
2 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

of drinking-water intakes were generally very low (concentrations less than 50 ng/L), much lower than those at sites 

downstream from a wastewater-effluent discharge. The most 

commonly detected compounds and maximum concentrations were caffeine, 517 ng/L; carbamazepine, 95 ng/L; 

sulfamethoxazole, 146 ng/L; and estrone, 3.15 ng/L. The 

concentrations and frequencies of detection of some of the 

contaminants of emerging concern appear to vary by season, 

which could be explained by compound use, flow regime, 

or differences in degradation rates. Concentrations of some 

contaminants were associated with lower flows as a result of 

decreased in-stream dilution of wastewater effluents or other 

contamination sources.

Twenty-two contaminants of emerging concern were 

detected once each in streamwater samples collected in 2007 

and 2008 from 16 fish-health stream sites located statewide. 

The highest concentrations were for the OWCs, including 

flame retardants tri(2-butoxyethyl)phosphate (604 ng/L) and 

tri(2-chloroethyl)phosphate (272 ng/L) and the fragrance isoquinoline (330 ng/L). Far fewer numbers of contaminants of 

emerging concern were detected at the fish-health sites than at 

the wastewater-effluent-discharge sites. Most of the fish-health 

sites were not located directly downstream from a wastewatereffluent discharge, but there were multiple wastewater-effluent 

discharges in the drainage basins upstream from the sampling 

sites. No distinct pattern of contaminant occurrence could be 

discerned for the fish-health stream sites.

Introduction

In recent years, certain groups of compounds referred to 

as “contaminants of emerging concern” have gained widespread attention in the scientific literature and in the public 

press. The attention has resulted, in part, because technological 

advancements have “made it possible to detect and quantify 

nearly any compound at diminishingly minute concentrations in water” (Snyder and others, 2009). Researchers have 

documented the occurrence of these contaminants in streams 

(Kolpin and others, 2002) and groundwater (Barnes and others, 2008), but the extent of their distribution and the consequences of their presence are largely unknown (Daughton and 

Ternes 1999; Jorgensen and Halling-Sorensen, 2000).

Virtually all chemical compounds used by humans have 

pathways to the environment. The combination of compound 

use and compound physical and chemical properties influences 

the likelihood of its detection in the environment. Persistent 

compounds remain in the environment for long periods of time 

in their original form and are more likely to be found in the 

environment than nonpersistent compounds that break down 

rapidly once they are in the environment. Compounds that partition strongly to solids are not likely to be detected in water 

but may accumulate in sediments. On the other hand, hydrophilic (water-loving) compounds are more likely to be transported to aquifers or streams as solutes and can be detected 

at levels in proportion to use and excretion. Compounds that 

degrade readily by chemical or biological processes may leave 

behind metabolite breakdown products in water or sediments.

Purpose and Scope

The purpose of this report is to summarize the occurrence and concentrations of three groups of contaminants of 

emerging concern in selected waters and streambed sediments in Pennsylvania, which are based on reconnaissance 

data collected from 2006 through 2009. The three groups of 

contaminants are pharmaceutical compounds, hormones, and 

organic wastewater compounds (OWCs). Analytical results 

are presented for 44 pharmaceutical compounds, 17 hormones 

and 2 animal sterols, and 56 OWCs analyzed in water, and 

for 27 antibiotics, 17 hormones and 2 animal sterols, and 51 

OWCs analyzed in streambed-sediment samples. This report 

summarizes and presents discussions of the findings from 

the reconnaissance sampling conducted from 2006 to 2009. 

Concentration ranges for compounds are listed in tables, and 

detection frequencies (detections per number of samples) are 

shown in figures.

Categories of Contaminants of Emerging 

Concern

Contaminants of emerging concern include manufactured and natural organic compounds that may be categorized 

as pharmaceutical compounds (human and veterinary drugs, 

including antibiotics), as natural and synthetic hormones, and 

as OWCs (substances associated with effluents from municipal wastewater-treatment plants). Because of the numerous sources and number of compounds, it is not practical to 

analyze for every compound that can potentially make its way 

into the environment. However, subsets of pharmaceutical, 

hormone, and organic wastewater compounds can be quantified using newly developed laboratory techniques. 

Pharmaceuticals are primarily organic compounds 

formulated to serve therapeutic purposes in humans and 

animals. Pharmaceuticals enter the environment as a result of 

the improper disposal of drugs and the discharge of excreted 

waste containing metabolized and un-metabolized pharmaceuticals into sanitary sewers. Khan and Ongerth (2002) point 

to the increasing frequency of detection of pharmaceutical 

residues in sewage sludge. Some of these compounds are considered endocrinologically active compounds termed “endocrine disruptors” and may disrupt the endocrine system of fish 

and other wildlife (Lintelmann and others, 2003). Increasing 

sales of prescription drugs substantially increase the likelihood that the drugs will be detected in streamwater and 

groundwater, and new drugs are continually being approved. 

The compounds included in the pharmaceutical analysis 

and their reporting levels are listed in table 1. Prescription 

and non-prescription medications, along with metabolite 
Introduction 3

breakdown products (para-xanthine and cotinine) and caffeine, are included in the pharmaceutical analysis. Although 

para-xanthine, cotinine, and caffeine are not strictly pharmaceuticals (table 1), they are included in the discussions under 

the general term pharmaceutical compounds because they are 

associated with human use.

Antibiotics represent a subset of the pharmaceutical compounds that are used in humans and animals to kill bacteria 

or prevent bacterial infections and to promote growth in farm 

animals. Antibiotics are widely used to treat common respiratory infections, urinary tract infections, sexually transmitted diseases, burns, and skin rashes. They are also used for 

more serious bacterial health issues like meningitis, cholera, 

Rickettsia, and others. Further, it is estimated that 70 percent 

of all antibiotics produced today are used in agriculture and 

animal husbandry (Mellon and others, 2001). Antibiotics are 

routinely fed to livestock, poultry, and commercially raised 

fish to promote faster growth and to compensate for the 

crowded conditions in which these animals are raised (Sarmah 

and others, 2006). One major concern is that bacteria are 

developing resistance to some legacy antibiotics so that different antibiotics, new antibiotics, or combinations of antibiotics 

are now needed to treat some bacterial infections. 

Hormones are chemical compounds manufactured in 

various body organs, such as the pineal gland, pituitary gland, 

thyroid, adrenal gland, ovaries, and testes. These compounds 

travel in the blood stream to send messages to other body 

organs to regulate their functions. Hormones affect growth, 

mood swings, metabolism, the immune system, and the reproductive cycle. Abnormalities in the production of hormones 

can lead to human-health problems such as Addison’s disease, 

Cushing’s disease, and diabetes (Hall, 2011). Only a small 

amount of a hormone is needed to alter cell metabolism. Thus, 

low concentrations of hormones in the environment may cause 

unwanted responses in organisms exposed to those hormones. 

Research provides compelling evidence that endocrine 

systems of certain fish and wildlife have been affected by 

chemical contaminants, resulting in development and reproductive problems. For example, feminization of fish has been 

documented (Iguchi and others, 2001), and intersex fish are 

common in the Potomac River Basin and elsewhere (Jobling 

and others, 2006; Hinck and others, 2006; Woodling and others, 2006; Blazer and others, 2007; Tyler and Jobling, 2008; 

Vajda and others, 2008). A 7-year long Canadian study in 

which a lake was dosed with low levels (5 nanograms per liter 

(ng/L)) of 17-alpha-ethynylestradiol (synthetic estrogen) over 

a 3-year period demonstrated that “continued inputs of natural 

and synthetic estrogens and estrogen mimics...could decrease 

the reproductive success and sustainability of fish populations” 

(Kidd and others, 2007). The animal sterols, cholesterol and 

3-beta-coprostanol, are included in the hormone analysis and 

in the discussion of hormone compounds. The compounds 

included in the hormone analysis and their reporting levels are 

listed in table 2.

Organic wastewater compounds (OWCs) are substances 

associated with effluents from municipal wastewater-treatment 

plants. The list of OWCs includes but is not limited to detergent metabolites, fragrances, flavors, pesticides, industrial 

compounds, disinfectants, polycyclic aromatic hydrocarbons 

(PAHs), fire retardants, and plasticizers. Although many of 

these compounds have both point and non-point sources, they 

can be used as indicators of wastewater. Many of the OWCs 

commonly detected in wastewater effluents have known or 

suspected endocrine disrupting potential. The plant sterols, 

beta-sitosterol and beta-stigmastanol, are included in the 

OWC analysis and in the discussion of OWC compounds. The 

compounds included in the OWC analysis and their reporting 

levels are listed in table 3.
4 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table 1. Pharmaceutical compounds analyzed in streamwater and streambed-sediment samples, medicinal uses, and reporting 

levels.—Continued

[NWIS, National Water Information System; NWQL, U.S. Geological Survey National Water Quality Laboratory, Denver Colorado; ORGL, U.S. Geological 

Survey Organic Geochemistry Research Laboratory, Lawrence, Kansas; na, not analyzed; --, no data; ng/L, nanograms per liter; μg/kg, micrograms 

per kilogram]

Compound 

name

Medicinal 

use

Analylizing

laboratory

Streamwater Streambed sediment 

NWIS 

parameter 

code

Reporting 

level 

(ng/L)

NWIS 

parameter 

code

Reporting 

level 

(μg/kg)

Nonprescription pharmaceuticals and metabolites

Acetaminophen Analgesic NWQL 62000 12 na --

Caffeine1 Stimulant NWQL 50305 8 na --

Ibuprofen Analgesic ORGL 62014 25 na --

Para-xanthine1,2,3 Caffeine metabolite NWQL 62030 10 na --

Codeine Analgesic NWQL 62003 11 na --

Cotinine1 Nicotine metabolite NWQL 62005 14 na --

Diphenhydramine Antihistamine, antimetic (antinausea), sleep aid, sedativeNWQL 62796 12 na --

Prescription pharmaceuticals

Carbamazepine Anticonvulsant and antimanic 

agent4

NWQL 62793 9 na --

Dehydronifedipine Antianginal NWQL 62004 11 na --

Diltiazem Antihypertensive NWQL 62008 9 na --

Salbutamol Antiasthmatic NWQL 62020 7 na --

Thiabendazol Anthelmintics (used to treat 

worm infections)

NWQL 62801 13 na --

Warfarin Anticoagulant NWQL 62024 9 na --

Macrolide antibiotics and metabolites

Azithromycin Human Antibiotic ORGL 62792 5 Code not 

established

1–5

Erythromycin Human antibiotic also used in 

fish hatcheries

ORGL 62797 8 Code not 

established

1–5

Erythromycin-H2O 

(anhydro-erythromycin)2

Erythromycin metabolite ORGL 63674 8 Code not 

established

--

Roxithromycin Human Antibiotic ORGL 62895 5 Code not 

established

1–5

Tylosin Veterinary antibiotic used on 

cattle, swine, and poultry

ORGL 62896 8 Code not 

established

1–5

Virginiamycin Veterinary antibiotic used on 

cattle and swine, also used in 

ethanol fuel industry

ORGL 62897 5 Code not

established

1–5
Introduction 5

Table 1. Pharmaceutical compounds analyzed in streamwater and streambed-sediment samples, medicinal uses, and reporting 

levels.—Continued

[NWIS, National Water Information System; NWQL, U.S. Geological Survey National Water Quality Laboratory, Denver Colorado; ORGL, U.S. Geological 

Survey Organic Geochemistry Research Laboratory, Lawrence, Kansas; na, not analyzed; --, no data; ng/L, nanograms per liter; μg/kg, micrograms 

per kilogram]

Compound 

name

Medicinal 

use

Analylizing

laboratory

Streamwater Streambed sediment 

NWIS 

parameter 

code

Reporting 

level 

(ng/L)

NWIS 

parameter 

code

Reporting 

level 

(μg/kg)

Quinoline antibiotics

Ciprofloxacin Human antibiotic ORGL 62898 5 Code not

established

1–5

Enrofloxacin Veterinary antibiotic used on 

domestic animals

ORGL 66495 5 Code not

established

1–5

Lomefloxacin Human antibiotic ORGL 62900 5 Code not

established

1–5

Norfloxacin Human antibiotic ORGL 62757 5 Code not

established

1–5

Ofloxacin Human antibiotic ORGL 62899 5 Code not

established

1–5

Sarafloxacin Veterinary antibiotic used on 

poultry and fish

ORGL 62771 5 Code not

established

1–5

Sulfonamide antibiotics

Sulfachloropyridazine Veterinary antibiotic ORGL 62774 5 Code not

established

1–5

Sulfadiazine Human antibiotic ORGL 62963 100 Code not

established

1–10

Sulfadimethoxine Veterinary antibiotic ORGL 62776 5 Code not

established

1–5

Sulfamethazine Veterinary antibiotic used on 

cattle, swine, and poultry

ORGL 61762 5 Code not

established

1–5

Sulfamethoxazole Human antibiotic often used 

in combination with trimethoprim

ORGL 62775 5 Code not

established

1–5

Sulfathiazole Human antibiotic and used in fish 

aquariums

ORGL 62778 20 Code not

established

1–10

Tetracycline antibiotics and metabolites

Chlorotetracycline Veterinary antibiotic ORGL 61744 10 Code not

established

1–5

Epi-chlorotetracycline 

(4-EC-tetracycline HCl)1

Chlorotetracycline metabolite ORGL 63731 10 Code not

established

--

Epi-iso-chlorotetracycline 

(Iso-epi-chlorotetracycline)2

Metabolite of chlorotetracycline ORGL 64047 10 Code not

established

--

Iso-chlorotetracycline2 Metabolite of chlorotetracycline ORGL 64175 10 Code not

established

--

Doxycycline Human antibiotic ORGL 62694 10 Code not

established

1–5

Oxytetracycline Human and veterinary antibiotic 

also used in fish hatcheries

ORGL 61759 10 Code not

established

1–5

Epi-oxytetracycline 

(4-Epi-oxytetracycline)2

Metabolite of oxytetracycline ORGL 63729 10 Code not

established

1

Tetracycline Human antibiotic ORGL 62781 10 Code not

established

1–5

Epi-tetracycline 

(4-Epi-tetracycline HCl)1

Metabolite of epi-tetracycline ORGL 63727 10 Code not

established

1–5
6 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table 1. Pharmaceutical compounds analyzed in streamwater and streambed-sediment samples, medicinal uses, and reporting 

levels.—Continued

[NWIS, National Water Information System; NWQL, U.S. Geological Survey National Water Quality Laboratory, Denver Colorado; ORGL, U.S. Geological 

Survey Organic Geochemistry Research Laboratory, Lawrence, Kansas; na, not analyzed; --, no data; ng/L, nanograms per liter; μg/kg, micrograms 

per kilogram]

Compound 

name

Medicinal 

use

Analylizing

laboratory

Streamwater Streambed sediment 

NWIS 

parameter 

code

Reporting 

level 

(ng/L)

NWIS 

parameter 

code

Reporting 

level 

(μg/kg)

Other antibiotics

Chloramphenicol Human antibiotic ORGL 65194 100 Code not

established

1

Lincomycin Human antibiotic ORGL 62894 5 Code not

established

1–5

Ormetoprim Veterinary antibiotic ORGL 62962 5 Code not

established

1–5

Trimethoprim Human antibiotic often used 

in combination with sulfamethoxazole

ORGL 62023 5 Code not

established

1–5

1

Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.

2

Metabolite breakdown product.

3

Para-xanthine also know as 1,7 dimethylxanthine.

4

Couper and Logan, 2004.
Introduction 7

Table 2. Hormones and animal sterols analyzed in streamwater and streambed-sediment samples, medicinal uses, and reporting 

levels.

[NWIS, National Water Information System; ng/L, nanograms per liter; μg/kg, micrograms per kilogram]

Compound Medicinal use

Streamwater Streambed sediment 

NWIS 

parameter 

code 

Reporting 

level 

(ng/L)

NWIS 

parameter 

code 

Reporting 

level 

(μg/kg)

Natural androgen

4-Androstene-3,17-dione Testosterone precursor, illicit steroid 64513 0.40 64473 0.05

cis-Androsterone Testosterone metabolite, used in deer 

repellent 64515 0.40 63607 0.05

Epitestosterone Human androgen 64517 2.00 64477 0.25

11-Ketotestosterone Very strong androgen 64507 0.40 64467 0.13

Stanolone (Dihydrotestosterone) Testosterone metabolite, very strong 

androgen 64524 0.40 64484 0.05

Testosterone Principal human androgen, strong 

androgen 64525 0.40 64485 0.05

Natural estrogen

Equilenin Equine estrogen, hormone replacement 

therapy 64518 1.00 63204 0.13

Equilin Equine estrogen, hormone replacement 

therapy 64519 2.00 64479 0.25

17-alpha-Estradiol Low occurrence in humans, common in 

other species 64508 0.40 64468 0.05

17-beta-Estradiol1 Principal estrogen in humans, strong 

estrogen

64510 0.40 63164 0.05

Estriol Metabolite of 17-beta-estradiol 64520 0.40 64480 0.13

Estrone Metabolite of 17-beta-estradiol 64521 0.40 63205 0.05

Synthetic estrogen

Diethylstilbestrol Pharmaceutical 64516 0.40 63620 0.05

17-alpha-Ethynylestradiol1 Used in oral contraceptives, very strong 

estrogen

64509 0.40 63207 0.05

Mestranol Used in oral contraceptives, metabolized 

to ethynyl estradiol1 prior to excretion 64522 0.40 63638 0.05

Natural progestin

Progesterone Principal human progestational hormone 64523 2.00 63657 0.25

Synthetic progestin

Norethindrone (19-Norethisterone) Used in oral contraceptives 64511 0.40 63644 0.05

Animal sterol

Cholesterol Ubiquitous, produced by animals and 

plants 64514 1,000 63196 125

3-beta-Coprostanol Carnivore fecal indicator, useful sewage 

tracer

64512 1,000 63170 250

1

 Known endocrine disrupting potential.
8 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table 3. Organic wastewater compounds analyzed in streamwater and streambed-sediment samples, uses or sources, and reporting 

levels.—Continued

[NWIS, National Water Information System; na, not analyzed; ng/L, nanograms per liter; μg/kg, micrograms per kilogram; --, no data; PAH, polycyclic aromatic hydrocarbon]

Compound Use or sources

Streamwater Streambed sediment 

NWIS 

parameter

code

Reporting 

level

(ng/L)

NWIS 

parameter

code

Reporting 

level

(μg/kg)

Detergent metabolites

4-Cumylphenol1 Nonionic detergent metabolite 62060 50 63173 34

4-n-Octylphenol1 Nonionic detergent metabolite 62061 80 63174 37

4-tert-Octylphenol1 Nonionic detergent metabolite 62062 50 63176 23

Nonylphenol, diethoxy- (total, 

NPEO2)1

Nonionic detergent metabolite 62083 2,500 63200 852

para-Nonylphenol (total, NP)1 Nonionic detergent metabolite 62085 500 63175 498

Octylphenol, diethoxy- 

(OPEO2)1

Nonionic detergent metabolite 61705 500 na --

Octylphenol, monoethoxy-

(OPEO1)1

Nonionic detergent metabolite 61706 500 na --

Fragrances and flavors

3-Methyl-1H-indole (skatol) Fragrance, stench in feces and coal tar 62058 20 63171 31

Acetophenone Fragrance in detergent and tobacco, flavor in beverages 62064 50 63178 100

Acetyl-hexamethyl-tetrahydronaphthalene (AHTN) Musk fragrance, persistent and widespread, in groundwater, concern for bioaccumulation and toxicity 62065 250 63179 13

Camphor Flavor, odorant, ointments 62070 30 63192 27

Hexahydrohexamethyl-cyclopentabenzopyran (HHCB) Musk fragrance, persistent and widespread, in ground 

water, concern for bioaccumulation and toxicity 

62075 300 63209 17

Indole Inert pesticide ingredient, fragrance in coffee 62076 40 63210 54

Isoborneol Fragrance in perfumery, in disinfectants 62077 30 63211 39

Isoquinoline Flavors and fragrances 62079 100 63214 83

Menthol Cigarettes, cough drops, liniment, mouthwash 62080 100 63215 42

 Pesticides and degradates

1,4-Dichlorobenzene2 Moth repellant, fumigant, deodorant 34572 20 63163 28

Atrazine Herbicide na -- 63182 59

Bromacil Herbicide, greater than 80 percent noncrop usage on 

grass

04029 200 63189 254

Carbaryl1 Insecticide, crop and garden uses, low persistence 82680 500 na --

Carbazole Insecticide, manufacturing of dyes, explosives, and 

lubricants 

62071 20 63194 22
Introduction 9

Table 3. Organic wastewater compounds analyzed in streamwater and streambed-sediment samples, uses or sources, and reporting 

levels.—Continued

[NWIS, National Water Information System; na, not analyzed; ng/L, nanograms per liter; μg/kg, micrograms per kilogram; --, no data; PAH, polycyclic aromatic hydrocarbon]

Compound Use or sources

Streamwater Streambed sediment 

NWIS 

parameter

code

Reporting 

level

(ng/L)

NWIS 

parameter

code

Reporting 

level

(μg/kg)

 Pesticides and degradates

Chlorpyrifos1 Insecticide, domestic pest and termite control (domestic 

use restricted as of 2001) 

38933 60 63195 34

d-Limonene Fungicide, antimicrobial, antiviral, fragrance in aerosols 62073 20 63203 24

Diazinon1 Insecticide, greater than 40 percent nonagricultural 

usage

39572 40 63198 49

Metalaxyl General use pesticide, herbicide, fungicide, mildew, 

blight, pathogens, golf/turf 

50359 40 na --

Metolachlor2 General use pesticide, indicator of agricultural drainage 39415 40 63218 37

N,N-diethyl-meta-toluamide 

(Deet) 

Insecticide, urban uses, mosquito repellent 62082 50 63219 56

Prometon Herbicide, noncrop only, applied prior to blacktop 04037 90 63226 44

Industrial compounds 

3-tert-Butyl-4-hydroxyanisole 

(BHA)1

Antioxidant, general preservative 62059 300 63172 101

5-Methyl-1H-benzotriazole Antioxidant in antifreeze and deicers 62063 40 na --

Anthraquinone Manufacturing of dye/textiles, seed treatment, bird 

repellant 

62066 80 63181 24

Benzophenone2 Fixative for perfumes and soaps 62067 60 63184 32

Isophorone Solvent for lacquer, plastic, oil, silicon, resin 34409 40 63212 43

Isopropylbenzene (cumene) Manufacturing phenol/acetone, fuels and paint thinner 62078 50 63213 87

Methyl salicylate Liniment, food, beverage, UV-absorbing lotion 62081 50 na --

para-Cresol2 Wood preservative 62084 90 63222 161

Tetrachloroethylene Solvent, degreaser, veterinary anthelmintic 34476 40 na --

Triethyl citrate (ethyl citrate) Cosmetics, pharmaceuticals 62091 100 na --

Disinfectants and by-products

Bromoform Wastewater ozination byproduct, military/explosives 34288 50 na --

Phenol Disinfectant, manuf several products, leachate 34466 100 63225 38

Triclosan2 Disinfectant, antimicrobial (concern for acquired microbial resistance) 62090 100 63232 50
10 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table 3. Organic wastewater compounds analyzed in streamwater and streambed-sediment samples, uses or sources, and reporting 

levels.—Continued

[NWIS, National Water Information System; na, not analyzed; ng/L, nanograms per liter; μg/kg, micrograms per kilogram; --, no data; PAH, polycyclic aromatic hydrocarbon]

Compound Use or sources

Streamwater Streambed sediment 

NWIS 

parameter

code

Reporting 

level

(ng/L)

NWIS 

parameter

code

Reporting 

level

(μg/kg)

Polycyclic aromatic hydrocarbon

1-Methylnaphthalene 2–5 percent of gasoline, diesel fuel, or crude oil 62054 20 63165 28

2,6-Dimethylnaphthalene Present in diesel/kerosene (trace in gasoline) 62055 60 63167 25

2-Methylnaphthalene 2–5 percent of gasoline, diesel fuel, or crude oil 62056 20 63168 28

Anthracene Wood preservative, component of tar, diesel, or crude 

oil, combustion product 

34221 20 63180 20

Benzo[a]pyrene1 Regulated PAH, used in cancer research, combustion 

product 

34248 40 63183 25

Fluoranthene Component of coal tar and asphalt (only traces in 

gasoline or diesel fuel)

34377 20 63208 24

Naphthalene Fumigant, moth repellent, major component (about 

10 percent) of gasoline 

34443 20 63220 24

Phenanthrene Manufacturing of explosives, component of tar, diesel 

fuel, or crude oil, combustion product 

34462 20 63224 21

Pyrene Component of coal tar and asphalt (only traces in 

gasoline or diesel fuel)

34470 20 63227 21

Flame retardants and plasticizers

2,2’,4,4’-Tetrabromo diphenylether (PDBE 47) Fire retardant na -- 63166 19

Diethyl phthalate Plasticizer na -- 63202 47

Tri(2-chloroethyl) phosphate2 Plasticizer, flame retardant 62087 60 63230 70

bis (2-ethylhexyl) phthalate Plasticizer na -- 63187 138

Tri(dichloroisopropyl) phosphate2Flame retardant 62088 60 63235 73

Tributyl phosphate Antifoaming agent, flame retardant 62089 100 63231 39

Triphenyl phosphate Plasticizer, resin, wax, finish, roofing paper 62092 50 63234 46

Tri(2-butoxyethyl) phosphate Flame retardant 62093 200 63229 99

Plant sterols

beta-Sitosterol Plant sterol 62068 800 63185 363

beta-Stigmastanol Plant sterol 62086 600 63186 367

1

Known endocrine disrupting potential.

2

Suspected endocrine disrupting potential.
Introduction 11

Potential Sources of Contaminants of Emerging 

Concern

Thousands of chemical compounds fall under the classification of contaminants of emerging concern. As of June 2009, 

nearly 47.6 million organic and inorganic substances had 

been indexed by the American Chemical Society’s Chemicals 

Abstracts Service (CAS) registry. Over 35 million of these 

chemicals were commercially available, though only 248,000, 

or 0.5 percent, of these were inventoried or regulated by government bodies worldwide. Five years earlier, in March 2004, 

only 23 million organic and inorganic substances had been 

indexed, with 7 million commercially available and 230,000 

inventoried and (or) regulated (American Chemical Society, 

2010). The doubling of the number of compounds indexed and 

inventoried from 2004 to 2009 shows that the list of manmade chemical compounds is growing rapidly. Of the total list 

of compounds, the Pennsylvania reconnaissance sampling, on 

which this report is based, assessed a small fraction. Newly 

developed compounds are often available commercially before 

they have been inventoried, tested, or regulated.

Agricultural Sources

 One path for the introduction of these contaminants to 

streamwater and groundwater is through land application of 

manure (Halling-Sorensen and others, 1998). Contaminants in 

manure may be transported to the groundwater system through 

recharge and reach the stream either through groundwater 

discharge or in surface-water runoff. For the agricultural sites 

included in this study, there was no confirmation that waste 

products from the agricultural operations were applied to land 

within the drainage area of the reach of the stream sampled or 

even applied to land within the same watershed.

Wastewater Effluents

Streams receiving wastewater-effluent discharges have 

been documented to contain detectable concentrations of contaminants of emerging concern (Halling-Sorensen and others, 

1998; Ternes, 1998; Daughton and Ternes, 1999; Loraine and 

Pettigrove, 2006; Roberts and Thomas, 2006; Vajda and others, 2008; Jobling and others, 2009; Sellin and others, 2009). 

Wastewater-treatment plants can concentrate compounds from 

a larger area and discharge them into a stream as a single 

point source.

Other Potential Sources of Contaminants of 

Emerging Concern

Contaminants of emerging concern have been detected in 

streams that do not receive wastewater-effluent discharge or 

are not affected by agricultural land use, indicating that there 

are other non-point sources. Other potential sources that contribute contaminants of emerging concern to the environment 

exist, but they were not directly evaluated as part of this study. 

These sources include, but are not limited to, pharmaceutical 

manufacturer discharges, land application of biosolids, landfill 

leachate, combined sewer overflows (CSOs), and non-point 

sources including residential, commercial, and institutional 

on-site wastewater systems (septic systems). The present study 

did not consider locations of potential contaminant of emerging concern sources as a criterion for sampling-site selection.

Pharmaceutical Manufacturing Facilities

The findings from a national study, which focused on 

determining the contribution to the environment of contaminants of emerging concern from pharmaceutical manufacturers 

to wastewater-treatment plants, indicate that discharges from 

pharmaceutical manufacturing processes can increase pharmaceutical concentrations 10 to 1,000 times from those typically 

found in wastewater-treatment-plant effluents without such 

input (Phillips and others, 2010).

Land Application of Biosolids

Land application of biosolids to fertilize agricultural 

lands is common in Pennsylvania and presents yet another 

avenue by which contaminants of emerging concern can enter 

the environment. A study by Kinney and others (2006) evaluated nine different biosolid products produced by municipal 

wastewater-treatment plants in seven different states for 87 

different OWCs. Results showed that a minimum of 30 and a 

maximum of 45 compounds were detected in any one biosolid 

sample. OWCs detected in biosolids can either infiltrate into 

groundwater and enter streams through base flow or act as a 

nonpoint source and enter streams in runoff. Contaminants of 

emerging concern also have been detected in crops and earthworms from land to which biosolids have been applied (Boxall 

and others, 2006; Kinney and others, 2008).

Landfill Leachate

Leaching from defective or poorly engineered landfills 

also can be a potential source of contaminants of emerging 

concern in water. Contaminants that have been sent to landfills are subject to biologic degradation processes; however 

some compounds that are resistant to degradation may leach 

into groundwater (Barnes and others, 2004). In a study by the 

Maine Department of Environmental Protection (2010), tests 

were conducted on leachate from three landfills in Maine. 

Results of laboratory analysis indicate that low concentrations 

of pharmaceuticals were present in the leachate as a result of 

the disposal of pharmaceuticals in household waste. In properly functioning landfills, leachate is collected and sent to a 

wastewater-treatment plant for treatment.
12 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Combined Sewer Overflows

Combined sewer overflows occur during storm runoff 

when sanitary waters bypass treatment plants and combine 

with stormwater that discharges directly to a stream. This 

untreated wastewater is a potential source of contaminants of 

emerging concern. A study by Philips and Chalmers (2009) 

evaluated the concentrations of OWCs in wastewater-treatment-plant effluent and combined sewer overflow (CSO) effluent. Results indicate that OWCs that are effectively removed 

through wastewater treatment were found in CSO effluent at 

concentrations equal to or greater than concentrations found in 

wastewater-treatment-plant effluent. OWCs that undergo little 

removal through wastewater treatment were found in CSO 

effluent at concentrations less than concentrations found in 

wastewater-treatment-plant effluent.

On-Site Wastewater Systems

On-site wastewater disposal systems (septic systems) 

have the potential to introduce contaminants of emerging 

concern into groundwater and ultimately into streams through 

base flow (Carrara and others, 2008). A U.S. Geological 

Survey study to determine the effect of on-site wastewater disposal on the quality of groundwater and base flow in 

Chester County, Pa., found that 30 OWCs were present in 

low levels, particularly in residential areas with a high density 

of on-site wastewater-disposal systems. Of the groundwater samples analyzed, more compounds were detected in 

samples from springs than in samples from wells. (Senior and 

Cinotto, 2007).

Similarly, a study of groundwater quality conducted in 

Adams County, Pa., reported that six different OWCs were 

detected out of the 67 compounds analyzed in six wells (Low 

and Conger, 2002). Concentrations ranged from 0.02 to 

1.2 micrograms per liter. Detections of some contaminants of 

emerging concern in groundwater also were documented in 

another study in Pike County, Pa. (Senior, 2009). Again, the 

potential for on-site wastewater systems to contribute these 

contaminants to groundwater and subsequently to streams was 

confirmed. The present study did not evaluate groundwater 

quality in areas served by on-site wastewater systems.

Previous and Current Investigations

Several studies of contaminants of emerging concern 

in streams and groundwater have been conducted in the last 

decade. Work on a national scale includes Terns, 1998; Kolpin 

and others, 2002; Jobling and others, 2006; Barnes and others, 

2008; Focazio and others, 2008. Work focused on individual 

states, watersheds, or streams includes Chambers and Leiker, 

2006; Roberts and Thomas, 2006; Woodling and others, 

2006; Oblinger and others, 2007; Alvarez and others, 2008; 

Tertuliani and others, 2008; Haack, 2009; Damschen and 

Lundgren, 2009.

A few streamwater and groundwater samples from 

Pennsylvania were included in the national surveys by Kolpin 

and others (2002) and Barnes and others (2008), respectively; 

some contaminants of emerging concern were detected in 

the samples. Organic wastewater compounds were detected 

in base-flow and well-water samples in Chester County, Pa., 

(Senior and Cinotto, 2007; Senior and Sloto 2010) and in 

well-water samples in Adams County, Pa., (Low and Conger, 

2002) and Pike County, Pa., (Senior, 2009) in areas with onsite wastewater disposal. Findings from these studies indicate 

that some of the contaminants of emerging concern enter 

the groundwater from surface or near-surface sources, such 

as septic systems, and may travel in groundwater discharge 

to streams.

Although some local or limited reconnaissance data have 

been collected on the occurrence of contaminants of emerging concern in selected areas of Pennsylvania, such as those 

reported by Low and Conger (2002) and Senior and Cinotto 

(2007), no comprehensive survey has been conducted for 

Pennsylvania waters to document the occurrence and distribution of these contaminants. The U.S. Geological Survey 

(USGS), in cooperation with the Pennsylvania Department of 

Environmental Protection (PADEP), Bureau of Water Quality Standards and Facility Regulation, conducted several 

reconnaissance studies from 2006 to 2009 to provide data to 

determine whether these compounds are present in Pennsylvania waters and, if so, which compounds are present and at 

what concentrations. As part of these USGS studies done in 

cooperation with PADEP, likely sources of the contaminants 

of emerging concern were confirmed, and an assessment of the 

possible environmental health implications was provided.

In addition to the study on which this report is based, two 

companion studies regarding contaminants of emerging concern in Pennsylvania waters were conducted. The first study 

was undertaken by scientists at the USGS Leetown Science 

Center National Fish Health Research Laboratory (2008–09); 

the study provided an assessment of fish health in Pennsylvania streams, targeting two species of fish, smallmouth 

bass (Micropterus dolomieu) and white sucker (Catostomus 

commersonii). The fish were subjected to external examinations, chemical analyses, and histopathological evaluations 

(V.S. Blazer, U.S. Geological Survey, written commun., 2009). 

The second study was conducted by scientists at the USGS 

Michigan Water Science Center (2007–09) and involved the 

identification of bacterial contamination at stream sites near 

drinking-water intakes. Factors associated with the occurrence 

of pathogenic bacteria were evaluated (J.W. Duris, U.S. Geological Survey, written commun., 2009).

The pharmaceutical and antibiotic data collected in 2006 

as part of the initial reconnaissance sampling for the current 

study were presented in a data series report by Loper and others, (2007). Other contaminant of emerging concern data from 

the 2007 to 2009 sampling have been published in the USGS 

annual Water Data Reports for 2006 to 2009 (U.S. Geological 

Survey, 2007–09).
Methods 13

Study Design

The overall design of the study was built around three 

separate reconnaissance sampling efforts conducted from 2006 

to 2009. Each component was designed to assess a different 

environmental issue and each component was designed to help 

address one of the overall study objectives (table 4). 

One reconnaissance sampling effort was designed to confirm suspected source(s) of contaminants of emerging concern. 

Three components of the study addressed this issue (table 4). 

1. Analysis of water samples from wells used to supply 

livestock allowed for an evaluation to determine whether 

agricultural operations nearby represent a source of contaminants of emerging concern to groundwater. 

2. Analysis of streamwater samples collected upstream and 

downstream from animal-feeding operations (AFOs) 

allowed for evaluation of contributions of contaminants of 

emerging concern from agriculture to surface water. 

3. Analysis of streamwater samples collected upstream 

and downstream from municipal wastewater-effluentdischarge sites allowed for an evaluation of contributions 

from wastewater-treatment plants.

Streambed-sediment samples also were collected at sites 

located downstream from municipal wastewater-effluentdischarge sites. All the sampling locations for the first three 

components of the study were in south-central Pennsylvania 

(fig. 1). South-central Pennsylvania was chosen as the sampling location because of its long history of agricultural land 

use. The area also contains numerous small streams that are 

affected by AFOs and wastewater-effluent discharges. Wells in 

limestone watersheds were selected to increase the possibility 

of contaminant detections. Limestone aquifers can transport 

contaminants to groundwater faster than aquifers in other rock 

types, making detection of contaminants more likely.

A second reconnaissance sampling effort was designed to 

evaluate the occurrence of contaminants of emerging concern 

in water used as sources for public drinking water. For this 

part of the study, 27 stream-sampling locations within 5 miles 

of drinking-water intakes were selected from the 157 sites in 

the Pennsylvania Water Quality Network (WQN). The WQN 

is an ambient fixed-station network operated by the PADEP 

Bureau of Water Standards and Facility Regulation. Sites 

selected for sampling are all within 5 miles of a drinkingwater intake. This component was designed to determine 

whether or not contaminants of emerging concern are present 

in intake waters that supply drinking water to Pennsylvania 

residents (fig. 2).

A third reconnaissance sampling effort was designed to 

evaluate the possible effects of contaminants of emerging concern on aquatic organisms. For this part of the study, streamwater and streambed-sediment samples from 16 stream sites 

across Pennsylvania were analyzed (fig. 2). Sites are located 

in all three major river basins and upstream and downstream 

from suspected contaminant sources. Concurrently, fish were 

collected and examined for a number of fish-health indicators 

including external and internal anomalies, histopathological, 

and physiological markers. The correlation of fish health indicators with the occurrence and concentrations of contaminants 

of emerging concern was addressed in a companion study done 

by the USGS (V.S. Blazer, U.S. Geological Survey, written 

commun., 2012) 

Methods

Methods used for site selection, streamflow measurements, 

field water-chemistry measurements, water-quality sampling 

and processing, laboratory analyses, data analysis, and quality 

assurance and quality control are described in this section.

Site Selection and Sampling Locations

Each component of the study required sampling sites 

within specific environmental settings. Five different types of 

sampling sites were selected.

1. Wells in agricultural areas used to supply livestock,

2. Streams receiving runoff from AFOs,

3. Streams receiving municipal wastewater effluent,

4. Streams used for public drinking-water sources, and

5. Streams used for fish-health evaluations.

Wells in Agricultural Areas Used to Supply 

Livestock

Six wells in agricultural areas used to supply livestock 

were sampled quarterly in 2006; samples were analyzed for 

pharmaceutical compounds (table 1). Wells selected for sampling (table 5; fig. 1) met the following criteria:

1. Located in the south-central Pennsylvania study area,

2. Currently used to supply water for livestock on a farm,

3. Used on a daily basis,

4. Shallow (less than or equal to a total depth of 300 feet (ft)),

5. Completed in a limestone aquifer, and

6. Documented driller records of completion on file with the 

homeowner or the Pennsylvania Geological Survey that 

would provide confirmation of the well depth and aquifer 

lithology.

Sampled wells range in depth from 147 to 300 ft. Characteristics for each individual well are listed by Loper and 

others (2007).
14 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 4. Objective addressed, study component, duration of sampling, number of locations sampled, sample medium, compounds analyzed, and number of samples collected for reconnaissance sampling of waters in Pennsylvania, 2006–09. [OWC, Organic wastewater compound] Objective addressed Study component Duration of sampling Number of locations sampled Location of sampling in Pennsylvania Sample medium Compounds analyzed Number of samples collected Contaminant sources 1—Wells used to supply livestock 2006 6 South-central Pa. Water Pharmaceuticals 24 Antibiotics 24 Contaminant sources 2—Streams upstream and downstream from animal-feeding operations 2006 12 South-central Pa. Water Pharmaceuticals 48 Antibiotics 48 Contaminant sources 3—Streams upstream and downstream from wastewater treatment-plant-effluent discharge 2006 10 South-central Pa. Water Pharmaceuticals 40 Antibiotics 40 Contaminant sources 3—Streams upstream and downstream from wastewater treatment-plant-effluent discharge 2007–2009 9 South-central Pa. Water Pharmaceuticals 27 Antibiotics 27 Hormones and animal sterols 27 OWC 27 Contaminant sources 3—Streams upstream and downstream from wastewater treatment-plant-effluent discharge 2007–2009 9 South-central Pa. Streambed sediment Antibiotics 27 Hormones and animal sterols 27 OWC 27 Contaminant occurrence Human health 4—Streams near drinking-water intakes 2007–2009 27 Statewide Water Pharmaceuticals 297 Antibiotics 294 Hormones and animal sterols 270 Contaminant occurrence Fish health 5—Streams targeted for fish-health evaluations 2007–2008 116 Statewide Water Pharmaceuticals 16 Antibiotics 16 Hormones and animal sterols 16 OWC 16 Contaminant occurrence Fish health 5—Streams targeted for fish-health evaluations 2007–2008 116 Statewide Streambed sediment Antibiotics 16 Hormones and animal sterols 16 OWC 16

1Eleven of the 16 sites were collocated with drinking-water intake sites. The results for pharmaceutical, antibiotic, and hormone and sterol compounds in streamwater were assigned to 

drinking-water intake sites and fish-health sites.
Methods 15

YORK

CENTRE

BERKS

PERRY

LANCASTER

FRANKLIN

ADAMS

HUNTINGDON

SCHUYLKILL

DAUPHIN

FULTON

MIFFLIN

UNION

JUNIATA

LUZERNE

CLINTON

SNYDER

COLUMBIA

CUMBERLAND

LEBANON

BLAIR

CHESTER

NORTHUMBERLAND

LYCOMING

CLEARFIELD

BEDFORD

MONTOUR

CARBON

CLINTON

LEHIGH

W6

W4 W5

W3

W2

W1

A9

A8

A7

A6

A5

A4 A3

A2

A1

A12

A11

A10

T9

T8

T7

T6

T5

T4

T3

T2

T1

T15

T16

T14

T11

T10 T13 T12

0 20 40 MILES

0 20 40 KILOMETERS

EXPLANATION

W1

T16

A11

Carbonate rock

County boundary

Livestock well and identifier

Stream sampling site near municipal wastewater-effluent-discharge

 site and identifier

Stream sampling site near animal-feeding operation and identifier

78° 77° 76°

41°

40°

PE N N S YLVA N I A

Study area

Base from U.S. Geological Survey digital data, 1980, 1:100,000

Albers Equal-Area Conic projection, NAD 83

Figure 1. Locations of wells used to supply livestock, stream-sampling sites near animal-feeding operations, and stream-sampling 

sites near municipal wastewater-effluent-discharge sites, south-central Pennsylvania.
16 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

0 40 80 MILES

0 40 80 KILOMETERS

EXPLANATION

75°

76° 79° 78° 77°

80°

42°

41°

40°

Base from U.S. Geological Survey digital data, 1980, 1:100,000

Albers Equal-Area Conic projection, NAD 83

F9

F8

F7

F2

F4 F3

F1

F6

F5

F12

F13

F14

F16

F15

F11

F10

D8

D7

D6

D5

D4

D3

D2

D1

D27

D26

D25

D24

D23

D22

D21

D20

D19

D18

D17

D16

D14

D13

D12 D11

D10

D15

D9

De laware

Ri v er

S c huylkill Ri v er

Juniata River

West Branch

Susquehanna River

Ohio

River

Allegheny

River

East Branch Susquehanna River

S us qu e h a n n a

River

Yo ughiogeny River

Monongohela River

D16 Stream sampling site near 

drinking-water intake 

and identifier

Fish-health sampling site 

and identifier

F7

Delaware River Basin

Ohio River Basin

Genesee River Basin

Lake Erie Basin

Susquehanna River Basin

Potomac River Basin

Chesapeake Bay Basin

Water features from U.S. Geological Survey National Hydrography

Dataset (NHD). Basin boundaries from U.S. Geological Survey Digital

Watershed Boundary Dataset coded by Hydrologic Unit Codes (HUC)

Figure 2. Locations of stream-sampling sites located near drinking-water intakes and sampling sites for evaluation of fish health in 

Pennsylvania.
Methods 17

Table 5. Description of well sites used to supply livestock, stream sites receiving runoff from animal-feeding operations, and stream sites near municipal wastewater-effluentdischarge sites, in south-central Pennsylvania, 2006–09.—Continued[na, not applicable]

U.S. Geological 

Survey station 

identification 

number

Map 

identification 

number

(figure 1)

Site or well name County Location Latitude Longitude

Drainage

area

(square

miles)

Dominant 

livestock 

raised in the 

watershed

Number of 

samples 

collected

Wells in agricultural areas used to supply water for livestock (2006)

394643077043101 W1 AD 653 Adams na 39°46ʹ45ʺ 077°04ʹ31ʺ na Horses 4400610076282501 W2 LN 2114 Lancaster na 40°06ʹ09ʺ 076°28ʹ25ʺ na Chickens 4401712076235101 W3 LB 1248 Lebanon na 40°17ʹ12ʺ 076°23ʹ51ʺ na Dairy cows 4401920078130101 W4 HU 426 Huntingdon na 40°19ʹ19ʺ 078°13ʹ00ʺ na Dairy cows 4402052076160101 W5 LB 1249 Lebanon na 40°20ʹ52ʺ 076°16ʹ01ʺ na Swine 4405931076555601 W6 UN 205 Union na 40°59ʹ31ʺ 076°55ʹ55ʺ na Dairy cows 4

Stream sites upstream and downstream from animal-feeding operations (2006)

01569346 A1 Three Square Hollow Run above Turnpike near Newburg, Pa. Cumberland Upstream 40°11ʹ46ʺ 077°32ʹ50ʺ 1.36 Cattle 401569349 A2 Three Square Hollow Run below Turnpike near Newburg, Pa. Cumberland Downstream 40°09ʹ55ʺ 077°30ʹ53ʺ 9.6 Cattle 401572146 A3 Trout Run near Ft. Indiantown Gap, Pa. Lebanon Upstream 40°28ʹ03ʺ 076°35ʹ24ʺ 1.29 Swine 401572148 A4 Trout Run at Scout Camp near Green Point, Pa. Lebanon Downstream 40°28ʹ30ʺ 076°34ʹ22ʺ 4.23 Swine 4401704076293101 A5 Bachman Run at Fontana, Pa. Lebanon Upstream 40°17ʹ04ʺ 076°29ʹ31ʺ 3.1 Poultry 401573095 A6 Bachman Run at Annville, Pa. Lebanon Downstream 40°18ʹ58ʺ 076°30ʹ58ʺ 7.3 Poultry 401574050 A7 Snitz Creek near Falmouth, Pa. Lancaster Upstream 40°08ʹ02ʺ 076°39ʹ17ʺ 0.23 Cattle 401574055 A8 Snitz Creek near Bainbridge, Pa. Lancaster Downstream 40°07ʹ28ʺ 076°39ʹ52ʺ 2.02 Cattle 401575771 A9 Little Chickies Creek at Camp Road near Mastersonville, Pa. Lancaster Upstream 40°13ʹ12ʺ 076°27ʹ56ʺ 0.52 Poultry 4015757724 A10 Little Chickies Creek at Elizabethtown Road near Milton Grove, Pa. Lancaster Downstream 40°11ʹ07ʺ 076°30ʹ58ʺ 7.57 Poultry 401578349 A11 Muddy Run at Cochranville near Parkesburg, Pa. Chester Upstream 39°52ʹ36ʺ 075°55ʹ50ʺ 0.48 Cattle 4015783492 A12 Muddy Run at Glennville near Parkesburg, Pa. Chester Downstream 39°52ʹ39ʺ 075°57ʹ14ʺ 2.34 Cattle 4
18 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 5. Description of well sites used to supply livestock, stream sites receiving runoff from animal-feeding operations, and stream sites near municipal wastewater-effluent- discharge sites, in south-central Pennsylvania, 2006–09.—Continued [na, not applicable] U.S. Geological Survey station identification number Map identification number (figure 1) Site or well name County Location Latitude Longitude Drainage area (square miles) Dominant livestock raised in the watershed Number of samples collected Stream sites upstream and downstream from municipal-wastewater-effluent discharge (2006)—Downstream sites sampled 2007–2009 01470857 T1 Spring Creek near Wernersville, Pa. Berks Upstream 40°20ʹ58ʺ 076°05ʹ03ʺ 19.6 na 4 01470858 T2 Spring Creek near Brownsville, Pa. Berks Downstream 40°21ʹ09ʺ 076°05ʹ03ʺ 19.6 na 7 015693155 T3 Middle Spring Creek at College at Shipensburg, Pa. Cumberland/ Franklin Upstream 40°03ʹ23ʺ 077°31ʹ43ʺ 20.4 na 4 015693158 T4 Middle Spring Creek above Burd Run below Shipensburg, Pa. Cumberland/ Franklin Downstream 40°03ʹ42ʺ 077°31ʹ58ʺ 20.7 na 7 01571193 T5 Mountain Creek at Mill Street at Mt Holly Springs, Pa. Cumberland Upstream 40°07ʹ16ʺ 077°11ʹ21ʺ 45.8 na 4 01571195 T6 Mountain Creek at Mt Zion at Mt Holly Springs, Pa. Cumberland Downstream 40°07ʹ54ʺ 077°11ʹ06ʺ 46.1 na 7 01573151 T7 Killinger Creek US Treatment Plant near Annville, Pa. Lebanon Upstream 40°19ʹ27ʺ 076°33ʹ22ʺ 13.6 na 4 01573153 T8 Killinger Creek DS Treatment Plant near Annville, Pa. Lebanon Downstream 40°19ʹ31ʺ 076°33ʹ19ʺ 13.8 na 7 01576420 T12 Lititz Run near Lititz, Pa. Lancaster Upstream 40°09ʹ12ʺ 076°17ʹ10ʺ 11.9 na 4 01576422 T13 Lititz Run at Rothsville, Pa. Lancaster Downstream 40°08ʹ51ʺ 076°16ʹ13ʺ 13.3 na 7 Stream sites with no direct effluent discharge (2006) 01574310 T10 Conoy Creek near Elizabethtown, Pa.1 Lancaster No effluent 40°08ʹ08ʺ 076°36ʹ54ʺ 7.05 na 4 01574314 T11 Conoy Creek near Stacktown, Pa.1 Lancaster No effluent 40°07ʹ25ʺ 076°37ʹ48ʺ 8.05 na 4 Stream sites downstream from municipal-wastewater-effluent discharge and Clark Creek (reference site) 2007–2009 01568590 T14 Clark Creek near Dauphin, Pa. Dauphin No effluent 40°23ʹ34ʺ 076°55ʹ53ʺ 39.1 na 3 01573160 T9 Quittapahilla Creek near Bellegrove, Pa. Lebanon Downstream 40°20ʹ34ʺ 076°33ʹ46ʺ 74.2 na 3 01618952 T16 East Branch Antietam Creek at SR316 near Waynesboro, Pa. Franklin Downstream 39°43ʹ27ʺ 077°36ʹ18ʺ 51.8 na 3 01638880 T15 Rock Creek at Culps Hill at Gettysburg, Pa. Adams Downstream 39°49ʹ16ʺ 077°12ʹ57ʺ 19.3 na 3

1Conoy Creek was originally in the project design as a stream receiving municipal wastewater effluent, but during the project, it was learned that this stream does not actually receive municipal wastewater 

effluent. The effluent from the Elizabethtown, Pa., municipal treatment plant is piped to the Susquehanna River and is not discharged to Conoy Creek.
Methods 19

Streams Draining Areas with Animal-Feeding 

Operations

At six paired stream sites, samples of streamwater were 

collected quarterly in 2006 for analysis of pharmaceutical compounds. Each paired stream site consisted of a site 

upstream and a site downstream from an AFO. The USGS and 

County Conservation District together determined the locations of stream sites with AFOs nearby (table 5, fig. 1) that 

met the following criteria:

1. In an agricultural setting that included AFOs,

2. Located in south-central Pennsylvania,

3. Small drainage area (less than 10 square miles (mi2)), so 

that agricultural inputs would be the primary land-use 

influence on the stream, and

4. Landowner permitted access to the stream upstream and 

downstream from AFOs.

Streams Receiving Municipal Wastewater 

Effluents

At six paired stream sites, samples of streamwater were 

collected quarterly in 2006 for analysis of pharmaceutical 

compounds (table 1). Each paired stream site consisted of a 

site upstream and a site downstream from a wastewater-treatment effluent-discharge area. Seven sites located downstream 

from a wastewater-treatment effluent-discharge area (four 

new sites and three of the downstream sites sampled in 2006) 

were sampled annually from 2007 to 2009 and analyzed for 

pharmaceutical compounds, hormones, and OWCs. PADEP 

and the USGS worked cooperatively to select sampling locations for streams receiving municipal wastewater discharge. 

Early in the study, PADEP provided the USGS with locations 

of municipal-wastewater-treatment plants. Streams selected 

(table 5; fig. 1) met the following criteria: 

1. Streams received wastewater effluent from one of the 

municipal-wastewater-plant locations provided by 

PADEP, 

2. Located in the south-central Pennsylvania study area, 

3. Moderately small streams (drainage area less than 

100 mi2) so effects from the wastewater input potentially 

would be large, and 

4. Landowner permitted access to the stream upstream and 

downstream from the wastewater discharge. 

Stream sites selected on Spring Creek, Middle Spring 

Creek, Mountain Creek, Killinger Creek, and Lititz Run 

met these criteria. A sixth stream, Conoy Creek, also was 

selected, but during the study, it was learned that effluent 

from a wastewater-treatment plant thought to be discharging 

to Conoy Creek was discharging directly to the Susquehanna 

River. Therefore, the Conoy Creek site could not be used to 

evaluate concentrations of compounds in streams receiving 

municipal wastewater, but the data from samples collected 

at the upstream and downstream sites on Conoy Creek are 

included in the report and discussed as background values in a 

basin dominated by agricultural land use. The Killinger Creek 

sites met the site-selection criteria, but following the sampling period study, staff learned of wastewater-treatment plant 

cleaning operations with the potential to alter water quality. 

Upon further discussions with staff from the plant discharging to Killinger Creek, it was learned that the cleaning process 

took place weekly on the same day. Three of the four samples 

(May, July, and September samples of 2008) at the downstream location on Killinger Creek were collected on the day 

of cleaning. Concentrations of compounds reported for this 

site, therefore, may not be representative of the normal wastewater effluent that enters Killinger Creek the other 6 days of 

the week.

Beginning in 2007, sampling continued at sites downstream from wastewater-treatment-plant effluent discharge 

but was discontinued at sites upstream from the wastewatertreatment-plant effluent discharge. Also starting in 2007, four 

additional sites were included in the sampling: three streams 

receiving wastewater effluents, Quittapahilla Creek, East 

Branch Antietam Creek, and Rock Creek and one stream that 

had no municipal wastewater effluents (reference stream), 

Clark Creek (table 5). Flow rates of the effluent discharges 

entering these streams along with the 7-day 10-year lowflow statistic (the average minimum streamflow that can be 

expected for 7 consecutive days once every 10 years) and the 

range of actual measured streamflows during the sampling 

effort are provided in table 6.

Stream Sites near Drinking-Water Intakes

At 27 PADEP stream sites, quarterly samples of water 

were collected for analysis of pharmaceutical compounds 

and hormones. The PADEP WQN is an extensive network 

of 157 (for the year 2009) stream water-quality monitoring 

sites distributed throughout Pennsylvania. The WQN sites 

are sampled for a wide range of constituents, including field 

characteristics, major ions, nutrients, total dissolved solids, 

metals, phenols, and bacteria. Many of the WQN sites have 

long-term records for water quality, with data collected for 

three decades or more. For this study, 22 WQN sites within 

5 miles of a public drinking-water intake were selected for 

sampling (table 7; fig. 2). Five additional WQN sites, Corey 

Creek (D5, 01516750), East Branch Antietam Creek (D16, 

01618800), George Run (D17, 03015554), Pitchpine Run 

(D18, 03031690), and Youghiogheny River (D23, 03082500) 

were established for this study of contaminants of emerging concern (table 7; fig. 2). Four of these sites are located in 

small watersheds (drainage area less than 25 mi2) with few or 

no permitted discharges. The Youghiogheny River site is in a 

large watershed (1,326 mi2) that contains 187 permitted discharges upstream from the sampling location. The 27 stream 
20 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

sites sampled from 2007 to 2009 represented a wide range of 

geography, hydrology, land use, and drainage area. Drainage 

areas at the sites ranged from 1.82 mi2 to 19,500 mi2 (table 7). 

Stream Sites Used to Evaluate Fish Health

At 16 stream sites (table 8), one-time-only samples of 

streamwater and streambed sediment were collected for analysis of pharmaceutical compounds, hormones, and OWCs. The 

fish-health sampling sites were selected to include locations 

in all three major river basins in Pennsylvania, the Delaware 

River, the Susquehanna River, and the Ohio River (fig. 2). The 

fish-health sampling sites were generally located on a large 

stream, and commonly a site upstream and a site downstream 

from potential emerging contaminant sources were selected. 

Eleven of the 16 fish-health sites were co-located with 

drinking-water intake sampling sites, and the pharmaceutical 

and hormone data from water samples are shared by both data 

sets (table 8). This allowed analytical results from drinkingwater intake samples to be used for the fish-health evaluations, 

thereby saving analytical costs.

Fish were collected at these same sites and examined for 

external and internal anomalies, histopathology, and physiological markers. The correlation of fish health indicators 

with the occurrence and concentrations of contaminants of 

emerging concern was the objective of this work by scientists 

at the USGS Leetown Science Center National Fish Health 

Research Laboratory. Only the chemical results are presented 

in this report.

Streamflow Measurement and Water-Quality 

Characteristics

Stream discharge was determined for each streamwater 

sample collected. Discharge was determined from the 

streamgage record for sampling locations near USGS continuous-record streamgaging stations. Stream discharge at sites 

without a USGS continuous-record streamgaging station was 

measured using documented USGS procedures (Rantz and 

others, 1982).

Field measurements of pH, specific conductance, dissolved oxygen, and water temperature were made in the 

stream cross section at 3 to 11 locations (depending on the 

stream width) and vertically at six-tenths of the depth of the 

stream using a multi-parameter meter. Water characteristics 

were used to determine whether the stream was well-mixed 

from bank to bank and whether there was variability along 

the stream cross section as a result of depth. Meter calibration 

was performed at the beginning of each day’s sampling and 

followed procedures documented in the USGS Techniques of 

Water-Resources Investigations (Wilde, variously dated). Field 

measurements and equipment accuracies are shown in table 9. 

Table 6. Characteristics of wastewater-treatment plants discharging to study streams.

[Mgal/d, million gallons per day; ft3/s, cubic feet per second; WWTP, wastewater-treatment plant; Q7-10, 7-day, 10 year low-flow statistic]

Name of wastewater-treatment plant

Design

flow

(Mgal/d)

Average

daily flow 

for 2008

(Mgal/d)

Receiving stream

1

Q7-10 flow at 

downstream 

sampling site2

Range of actual 

measured stream 

flows during sampling

(ft3 Mgal/d /s) ft3

/s

Robesonia-Wernersville Municipal Authority 1.30 0.82 Spring Creek 2.91 4.51 13–33

Borough of Shippensburg WWTP 3.30 1.74 Middle Spring Creek 4.39 6.79 11–30

Borough of Mount Holly Springs WWTP 0.83 0.45 Mountain Creek 4.89 7.57 18–147

Borough of Palmyra WWTP 1.42 0.86 Killinger Creek 2.88 4.45 1.3–31

Lititz Sewer Authority WWTP 3.85 2.86 Lititz Run 0.43 0.66 9.3–45

Gettsburg Municipal Authority 2.45 1.67 Rock Creek 0.41 0.63 0.8–2.0

Washington Township Municipal Authority 1.94 0.88 East Branch Antietam Creek 6.53 10.10 17–34

Borough of Waynesboro WWTP 1.60 0.88 East Branch Antietam Creek 6.53 10.10 17–34

City of Lebanon Authority 8.00 5.14 Quittapahilla Creek 30.70 47.50 75–96

Township of Annville 0.96 0.57 Quittapahilla Creek 30.70 47.50 75–96

Borough of Palmyra 1.42 0.86 Quittapahilla Creek 30.70 47.50 75–96

1

Q7-10 flow is the average minimum streamflow that can be expected for 7 consecutive days once every 10 years.

2

 Estimated using U.S. Geological Survey StreamStats (Stuckey, 2006).
Methods 21

Table 7. Description of sampling sites near selected drinking-water intakes in Pennsylvania.

U.S. Geological 

Survey station 

identification 

number

Map 

identification 

number

(figure 1)

Site name County Latitude Longitude Drainage area (square miles)

Number of 

wastewater, 

stormwater, 

and industrial 

discharges in 

the basin

01440650 D1 Brodhead Creek near East Stroudsburg, Pa. Monroe 41°02ʹ10ʺ 075°12ʹ45ʺ 121 1601452040 D2 Jordan Creek at mouth at Allentown, Pa. Lehigh 40°36ʹ06ʺ 075°27ʹ43ʺ 82.3 2201463500 D3 Delaware River at Trenton, N.J. Bucks 40°13ʹ18ʺ 074°46ʹ42ʺ 6,780 72501474010 D4 Schuylkill River at Falls Bridge at Philadelphia, Pa. Philadelphia 40°00ʹ30ʺ 075°11ʹ52ʺ 1,893 1,27501516750 D5 Corey Creek at Mansfield, Pa. Tioga 41°48ʹ40ʺ 077°04ʹ15ʺ 22 4015400021 D6 Fishing Creek near Bloomsburg, Pa. Columbia 40°59ʹ37ʺ 076°28ʹ33ʺ 379 4101540500 D7 Susquehanna River at Danville, Pa. Montour 40°57ʹ29ʺ 076°37ʹ10ʺ 11,220 79001553500 D8 West Branch Susquehanna River at Lewisburg, Pa. Union 40°58ʹ05ʺ 076°52ʹ25ʺ 6,847 93801553990 D9 Susquehanna River above dam at Sunbury, Pa. Northumberland 40°51ʹ13ʺ 076°48ʹ08ʺ 18,300 1,84701562000 D10 Raystown Branch Juniata River at Saxton, Pa. Bedford 40°12ʹ57ʺ 078°15ʹ56ʺ 756 16701566005 D11 East Licking Creek above reservoir near Lewistown, Pa. Juniata 40°32ʹ48ʺ 077°31ʹ40ʺ 21.9 001567000 D12 Juniata River at Newport, Pa. Perry 40°28ʹ42ʺ 077°07ʹ46ʺ 3,354 53401570000 D13 Conodoguinet Creek near Hogestown, Pa. Cumberland 40°15ʹ08ʺ 077°01ʹ17ʺ 470 17201571505 D14 Yellow Breeches Creek at New Cumberland, Pa. Cumberland/York 40°13ʹ27ʺ 076°51ʹ38ʺ 206 7901573560 D15 Swatara Creek near Hershey, Pa. Dauphin 40°17ʹ54ʺ 076°40ʹ05ʺ 483 16601618800 D16 East Branch Anteitam Creek near South Mountain, Pa. Franklin 39°47ʹ18ʺ 077°29ʹ16ʺ 13.4 003015554 D17 George Run near Tidioute, Pa. Warren 41°42ʹ51ʺ 079°27ʹ20ʺ 4.15 103031690 D18 Pitchpine Run at Reynoldsville, Pa. Jefferson 41°05ʹ52ʺ 078°53ʹ15ʺ 1.82 003036500 D19 Allegheny River at Kittaning, Pa. Armstrong 40°49ʹ13ʺ 079°31ʹ54ʺ 8,973 1,66603049652 D20 Allegheny River at Hulton Bridge at Oakmont, Pa. Allegheny 40°31ʹ39ʺ 079°50ʹ51ʺ 11,577 3,26503071700 D21 Cheat River at Point Marion, Pa. Fayette 39°44ʹ31ʺ 079°53ʹ59ʺ 1,422 603075001 D22 Monongahela River at North Charleroi, Pa. Washington 40°04ʹ07ʺ 079°54ʹ16ʺ 5,230 38403082500 D23 Youghiogheny River at Connellsville, Pa. Fayette 40°01ʹ03ʺ 079°35ʹ38ʺ 1,326 18703086000 D24 Ohio River at Sewickley, Pa. Allegheny 40°32ʹ57ʺ 080°12ʹ21ʺ 19,500 5,87303103500 D25 Shenango River at Sharpsville, Pa. Mercer 41°15ʹ58ʺ 080°28ʹ22ʺ 584 20303106500 D26 Slippery Rock Creek at Wurtemburg, Pa. Lawrence 40°53ʹ02ʺ 080°14ʹ02ʺ 398 11103107500 D27 Beaver River at Beaver Falls, Pa. Beaver 40°45ʹ48ʺ 080°18ʹ55ʺ 3,106 1,008
22 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 8. Description of sampling sites used for evaluations of fish health in Pennsylvania. U.S. Geological Survey station identification number Map identification number (figure 1) Site name Basin Year sampled County Latitude Longitude Drainage area (square miles) 01440650 F5 Brodhead Creek near East Stroudsburg, Pa.1 Delaware 2007 Monroe 41°02ʹ10ʺ 075°12ʹ34ʺ 121 01442500 F6 Brodhead Creek at Minisink Hills, Pa. Delaware 2007 Monroe 40°59ʹ55ʺ 075°08ʹ35ʺ 259 01474010 F1 Schuylkill River at Falls Bridge at Philadelphia, Pa.1 Delaware 2007 Philadelphia 40°00ʹ30ʺ 075°11ʹ52ʺ 1,893 01540500 F3 Susquehanna River at Danville, Pa.1 Susquehanna 2007 Montour 40°57ʹ29ʺ 076°37ʹ10ʺ 11,220 01540538 F4 Susquehanna River at Wolverton near Northumberland, Pa. Susquehanna 2007 Montour 40°55ʹ22ʺ 076°43ʹ08ʺ 11,300 01567000 F10 Juniata River at Newport, Pa.1 Susquehanna 2007 Perry 40°28ʹ42ʺ 077°07ʹ46ʺ 3,354 01570000 F2 Conodoguinet Creek near Hogestown, Pa.1 Susquehanna 2007 Cumberland 40°15ʹ08ʺ 077°01ʹ17ʺ 470 01571505 F11 Yellow Breeches Creek at New Cumberland, Pa.1 Susquehanna 2007 Cumberland/York 40°13ʹ27ʺ 076°51ʹ38ʺ 206 01573000 F7 Swatara Creek at Harper Tavern, Pa. Susquehanna 2007 Lebanon 40°24ʹ09ʺ 076°34ʹ39ʺ 337 01573560 F8 Swatara Creek near Hershey, Pa.1 Susquehanna 2007 Dauphin 40°17ʹ54ʺ 076°40ʹ05ʺ 483 01573583 F9 Swatara Creek below US 322 near Hummelstown, Pa. Susquehanna 2007 Dauphin 40°14ʹ58ʺ 076°44ʹ11ʺ 549 03036500 F15 Allegheny River at Kittaning, Pa.1 Ohio 2008 Armstrong 40°49ʹ13ʺ 079°31ʹ54ʺ 8,973 03049652 F16 Allegheny River at Hulton Bridge at Oakmont, Pa.1 Ohio 2008 Allegheny 40°31ʹ39ʺ 079°50ʹ51ʺ 11,577 03075001 F14 Monongahela River at North Charleroi, Pa.1 Ohio 2008 Washington 40°04ʹ07ʺ 079°54ʹ16ʺ 5,230 03085000 F13 Monongahela River at Braddock, Pa. Ohio 2008 Allegheny 40°23ʹ28ʺ 079°51ʹ30ʺ 7,337 03086000 F12 Ohio River at Sewickley, Pa.1 Ohio 2008 Allegheny 40°32ʹ57ʺ 080°12ʹ21ʺ 19,500

1Site collocated with a drinking-water intake site.
Methods 23

Table 9. Description of field measurement with reporting units and instrument reporting accuracies used in 

this study.

[NWIS, National Water Information System; ft3/s, cubic feet per second; °C, degrees Celsius; μS/cm, microsiemens per centimenter 

at 25°C; mm, millimeters; mg/L, milligrams per liter; %, percent]

Measurement NWIS code Reporting units Instrument reporting accuracy

Stream discharge 00061 ft3/s ± 0.003 ft3/s

Temperature 00010 °C ± 0.15°C

pH 00400 standard units ± 0.2

Specific conductance 00095 μS/cm at 25°C ± 0.5% of the reading or 1 μS/cm, whichever is greater

Dissolved oxygen 00300 mg/L ± 2% of the reading or 0.2 mg/L, whichever is greater

Barometric pressure 00025 mm mercury ± 0.75 to 1.5 mm mercury

Collection and Processing of Water-Quality 

Samples

All sampling equipment was cleaned thoroughly prior to 

sample collection, following protocols for organic-compound 

sampling (Wilde, 2004). Special considerations for personal 

safety and sample integrity were followed when working 

with samples from streams receiving municipal wastewater or 

water from AFOs.

Streamwater

Streamwater samples were collected according to standard USGS field sample collection techniques (U.S. Geological Survey, 2006). Wadeable sites were sampled at intervals of 

equal width (minimum of 3 and a maximum of 11 locations) 

along the stream cross section by using a US DH-81 depthintegrated sampler fitted with a Teflon bottle and nozzle (U.S. 

Geological Survey, 2006; fig. 3). If the stream was too shallow 

or the stream velocities were less than 1.5 feet per second (ft/s) 

the US DH-81 sampler nozzle was removed, and samples were 

collected directly into the Teflon bottle. Non-wadeable sites 

were sampled at a minimum of nine locations along the stream 

cross section from a boat or a bridge by using a US DH-95 

depth-integrating sampler fitted with a Teflon bottle and nozzle 

(U.S. Geological Survey, 2006). Each stream cross-section 

sub-sample was sequentially poured into a single pre-cleaned 

and stream-rinsed Teflon churn splitter and mixed, resulting in 

a homogenous composite sample. All locations of the verticals were noted on the field data sheets. Specific streamflows 

were not targeted during sampling. Reconnaissance sampling 

upstream and downstream from AFOs and wastewatertreatment effluent discharge generally were collected during 

base-flow conditions. Reconnaissance sampling at the drinking-water-intake and fish-health sites was conducted during a 

range of hydrologic conditions.

Sample processing and shipping protocols developed for 

pharmaceuticals, hormones, and OWCs were followed (Wilde 

and others, 2004 [update 5.6.1.F]). In brief, all streamwater 

samples were processed at the sampling site by filtering the 

composite sample using a peristaltic pump fitted with a Teflon 

head and hoses through a pre-cleaned 0.7-micron glass fiber 

filter (GFF) that had been rinsed and preconditioned with 

sample water. Samples for analysis of pharmaceuticals and 

OWCs were filtered into amber glass bottles that had been 

cleaned and fired (baked at 450 degrees Celsius (°C) to burn 

off all residual organic compounds). Samples for analysis of 

hormones were filtered into plastic bottles and frozen until 

thawed for analysis at the laboratory. Samples for analysis 

of antibiotics were shipped on ice overnight to the USGS 

Organic Geochemistry Research Laboratory (ORGL) in Lawrence, Kansas. All other streamwater samples were shipped on 

ice overnight to the USGS National Water Quality Laboratory 

(NWQL) in Denver, Colorado, for analysis. 

Groundwater

Collection of groundwater samples followed protocols 

documented by the USGS National Field Manual for the Collection of Water-Quality Data (U.S. Geological Survey, 2006) 

with modifications. A modification to the protocol included 

the use of brass fittings instead of Teflon to connect to water 

sources; a flow manifold or processing chamber was not used. 

At all wells sampled, existing in-situ submersible pumps 

provided sample water to a tap either at the base of the pressure tank or at an outside faucet. As the well was purged, pH, 

specific conductance, dissolved oxygen, and water temperature were monitored using a calibrated multi-parameter meter. 

When readings became stable (variation between five or more 

5-minute sequential field-measurement values: ± 0.05 units 

for pH; ± 0.2°C for water temperature; ± 0.3 milligram per 

liter (mg/L) for dissolved oxygen; and ± 3 percent for specific 

conductance greater than 100 microsiemens per centimeter (μS/cm)), the groundwater samples were collected. All 

groundwater samples were processed at the sampling site. A 

pre-cleaned Teflon in-line filter-unit holder with a baked, glass 

microfiber filter (47-millimeter (mm) diameter, 0.7-micrometer (μm) pore-size) was used to filter the sample directly 

from the tap or faucet into two 1-liter (L) amber glass bottles 

cleaned and baked at 450°C to burn off all residual organic 
24 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Figure 3. U.S. Geological Survey hydrologist collects a water sample for analysis of contaminants of emerging concern using 

a DH-81 sampler fitted with Teflon adapter, Teflon nozzle, and Teflon 1-L bottle.

compounds. One bottle was sent to the NWQL for analysis 

of pharmaceutical compounds (excluding antibiotics). The 

second bottle was held as an archive sample. Three 125-milliliter (mL) cleaned-and-burned glass bottles were used to 

collect filtered water for antibiotic analyses. All sample bottles 

were kept chilled at 4°C until they were shipped to the NWQL 

or OGRL for analysis. All samples were double bagged and 

shipped on ice within 2 days of collection via overnight delivery to the analytical laboratories.

Streambed Sediments

Because organic compounds are known to adsorb preferentially to fine-grained sediments, deposits of fine-grained 

material were targeted for collection as streambed-sediment 

samples. Samples of streambed sediments were collected 

from five locations within 100 ft of a sampling site using a 

Teflon cylinder (open at both ends) and wafer (fig. 4). The 

technique requires that the cylinder be inserted into the 

sediment to a depth of 2 centimeters (cm) and the wafer be 

inserted underneath the cylinder, trapping sediment inside the 

cylinder. To the extent possible, sediment inside the cylinder 

was not disturbed. The five cylinders of streambed sediment 

collected near a stream-sampling site were composited in a 

pre-cleaned stainless steel bowl. Sediment in the bowl was 

thoroughly mixed, then sieved into a second stainless steel 

bowl. Sub-samples needed for laboratory analyses were placed 

into pre-cleaned 500 mL glass jars (fig. 5) that had been 

baked at 450°C to burn off all residual organic compounds. 

Sample jars were then placed on ice in the field. Upon return 

to the USGS office, the sample jar was frozen to a temperature of -20°C. The sample was shipped frozen to the analyzing laboratory where it remained frozen until thawed for 

analytical determinations.

Laboratory Analyses

The analytical methods used at NWQL and other USGS 

laboratories to determine contaminant of emerging concern 

concentrations are relatively new, having been developed 

within the last decade (Appendix A). Others methods are still 

in the development and testing phase, have not received USGS 
Methods 25

Figure 4. Teflon cylinder and Teflon wafer used to collect streambed-sediment samples.

Figure 5. U.S. Geological Survey and Pennsylvania Department 

of Environmental Protection scientists processing a streambedsediment sample in the field.

approval, and were considered to be research methods as of 

2009. As of 2011, the pharmaceutical (excluding antibiotics) and OWC analyses are performed at the NWQL using 

approved USGS methods. Antibiotic (table 1) and hormone 

and animal sterol (table 2) analyses are performed at ORGL 

and the NWQL using USGS research methods. Therefore, 

descriptions provided here for analytical methods in development will be detailed. The new analytical methods now allow 

for a number of additional contaminants of emerging concern 

in water and streambed sediments to be detected and quantified. These new methods have been developed by USGS 

researchers in Denver, Colorado, and in Lawrence, Kansas. 

The compounds analyzed using these techniques represent a 

combination of high-use compounds, compounds with a high 

probability of detection, and compounds with an analytical 

technique available to quantify their occurrence.

The minimum reporting level (MRL) is the smallest measured concentration of a substance that can be reliably measured by using a given analytical method. The method detection limit (MDL) is the minimum concentration of a substance 

that can be measured and reported with 99-percent confidence 
26 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

that the analyte concentration is greater than zero. The USGS 

NWQL has established a data reporting convention described 

in Childress and others (1999). An estimated concentration 

(qualifying remark code E) denotes a semi-quantitative result 

reported because it is outside the calibration range; it is commonly associated with detections greater than the MDL but 

below the MRL for that analyte. In this report, each compound 

had an established reporting level, which was based on either 

a MRL (antibiotics) or MDL (pharmaceuticals, excluding antibiotics, hormones, and OWCs). Estimated values greater than 

the reporting level were used in all data analysis. 

Streamwater Samples

Pharmaceutical Compounds

Streamwater samples were analyzed for pharmaceutical 

compounds (excluding antibiotics) at the USGS NWQL in 

Denver, Colorado. The research analytical method consisted of 

a solid-phase extraction followed by high-performance liquid 

chromatography/mass spectrometry (HPLC-MS), using a polar 

reverse-phase octylsilane (C8) HPLC column following the 

procedure described in Cahill and others (2004) and Furlong 

and others (2008). All pharmaceutical compounds except for 

antibiotics and ibuprofen were analyzed at the USGS NWQL. 

The compounds included in the USGS NWQL pharmaceutical 

analysis and their reporting levels are listed in table 1.

Antibiotics and Ibuprofen

Antibiotics and ibuprofen were analyzed at the USGS 

OGRL in Lawrence, Kansas, using a research method modified from an online solid-phase extraction (SPE) method from 

Meyer and others (2007). Streamwater samples were analyzed 

for antibiotics and ibuprofen using online SPE and liquid 

chromatography/tandem mass spectrometry (LC/MS/MS) with 

electrospray ionization (ESI) and multiple reaction monitoring 

(MRM). This technique allowed quantitation of chloramphenicol, lincomycin, ormetoprim, trimethoprim, five macrolides, 

six sulfonamides, six quinolines, four tetracycline antibiotics, 

six antibiotic metabolite breakdown products, and ibuprofen.

The antibiotics analyzed at the USGS OGRL and their 

reporting levels are listed in table 1. Ibuprofen is analyzed 

at the USGS OGRL but is reported with the pharmaceuticals 

in table 1. The reporting levels for the 31 compounds ranged 

from 1 ng/L to 10 ng/L. The OGRL reported only concentrations greater than the MRLs for samples collected for 

this study.

Hormones

Streamwater samples were analyzed for hormones at 

the USGS NWQL in Denver Colorado. Filtered streamwater 

samples were fortified with deuterated analogs of 13 analytes 

as isotope dilution standards (IDSs), and the samples were 

poured into stainless steel extraction tubes equipped with a 

multigrade GFF over a 47-mm C18 solid-phase extraction 

(SupelcoENVI) disk. The sample was passed through the 

GFF/C18 disk under pressure, as needed. Following compound isolation, the GFF/C18-disk was rinsed with 25 percent 

methanol in reagent water and dried with nitrogen, and the 

compounds were eluted with methanol. The methanol eluent 

was evaporated to dryness and reconstituted in a mixture of 

5 percent methanol in dichloromethane (DCM/MeOH). The 

extract was passed through a 1-gram Florisil SPE column and 

eluted with the DCM/MeOH solution. The eluent was reduced 

in volume and transferred to a 5-mL reaction vial, then evaporated to dryness. Ketone and alcohol groups on the analytes 

and IDSs were derivatized to trimethylsilyl or trimethylenol 

ether analogs to make them stable for analysis by gas chromatography. Derivation was accomplished by addition of 

200 microliters (μL) of N-methyl-N-(trimethylsilyl)- trifluoroacetamide (MSTFA) activated with 2(trimethylsilyl)ethanethiol and ammonium iodide (NH4

I), then heating the MSFTA 

solution to 65°C for 1 hour. The analytes were separated by 

gas chromatography and quantified by tandem quadrupole 

mass spectrometry using an isotope dilution procedure. The 

procedure allowed for quantitation of 17 natural and synthetic 

hormones and 2 animal sterols (James Gray, U.S. Geological 

Survey, written commun., 2010, table 2). The relative percent difference for compounds detected in duplicate samples 

collected during the sampling period ranged from 1.3 percent 

to 26 percent (Appendix B, table B-1). Percent recoveries 

from spiked reagent-water samples ranged from 66 percent to 

114 percent (Appendix C, table C-1).

Organic Wastewater Compounds

Samples were analyzed for OWCs at the USGS NWQL 

in Denver, Colorado, by capillary-column gas chromatography/mass spectrometry (GC/MS) using methods described in 

Zaugg and others (2002). The list of target compounds in the 

analytical schedule for OWCs includes detergent metabolites, 

fragrances, flavors, pesticides, industrial compounds, disinfectants, PAHs, fire retardants and plasticizers, and plant sterols 

(table 3).

Streambed-Sediment Samples

Antibiotics and Ibuprofen

Antibiotics and ibuprofen in streambed-sediment samples 

were analyzed at the USGS OGRL in Lawrence, Kansas. The 

analytical method consisted of accelerated solvent extraction 

and LC/MS/MS with ESI using MRM. Samples were analyzed 

in positive-ion mode except for chloramphenicol and ibuprofen, which were analyzed in negative-ion mode. Eleven compounds were used as internal standards and four compounds 
Methods 27

were used as surrogate standards. All of the internal standards 

except simetone were applied to all samples before extraction. Surrogates were amended to extracts before evaporation 

of the organic phase of the extraction buffer. Simetone was 

used as a sample post-processing instrument internal standard 

to compensate for potential variation in the chromatographic 

analysis (M. Meyer, U.S. Geological Survey, written commun., April 6, 2009). This analytical method has not received 

USGS approval. A list of the compounds covered by this 

analytical technique is provided in table 1. The relative percent difference for compounds detected in duplicate samples 

collected during the sampling period ranged from 0 percent to 

69 percent (Appendix B, table B-4).

Hormones

Streambed-sediment samples were analyzed for hormones at the USGS NWQL in Denver, Colorado. Extraction 

of solid samples by the USGS NWQL uses about 10 grams of 

material (dry weight), with lesser amounts used for matrices 

anticipated to have high organic matter or high concentrations 

of target analytes (for example, biosolids). Samples were 

stored frozen (–15°C) if not extracted within about 4 days following receipt. Thawed samples were homogenized prior to 

sub-sampling for extraction or for separate dry weight determination. Dry weight was obtained by weighing a sample 

aliquot in a tared aluminum pan after heating at 130°C for at 

least 16 hours. Sample aliquots for extraction were placed in 

a tared Accelerated Solvent Extraction (ASE; Dionex Corp.) 

cell and reweighed to determine the wet weight of extracted 

sample aliquot. Reagent sand was added to the cell, as 

needed, on the basis of cell and sample size. The sample was 

fortified with 100 nanograms (ng) of the same 13 deuteriumlabeled IDSs that were used for the hormones in water methods. The sample was extracted by pressure solvent extraction using the ASE instrument with a mixture of water and 

isopropyl alcohol (50:50, volume/volume [v/v]) at 120oC and 

water and isopropyl alcohol (20:80, v/v) at 200oC using three 

static cycles (40 minutes total) at each temperature at a pressure of 13.8 megaPascals. The resultant ASE extract portions 

were sequentially passed through an OASIS® HLB (Waters 

Corp.) SPE column to isolate the method compounds on the 

column using the procedure given in Burkhardt and others 

(2006). The column was dried with nitrogen gas at 2 liters per 

minute flow of nitrogen for 15 minutes. Method compounds 

were eluted from the OASIS column and passed through a 

2-gram (g) Florisil cleanup column (containing about 2.5 g 

of sodium sulfate above the Florisil) by using a 25-mL 

dichloromethane-methanol (95:5 v/v) mixture. The resultant 

extract was concentrated to 1 to 2 mL by using nitrogen gas 

evaporation, and then transferred to a silanized 5-mL reaction 

vial by using a 1.5-mL rinse with the dichloromethane-methanol (95:5) mixture. The extract was evaporated to dryness 

using nitrogen gas. The method compounds were derivatized 

using 500-μL of activated MSTFA derivatization reagent and 

analyzed by GC/MS as described for the hormones in water 

method (James Gray, U.S. Geological Survey, written commun., 2010).

The hormone analysis for this study included natural 

and synthetic hormones and animal sterols. All compounds 

analyzed are listed in table 2.

Organic Wastewater Compounds

Streambed-sediment samples were analyzed for OWCs 

at the USGS NWQL in Denver, Colorado using methods 

described by Burkhardt and others, 2006. These compounds 

include the detergent metabolites, fragrances, flavors, pesticides, industrial compounds, disinfectants, PAHs, fire retardants, and plasticizers (Burkhardt and others, 2006) (table 3).

For analysis of OWCs in streambed sediment, samples 

were extracted using a pressurized solvent extraction system. 

The compounds of interest were extracted from interfering 

matrix components by high-pressure water/isopropyl alcohol 

extraction. The compounds were isolated using disposable 

SPE cartridges containing chemically modified polystyrenedivinylbenzene resin. The cartridges were dried with nitrogen 

gas. Sorbed compounds were eluted with methylene chloride 

(80 percent)-diethyl ether (20 percent) through a Florisil/

sodium sulfate SPE cartridge, then identified using capillarycolumn GC/MS. Details of the method are provided in Burkhart and others (2006).

Data Analysis

The reporting level for each compound is listed in tables 

1 to 3. Reporting levels used for pharmaceutical compounds 

(excluding antibiotics) in water are the method detection limits 

used by Loper and others (2007). Reporting levels used for 

antibiotic compounds in water and streambed-sediment are 

MDLs reported by the ORGL. Reporting levels for hormones 

and OWCs in water and streambed sediments are the lowest 

MDLs reported by the NWQL during the sampling period. The 

data included in this report contained concentrations below 

the reporting levels listed in tables 1 to 3 and concentrations 

reported as estimated values. Concentrations less than the 

reporting level are considered to be less quantitative than concentrations greater than the reporting level. All concentrations 

reported as estimated were used in the data analysis. Tables 

present a summary of the data at concentrations greater than 

and less than the reporting level. All figures indicate if data 

less than the reporting level are included in the data presentation. Data have been published in Loper and others (2007) 

and in the USGS Water-Data Reports from 2007 to 2010 (U.S. 

Geological Survey, 2007–2010).
28 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Quality Assurance and Quality Control

The value of chemical measurements depends upon 

the level of confidence that can be placed in the laboratory 

results. Quality assurance and quality control are particularly important for this study because concentrations of the 

compounds under investigation are in the nanogram per 

liter (water sample) or mid-microgram per kilogram range 

(streambed-sediment samples). These concentrations are at 

the lower end of the detection limits for the newly developed 

laboratory methods.

Quality Control for Field Measurements

Various controls were used to quality-assure field-meter 

measurements. Thermistors for field instruments were checked 

against a National Institute of Standards and Technology certified thermometer one time prior to each sampling season using 

methods described by Wilde (variously dated). Calibrationacceptance limits were ± 0.15°C. Certified standards and 

buffers were used to calibrate multi-parameter meters on the 

day of sampling using methods described in Wilde (variously 

dated). All field meter calibration data were recorded in the 

respective meter log book and on the site field data sheet. 

Quality Control for Streamwater and StreambedSediment Samples

Blanks

The primary purpose of blanks is to determine the 

likelihood that samples were contaminated by sampling and 

processing procedures. Secondarily, blanks are used to trace 

sources of contamination. Because of the ease with which 

extremely low levels of the analytes measured in this study 

can be contaminated, frequent blank samples were needed to 

achieve the study’s data-quality objectives.

An equipment-blank or field-blank sample was collected 

by pouring certified organic-free water through field equipment either in a USGS Pennsylvania Water Science Center 

(PA-WSC) laboratory or at a field site and processing the 

sample through a filter assembly that had been cleaned according to USGS protocols (Wilde, 2004) after having been used 

previously for environmental sample collection. Blanks made 

up approximately 5 percent of all samples submitted for analyses. Six equipment blanks were collected in the PA-WSC laboratory in 2006, three for pharmaceutical compounds (excluding antibiotics) in water and three for antibiotic compounds in 

water. From 2006 through 2009, 77 field-blank samples were 

collected: 31 samples for pharmaceutical compounds (excluding antibiotics), 32 samples for antibiotics compounds, 11 

samples for hormones, and 3 samples for OWCs. No blanks 

samples were submitted for sediment analyses.

Detection of contaminants of emerging concern in 

blank samples was rare. There were seven total detections at 

concentrations greater than the reporting level in the 79 blank 

samples collected from 2006 to 2009. One measured concentration was reported for an equipment blank, and the remaining six detections were reported for six separate field blanks. 

One pharmaceutical compound, salbutamol, was detected 

in one blank sample at a concentration of 11 ng/L (table 10). 

Salbutamol was detected in four environmental samples at a 

concentration range of 9–30 ng/L. For the antibiotics, tylosin was detected in one equipment blank submitted to the 

OGRL in 2006 at a concentration of 6 ng/L (table 10). OGRL 

statistics for 2006 show that 15 percent of all the laboratory 

reagent blanks (LRBs) had detections of tylosin, and the 

average concentration of the detections was 7 ng/L. LRBs are 

used to monitor for contamination during the extraction and 

analysis process. These findings indicate that the contamination was introduced from the equipment or during the analysis. 

Table 10. Compounds detected in equipment and field-blank samples collected 

from 2006 to 2009.

[ng/L, nanograms per liter]

Compound Number of 

analyses

Number of detections

at concentrations

greater than 

reporting level

Concentration

(ng/L)

Prescription pharmaceutical

Salbutamol 33 1 11

Macrolide antibiotics and metabolites

Erythromycin-H2O 32 1 8

Tylosin 32 1 6

Natural androgen

Testosterone 11 1 1

Organic wastewater compound

Bisphenol A 11 3 396, 443, 478
Quality Assurance and Quality Control 29

Erythromycin-H2O, an antibiotic metabolite, was detected at 

the reporting level (8 ng/L) in one field blank in 2007. The 

hormone compound testosterone was found in one blank sample at a concentration of 1 ng/L (reporting limit of 0.8 ng/L), 

and there were three detections of bisphenol A in blank 

samples at concentrations of 396 ng/L, 478 ng/L, and 443 ng/L 

(reporting level of 100 ng/L). The LRL for bisphenol A was 

raised to 200 ng/L in 2010. Because of the blank results and 

increased MRL, results for bisphenol A will not be presented 

in this report. Overall, the blank data indicate environmentalsample results for all water compounds were not affected by 

contamination introduced from cleaning procedures, sampling 

procedures, or analytical processes.

Duplicates

Field duplicate samples were collected during the study 

to evaluate variability (reproducibility) in the analytical results 

introduced during collection, processing, and laboratory analysis. Field duplicates are separate samples collected at the same 

time, shipped, and stored under identical conditions. Duplicate 

streamwater or streambed-sediment samples are either split 

from the primary environmental sample or collected immediately after primary environmental samples; these duplicates 

are referred to as split duplicates and sequential duplicates, 

respectively. Variability in sequential-duplicate results also can 

reflect temporal changes in environmental conditions because 

the sequential duplicate is collected as a separate sample after 

the primary sample.

Duplicate samples for analysis of pharmaceuticals 

in streamwater were collected during the 4 years of study 

(2006–09). Duplicates for hormones and OWCs in water and 

antibiotics, hormones, and OWCs in streambed sediment 

were collected from 2007 to 2009 when the scope of the study 

was expanded to include additional compounds in water and 

streambed sediment. Duplicates made up about 3.7 percent of 

all samples submitted for analysis. Forty-nine samples were 

collected as duplicates of primary environmental samples. 

Duplicates for 34 water samples, including 15 samples to be 

analyzed for antibiotics, 13 samples for other pharmaceuticals, 

3 samples for hormones, and 3 samples for OWCs, and duplicates for 15 streambed-sediment samples included 5 samples 

to be analyzed for antibiotics, 6 samples for hormones, and 

4 samples for OWCs. Two of the duplicates for antibiotics in 

water and one duplicate for hormones in sediment were split 

samples divided at either the OGRL or the NWQL. The 6 

duplicate samples from sites near drinking-water intakes were 

collected as field-split duplicates; the remaining 40 duplicate 

samples were collected as field-sequential duplicates. 

Variability was evaluated by calculating relative percent difference (RPD) using constituent concentrations from 

the primary environmental sample and the duplicate sample 

(henceforth called a duplicate pair) but only if the results from 

the duplicate pair were greater than the reporting level. RPD

calculations were not made when constituent concentrations in 

both samples in the duplicate pair were less than the reporting 

level or if one or both samples in the duplicate pair had estimated concentrations. RPD was calculated according to the 

following equation:

RPD = ((|E – D|) / ((E + D) / 2)) × 100, (1)

where

E is the concentration of the environmental (or 

parent) sample

and

D is the concentration of the duplicate sample.

In general, variability was 30 percent or less for most 

contaminants of emerging concern analyzed in duplicate water 

samples. Exceptions to this generalization are diphenhydramine, diltiazem, tylosin, and sulfadiazine. Variability was 

much greater for compounds analyzed in duplicate streambedsediment samples. Two antibiotics, 5 hormones, 2 animal sterols, and 18 OWCs had median RPDs greater than 30 percent 

(table 11). Results from duplicate samples collected in 2006 

are presented in a report by Loper and others (2007). Summary tables for duplicate samples, by compound, are presented 

in Appendix B (tables B-1–B-4). 

Laboratory-Matrix Spikes 

A laboratory-matrix spike (LMS) (or laboratory-spiked 

environmental sample) is prepared when a chemist adds 

known quantities of method analytes to an environmental sample. The LMS is analyzed exactly like an un-spiked sample. 

 The purpose of a LMS is to determine whether the environmental water or sediment matrix creates interferences in 

analytical recoveries of compounds that may cause positive or 

negative bias in reported data (Furlong and others, 2008) and 

to determine the likelihood of false negatives. False-negative 

results would occur if a spiked compound was not detected in 

the spiked sample.

If a spike is added to an environmental sample that 

already contains concentrations of the same compound, the 

evaluation of spike recovery takes into consideration the measured concentration of the compound in the un-spiked sample. 

In this case, the concentration in the environmental sample 

is subtracted from the value of the spiked sample before the 

measured value of the spike is compared to the expected value 

of the spike (eq. 2). If there is no compound reported in the 

environmental sample associated with the spiked sample, no 

adjustments are needed.

Percent recovery = (Cspiked – Cunspiked) / Cexpected or theoretical (2)

Spiked environmental results reflect the analytical recovery efficiencies and matrix effects of the environmental water. 

Very high or low compound recoveries affect the ability of the 

instrument to quantify the concentrations of the compounds 

but do not affect the capability of the analytical method to 

detect the compound.
30 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Nine samples, about 1 percent of all samples analyzed 

for the study, were submitted as LMSs. Three samples were 

submitted for analysis of antibiotics in water, two samples 

for other pharmaceuticals in water, one sample each for 

hormones and OWCs in water, and one sample for OWCs in 

streambed sediment.

Results for LMSs were evaluated (1) to determine 

whether false-negatives were present (negative-detection 

bias) and (2) to determine whether matrix interferences were 

present that would cause positive or negative bias in reported 

results for the primary environmental sample associated with 

the spike. Therefore, for the purposes of this report, discussion 

and presentation of LMS recoveries will be limited to compounds that were detected in associated un-spiked environmental samples (Appendix C, tables C-2 to C-9).

Table 11. Statistical summary of relative percent differences for contaminants of emerging concern 

in duplicate samples of streamwater and streambed sediment collected in Pennsylvania, 2007–09.

[NWQL, U.S. Geological Survey National Water Quality Laboratory in Denver, Colorado: OGRL, Organic Geochemistry 

Research Laboratory in Lawrence, Kansas; RPD, relative percent difference]

Laboratory and 

analytical method

Number of duplicate 

pairs where both 

results were above 

the reporting level

Minimum RPD, 

in percent

Maximum RPD, 

in percent

Median RPD, 

in percent

Streamwater samples

NWQL pharmaceutical1 21 0 40 18

NWQL hormones 7 1.3 26 10

NWQL OWCs 10 0 11 5

ORGL antibiotics2 44 0 140 18

Streambed-sediment samples

NWQL hormones 15 5 159 46

NWQL OWCs 49 0 138 32

ORGL antibiotics2 13 0 69 27 1

 Analysis did not include antibiotic compounds.

2

 Analysis included the pharmaceutical compound ibuprofen.

Table 12. Statistical summary of recoveries of laboratory-matrix spike samples 

for selected analytical methods used in this study.

[ NWQL, U.S. Geological Survey National Water Quality Laboratory in Denver, Colorado: 

OGRL, Organic Geochemistry Research Laboratory in Lawrence, Kansas; OWCs, organic 

wastewater compounds]

Laboratory and 

analytical method

Number of 

laboratory-matrix 

spike compounds 

analyzed

Minimum Maximum Mean

Recovery, in percent

Streamwater samples

NWQL pharmaceutical1 12 38 116 81

NWQL hormones 19 42 127 90

NWQL OWCs 56 31 123 99

ORGL antibiotics2 26 18 237 102

Streambed-sediment samples

NWQL OWCs 50 (-81) 1,669 123 1

 Analysis did not include antibiotic compounds 

2

 Analysis included the pharmaceutical compound ibuprofen.

In general, mean recoveries for most compounds in 

streamwater samples were 70 to 120 percent. Recoveries in 

water ranged from 18 percent (lincomycin) to 237 percent 

(total chlorotetracycline). Mean recoveries for OWCs in 

streambed-sediment samples were variable with a typical 

mean recovery in the 40 to 200 percent range. Recoveries 

for most of the OWCs were lower than 80 percent and many 

were lower than 50 percent. Recoveries in streambed sediment ranged from 81 percent (negative recovery) (indole) to 

1,669 percent (beta-sitosterol) (table 12). False negatives were 

reported for 10 compounds in streambed-sediment LMS samples. Negative recoveries were reported for four compounds in 

spiked streambed-sediment samples. 
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 31

Pharmaceuticals, Hormones, and 

Organic Wastewater Compounds in 

Pennsylvania Waters

The targeted contaminants of emerging concern in water 

samples collected for these studies occurred in very low 

(nanograms per liter) concentrations. Many of the compounds 

were not detected in most of the streamwater or streambedsediment samples. Others were not detected in any samples 

at all.

Compounds in Groundwater Used to Supply 

Livestock

Six wells located in agricultural areas underlain by 

limestone geological formations were selected for study 

(table 5). These wells were sampled four times (approximately 

quarterly) during 2006. Samples were analyzed for a suite 

of 44 pharmaceutical compounds (table 1) in filtered water. 

Complete analytical results of these samples are presented in a 

report by Loper and others (2007).

Four pharmaceutical compounds were detected in the 24 

samples collected from 6 wells located in agricultural areas 

(table 13). Cotinine (nicotine metabolite) was detected once 

at a concentration of 24 ng/L (greater than reporting level) 

in one sample from a Lebanon County well W5 (LB1249), 

and diphenhydramine was detected once at a concentration 

of 3 ng/L (less than reporting level) in one sample from a 

Huntingdon County well W4 (HU 426). Tylosin was detected 

in one Lebanon County well W3 (LB 1248) and in one Lancaster County well W5 (LN 2114), and sulfamethoxazole was 

detected in one of the Lebanon County wells W5 (LB 1249). 

The largest concentration of any pharmaceutical compound 

measured in the groundwater samples was for cotinine, with 

a concentration of 24 ng/L in a water sample from a Lebanon 

County well W5 (LB 1249) (table 13). Tylosin is a veterinary 

antibiotic, and its presence in a groundwater sample may 

be related to the agricultural land use at the sampling site. 

Cotinine and sulfamethoxazole are for human use and are not 

related to agricultural land use at the sampling site. Overall 

the detection of pharmaceutical compounds in groundwater 

samples in agricultural areas was rare, and the detections that 

did occur were at very low concentrations (less than 24 ng/L). 

Compounds in Streamwaters Upstream and 

Downstream from Animal-Feeding Operations

Animal-feeding operations are present in the watersheds 

of six streams in south-central Pennsylvania that were selected 

for sampling (table 5). Four times (approximately quarterly) 

during 2006, streamwater samples were collected from 

the six streams at sites upstream and downstream from the 

AFOs. Samples were collected during base-flow conditions. 

The filtered water samples were analyzed for a suite of 44 

pharmaceutical compounds (table 1). Complete analytical 

results of these samples are presented in a report by Loper and 

others (2007).

Nine different pharmaceutical compounds (including 4 

antibiotics) were detected in the 48 samples collected from 

six streams at sites upstream and downstream from the AFOs 

(table 13). Three compounds were detected at concentrations 

greater than their reporting levels, including acetaminophen 

(analgesic), caffeine (stimulant), and carbamazepine (anticonvulsant). Two compounds, cotinine (nicotine metabolite) and 

diphenhydramine (antihistamine), were detected at concentrations less than the reporting levels (fig. 6). The antibiotic 

compounds detected were tylosin, sulfadimethoxine, sulfamethoxazole, and oxytetracycline (table 13). The greatest concentration for a pharmaceutical compound was 157 ng/L for 

the antibiotic sulfamethoxazole in a sample from the upstream 

site on Snitz Creek (A7, 01574050). 

In general, few pharmaceutical compounds were detected 

in streamwater samples collected upstream and downstream 

from AFOs. Only 9 of the 44 compounds analyzed were 

detected at least once in the 48 samples analyzed for a total 

detection frequency of 2 percent. The detected compounds 

that are related to agricultural use are the antibiotics tylosin, 

sulfadimethoxine, and oxytetracycline. The presence of these 

compounds may be related to AFOs, but tylosin and sulfadimethoxine were also detected in samples collected on the same 

day upstream and downstream from AFOs. Non-veterinary 

compounds also were detected in samples collected upstream 

and downstream from the AFOs. This finding is an indication 

that these compounds are not directly related to the specific 

AFOs but are generally present in groundwater discharge in 

the entire watershed. Most of these sites are located in small 

agricultural-dominated drainage areas with a few single-family 

residential homes that have on-lot septic systems for wastewater disposal. General agricultural land use and the on-lot septic 

systems may be a source of contaminants upstream of the AFO 

locations, especially during low-flow conditions (Senior and 

Cinotto, 2007).

Compounds in Streamwater and Streambed 

Sediments Upstream and Downstream from 

Wastewater Discharges

In 2006, water samples from five streams were collected 

at sites upstream and downstream from municipal wastewatereffluent-discharge sites (table 5). Samples were collected four 

times (approximately quarterly) from March to September 

at base-flow conditions and analyzed for pharmaceutical 

compounds. Complete analytical results of these samples are 

presented in a report by Loper and others (2007).

In 2007, 2008, and 2009, sampling continued at the sites 

downstream from the wastewater-effluent-discharge sites; four 

additional sites were added to the sampling, including sites 

on three streams receiving wastewater effluents, Quittapahilla 
32 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table 13. Pharmaceutical compounds detected in quarterly samples collected from 6 wells in 

agricultural areas and 12 stream sites located upstream and downstream from animal-feeding operations 

in Pennsylvania.

[ng/L, nanograms per liter]

Compound Number of

analyses

Number of detections 

at concentrations 

greater than 

reporting level

Number of detections 

at concentrations 

less than 

reporting level

Concentration

range

(ng/L)

Wells in agricultural areas

Nonprescription pharmaceuticals and metabolites

Cotinine1 24 1 0 24

Diphenhydramine 24 0 1 3

Macrolide antibiotics

Tylosin 24 2 0 12–17

Sulfonamide antibiotics

Sulfamethoxazole 24 1 0 6

Stream sites upstream from animal-feeding operations 

Nonprescription pharmaceuticals and metabolites

Caffeine1 24 2 0 16–19

Diphenhydramine 24 0 1 10

Prescription pharmaceuticals

Carbamazepine 24 2 2 5–25

Macrolide antibiotics and metabolites

Tylosin 24 1 0 17

Sulfonamide antibiotics

Sulfadimethoxine 24 1 0 26

Sulfamethoxazole 24 2 0 19–157

Stream sites downstream from animal-feeding operations 

Nonprescription pharmaceuticals and metabolites

Acetaminophen 24 1 3 3–18

Caffeine1 24 4 0 18–53

Cotinine1 24 0 2 7

Prescription pharmaceuticals

Carbamazepine 24 0 2 5

Macrolide antibiotics and metabolites

Tylosin 24 1 1 7–27

Sulfonamide antibiotics

Sulfadimethoxine 24 3 0 5–26

Sulfamethoxazole 24 1 0 19

Tetracycline antibiotics and metabolites

Oxytetracycline 24 1 0 19

1

Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated 

with human use.
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 33

0

1

2

3

4

5

Acetaminophen 

Caffeine 

Cotinine 

Diphenhydramine 

Carbamazepine 

Tylosin 

Sulfadimethoxine 

Sulfamethoxazole 

Oxytetracycline 

Acetaminophen 

Caffeine 

Cotinine 

Diphenhydramine 

Carbamazepine 

Tylosin 

Sulfadimethoxine 

Sulfamethoxazole 

Oxytetracycline 

Sites located upstream from animal-feeding operation Sites located downstream from animal-feeding operation 

Number of detections

Pharmaceutical compounds

Detections at concentrations

 less than reporting level

Detections at concentrations

 greater than reporting level

EXPLANATION

Figure 6. Pharmaceutical compounds detected in 24 streamwater samples collected from paired stream sites located upstream 

and downstream from five animal-feeding operations in Pennsylvania, 2006. 
34 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Creek, East Branch Antietam Creek, and Rock Creek and on 

one stream that received no municipal wastewater effluents 

(Clark Creek). Conoy Creek was omitted from the streams 

sampled (see footnote on table 5). During 2007–09, sampling 

was done once each year during summer low-flow periods. 

Samples of streambed sediments were collected and analyzed, in addition to water samples. Laboratory analyses were 

expanded to include hormones (table 2) and OWCs (table 3) in 

water, in addition to pharmaceutical compounds. Laboratory 

analyses of the streambed-sediment samples included antibiotics (table 1), hormones (table 2), and OWCs (table 3).

2006 Sampling Upstream and Downstream from 

Wastewater-Effluent-Discharge Sites

The sampling design used in 2006 allowed for a comparison of contaminant of emerging concern occurrence 

upstream and downstream from wastewater-treatment plants. 

Eleven different pharmaceutical compounds were detected 

(12 total detections) in the 20 samples collected from the five 

sites located upstream from a wastewater-effluent-discharge 

site (table 14). Acetaminophen, caffeine, para-xanthine, 

carbamazepine, erythromycin H2O, roxithromycin, ofloxacin, 

sulfamethoxazole, oxytetracycline, and trimethoprim were 

detected at concentrations greater than the reporting level, and 

cotinine was detected at a concentration less than the reporting level (table 14). All eleven compounds also were detected 

in the samples collected at the corresponding sites located 

downstream from the wastewater-effluent-discharge site. 

Twenty-three pharmaceutical compounds were detected (166 

total detections) in samples from the five sites located downstream from a wastewater-effluent-discharge site (table 14). 

All 23 compounds were detected at least once at concentrations greater than the reporting level. A greater number of 

compounds were detected and at a greater detection frequency 

at sites downstream from wastewater-effluent discharges than 

at sites upstream from wastewater-effluent discharges (fig. 7 

and fig. 8). Concentrations of individual constituents also were 

greater at the five sites located downstream from wastewatereffluent discharges than at the five sites located upstream from 

wastewater-effluent discharges. Carbamazepine was detected 

once in the four samples collected at Killinger Creek (T7, 

01573151) upstream from the wastewater-effluent-discharge 

site at a concentration of 9 ng/L but was detected in all four 

samples collected at the site (T8, 01573153) downstream from 

the wastewater-effluent discharge at an average concentration 

of 138 ng/L (fig. 9). Similarly, diltiazem and diphenhydramine 

were not detected in the four samples collected from Middle 

Spring Creek (T3, 015693155) upstream from the wastewater-effluent discharge but were detected in all four samples 

collected at the site (T4, 015693158) downstream from the 

wastewater-effluent discharge at average concentrations of 

36 ng/L and 32 ng/L, respectively. Sulfamethoxazole and 

ofloxacin were detected once each at concentrations of 67 ng/L 

and 6 ng/L, respectively, in the four samples collected at Lititz 

Run (T12, 01576420) upstream from the wastewater-effluent 

discharge. Sulfamethoxazole and ofloxacin were also detected 

in all four samples collected at the site (T13, 01576422) 

downstream from the wastewater-effluent discharge at average 

concentrations of 126 ng/L and 46 ng/, respectively (fig. 10). 

The increased number of detections and higher concentrations 

detected downstream from the wastewater-effluent discharges 

are indications that, although some compounds are present 

upstream from the wastewater-effluent discharge, the effluent 

is a source of pharmaceutical compounds.

No pharmaceutical compounds were detected in samples 

from Spring Creek site (T1, 01470857) and Middle Spring 

Creek site (T3, 015693155) upstream from the wastewatereffluent discharges, and roxithromycin was detected only 

once in a sample from the Mountain Creek upstream site (T5, 

01571193). This finding is an indication that these streams 

receive little or no input from agriculture or septic sources. 

These sites are in watersheds with greater than 45 percent 

forested land use. Six compounds were detected in samples 

from the Killinger Creek upstream site, and five compounds 

were detected in samples from Lititz Run upstream from the 

wastewater-effluent discharge. Two sites on Conoy Creek were 

originally sampled as part of the paired upstream-downstream 

wastewater-effluent sampling until it was discovered that the 

effluent from the water-treatment plant was piped directly to 

the Susquehanna River and not discharged directly into Conoy 

Creek. Acetaminophen, caffeine, and cotinine were detected 

in more than 50 percent of the samples from the two Conoy 

Creek sites. The most likely source of the contaminants for the 

sites located upstream from the wastewater-effluent discharge 

on Killinger Creek, Lititz Run, and on both Conoy Creek sites 

is on-lot septic systems (Carrara and others, 2008) or agricultural land use. These three sites are in watersheds with greater 

than 50 percent agricultural land use. 

Although more compounds were detected at the five sites 

downstream from wastewater-effluent-discharge sites and in 

greater concentrations, there were differences in the detection 

patterns and concentrations among the five streams. Of the 

five sites located downstream from wastewater discharges, the 

Killinger Creek site (T8, 01573153) had the most compounds 

detected (19) and the highest number of total detections (52). 

The maximum concentration for 17 of the 23 compounds 

detected downstream from a wastewater-effluent-discharge 

site was at the Killinger Creek site (T8, 01573153). Factors 

such as wastewater-treatment-plant design and efficiency and 

dilution in the receiving stream can be factors in the number 

of compounds detected and the concentrations. Killinger 

Creek is a small stream (drainage area of less than 14 mi2). 

Streamflow measurements made at the upstream and downstream sampling sites on Killinger Creek indicate that the 

average streamflow at the downstream site was 49 percent 

higher than that at the upstream site (table 15). Although the 

actual flow from the wastewater-treatment plant at the time 

of sampling is not known, most of the 49 percent difference 

between the two sampling sites is likely due to the wastewatereffluent discharge. The Palmyra wastewater-treatment plant, 
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 35

Table 14. Pharmaceutical compounds detected in streamwater samples collected from paired stream sites located upstream and 

downstream from five municipal wastewater-effluent-discharge sites in Pennsylvania, 2006.

[ng/L, nanograms per liter]

Compound Number of 

analyses

Stream sites upstream from 

wastewater-effluent-discharge sites

Stream sites downstream from 

wastewater-effluent-discharge sites

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(ng/L)

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(ng/L)

Nonprescription pharmaceuticals and metabolites

Acetaminophen 20 1 0 48 2 3 7–98

Caffeine1 20 1 0 65 7 0 15–4,750

Ibuprofen 20 0 -- -- 1 0 277

Para-xanthine1,2,3 20 1 0 20 1 0 853

Codeine 20 0 -- -- 6 3 5–156

Cotinine1 20 0 1 10 2 5 3–43

Diphenhydramine 20 0 -- -- 12 1 7–135

Prescription pharmaceuticals

Carbamazepine 20 1 0 9 15 1 8–276

Dehydronifedipine 20 0 -- -- 2 2 5–15

Diltiazem 20 0 -- -- 9 1 5–79

Salbutamol 20 0 -- -- 2 2 4–12

Warfarin 20 0 -- -- 1 0 30

Macrolide antibiotics and metabolites

Azithromycin 20 0 -- -- 11 0 21–1,650

Erythromycin 20 0 -- -- 5 0 8- 16

Erythromycin-H2O 2 20 1 0 11 11 0 8–168

Roxithromycin 20 1 0 9 1 0 5

Tylosin 20 0 -- -- 3 0 5–23

Quinoline antibiotics

Ciprofloxacin 20 0 -- -- 7 0 7–182

Ofloxacin 20 1 0 6 16 0 5–329

Sulfonamide antibiotics

Sulfadiazine 20 0 -- -- 1 0 121

Sulfamethoxazole 20 2 0 13–67 16 0 23–1,340

Tetracycline antibiotics and metabolites

Oxytetracycline 20 1 0 38 1 0 15

Other antibiotics

Trimethoprim 20 1 0 15 16 0 9–256

1

Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.

2

Metabolite breakdown product.

3

Para-xanthine also know as 1,7 dimethylxanthine.
36 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Acetaminophen

Caffeine

Ibuprofen

Para-xanthine

CodeineCotinine

Diphenhydramine

Carbamazepine

Deydronifedipine

Diltiazem

Salbutamol

Warfarin

Acetaminophen

Caffeine

Ibuprofen

Para-xanthine

CodeineCotinine

Diphenhydramine

Carbamazepine

Deydronifedipine

Diltiazem

Salbutamol

Warfarin

Pharmaceutical compounds (excluding antibiotics)

0

2

4

6

8

10

12

14

16

18

Number of detections 

Sites located downstream from a

wastewater-effluent-discharge site

Sites located upstream from a

wastewater-effluent-discharge site

Detections at concentrations

 less than reporting level

Detections at concentrations

 greater than reporting level

EXPLANATION

Figure 7. Number of detections of pharmaceutical compounds, excluding antibiotics, in 20 streamwater samples collected from 

paired stream sites located upstream and downstream from five municipal wastewater-effluent-discharge-sites in Pennsylvania, 

2006.
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 37

Sampling site

Carbamazepine concentration, in nanograms per liter

0

25

50

75

100

125

150

175

200

225

250

275

300

(T1)Spring Creek –upstream

(T2) Spring Creek – downstream

(T3) Middle Spring Creek –upstream

(T4) Middle Spring Creek – downstream

(T5) Mountain Creek – upstream

(T6) Mountain Creek – downstream

(T7) Killinger Creek – upstream

(T8) Killinger Creek – downstream

(T12) Lititz Creek – upstream

(T13) Lititz Creek – downstream

(4)

(4)

(4)

(4)

(4) (4) (4)

(4)

(4)

(4)

75th percentile

25th percentile

Median (50th percentile)

Mean

1.5 times interquartile range or largest value

Number of samples

-1.5 times interquartile range or largest value

Far outlier

(4)

EXPLANATION

Figure 8. Number of detections of antibiotic compounds at concentrations greater than the reporting level in 20 streamwater 

samples collected from paired stream sites located upstream and downstream from five municipal wastewater-effluent-discharge 

sites in Pennsylvania, 2006.
38 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Azithromycin

Erythromycin

Erythromycin-H2O

Roxithromycin

Tylosin

Ciprofloxacin

Ofloxacin

Sulfadiazine

Sulfamethoxazole

Oxytetracycline

Trimethoprim

Azithromycin

Erythromycin

Erythromycin-H2O

Roxithromycin

Tylosin

Ciprofloxacin

Ofloxacin

Sulfadiazine

Sulfamethoxazole

Oxytetracycline

Trimethoprim

Sites located downstream from

a wastewater-effluent-discharge site

Sites located upstream from

a wastewater-effluent-discharge site

0

2

4

6

8

10

12

14

16

18

Number of detections at concentrations

greater than reporting level

Antibiotic compounds 

Figure 9. Carbamazepine concentrations in streamwater samples collected from paired stream sites located upstream and 

downstream from five municipal wastewater-effluent-discharge sites in Pennsylvania, 2006. 
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 39

(4)

(4)

(4)

(4)

Compound

Concentration, in nanograms per liter

0

20

40

60

80

100

120

140

160

Sulfamethoxazole – upstream

Sulfamethoxazole – downstream

Ofloxacin – upstream

Ofloxacin – downstream

75th percentile

25th percentile

Median (50th percentile)

Mean

1.5 times interquartile range or largest value

Number of samples

-1.5 times interquartile range or largest value

Far outlier

(4)

EXPLANATION

Figure 10. Sulfamethoxazole and ofloxacin concentrations detected in samples collected from Lititz Creek near Lititz, 

Pennsylvania, the upstream site, T12, 01576420 and Lititz Creek at Rothsville, Pennsylvania, the downstream site, T13, 

01576422, in 2006.
40 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

which discharges effluent to Killinger Creek, has a design 

flow of 2.2 cubic feet per second (ft3/s). In 2008, the annual 

average flow from this plant was 1.3 ft3/s (Gannett Fleming, 

2009). The large percentage of flow from wastewater effluent 

reduces the amount of dilution that can occur and can lead to 

increased loads of contaminants. The average streamflow difference between the upstream and downstream sampling sites 

at the other four wastewater-effluent-discharge sites ranged 

from 5 percent at Mountain Creek to 40 percent at Lititz Run 

(table 15). 

Conoy Creek, where there is no waste effluent entering the stream, provides additional evidence of the presence 

of contaminants of emerging concern that are not related to 

a direct point source. Four pharmaceutical compounds were 

detected in samples from Conoy Creek. Acetaminophen was 

detected at concentrations greater than the reporting level in 

three of eight samples with a concentration range of 14 to 

350 ng/L. Caffeine was detected at concentrations greater than 

the reporting level in all eight samples with a concentration 

range of 15 to 363 ng/L. Cotinine was detected in one of eight 

samples at a concentration of 17 ng/L, which is greater than 

the reporting level. The veterinary antibiotic tylosin was the 

only antibiotic detected in samples from Conoy Creek. It was 

detected in six of the eight samples at concentrations ranging from 5 to 30 ng/L. The presence of caffeine and tylosin 

indicates that human and animal waste entered Conoy Creek. 

These wastes are most likely related to on-lot septic systems 

or urban and agricultural land use.

2007 to 2009 Sampling Downstream from 

Wastewater-Effluent Discharges 

From 2007 to 2009 streamwater and streambed-sediment 

samples were collected annually at eight sites (table 5) located 

downstream from a wastewater-effluent discharge and analyzed for contaminants of emerging concern. Samples also 

were collected from Clark Creek (a reference site), which 

receives no wastewater-effluent discharge. Four of the 119 

(3 percent) compounds analyzed in streamwater samples and 

24 of the 98 (24 percent) compounds analyzed in streambedsediment samples collected from Clark Creek were detected at 

least once at concentrations greater than the reporting level. At 

the eight sites located downstream from wastewater-effluent 

discharges, 54 of the 119 (45 percent) compounds analyzed in 

streamwater samples and 51 of the 98 (52 percent) compounds 

analyzed in streambed-sediment samples were detected at least 

once at concentrations greater than the reporting level. These 

results are similar to the results for the 2006 sampling at the 

paired sampling sites upstream and downstream from wastewater-effluent-discharge sites for which more contaminants 

of emerging concern were detected at sites downstream from 

wastewater-effluent discharges than at upstream sites. 

Nine of 13 pharmaceutical compounds (excluding 

antibiotics) analyzed were detected in streamwater samples 

from the eight sites located downstream from a wastewatereffluent discharge from 2007 to 2009. Acetaminophen, caffeine, codeine, cotinine, diphenhydramine, carbamazepine, 

Table 15. Description of sampling sites downstream from wastewater-effluent-discharge sites, number of compounds detected, total 

number of detections, average flow difference between upstream and downstream sampling sites, and drainage area for streamwater

samples collected in Pennsylvania, 2006.

U.S. Geological 

Survey station 

identification 

number

Map 

identification 

number 

(figure 1)

Stream 

Number of 

compounds 

detected at 

concentrations 

greater than 

reporting level

Total number of 

detections at 

concentrations 

greater than 

reporting level

Average flow 

difference 

between 

upstream and 

downstream 

sites1

(percent)

 Drainage area 

(square miles)

Stream sites downstream from wastewater-effluent-discharge sites

01470858 T2 Spring Creek near Brownsville, 

Pa. 8 19 7 19.6

015693158 T4 Middle Spring Creek above Burd 

Run below Shipensburg, Pa. 10 36 22 20.7

01571195 T6 Mountain Creek at Mt Zion 

at Mt Holly Springs, Pa. 7 7 5 47.1

01573153 T8 Killinger Creek DS Treatment 

Plant near Annville, Pa. 19 52 49 13.8

01576422 T13 Lititz Run at Rothsville, Pa. 14 34 40 13.3

1

Flow difference between the upstream and downstream sites is the result of wastewater-effluent discharge and growndwater inputs.
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 41

and diltiazem were detected at concentrations greater than 

the reporting level. Ibuprofen and dehydronifedipine were 

detected only at concentrations less than the reporting level 

(table 16). Caffeine (detected once at 9 ng/L) was the only 

pharmaceutical compound (excluding antibiotics) detected 

in the three samples collected from the reference site (Clark 

Creek). The pharmaceutical compounds (excluding antibiotics) most frequently detected at concentrations greater than 

the reporting level are the anticonvulsant drug carbamazepine 

(87 percent of samples), caffeine (67 percent), and the antihistamine diphenhydramine (46 percent). The pharmaceutical 

compounds (excluding antibiotics) detected in the greatest 

concentrations were caffeine (440 ng/L), carbamazepine 

(212 ng/L), and acetaminophen (158 ng/ L). Samples from 

the downstream site on Killinger Creek (T8, 01573153) had 

the greatest number of pharmaceutical compounds (excluding 

antibiotics) detected (7), the most total detections (14, fig. 11), 

and the highest concentrations detected for six of the seven 

pharmaceutical compounds (excluding antibiotics) detected. 

No pharmaceutical compounds (excluding antibiotics) were 

detected in the samples collected from the downstream site on 

Mountain Creek (T6, 01571195).

Eleven antibiotic compounds were detected at least once 

in streamwater or streambed-sediment samples collected at the 

eight sites downstream from a wastewater-effluent-discharge 

site from 2007 to 2009. Clark Creek (reference site) had one 

antibiotic detected in the three streamwater samples collected 

and one antibiotic detected in the three streambed-sediment 

samples collected. Detections of all antibiotics were at concentrations greater than the reporting level. The antibiotics 

that were frequently detected in streamwater or streambedsediment samples are azithromycin, erythromycin and its 

metabolite erythromycin-H2O, ciprofloxacin, ofloxacin, sulfamethoxazole, tetracycline, and trimethoprim (table 16). Some 

compounds were detected more frequently in streamwater 

samples (sulfamethoxazole and erythromycin), whereas others 

were detected more frequently in streambed-sediment samples 

(tetracycline and ciprofloxacin). The maximum concentration of an antibiotic in streamwater samples was 1,150 ng/L 

of sulfamethoxazole, and the maximum concentration of an 

antibiotic in streambed-sediment samples was 1,760 μg/kg for 

ciprofloxacin. Streamwater and streambed-sediment samples 

from Killinger Creek (T8, 01573153) had the most total 

detections. The maximum concentrations detected for six of 

the nine antibiotics in streamwater samples and seven of nine 

antibiotics in streambed-sediment samples were also detected 

in samples collected from Killinger Creek (T8, 01573153). 

Two antibiotic compounds were detected in the streamwater 

and streambed-sediment samples from Mountain Creek (T6, 

01571195), the fewest for the eight sites sampled downstream 

from wastewater-effluent discharge.

Eight of the 19 hormones and animal sterol compounds 

analyzed in streamwater samples and 15 of the 19 hormones 

and animal sterol compounds analyzed in streambed-sediment samples were detected at least once at concentrations 

greater than their reporting levels at the eight sites located 

downstream from a wastewater-effluent-discharge site from 

2007 to 2009. For Clark Creek (reference site) no hormones or 

animal sterols were detected in the streamwater samples, but 

two hormones and two animal sterols (6 total detections) were 

detected in the three streambed-sediment samples collected 

(table 17). The natural estrogen estrone was the hormone 

compound detected most frequently in both streamwater 

and streambed-sediment samples (table 17). Most hormones 

were present in streamwater and streambed-sediment samples at similar detection frequencies. The natural androgen 

4-androstene-3,17-dione was present more frequently in 

streamwater samples than in streambed-sediment samples, 

and the animal sterols cholesterol and 3-beta-coprostanol were 

detected more frequently in streambed-sediment samples. The 

natural estrogen 17-beta-estradiol and the synthetic estrogen 17-alpha-ethynylestradiol are known to have endocrine 

disrupting potential but were rarely detected. The hormone 

17-beta-estradiol was detected in four streamwater samples 

(0.5–0.9 ng/L) and in eight streambed-sediment samples 

(0.1–1.9 μg/kg), and 17-alpha-ethynylestradiol was detected 

in two streambed-sediment samples (0.3–1.7 μg/kg). Overall, the detection of hormones and animal sterols was rare; 

most compounds were detected in less than 20 percent of 

the samples. The exception to this was estrone, which was 

detected in 50 percent of streamwater samples and 96 percent 

of streambed-sediment samples. The hormones detected in 

the greatest concentrations were estrone, which was detected 

in streamwater samples (25 ng/L), and progesterone, which 

was detected in streambed-sediment samples (8.4 μg/kg). 

The animal sterol cholesterol was detected at concentrations 

ranging from 2,230 to 9,760 ng/L in streamwater samples and 

from 1,700 to 115,000 μg/kg in streambed-sediment samples. 

The animal sterol 3-beta-coprostanol was detected at concentrations of 2,500 to 4,520 ng/L in streamwater and 330 

to 10,600 μg/kg in streambed-sediment samples (table 17). 

Samples from Killinger Creek (T8, 01573153) had the most 

total detections of hormones and animal sterols in streamwater 

and streambed-sediment samples (figs. 11 and 12). The maximum concentrations detected for seven of the eight hormones 

and animal sterols in streamwater samples and six of nine 

hormones and animal sterols in streambed-sediment samples 

were detected in samples collected from Killinger Creek 

(T8, 01573153). Quittapahilla Creek (T9, 01573160) had the 

least total detections (1) of hormones and animal sterols in 

the streamwater samples, and Clark Creek (T14, 01568590) 

had the least detections (4) of hormones and animal sterols in 

streambed-sediment samples.

Forty of the 56 OWCs analyzed in streamwater samples 

and 34 of 51 OWCs analyzed in streambed-sediment samples 

were detected at least once at the eight sites located downstream from wastewater-effluent-discharge sites from 2007 

to 2009 (table 18, at end of report). Four of 56 OWCs analyzed in streamwater samples and 21 of 51 OWCs analyzed 

in streambed-sediment samples were detected at least once in 

the three samples collected from the reference site located on 

Clark Creek (table 18). The OWCs most frequently detected 
42 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 16. Pharmaceutical compounds detected in streamwater and streambed-sediment samples collected from Clark Creek and eight stream sites downstream from wastewater-effluent-discharge sites in Pennsylvania, 2007–09.—Continued [ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed; --, no data] Compound Streamwater Streambed sediment Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (ng/L) Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (μg/kg) Clark Creek (reference site, no effluent discharge upstream) Nonprescription pharmaceuticals and metabolites Caffeine1 3 1 0 9 0 -- -- -- Macrolide antibiotics Erythromycin-H

O2

2 3 1 0 8 0 na 0 --

Sulfonamide antibiotics

Sulfamethoxazole 3 0 0 -- 3 1 0 1

Eight stream sites downstream from wastewater-effluent-discharge sites

Nonprescription pharmaceuticals and metabolites

Acetaminophen 24 3 1 3–158 0 -- -- --Ibuprofen 24 0 1 8 0 -- -- --Caffeine1 24 16 0 11–440 0 -- -- --Codeine 24 1 2 4- 74 0 -- -- --Cotinine1 24 3 2 7–86 0 -- -- --Diphenhydramine 24 11 3 3–85 0 -- -- --

Prescription pharmaceuticals

Carbamazepine 24 21 0 15–212 0 -- -- --Dehydronifedipine 24 0 4 2–10 0 -- -- --Diltiazem 24 5 1 7–107 0 -- -- --

Macrolide antibiotics and metabolites

Azithromycin 24 13 0 7–402 16 11 0 13–1,000Erythromycin 24 7 0 8–58 24 2 0 5–10Erythromycin-H

O2

2 24 17 0 8–291 0 na 0 --

Quinoline antibiotics

Ciprofloxacin 24 6 0 6–127 24 13 0 40–1,760Ofloxacin 24 15 0 5–242 24 21 0 2–1,000
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 43

Table 16. Pharmaceutical compounds detected in streamwater and streambed-sediment samples collected from Clark Creek and eight stream sites downstream from wastewater-effluent-discharge sites in Pennsylvania, 2007–09.—Continued[ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed; --, no data]

Compound

Streamwater Streambed sediment

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range

(ng/L)

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range

(μg/kg)

Sulfonamide antibiotics

Sulfadimethoxine 24 2 0 16–105 24 0 0 --Sulfamethoxazole 24 24 0 5–1,150 24 9 0 1–30

Tetracycline antibiotics and metabolites

Tetracycline 24 0 0 -- 24 8 0 8–60Epi-tetracycline (4-Epi-tetracycline HCl)2 24 0 0 -- 24 1 0 5

Other antibiotics

Ormetoprim 24 1 0 12 24 1 0 2Trimethoprim 24 18 0 6–704 24 20 0 2–140

1Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.2 Metabolite breakdown product.
44 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Figure 11. Number of contaminants of emerging concern detected at concentrations greater 

than the reporting level in streamwater samples collected from sites downstream from municipal 

wastewater-effluent-discharge sites in Pennsylvania, 2007–09.

(T14) Clark Creek (Reference site) 

( T15) Rock Creek 

( T16) East Branch Antietam Creek 

(T2) Spring Creek 

(T4) Middle Spring Creek 

(T6) Mountain Creek 

(T8) Killinger Creek 

(T9) Quittapahilla Creek 

(T13) Litiz Creek 

Sampling site

0

5

10

15

20

25

30

35

40

45

50

Number of compounds detected at concentrations

greater than the reporting level

Organic wastewater compounds

EXPLANATION

Hormones and animal sterols

Antibiotics

Pharmaceuticals (excluding antibiotics)
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 45

Table 17. Hormone and animal sterol compounds detected in streamwater and streambed-sediment samples collected annually from Clark Creek and eight stream sites located downstream from municipal wastewater-effluent-discharge sites in Pennsylvania, 2007–09.[ng/L, nanograms per liter; μg/kg, micrograms per kilogram; --, no data]

Compound

Number 

of 

analyses

Streamwater Streambed sediment

Number of detections 

at concentrations 

greater than 

reporting level

Number of detections 

at concentrations 

less than 

reporting level

Concentration 

range 

(ng/L)

Number of detections 

at concentrations 

greater than 

reporting level

Number of detections 

at concentrations 

less than 

reporting level

Concentration 

range 

(μg/kg)

Clark Creek (no effluent discharge upstream)

Natural estrogen

17-beta-Estradiol1 3 0 0 -- 1 0 0.3Estrone 3 0 0 -- 2 0 0.2–0.8

Animal sterols

Cholesterol 3 0 0 -- 2 0 2,500–3,0003-beta-Coprostanol 3 0 0 -- 1 0 325

Eight sites downstream from wastewater-effluent-discharge sites

Natural androgen

4-Androstene-3,17-dione 24 11 0 0.5–6.5 4 0 1.2–5.1cis-Androsterone 24 3 1 0.2–2.1 8 0 0.1–5.9Epitestosterone 24 0 0 -- 4 1 0.2–1.0Testosterone 24 0 0 -- 2 0 0.3–0.7

Natural estrogen

Equilenin 24 2 0 2.1–3.6 1 0 2.517-alpha-Estradiol 24 0 0 -- 3 0 0.1–0.717-beta-Estradiol1 24 4 0 0.5–0.9 8 0 0.1–1.9Estriol 24 2 0 0.6- 0.9 1 0 0.4Estrone 24 12 0 0.6–25 23 0 0.3–4.0

Synthetic estrogen

Diethylstilbestrol 24 0 0 -- 1 0 0.317-alpha-Ethynylestradiol1 24 0 0 -- 2 0 0.3–1.7Mestranol 24 0 0 -- 1 0 0.5

Natural progestin

Progesterone 24 0 0 -- 4 0 1.0–8.4

Animal sterols

Cholesterol 24 3 0 2,230–9,760 23 0 1,700–115,0003-beta-Coprostanol 24 2 0 2,500–4,520 15 0 330–10,600

1 Known endocrine disruping potential.
46 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Figure 12. Number of contaminants of emerging concern detected at concentrations greater than the reporting level in streambedsediment samples collected from the Clark Creek reference site and eight stream sites located downstream from municipal wastewatereffluent-discharge sites in Pennsylvania, 2007–09.

Organic wastewater compounds

EXPLANATION

Hormones and animal sterols

Antibiotics

(T14) Clark Creek (Reference site) 

( T15) Rock Creek 

( T16) East Branch Antietam Creek 

(T2) Spring Creek 

(T4) Middle Spring Creek 

(T6) Mountain Creek 

(T8) Killinger Creek 

(T9) Quittapahilla Creek 

(T13) Litiz Creek 

0 

5 

10 

15 

20 

25 

30 

35 

40 

45 

50 

Sampling site

Number of compounds detected at concentrations

greater than the reporting level
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 47

in streamwater at eight sites downstream from wastewatereffluent-discharge sites at concentrations greater than their 

reporting levels are the flame retardants tri(dichloroisopropyl) 

phosphate (83 percent), tri(2-chloroethyl) phosphate 

(62 percent), and tri(2-butoxyethyl) phosphate (33 percent). 

Tri(dichloroisopropyl) phosphate and tri(2-chloroethyl) 

phosphate are suspected endocrine disruptors (Zaugg and 

others, 2002). The OWCs most frequently detected in 

streambed-sediment samples at eight sites downstream of 

wastewater-effluent-discharge sites at concentrations greater 

than their reporting levels are fluoranthene, phenanthrene, and 

pyrene (100 percent) and benzo[a]pyrene and beta-sitosterol 

(96 percent). Fluoranthene, pyrene, and beta-sitosterol had 

high (297–1,669 percent) recoveries reported for laboratory spiked environmental streambed-sediment samples; 

the reported concentrations of these compounds may be an 

overestimate of actual concentrations (Appendix C, table C-9). 

Other known or suspected endocrine disruptors detected in 

streamwater and streambed-sediment samples are detergent 

metabolites, pesticides, industrial compounds, disinfectants, 

and PAHs (table 18). Some compounds were found primarily 

in streamwater or streambed-sediment samples, and others 

were found in both mediums. Although the number of OWCs 

detected at least once in streamwater and streambed-sediment 

samples was similar, the detection frequency was greater for 

the streambed-sediment samples. There were two frequently 

detected compounds (detected in more than 50 percent of 

samples collected) in the 24 streamwater samples collected 

and there were 17 frequently detected compounds in the 

24 streambed-sediment samples collected (table 18). The 

OWC detected in the greatest concentration in streamwater 

and streambed-sediment samples is nonylphenol, diethoxy- 

(total, NPEO2) (15,000 ng/L in a streamwater sample and 

9,589 μg/kg in a streambed-sediment sample). Total, NPEO2 

is a known endocrine disruptor (Zaugg and others, 2002).

Streamwater and streambed-sediment samples from 

Killinger Creek (T8, 01573153) had the highest number of 

detections of OWCs (fig. 11 and 12) of any of the sites located 

downstream from wastewater-effluent-discharge sites. The 

maximum concentrations detected for seven of the eight 

hormones and animal sterols in streamwater samples and six 

of nine hormones and animal sterols in streambed-sediment 

samples also were detected in samples collected from Killinger Creek (T8, 01573153). Killinger Creek had the highest 

concentrations detected for 19 of the 27 OWCs detected in 

streamwater samples and for 15 of the 28 OWCs detected 

in streambed-sediment samples. Quittapahilla Creek (T9, 

01573160) had the fewest hormones and animal sterols and 

OWCs detected (2) in streamwater samples, and Mountain 

Creek (T6, 01571195) had the fewest total number of pharmaceuticals detected (3) in the streamwater samples collected at 

the eight sites located downstream from wastewater-effluentdischarge sites (fig. 11). Mountain Creek (T6, 01571195) had 

the fewest number of antibiotic and OWC detections (16) and 

the fewest total number of detections in streambed-sediment 

samples collected at the eight sites located downstream from 

wastewater-effluent-discharge sites (fig. 12).

Results from the 2006 sampling upstream and downstream from wastewater-effluent discharges indicate that 

all classes of compounds (pharmaceuticals, hormones, and 

OWCs) were detected in greater numbers, at increased detection frequencies, and at higher concentrations in samples 

downstream from a wastewater-effluent discharge. The detection patterns from the 2006 sampling along with the concentrations measured during the 2007 to 2009 sampling downstream 

from wastewater-effluent discharges, indicate that streams like 

Killinger Creek (T8, 01573153), to which wastewater-effluent 

discharge contributes a large percentage of the total flow, are 

likely to have higher numbers of compounds detected and at 

higher concentrations than streams such as Mountain Creek 

(T6, 01571195), which have relatively small percentages of the 

total flow attributable to wastewater effluent.

Although samples from the upstream sampling locations 

had fewer compounds detected, had compounds detected less 

frequently, and had compounds detected in smaller concentrations than the downstream locations, contaminants of emerging concern were, nevertheless, present upstream from the 

wastewater-effluent discharge. Non-point discharge contamination from on-lot septic systems and agricultural land use are 

the most likely sources of the contamination upstream from 

the wastewater-effluent discharges. Leaking sewer pipes and 

urban runoff also can be a source of contaminants of emerging concern (Phillips and Chalmers, 2009). Contaminants 

of emerging concern also were found more frequently in the 

streambed-sediment samples than in the streamwater samples. 

Antibiotic compounds were often found in both the water and 

sediment samples but some OWCs were found exclusively in 

the streambed-sediment samples and not in the streamwater 

samples (fig. 13). Streambed sediments can accumulate and 

store many organic wastewater compounds, then redistribute 

them downstream during periods of high flow, becoming an 

in-stream source of contamination.

Compounds in Streamwaters near DrinkingWater Intakes

Twenty-seven stream sampling sites near drinking-water 

intakes were sampled quarterly from March 2007 to September 

2009 at various flow conditions and analyzed for pharmaceutical compounds and hormones in streamwater samples (fig. 14). 

The total number of samples analyzed, by compound, is 297 

for pharmaceuticals (excluding antibiotics), 294 for antibiotics, and 270 for hormones. Nineteen of the 63 compounds 

analyzed were detected at least once at concentrations greater 

than the reporting level. All concentrations of pharmaceutical 

compounds measured at the sites near drinking-water intakes 

were within the range of concentrations previously reported in 

a national reconnaissance of untreated drinking-water sources 

across the United States (Focazio and others, 2008). 
48 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Streamwater

EXPLANATION

Streambed sediment

0 

20 

40 

60 

80 

100 

120 

Azithromycin 

Ciprofloxacin 

Sulfamethozazole 

Tetracycline 

Trimethoprim 

4-androstene-3,17-dione 

Estrone 

Progesterone 

Indole 

Cabazole 

Phenol 

Fluoranthene 

Napthalene 

Phenanthrene 

Tri(dichloroisopropyl)phosphate 

Compound

Detection frequency of contaminants of emerging

concern (detections at concentrations greater

than the reporting level)

Antibiotics Hormones Organic wastewater compounds

Figure 13. Detection frequency of selected contaminants of emerging concern detected at concentrations greater than the reporting 

level in streamwater and streambed-sediment samples collected from eight sites located downstream from municipal wastewatereffluent-discharge sites in Pennsylvania, 2007–09. (Detection frequency is detections at concentrations greater than the reporting 

level per number of samples.)
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 49

Figure 14. Locations of 27 streamwater-sampling sites near drinking-water intakes with the number of total detections at 

concentrations greater than the reporting level, by compound class, in Pennsylvania, 2007–09. 

0 40 80 MILES

0 40 80 KILOMETERS

EXPLANATION

75°

76° 79° 78° 77°

80°

42°

41°

40°

Base from U.S. Geological Survey digital data, 1980, 1:100,000

Albers Equal-Area Conic projection, NAD 83

D8 D7 D6

D5

D4

D3

D2

D1

D27

D26

D25

D24

D23

D22

D21

D20

D19

D18

D17

D16

D15

D14

D13

D12 D11

D10

D9 Delaware

River

S c huylkill Ri v er

Juniata River

West Branch

Susquehanna River

Ohio

River

Alleghen y

River

East Branch Susquehanna River

S us qu e h a n n a

River

Yo ughiogeny River

Monongohela River

Hormones

0–2

3–9

Antibiotics

0–2

3–15

16–24

Pharmaceuticals

0–2

3–15

16–33

Number of detections greater than the reporting 

level, by compound class, for streamwatersampling sites near a drinking-water intake

Delaware River Basin

Ohio River Basin

Genesee River Basin

Lake Erie Basin

Susquehanna River Basin

Potomac River Basin

Chesapeake Bay Basin

Water features from U.S. Geological Survey National Hydrography

Dataset (NHD). Basin boundaries from U.S. Geological Survey Digital

Watershed Boundary Dataset coded by Hydrologic Unit Codes (HUC)
50 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Pharmaceutical Compounds

Seventeen of the 44 pharmaceutical compounds (table 1) 

were detected at the 27 stream sites located near a drinkingwater intake from 2007 to 2009. Fourteen of the 17 compounds 

were detected at concentrations greater than the reporting 

level, and 3 compounds were detected at concentrations less 

than the reporting level (table 19, fig. 15). The pharmaceutical compounds most frequently detected at concentrations 

greater than the reporting levels were caffeine (71 percent), 

sulfamethoxazole (40 percent), acetaminophen (25 percent), 

carbamazepine (20 percent), trimethoprim (8 percent), paraxanthine (6 percent), and erythromycin-H2

O (6 percent). 

Acetaminophen, caffeine, carbamazepine, erythromycin-H2O, 

para-xanthine, sulfamethoxazole, and trimethoprim accounted 

for 94 percent of all the pharmaceutical detections in the 297 

samples collected. All other compounds were detected at 

concentrations greater than the reporting level in 3 percent or 

less of all samples (table 19). These results are consistent with 

results from a national USGS study that found acetaminophen, 

caffeine, carbamazepine, para-xanthine, and sulfamethoxazole, 

were among the most commonly detected contaminants of 

emerging concern nationwide (Kolpin and others, 2002). The 

pharmaceutical compounds detected in the greatest concentrations were caffeine (517 ng/L), acetaminophen (210 ng/ L), 

sulfamethoxazole (146 ng/L), and para-xanthine (101 ng/L). 

At least one pharmaceutical compound (including 

antibiotics) was detected at concentrations greater than the 

reporting level in samples from all 27 stream sites (fig. 16). 

The sampling locations with the most compounds detected 

and the most total detections at concentrations greater than 

the reporting level are the Schuylkill River (D4, 01474010; 

10 compounds detected and 57 total detections), Beaver River 

(D27, 03107500; 10 compounds detected and 47 total detections), Susquehanna River at Sunbury (D9, 01553990; 8 compounds detected and 26 total detections), Swatara Creek (D15, 

01562000; 10 compounds detected and 34 total detections), 

Susquehanna River at Danville (D7, 01553990; 7 compounds 

detected and 29 total detections), and Ohio River (D24, 

03086000; 7 compounds detected and 39 total detections). 

Sampling locations with multiple detections at concentrations 

greater than 100 ng/L are the Schuylkill River (D4, 01474010), 

Jordan Creek (D2, 01452040), Monongahela River (D22, 

03075001), Ohio River (D24, 03086000), and the Beaver River 

(D27, 03107500). The sampling locations with the fewest 

pharmaceutical compounds detected at concentrations greater 

than the reporting level are George Run (D17, 03015554) and 

East Branch Antietam Creek (D16, 01618800). Both sites had 

one compound that was detected one time (fig. 16). 

Carbamazepine was the only prescription pharmaceutical 

commonly detected and sulfamethoxazole was by far the most 

commonly detected antibiotic. Detection of the remaining prescription pharmaceuticals and antibiotic compounds (fig. 15) 

was rare. All antibiotics detected are for human use except 

for tylosin, which is for veterinary use. Sulfamethoxazole 

was the antibiotic that was detected at the highest concentrations. It was detected at concentrations greater than 100 ng/L 

in three samples collected from the Schuylkill River (D4, 

01474010) and in one sample collected from the Beaver River 

(D27, 03107500).

Hormones

Six of the 17 hormone and 2 animal sterol compounds 

were detected at least once in 270 samples collected from the 

27 stream sites located near a drinking-water intake from 2007 

to 2009 (table 19). Compounds detected at concentrations 

greater than the reporting levels were the hormones 4-androstene-3,17-dione, cis-androsterone, 17-alpha-estradiol, estriol, 

and estrone and the animal sterols cholesterol and 3-betacoprostanol (fig. 17). The hormone 17-beta-estradiol was 

detected once at a concentration less than the reporting level. 

The most frequently detected hormones that were detected 

at concentrations greater than the reporting levels are estrone 

(detected in 18 percent of all samples), cis-androsterone 

(5 percent), and 4-androstene-3,17-dione (3 percent). All other 

compounds were detected in less than 1 percent of all samples. 

The only hormone detected from the 27 stream sites located 

near a drinking-water intake that is listed as an endocrine 

disruptor was 17-beta-estradiol. It was detected in one sample 

at a concentration below the reporting level.

The hormone compounds detected in the greatest concentrations in streamwater near drinking-water intakes are 

cis-androsterone (6.2 ng/L), estrone (3.1 ng/ L), and 4-androstene-3,17-dione (1.8 ng/L, table 19). The highest measured 

concentrations of cis-androsterone, estrone, and 4-androstene3,17-dione were detected in a sample collected from Jordan 

Creek (D2, 01452040). Estrone is a naturally occurring female 

hormone, and 4-androstene-3,17-dione and cis-androsterone 

are naturally occurring male hormones. The maximum concentrations of hormones detected are much lower than those of 

pharmaceuticals and antibiotics. The maximum concentration 

of any animal sterol detected in streamwater near drinkingwater intakes was 6,790 ng/L for cholesterol (table 19), which 

was detected in a sample collected from Susquehanna River 

at Danville (D7, 01540500). The sampling locations with 

the most compounds detected and the most total detections 

are Jordan Creek (D2, 01452040; 3 compounds detected and 

9 total detections) and Susquehanna River at Danville (D7, 

01540500; 4 compounds detected and 5 total detections). 

Eight of the 27 sites had no detections of hormone or animal 

sterol compounds at concentrations greater than the reporting levels in the 10 samples collected from each site (fig. 16). 

Detection of most of the hormone and animal sterol compounds was rare. Only 1.5 percent of the analyses (73 detections in 5,130 analytical results) resulted in a detection at a 

concentration greater than the reporting level.
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 51

Table 19. Pharmaceutical and hormone and animal sterol compounds detected in streamwater samples collected from 27 stream 

sites located near drinking-water intakes in Pennsylvania, 2007–09.

[ng/L, nanograms per liter; <, less than]

Compound Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Percent 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Percent 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(ng/L)

Pharmaceutical compounds

Nonprescription pharmaceuticals and metabolites

Acetaminophen 297 74 25 35 12 1–210

Caffeine1 297 212 71 6 2 6–517

Para-xanthine1,2,3 297 17 6 0 0 11–101

Codeine 297 0 0 1 <1 5

Cotinine1 297 9 3 35 12 2–22

Diphenhydramine 297 0 0 20 7 1–6

Prescription pharmaceuticals

Carbamazepine 297 61 20 36 12 1–95

Dehydronifedipine 297 0 0 1 <1 1

Diltiazem 297 2 1 3 1 4–26

Salbutamol 297 4 1 0 0 9–12

Macrolide antibiotics and metabolites

Azithromycin 294 8 3 0 0 7–72

Erythromycin-H2O 294 18 6 0 0 8–70

Roxithromycin 294 1 <1 0 0 10

Tylosin 294 3 1 0 0 10

Quinoline antibiotics

Ofloxacin 294 7 2 0 0 7–19

Sulfonamide antibiotics

Sulfamethoxazole 294 119 40 0 0 5–146

Other antibiotics

Trimethoprim 294 23 8 0 0 5–18

Hormones and animal sterols

Natural androgen

4-Androstene-3,17-dione 270 7 3 2 <1 0.37–1.8

Cis-Androsterone 270 13 5 2 <1 0.32–6.2

Natural estrogen

17-alpha-Estradiol 270 1 <1 0 0 0.43

17-beta-Estradiol4 270 0 0 1 <1 0.39

Estriol 270 1 <1 2 <1 0.23–0.44

Estrone 270 48 18 3 1 0.32–3.1

Animal sterols

Cholesterol 270 2 <1 1 <1 255–6,790

3-beta-Corprostanol 270 1 <1 0 0 3,170

1

Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.

2

Metabolite breakdown product.

3

Para-xanthine also know as 1,7 dimethylxanthine.

4

Known endocrine disrupting potential.
52 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Figure 15. Number of detections of pharmaceutical compounds in streamwater samples collected from 27 stream sites located 

near drinking-water intakes in Pennsylvania, 2007–09.

0

50

100

150

200

250

Number of detections

Acetaminophen

Caffeine

Para-xanthine

Codeine

Cotinine

Diphenhydramine

Dehydronifedipine

Diltiazem

Salbutamol

Azithromycin

Erythromycin-H2O

Roxithromycin

Tylosin

Ofloxacin

Sulfamethoxazole

Trimethoprim

Carbamazepine

Pharmaceuticals

Detections at concentrations

 less than reporting level

Detections at concentrations

 greater than reporting level

EXPLANATION
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 53

(D1) Brodhead Creek

(D2) Jordan Creek

(D3) Delaware River

(D4) Schuylkill River

(D5) Corey Creek

(D6) Fishing Creek

(D7) Susquehanna River-Danville

(D8) WB Susquehanna River

(D9) Susquehanna River-Sunbury

(D10) Raystown Branch-Juniata River

(D11) East Licking Creek

(D12) Juniata River-Newport

(D13) Conodoguinet Creek

(D14) Yellow Breeches Creek

(D15) Swatara Creek

(D16) East Branch Antietam Creek

(D17) George Run

(D18) Pitchpine Run

(D19) Allegheny River-Kittanning

(D20) Allegheny River-Oakmont

(D21) Cheat River

D22) Monongahela River

(D23) Youghiogheny River

(D24) Ohio River

(D25) Shenango River

(D26) Slippery Rock Creek

(D27) Beaver River

0

2

4

6

8

10

12

14

Number of compounds detected at concentrations

greater than the reporting level

Sampling site

Hormones and animal sterols

EXPLANATION

Antibiotics

Pharmaceuticals (excluding antibiotics)

Figure 16. Number of contaminants of emerging concern detected at concentrations greater than the reporting level in streamwater 

samples collected from 27 stream sites near drinking-water intakes in Pennsylvania, 2007–09.
54 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Patterns of Contaminant Occurrence

Concentrations of contaminants of emerging concern in 

samples from sites near drinking-water intakes are often lower 

than the concentrations at the source as a result of dilution, 

sorption, volatilization, and degradation (Glassmeyer and 

others, 2005; Fono and others, 2006). Concentrations of contaminants of emerging concern in streams near drinking-water 

intake sites are dependent on many factors, including concentrations at the source, number of sources, source pathways, 

distance from the source, watershed size, and hydrologic 

conditions (Kolpin and others, 2002).

Hydrologic Conditions

Flow conditions can control the dilution of contaminants from point sources. During low-flow conditions, there 

may be little streamwater to dilute contaminants from a point 

source; therefore, in-stream concentrations typically are highest during low flows. Increases in streamflow can dilute the 

concentrations of contaminants from a point source, lowering 

the concentrations in stream samples, often to below detectable concentrations. For example, at the Schuylkill River at 

Philadelphia, Pa., (D4, 01474010), the concentration of the 

antibiotic sulfamethoxazole was inversely related to streamflow (fig. 18). The highest concentrations of sulfamethoxazole 

(142 ng/L and 146 ng/L) were measured when streamflow 

was lowest, and the lowest concentration of sulfamethoxazole 

(17 ng/L) was measured when streamflow was highest, 

indicating that the concentration is controlled by in-stream 

dilution. There are 1,275 permitted discharges upstream from 

the Schuylkill River at Philadelphia, Pa., sampling site, which 

provide a steady source of contaminants to the stream.

The most commonly detected compounds had different 

patterns of detection related to streamflow (fig. 19). Carbamazepine and estrone followed patterns similar to that of sulfamethoxazole with the highest detection frequency for samples 

collected during low flows and lowest detection frequency 

for samples collected during higher flows. Other compounds 

did not follow the low-flow, high-detection frequency pattern. 

For example, acetaminophen and caffeine were found more 

frequently in samples collected during high flows (fig. 19). 

These apparent relations of concentration to flow conditions 

are a further indication that the occurrence and concentration 

of many of these compounds are variable and dependent on 

factors such as concentrations at the source, mode of transport 

from the source (point source, non-point source, combined 

sewer overflows), sorption, volatilization, and degradation. 

These factors can be compound specific. The occurrence and 

concentrations of contaminants of emerging concern also 

could be related to the contribution of flow from combined 

sewer overflows and decreased removal efficiency at wastewater-treatment plants during high-flow events (Philips and 

Chalmers, 2009).

Number of Permitted Discharges

One of the major factors controlling the occurrence of 

contaminants of emerging concern in a particular watershed 

is the number of wastewater, stormwater, and industrial 

discharges in the watershed relative to the base flow. As the 

amount of effluent water increases relative to non-effluent 

water, the dilution of organic waste compounds in the stream 

decreases, and concentrations of organic waste compounds 

become more detectable.

 The 27 stream sites sampled were associated with different numbers of permitted discharges upstream from the sampling site. The number of permitted discharges ranged from 0 

to 5,873 in drainage areas ranging from 1.82 mi2 to 19,500 mi2

(table 7). To analyze the effect of the number of permitted discharges on contaminant detections, the 27 sites were 

divided into three categories of wasteload—high, mid, and low 

(9 sites per category)—on the basis of the number of permitted 

discharges per unit of drainage area. This approach does not 

account for the differences in waste volumes at discharge sites 

and, therefore, is only an estimate of relative wasteloads to 

the streams. The largest number of detections occurred at sites 

where the ratio of discharges per square mile of drainage area 

was greater than 0.28 (fig. 20). The sites that fell into the high 

wasteload category (greater than 0.28 discharges per square 

mile of drainage area) ranged from relatively small streams 

like Yellow Breeches near New Cumberland, Pa. (D14, 

01571505; 206 mi2) to the Ohio River at Sewickley, Pa. (D24, 

03086000; 19,500 mi2). The 9 sites with greater than 0.28 

0

10

20

30

40

50

60

4-androstene-3,17-dione

Cis-androsterone

17-alpha-estradiol

17-beta-estradiol

Estriol

Estrone

Cholesterol

3-beta-corprostanol

Number of detections

Hormone or animal sterol compounds

Detections at concentrations

 less than reporting level

Detections at concentrations

 greater than reporting level

EXPLANATION

Figure 17. Number of detections of hormone and animal sterol 

compounds in 270 streamwater samples collected from 27 stream 

sites near drinking-water intakes in Pennsylvania, 2007–09.
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 55

Figure 18. Concentration of sulfamethoxazole in streamwater 

samples collected from the Schuylkill River at Philadelphia, 

Pennsylvania, in relation to streamflow, 2007–09.

Figure 19. Detection frequency of commonly detected 

contaminants of emerging concern in each of four flow 

categories for streamwater samples taken from 27 stream sites 

located near drinking-water intakes in Pennsylvania, 2007–09. 

(Detections frequency is detections at concentrations greater 

than the reporting level per number of samples.)

0

20

40

60

80

100

120

140

160

445 519 730 1,050 1,190 1,610 1,810 2,860 2,910 4,330 5,260

Streamflow, in cubic feet per second

Sulfamethoxazole concentration,

in nanograms per liter

0

10

20

30

40

50

60

70

80

90

Acetaminophen

Caffeine

Carbamazepine

Sulfamethoxazole

Estrone

Detection frequency

(detections at concentrations 

greater than the reporting level)

Compound

Normal low flow

Low flow

EXPLANATION

Normal high flow

High flow

Low

(less than or

equal to 0.11)

Mid

(0.12–0.27)

High

(greater than or

equal to 0.28)

Total permitted discharges per drainage area

0

20

40

60

80

100

120

140

160

180

200

Number of detections at concentrations

greater than the reporting level

Pharmaceuticals (excluding antibiotics)

EXPLANATION

Antibiotics

Hormones and animal sterols

Figure 20. Number of detections of contaminants of emerging 

concern at concentrations greater than the reporting level 

by permitted discharges categories—low, mid, and high—

for 27 stream sites located near drinking-water intakes in 

Pennsylvania, 2007–09.
56 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

discharges per square mile of drainage area (high wasteload 

category) had more than double the number of detections of 

contaminants of emerging concern than the 18 sites that had 

less than 0.27 discharges per square mile of drainage area (mid 

and low wasteload categories). The four sites with the lowest number of discharges per unit of drainage area ratio had a 

total of 24 detections of contaminants of emerging concern, 

whereas the four sites with the highest discharges per unit of 

drainage area ratio had a total of 130 detections. For example, 

the Susquehanna River at Danville, Pa., (D7, 01540538), had 

1,847 permitted discharge sites upstream from the sampling 

site and a drainage area of 11,220 mi2 (or 0.16 discharges 

per mi2). The Schuylkill River at Philadelphia, Pa., (D4, 

01474010) had 1,275 permitted discharge sites upstream from 

the sampling site and a drainage area of 1,893 mi2 (or 0.67 

discharges per mi2). Despite having more permitted discharges 

in the watershed, the Susquehanna River site (D7, 01540538) 

had fewer detections of contaminants of emerging concern (24 

total detections) than the Schuylkill River site (D4, 01474010), 

which had 60 total detections. Dilution at the Susquehanna 

River site (50-percentile flow duration of 15,900 ft3/s) reduced 

the constituent concentrations more than at the Schuylkill 

River site (50-percentile flow duration of 1,670 ft3/s). The 

occurrence of more total detections at sites with greater than 

0.28 discharges per drainage area (high wasteload category) 

was consistent for all five of the most frequently detected compounds (fig. 21). Concentrations of detected compounds also 

were greater at the sites with greater than 0.28 discharges per 

drainage area. The average concentration of sulfamethoxazole 

for the 29 detections at sites in the low wasteload category was 

0.017 ng/L, whereas the average concentration was 0.015 ng/L 

for the 22 detections in the mid wasteload category and 

0.34 ng/L in the 66 detections in the high wasteload category. 

Acetaminophen, caffeine, carbamazepine, and estrone also 

were detected at the highest average concentrations in the 

samples collected from sites in the high wasteload category.

Land Use

Land use at the 27 sites near drinking-water intakes 

ranged from forest dominated watershed to agriculture or 

urban dominated watersheds. Forested land use at the 27 

sites ranged from about 97 percent at East Licking Creek 

(D11, 01566005) to about 27 percent at Jordan Creek (D2, 

01452040). Agricultural land use ranged from about 51 percent at Conodoguinet Creek (D13, 01570000) to 0 percent at 

East Licking Creek (D11, 01566005). Urban land use ranged 

from about 21 percent at Jordan Creek (D2, 01452040) to 

0 percent at George Run (D17, 03015554) (table 20; Homer 

and others, 2004).

The occurrence of contaminants of emerging concern 

is generally related to patterns of land use in the watershed. 

Watersheds that have high percentages of forested lands and 

low percentages of agricultural and urban lands generally have 

few point discharges or AFO discharges. Increases in agricultural and urban land use increases the likelihood of wastewater 

Figure 21. Detection frequency of selected contaminants of emerging concern by permitted discharge category—low, 

mid, and high—for 27 stream sites located near drinking-water intakes in Pennsylvania, 2007–09. (Detection frequency is 

detections at concentrations greater than the reporting level per number of samples.) Detection frequency (detections at concentrations greater than the reporting level)

Compound

Acetaminophen Caffeine Carbamazepine Sulfamethoxazole Estrone

0

10

20

30

40

50

60

70

80

90

100

Low (less than or equal to 0.11)

EXPLANATION

Mid (0.12–0.27)

High (greater than or equal to 0.28)

Number of permitted discharges per 

 square mile of drainage area
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 57

Table 20. Land-use statistics for 27 stream sites near drinking-water intakes in Pennsylvania, 2007–09.[Land use determined from Homer and others, 2004.]

U.S. Geological Survey 

station identification 

number

Map 

identification 

number 

(figure 1)

Site name Drainage area (square miles) Percent forest Percent agriculture Percent urban 

01440650 D1 Brodhead Creek near East Stroudsburg, Pa. 121 78.2 11.8 10.001452040 D2 Jordan Creek at mouth at Allentown, Pa. 82.3 27.2 50.6 21.201463500 D3 Delaware River at Trenton, N.J. 6,780 67.2 16.6 9.401474010 D4 Schuylkill River at Falls Bridge at Philadelphia, Pa. 1,893 39.8 38.2 19.001516750 D5 Corey Creek at Mansfield, Pa. 22 41.6 50.4 7.1015400021 D6 Fishing Creek near Bloomsburg, Pa. 379 60.2 32.1 5.501540500 D7 Susquehanna River at Danville, Pa 11,220 59.5 27.7 6.501553500 D8 West Branch Susquehanna River at Lewisburg, Pa. 6,847 79.0 12.0 4.801553990 D9 Susquehanna River above dam at Sunbury, Pa 18,300 66.3 22.3 5.901562000 D10 Raystown Branch Juniata River at Saxton, Pa. 756 65.8 26.3 7.501566005 D11 East Licking Creek above reservoir near Lewistown, Pa. 21.9 97.3 0.0 2.701567000 D12 Juniata River at Newport, Pa. 3,354 69.5 21.9 7.501570000 D13 Conodoguinet Creek near Hogestown, Pa. 470 35.0 50.8 12.701571505 D14 Yellow Breeches Creek at New Cumberland, Pa. 206 51.5 29.5 17.301573560 D15 Swatara Creek near Hershey, Pa. 483 43.1 41.2 14.101618800 D16 East Branch Anteitam Creek near South Mountain, Pa. 13.4 93.6 1.0 5.103015554 D17 George Run near Tidioute, Pa. 4.15 89.4 4.5 0.003031690 D18 Pitchpine Run at Reynoldsville, Pa. 1.82 58.6 28.6 10.503036500 D19 Allegheny River at Kittaning, Pa. 8,973 68.8 17.9 5.203049652 D20 Allegheny River at Hulton Bridge at Oakmont, Pa. 11,577 68.2 18.5 6.603071700 D21 Cheat River at Point Marion, Pa. 1,422 85.6 6.8 4.903075001 D22 Monongahela River at North Charleroi, Pa. 5,230 76.8 13.1 8.103082500 D23 Youghiogheny River at Connellsville, Pa. 1,326 70.5 19.8 7.003086000 D24 Ohio River at Sewickley, Pa. 19,500 68.9 17.1 9.103103500 D25 Shenango River at Sharpsville, Pa. 584 37.2 40.5 9.003106500 D26 Slippery Rock Creek at Wurtemburg, Pa. 398 58.0 28.0 9.403107500 D27 Beaver River at Beaver Falls, Pa. 3,106 41.4 32.4 17.8
58 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

and AFO discharges. To analyze the effect of the land use on 

contaminant detections, the 27 sites were divided into three 

categories of high, mid, and low percentages of forested land 

use, urban land use, and agricultural land use (9 sites per category). There were relatively few detections of contaminants of 

emerging concern at sites in watersheds with high percentages 

(greater than 69 percent) of forested land use and low percentages of agricultural (less than 17 percent) and urban (less than 

6.5 percent) land uses. The number of compounds detected 

increased as the percentage of forested land use decreased in 

the watershed (fig. 22).

George Run (D17, 03015554), East Licking Creek (D11, 

01566005) and East Branch Antietam Creek (D16, 01618800) 

were all in the high category for the percentage of forested 

land use and in the low category for the percentage of agricultural and urban land uses (table 20). East Licking Creek 

and East Branch Antietam Creek had no permitted discharges 

upstream from the sampling site, and George Run had one 

permitted discharge upstream from the sampling site. These 

relatively undisturbed sites had the fewest number of contaminants of emerging concern. Schuylkill River (D4, 01474010), 

Beaver Creek (D27, 03107500), and Swatara Creek (D15, 

01573560) were in the low category for percentages of forested land use and in the high category for the percentages of 

agricultural and urban land use (table 20). These three highly 

disturbed watersheds along with the Ohio River site (D24, 

03086000) had the greatest number of total detections of the 

27 sites sampled (fig. 23).

Seasonal Variability

The frequency of detection of contaminants of emerging 

concern throughout the year in streamwater may be the result 

of differences in concentrations at the source, the transport 

route that each compound takes to the stream, and variations 

in degradation within the stream. The rate of use for each 

contaminant may vary throughout the year. For example some 

pharmaceuticals may be used more in late fall through early 

spring during flu season, whereas others, such as hormones 

and those compounds used for chronic conditions like hypertension, would be expected to have consistent use and disposal 

rates. Also, pathways may be seasonally affected because sewage sludge and farm manure, for example, may be applied to 

fields in the spring and fall and uptake and runoff might vary 

during the growing season.

In general, the occurrence of contaminants of emerging 

concern did not vary consistently by season. Pharmaceutical (excluding antibiotics) and hormone detection frequencies were variable throughout the year. Antibiotic detection 

frequencies followed the seasonal flow patterns of detection 

frequencies, increasing during the summer and fall, which are 

seasons with low base flow (fig. 24).

Detection frequencies for the antibiotic sulfamethoxazole 

followed a pattern related to seasonal flow conditions. The 

lowest frequency of detection occurred during the high baseflow seasons (winter and spring), and the highest frequencies 

of detections occurred during the low base-flow seasons (summer and fall; fig. 25). The temporal variability in sulfamethoxazole occurrence does not indicate different seasonal use rates 

but rather a seasonal pattern related to dilution by streamflow. 

The detection frequency pattern of the analgesic acetaminophen was the opposite of the detection frequency pattern of 

sulfamethoxazole and the seasonal pattern. Acetaminophen 

was detected most frequently in winter (0.56 detections per 

sample); detection frequencies decreased through the spring 

and were lowest in the summer and fall (fig. 25). This pattern 

of detection may be the result of increased acetaminophen use 

in the winter, or degradation or sorption of the acetaminophen 

may be lower in cold water during the winter months when 

biological activity is decreased.

Figure 22. Number of detections of contaminants of emerging 

concern at concentrations greater than the reporting level in 

samples collected from 27 stream sites near drinking-water 

intakes by percentage of forested land use in Pennsylvania, 

2007–09.

25–58 59–69 70–100

Percentage of forested land use in watershed

upstream from sampling site

0

20

40

60

80

100

120

140

160

180

Number of detections at concentrations

greater than the reporting level

Pharmaceuticals (excluding antibiotics)

EXPLANATION

Antibiotics

Hormones and animal sterols
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 59

Hormones and animal sterols

EXPLANATION

Antibiotics

Pharmaceuticals (excluding antibiotics)

0

20

40

30

10

50

60

70

(D2) Jordan Creek

(D13) Conodoguinet Creek

(D25) Shenango River

(D4) Schuylkill River

(D27) Beaver Run

(D5) Corey Creek

(D15) Swatara Creek

(D14) Yellow Breeches Creek

(D26) Slippery Rock Creek

(D18) Pitchpine Run

(D7) Susquehanna River-Danville 

(D6) Fishing Creek

(D10) Raystown Branch-Juniata River

(D9) Susquehanna River-Sunbury

(D3) Delaware River

(D24) Ohio River

(D12) Juniata River-Newport

(D23) Youghiogheny River

(D22) Monongahela River

(D20) Allegheny River-Oakmont

(D19) Allegheny River-Kittanning

(D1) Brodhead Creek

(D11) East Licking Creek

(D8) West Bank Susquehanna River

(D21) Cheat Run

(D16) East Branch Antietam Creek

(D17) George Run

Sampling site

Number of detections at concentrations

greater than the reporting level

Increasing percentage of forested land use in basin

Winter Spring Summer Fall

0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

Detection frequency

(detections at concentrations

greater than the reporting level)

Season

Pharmaceuticals (excluding antibiotics)

EXPLANATION

Antibiotics

Hormones and animal sterols

Figure 23. Number of detections of contaminants of emerging concern at concentrations greater than the reporting level in streamwater 

samples collected from 27 stream sites near drinking-water intakes in Pennsylvania, 2007–09.

Figure 24. Detection frequency of contaminants of emerging 

concern, by season, in 297 streamwater samples collected from 27 

stream sites near drinking-water intakes in Pennsylvania, 2007–09.

Winter Spring Summer Fall 

Detection frequency of sulfamethoxazole

(detections at concentrations

greater than the reporting level)

0

10

20

30

40

50

60

70

Season

Sulfamethoxazole

EXPLANATION

Acetaminophen

Figure 25. Detection frequency of sulfamethoxazole and 

acetaminophen, by season, in 297 streamwater samples collected 

from 27 stream sites near drinking-water intakes in Pennsylvania, 

2007–09.
60 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Compounds in Streamwaters and Streambed 

Sediment at Fish-Health Sites

In 2007 and 2008, sampling was conducted to evaluate associations between contaminants of emerging concern 

and fish health. Three sites in the Delaware River Basin and 

eight sites in the Susquehanna River Basin were sampled 

in 2007, five sites in the Ohio River Basin were sampled in 

2008 (table 8). Sites were selected upstream and downstream 

from potential sources of contaminants of emerging concern 

in watersheds of various sizes. Eleven of the 16 sites were 

collected at sites previously established as part of the drinkingwater intake reconnaissance sampling. One-time-only samples 

of streamwater and streambed sediments were collected 

from the 16 sites when the streams were at base-flow levels. 

Pharmaceuticals, hormones, and OWCs were analyzed in 

streamwater samples, and antibiotics, hormones, and OWCs 

were analyzed in streambed-sediment samples. Concurrent 

with streamwater and streambed-sediment sampling, fish were 

collected for morphological, histopathological, chemical, and 

molecular-biological examinations. The goal of this work 

was to determine whether contaminants of emerging concern 

contribute to declines in fish health. Only chemical data from 

the one-time-only samples collected in 2007 or 2008 are 

discussed.

Compounds in Streamwater

Forty-eight of the 119 (40 percent) contaminants of 

emerging concern were detected in streamwater at the 16 

fish-health sites sampled in 2007 or 2008 (table 21, at end 

of report). Twenty-nine of the compounds were detected at 

least once at concentrations greater than the reporting levels and 19 were detected only at concentrations below the 

reporting levels. The compounds most frequently detected at 

concentrations greater than the reporting levels are caffeine 

(found in 81 percent of samples), the anticonvulsant drug 

carbamazepine (63 percent), the antibiotic sulfamethoxazole 

(63 percent), the natural estrogen estrone (56 percent), and the 

analgesic acetaminophen (31 percent). All other compounds 

were present at concentrations greater than the reporting 

levels in no more than 3 of the 16 samples collected. The most 

frequently detected compounds that are known or suspected 

endocrine disruptors were the pesticides 1,4-dichlorobenzene 

and metolachlor, the industrial compound benzophenone, 

and the flame retardants tri(2-chloroethyl)phosphate and 

tri(dichloroisopropyl)phosphate (Zaugg and others, 2002). 

The maximum concentration in streamwater samples of a 

known or suspected endocrine disruptor was 272 ng/L for the 

flame retardant tri(2-chloroethyl)phosphate. The concentrations of compounds detected in streamwater from the 16 fish 

health-sites ranged from 0.2 ng/L for the natural estrogen 

estriol to 604 ng/L for the flame retardant tri(2-butoxyethyl) 

phosphate. Hormones had the lowest detected concentrations 

(0.2–2.7 ng/L), and OWCs had the highest concentrations 

(2–604 ng/L). 

In general, the number of compounds detected at any particular site was low (fig. 26). The maximum number of detections at any site was eight, which occurred for Schuylkill River 

at Philadelphia (F1, 01474010), Brodhead Creek at Minisink 

Hills (F6, 01442500), and Swatara Creek at Harper Tavern 

(F7, 01573000, fig. 27). The Schuylkill River and Brodhead 

Creek sites are both affected by wastewater-effluent discharge. 

None of the contaminants of emerging concern were detected 

in the sample from the Brodhead Creek near East Stroudsburg 

(F5, 01440650) (fig. 27). This site is upstream from the towns 

of Stroudsburg and East Stroudsburg and in a largely forested 

watershed (78 percent forested). The concentration ranges for 

samples from the 16 fish-health sites were generally lower 

than those for samples collected downstream from wastewater-effluent discharges and were similar to those for samples 

collected near drinking-water intakes (table 22).

Compounds in Streambed Sediment

A single streambed-sediment sample was collected at 

each of the 16 fish-health sites (table 7) in 2007 or 2008 and 

analyzed for antibiotics, hormones, and OWCs. Thirty-six of 

the 98 (37 percent) contaminants of emerging concern were 

detected at the 16 fish-health sites sampled in 2007 or 2008 

(table 21). All of the 36 compounds were detected at least 

once at concentrations greater than their reporting level. The 

most frequently detected compounds in streambed-sediment 

samples were the OWCs phenanthrene and pyrene, which 

were detected in all 16 samples, and benzo[a]pyrene and fluoranthene, which were detected in 15 of 16 samples (table 21). 

Benzo[a]pyrene, para-cresol, and 17-beta-estradiol were the 

most frequently detected OWCs that are known or suspected 

endocrine disruptors (Zaugg and others, 2002). Benzo[a]

pyrene was detected at concentrations greater than the reporting level in 94 percent of streambed-sediment samples with 

a maximum concentration of 801 μg/kg, and para-cresol was 

detected at concentrations greater than the reporting level 

in 38 percent of streambed-sediment samples with a maximum concentration of 2,450 μg/kg. Four of the 27 antibiotic 

compounds and 7 of the 17 hormones and 2 animal sterols 

analyzed were detected. Ofloxacin was the most frequently 

detected antibiotic (50 percent), and estrone was the most frequently detected hormone (75 percent). The maximum number 

of detections in streambed-sediment samples of contaminants 

of emerging concern at concentrations greater than the reporting level at any one site was 25 for Swatara Creek near Hummelstown (F9, 01573583). Brodhead Creek at Minisink Hills 

(F6, 01442500) had the fewest (6) detections of contaminants 

of emerging concern (fig. 28).
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 61

0 40 80 MILES

0 40 80 KILOMETERS

EXPLANATION

75°

76° 79° 78° 77°

80°

42°

41°

40°

Base from U.S. Geological Survey digital data, 1980, 1:100,000

Albers Equal-Area Conic projection, NAD 83

F9

F7

F2

F4

F3

F1

F6

F5

F12

F13

F14

F16

F15

F11

F10

F8

De laware

Ri v er

S c huylkill Ri v er

Juniata River

West Branch

Susquehanna River

Ohio

River

Allegheny

River

East Branch Susquehanna River

S us qu e h a n n a

River

Yo ughiogeny River

Monongohela River

Wastewater compounds

0

1–2

3–6

Hormones

0

1–2

Antibiotics

0

1–2

3

Pharmaceuticals

0

1–2

3

Number of detections greater than the 

reporting level, by compound class, 

for fish-health sampling sites

Delaware River Basin

Ohio River Basin

Genesee River Basin

Lake Erie Basin

Susquehanna River Basin

Potomac River Basin

Chesapeake Bay Basin

Water features from U.S. Geological Survey National Hydrography

Dataset (NHD). Basin boundaries from U.S. Geological Survey Digital

Watershed Boundary Dataset coded by Hydrologic Unit Codes (HUC)

Figure 26. Location of fish-health sites sampled with the number of total detections greater than the reporting level, by compound 

class, in Pennsylvania, 2007 or 2008. 
62 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Figure 27. Number of contaminants of emerging concern detected at concentrations greater than the reporting level in 

streamwater samples collected at 16 fish-health sites in Pennsylvania, 2007 or 2008.

(F5) Brodhead Creek - East Stroudsburg

(F6) Brodhead Creek-Minisink Hills

(F1) Schuylkill River

(F1)Susquehanna River-Danville

(F4) Susquehanna River-Wolverton

(F10) Juniata River

(F2) Conodoguinet Creek

(F11) Yellow Breeches Creek

(F7) Swatara Creek-Harper Tavern

(F8) Swatara Creek-Hershey

(F9) Swatara Creek-Hummelstown

(F15) Allegheny River-Kittaning

(F15) Allegheny River-Oakmont

(F14) Monongahela River-North Charleroi

(F13) Monongahela River-Braddock

(F12) Ohio River

Sampling site

0

1

2

3

4

5

6

7

8

9

Number of contaminants of emerging concern

detected at concentrations greater than

the reporting level

Organic wastewater compounds 

EXPLANATION

Hormones and animal sterols 

Antibiotics 

Pharmaceuticals (excluding antibiotics)
Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters 63

Table 22. Detection frequencies of selected compounds in samples collected from sites downstream from 

wastewater-effluent-discharge sites, 2007–09; sites near drinking-water intakes, 2007–09; and fish-health sites, 

2007 and 2008, in Pennsylvania.

[ng/L, nanograms per liter]

Compound Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Percent 

detections 

at any 

concentration 

Concentration 

range 

(ng/L)

Sites located downstream from wastewater-effluent-discharge sites (2007–2009)

Carbamazepine 24 21 0 87 15–212

Diphenhydramine 24 11 3 58 3–85

Sulfamethoxazole 24 24 0 100 5–1,150

Trimethoprim 24 18 0 75 6–704

Estrone 24 12 0 50 0.6–25

Sites located near drinking-water intakes (2007–2009)

Carbamazepine 297 61 36 33 1–95

Diphenhydramine 297 0 20 7 1–6

Sulfamethoxazole 294 119 0 40 5–146

Trimethoprim 294 23 0 8 5–18

Estrone 270 48 3 19 0.3–3.1

Fish-health sites (2007 and 2008)

Carbamazepine 16 10 3 81 3–64

Diphenhydramine 16 0 0 0 0

Sulfamethoxazole 16 10 0 62 7–101

Trimethoprim 16 1 0 6 12

Estrone 16 9 1 62 0.3–2.72
64 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Figure 28. Number of contaminants of emerging concern detected at concentrations greater than the reporting level in streambedsediment samples from 16 fish-health sites sampled in Pennsylvania, 2007 or 2008.

0

5

10

15

20

25

30

(F5) Brodhead Creek-East Stroudsburg 

(F6) Brodhead Creek-Minisink Hills 

(F1) Schuylkill River 

(F1)Susquehanna River-Danville 

(F4) Susquehanna River-Wolverton 

(F10) Juniata River 

(F2) Conodoguinet Creek 

(F11) Yellow Breeches Creek 

(F7) Swatara Creek-Harper Tavern 

(F8) Swatara Creek-Hershey 

(F9) Swatara Creek-Hummelstown 

(F15) Allegheny Rriver-Kittaning 

(F15) Allegheny River-Oakmont 

(F14) Monongahela River-North Charleroi 

(F13) Monongahela River-Braddock 

(F12) Ohio River 

Sampling site

Number of contaminants of emerging concern

detected at concentrations greater than

the reporting level

Organic wastewater compounds 

EXPLANATION

Hormones and animal sterols 

Antibiotics 
Implications of Contaminants of Emerging Concern in Pennsylvania Waters 65

Implications of Contaminants of 

Emerging Concern in Pennsylvania 

Waters

Water-quality standards have not been established for the 

contaminants of emerging concern considered in this study. 

Therefore, it is difficult to quantitatively evaluate the effects of 

these compounds. Yet, a body of literature is growing that can 

help in understanding the likely implications of the presence 

of these compounds in streamwater and streambed sediment. 

In this section of the report, data collected for this study are 

evaluated in light of existing scientific literature.

Implications for Ecosystem Health

The contaminants of emerging concern detected in this 

study were measured at low levels with concentrations in 

nanograms per liter in streamwater. Even at low concentrations, the effects on aquatic organisms of constant exposure, 

long-term exposure, and exposure to a mix of chemicals are 

largely unknown (Daughton and Ternes, 1999; Jorgensen 

and Halling-Sorensen, 2000). Water-quality criteria for the 

protection of aquatic life have not been established for the 

compounds studied, so there are no benchmarks by which to 

judge the concentrations measured. But, these chemicals may 

pose a risk because they were developed to be stable and to 

trigger specific biological effects at low doses. Further, many 

of the contaminants of emerging concern in question are disposed of or discharged to the environment continuously, which 

results in lifetime exposure of organisms to some compounds 

(Daughton and Ternes, 1999; Monteiro and Boxall, 2010).

Further evidence of population effects on fish was 

found during a 7-year-long Canadian study (Kidd and others, 

2007) in which a lake was dosed with low levels (5 ng/L) of 

17-alpha-ethynylestradiol over a 3-year period. Male fathead minnows (Pimephales promelas) in the lake developed 

increased levels of vitellogenin messenger ribonucleic acid 

(RNA) and protein (associated with oocyte maturation in 

females) and early-stage eggs in their testes, whereas fish in 

two control lakes did not. Reproductive failure occurred in the 

dosed lake, and the fish population declined dramatically. The 

population remained healthy in the control lakes. The fathead 

minnow population in the dosed lake recovered once the 

17-alpha-ethynylestradiol dosing was terminated. “The results 

from this whole lake experiment demonstrate that continued 

inputs of natural and synthetic estrogens and estrogen mimics...could decrease the reproductive success and sustainability of fish populations” (Kidd and others, 2007). In the present 

study, the highest concentrations for most of the hormones 

were measured at sites downstream from wastewater-effluentdischarge sites. The hormone 17-alpha-ethynylestradiol was 

not found in any water samples and was detected only twice in 

the streambed-sediment samples at a maximum concentration 

of 1.7 μg/kg.

Thorpe and others (2003) determined in laboratory studies that plasma vitellogenin response can be induced in rainbow trout at 17-beta-estradiol concentrations as low as 5 ng/L. 

Vajda and others (2008) found several indicators of reproductive disruption in Boulder Creek, Colorado, downstream 

from a wastewater-effluent-discharge site. Concentrations of 

17-beta-estradiol at this site were about 2 ng/L. The highest 

concentrations of 17-beta-estradiol measured in the present 

study were 0.9 ng/L in a streamwater sample and 1.9 μg/kg in 

a streambed-sediment sample.

The body of evidence in the scientific literature is building that estrogenic compounds can act together to produce 

reproductive effects in fish (Thorpe and others, 2003; Brian 

and others, 2005; Kortenkamp, 2007). Some researchers 

(Brian and others, 2005) have demonstrated that the effects of 

several compounds in the estrogen family are additive. Others 

researchers have argued for expressing effects in terms of 

estradiol equivalents (Thorpe and others, 2006). Thus, concentrations of individual estrogen compounds may not be as 

revealing as the total concentration or the estradiol-equivalent 

concentration of the compounds present. The results from the 

present study indicate that concentrations of estrogen-related 

compounds are greatest at sites downstream from wastewater-effluent discharges; however detections of individual 

compounds were rare, and concentrations were below levels 

reported to cause physiological and reproductive issues in fish. 

In the Susquehanna River in Pennsylvania, populations of 

smallmouth bass (Micropterus dolomieu) have been declining during the past 5 years (2007–2011). Annual surveys of 

young-of-the-year smallmouth bass conducted by the Pennsylvania Fish and Boat Commission have documented that many 

of the young fish are in moribund condition and have bacterial 

infections (Chaplin and others, 2009). Conclusions on causative factors have not been reached, although contaminants 

of emerging concern have been suggested as one possible 

cause because they may act as immunosuppressors. Research 

in other rivers indicated that if the immune system of the fish 

is compromised, the fish may be infected by the ubiquitous 

bacteria that are ever-present in the stream (Ripley and others, 

2008; Robertson and others, 2009).

Another line of thinking regarding the decline of smallmouth bass populations in the Susquehanna River is that exposure to estrogenic compounds may disrupt endocrine functioning in the fish. The reconnaissance studies were not designed 

to investigate Susquehanna River smallmouth bass issues, but 

the limited data do not indicate the presence of estrogenic or 

endocrine disrupting compounds in higher concentrations at 

the sampling sites in the Susquehanna River Basin than at sites 

in the Delaware River Basin. However, water samples from 

the Susquehanna River Basin had consistently higher concentrations of estrogenic compounds than samples from the 

Ohio River Basin where no hormones were detected in water 

samples. The hypotheses for the decline in smallmouth bass 

populations in the Susquehanna River Basin are associated 

with little experimental evidence and, therefore, are likely to 

be adjusted as more information becomes available.
66 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Implications for Contaminants in Source Waters 

for Public Drinking-Water Supplies

The effectiveness of conventional drinking-water-treatment processes can vary widely within and among different 

classes of compounds. Studies of finished drinking-water 

supplies indicate that the removal of contaminants of emerging concern through the drinking-water-treatment process is 

incomplete. Pharmaceutical compounds, such as acetaminophen, caffeine, and carbamazepine, along with OWCs such 

as DEET, AHTN, and camphor, have been frequently found 

in finished drinking-water supplies and may be a source of 

human exposure (Stackelberg and others, 2007). Groundwater 

used for household drinking-water supply, which may be susceptible to contamination from on-lot sewage disposal, often 

receives no treatment or less treatment than surface water used 

as a source of drinking-water supply and, therefore, may also 

represent threats to public health. Drinking-water standards 

have not been established for these individual compounds 

or mixtures of these compounds; therefore, the potential 

health risk is not known. However, some studies indicate that 

there is a low risk to human health (Webb and others, 2003; 

Schwab and others, 2005). These findings are based on limited 

knowledge about the chronic effects of low-dose exposure to 

a mixture of compounds, and the findings do not rule out the 

possibility of negative effects on human health.

Although pharmaceutical compounds were detected in 

drinking water, exposure was very small in comparison to 

the amount that is voluntarily ingested or applied to the body. 

For humans who do not spend a lifetime submerged in water 

containing these trace compounds, concentrations are substantially below the levels currently associated with adverse health 

effects. For several compounds detected at trace concentrations, thousands of liters of water per day would need to be 

consumed to meet the effective daily intake dose for that 

compound (Snyder and others, 2009).

The highest concentration of acetaminophen measured 

in a streamwater sample in this study was 210 ng/L. A typical, voluntarily ingested, human dose of acetaminophen is 

500 mg, which is approximately 2.3 million times the highest 

concentration measured in this study. For carbamazepine, the 

highest concentration measured in this study was 276 ng/L in a 

streamwater sample collected downstream from a wastewatereffluent-discharge site. A typical daily dose of carbamazepine is 400 mg (U.S. Food and Drug Administration, 2005). 

So, the daily medical dose is about 1.5 million times the 

amount of carbamazepine in a liter of water measured in the 

present study.

Many conventional and advanced treatment processes 

reduce the concentration of some of these compounds in 

drinking water (Stackelberg and others, 2004; Stackelberg and 

others, 2007; Huerta-Fontela and others, 2008; Snyder and 

others, 2008; Benotti and others, 2009). Removal depends 

greatly on the structure and concentration of the compound. It 

has been shown that estrogenic compounds are degraded by 

chlorine, the principal chemical used in many water-treatment 

processes. Ozone is much more effective than chlorine and can 

remove a substantial amount of most of the target analytes. 

Other technologies proven effective in reducing estrogenicity 

include Granular Activated Carbon (GAC) and Nanofiltration/

Reverse Osmosis (NF/RO) (Snyder and others, 2008).

A potential human-health implication resulting from 

the abundance of antibiotics entering the environment is the 

emergence of antibiotic resistant bacteria (Fogarty and others, 

2007). Antibiotic resistance in the environment may result 

from the application to land of antibiotics in wastewatertreatment-plant biosolids or manure from livestock operations 

that intensely use antibiotics. Research has also shown that not 

all antibiotic resistance is caused by direct use of antibiotics; 

other variables may include heavy metals. Ecological interactions among soil microbes could also play a role (Wohl and 

Bowne, 2008).

Summary

Reconnaissance sampling for contaminants of emerging concern in Pennsylvania groundwater, streamwater, and 

streambed sediment was conducted during a 4-year period, 

2006 to 2009, by the U.S. Geological Survey (USGS), in 

cooperation with the Pennsylvania Department of Environmental Protection. The contaminants considered include 

pharmaceutical compounds, hormones, and organic wastewater compounds (OWCs). The multicomponent study evaluated 

contaminants of emerging concern in (1) groundwater from 

wells used to supply livestock, (2) streamwater upstream and 

downstream from animal-feeding operations, (3) streamwater 

upstream from and streamwater and streambed sediments 

downstream from municipal wastewater-effluent discharges, 

(4) streams within 5 miles of drinking-water intakes, and (5) 

streams where additional studies of fish health were being 

conducted. The wells and stream sites sampled upstream and 

downstream from animal-feeding operations and wastewatereffluent-discharge sites (first three components of the study) 

are located in south-central Pennsylvania, and the fish-heath 

and drinking-water stream sites are located statewide. The 

stream sites in south-central Pennsylvania, in general, were 

sampled under base-flow conditions three or more times for 

1 to 3 years, and statewide sites near drinking-water intakes 

were sampled quarterly for 3 years under a range of hydrologic conditions. Reconnaissance sampling was conducted 

from 2006 to 2009 with a limited number of sites and limited 

number of samples collected for the investigation of suspected 

sources of contaminants of emerging concern.

Detections of pharmaceutical compounds in water 

samples collected from wells in agricultural areas and streamwater samples upstream and downstream from animal-feeding 

operations were rare. Many of the compounds detected in 
Summary 67

these samples were not veterinary-use compounds, but humanuse compounds. This finding indicates that agricultural land 

use and animal-feeding operations were not a major source 

of pharmaceuticals.

A greater number of contaminants of emerging concern 

were detected at higher detection frequencies and at greater 

concentrations in samples from sites downstream from a 

municipal wastewater-effluent-discharge site than in samples 

from sites upstream from a municipal wastewater-effluentdischarge site. For the sites downstream from wastewatereffluent discharges, the most commonly detected contaminants 

in streamwater samples were carbamazepine (anticonvulsant), 

sulfamethoxazole (antibiotic), and tri(dichloroisopropyl)phosphate (flame retardant). The contaminants most commonly 

detected in streambed-sediment samples collected downstream 

from wastewater-effluent discharges were the antibiotics 

ofloxacin and trimethoprim, the natural estrogen estrone, and 

the polycyclic aromatic hydrocarbons benzo[a]pyrene, fluoranthene, phenanthrene, and pyrene. This finding confirms the 

finding of other researchers, which is that wastewater effluents 

constitute a source of these compounds.

Compounds with known or suspected endocrine disrupting potential were detected in both streamwater and 

streambed-sediment samples. Although samples collected 

downstream from a municipal wastewater-effluent-discharge 

site contained the most compounds detected and highest concentrations detected, samples without a wastewater-effluent 

discharge or sites distant from a wastewater-effluent-discharge 

site also had detectable concentrations of contaminants of 

emerging concern. Nonpoint sources of contamination may 

include on-lot septic systems, combined sewer overflows, and 

agricultural land use.

Results from this study identified Killinger Creek as the 

sampling site with the greatest number of contaminants of 

emerging concern detected and at the greatest concentrations. 

Streams like Killinger Creek, in which the wastewater-effluent 

discharge constitutes a large percentage of the total streamflow, are more likely to have a higher number of compounds 

detected at higher concentrations than streams without 

wastewater-effluent discharge because of a lack of dilution of 

the wastewater effluent.

Twenty-one of the 63 contaminants of emerging concern 

analyzed were detected one or more times at concentrations 

greater than their reporting levels in samples collected at 27 

stream sites near drinking-water intakes in Pennsylvania from 

2007 to 2009. The 10 most frequently detected compounds 

represent a wide variety of uses, but all were derived from 

human sources. None of the most commonly detected compounds are typically used in agricultural operations. This finding indicates that most of the contaminants of emerging concern detected near the 27 drinking-water intake sites entered 

the stream environment via municipal wastewater-treatment 

effluent or on-lot septic systems.

Measured concentrations of contaminants of emerging concern at the stream sites near drinking-water intakes 

generally were very low (generally less than 100 nanograms 

per liter). These compounds do not have established guidelines. Most of the compounds analyzed were never or rarely 

detected. Forty-two of the 63 compounds were never detected 

at concentrations greater than their reporting level, and only 

8 compounds were detected in more than 5 percent of the 

samples analyzed. The most commonly detected compounds 

were caffeine; the pharmaceutical compounds acetaminophen, carbamazepine, sulfamethoxazole, and trimethoprim; 

and the hormone estrone. All concentrations of pharmaceutical compounds measured at the sites near drinking-water 

intakes were within the range of concentrations reported in a 

national reconnaissance of sites near drinking-water sources. 

The compounds frequently detected near the 27 drinkingwater intake sites also were the same as those previously 

reported in another national reconnaissance.

The major factors that appear to affect the detection 

of contaminants of emerging concern at the 27 stream sites 

located near drinking-water intakes are related to wastewater 

sources, land use, and in-stream dilution. Samples from sites 

in watersheds with a large number of wastewater discharges 

and a high percentage of non-forested land had the greatest 

number of detections of pharmaceutical compounds and hormones. This finding supports the hypothesis that the largest 

inputs of contaminants of emerging concern are most likely 

from wastewater-effluent discharge. At individual sampling 

sites, the largest concentrations and greatest number of detections typically occurred at times of low streamflow when 

contaminants are most concentrated, although at least one 

compound, acetaminophen, did not follow this pattern.

The sites near drinking-water intakes that had greatest 

number of detections of contaminants of emerging concern 

were generally on mid-sized to large rivers with mixed urban 

and agricultural land use and a large number of discharges 

per unit of drainage area. Sites on the Schuylkill River, 

Beaver River, Ohio River, and Swatara Creek are associated 

with more than 20 detections of contaminants of emerging concern during 2007-09. Sites with the fewest numbers 

of detections of contaminants of emerging concern were 

generally on small- to mid-size streams in heavily forested 

watersheds with few point discharges. Brodhead Creek, East 

Licking Creek, East Branch Antietam Creek, George Run, 

and Pitchpine Run had less than three detections of contaminants per site.

Unlike fish and other aquatic organisms, humans are 

not in contact with water at all times. Human exposure to 

contaminants of emerging concern is likely to be primarily 

through ingestion. The drinking-water sources examined in 

the present study contained a mix of a few targeted contaminants of emerging concern. However, those contaminants 

were measured in low concentrations, many times lower than 

a typical human pharmaceutical dose. Acute effects on human 

health or aquatic biota arising from contaminants of emerging concern appear limited because of the low concentrations detected in the environment. Subtle, chronic effects on 

aquatic biota as a result of constant low-level environmental 

exposure are possible.
68 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Detection frequencies of contaminants of emerging concern for samples from 16 fish-health sites were generally low 

and were similar to those for samples from sites near drinkingwater intakes. Concentrations of the detected contaminants 

were below levels reported to cause physiological and reproductive issues in fish.

 Contaminants of emerging concern were found more 

frequently in the streambed-sediment samples than in streamwater samples. Antibiotic compounds were often found in 

both streamwater and streambed-sediment samples, but many 

organic wastewater compounds were found exclusively in the 

streambed-sediment samples.

Compounds with known or suspected endocrine disrupting potential were detected in streamwater and streambedsediment samples. Detection of these compounds was rare 

in samples collected at sites distant from wastewater-effluent 

discharge. Sites directly affected by a wastewater-effluent 

discharge were associated with greater detection frequencies and higher concentrations of compounds with known 

or suspected endocrine disrupting potential. Flame retardant 

and pesticide compounds were more likely to be detected 

in streamwater, and polycyclic aromatic hydrocarbons and 

detergent metabolites were more likely to be detected in 

streambed-sediment samples.

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74 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 18. Organic wastewater compounds detected in annual streamwater or streambed-sediment samples collected at Clark Creek and eight stream sites located downstream from municipal wastewater-effluent-discharge sites in Pennsylvania, 2007–09.—Continued [ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed,--, no data] Compound Streamwater Streambed sediment Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (ng/L) Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (μg/kg) Clark Creek (no effluent discharge upstream) Detergent metabolites para-Nonylphenol (total, NP)1 3 0 0 -- 3 1 0 828 Fragrances and flavors 3-Methyl-1H-indole (skatol) 3 0 0 -- 3 2 1 4–63 Acetophenone 3 0 0 -- 3 1 0 469 Camphor 3 1 1 28–42 3 2 1 19–55 Hexahydrohexamethyl-cyclopentabenzopyran (HHCB) 3 0 1 6 3 0 0 -- Indole 3 0 0 -- 3 3 0 59–427 Pesticides and degradates Carbazole 3 0 0 -- 3 1 0 28 d-Limonene 3 0 0 -- 3 3 0 32–166 N,N-diethyl-meta-toluamide (Deet) 3 1 2 12–159 3 0 0 -- Industrial compounds Anthraquinone 3 0 0 -- 3 3 0 17–29 Isophorone 3 0 0 -- 3 1 1 1–45 para-Cresol2 3 0 0 -- 3 1 2 73–254 Disinfectants and by-products Phenol 3 0 0 -- 3 2 0 204–1,050 Polycyclic aromatic hydrocarbon 1-Methylnaphthalene 3 0 0 -- 3 0 1 6 2,6-Dimethylnaphthalene 3 0 0 -- 3 1 2 4–28 Anthracene 3 0 0 -- 3 2 1 15–72 Benzo[a]pyrene1 3 0 0 -- 3 3 0 32–123 Fluoranthene 3 0 0 -- 3 3 0 94–422 Naphthalene 3 0 0 -- 3 0 2 12–16 Phenanthrene 3 0 0 -- 3 3 0 56–350 Pyrene 3 0 0 -- 3 3 0 86–367
Table 18 75

Table 18. Organic wastewater compounds detected in annual streamwater or streambed-sediment samples collected at Clark Creek and eight stream sites located downstream from municipal wastewater-effluent-discharge sites in Pennsylvania, 2007–09.—Continued[ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed,--, no data]

Compound 

Streamwater Streambed sediment

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(ng/L)

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(μg/kg)

Flame retardants and plasticizers

Triphenyl phosphate 3 0 1 11 3 0 0 --

Plant sterols

beta-Sitosterol 3 0 0 -- 3 3 0 1,660–3,030beta-Stigmastanol 3 0 0 -- 3 1 1 290–460

Eight sites downstream from wastewater-effluent-discharge sites

Detergent metabolites

4-tert-Octylphenol1 24 1 2 34–130 24 1 1 9–104Nonylphenol, diethoxy- (total, NPEO2)1 24 1 0 15,000 24 5 2 488–9,589para-Nonylphenol (total, NP)1 24 1 0 2,900 24 7 7 154–1363Octylphenol, diethoxy- (OPEO2)1 24 1 1 160–660 0 na na --

Fragrances and flavors

3-Methyl-1H-indole (skatol) 24 4 7 3–110 24 13 6 9–94Acetophenone 24 0 0 -- 24 11 4 15–377Acetyl-hexamethyl-tetrahydro-naphthalene (AHTN) 24 1 15 9–270 24 10 6 1–170Camphor 24 3 4 11–58 24 0 0 --Hexahydrohexamethyl-cyclopentabenzopyran (HHCB) 24 9 14 26–2,700 24 18 2 3–1,540Indole 24 0 2 4–6 24 22 2 12–1,340Menthol 24 1 0 135 0 na na --

Pesticides, herbicides, fungicides, and degradates

1,4-Dichlorobenzene2 24 7 6 3–63 24 0 11 6–22Carbaryl1 24 1 9 14–1,100 0 na na --Carbazole 24 0 1 18 24 19 4 5–236d-Limonene 24 0 0 -- 24 8 0 45–123Metolachlor2 24 3 10 6–371 24 0 0 --N,N-diethyl-meta-toluamide (Deet) 24 11 9 9–550 24 0 0 --Prometon 24 2 3 9–235 24 0 0 --
76 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 18. Organic wastewater compounds detected in annual streamwater or streambed-sediment samples collected at Clark Creek and eight stream sites located downstream from municipal wastewater-effluent-discharge sites in Pennsylvania, 2007–09.—Continued [ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed,--, no data] Compound Streamwater Streambed sediment Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (ng/L) Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (μg/kg) Industrial compounds 5-Methyl-1H-benzotriazole 24 3 0 83–512 0 na na -- Anthraquinone 24 2 3 27–132 24 19 1 18–610 Benzophenone2 24 9 6 24–350 24 2 0 52–228 Isophorone 24 0 7 5–28 24 4 11 4–66 Isopropylbenzene (cumene) 24 0 0 -- 24 0 3 24–71 Methyl salicylate 24 0 5 8–14 0 na na -- para-Cresol2 24 4 7 33–134 24 11 13 31–2,090 Tetrachloroethylene 24 0 4 10–32 0 na na -- Triethyl citrate (ethyl citrate) 24 6 15 18–550 0 na na -- Disinfectants and by-products Bromoform 24 0 7 2–34 0 na na -- Phenol 24 2 0 102–200 24 18 0 40–2,700 Triclosan2 24 3 3 28–210 24 7 0 54–1,560 Polycyclic aromatic hydrocarbon 1-Methylnaphthalene 24 0 1 14 24 16 5 5–323 2,6-Dimethylnaphthalene 24 0 1 12 24 17 5 9–245 2-Methylnaphthalene 24 1 1 19–22 24 15 6 8–420 Anthracene 24 0 0 -- 24 18 4 9–1,000 Benzo[a]pyrene1 24 0 0 -- 24 23 1 11–1,160 Fluoranthene 24 1 7 5–20 24 24 0 48–5,270 Naphthalene 24 1 1 17–42 24 19 1 11–401 Phenanthrene 24 0 6 4–18 24 24 0 21–2,110 Pyrene 24 0 5 4–7 24 24 0 44–5,090 Flame retardants and plasticizers Diethyl phthalate 0 na na -- 24 0 2 22–34 Tri(2-chloroethyl) phosphate2 24 15 6 23- 513 24 0 0 -- bis (2-ethylhexyl) phthalate 24 na na -- 24 10 1 132–1,460 Tri(dichloroisopropyl) phosphate2 24 20 3 11–1,250 24 0 1 12 Tributyl phosphate 24 3 13 8–168 24 0 0 --

Triphenyl phosphate 24 3 10 6–74 24 0 1 5Tri(2-butoxyethyl) phosphate 24 8 2 116–4,000 24 0 1 52
Table 18 77

Table 18. Organic wastewater compounds detected in annual streamwater or streambed-sediment samples collected at Clark Creek and eight stream sites located downstream from municipal wastewater-effluent-discharge sites in Pennsylvania, 2007–09.—Continued[ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed,--, no data]

Compound 

Streamwater Streambed sediment

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(ng/L)

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range 

(μg/kg)

Plant sterols

beta-Sitosterol 24 0 0 -- 24 23 1 287–6,010beta-Stigmastanol 24 1 0 4,780 24 14 3 105–1,470

1Known endocrine disruping potential.2Suspected endocrine disruping potential.
78 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 21. Contaminant of emerging concern compounds detected in streamwater and streambed-sediment samples collected from 16 fish-health sites in Pennsylvania, 2007–09.—Continued [ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed; --, no data] Compound Streamwater Streambed sediment Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (ng/L) Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (μg/kg) Pharmaceutical compounds Nonprescription pharmaceuticals Acetaminophen 16 5 0 20–85 na -- -- -- Caffeine1 16 13 0 15–121 na -- -- -- Para-xanthine1,2,3 16 2 0 30–35 na -- -- -- Cotinine1 16 1 3 8–19 na -- -- -- Prescription pharmaceuticals Carbamazepine 16 10 3 3–64 na -- -- -- Macrolide antibiotics Azithromycin 16 1 0 6 5 0 0 -- Tylosin 16 1 0 10 16 0 0 -- Quinoline antibiotics Ciprofloxacin 16 0 0 -- 16 3 0 6–44 Ofloxacin 16 2 0 7–8 16 8 0 1–47 Sulfonamide antibiotics Sulfamethoxazole 16 10 0 7–101 16 6 0 1–3 Tetracycline antibiotics and degradation products Trimethoprim 16 1 0 12 16 2 0 1–4 Hormones and animal sterols Natural androgen 4-Androstene-3,17-dione 16 1 2 0.4–0.6 16 0 0 -- cis-Androsterone 16 1 0 1.5 16 1 0 0.8 Natural estrogen 17-alpha-Estradiol 16 0 0 -- 16 2 0 0.1 17-beta-Estradiol4 16 0 1 0.4 16 8 0 0.1–0.6 Estriol 16 0 1 0.2 10 0 0 -- Estrone 16 9 1 0.3–2.7 16 12 0 0.4–2.9 Natural progestin Progesterone 16 0 0 -- 15 2 0 1.0–3.5 Animal sterols Cholesterol 16 0 0 -- 16 6 0 423–8,370

3-beta-Coprostanol 16 0 0 -- 16 3 2 94–16,600
Table 21 79

Table 21. Contaminant of emerging concern compounds detected in streamwater and streambed-sediment samples collected from 16 fish-health sites in Pennsylvania, 2007–09.—Continued[ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed; --, no data]

Compound 

Streamwater Streambed sediment

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range

(ng/L)

Number of 

analyses

Number of 

detections at 

concentrations 

greater than 

reporting level

Number of 

detections at 

concentrations 

less than 

reporting level

Concentration 

range

(μg/kg)

Organic wastewater compounds

Detergent metabolites

para-Nonylphenol (total, NP)4 16 0 0 -- 16 1 5 102–1,090

Fragrances and flavors

3-Methyl-1(H)-indole (skatol) 16 0 5 4–12 16 5 5 3–90Acetophenone 16 0 0 -- 16 1 3 22–312Acetyl-hexamethyl-tetrahydro-naphthalene (AHTN) 16 0 1 10 16 0 0 --Camphor 16 0 3 14–16 16 0 0 --Hexahydrohexamethyl-cyclopentabenzopyran (HHCB) 16 0 8 15–76 16 0 0 --Indole 16 0 1 7 16 12 3 28–394Isoquinoline 16 1 0 330 16 0 0 --

Pesticides and degradates

1,4-Dichlorobenzene5 16 3 1 9–38 16 1 4 7–76Carbaryl4 16 0 1 44 0 na na --Carbazole 16 0 1 11 16 8 6 7–141d-Limonene 16 0 0 -- 16 1 0 25Metolachlor5 16 1 12 11–46 16 0 0 --N,N-diethyl-meta-toluamide (Deet) 16 1 13 8–113 16 0 0 --Prometon 16 0 2 33–38 16 0 0 --

Industrial compounds

5-Methyl-1H-benzotriazole 16 1 0 120 0 na na --Anthraquinone 16 0 0 -- 16 12 4 8–470Benzophenone5 16 1 4 11–79 16 0 0 --Isophorone 16 0 4 6–17 16 1 3 13–47Isopropylbenzene (cumene) 16 0 0 -- 16 1 4 7–92Methyl salicylate 16 0 7 9–17 0 na na --para-Cresol5 16 1 0 97 16 6 10 7–2450Triethyl citrate (ethyl citrate) 16 0 3 5–19 0 na na --

Disinfectants and by-products

Bromoform 16 0 5 8–29 0 na na --

Phenol 16 1 0 162 16 8 5 15–459
80 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table 21. Contaminant of emerging concern compounds detected in streamwater and streambed-sediment samples collected from 16 fish-health sites in Pennsylvania, 2007–09.—Continued [ng/L, nanograms per liter; μg/kg, micrograms per kilogram; na, not analyzed; --, no data] Compound Streamwater Streambed sediment Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (ng/L) Number of analyses Number of detections at concentrations greater than reporting level Number of detections at concentrations less than reporting level Concentration range (μg/kg) Polycyclic aromatic hydrocarbons 1-Methylnaphthalene 16 1 0 28 16 10 2 14–1,410 2,6-Dimethylnaphthalene 16 0 1 19 16 10 2 11–598 2-Methylnaphthalene 16 1 0 59 16 9 5 16–1,820 Anthracene 16 0 1 2 16 11 5 8–372 Benzo[a]pyrene4 16 0 0 -- 16 15 1 24–801 Fluoranthene 16 0 3 6–10 16 15 1 2–2,350 Naphthalene 16 3 0 21–65 16 12 3 8–1,610 Phenanthrene 16 1 3 6–47 16 16 0 31–2,240 Pyrene 16 1 3 7–20 16 16 0 46–1,920 Flame retardant and plasticizers Diethyl phthalate 0 na na -- 16 2 1 41–480 Tri(2-chloroethyl)phosphate5 16 1 8 4–272 16 0 0 -- bis (2-ethylhexyl) phthalate 0 na na -- 16 1 1 55–204 Tri(dichlorisopropyl)phosphate5 16 3 7 12–85 16 0 0 -- Tributyl phosphate 16 0 2 8–45 16 0 0 -- Triphenyl phosphate 16 0 1 8 16 0 0 -- Tri(2-butoxyethyl)phosphate 16 3 3 117–604 16 0 0 -- Plant sterols beta-Sitosterol 16 0 0 -- 16 14 2 177–6,620 beta-Stigmastanol 16 0 0 -- 16 5 6 53–1,420

1Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.2Metabolite breakdown product.3Para-xanthine also known as 1,7 dimethylxanthine.4Known endocrine disruping potential.5Suspected endocrine disruping potential.
Appendixes A–C
82 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

[USGS, U.S. Geological Survey; NWQL, National Water Quality Laboratory; ORGL, Organic Research Geochemistry Laboroatory]

Emerging 

contaminant class Extraction method Analyticals method

Laboratory 

performing 

the analysis

Reference

Pharmaceutical 

compounds in water

Solid-phase extraction 

with a modified 

styrene-divinylbenzene 

stationary phase

High-performance liquid 

chromatography using positive 

electrospray ionization 

operated in selective-ion 

monitoring mode

USGS–NWQL Cahill and others, 2004

Furlong and others, 2008

Antibiotics in water On-line-solid phase extraction 

using HLB Prospekt 

cartridges

Liquid chromatography followed 

by multiple-reaction monitoring

USGS–OGRL Modified from Meyer 

and others, 2007

Antibiotics in 

streambed sediment

Sonication followed by 

accelerated solvent 

extraction using methanol

Liquid chromatography followed 

by tandem mass spectrometry

USGS–OGRL M. Meyer, U.S. 

Geological Survey, 

written commun., 

April 2009

Hormones and animal 

sterols in water

Multigrade glass-fiber filter 

over a C18 solid-phase 

extraction disk

Elution with dichloromethane/

methanol using solid-phase 

extraction and analyzed using 

gas chromatography/tandem 

quadropole mass spectrometry

USGS–NWQL W. Foreman, U.S. 

Geological Survey, 

written commun., 

October 2008

Hormones and 

animal sterols in 

streambed sediment

Pure solvent extraction in 

an accelerated solvent 

extraction cell using 

water:isopropyl alcohol 

followed by solidphase extraction

Elution with dichloromethane/

methanol using solid-phase 

extraction and analyzed using 

gas chromatography/tandem 

quadropole mass spectrometry

USGS–NWQL W. Foreman, U.S. 

Geological Survey, 

written commun., 

October 2008

Organic wastewater 

compounds in water 

Continuous liquidliquid extraction using 

methylene chloride

Capillary-column gas 

chromatography/

mass spectrometry

USGS–NWQL Zaugg and others, 2002

Organic wastewater 

compounds in 

streambed sediment

High pressure water/isopropyl 

alcohol extraction onto 

solid-phase extraction 

cartridges using polystyrenedivinylbenzene resin

Methylene chloride-diethyl 

ether elution through a 

Florisil/sodium sulfate 

solid-phase extraction 

cartridge and determination 

by gas chromatography/

mass spectrometry

USGS–NWQL Burkhart and others, 

2006

Appendix A. Summary of laboratory methods
Appendix B 83

Table B-1. Variability of pharmaceuticals (excluding antibiotics), hormones and animal sterols, and organic wastewater 

compounds using median relative percent differences for duplicate streamwater samples collected in Pennsylvania, 2006–09.

[Only compounds that had results greater than the reporting level in both samples were included. Analysis were conducted at the U.S. Geological Survey 

National Water Quality Laboratory in Denver, Colorado, unless otherwise indicated. RPD, relative percent difference]

Compound

Variability, using median relative percent difference of concentrations 

greater than the reporting level in duplicate sets

Number of duplicate pairs 

where both results 

were greater than 

the reporting level

Median RPD RPD or range 

of RPDs

Pharmaceuticals in water 

Nonprescription pharmaceuticals

Acetaminophen 2 10 3.4, 17

Caffeine 5 9 1.3–25

Ibuprofen1 1 28 28

Para-xanthine 1 16 16

Codeine 2 11 8.6, 13

Cotinine 2 17 12, 22

Diphenhydramine 2 30 22, 39

Prescription pharmaceuticals

Carbamazepine 4 3.2 2–21

Diltiazem 2 34 29, 40

Hormones and animal sterols in water 

17-alpha-Ethynylestradiol 1 11 11

3-beta-Coprostanol 1 2.8 2.8

4-Androstene-3,17-dione 1 6.7 6.7

Cholesterol 1 1.3 1.3

Bisphenol A 1 17 17

Estrone 2 20 14, 26

Organic wastewater compounds in water

Benzophenone 1 3.1 3.1

DEET 1 10 10

HHCB 1 0 0

Triethyl citrate 1 11 11

Tris(2- chloroethyl) phosphate 2 0.26 0, 0.53

Tris(dichlorisopropyl) phosphate 2 5.2 1.8, 8.5

4-Nonylphenol, all isomers 1 8 8

4-Nonylphenol diethoxylate 1 0 0

1

 Analyzed at the U.S. Geological Survey Organic Research Geochemistry Laboratory in Lawrence, Kansas.

Appendix B. Summary of duplicate sample results
84 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table B-2. Variability of antibiotics using median relative percent differences for duplicate streamwater samples collected in 

Pennsylvania, 2006–09.

[Analyses were conducted at the U.S. Geological Survey Organic Research Geochemistry Laboratory in Lawrence Kanas. RPD, relative percent difference]

Compound

Variability, using median relative percent difference of concentrations 

greater than the reporting level in duplicate sets

Number of duplicate pairs 

where both results 

were greater than 

the reporting level

Median RPD RPD or range 

of RPDs

Antibiotics in water

Macrolide antibiotics

Azithromycin 7 25 8.5–140

Erythromycin 4 8 0–12

Erythromycin-H2O (anhydro-erythromycin) 6 15 4.2–55

Tylosin 1 33 33

Quinoline antibiotics

Ciprofloxacin 3 13 12–30

Ofloxacin 7 17 0–88

Sulfonamide antibiotics

Sulfadiazine 1 30 30

Sulfamethoxazole 8 12 0.77–84

Other antibiotics

Trimethoprim 7 8.9 2.6–11
Appendix B 85

Table B-3. Variability of hormones and animal sterols, and organic wastewater compounds in streambed sediments using median 

relative percent differences for duplicate streambed-sediment samples collected in Pennsylvania, 2007–09.

[Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory in Denver, Colorado. RPD, relative percent difference]

Compound name

Variability, using median relative percent difference of concentrations 

greater than the reporting level in duplicate sets

Number of duplicate pairs 

where both results 

were greater than 

the reporting level

Median RPD RPD or range 

of RPDs

Hormones and animal streols in streambed sediment

Natural androgen

4-Androstene-3,17-dione 1 21 21

cis-androsterone 1 65 65

Natural estrogen

Equilenin 1 34 34

Estrone 3 33 5–45

17-beta-Estradiol 1 73 73

Synthetic estrogen

17-alpha-Ethynylestradiol 1 43 43

Animal sterols

Cholesterol 4 54 5.9–159

3-beta-Coprostanol 1 70 70

Organic wastewater compounds in streambed sediment

Detergent metabolites

Nonylphenol, diethoxy- (total, NPEO2) 1 7 7

Octylphenol, monoethoxy-(OPEO1) 1 10 10

Octylphenol, diethoxy- (OPEO2) 1 8 8

para-Nonylphenol (total, NP) 1 113 13

Fragrances and flavors

3-Methyl-1H-indole (skatol) 1 32 32

Acetophenone 1 1.3 1.3

Hexahydrohexamethylcyclopentabenzopyran (hhcb) 2 28 14, 43

Indole 2 27 14, 41

Pesticides and degradents

Carbazole 1 19 19

Industrial compounds

Anthraquinone 1 15 15

Benzophenone 1 14 14

Para-cresol (p-cresol) 2 72 7, 136

Disinfectants and by-products

Phenol 1 52 52

Triclosan 1 12 12

Polycyclic aromatic hydrocarbons

1-Methylnapthalene 1 38 38

2,6-Dimethylnaphthalene 2 11 5.9, 16

2-Methylnaphthalene 2 20 4.4, 36

Anthracene 1 0 0

Benzo[a]pyrene 2 45 74, 16

Fluoranthene 4 57 3.6–108

Naphthalene 2 21 5.3, 36

Phenanthrene 4 64 4.7–138

Pyrene 4 53 2.3–99

Plant sterol

Beta-Sitosterol 4 54 2–85
86 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table B-4. Variability of antibiotics using median relative percent differences for duplicate streambed-sediment samples collected 

in Pennsylvania, 2007–09.

[Analyses were conducted at the U.S. Geological Survey Organic Research Geochemistry Laboratory in Lawrence, Kansas. RPD, relative percent difference]

Compound name

Variability, using median relative percent difference of concentrations 

greater than the reporting level in duplicate sets

Number of duplicate pairs 

where both results 

were greater than 

the reporting level

Median RPD RPD or range 

of RPDs

Antibiotics in streambed sediments

Quinoline antibiotics

Ciprofloxacin 2 44 28, 60

Ofloxacin 3 7.2 6.7–17

Sulfonamide antibiotic

Sulfamethoxazole 2 20 0, 40

Other antibiotic

Trimethoprim 4 20 4.5–44

Macrolide antibiotic

Azithromycin 1 69 69

Tetracycline antibiotic

Tetracycline 1 0 0
Appendix C 87

Appendix C. Reagent-spiked and laboratory-spiked sampled results

Table C-1. Hormone compound recoveries in a reagent-spiked laboratory sample, 

November 11, 2007.

[Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) 

in Denver, Colorado; ng/L, nanograms per liter]

Compound

Spike 

concentration

(ng/L)

Spiked reagent 

sample concentration

(ng/L)

Percent 

recovery

Natural androgen

4-Androstene-3,17-dione 4.24 4.49 106.0

cis-Androsterone 1.56 1.65 106.0

11-Ketotestosterone 1.34 1.11 83.1

Natural estrogen

Equilenin 4.08 1.94 47.0

Equilin 6.80 4.98 73

17-alpha-Estradiol 2.01 1.38 69

17-beta-Estradiol 2.79 2.26 81

Estrone 4.20 4.79 114

Synthetic estrogen

17-alpha-Ethynylestradiol 2.12 1.39 65.80

Mestranol 1.61 1.74 108

Synthetic progestin

Norethindrone 3.35 2.60 77.8
88 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table C-2. Antibiotic and pharmaceutical compound recoveries in the laboratory-spiked environmental streamwater sample collected 

from Snitz Creek (A7, 01574050), Pennsylvania, on March 16, 2006.

[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey 

Organic Geochemistry Research Laboratory in Lawrence, Kansas. Less-than values were set equal to zero for calculations. <, less than; ng/L, nanograms 

per liter]

Compound

Laboratory-spiked 

environmental sample 

concentration

(ng/L)

Primary 

environmental sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

A B C (A – B) / C x 100

Macrolide antibiotics

Azithromycin 449 <5 200 220

Total erythromycin (parent and 1 degradate) 152 <8 200 76

Roxithromycin 110 <5 200 55

Tylosin 108 <5 200 54

Virginiamycin 315 <5 200 160

Quinoline antibiotics

Ciprofloxacin 308 <5 200 150

Enrofloxacin 183 <5 200 92

Lomefloxacin 295 <5 200 150

Norfloxacin 348 <5 200 170

Ofloxacin 328 <5 200 160

Sarafloxacin 237 <5 200 120

Sulfonamide antibiotics

Sulfachloropyridazine 121 <5 200 60

Sulfadiazine 181 <50 200 90

Sulfadimethoxine 141 <5 200 70

Sulfamethazine 145 <5 200 72

Sulfamethoxazole 139 <5 200 70

Sulfathiazole 115 <20 200 58

Tetracyclines, antibiotics, and degredation products

Total Chlorotetracycline 262 <10 200 130

Doxycycline 244 <10 200 120

Oxytetracycline 239 <10 200 120

Tetracycline 339 <10 200 170

Other antibiotics

Chloramphenicol 71 <50 200 36

Lincomycin 35 <5 200 18

Ormetoprim 109 <5 200 54

Trimethoprim 88 <5 200 44

Pharmacuetical

Ibuprofen 69 <50 200 34
Appendix C 89

Table C-3. Antibiotic and pharmaceutical compound recoveries in the laboratory-spiked environmental streamwater 

sample collected from Snitz Creek (A8, 01574055), Pennsylvania, on May 1, 2006.

[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. 

Geological Survey Organic Geochemistry Research Laboratory in Lawrence, Kansas. Less-than values were set equal to zero for 

calculations. <, less than; shading indicates detection in primary environmental sample; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental sample 

concentration

(ng/L)

Primary 

environmental sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

A B C (A – B) / C x 100

Macrolide antibiotics

Azithromycin 106 <5 200 53

Erythromycin (total) 140 <8 200 70

Roxithromycin 170 <5 200 85

Tylosin 365 27 200 170

Virginiamycin 150 <5 200 75

Quinoline antibiotics

Ciprofloxacin 219 <5 200 110

Enrofloxacin 288 <5 200 140

Lomefloxacin 166 <5 200 83

Norfloxacin 151 <5 200 76

Ofloxacin 186 <5 200 93

Sarafloxacin 189 <5 200 94

Sulfonamide antibiotics

Sulfachloropyridazine 269 <5 200 130

Sulfadiazine 266 <50 200 130

Sulfadimethoxine 244 <5 200 120

Sulfamethazine 334 <5 200 170

Sulfamethoxazole 229 <5 200 110

Sulfathiazole 277 <20 200 140

Tetracycline antibiotics and degradation products

Chlorotetracycline (total) 254 <10 200 130

Doxycycline 292 <10 200 150

Oxytetracycline 202 <10 200 100

Tetracycline 236 <10 200 120

Other antibiotics

Chloramphenicol 155 <50 200 78

Lincomycin 107 <5 200 54

Ormetoprim 334 <5 200 170

Trimethoprim 338 <5 200 170

Pharmaceutical

Ibuprofen 202 <50 200 100
90 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table C-4. Antibiotic and pharmaceutical compound recoveries in the laboratory-spiked environmental streamwater 

sample collected from Quittapahilla Creek (T9, 01573160), Pennsylvania, on July 12, 2007.

[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. 

Geological Survey Organic Geochemistry Research Laboratory in Lawrence, Kansas. Less-than values were set equal to zero for 

calculations. <, less than; shading indicates detection in primary environmental sample; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental sample

concentration

(ng/L)

Primary 

environmental sample

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recover

(percent)

A B C (A – B) / C x 100

Macrolide antibiotics

Azithromycin 167 <5 200 84

Erythromycin (total) 262 31 200 116

Roxithromycin 164 <5 200 82

Tylosin 237 <5 200 118

Virginiamycin 139 <5 200 70

Quinoline antibiotics

Ciprofloxacin 137 <5 200 68

Enrofloxacin 140 <5 200 70

Lomefloxacin 190 <5 200 95

Norfloxacin 155 <5 200 78

Ofloxacin 176 6 200 85

Sarafloxacin 192 <5 200 96

Sulfonamide antibiotics

Sulfachloropyridazine 193 <5 200 96

Sulfadiazine 224 <100 200 112

Sulfadimethoxine 218 <5 200 109

Sulfamethazine 186 <5 200 93

Sulfamethoxazole 214 13 200 100

Sulfathiazole 208 <20 200 104

Tetracycline antibiotics and degradation products

Chlorotetracycline (total) 474 <10 200 237

Doxycycline 200 <10 200 100

Oxytetracycline 162 <10 200 81

Tetracycline 178 <10 200 89

Other antibiotics

Chloramphenicol 138 <100 200 69

Lincomycin 154 <5 200 77

Ormetoprim 196 <5 200 98

Trimethoprim 223 25 200 99

Pharmaceutical

Ibuprofen 79 <50 200 40
Appendix C 91

Table C-5. Pharmaceutical compound recoveries in a laboratory-spiked environmental streamwater sample collected from Middle 

Spring Creek (T4, 01563158), Pennsylvania May 10, 2006.

[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey 

National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; 

shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental sample 

concentration

(ng/L)

Primary 

environmental sample

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

LRS, NWQL 

quality-control 

preparation set 

recovery

A B C (percent) (A – B) / C x 100

Nonprescription pharmaceuticals

Acetaminophen 269 e 8 257 102 71

Caffeine1 280 <15 257 109 98

Para-xanthine1,2 243 <21 257 95 80

Codeine 293 29 257 103 87

Cotinine1 251 e 4 257 96 101

Diphenhydramine 196 71 257 49 64

Prescription pharmaceuticals

Carbamazepine 263 108 257 61 90

Dehydronifedipine 299 <22 257 116 82

Diltiazem e 148 e 32 257 45 e 15

Salbutamol (albuterol) 264 e 5 257 101 77

Thiabendazole 97 <25 257 38 86

Warfarin 229 <19 257 89 31

1

Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.

2

Degradation product of caffeine. Also known as p-xanthine and 1,7 dimethylxanthine.
92 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09

Table C-6. Pharmaceutical compound recoveries in a laboratory-spiked environmental streamwater sample collected from 

Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.

[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey 

National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations; e, estimated value; <, less than; 

shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental 

sample 

concentration

(ng/L)

Primary 

environmental 

sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

LRS, NWQL 

quality-control 

preparation set 

recovery

(percent) A B C (A – B) / C x 100

Non-prescription pharmaceuticals

Acetaminophen 144 <24 269 53 e 130

Caffeine1 e 222 <15 269 82 131

Para-xanthine1,2 e 162 <21 269 60 e 163

Codeine 219 <22 269 81 84

Cotinine1 199 <28 269 74 92

Diphenhydramine 188 <23 269 70 59

Prescription pharmaceuticals

Carbamazepine 341 85 269 95 102

Dehydronifedipine 299 <22 269 111 99

Diltiazem e 170 <18 269 63 e 23

Salbutamol (albuterol) 246 <14 269 92 111

Thiabendazole 147 <25 269 55 96

Warfarin 288 <19 269 107 51

1

Compounds are not strictly pharmaceuticals but are included in the pharmaceutical analysis because they are associated with human use.

2

Degradation product of caffeine. Also known as p-xanthine and 1,7 dimethylxanthine.
Appendix C 93

Table C-7. Hormone and animal sterol compound recoveries in a laboratory-spiked environmental streamwater sample collected 

from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.

[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey 

National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations; e, estimated value; <, less than; 

shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental 

sample 

concentration

(ng/L)

Primary 

environmental 

sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

LRS, NWQL

quality-control 

preparation set 

recovery

(percent) A B C (A – B) / C x 100

Natural androgen

4-Androstene-3,17-dione 21.3 <1.8 22.4 95 84

cis-Androsterone 28.5 <0.8 22.4 127 93

Epitestosterone 19.8 <4 22.4 88 96

11-Ketotestosterone 11.9 <0.8 22.4 53 93

Dihydrotestosterone 20.6 <4 22.4 92 93

Testosterone 18.6 <0.8 22.4 83 78

Natural estrogen

Equilenin 15.4 <2 22.4 69 45

Equilin 18.3 <4 22.4 82 84

17-alpha-Estradiol 20.6 <0.8 22.4 92 82

17-beta-Estradiol 23.7 <0.8 22.4 106 109

Estriol 21.4 <0.8 22.4 96 88

Estrone 25.1 <1 22.4 112 98

Synthetic estrogen

Diethylstilbestrol 18.7 <0.8 22.4 84 76

17-alpha-Ethynylestradiol 19.1 <0.8 22.4 85 91

Mestranol 19.3 <0.8 22.4 86 87

Natural progestin

Progesterone 15.1 <4 22.4 68 88

Synthetic progestin

Norethindrone 9.4 <0.8 22.4 42 82

Animal sterols

Cholesterol e 2,122 258 2,240 83 208

3-beta-Coprostanol 1,880 87.3 2,240 80 194
94 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table C-8. Organic wastewater compound recoveries in a laboratory-spiked environmental streamwater sample collected from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.—Continued [Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter] Compound Laboratory-spiked environmental sample concentration (ng/L) Primary environmental sample concentration (ng/L) Calculated concentration in spike (ng/L) Laboratory-spiked recovery (percent) LRS, NWQL quality-control preparation set recovery (percent)

A

B C (A – 

B) / 

C x 100

Detergent metabolites

4-Cumylphenol 870 <140 830 105 1044-n-Octylphenol 690 <160 830 83 894-tert-Octylphenol 850 <100 830 102 51Nonylphenol, diethoxy- (total, NPEO2) e 16,000 <5,000 13,290 123 116para-Nonylphenol (total, NP) e 7,300 <1,800 6.65 109 113Octylphenol, diethoxy- (OPEO2) e 940 <1,000 580 162 108Octylphenol, monoethoxy-(OPEO1) e 1,600 <1,000 1,660 96 113

Fragrances and flavors

3-Methyl-1H-indole (skatol) 820 <80 830 98 93Acetophenone e 930 <100 830 112 116Acetyl-hexamethyl-tetrahydro-naphthalene (AHTN) 680 e 100 830 81 86Camphor 890 <100 830 108 100Hexahydrohexamethyl-cyclopentabenzopyran (HHCB) 950 e 100 830 103 103Indole 670 <140 830 81 87Isoborneol e 950 <60 830 115 98Isoquinoline 850 <400 830 103 94Menthol e1,400 <200 830 170 95

 Pesticides and degradates

1,4-Dichlorobenzene e 570 <80 830 68 61Bromacil 3,860 <400 3,320 116 111Carbaryl e 940 e 10 830 112 100Carbazole 840 <80 830 101 102Chlorpyrifos 780 <200 830 94 99d-Limonene e 370 <1,400 830 44 47Diazinon 890 <160 830 107 104Metalaxyl 970 <100 830 116 114Metolachlor 880 e 10 830 105 105N,N-diethyl-meta-toluamide (Deet) 930 e 300 830 108 106Prometon 940 <400 830 113 108
Appendix C 95

Table C-8. Organic wastewater compound recoveries in a laboratory-spiked environmental streamwater sample collected from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.—Continued[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental sample 

concentration

(ng/L)

Primary 

environmental sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

LRS, NWQL 

quality-control 

preparation set 

recovery

(percent) A B C (A – B) / C x 100

Industrial compounds 

3-tert-Butyl-4-hydroxyanisole (BHA) e 540 <600 830 65 565-Methyl-1H-benzotriazole e 6,100 <1,800 6650 91 94Anthraquinone 900 <0.16 830 109 110Benzophenone 910 e 200 830 107 105Isophorone 880 <140 830 106 99Isopropylbenzene (cumene) e 460 <100 830 56 49Methyl salicylate 920 e 100 830 110 106para-Cresol 900 <180 830 109 101Tetrachloroethylene e 250 <180 830 31 31Triethyl citrate (ethyl citrate) 960 e 50 830 109 105

Disinfectants and by-products

Bromoform e 660 <80 830 79 72Phenol 900 <400 830 108 100Triclosan 870 <200 830 104 105

Polycyclic aromatic hydrocarbon

1-Methylnaphthalene 700 <100 830 81 802,6-Dimethylnaphthalene 580 <200 830 70 722-Methylnaphthalene 630 <80 830 76 75Anthracene 760 <80 830 91 92Benzo[a]pyrene 690 <120 830 83 92Fluoranthene 790 <80 830 95 101Naphthalene 740 <100 830 89 83Phenanthrene 840 <80 830 101 99Pyrene 780 <80 830 94 100
96 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table C-8. Organic wastewater compound recoveries in a laboratory-spiked environmental streamwater sample collected from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.—Continued [Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter] Compound Laboratory-spiked environmental sample concentration (ng/L) Primary environmental sample concentration (ng/L) Calculated concentration in spike (ng/L) Laboratory-spiked recovery (percent) LRS, NWQL quality-control preparation set recovery (percent)

A

B C (A – 

B) / 

C x 100

Flame retardants and plasticizers

Tri(2-chloroethyl) phosphate 940 e 40 830 107 107Tri(dichloroisopropyl) phosphate 910 e 80 830 100 98Tributyl phosphate 960 <200 830 116 106Triphenyl phosphate 830 <160 830 100 100Tri(2-butoxyethyl) phosphate e 910 <500 830 110 96

Plant sterols

beta-Sitosterol e 3,400 <2,000 3,320 103 77beta-Stigmastanol e 3,300 <2,000 3,320 99 85
Appendix C 97

Table C-9. Organic wastewater compound recoveries in a laboratory-spiked environmental streambed-sediment sample collected from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.—Continued[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental sample 

concentration

(ng/L)

Primary 

environmental sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

LRS, NWQL

quality-control 

preparation 

set recovery

(percent) A B C (A – B) / C x 100

Detergent metabolites

4-Cumylphenol 140 <50.0 133.3 105 744-n-Octylphenol 111 <50.0 133.3 83 664-tert-Octylphenol 138 <50.0 133.3 104 81Nonylphenol, diethoxy- (total, NPEO2) e 2,970 <1,000 2,133 139 107para-Nonylphenol (total, NP) e 1,170 <750 1,067 110 96

Fragrances and flavors

3-Methyl-1H-indole (skatol) 52.5 e 9.52 133.3 32 75Acetophenone e 85.2 e 113 133.3 (-20.86) 68Acetyl-hexamethyl-tetrahydro-naphthalene (AHTN) 68.7 e 15.7 133.3 40 72Camphor 60.0 <50.0 133.3 45 75Hexahydrohexamethyl-cyclopentabenzopyran (HHCB) 103 e 44.5 133.3 44 90Indole e 22.8 131 133.3 (-81) 41Isoborneol e 134 <50.0 133.3 100 62Isoquinoline <80.0 <100 133.3 0 65Menthol e 142 <50.0 133.3 107 73

 Pesticides and degradates

1,4-Dichlorobenzene e 95.5 <50.0 133.3 72 62Atrazine e 45.6 <100 133.3 34 101Bromacil e 194 <500 533.3 36 67Carbazole 174 73.3 133.3 76 86Chlorpyrifos e 65.3 <50.0 133.3 49 59d-Limonene e 59.9 <50.0 133.3 45 63Diazinon 98.1 <50.0 133.3 74 73Metolachlor 112 <50.0 133.3 84 86N,N-diethyl-meta-toluamide (Deet) e 31.2 <100 133.3 23 60Prometon e 43.2 <50.0 133.3 32 75
98 Occurrence of Pharmaceuticals, Hormones and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09 Table C-9. Organic wastewater compound recoveries in a laboratory-spiked environmental streambed-sediment sample collected from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.—Continued [Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter] Compound Laboratory-spiked environmental sample concentration (ng/L) Primary environmental sample concentration (ng/L) Calculated concentration in spike (ng/L) Laboratory-spiked recovery (percent) LRS, NWQL quality-control preparation set recovery (percent)

A

B

C (A – 

B) / 

C x 100

Industrial compounds 

3-tert-Butyl-4-hydroxyanisole (BHA) e 72.4 <150 133.3 54 24Anthraquinone 249 167 133.3 62 44Benzophenone 124 <50.0 133.3 93 83Isophorone e 25.4 e 24.5 133.3 1 29Isopropylbenzene (cumene) e 43.3 <100 133.3 32 53para-Cresol 368 e 128 133.3 180 89

Disinfectants and by-products

Phenol e 361 e 460 133.3 (-74) 76Triclosan e 210 <50.0 133.3 157 86

Polycyclic aromatic hydrocarbon

1-Methylnaphthalene 214 92.3 133.3 92 792,6-Dimethylnaphthalene 212 70.2 133.3 106 842-Methylnaphthalene 274 141 133.3 100 80Anthracene 240 102 133.3 104 76Benzo[a]pyrene 524 259 133.3 199 96Fluoranthene 1,350 924 133.3 319 88Naphthalene 400 233 133.3 125 77Phenanthrene 621 475 133.3 109 90Pyrene 1140 743 133.3 297 87

Flame retardants and plasticizers

Diethyl phthalate 106 <100 133.3 80 64Tri(2-chloroethyl) phosphate e 41.1 <100 133.3 31 53bis (2-ethylhexyl) phthalate 358 <250 133.3 269 96Tri(dichloroisopropyl) phosphate e 93.5 <100 133.3 70 28Tributyl phosphate 123 <50.0 133.3 92 90Triphenyl phosphate e 88.3 <50.0 133.3 66 35Tri(2-butoxyethyl) phosphate e 163 <150 133.3 122 83
Appendix C 99

Table C-9. Organic wastewater compound recoveries in a laboratory-spiked environmental streambed-sediment sample collected from Quittaphilla Creek Creek (T9, 01573160), Pennsylvania, July 12, 2007.—Continued[Only compounds that were detected in associated un-spiked environmental samples are included. Analyses were conducted at the U.S. Geological Survey National Water Quality Laboratory (NWQL) in Denver, Colorado. Less-than values were set equal to zero for calculations. e, estimated value; <, less than; shading indicates detection in primary environmental sample; LRS, laboratory-reagent spike; ng/L, nanograms per liter]

Compound

Laboratory-spiked 

environmental sample 

concentration

(ng/L)

Primary 

environmental sample 

concentration

(ng/L)

Calculated 

concentration 

in spike

(ng/L)

Laboratory-spiked 

recovery

(percent)

LRS, NWQL

quality-control 

preparation 

set recovery

(percent) A B C (A – B) / C x 100

Plant sterols

beta-Sitosterol e 10,700 e 1,750 533.3 1,669 57beta-Stigmastanol e 2,020 e 454 533.3 293 42

For additional information:

Director

U.S. Geological Survey

215 Limekiln Road

New Cumberland, PA 17070

http://pa.water.usgs.gov/

Document prepared by the West Trenton Publishing Service Center
Reif and others—Occurrence of Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters, 2006–09—Scientific Investigations Report 2012–5106