U.S. Department of the Interior

U.S. Geological Survey

Open-File Report 2008–1231

Prepared in cooperation with the Virginia Department of Environmental Quality

Reconnaissance of Persistent and Emerging Contaminants 

in the Shenandoah and James River Basins, Virginia, During 

Spring of 2007
Cover. Photograph of South Fork Shenandoah River upstream of Luray Avenue. (Photograph provided by Virginia Department of 

Environmental Quality.)
Reconnaissance of Persistent and 

Emerging Contaminants in the Shenandoah 

and James River Basins, Virginia, During 

Spring of 2007

By David Alvarez, Walter Cranor, Stephanie Perkins, Vickie Schroeder, 

Stephen Werner, Edward Furlong, Donald Kain, and Robert Brent

Prepared in cooperation with the Virginia Department of Environmental Quality

Open-File Report 2008–1231

U.S. Department of the Interior

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

DIRK KEMPTHORNE, Secretary

U.S. Geological Survey

Mark D. Myers, Director

U.S. Geological Survey, Reston, Virginia: 2008

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Suggested citation:

Alvarez, D.A., Cranor, W.L., Perkins, S.D., Schroeder, V.L., Werner, S.L., Furlong, E.T., Kain, D., and Brent, R., 2008, 

Reconnaissance of persistent and emerging contaminants in the Shenandoah and James River Basins, Virginia, during 

Spring of 2007: U.S. Geological Survey Open-File Report 2008–1231, 19 p.
iii

Contents

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

Introduction.....................................................................................................................................................1

Methodology...................................................................................................................................................2

Passive Sampler Construction ...........................................................................................................2

Sampling Sites and Field Deployment...............................................................................................2

Sample Processing and Chemical Analysis.....................................................................................3

Polycyclic Aromatic Hydrocarbons (PAHs).............................................................................6

Organochlorine (OC) Pesticides and Polychlorinated Biphenyls (PCBs)...........................6

Agricultural Pesticides ...............................................................................................................6

Waste Indicator Chemicals........................................................................................................6

Pharmaceuticals..........................................................................................................................6

Hormones......................................................................................................................................6

Yeast Estrogen Screen (YES Assay) .........................................................................................6

Quality Control (QC) ..............................................................................................................................7

Estimation of Ambient Water Concentrations..................................................................................7

Results and Discussion.................................................................................................................................8

Chemical Analyses ...............................................................................................................................8

Polycyclic Aromatic Hydrocarbons (PAHs).............................................................................8

Organochlorine (OC) Pesticides and Polychlorinated Biphenyls (PCBs)...........................8

Agricultural Pesticides ...............................................................................................................8

Waste Indicator Chemicals......................................................................................................16

Pharmaceuticals........................................................................................................................16

Hormones....................................................................................................................................16

Yeast Estrogen Screen (YES Assay) ................................................................................................17

Acknowledgements.....................................................................................................................................17

References Cited..........................................................................................................................................17

Figure

1. Map of Virginia showing the sites where passive samplers were deployed.....................3

Tables

1. Location of the sites in the Shenandoah and James River Basins, Virginia where 

passive samplers were deployed during spring of 2007 ........................................................4

2. Chemicals selected for analysis in the passive samplers deployed in the Shenandoah 

and James River Basins during spring of 2007........................................................................5

3. Estimated water concentrations of select polycyclic aromatic hydrocarbons (PAHs) 

measured by semipermeable membrane devices (SPMDs) in the Shenandoah and 

James River Basins, Virginia, during spring of 2007...............................................................9
iv

4. Estimated water concentrations of select organochlorine pesticides and total polychlorinated biphenyls (PCBs) measured by semipermeable membrane devices 

(SPMDs) in the Shenandoah and James River Basins, Virginia, during spring 

of 2007...........................................................................................................................................10

5. Estimated water concentrations and identification of select agricultural herbicides and 

pesticides measured by polar organic chemical integrative samplers (POCIS) in the 

Shenandoah and James River Basins, Virginia, during spring of 2007 .............................11

6. Identification of select waste-indicator chemicals measured by polar organic chemical integrative samplers (POCIS) and semipermeable membrane devices (SPMDs) in 

the Shenandoah and James River Basins, Virginia, during spring of 2007.......................12

7. Identification of select pharmaceuticals measured by polar organic chemical integrative samplers (POCIS) in the Shenandoah and James River Basins, Virginia, during 

spring of 2007...............................................................................................................................13

8. Estimated water concentrations of select hormones measured by polar organic chemical integrative sampler (POCIS) in the Shenandoah and James River Basins, Virginia, 

during spring of 2007. .................................................................................................................14

9. Relative estrogenic potential of chemicals sampled by the polar organic chemical 

integrative samplers (POCIS) deployed in the Shenandoah and James River Basins, 

Virginia, during spring of 2007 as determined by the Yeast Estrogen Screen (YES) .......15
v

Conversion Factors

Multiply By To obtain

Volume

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

milliliter (mL) 0.03382 ounce, fluid (fl. oz)

microliter (μL) 3.382 x 10-5 ounce, fluid (fl. oz)

Length

centimeter (cm) 0.3937 inch (in.)

millimeter (mm) 0.03937 inch (in.)

micrometer (μm) 3.937 x 10-5 inch (in.)

Mass

gram (g) 0.03527 ounce (oz)

milligram (mg) 3.527 x 10-5 ounce (oz)

microgram (μg) 3.527 x 10-8 ounce (oz)

nanogram (ng) 3.527 x 10-11 ounce (oz)

Pressure

pound per square inch (lb/in2) 6.895 kilopascal (kPa)

Flow

cubic meters per second (m3/sec) 0.0283 cubic feet per second (ft3/sec)

Concentration

nanogram per liter (ng/L) = part per trillion (ppt; 1012)

picogram per liter (pg/L) = part per quadrillion (ppb; 1015)

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

°F=(1.8×°C)+32

Concentrations of chemical constituents in passive samplers are given in nanogram per sampler 

(ng/SPMD or ng/POCIS). Estimated water concentrations of chemical constituents are given in 

nanogram per liter (ng/L) or picogram per liter (pg/L).

Abstract 

Fish exhibiting external lesions, incidences of intersex, 

and death have recently been observed in the Shenandoah 

and James River Basins. These basins are characterized by 

widespread agriculture (intensive in some areas), several 

major industrial discharges, numerous sewage treatment plant 

discharges, and urban, transportation, and residential growth 

that has increased rapidly in recent years. Nine locations in 

the Shenandoah River Basin, Virginia, and two in the James 

River Basin, Virginia, were selected for study in an attempt 

to identify chemicals that may have contributed to the declining fish health. Two passive sampling devices, semipermeable membrane devices (SPMDs) and polar organic chemical 

integrative samplers (POCIS), were deployed during the 

spring and early summer of 2007 to measure select organic 

contaminants to which fish may have been exposed. This 

study determined that concentrations of persistent hydrophobic contaminants, such as polycyclic aromatic hydrocarbons 

(<17,000 picograms per liter), legacy pesticides (<510 picograms per liter), and polychlorinated biphenyls (<1,600 

picograms per liter) were generally low and indicative of a 

largely agricultural area. Chlorpyrifos, endosulfan, and lindane were the most commonly detected chlorinated pesticides. 

Atrazine, which was detected at concentrations much greater 

than other pesticides associated with agricultural use, ranged 

from <0.18 to 430 nanograms per liter during the deployment 

period. Few chemicals characteristic of wastewater treatment 

plant effluent or septic tank discharges were detected. The 

fragrance components, galaxolide, indole, and tonalide, were 

the predominant waste indicator chemicals detected. Caffeine, 

the caffeine metabolite 1,7-dimethylxanthine, the nicotine 

metabolite cotinine, and the prescription pharmaceuticals 

carbamazepine, venlafaxine, and trimethoprim were detected 

at several sites. Natural and synthetic hormones were detected 

at a few sites with 17α-ethynylestradiol concentrations estimated up to 8.1 nanograms per liter. Screening of the POCIS 

extracts for estrogenic chemicals by using the yeast estrogen 

screen revealed estrogenicity similar to levels reported for 

rural areas with minor effect from wastewater effluents. 

Introduction

Anthropogenic pollution is recognized as a global problem contributing to degradation of ecosystem quality, loss 

of numerous plant and animal species, and potential adverse 

effects on human health. Sources of these environmental 

stressors include point and nonpoint inputs of a broad spectrum of agricultural, industrial, and residential related chemicals. Increasingly, environmental scientists are acknowledging 

that in addition to contaminants of historic concern, emerging 

contaminants, including pharmaceuticals, new generation 

pesticides, personal care products, and natural and synthetic 

hormones, are potential sources of adverse effects. 

Fish kills have been increasing in regularity in the 

Shenandoah River and Potomac River Basins in Virginia 

(Blazer and others, 2007). These observations were made 

primarily during the spring, and mostly in smallmouth bass 

(Micropterus dolomieu), red-breast sunfish (Lepomis auritus), 

and various species of suckers. The cause(s) of these phenomena are unknown; however, the input of anthropogenic organic 

chemicals into the basin may be a factor. A sampling approach 

that provides a time weighted average assessment is critical in 

understanding the consequences of exposure to these diverse 

mixtures of chemicals. The SPMD and the POCIS are two 

commonly used passive sampling technologies that provide a 

Reconnaissance of Persistent and Emerging Contaminants 

in the Shenandoah and James River Basins, Virginia, 

During Spring of 2007

By David Alvarez1, Walter Cranor1, Stephanie Perkins1, Vickie Schroeder2, Stephen Werner3, Edward Furlong3, 

Donald Kain4, and Robert Brent4

1

 U.S. Geological Survey, Columbia Environmental Research Center, 

4200 New Haven Road, Columbia, Missouri 65201.

2

 Arctic Slope Regional Corporation (ASRC), 4200 New Haven Road, 

Columbia, Missouri 65201.

3

 U.S. Geological Survey, National Water Quality Laboratory, Denver, 

Colorado 80225.

4

 Virginia Department of Environmental Quality, Valley Regional Office, 

Harrisonburg, Virginia 22801.
2 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007

means of integratively sampling a wide array of bioavailable 

waterborne nonpolar and polar organic contaminants. 

Passive samplers are deployed for weeks to months, 

extract chemicals continuously from the water, and sample 

only dissolved chemicals, excluding chemicals associated with 

particulate, suspended sediment, or colloidal matter. During a 

typical one-month exposure, a passive sampler potentially can 

sample tens to hundreds of liters (L) of water, allowing for the 

detection of chemicals at low concentrations, or those that are 

present episodically. This time integration of contaminants is 

not readily achievable using standard sampling methods that 

collect discrete 1- or 2-L water samples. 

The SPMD consists of a layflat low-density polyethylene membrane tube containing a neutral lipid (triolein). The 

SPMD is designed to mimic key aspects of the bioconcentration process that results in elevated contaminant concentrations in organism tissues after exposure to trace hydrophobic 

organic contaminants in aquatic environments (Huckins and 

others, 2006). Sampling of compounds with moderate to high 

(greater than 3) octanol to water partition coefficients (Kows) is 

integrative, meaning extracted residues are constantly accumulated without significant losses back into the environment. As 

such, chemcial concentrations are reported as time weighted 

average values. Like SPMDs, the POCIS is designed to mimic 

key aspects of the bioconcentration process and exposure of 

an organism to hydrophilic organic contaminants. The POCIS 

consists of a solid phase sorbent or mixture of sorbents contained between two sheets of a microporous polyethersulfone 

membrane (Alvarez and others, 2004, 2007). Sampling of 

compounds with low to moderate (less than 3) Kows is integrative and chemical concentrations are reported as time weighted 

average values.

 The U.S. Geological Survey (USGS) in cooperation 

with the Virginia Department of Environmental Quality 

(VADEQ), conducted this study to identify anthropogenic 

organic chemicals and assess the estrogenicity of the complex 

mixtures of chemicals by using an in vitro assay. Passive 

samplers were used to detect potentially endocrine disrupting 

compounds and other chemicals at 10 locations on various 

rivers and streams within the Shenandoah and James River 

Basins. SPMDs and POCIS were deployed between March 

and May 2007 to address the potential effect of agricultural 

and municipal inputs into the basin during the months when 

fish kills have been most prevalent. A suite of anthropogenic 

organic contaminants was selected for study, including polycyclic aromatic hydrocarbons (PAHs), legacy organochlorine 

pesticides (OCs), polychlorinated biphenyls (total PCBs), 

select natural and synthetic hormones, current-use agricultural 

pesticides, pharmaceuticals, and waste indicator contaminants. 

Methodology

Passive Sampler Construction

The passive samplers used in this study were purchased 

from Environmental Sampling Technologies (EST Labs, St. 

Joseph, Missouri). For each site, six POCIS and three SPMDs 

were used. The POCIS used in this study contained Oasis 

HLB as the chemical sequestration medium enclosed between 

two polyethersulfone membranes. Oasis HLB is a functionalized polystyrene-divinylbenzene polymer with blended 

hydrophilic-lipophilic properties, commonly used in environmental monitoring studies for a range of organic contaminants 

(Kolpin and others, 2002; Cahill and others, 2004; Tran and 

others, 2007). Each POCIS unit had an effective sampling 

surface area of 41 square centimeters and a membrane surface 

area to sorbent mass ratio of 180 square centimeters per gram 

conforming to the specification of a standard POCIS (Alvarez 

and others, 2004). 

Each SPMD consisted of a 97 centimeter (cm) long 

(86 cm between the lipid-containment seals) by 2.5 cm wide 

layflat low-density polyethylene tubing containing 1.0 milliliter (mL) of purified triolein (Lebo and others, 2004). The 

membrane surface area to total SPMD volume ratio of SPMDs 

used in this study was 86 square centimeters per mL (cm2/mL), 

and triolein represented 20 percent of the mass of the SPMDs 

conforming to a “standard SPMD” as defined by Huckins and 

others (2006). Two of the three SPMDs used at each site were 

fortified with about 21 to 24 nanograms (ng) of each of the 

three PCB congeners 14, 29, and 50 which were selected as 

performance reference compounds (PRCs). A description of 

the PRC approach is given in the Estimation of Ambient Water 

Concentrations section. In addition to the field deployed 

SPMDs, two freshly prepared SPMDs were fortified with the 

PRC mixture and were used as a measure of the initial concentration for the PRC modeling.

Sampling Sites and Field Deployment

Eleven sites were selected by members of VADEQ. 

These sites included eight fish kill sites in the Shenandoah 

River Basin, one “control” site in the Shenandoah River Basin, 

and two “control” sites in the James River Basin. The control 

sites were streams with similar characteristics, including fish 

communities, which had not experienced fish kills in previous 

years. However, during the 2007 passive sampler sampling, 

a few dead fish were found at the Cedar Creek control site 

and a substantial fish kill was observed at the Cowpasture 
Methodology 3

River control site. At each site, custom protective deployment 

cages were used to contain three SPMDs and six POCIS in the 

water for periods of 42 to 49 days between March and May 

2007. The samplers from South Fork Shenandoah River at 

Front Royal, Virginia (USGS stream-gaging station #1631000) 

was found on the river bank, the apparent result of vandalism 

and could not be used. At the remaining 10 sites, the samplers were found intact and submerged in the water. During 

retrieval from the field, the SPMDs were removed from the 

deployment cages and placed in clean, metal cans and returned 

to the laboratory in coolers on ice where the SPMDs were 

inspected and stored at less than -20 degress Celsius (°C) until 

processing and analysis. The POCIS were removed from the 

deployment cages, wrapped in clean aluminum foil and sealed 

in zipper-type plastic bags. The plastic bags were stacked 

in a cooler with ice and returned to the laboratory where the 

POCIS were inspected and stored as described for the SPMDs.

Sample Processing and Chemical Analysis

Each SPMD and POCIS was extracted individually 

before designating extracts for specific processing and 

analysis procedures. SPMDs were processed and analyzed 

for PAHs, OC pesticides, total PCBs, and waste indicator chemicals (table 2). Agricultural pesticides, hormones, 

pharmaceuticals, and select waste indicator contaminants 

were measured in the POCIS (table 2). Some chemicals are 

measured in multiple analysis methods and, therefore, the 

generic chemical group name given for a method may not be 

fully descriptive of all chemicals analyzed in that method. For 

example, atrazine is included in both the agricultural pesticides method and the waste indicator chemicals method. Even 

though atrazine would not be considered a typical contaminant 

expected in treated wastewater effluent, atrazine has been 

found in watersheds receiving wastewater effluent in rural 

areas where atrazine is applied to fields (Alvarez and others, 

2008). POCIS extracts also were screened by using the yeast 

estrogen screen (YES assay) to test for the total estrogenicity of sampled chemicals (Alvarez and others, 2008a, 2008b; 

Rastall and others, 2004). 

The procedures used for preparing SPMD samples for 

analysis were similar to previously published approaches 

(Alvarez and others, 2008b; Petty and others, 2000). The 

target chemicals were recovered from the SPMDs by dialysis 

with hexane, filtration through 0.45 micrometer (μm) filter 

cartridges, isolation of the target chemicals by size exclusion 

chromatography (SEC), followed by class-specific cleanup 

and analysis. One of the PRC-SPMDs from each site was 

used for the analysis of PAHs; the other was used for OC pesticides and total PCB measurements. The remaining SPMD 

from each site, which did not contain PRCs, was analyzed for 

the waste indicator chemicals.

Published procedures were used for preparing the POCIS 

samples for analysis in this study (Alvarez and others, 2004, 

2007, 2008b). Chemicals of interest were recovered from the 

POCIS sorbent by using 40 mL of methanol, with the exception of two POCIS from each site that were designated for 

waste indicator chemical analysis. These two POCIS were 

extracted by using 25 mL of an 80:20 volume-to-volume 

ratio (v:v) dichloromethane:methyl-tert-butyl ether solution. 

The liquid volume of each extract was reduced by rotary 

Figure 1. Sites in Virginia where passive samplers were deployed. Locations identified by numbers on the map 

correspond to the following sampling sites: 1, Shenandoah mainstem at Berryville; 2, North Fork Shenandoah River–Cootes 

Store; 3, North Fork Shenandoah River–Linville Creek at Broadway WWTP; 4, North Fork Shenandoah River–Strasburg 

Route 55 bridge; 5, South Fork Shenandoah River–White House (Luray) at Route 211; 6, South Fork Shenandoah River–North 

River at Port Republic Bridge; 7, South Fork Shenandoah River–South River at Harriston; 8, Maury River; 9, Cowpasture 

River; 10, Cedar Creek Stalhlnaker Property; 11, South Fork Shenandoah River–Front Royal.

0 20 40 60 80 KILOMETERS

0 20 40 60 80 MILES

37°

38°

39°

83°

82°

81°

80°

79°

78°

76°

77°

Base from U.S. Geological Survey digital data, 1987, 1:2,000,000

Decimal degrees

Horizontal coordinate information is referenced to the North American

 Datum of 1983 (NAD 83)

North Fork

Shenandoah River

VIRGINIA

4 10

5

11

2

3

6

6

9 7

8

9

1

EXPLANATION

U.S. Geological Survey gaging

 station and map identifier

 used in tables

Sample site and map identifier

 used in tables

Z:\rol08_8335_0262alvarez
4 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007 Table 1. Location of the sites in the Shenandoah and James River Basins, Virginia, where passive samplers were deployed during spring of 2007. [USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality] Site name USGS station VADEQ number Sampling dates Deployment time (days) Average water tem- perature2 (degrees Celsius) Average streamflow2 (cubic meters per second) Shenandoah mainstem–Berryville NA1 1BSHN022.63 March 28, 2007 to May 9, 2007 42 314 3117 North Fork Shenandoah River–Cootes Store 1632000 1BNFS093.53 March 22, 2007 to May 9, 2007 48 12 13 North Fork Shenandoah River–Linville Creek at Broadway WWTP 1632082 1BLNV000.16 March 22, 2007 to May 9, 2007 48 14 1.2 North Fork Shenandoah River–Strasburg Route 55 Bridge 1634000 1BNFS010.34 March 22, 2007 to May 9, 2007 48 13 28 South Fork Shenandoah River–White House (Luray) at Route 211 1629500 1BSSF054.20 March 23, 2007 to May 9, 2007 47 14 66 South Fork Shenandoah River–North River at Port Republic Bridge 1622000 1BNTH000.18 March 22, 2007 to May 10, 2007 49 12 20 South Fork Shenandoah River–South River at Harriston 1627500 1BSTH007.80 March 22, 2007 to May 9, 2007 48 13 10 Control Site–Maury River 2024000 2-MRY020.16 March 23, 2007 to May 9, 2007 47 14 36 Control Site–Cowpasture River NA 2-CWP025.30 March 23, 2007 to May 9, 2007 47 413 433 Control Site–Cedar Creek Stalhlnaker Property 1635090 1BCDR001.65 March 22, 2007 to May 9, 2007 48 12 7.3 South Fork Shenandoah River–Front Royal 1631000 1BSSF003.50 -----5 ----- ----- -----

1NA, not applicable. There was no USGS streamflow-gaging station near this location.2Average water temperature and streamflow were determined from daily measurements taken by the USGS streamflow-gaging station.3Average water temperature and streamflow values were estimated by summing the values from gages on nearby tributaries and averaging that value with measured values from an upstream gage.4Average water temperature and streamflow value was estimated from measurements from a streamflow-gaging station (02016000) about 37 kilometers downstream of the sampling site.5-----, Protective deployment cages were found out of the water; therefore, these samplers were not usable.
Methodology 

5

Table 2. Chemicals selected for analysis in passive samplers deployed in the Shenandoah and James River Basins, Virginia, during spring of 2007.

Polycyclic aromatic 

hydrocarbons1

Organochlorine pesticides/

PCBs1

Agricultural 

pesticides2 Waste indicator chemicals1, 2 Pharmaceuticals2 Hormones2

Naphthalene Trifluralin EPTC Tetrachloroethylene Phenanthrene 1,7-dimethylxanthine 17β-EstradiolAcenaphthylene Hexachlorobenzene (HCB) Desisopropylatrazine Bromoform Anthracene Acetaminophen 17α-EthynylestradiolAcenaphthene Pentachloroanisole (PCA) Desethylatrazine Isopropylbenzene (cumene) Diazinon Albuterol EstroneFluorene Tefluthrin Trifluralin Phenol Musk Ambrette Azithromycin EstriolPhenanthrene alpha-Benzenehexachloride (a-BHC) Atraton 1,4-Dichlorobenzene Carbazole CaffeineAnthracene Diazinon Simazine d-Limonene Caffeine CarbamazepineFluoranthene Lindane Prometon Acetophenone Traseolide (ATII) CimetidinePyrene beta-Benzenehexachloride (b-BHC) Dimethoate para-Cresol Galaxolide (HHCB) CodeineBenz[a]anthracene Heptachlor Atrazine Isophorone Tonalide (AHTN) CotinineChrysene delta-Benzenehexachloride (d-BHC) Propazine Camphor Musk Xylene DehydronifedipineBenzo[b]fluoranthene Dacthal Terbuthylazine Menthol Carbaryl DiltiazemBenzo[k]fluoranthene Chlorpyrifos Fonofos Naphthalene Metalaxyl DiphenhydramineBenzo[a]pyrene Oxychlordane Cyromazine Methyl salicylate Bromacil ErythromycinIndeno[1,2,3-c,d]pyrene Heptachlor Epoxide Diazinon Dichlorvos Anthraquinone MiconazoleDibenz[a,h]anthracene trans-Chlordane Metribuzin Isoquinoline Musk Ketone RanitidineBenzo[g,h,i]perylene trans-Nonachlor Acetochlor Indole Chlorpyrifos SulfamethoxazoleBenzo[b]thiophene o,p'-DDE Methyl Parathion 2-Methyl naphthalene Fluoranthene Thiabendazole2-methylnaphthalene cis-Chlordane Simetryn 1-Methyl naphthalene Triclosan Trimethoprim1-methylnaphthalene Endosulfan Alachlor 2,6-Dimethylnaphthalene Pyrene WarfarinBiphenyl p,p'-DDE Ametryn Cashmeran (DPMI) Bisphenol A Bupropion1-ethylnaphthalene Dieldrin Prometryn N,N-diethyltoluamide (DEET) Tri(dichloroisopropyl) phosphate Citalopram1,2-dimethylnaphthalene o,p'-DDD Carbaryl Diethyl phthalate Tri(butoxyethyl) phosphate Duloxetine4-methylbiphenyl Endrin Terbutryn p-tert-Octylphenol Triphenyl phosphate Fluoxetine2,3,5-trimethylnaphthalene cis-Nonachlor Malathion Benzophenone Diethylhexylphthalate (DEHP) Fluvoxamine1-methylfluorene o,p'-DDT Metolachlor Tributyl phosphate Benzo[a]pyrene NorfluoxetineDibenzothiophene p,p'-DDD Chlorpyrifos Ethyl citrate Cholesterol Norsertraline2-methylphenanthrene Endosulfan-II Dacthal Cotinine Paroxetine9-methylanthracene p,p'-DDT Pendimethalin Celestolide (ADBI) Paroxetine Metabolite3,6-dimethylphenanthrene Endosulfan Sulfate Fipronil Prometon Sertraline2-methylfluoranthene p,p'-Methoxychlor Ethopabate Atrazine VenlafaxineBenzo[b]naphtho[2,1-d]thiophene Mirex Endosulfan I Phantolide (AHMI)Benzo[e]pyrene cis-Permethrin Tetrachlorvinphos 4-OctylphenolPerylene trans-Permethrin Endosulfan II Tri(2-chloroethyl) phosphate3-methylcholanthrene Total PCBs cis-Permethrin N-butyl benzenesulfonamide

trans-Permethrin Pentachlorophenol

1Chemicals under this general chemical classification were measured in semipermeable membrane device (SPMD) extracts.2Chemicals under this general chemical classification were measured in polar organic chemical integrative sampler (POCIS) extracts.
6 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007

evaporation and filtered through 0.45 micrometer (μm) filter 

cartridges. From each site, the extracts from the two waste 

indicator POCIS were composited into a 2-POCIS equivalent 

sample, thereby, increasing the amount of chemical in each 

sample to aid in detection. The remaining four POCIS extracts 

from each deployment canister were kept as individual 

samples designated for processing for agricultural pesticides, 

hormones, pharmaceuticals, and the YES assay.

Between one and four of the original six POCIS deployed 

at each site were received at the laboratory damaged and could 

not be used. In these cases, the extracts from the remaining 

intact POCIS were split to best accommodate the needs of 

the planned chemical analyses. This practice may have had 

the unfortunate result that some chemicals that may have 

been in the extract at a concentration near the method detection limit may not have been detected. None of the SPMDs 

were damaged.

Polycyclic Aromatic Hydrocarbons (PAHs)

Following SEC, samples designated for PAHs were 

processed by using a tri-adsorbent column consisting of phosphoric acid silica gel, potassium hydroxide impregnated silica 

gel, and silica gel (Petty and others, 2000). The gas chromatographic (GC) analyses for selected PAHs were conducted by 

using a GC system with a mass selective detector (GC/MSD) 

as described by Alvarez and others (2008b).

Organochlorine (OC) Pesticides and 

Polychlorinated Biphenyls (PCBs)

The OC/PCB SPMD samples were further enriched 

after SEC by using a Florisil column followed by fractionation on silica gel (Petty and others, 2000). The first silica 

gel fraction (SG1) contained greater than 95 percent of the 

total PCBs, hexachlorobenzene, heptachlor, mirex and 40 to 

80 percent of the p,p’-DDE when present in the extracts. The 

second fraction (SG2) contained the remaining 28 target OC 

pesticides and less than 5 percent of the total PCBs (largely, 

mono- and dichlorobiphenyl congeners). SPMD samples were 

analyzed for PCBs and OCs by using a GC equipped with an 

electron capture detector (ECD). Instrumental conditions for 

the OC/PCB analyses have been previously reported (Alvarez 

and others, 2008b).

Agricultural Pesticides

Details for the processing and analysis of POCIS for 

agricultural pesticides have been reported previously (Alvarez and others, 2008b). The extracts were fractionated using 

SEC, followed by sample cleanup and enrichment by Florisil 

adsorption chromatography. Analysis was performed using a 

GC/MSD as described by Alvarez and others (2008b).

Waste Indicator Chemicals

Analysis of waste indicator chemicals was initially 

performed on raw SPMD and POCIS extracts because of 

the difficulty in adequately “cleaning up” a sample while 

maintaining the integrity of such a diverse set of chemicals. 

Because of matrix specific interferences, such as residual lipid, 

the analysis of the SPMDs resulted in inconclusive data that 

required additional processing of the SPMD samples by using 

SEC prior to reanalysis. Analyses were performed on the 

GC/MSD system previously described by Alvarez and others 

(2008b). Identification of the targeted chemicals was performed by using full-scan mass spectrometry, and quantification was performed by selecting ions unique to each chemical.

Pharmaceuticals

Extracts for pharmaceutical analysis were solvent 

exchanged into acetonitrile and sealed in amber glass ampules 

before being shipped to the USGS National Water Quality 

Laboratory in Denver, Colorado, for analysis by using liquid 

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

Two analyses of the POCIS extracts were performed: one for 

a suite of commonly used prescription and over-the-counter 

pharmaceuticals, and a second for current use antidepressants. 

Instrumental parameters for these analyses have been previously described (Alvarez and others, 2008a; Cahill and others, 

2004; Schultz and Furlong, 2008).

Hormones

Four common hormones were selected in this study. 

These hormones included the synthetic hormone 17αethynylestradiol used in oral contraceptives, the natural hormone 17β-estradiol, and two metabolites, estrone and estriol. 

Extracts selected for hormone analysis required derivatization 

of the hormones to facilitate analysis by using a GC/MSD. 

Derivatization of extracts, quality control (QC) samples, and 

calibration standards for GC/MSD analysis were performed as 

described by Alvarez and others (2008a). 

Yeast Estrogen Screen (YES Assay)

The YES assay uses recombinant yeast cells transfected 

with the human estrogen receptor. Upon binding these cells 

to an estrogen or estrogen-mimic, a cascade of biochemical reactions results in a color change that can be measured 

spectrophotometrically (Routledge and Sumpter, 1996; Rastall 

and others, 2004). SPMDs and POCIS extracts from each 

site were screened for total estrogenicity in conjunction with 

a series of negative (solvent) and positive (17β-estradiol) 

controls (Alvarez and others, 2008b; Rastall and others, 2004). 

Estradiol equivalent factors (EEQ) for the samples were 

determined to provide a relative measure of estrogenicity. The 

EEQ is an estimate of the amount of 17β-estradiol, a natural 
Methodology 7

hormone, that would be required to give a response equivalent to that of the complex mixture of chemicals sampled at 

each site.

Quality Control (QC)

A rigorous QC plan was employed to ensure the reliability of the data obtained. The QC samples for the SPMDs 

and POCIS consisted of laboratory controls such as reagent 

blanks, matrix blanks, surrogate recovery, and fortified matrix 

recovery checks were included in the processing of the study 

samples. Instrument verification checks, reference standards, 

and positive and negative controls for the YES assay were 

used. Detailed discussions on the benefits of each type of control sample have been reported by Alvarez and others (2007) 

and Huckins and others (2006).

Radiolabeled surrogates of model compounds were used 

to allow for a rapid determination of results. Proper operation of the SEC system was verified by the recovery of 14C 

phenanthrene (a common PAH) solvent spikes that averaged 

96 percent with 2.0 percent relative standard deviation (n=5). 

A freshly prepared SPMD was fortified with 14C phenanthrene 

and processed concurrently with the remainder of the study 

SPMDs. The measured recovery of the 14C phenanthrene of 

92 percent following dialysis and SEC indicated acceptable 

performance of the method. Select POCIS were spiked with 

3

H 17α-ethynylestradiol (a widely used synthetic hormone) 

and 14C diazinon (a common organophosphate insecticide) 

resulting in mean recoveries of 98 percent (1.4 percent relative 

standard deviation, n=2) and 86 percent (3.4 percent relative 

standard deviation, n=5), respectively. 

No matrix (fabrication and field) blanks for the passive 

samplers supplied by the commercial vendor were included 

with the deployed samplers for processing and analysis. The 

lack of these blanks makes it difficult to determine whether 

part or all of the measured chemicals in the deployed samplers 

were sampled from the water or because of airborne contamination or from handling of the samplers during construction, deployment, retrieval, and shipping. Laboratory matrix 

(SPMD and POCIS) blanks were created immediately prior 

to the initiation of each processing set and were processed 

concurrently with the field deployed samplers. Overall, 

the blanks indicated no sample contamination related to the 

processing and handling of the samplers in the laboratory. On 

the basis of past studies, field blanks, if used, likely would not 

have shown a substantial background contamination (Alvarez 

and others, 2008a; 2008b; Petty and others, 2000).

Method detection (MDL) and method quantification 

(MQL) limits were estimated from low-level calibration 

standards as determined by the signal-to-noise ratio of the 

response from the instrumental analysis (Keith, 1991). The 

MDLs were determined as the mean plus three standard deviations of the response of a coincident peak during instrumental 

analysis. The MQLs were determined as the greater of either 

the coincident peak mean plus 10 standard deviations, or the 

concentration of the lowest-level calibration standard. In 

cases of no coincident peak, the MQL was set at the lowestlevel calibration standard and the MDL was estimated to be 

20 percent of the MQL. For reporting purposes, the MDLs 

and MQLs for each sample set were determined as ambient 

water concentrations on the basis of the average PRC data 

across the sites for each sampling period. When sampling 

rate information was not available, the MDLs and MQLs were 

expressed as the mass of chemical sequestered by a single 

sampler (ng/POCIS or ng/SPMD).

Estimation of Ambient Water Concentrations

SPMD and POCIS uptake kinetics (sampling rates) are 

required to estimate aquatic concentrations of environmental contaminants. By using developed models (Alvarez and 

others, 2004, 2007; Huckins and others, 2006) along with 

data from the analysis of the PRC concentrations and sampling rates (when available), the bioavailable aqueous concentrations of analytes detected in POCIS and SPMDs can 

be estimated.

 The effects of exposure conditions on the chemical 

uptake and dissipation rates into passive samplers are largely 

a function of exposure medium temperature; facial velocity/

turbulence at the membrane surface, which in turn is affected 

by the design of the deployment apparatus (baffling of media 

flow-turbulence); and membrane biofouling. PRCs analytically are non interfering organic compounds with moderate to 

high fugacity from SPMDs that are added to the lipid before 

membrane enclosure and field deployment (Huckins and others, 2006). By comparing the rate of PRC loss during field 

exposures to that of laboratory studies, an exposure adjustment 

factor (EAF) can be derived and used to adjust sampling rates 

to more accurately reflect the site-specific sampling rates. A 

mixture of PRCs often is used to ensure at least one will have 

the optimal 20-80 percent loss (Huckins and others, 2006). 

PRCs will undergo increased loss as their log Kow value 

decreases. The amount of loss will be dependent on the same 

environmental factors that affect chemical uptake. Because 

of the strong sorptive properties of the adsorbents used in the 

POCIS, attempts to incorporate PRCs into the POCIS have 

failed (Alvarez and others, 2007). 

Uptake of hydrophobic chemicals into SPMDs follows linear, curvilinear, and equilibrium phases of sampling. 

Integrative (or linear) sampling is the predominant phase for 

compounds with log Kow values ≥ 5.0 and exposure periods of 

up to one month. During the linear uptake phase the ambient 

chemical concentration (Cw) is determined by

Cw = N/Rst (1)

where N is the amount of the chemical sampled by an SPMD 

(typically ng), Rs is the SPMD sampling rate (L/d), and t is the 

exposure time (d). Estimation of a site specific Rs of a chemical in an SPMD is the calculated EAF from the PRC data 
8 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007

multiplied by the Rs measured during laboratory calibration 

studies (Huckins and others, 2006). A key feature of the EAF 

is that it is relatively constant for all chemicals that have the 

same rate-limiting barrier to uptake, allowing PRC data to be 

applied to a range of chemicals. 

Uptake of hydrophilic organic chemicals by the POCIS is 

controlled by many of the same rate-limiting barriers allowing the use of the same models to determine ambient water 

concentrations. Previous data indicate that many chemicals 

of interest remain in the linear phase of sampling for at least 

56 days (Alvarez and others, 2004, 2007); therefore, the use 

of a linear uptake model (eq. 1) for the calculation of ambient 

water concentrations was justified.

Results and Discussion

Chemical Analyses

The data presented in tables 3–9 are reported as estimated 

water concentrations, when possible. In cases where the sampling rate for a chemical was not known, the data were flagged 

as not calculated (NC), and the result was given as mass of 

chemical in the passive sampler. Although the mass of chemical per sampler data is more qualitative, the data are still useful in identifying chemicals present at a site and comparing the 

relative amounts of a chemical between sites. Data that were 

less than the MDL were given as a less than (<) value based on 

the estimated water concentration of the detection limit during 

those site conditions (deployment time, flow, temperature, and 

biofouling) or as the mass of chemical per sampler. Data that 

are greater than the MDL, but less than the MQL, are shown 

in italics. Any data less than the MQL have a large degree 

of statistical uncertainty and are presented for informational 

purposes only. All reportable data greater than the MQL are 

shown in bold type.

Polycyclic Aromatic Hydrocarbons (PAHs)

PAHs (table 3) detected in the study were generally at 

low concentrations indicative of a rural setting with minimal 

urbanization or industrial effect. The primary PAHs detected 

included fluoranthene, pyrene, phenanthrene, naphthalene, 

and the substituted naphthalenes that are common in environmental samples. The two sites with the greatest number 

of PAHs detected were the Cootes Store and Strasburg sites 

on the North Fork of the Shenandoah River with 13 and 

11 of the 16 priority pollutant PAHs detected. Naphthalene 

was detected at all sites with the greatest concentrations of 

12,000 to 17,000 picograms per liter (pg/L) found at the three 

control sites. However, these concentrations are substantially 

below the reported long-term no effect level of 0.45 milligram per liter (mg/L) for fathead minnow and rainbow trout 

(DeGraeve and others, 1982). The Maury River control site 

also contained elevated concentrations of PAHs that were 

greater than many of the other study sites. 

Organochlorine (OC) Pesticides and 

Polychlorinated Biphenyls (PCBs)

Several OC pesticides were detected at reportable 

concentrations greater than the MQL (table 4). Lindane, 

chlorpyrifos, and endosulfan were detected most often and 

at the greatest concentrations. Lindane, an OC insecticide 

banned for agricultural use in 2006 but still approved for 

treatment of lice, was at quantifiable concentrations at five 

sites with a maximum concentration of 240 pg/L at the South 

Fork Shenandoah River at Route 211 site. Lindane has been 

shown to cause anemia, inhibiton of ATPase activity and 

alterations in nervous function in fish (Joy, 1982; Hanke and 

others, 1983; Gonzalez and others, 1987). Chlorpyrifos (also 

known as Dursban or Lorsban) is an organophosphate insecticide widely used until banned in 2000 for residential use; 

however, chlorpyrifos is still used for agricultural purposes. 

Carr and others (1997) reported up to 97 percent inhibition 

of acetylcholinesterase in the brains and skeletal muscles of 

bass, bluegill, and shiners resulting from exposure of chlorpyrifos runoff from an adjacent construction site. Chlorpyrifos 

was found at 9 of 10 sites with a maximum concentration 

of 300 pg/L at the North Fork Shenandoah River–Linville 

Creek at Broadway wastewater treatment plant (WWTP) site. 

Endosulfan is a neurotoxic OC insecticide banned in many 

countries but widely used in agriculture in the United States. 

Exposure of various fish species to sublethal doses of endosulfan resulted in the onset of lesions on livers and brains and 

reduction in enzyme activity (Matthiessen and Roberts, 1982; 

Tripathi and Verma, 2004). Endosulfan was detected at all 

sites with a maximum concentration of 270 pg/L at the Cedar 

Creek control site. Both chlorpyrifos and endosulfan are listed 

by the USEPA as suspected endocrine disruptors. Many of the 

persistent legacy pesticides such as cis- and trans-chlordane, 

cis- and trans-nonachlor, and DDT complex were detected at 

low concentrations up to 64 pg/L (p,p’-DDE at North Fork 

Shenandoah River at Strasburg). The detection of these 

pesticides was not surprising because of the nearly ubiquitous global distribution from years of excessive use before 

being banned. PCBs were detected at concentrations greater 

than the MQL at the Shenandoah River mainstem at Berryville (740 pg/L), North Fork Shenandoah River at Strasburg 

(1,600 pg/L) and South Fork Shenandoah River at Route 211 

(560 pg/L). 

Agricultural Pesticides

Atrazine, simazine, and metolachlor were the most 

commonly detected herbicides in this study. Atrazine concentrations ranged from below detection (<0.18 ng/L) to 

430 nanograms per liter (ng/L). The atrazine metabolite 

desethylatrazine was detected at several sites. Atrazine and 
Results and Discussion 

9

Table 3. Estimated water concentrations of select polycyclic aromatic hydrocarbons (PAHs) measured by semipermeable membrane devices (SPMDs) in the Shenandoah and James River Basins, Virginia, during spring of 2007.[USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; pg/L, estimated water concentration of chemicals expressed as picograms per liter; MDL, method detection limit; MQL, method quantitation limit; WWTP, wastewater treatment plant]

Site name

Shenandoah 

mainstem–

Berryville

North Fork 

Shenandoah 

River–

Cootes Store

North Fork 

Shenandoah 

River–

Linville 

Creek at 

Broadway 

WWTP

North Fork 

Shenandoah 

River–

Strasburg 

Route 55 

Bridge

South Fork 

Shenandoah 

River–White 

House 

(Luray) at 

Route 211

South Fork 

Shenandoah 

River–North 

River at Port 

Republic 

Bridge

South Fork 

Shenandoah 

River–South 

River at 

Harriston

Control 

Site–Maury 

River

Control Site–

Cowpasture 

River

Control Site–

Cedar Creek 

Stalhlnaker 

Property

USGS streamflow-gaging 

station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090

VADEQ station number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65

PAHs2 (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L)

Naphthalene 32,700 2,800 2,700 1,400 9,500 5,500 2,700 12,000 17,000 17,000Acenaphthene 4<22 150 <22 <22 <22 200 <22 790 200 110Fluorene <17 370 571 290 300 210 71 520 <17 180Phenanthrene 86 1,800 240 1,900 1,300 670 360 1,200 120 710Anthracene <14 110 <14 130 <14 52 <14 140 <14 71Fluoranthene 52 1,900 77 2,800 630 150 100 1,600 20 490Pyrene <7.9 770 18 1,200 170 29 15 840 <7.9 170Benz[a]anthracene <7.9 82 <7.9 100 51 <7.9 <7.9 85 <7.9 <7.9Chrysene <7.6 380 15 670 150 21 10 290 <7.6 84Benzo[b]fluoranthene <7.7 160 <7.7 200 <7.7 <7.7 <7.7 <7.7 <7.7 <7.7Benzo[k]fluoranthene <8.6 90 <8.6 110 <8.6 <8.6 <8.6 <8.6 <8.6 <8.6Benzo[a]pyrene <9.1 96 <9.1 120 <9.1 <9.1 <9.1 <9.1 <9.1 <9.1Benzo[g,h,i]perylene <12 130 <12 <12 <12 <12 <12 <12 <12 <122-methylnaphthalene 490 810 230 290 930 700 230 950 1,400 1,4001-methylnaphthalene 240 540 <47 290 930 470 230 710 930 950Biphenyl <43 <43 <43 <43 <43 <43 <43 220 <43 2204-methylbiphenyl 110 140 85 160 350 84 84 200 590 2002,3,5-trimethylnaphthalene <10 <10 <10 <10 220 <10 <10 <10 <10 <101-methylfluorene <9.1 160 <9.1 200 200 48 <9.1 240 26 98Dibenzothiophene <17 120 <17 140 <17 <17 <17 87 <17 <172-methylphenanthrene <10 340 28 410 290 54 27 200 <10 <103,6-dimethylphenanthrene <7.7 76 <7.7 190 52 <7.7 <7.7 41 <7.7 <7.72-methylfluoranthene <7.7 <7.7 <7.7 94 52 <7.7 <7.7 41 <7.7 <7.7Benzo[b]naphtho[2,1-d]thiophene <7.8 76 <7.8 94 <7.8 <7.8 <7.8 42 <7.8 <7.8Benzo[e]pyrene <9.3 99 <9.3 130 <9.3 <9.3 <9.3 50 <9.3 <9.3Perylene <8.3 260 <8.3 220 110 <8.3 <8.3 130 <8.3 46

1 NA, not applicable. There was no USGS streamflow-gaging station near this location.2Only chemicals that were measured in at least one site are listed. See table 2 for a complete targeted chemical list.3Bold values are reportable values greater than the MQL.4Less than (<) values are below the MDL.5Italic values are estimates greater than the MDL but less than the MQL and shown for informational purposes only.
10 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007 Table 4. Estimated water concentrations of select organochlorine pesticides and total polychlorinated biphenyls (PCBs) measured by semipermeable membrane devices (SPMDs) in the Shenandoah and James River Basins, Virginia, during spring of 2007. [USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; pg/L, estimated water concentration of chemicals expressed as picograms per liter; MDL, method detection limit; MQL, method quantitation limit; WWTP, wastewater treatment plant] Site name Shenandoah mainstem– Berryville North Fork Shenandoah River– Cootes Store North Fork Shenando- ah River– Linville Creek at Broadway WWTP North Fork Shenandoah River– Strasburg Route 55 Bridge South Fork Shenandoah River–White House (Luray) at Route 211 South Fork Shenandoah River–North River at Port Republic Bridge South Fork Shenandoah River–South River at Harriston Control Site–Maury River Control Site– Cowpasture River Control Site– Cedar Creek Stalhlnaker Property USGS streamflow-gaging station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090 VADEQ station number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65 Organochlorine Pesticides and Total PCBs2 (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) (pg/L) Trifluralin 3<0.20 <0.20 <0.20 40.94 <0.20 <0.20 <0.20 0.42 <0.20 <0.20 Hexachlorobenzene (HCB) 522 14 <6.5 35 11 <6.5 <6.5 <6.5 <6.5 11 Pentachloroanisole (PCA) 28 41 2.9 59 15 5.4 2.3 24 7.9 37 alpha-Benzenehexachloride (a-BHC) <4.7 <4.7 <4.7 <4.7 <4.7 47 45 <4.7 <4.7 <4.7 Lindane 93 89 <17 220 240 78 83 140 71 <17 beta-Benzenehexachloride (b-BHC) <19 <19 21 <19 <19 110 98 <19 <19 21 delta-Benzenehexachloride (d-BHC) <2.7 <2.7 <2.7 <2.7 <2.7 <2.7 34 <2.7 <2.7 <2.7 Dacthal 9.1 <2.7 <2.7 <2.7 5.7 29 8.7 <2.7 <2.7 <2.7 Chlorpyrifos 110 180 300 120 73 130 39 36 <6.8 73 Oxychlordane <.77 1.5 <.77 <.77 <.77 7.1 1.3 .82 <.77 <.77 Heptachlor Epoxide 35 5.5 8.2 24 42 12 16 20 2.2 7.4 trans-Chlordane 19 16 7.4 37 31 4.9 5.4 22 <4.8 6.8 trans-Nonachlor 28 11 3.4 38 22 <2.4 <2.4 15 1.2 7.6 cis-Chlordane 31 21 <7.1 54 30 <7.1 7.3 22 <7.1 <7.1 Endosulfan 220 210 130 160 180 48 66 130 110 270 p,p’-DDE 30 <9.8 <9.8 64 18 <9.8 <9.8 13 <9.8 28 Dieldrin 39 <16 <16 56 44 50 <16 23 <16 35 o,p’-DDD 6.6 <2.7 <2.7 29 5.8 5.9 <2.7 <2.7 <2.7 <2.7 Endrin 19 21 <1.2 <1.2 <1.2 <1.2 4.8 13 <1.2 20 cis-Nonachlor 7.4 6.3 <2.9 18 6.0 <2.9 <2.9 6.0 <2.9 5.2 o,p’-DDT 10 21 2.9 <.76 <.76 1.9 <.76 11 3.2 4.6 p,p’-DDD 7.6 13 2.6 79 13 <2.6 <2.6 15 4.9 23 Endosulfan-II <180 <180 180 510 <180 <180 <180 370 <180 210 p,p’-Methoxychlor 21 25 13 <12 34 <12 47 <12 <12 <12 cis-Permethrin <46 <46 <46 <46 101 <46 <46 66 <46 <46 trans-Permethrin <2.6 <2.6 <2.6 140 16 <2.6 19 57 <2.6 <2.6 Total PCBs 740 470 <220 1,600 560 <220 <220 370 <220 <220

1 NA, not applicable. There was no USGS streamflow-gaging station near this location.2 Only chemicals that were measured in at least one site are listed. See table 2 for a complete targeted chemical list.3 Less than (<) values are below the MDL.4 Italic values are estimates greater than the MDL but less than the MQL and shown for informational purposes only.5 Bold values are reportable values greater than the MQL.
Results and Discussion 11

Table 5. Estimated water concentrations and identification of select agricultural herbicides and pesticides measured by polar organic chemical integrative samplers (POCIS) in the Shenandoah and James River Basins, Virginia, during spring of 2007. [USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; ng/L, estimated water concentration of chemicals expressed as nanograms per liter; NC, not calculated; ng/POCIS, nanograms of chemicals sampled by a single POCIS; MDL, method detection limit; MQL, method quantitation limit; WWTP, wastewater treatment plant]

Site name

Shenandoah 

mainstem–

Berryville

North Fork 

Shenandoah 

River–Cootes 

Store

North Fork 

Shenandoah 

River–Linville 

Creek at Broadway WWTP

North Fork 

Shenandoah 

River–

Strasburg 

Route 55 

Bridge

South Fork 

Shenandoah 

River–White 

House (Luray) 

at Route 211

South Fork 

Shenandoah 

River–North 

River at Port 

Republic 

Bridge

South Fork 

Shenandoah 

River–South 

River at 

Harriston

Control 

Site–Maury 

River

Control Site–

Cowpasture 

River

Control Site 

Cedar Creek 

Stalhlnaker 

Property

USGS streamflow-gaging 

station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090

VADEQ station number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65

Agricultural pesticides2 (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L)

Desethylatrazine 36.9 2.0 37 13 12 5.8 4.1 4<0.33 <0.33 8.7Atraton <.08 <.08 <.08 <.08 <.08 1.8 <.08 <.08 <.08 <.08Simazine 3.5 <.19 13 8.3 4.0 3.6 1.6 <.19 <.19 <.19Prometon .8 <.09 1.3 2.5 .7 2.2 .5 <.09 <.09 <.09Atrazine 79 <.18 430 210 40 26 <.18 <.18 <.18 <.18Simetryn <.11 <.11 <.11 <.11 <.11 1.8 <.11 <.11 <.11 <.11Metolachlor 2.0 5.31 5.5 7.5 3.7 1.4 1.0 <.10 <.10 <.10Pendimethalin <.16 <.16 <.16 <.16 <.16 <.16 <.16 <.16 .32 <.16cis-Permethrin NC [<1.5 

ng/POCIS]6

NC [<1.5 

ng/POCIS]

NC [<1.5 

ng/POCIS]

NC [<1.5 

ng/POCIS]

NC [<1.5 

ng/POCIS]

86 ng/POCIS 25 ng/POCIS NC [<1.5 

ng/POCIS]

NC [<1.5 

ng/POCIS]

NC [<1.5 

ng/POCIS]

trans-Permethrin NC [<0.48 

ng/POCIS]

NC [<0.48 

ng/POCIS]

NC [<0.48 

ng/POCIS]

NC [<0.48 

ng/POCIS]

NC [<0.48 

ng/POCIS]

30 ng/POCIS 11 ng/POCIS NC [<0.48 

ng/POCIS]

NC [<0.48 

ng/POCIS]

NC [<0.48 

ng/POCIS]

1NA, not applicable. There was no USGS streamflow-gaging station near this location.2Only chemicals that were measured in at least one site are listed. See table 2 for a complete targeted chemical list.3Bold values are reportable values greater than the MQL.4Less than (<) values are below the MDL.5Italic values are estimates greater than the MDL but less than the MQL and shown for informational purposes only.6Sampling rates were not available to estimate ambient water concentrations; therefore results are presented as ng of chemical sequestered per sampler.
12 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007 Table 6. Identification of select waste-indicator chemicals measured by polar organic chemical integrative samplers (POCIS) and semipermeable membrane devices (SPMDs) in the Shenandoah and James River Basins, Virginia, during spring of 2007. [USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; ng/POCIS, nanograms of chemicals sampled by a single POCIS; MDL, method detection limit; MQL, method quantitation limit; ng/SPMD, nanograms of chemicals sampled by a single SPMD; WWTP, wastewater treatment plant] Site name Shenandoah mainstem– Berryville North Fork Shenandoah River–Cootes Store North Fork Shenandoah River–Lin- ville Creek at Broadway WWTP North Fork Shenandoah River– Strasburg Route 55 Bridge South Fork Shenandoah River–White House (Luray) at Route 211 South Fork Shenandoah River–North River at Port Republic Bridge South Fork Shenandoah River–South River at Harriston Control Site– Maury River Control Site– Cowpasture River Control Site– Cedar Creek Stalhlnaker Property USGS streamflow- gaging station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090 VADEQ station number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65 Waste-indicator chemicals2 (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) Isophorone 3<20 <20 420 20 <20 <20 <20 <20 <20 <20 Indole 51,100 30 60 50 <20 <20 1,200 <20 <20 <20 Diethyl phthalate 80 70 80 45 10 <20 40 <20 <20 60 Benzophenone <20 20 <20 <20 <20 <20 <20 <20 <20 <20 Prometon <20 <20 30 25 <20 <20 <20 <20 <20 <20 Atrazine 800 <20 5,000 2,400 450 300 <20 <20 <20 <20 Galaxolide (HHCB) 40 20 20 110 60 140 260 200 <20 20 Tonalide (AHTN) <20 <20 <20 <20 <20 20 20 <20 <20 <20 Diethylhexylphthalate (DEHP) 670 660 890 400 800 420 630 360 480 600 Cholesterol 1,500 1,500 1,600 420 3,500 320 280 <20 600 710 Waste-indicator chemicals (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) (ng/SPMD) Indole 47 460 1,500 300 <20 <20 <20 <20 <20 110 Diethyl phthalate <20 <20 <20 24 <20 <20 100 35 <20 <20 Atrazine <20 <20 <20 <20 34 26 <20 <20 <20 30 Phenanthrene <20 <20 31 <20 25 25 25 <20 <20 <20 Galaxolide (HHCB) 75 <20 <20 190 140 310 170 700 <20 <20 Tonalide (AHTN) <20 <20 <20 <20 <20 31 33 73 <20 <20 Fluoranthene 26 <20 61 <20 25 30 38 42 <20 <20 Pyrene <20 <20 <20 <20 <20 <20 20 24 <20 <20 Diethylhexylphthalate (DEHP) <20 <20 22 32 <20 <20 <20 <20 <20 <20 Cholesterol 310 150 790 300 540 25 180 170 52 88

1NA, not applicable. There was no USGS streamflow-gaging station near this location.2Only chemicals that were measured in at least one site are listed. See table 2 for a complete targeted chemical list.3Less than (<) values are below the MDL.4Italic values are estimates greater than the MDL but less than the MQL and shown for informational purposes only.5Bold values are reportable values greater than the MQL.
Results and Discussion 13

Table 7. Identification of select pharmaceuticals measured by polar organic chemical integrative samplers (POCIS) in the Shenandoah and James River Basins, Virginia, during spring of 2007. [USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; ng/POCIS, nanograms of chemicals sampled by a single POCIS; IDL, instrument detection limit; LOQ, limit of quantitation; WWTP, wastewater treatment plant]

Site name

Shenandoah 

mainstem–

Berryville

North Fork 

Shenandoah 

River–

Cootes Store

North Fork 

Shenandoah 

River–Linville 

Creek at 

Broadway 

WWTP

North Fork 

Shenandoah 

River–

Strasburg 

Route 55 

Bridge

South Fork 

Shenandoah 

River–White 

House (Luray) 

at Route 211

South Fork 

Shenandoah 

River–North 

River at Port 

Republic 

Bridge

South Fork 

Shenandoah 

River–South 

River at 

Harriston

Control Site–

Maury River

Control Site–

Cowpasture 

River

Control Site–

Cedar Creek 

Stalhlnaker 

Property

USGS streamflowgaging station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090

VADEQ station 

number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65

Pharmaceuticals2 (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS) (ng/POCIS)

1,7-dimethylxanthine 3< 5 42.2 < 5 9.5 < 5 < 5 < 5 < 5 < 5 12Caffeine 48 4.0 < 5 36 40 < 5 < 5 < 5 10 5.7Carbamazepine < 5 < 5 < 5 3.4 < 5 < 5 13 17 < 5 < 5Codeine 2.9 < 5 < 5 7.0 < 5 < 5 < 5 < 5 < 5 2.9Cotinine 1.6 < 5 2.5 .90 < 5 < 5 < 5 < 5 < 5 < 5Sulfamethoxazole < 5 < 5 < 5 < 5 < 5 < 5 < 5 3.7 < 5 < 5Trimethoprim 7.9 < 5 54 5.1 16 100 65 53 < 5 36Venlafaxine .61 5< .9 < .9 2.0 4.1 16 40 46 < .9 < .9

1NA, not applicable. There was no USGS streamflow-gaging station near this location.2Only chemicals that were measured in at least one site are listed. See table 2 for a complete targeted chemical list.3For common-use pharmaceuticals, the lowest end of the calibration range, equivalent to 5 ng/POCIS, was set at the IDL of the compounds with the least sensitivity in the analysis; a number of compounds 

had IDLs considerably lower.

4Bold values are reportable values greater than the IDL (common-use pharmaceuticals) or the LOQ (current-use antidepressants).5For the current-use antidepressants, the LOQ is on the order of 0.9 ng/POCIS, based on the LOQ reported in Schultz and Furlong (2008).
14 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007 Table 8. Estimated water concentrations of select hormones measured by polar organic chemical integrative sampler (POCIS) in the Shenandoah and James River Basins, Virginia, during spring of 2007. [USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; ng/L, estimated water concentration of chemicals expressed as nanograms per liter; MDL, method detection limit; MQL, method quantitation limit; WWTP, wastewater treatment plant] Site name Shenandoah mainstem– Berryville North Fork Shenandoah River– Cootes Store North Fork Shenandoah River–Linville Creek at Broadway WWTP North Fork Shenandoah River–Stras- burg Route 55 Bridge South Fork Shenandoah River–White House (Luray) at Route 211 South Fork Shenandoah River–North River at Port Republic Bridge South Fork Shenandoah River–South River at Harriston Control Site– Maury River Control Site– Cowpasture River Control Site– Cedar Creek Stalhlnaker Property USGS streamflow-gaging station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090 VADEQ station number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65 Hormones2 (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) 17β-Estradiol 31.0 0.91 4<0.46 <0.46 52.3 -----6 <0.46 <0.46 <0.46 <0.46 17α-Ethynylestradiol 2.0 <.91 <.91 <.91 8.1 ----- <.91 <.91 <.91 <.91 Estrone <.55 <.55 <.55 <.55 1.6 ----- <.55 <.55 <.55 <.55 Estriol .63 <.56 <.56 <.56 3.4 ----- <.56 <.56 <.56 <.56

1NA, not applicable. There was no USGS streamflow-gaging station near this location.2Only chemicals that were measured in at least one site are listed. See table 2 for a complete targeted chemical list.3Italic values are estimates greater than the MDL but less than the MQL and shown for informational purposes only.4Less than (<) values are below the MDL.5Bold values are reportable values greater than the MQL.6No data because of insufficient amounts of sample available for analysis.
Results and Discussion 15

Table 9. Relative estrogenic potential of chemicals sampled by the polar organic chemical integrative samplers (POCIS) deployed in the Shenandoah and James River Basins, Virginia, during spring of 2007 as determined by the Yeast Estrogen Screen (YES).[USGS, U.S. Geological Suvey streamflow-gaging station number; VADEQ, Virginia Department of Environmental Quality; EEQ, estimated estradiol equivalents; ng E2/POCIS, estimated nanograms of 17b-estradiol per POCIS that gives an equivalent response; WWTP, wastewater treatment plant]

Site name

Shenandoah 

mainstem–

Berryville

North Fork 

Shenandoah 

River–Cootes 

Store

North Fork 

Shenandoah 

River–Linville 

Creek at 

Broadway 

WWTP

North Fork 

Shenandoah 

River–

Strasburg 

Route 55 

Bridge

South Fork 

Shenandoah 

River–White 

House (Luray) 

at Route 211

South Fork 

Shenandoah 

River–North 

River at Port 

Republic 

Bridge

South Fork 

Shenandoah 

River–South 

River at 

Harriston

Control Site–

Maury River

Control Site– 

Cowpasture 

River

Control Site– 

Cedar Creek 

Stalhlnaker 

Property

USGS streamflowgaging station NA1 1632000 1632082 1634000 1629500 1622000 1627500 2024000 2016000 1635090

VADEQ station 

number 1BSHN022.63 1BNFS093.53 1BLNV000.16 1BNFS010.34 1BSSF054.20 1BNTH000.18 1BSTH007.80 2-MRY020.16 2-CWP025.30 1BCDR001.65

(ng E2/

POCIS) (ng E2/POCIS) (ng E2/POCIS) (ng E2/ POCIS) (ng E2/ POCIS) (ng E2/POCIS) (ng E2/POCIS) (ng E2/POCIS) (ng E2/POCIS) (ng E2/POCIS)

EEQ 2.3 2.4 12 4.1 5.9 5.5 11 4.9 2.3 7.8

1NA, not applicable. There was no USGS streamflow-gaging station near this location.
16 Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Virginia, Spring of 2007

desethylatrazine concentrations at the study sites mirrored 

each other with maximum concentrations for each found at 

the North Fork Shenandoah River–Linville Creek at Broadway WWTP site. The broad spectrum insecticide, permethrin 

(both the cis- and trans- stereoisomers) was detected at the 

South Fork Shenandoah River–North River at Port Republic 

and South River at Harriston sites. Prometon, a nonselective 

herbicide used for weed control along roadways, recreational 

areas, railroads, industrial, and military areas, was detected at 

low concentrations at six sites. The identification of atrazine and prometon was confirmed by a secondary analysis of 

separate POCIS extracts during the waste indicator chemical 

screen. A direct link between atrazine concentrations and 

impaired reproductive health of fish has not been identified; 

however, atrazine remains a suspect because of widespread 

use and elevated concentrations in the study areas (Bringolf 

and others, 2004; Chang and others, 2005; Richter and others, 2006).

Waste Indicator Chemicals

Few waste indicator chemicals were detected, indicating that the sites are minimally effected by effluents from 

WWTPs or leaking septic systems (table 6). The fragrance 

compounds galaxolide, tonalide, and indole were detected at 

low levels at several of the sites, indicating a minor influence 

from WWTPs. The sites with the highest detected concentrations of the fragrances were the Shenandoah River mainstem 

at Berryville, North Fork Shenandoah River–Linville Creek 

at Broadway WWTP site, and the South Fork Shenandoah 

River–South River at Harriston. Concentrations of diethyl 

phthalate, diethylhexylphthalate, and cholesterol in the 

SPMDs were greatly reduced from the original levels as these 

compounds were largely removed from the samples during the 

SEC fractionation prior to analysis. The SEC fractionation 

was a necessary step to remove interferences that impaired the 

initial analysis of the raw SPMD extracts.

The presence of certain selected chemicals in both the 

SPMD and POCIS can be used for confirmation purposes; 

however, lack of the presence of a chemical in one sampler 

does not indicate an incorrect identification. Many chemicals 

will be selectively sampled by one device or the other. For 

example, atrazine was readily sampled by the POCIS; however, only traces of the chemical were found in the SPMDs 

from the same sites. SPMDs and POCIS often have large 

differences in the sampling rates of similar chemicals that 

can result in greatly different amounts of a chemical present 

in each device. Without knowledge of the sampling rate for 

the chemical in each sampler, direct comparisons on the basis 

of the amount of chemical detected in each sampler cannot 

be made.

Pharmaceuticals

As observed for the waste indicator chemicals, few 

pharmaceuticals were detected in the POCIS extracts (table 7). 

Caffeine, 1,7-dimethylxanthine (a major metabolite of caffeine), cotinine (the metabolite of nicotine), codeine (a narcotic analgesic), and carbamazepine (an anticonvulsant drug) 

were each detected at several sites. Trimethoprim, an antibiotic commonly prescribed in tandem with sulfamethoxazole, 

was detected in 8 of 10 sites; however, sulfamethoxazole 

was detected only at one of these sites. The antidepressant 

venlafaxine, currently the 13th most prescribed drug in the 

United States and sold under the tradename Effexor (RxList, 

2008), was detected at several sites. The detected amounts 

of venlafaxine in the POCIS extracts (<0.9-46 ng/POCIS) are 

much lower than levels detected in WWTP effluent dominated 

stream samples (600–1,000 ng/L) reported by Schultz and 

Furlong (2008). Little is known about the long-term chronic 

effects due to exposure to trace concentrations of pharmaceuticals; however, effects are expected to occur as the pharmaceuticals are designed to elicit a biological response (Daughton 

and Ternes, 1999).

Hormones

Four steroidal hormones were selected for this study 

including the natural hormone 17β-estradiol, the synthetic 

hormone 17α-ethynylestradiol (the main ingredient in oral 

contraceptives), and the 17β-estradiol metabolites, estriol and 

estrone. The hormones were detected at three sites with measurable concentrations at the South Fork Shenandoah River 

Route 211 site. The synthetic hormone 17α-ethynylestradiol 

had a maximum concentration of 8.1 ng/L at this site that is 

important as concentrations as low as 1 ng/L have been shown 

to induce intersex in fishes (Länge and others, 2001). Immature rainbow trout have been shown to increase vitellogenin 

synthesis upon exposure to 17α-ethynylestradiol concentrations of 0.1 ng/L (Purdom and others, 1994). Chronic 

exposure of fathead minnows (Pimephales promelas) to 

17α-ethynylestradiol at concentrations of 5-6 ng/L resulted 

in feminization of males, altered reproduction in females, 

and near extinction of the species from an experimental 

test lake in Canada over a seven-year study (Kidd and others, 2007). Routledge and others (1998) indicated that 

17α-ethynylestradiol could produce an estrogenic response 

at concentrations 10-fold lower than other natural steroids. 

Denny and others (2005) indicated that 17α-ethynylestradiol 

has a higher affinity for the fish estrogen receptor than natural 

estrogens and presumably a greater biological potency.
References Cited 17

Yeast Estrogen Screen (YES Assay)

There was measurable estrogenicity in each of the site 

samples (table 9), although at levels lower than what has been 

reported in samples from areas heavily effected by WWTP 

effluent (Vermeirssen and others, 2005). The EEQs estimated in this study were similar to other studies where the 

surrounding land use was primarily agricultural (Alvarez and 

others, 2008b; Matthiessen and others, 2006). There were no 

field blanks used in this study that could be used to determine any potential estrogenicity from the sampler matrix or 

field contamination. However, no estrogenic response was 

observed from a laboratory matrix blank, indicating that the 

sample processing steps and likely the original sample matrix 

did not contribute to the total measured estrogenicity. The 

presence of natural and synthetic hormones at some of the 

sites (table 8) would have contributed to some of the measured 

estrogenicity in the samples; however, the elevated EEQs at 

the North Fork Shenandoah River–Linville Creek at Broadway 

WWTP site and South Fork Shenandoah River–South River 

at Harriston, neither of which had any measurable hormones, 

indicate that one or more chemicals capable of mimicking the 

estrogen mode of action were present. The definitive identification of these chemicals was beyond the scope of this study. 

Because the estrogenicity was found in the POCIS extracts, 

it is likely the chemical or chemicals responsible for promoting the estrogenic response are more water soluble and less 

likely to bioaccumulate in fish and other aquatic organisms. 

Nevertheless, polar chemicals are suspected to have adverse 

effects on aquatic organisms, even though these chemicals 

may not bioaccumulate, because of the constant input into the 

basin (Daughton and Ternes, 1999). However, since extracts 

from SPMDs were not tested using the YES assay, it cannot 

be determined how much of the potential estrogenicity from 

chemicals at the sites was because of hydrophobic chemicals. 

A definitive study into the identity of the estrogenic chemicals 

was beyond the scope of this study.

Acknowledgements

The authors graciously thank the U.S. Environmental 

Protection Agency and the Virginia Poultry Foundation, for 

providing funding for this work. We also thank Donald Kain, 

Ted Turner, and other colleagues with the Virginia Department 

of Environmental Quality for their efforts in the planning, 

logistics, and field work part of the project.

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Alvarez and others—Persistent and Emerging Contaminants in the Shenandoah and James River Basins, Spring 2007, Virginia—Open-File Report 2008–1231

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