Polycyclic Aromatic Hydrocarbons in 

Bottom Sediment and Bioavailability in 

Streams in the New River Gorge National 

River and Gauley River National Recreation 

Area, West Virginia, 2002

By Terence Messinger

U.S. Department of the Interior 

U.S. Geological Survey

In cooperation with the National Park Service

Scientific Investigations Report 2004-5045
U.S. Department of the Interior

Gale A. Norton, Secretary

U.S. Geological Survey

Charles G. Groat, Director

U.S. Geological Survey, Reston, Virginia: 2004

For sale by U.S. Geological Survey, Information Services 

Box 25286, Denver Federal Center 

Denver, CO 80225

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endorsement by the U.S. Government.

Although this report is in the public domain, permission must be secured from the individual copyright owners to reproduce any copyrighted materials contained within this report.

Suggested citation:

Messinger, Terence, 2004, Polycyclic aromatic hydrocarbons in bottom sediment and bioavailability in streams in the 

New River Gorge National River and Gauley River National Recreation Area, West Virginia, 2002: U.S. Geological Survey 

Scientific Investigations Report 2004-5045, 24 p.
 iii

Contents

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

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

Polycyclic Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

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

Description of Study Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Data Collection and Study Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Bottom Sediment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Semipermeable Membrane Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

PAHs in Bottom Sediment in Kanawha River Basin Streams, 1996-2002 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

Kanawha River Basin Reconnaissance Study, 1996-1997 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

Regional Coal-Mining Study, 1998 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

New River Gorge and Gauley River National Recreation Area Study, 2002 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Possible Sources of PAHs in Bottom Sediment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

PAH Bioavailability in New River Gorge National River and Gauley River National Recreation Area streams, 

2002 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Literature Cited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
iv 

Figures

1. Sampling sites, selected streams, towns, and national parks in the Kanawha River Basin, West 

Virginia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2. Coal mines in the Kanawha River Basin, and coal mines, selected streams, and sampling sites 

in and near the New River Gorge National River, West Virginia. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Tables

1. Sampling sites in the Kanawha River Basin, West Virginia, and their map numbers, station numbers, and years sampled . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2. Deployment dates and durations for semipermeable membrane devices . . . . . . . . . . . . . . . . . . . . 7

3. Probable effects level (PEL) and threshold effects level (TEL)1 for 12 polycyclic aromatic hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

4. Polycyclic aromatic hydrocarbon concentrations measured in fine bottom sediment at selected 

sites in coal-mining areas in the Kanawha River Basin in West Virginia, in July 1998 . . . . . . . . 15

5. Polycyclic aromatic hydrocarbon concentrations in fine stream-bottom sediment at selected 

sites in the New River Gorge National River and Gauley River National Recreation Area, West 

Virginia, in 1996 and July 2002 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

6. Polycyclic aromatic hydrocarbon concentrations measured in semipermeable membrane 

devices in streams in the New River Gorge National River and Gauley River National Recreation 

Area, 2002 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

7. Maximum polycyclic aromatic hydrocarbon (PAH) concentrations measured in semipermeable membrane devices (SPMDs) in streams managed by the National Park Service in West 

Virginia in 2002, with the lowest dissolved concentrations at which the PAHs had significant 

adverse biological effects, and estimates of the concentrations those PAHs would reach in 

SPMDs under exposure to the stated dissolved concentration at 20oC for the time the SPMD 

was deployed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

8. Maximum observed polycyclic aromatic hydrocarbon (PAH) concentration in semipermeable 

membrane devices (SPMDs), threshold concentration at which acute toxic effects were 

observed in aquatic vertebrates and invertebrates, and maximum exposure times under ideal 

uptake conditions for the observed concentrations in the SPMDs to be reached in a solution at 

the threshold concentration of the PAH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
 v

Conversion Factors and Datum

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

 ̊F = (1.8 x  ̊C) + 32

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

 ̊C = ( ̊F - 32) / 1.8

Vertical coordinate information is referenced to the North American Vertical Datum of 1988 

(NAVD 88). Horizontal coordinate information is referenced to the North American Datum of 1983 

(NAD 83).

Altitude, as used in this report, refers to distance above the vertical datum.

Concentrations of chemical constituents in water are given either in milligrams per liter (mg/L) or 

micrograms per liter ( g/L).

Multiply By To obtain

Length

inch (in.) 2.54 centimeter (cm)

mile (mi) 1.609 kilometer (km)

Area

square mile (mi2) 2.590 square kilometer (km2)

Volume

ounce, fluid (fl. oz) 0.02957 liter (L)

Mass

ounce, avoirdupois (oz) 28.35 gram (g)

ton, short (2,000 lb) 0.9072 megagram (Mg)

Concentration

ounce per pound (oz/lb) 62,500,000 nanograms per gram (ng/g)

ounce per pound (oz/lb) 62,500,000 micrograms per kilogram (μg/kg)

ounce per gallon (oz/gal) 7,489,151 microgam per liter (μg/L)

Polycyclic Aromatic Hydrocarbons in Bottom Sediment 

and Bioavailability in Streams in the New River Gorge 

National River and Gauley River National Recreation 

Area, West Virginia, 2002

By Terence Messinger

Abstract 

Polycyclic aromatic hydrocarbons (PAHs), including 

some on the U.S. Environmental Protection Agency’s priority 

pollutant list, were found in bottom sediment in streams in the 

coal-producing region of the Kanawha River Basin in 1996-

1998, and in and near the New River Gorge National River in 

2002, in concentrations exceeding those thought likely to cause 

adverse effects to wildlife. Very low concentrations of bioavailable PAHs were measured in streams in and near the New River 

Gorge National River by the use of semipermeable membrane 

devices. The apparent contradiction between the high concentrations of total PAHs and the low concentrations of bioavailable PAHs may result from the presence of a substantial amount 

of particulate coal in bottom sediment. 

Introduction

Polycyclic aromatic hydrocarbons (PAHs) are a group of 

organic compounds (Sander and Wise, 1997). Many PAHs are 

toxic or carcinogenic, and were the first compounds to be linked 

to cancer in humans, among London chimney sweeps in the 

1700s (Agency for Toxic Substances and Disease Registry, 

1995). PAHs are found in petroleum, coal, and as products of 

combustion; they are produced by humans most commonly as a 

byproduct of fossil fuel combustion.

PAHs were measured in bottom sediment in streams of the 

Kanawha River Basin in 1996-1998 in concentrations at which 

adverse effects to aquatic life are thought to be probable (Paybins and others, 2001). One site in the New River Gorge 

National River and another site in the Gauley River National 

Recreation Area were among those where PAH concentrations 

were of concern. To determine if high concentrations of PAHs 

in bottom sediment posed a threat to wildlife, the U.S. Geological Survey (USGS), in cooperation with the National Park Service, studied PAH concentrations in bottom sediment and bioavailability in five streams in the New River Gorge National 

River and the Gauley River National Recreation Area in the 

summer of 2002.

Polycyclic Aromatic Hydrocarbons

The simplest “aromatic” hydrocarbon is benzene, which 

has a chemical formula of C6H6 and a molecular weight of 78 

(Streitweiser and others, 1992). In benzene, six carbon atoms 

are bonded in a ring, or cyclic, structure and some of the electrons are distributed around the ring, so that a single hydrogen 

atom is bonded to each carbon atom in the ring. A “polycyclic 

aromatic” hydrocarbon is one in which two or more aromatic 

rings are bonded together. The simplest PAH is naphthalene, 

the structure of which is two fused benzene rings. One or more 

of the hydrogen atoms bonded to an aromatic or polycyclic aromatic group may be substituted with an alkyl or other functional 

group. Alkyl-substituted PAHs are called “alkyl homologues” 

of the unsubstituted or “parent” molecules. Numbering of carbon atoms begins with the uppermost ring the furthest to the 

right in a diagram of the molecule, with the most counterclockwise carbon atom not involved with ring fusion (Sander and 

Wise, 1997). For example, 1,-2,-dimethylnaphthalene is an 

alkyl homologue of the parent naphthalene molecule, in which 

methyl groups have been substituted for the hydrogens at the 

first and second carbons clockwise around the ring depicted on 

the right from a carbon atom shared by the two rings.

PAHs do not ionize and are only slightly soluble in water 

(Moore and Ramamoorthy, 1984). The solubility of PAHs in 

water increases three- to four-fold with an increase in temperature from 5 to 30  ̊C. Dissolved and colloidal organic substances 

also increase the solubility of PAHs. Because they are only 

slightly water-soluble, PAHs entering a water body have a high 

affinity for suspended particles. PAHs sorb to these particles, 

and eventually settle out of the water column onto bottom sediment. Thus, the PAH concentrations in water are usually low 

relative to the concentrations in bottom sediment.
2 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

Sixteen PAHs (acenaphthene, acenaphthylene, 

anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[g,h,i]perylene, benzo[k]fluoranthene, chrysene, dibenzo[a,h]anthracene, fluoranthene, fluorene, 

ideno[1,2,3-cd]pyrene, naphthalene, phenanthrene, and pyrene) 

are on the U.S. Environmental Protection Agency’s list of priority pollutants (U.S. Environmental Protection Agency, 2003). 

PAHs can harm human health; the principal modes of exposure 

to them are by inhaling airborne PAHs or eating them in 

smoked food (Agency for Toxic Substances and Disease Registry, 1995). PAHs are absorbed passively by fish, but are rapidly 

metabolized. PAHs in aquatic systems do not accumulate in fish 

tissue and are not considered to pose a direct risk to humans 

who eat fish from water bodies contaminated with PAHs. However, PAHs in high concentrations present a threat to aquatic 

life. High PAH concentrations in bottom sediment of Lake Erie 

tributaries were correlated with liver tumors in brown bullhead 

(Baumann and others, 1991; Smith and others, 1994). PAHs 

accumulate in some invertebrates; alkylated PAHs are thought 

to accumulate more readily than parent PAHs (Irwin and others, 

1998).

PAHs are bioavailable only if they are dissolved (Huckins 

and others, 1996). Solubility of PAHs depends partly on their 

source. Soot, smoke, petroleum, and coal are common substances that are rich in PAHs. A great deal of work has been 

done to develop techniques to “fingerprint” PAH sources, in 

particular petroleum and different combustion sources (Yunker 

and others, 2002). Relatively little work has been done to 

develop PAH fingerprints for coal, partly because PAHs from 

coal are thought not to be bioavailable (Chapman and others, 

1996; Hostettler and others, 1999). 

Purpose and Scope

The purpose of this report is to present the findings of a 

study of PAH bottom sediment concentrations and bioavailability, as measured with semipermeable membrane devices, done 

at five stream sites in the New River Gorge National River and 

the Gauley River National Recreation Area during the summer 

of 2002. To provide a context for these findings, this report discusses the previously uninterpreted results of a 1996-1997 U.S. 

Geological Survey (USGS) reconnaissance study of PAH concentrations in bottom sediment of streams throughout the 

Kanawha River Basin (Ward and others, 1998), and previously 

unpublished results of a 1998 USGS study of PAH concentrations in bottom sediment of streams that drain the part of the 

Kanawha River Basin, in West Virginia, where mineable coal is 

present. The relations between land use and PAH concentrations in bottom sediment from the 1996-1998 studies are briefly 

discussed to provide the rationale for the 2002 study.

Description of Study Area

The New River forms in North Carolina, and flows north 

to Gauley Bridge, West Virginia, where it joins the Gauley 

River to form the Kanawha River (fig. 1). The Gauley River 

forms in the Allegheny Mountains in central West Virginia. The 

New River Gorge National River, Gauley River National Recreation Area, and Bluestone National Scenic River are administered as a single management unit by the National Park Service 

to protect scenic canyons in south-central West Virginia. The 

New and Gauley Rivers inside National Park lands are heavily 

used by whitewater kayakers and rafters, and are considered to 

be world-class whitewater boating destinations (American 

Whitewater, 2003). The New River Gorge National River is 

between Bluestone Dam and the upstream limits of the pool 

formed by Hawks Nest Dam. The Gauley River National Recreation Area is downstream from Summersville Dam and 

upstream from Swiss, WV. The New, Gauley, and Bluestone 

Rivers, and the tributaries that enter them in national parks, all 

form upstream from park boundaries. As a result, the National 

Park Service manages streams that are influenced, and often 

degraded in quality, by activities outside the parks.

Most tributaries of the reaches of the New and Gauley Rivers managed by the National Park Service form in uplands and 

flow across a plateau, then plunge sharply as they approach the 

steep, rugged gorges. In their upstream reaches, these tributaries 

typically have low gradients, whereas in their lower reaches, 

they have steep gradients and coarse substrates associated with 

headwater streams. 

The economy of the study area relies heavily on extractive 

industries such as coal mining and timbering, and historically, 

relied more heavily on these industries (Messinger and Hughes, 

2000). Tourism, especially adventure tourism such as whitewater boating, rock climbing, and mountain biking, is now an 

important economic activity. Most of the population of the 

study area lives in rural areas, although cities and towns including Beckley, Mount Hope, Oak Hill, and Fayetteville are within 

basins draining to the New River Gorge. 

Coal mining is an important economic activity in the study 

area (fig. 2). Land now managed by the National Park Service 

in West Virginia has an extensive history of mining, especially 

underground mining, that predates the creation of the parks. As 

a land use, coal mining is difficult to quantify (Paybins and others, 2001), for reasons including the following: (1) Unlike many 

other land uses, mining is three-dimensional instead of twodimensional; seams are of different thicknesses, require different amounts of disturbance to overburden, and multiple seams 

may have been mined, one over the other, at different times; (2) 

the amount of drainage from mines differs greatly depending on 

factors such as mine depth, dip of the coal seams, and the mining method used; (3) both underground and surface mining may 

change the flow paths of water; (4) coal production may not be 

correlated with any measure of mining-related land disturbance; 

and (5) historical coal production information is limited and 

flawed. For these reasons, no effort was made in this report to 

quantify mining in the basins of the streams sampled in this 

study.

Several streams that drain to the New River Gorge were 

flooded in July 2001, from a series of thunderstorms that produced flows in excess of the 100-year recurrence interval in
Introduction 3

Kanawha River

Elk River

Coal River

Big Coal River

Coal River

Little

Bluestone River

Greenbrier River

Meadow River

Cherry River

New River

Birch River

Holly

River

Gauley River

22

6 9 19

8

21

20

18

1

14

15

16

17

12 7

13

3

11

5

4

10

2

Summersville

Dam

Bluestone

Bluestone National Dam

Scenic River

New River Gorge

National River

Gauley River National

Recreation Area

Charleston

Gauley

Bridge

Fayetteville

Oak

Hill

Beckley

Princeton

Bluefield

38o

80 30' o

81o

81 30' o

82o

38 30' o

80 o

37 30' o

Study area location

OH

PA

WV

VA

EXPLANATION

Major rivers

Site sampled in:

1996

1998

National park boundaries

Kanawha River Basin,

within West Virginia

2002

1 Site map number (Table 1)

0 5 10 20 MILES

0 5 10 20 KILOMETERS

Kanawha River

Elk River

Coal River

Big Coal River

Coal River

Little

Bluestone River

Greenbrier River

Meadow River

Cherry River

New River

Birch River

Holly

River

Gauley River

22

6 9 19

8

21

20

18

1

14

15

16

17

12 7

13

3

11

5

4

10

2

Summersville

Dam

Bluestone

Bluestone National Dam

Scenic River

New River Gorge

National River

Gauley River National

Recreation Area

Charleston

Gauley

Bridge

Fayetteville

Oak

Hill

Beckley

Princeton

Bluefield

38 o

80 30' o

81o

81 30' o

82 o

38 30' o

80 o

37 30' o

Study area location

OH

PA

WV

VA

EXPLANATION

Major rivers

Site sampled in:

1996

1998

National park boundaries

Kanawha River Basin,

within West Virginia

2002

1 Site map number (Table 1)

0 5 10 20 MILES

0 5 10 20 KILOMETERS

Figure 1. Sampling sites, selected streams, towns, and national parks in the Kanawha River Basin, West Virginia.
4 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

38

o

30'

38o

37o

30'

80o

82o

80o

30' 81o

30'

81o00'

0 5 10 20 MILES

0 10 20 KILOMETERS

0 5 10

0 2.5 5 10 MILES

KILOMETERS

INS T

New River Gorge

National River

Gauley River 

National Recreation Area

Peters

Creek

Manns

Creek

Arbuckle

Creek

Dunloup

Creek

Laurel

Creek Piney

Creek

G al de Creek

6

9

8

3

10

5

4

2

11

Miller

Creek

Sewell

Creek

Mill

Creek

New River

Gauley River

Meadow R vi er

New River

PLANATI N

Abandoned mines

Extent of active mines

National parks

Streams

Sites sampled in:

1996

1998

2002

Figure 2. Coal mines in the Kanawha River Basin, and coal mines, selected streams, and sampling sites in and near the New River Gorge 

National River, West Virginia.
Data Collection and Study Design 5

parts of southern West Virginia (Wiley and Brogan, 2003). 

Because the storm cells were extremely localized, some streams 

were flooded so severely that they were scoured to bedrock 

while flows in adjacent streams remained within the stream 

banks. The extreme nature of flood scouring in some New River 

Gorge tributaries influenced site selection in this study. In 

streams such as Arbuckle Creek and Laurel (Quinnimont) 

Creek, that were severely flooded and scoured to bedrock in 

2001, the small amount of fine sediment that could be found in 

July 2002 was thought to be unrepresentative of fine sediment 

transported under normal conditions. On that basis, these 

streams were not sampled in favor of streams that did not flood, 

regardless of other basin characteristics.

Acknowledgments

Julie A. Archer of Tango, West Virginia, volunteered her 

time to help with data collection during the summer 2002. Jesse 

Purvis, a fisheries biologist with the National Park Service at 

the New River Gorge National River, helped in site reconnaissance and provided helpful comments throughout the study.

Data Collection and Study Design

Data discussed in this report were collected over several 

years (1996-2002) during the course of three separate studies. 

The initial data were collected in 1996 and 1997 as part of a 

reconnaissance study to determine the distribution of trace elements and organic contaminants in bottom sediment of streams, 

which was done as part of the USGS National Water Quality 

Assessment (NAWQA) Program, a broad assessment of water 

quality in the U.S. (Paybins and others, 2001). Stream sites sampled during this reconnaissance study were selected in the 

Kanawha River Basin to characterize important physiographic, 

geologic, and land-use characteristics. Bottom sediment was 

collected at 19 sites (Ward and others, 1998, 1999). At 12 of 

these sites, fish-community data were also collected (Messinger 

and Chambers, 2001). The 1996-1997 NAWQA study indicated 

that PAHs could be an important contaminant of bottom sediment in areas of the Appalachian Plateaus Province where coal 

was mined. 

In 1998, as part of the NAWQA, parts of the Kanawha and 

Allegheny-Monongahela River Basins where coal is mined 

were studied, to characterize changes in water quality since the 

Coal Hydrology Program ended in 1981 (Ehlke and others, 

1982; Paybins and others, 2001; Chambers and Messinger, 

2001). At 16 stream sites, bottom-sediment samples were collected and analyzed for PAHs (fig. 1; table 1). At nine of these 

16 sites, fish-community data were also collected (Messinger 

and Chambers, 2001). The PAH data from the 1998 study have 

not been published previously, but were an important consideration in planning the 2002 study, so they are presented and discussed here. Total 1980-1995 coal production, and other landuse characteristics, have been published for the areas drained by

all the streams sampled in this study (Chambers and Messinger, 

2001).

For the current (2002) study, bottom-sediment samples 

were collected at five sites in the New River Gorge National 

River and Gauley River National Recreation Area during July 

and August 2002 and analyzed for PAHs. At these sites, semipermeable membrane devices (SPMDs) were used to assess the 

bioavailability of PAHs in the streams during a 5-week period.

Bottom Sediment

All bottom-sediment samples were collected from the top 

2 centimeters of depositional areas that appeared to have been 

continuously underwater for the previous year (Shelton and 

Capel, 1993). At each site, a composite sediment sample was 

collected from ten or more depositional areas, on both sides of 

the stream, by dipping sediment with a teflon scoop into a glass 

bowl. The sample was homogenized, and sediment with a grainsize diameter smaller than 2 mm was rubbed through a pesticide-grade, methanol-rinsed stainless steel sieve into a glass jar, 

refrigerated, and shipped to the USGS National Water-Quality 

Laboratory within two days. All equipment used to collect and 

process sediment samples was washed and triple-rinsed in 

deionized water, then rinsed in methanol, and wrapped in aluminum foil until samples were collected.

Samples were analyzed for PAHs at the USGS National 

Water-Quality Laboratory, according to methods described by 

Furlong and others (1996). Surrogate compounds were added to 

the sample prior to extraction to verify method recoveries. Surrogate recoveries were within limits considered acceptable 

according to criteria cited by Furlong and others (1996). 

The Method Reporting Limit (MRL), or the smallest measured concentration of a constituent that may be reliably 

reported using a given analytical method, was 50 g/kg for the 

1996-1997 reconnaissance study, 5 g/kg for the 1998 regional 

coal-mining study, and varied by compound for the 2002 study. 

The method detection limit (MDL), the minimum concentration 

of a substance that can be measured and reported with 99 percent confidence that the analyte concentration is greater than 

zero, was 5 g/kg for the 1996-1997 reconnaissance study, 1 

g/kg for the 1998 regional coal-mining study, and varied by 

compound for the 2002 study. Concentrations of analytes that 

were less than the MRL but greater than the MDL were qualified as estimates. If a compound was not detected above the 

MDL, it was reported as less than the MRL. For example, a 

sample from 1998 with an estimated concentration of 2 g/kg 

of a constituent probably contained more of that constituent 

than a sample from 1998 with a reported concentration of <5 

g/kg.

No field blanks were used in any of these studies, because 

sediment certified as free of organic compounds was not available. Duplicate samples were collected concurrently at two sites 

in the 1998 regional coal-mining study, Kellys Creek at Cedar 

Grove and Sewell Creek at East Rainelle. The average difference in PAH concentrations was 23 percent for the samples
6 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

from Kellys Creek, and 49 percent for the samples from Sewell 

Creek; the standard deviation among average differences in 

PAH concentrations was 17 percent for the samples from Kellys 

Creek and 12 percent for the samples from Sewell Creek. Part 

of the high relative difference among the duplicate samples 

from Sewell Creek can be explained by low concentrations of 

the PAHs. However, concentrations of 8 of 26 PAH compounds 

from the Sewell Creek site were reported as estimates because 

they were less than the MRL, although the average relative difference among estimated values was less (42 percent) than 

among measured values (52 percent).

Semipermeable Membrane Devices

Semipermeable membrane devices (SPMDs) were 

obtained from Environmental Sampling Technologies (EST) 

Laboratories in St. Joseph, Missouri. The SPMD is composed 

of low-density polyethylene (LDPE) lay-flat tubing filled with 

high purity synthetic triolein, which represents a major portion 

of the lipid in fish (Huckins and others, 1990). Hydrophobic 

molecules that can pass through openings in the membrane are 

preferentially dissolved and retained in the lipid. SPMDs are not 

meant to estimate the approximate concentrations of organic 

contaminants in fish, but rather to estimate the amount of a contaminant available for uptake by animals.

Table 1. Sampling sites in the Kanawha River Basin, West Virginia, and their map numbers, station numbers, and years sampled 

Site Map number 

(Figure 1) Station number Year[s] sampled

Camp Creek upstream from Mash Fork near Camp Creek 1 373017081080230 1998

Piney Creek near McCreery 2 375041081054201 1996, 2002

New River at Thurmond 3 03185400 1996, 2002

Dunloup Creek near Thurmond 4 375635081051601 2002

Manns Creek near Cunard 5 380001081013001 2002

Mill Creek near Hopewell 6 380715081045001 1998

North Fork Cherry River at Highway 39 Bridge 7 381312080234339 1998

Peters Creek near Lockwood 10 03191500 1996

Peters Creek near Lyonsville 11 381500081023101 2002

Sewell Creek at East Rainelle 8 375826080455339 1998

Miller Creek at Nallen 9 380624080521601 1998

Kellys Creek at Cedar Grove 12 381313081253739 1998

Cabin Creek at Dry Branch 13 381056081280839 1998

Davis Creek upstream from Trace Fork at Davis Creek 17 382032081423439 1998

Laurel Fork at Hacker Valley 14 384119080260139 1998

Left Fork Holly River near Replete 15 03195250 1998

Birch River at Boggs 16 382811080383339 1998

Sandlick Creek near Arnett 18 374928081245239 1998

Laurel Creek below Hopkins Fork at Hopkins Fork 19 380516081382139 1998

Spruce Laurel Fork at Clothier 20 375645081482339 1998

Hewitt Creek at Jeffrey 21 375814081493339 1998

Big Horse Creek at Altman 22 380952081520839 1998
PAHs in Bottom Sediment in Kanawha River Basin Streams, 1996-2002 7

The SPMDs were shipped from EST Laboratories in clean, 

sealed metal paint cans. When deployed, they were suspended 

in the water column in streams in anchored, stainless steel 

cages. Deployment locations were chosen to minimize visibility 

to passers-by. At four stream sites, SPMDs were deployed for 

one-week, two-week, and five-week intervals (table 2). At the 

fifth site, New River at Thurmond, three SPMDs were deployed 

and one was retrieved after one week; the other two were gone 

from the site at the next visit. 

All SPMDs were lightly or moderately biofouled on 

retrieval, which probably slightly decreased the absorption of 

PAHs. SPMDs were returned to their cans after collection, and 

the cans were sealed, frozen, and stored until SPMD collection 

was complete. They were shipped, chilled, to EST. SPMDs 

were cleaned, dialyzed in hexane, and 5 mL extracts were prepared by EST. 

SPMD extracts were analyzed by the USGS National 

Water-Quality Laboratory. The instrumental analysis of the 

SPMD extracts is slightly modified from the sediment analysis 

procedure; parent PAHs were separated from their alkylated 

homologues, alkylated PAHs were identified according to the 

parent compound and the number of alkyl substitutions, but 

individual alkylated PAH homologues were not identified (Jana 

Iverson, U.S. Geological Survey National Water-Quality Laboratory, written commun., 2002). The MRL for the SPMD samples was 25 ng/g. As with the sediment samples, concentrations 

of analytes were estimated for values that were below the MRL 

but above the method detection limit, which was 1 ng/g, and 

these values are qualified as estimates. If a compound was not 

detected above the method detection limit, it was reported as 

less than the MRL.

SPMDs efficiently sequester PAHs and other organic compounds from the air, and therefore are easily contaminated by 

brief exposure to airborne PAHs, potentially even while an 

SPMD is exposed to air while being deployed. Because of this, 

for each SPMD deployed in the stream, a second SPMD was 

used as a trip blank. Each trip blank was exposed to the air while 

the deployed SPMD was moved from its can to the stream at 

deployment, from the stream to its can at retrieval, and analyzed 

according to the same procedure as the environmental SPMDs. 

One trip blank, for the SPMD deployed at Manns Creek near 

Cunard for two weeks, apparently was contaminated; concentrations of 31 PAHs were estimated for this blank at concentrations exceeding those estimated for the SPMD deployed in the 

stream. Naphthalene was measured in this blank at a concentration above the MRL. Naphthalene was also measured in the trip 

blank for the SPMD deployed at Dunloup Creek for five weeks; 

it was not measured above the MRL, however, in either of the 

environmental SPMDs these blanks were meant to check. The 

concentrations of PAHs in SPMDs discussed in this report were 

obtained by subtracting the concentration measured or estimated for the trip blank from the concentration measured or 

estimated for the environmental SPMD.

PAHs in Bottom Sediment in Kanawha River 

Basin Streams, 1996-2002

During 1996-1998, as part of the NAWQA Program’s 

study of the Kanawha River Basin, the USGS did two surveys 

of PAHs in stream-bottom sediment (Paybins and others, 2001). 

The first was a reconnaissance study of streams throughout the 

Kanawha River Basin of North Carolina, Virginia, and West 

Virginia. To determine which contaminants from a broad suite 

of organic compounds and trace metals were present, streams 

representing important land uses and physiographic and geological settings were sampled throughout the study area. 

The second stream-bottom sediment contaminant survey 

was a component of a study done in 1998 to determine status 

Table 2. Deployment dates and durations for semipermeable membrane devices

Site

Deployment 

time (in 

weeks)

Deployment 

date

Retrieval 

date

Piney Creek 

near McCreery

1 6/18/2002 6/25/2002

Piney Creek 

near McCreery

2 6/18/2002 7/2/2002

Piney Creek 

near McCreery

5 6/18/2002 7/18/2002

Dunloup Creek 

near Thurmond

1 6/18/2002 6/25/2002

Dunloup Creek 

near Thurmond

2 6/18/2002 7/2/2002

Dunloup Creek 

near Thurmond

5 6/18/2002 7/22/2002

New River at 

Thurmond

1 6/17/2002 6/24/2002

Manns Creek 

near Cunard

1 6/17/2002 6/24/2002

Manns Creek 

near Cunard

2 6/17/2002 7/1/2002

Manns Creek 

near Cunard

5 6/17/2002 7/19/2002

Peters Creek 

near Lyonsville

1 7/3/2002 7/10/2002

Peters Creek 

near Lyonsville

2 7/3/2002 7/18/2002

Peters Creek 

near Lyonsville

5 7/3/2002 8/7/2002
8 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

and trends in the effects of coal mining on water quality 

throughout a region in the Central Appalachians (Paybins and 

others, 2001). This study was done in parts of the Kanawha, 

Allegheny, and Monongahela River Basins, on streams draining 

basins where mineable coal was present. Stream basins represented a gradient of mining intensity, and included some where 

no coal had been mined. PAH concentrations were measured in 

stream-bottom sediment from some sites in the Kanawha River 

Basin, but not from any sites in the Allegheny or Monongahela 

River Basins. 

Kanawha River Basin Reconnaissance Study, 1996-

1997

Bottom sediment from 19 streams in the Kanawha River 

Basin was sampled during 1996 and 1997 to determine the distribution of PAHs and other contaminants (Messinger and 

Chambers, 1998; Ward and others, 1997, 1998; Paybins and 

others, 2001). The study area has previously been described 

(Messinger and Hughes, 2000). Six of the 12 PAHs for which 

criteria were available were found in concentrations exceeding 

those at which the Canadian Council of Ministers of the Environment (1999) found harmful effects to aquatic life to be probable (the Probable Effects Level, or PEL). The other six were 

found in concentrations exceeding those at which harmful 

effects were found to be minimal (the Threshold Effects Level, 

or TEL) (table 3) (Paybins and others, 2001). Some of the sites 

where the highest PAH concentrations were measured drained 

some of the most heavily mined subbasins in the study unit, 

although not all basins that yielded high PAH concentrations 

were heavily mined. The highest concentrations of PAHs measured (as a sum of measured and estimated concentrations of 

individual compounds) during any of the three studies were 

found in the 1996 sample from Peters Creek near Lockwood, a 

site on a stream that drains into the Gauley River National Recreation Area from a heavily mined basin. 

In the 1996-1997 data, log-transformed total PAH concentration in bottom sediment was significantly correlated with the 

proportion of fish with external anomalies (R2 = 0.43, p = 0.03). 

The external anomalies assessed included DELT (deformities, 

erosion [both dermal and fin], lesions, and apparent tumors) 

anomalies, which can be caused by exposure to toxic contaminants (Barbour and others, 1999); external parasites are 

assessed as part of the NAWQA Program, but were not included 

in this regression analysis.

Regional Coal-Mining Study, 1998

To further investigate these findings, bottom sediment 

samples were collected for PAH analysis during a regional 

study of stream quality in the coal region (table 4. p. 15). PAH 

data were collected at 16 sites in the coal region in the Kanawha

River Basin. When PAH and fish data from nine of those sites 

where fish data were collected were combined with the 1996-97 

data, the relation between PAH concentrations and the proportion of fish with external anomalies (excluding parasites) was 

weaker than the relation from the 1996-1997 data, but was significant (R2 = 0.321, p = 0.01, with one outlying site excluded).

Among the sites sampled in the regional coal mining 

study, summed PAH concentrations ranged from 360 to 36,000 

g/kg. The correlation between coal production and the sum of 

PAH concentrations in bottom sediment was significant (R2 = 

0.596, p < 0.001). The five sites on streams that drained basins 

with coal production exceeding 20 t/mi2 were among the six 

sites with the highest summed PAH concentrations. Field crews 

observed a substantial amount of sand- or finer-sized coal particles in bottom sediment and benthic invertebrate samples collected from many streams, particularly those draining heavily 

mined areas. 

Generally, PAHs in particulate coal are thought not to be 

bioavailable, based principally on the results of a toxicological 

study in saltwater (Chapman and others, 1996). However, the 

high PAH concentrations and the correlation of PAH concentrations with fish anomalies were of concern. Several possible 

explanations might have reconciled the apparent contradictions 

in the correlation between PAH concentrations and fish anomalies, the correlation between PAHs and coal production, and 

Table 3. Probable effects level (PEL)1 and threshold effects level (TEL)1

for 12 polycyclic aromatic hydrocarbons. 

[PAH, polycyclic aromatic hydrocarbon; concentrations are in micrograms per 

kilogram]

1Source—Canadian Council of Ministers of the Environment, 1999

PAH PEL TEL

Acenaphthene 88.9 6.71

Acenaphthylene 128 5.87

Anthracene 245 46.9

benzo[a]anthracene 385 31.7

Benzo[a]pyrene 782 31.9

Chrysene 862 57.1

Dibenzo[a,h]anthracene 135 6.22

Fluoranthene 2,355 111

Fluorene 144 21.2

Naphthalene 391 34.6

Phenanthrene 515 41.9

Pyrene 875 53
PAHs in Bottom Sediment in Kanawha River Basin Streams, 1996-2002 9

PAHs in coal not being bioavailable. The PAHs might not have 

been, or might not primarily have been, from coal. PAHs in coal 

might have been bioavailable in freshwater systems. The PAHs 

in sediments might not have caused the fish anomalies themselves, but instead have been a marker for another stressor that 

was not measured. The correlation between PAH concentrations and fish anomalies might have been spurious, and merely 

a statistical artifact. The current study is an attempt to reconcile 

these contradictions and narrow down possible explanations.

New River Gorge and Gauley River National 

Recreation Area Study, 2002

PAH concentrations measured in 2002 were generally 

greater than median concentrations from the two previous studies, but less than the 75th percentile of concentrations measured 

in those studies (table 5, p. 18). For the 24 PAHs measured in 

this study, all measurements at all sites (except for six measurements from Manns Creek near Cunard) exceeded the medians 

from the two previous studies. The lowest concentrations measured in 2002 for 22 of the 24 PAHs were in the sample from 

Manns Creek near Cunard. The highest concentrations of 17 

PAHs, including 11 of the 12 for which criteria were available, 

were measured in the sample from New River near Thurmond. 

The highest concentration of four PAHs, including one (naphthalene) for which criteria were available, was measured in the 

sample from Peters Creek near Lyonsville, and the highest concentration of three PAHs was measured in the sample from 

Dunloup Creek near Thurmond.

For the twelve PAHs for which criteria were available, the 

bottom sediment concentration of only one PAH at one site, 

phenanthrene at New River at Thurmond, exceeded the PEL. 

PAH concentrations less than the TEL were measured in the 

sample from Manns Creek near Cunard, for five of the twelve 

PAHs for which criteria were available, and in the sample from 

Piney Creek near McCreery, for one PAH. All other PAH measurements from 2002 were between the TEL and PEL. 

Direct comparison of summed PAH concentrations 

between the 1996 and 2002 samples from Piney Creek near 

McCreery and New River at Thurmond would not have been 

valid because the samples were analyzed with different detection limits. Linear regression of the detected analytes in common between the two samples (non-detected PAHs were 

excluded from the analysis) showed a weaker correlation 

between the Piney Creek samples (R2 = 0.726, p < 0.001) than 

between the samples from the New River at Thurmond (R2 = 

0.870, p < 0.001). The Peters Creek samples, from different 

sites on Peters Creek, had a weaker correlation (R2 = 0.577, p < 

0.001) than the Piney Creek samples. To put the strength of 

these correlations in context, all of the correlations among the 

three New River tributary sites sampled in 2002 were stronger 

(R2 ranging between 0.905 and 0.946; p < 0.001) than the strongest correlation between the 1996 and the 2002 samples, than 

for New River at Thurmond. The correlations between Peters 

Creek and the three New River tributary sites were stronger (R2

= 0.808, 0.828, 0.838; p < 0.001) than the correlation between 

the 1996 and 2002 samples from Piney Creek near McCreery. 

Three of the correlations between the 2002 samples from Thurmond and the smaller stream sites were the weakest among the 

2002 samples (R2 ranging between 0.732 and 0.798; p < 0.001), 

although the correlation between Dunloup Creek and New 

River at Thurmond was stronger (R2 =0.838; p < 0.001). The 

sampling technique is intended to characterize the fine-grained 

bottom sediment that would have been transported within the 

previous year (Shelton and Capel, 1993), so it is not particularly 

surprising that samples from the same stream several years later 

would be more weakly correlated than samples from streams 

near each other collected in the same year.

Possible Sources of PAHs in Bottom Sediment

Efforts to distinguish sources of PAHs found in sediment 

have often concentrated on distinguishing between PAHs from 

petroleum and PAHs from combustion (Yunker and others, 

2002; Stark and others, 2003). Only a few times, however, have 

researchers attempted to distinguish coal from combustion, or 

coal from petroleum, as sources of PAHs in sediment (Short and 

others, 1999; Hostetler and others, 1999). The rationale used to 

develop most of the metrics for distinguishing petroleum from 

combustion is differential rates of persistence in the environment among different PAH parent compounds or between parent compounds and alkylated homologues (Yunker and others, 

2002). It would seem to suggest that these metrics could be useful in distinguishing PAHs from any mature sources such as 

petroleum or coal, from PAHs from recent sources, such as 

combustion of wood or fossil fuels.

However, when applied to coal, these metrics give results 

that are at best ambiguous. Values of these metrics overlap 

between coal and other plausible PAH sources in these basins, 

including some combustion sources. Additionally, most of the 

available information on the PAH composition of coal is from a 

single study, which was limited in scope to 27 samples from 

representative coal seams of Washington (Barrick and others, 

1984). PAH-source metrics (Yunker and others, 2002), applied 

to bottom-sediment data from the Kanawha River Basin, generally did not indicate a combustion source was predominant for 

most basins. Beyond that, they were contradictory, complex, 

and did not clearly indicate what the sources were of most 

PAHs measured in these studies, possibly because of the limited 

available information of the composition of the aromatic fraction of coal. Coal was probably one of the major sources of 

PAHs measured in bottom sediment in this study, and the most 

compelling evidence is that particulate coal is often visible in 

sediment samples or sand bars in these streams.
10 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

PAH Bioavailability in New River Gorge 

National River and Gauley River National 

Recreation Area streams, 2002

Only 3 PAHs were measured in SPMDs in only 4 of 13 

SPMDs at concentrations high enough to report without qualifiers (exceeding the MRL, 25 g/g) (table 6, p. 20). Fluoranthene and pyrene were measured at concentrations less than 

twice the MRL in the 5-week SPMDs from Dunloup Creek near 

Thurmond and Piney Creek near McCreery. Naphthalene was 

measured at a concentration slightly greater than the MRL in the 

1-week SPMD from New River at Thurmond. 

Some PAHs were detected at concentrations less than the 

MRL for all SPMDs, and estimated concentrations were 

reported for these. The 5-week SPMD from Piney Creek near 

McCreery had the largest sum of estimated and measured PAH 

concentrations of any SPMD. The 1-week SPMD from New 

River at Thurmond, the only SPMD that was retrieved from that 

site, had the largest sum of PAHs of any 1-week SPMD, which 

indicates that New River at Thurmond may have had more bioavailable PAHs than any of the other sites. No SPMD from 

Manns Creek near Cunard had a concentration of PAHs exceeding that from any of the other SPMDs from this study. The ranks 

of sites in the sum of PAH concentrations in SPMDs was not the 

same as their ranks in total PAHs in sediment. The relative error 

in these measurements was high as a result of the low PAH concentrations in the SPMDs relative to the MRL—most measurements were reported as estimated concentrations—which might 

affect the ranks.

SPMDs have the capacity to take up large amounts of 

PAHs if dissolved PAHs are present (Huckins and others, 1996, 

1999). On the basis of uptake rate constants determined by 

Luellen and Shea (2002), estimates of PAH concentrations in 

SPMDs exposed for seven days to the lowest dissolved concentrations of selected PAHs that had been shown to have significant adverse biological effects (Germain and others, 1993) 

ranged between four and six orders of magnitude greater than 

the PAH concentrations measured in this study (table 7). Sustained dissolved PAH concentrations in streams were therefore 

much lower than concentrations that have significant biological 

effects. 

SPMDs effectively detect episodic increases in organic 

contaminants, although a particular SPMD concentration of a 

compound could be the result of a brief exposure to a relatively 

high concentration of the compound, a prolonged exposure to a 

relatively low concentration of the compound, or an intermediate exposure to an intermediate concentration of the compound 

(Huckins and others, 1990). One way to assess the potential for 

significant episodic exposure of SPMDs to contaminants is to 

determine the time that an SPMD under ideal conditions for 

uptake might have been exposed to a biologically important

Table 7. Maximum polycyclic aromatic hydrocarbon (PAH) concentrations measured in semipermeable membrane devices (SPMDs) in streams 

managed by the National Park Service in West Virginia in 2002, with the lowest dissolved concentrations at which the PAHs had significant adverse biological effects, and estimates of the concentrations those PAHs would reach in SPMDs under exposure to the stated dissolved concentration at 20o

C for the time the SPMD was deployed

[SPMD, semipermeable membrane device; g/L, microgram per liter; ng/g, nanograms per gram]

Compound Threshold dissolved 

concentration1

 ( g/L)

1From Germain and others (1993)

Estimated SPMD concentration 

at threshold2 (ng/g)

2Determined using uptake rates from Luellen and Shea (2002)

Maximum observed SPMD 

concentration1

 (ng/g)

Deployment 

time2 (weeks)

Acenaphthene 60 1,000 5.6 1

Anthracene 6.6 1,100 2.6 5

Benzo[a]anthracene 5.0 850 5.4 5

Benzo[a]pyrene 5.0 540 3.2 5

Benzo[k]fluoranthene 0.2 21.5 3.3 5

Fluoranthene 38 7,300 39.5 5

Fluorene 125 8,000 4.7 2

Naphthalene 10 480 54.2 2

Phenanthrene 8.0 560 17.2 2

Pyrene 91 20,000 43.8 5
PAH Bioavailability in New River Gorge National River and Gauley River National Recreation Area streams, 2002 11

contaminant concentration. Germain and others (1993) published concentrations of several PAHs at which acute toxic 

effects (effects caused by exposure to a contaminant for less 

than four days) were observed for some aquatic organisms. 

Exposure for about 80 seconds of an SPMD under ideal uptake

conditions to benzo[a]pyrene at 1 g/L, a concentration at 

which acute toxic effects were observed in aquatic vertebrates, 

would have resulted in the maximum concentration of 

benzo[a]pyrene estimated in this study (table 8). For the other 

five PAHs for which data on acute toxic effects were available, 

the maximum exposure time under ideal uptake conditions at 

the lowest concentration for which acute toxic effects to aquatic 

vertebrates were reported ranged from less than 1 second to 

about 7 seconds. PAH concentrations reported to cause acute 

toxic effects to aquatic invertebrates were generally lower than 

those for aquatic vertebrates. Exposure for about 8 minutes of 

an SPMD under ideal uptake conditions to benzo[k]fluoranthene at 0.2 g/L, a concentration at which acute toxic effects 

were observed to aquatic invertebrates, would have resulted in 

the maximum concentration of benzo[k]fluoranthene estimated 

in this study (table 8). For the other seven PAHs for which data 

on acute toxic effects were available, the maximum exposure 

time under ideal uptake conditions at the lowest concentration 

for which acute toxic effects to aquatic invertebrates were 

reported ranged from less than 1 second to about 18 seconds. 

This comparison of observed PAH concentrations in 

SPMDs to estimated concentrations and exposure times has 

limitations. Four of the possible problems include the following: (1) All the SPMDs that were deployed for this study were 

affected by moderate biofouling. Biofouling decreases PAH 

uptake by SPMDs, but moderate biofouling only decreases 

uptake moderately (Huckins and others, 1996). (2) The uptake 

rate constants published by Luellen and Shea (2002) included 

error terms as high as 21 percent of the rates. (3) The most 

recent review that compiled threshold and acute toxicity concentrations was published in 1993 (Germain and others, 1993). 

That study attempted to be as comprehensive as possible, and as 

a result, included some inconsistencies such as publishing a 

concentration at which acute lethal effects were observed that 

was lower than the concentration of the same compound at 

which acute sublethal effects were observed. Such inconsistencies suggest, and Germain and others (1993) point out, that the 

best available information on PAH toxicity is limited and may 

not be relevant to common environmental conditions. (4) The 

available toxicity data were obtained by exposing organisms to 

extremely high concentrations of single PAHs (Germain and 

others, 1993). Effects of low concentrations of PAHs, or of mixtures of PAHs, could be greatly different. Nevertheless, the differences are large between the observed PAH concentrations in 

SPMDs, and the concentrations estimated for SPMDs

Table 8. Maximum observed polycyclic aromatic hydrocarbon (PAH) concentration in semipermeable membrane devices (SPMDs), threshold 

concentration at which acute toxic effects were observed in aquatic vertebrates and invertebrates, and maximum exposure times under ideal 

uptake conditions for the observed concentrations in the SPMDs to be reached in a solution at the threshold concentration of the PAH

[ng/g, nanograms per gram; ng/L, nanograms per liter; min:sec, time in minutes and seconds]

PAH

Maximum 

observed 

concentration in 

SPMD (ng/g)

Lowest concentration 

producing acute 

effects, vertebrates1

(ng/L)

1From Germain and others (1993)

Exposure time at 

acute threshold, 

vertebrates2

(min:sec)

2Determined using uptake rates from Luellen and Shea (2002)

Lowest concentration 

producing acute 

effects, invertebrates1

(ng/L)

Exposure time at 

acute threshold, 

invertebrates2

(min:sec)

Acenaphthene 5.6 580,000 <0:01 60,000 0:02

Anthracene 2.6 6,600 :07 10,000 :05

Benz[a]anthracene 5.4 -- -- 10,000 :10

Benzo[a]pyrene 3.2 1,000 1:29 5,000 :18

Benzo[k]fluoranthene 3.3 -- -- 200 7:45

Fluoranthene 39.5 -- -- 45,000 :14

Fluorene 4.7 820,000 <:01 212,000 <:01

Naphthalene 54.2 1,600,000 :01 1,000,000 :01

Phenanthrene 17.2 234,000 :01 96,000 :03

Pyrene 43.8 -- -- 91,000 :07
12 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

exposed to aquatic concentrations of PAHs known to be harmful 

to aquatic life, and indicate that the concentration of bioavailable PAHs was low in the streams that were studied in 2002.

The bioavailable portion of PAHs in streams in and near 

the New River Gorge appears to have been small during the 

summer of 2002. This is consistent with the idea that fine coal 

particles are the source of much of the PAH in bottom sediment 

of streams in this area. This suggests that the apparent relation 

between external fish anomalies and bottom-sediment PAHs in 

the mining region of the Kanawha River Basin may be spurious, 

or that PAHs are a marker for other stressors. Further investigation into the causes of external fish anomalies in this area could 

concentrate on other possible stressors. 

Summary and Conclusions

Polycyclic aromatic hydrocarbons, or PAHs, are a group 

of organic compounds, many of which are toxic or carcinogenic. PAHs do not ionize and are only slightly soluble in water. 

PAHs in aquatic systems do not accumulate in fish tissue and 

are not considered to pose a direct risk to humans who eat fish 

from water bodies contaminated with PAHs. However, PAHs in 

high concentrations present a threat to aquatic life. PAHs were 

measured in bottom sediment in streams of the Kanawha River 

Basin in 1996-1998 in concentrations at which adverse effects 

to aquatic life are thought to be likely. One site in the New River 

Gorge National River and another site in the Gauley River 

National Recreation Area were among those where PAH concentrations were of concern. 

Data discussed in this report were collected over several 

years (1996-2002) by the U.S. Geological Survey in three studies. The initial data were collected in 1996 and 1997 as part of 

a reconnaissance study of the distribution of trace elements and 

organic contaminants in bottom sediment of streams, which was 

done as part of the National Water Quality Assessment 

(NAWQA) Program, a broad assessment of water quality in the 

United States. Six of the 12 PAHs for which criteria were available were found in concentrations exceeding those at which the 

Canadian Council of Ministers of the Environment (1999) 

found harmful effects to aquatic life to be probable (the Probable Effects Level, or PEL), and the other six were found in concentrations exceeding those at which harmful effects were 

found to be minimal (the Threshold Effects Level, or TEL). 

Some of the sites where the greatest PAH concentrations were 

measured drained some of the most heavily mined subbasins in 

the study unit, although not all basins yielding high PAH concentrations were heavily mined. The highest concentrations of 

summed PAHs measured during any of the three studies were 

found in the 1996 sample from Peters Creek near Lockwood, a 

site on a stream that drains into Gauley River National Recreation Area from a heavily mined basin.

In 1998, also as part of NAWQA, a study was done in parts 

of the Kanawha and Allegheny-Monongahela River Basins 

where coal is mined, to characterize changes in water quality 

since the Coal Hydrology Program ended in 1981. The relation 

between the sum of PAH concentrations and the proportion of 

fish with external anomalies (excluding parasites) was weak but 

significant (R2 = 0.321, p = 0.01, with one outlying site 

excluded) among all sites where fish communities and bottom 

sediment were sampled. The correlation between coal production and the sum of PAH concentrations in bottom sediment was 

significant (R2 = 0.596, p < 0.001), and the five sites on streams 

that drained basins with coal production exceeding 20 tons per 

square mile were among the six sites with the highest summed 

PAH concentrations. Field crews observed a substantial amount 

of sand- or finer-sized coal particles in bottom sediment and 

benthic invertebrate samples collected from streams, particularly those draining heavily mined areas. Generally, PAHs in 

particulate coal are thought not to be bioavailable. However, the 

high PAH concentrations, and the correlation of PAH concentrations and fish anomalies, were of concern. 

Bottom sediment samples were collected at five sites in the 

New River Gorge National River and Gauley River National 

Recreation Area in July-August 2002 and analyzed for PAHs. 

At these sites, semipermeable membrane devices (SPMDs) 

were used to assess the bioavailability of PAHs in the stream 

during a 5-week period. PAH concentrations measured in 2002 

were generally greater than median concentrations from the two 

previous studies, but less than the 75th percentile of concentrations measured in those studies. For the twelve PAHs for which 

criteria were available, the bottom sediment concentration of 

only one PAH at one site, phenanthrene at New River at Thurmond, exceeded the Probable Effects Level (PEL). PAH concentrations less than the Threshold Effects Level (TEL) were 

measured in the sample from Manns Creek near Cunard, for 

five of the twelve PAHs for which criteria were available, and 

in the sample from Piney Creek near McCreery, for one PAH. 

All other PAH measurements from 2002 were between the TEL 

and PEL.

Three PAHs were measured at concentrations greater than 

the Method Reporting Limit (MRL) (25 g/g) in only 3 of 13 

SPMDs. Some PAHs were detected at concentrations less than 

the MRL for all SPMDs, and estimated concentrations were 

reported for these. The 5-week SPMD from Piney Creek near 

McCreery had the largest sum of estimated and measured PAH 

concentrations of any SPMD. The 1-week SPMD from New 

River at Thurmond, the only SPMD that was retrieved from that 

site, had the largest sum of PAHs of any 1-week SPMD, which 

indicates that New River at Thurmond may have had more bioavailable PAHs than any of the other sites. No SPMD from 

Manns Creek near Cunard had a concentration of PAHs exceeding that from any of the other SPMDs from this study. Estimates 

of PAH concentrations in SPMDs that would have been 

exposed in a laboratory for seven days to the lowest dissolved 

concentrations of selected PAHs that had been shown to have 

significant adverse biological effects ranged between two and 

four orders of magnitude greater than the PAH concentrations 

measured in this study. The low concentration of bioavailable 

PAHs measured suggests that coal may be the primary source 

of PAHs in the study area, and indicates that the apparent rela-
Literature Cited 13

tion between external fish anomalies and bottom-sediment 

PAHs in the mining region of the Kanawha River Basin may be 

spurious, or that PAHs may be a marker for other stressors.

Literature Cited

Agency for Toxic Substances and Disease Registry, 1995, Toxicological profile for polycyclic aromatic hydrocarbons 

(PAHs): U.S. Department of Health and Human Services, 

Public Health Service, accessed July 30, 2003, at URL http:/

/www.atsdr.cdc.gov/toxprofiles/tp69.html.

American Whitewater, 2003, River guide: accessed August 25, 

2003, at URL http://www.americanwhitewater.org/rivers/

state/WV/.

Barbour, M.T., Gerritsen, J., Snyder, B.D., and Stribling, J.D., 

1999, Rapid bioassessment protocols for use in streams and 

wadeable rivers—periphyton, benthic macroinvertebrates 

and fish, second edition: U.S. Environmental Protection 

Agency 841-B-99-002, variously paged. Accessed September 2, 2003, at URL http://www.epa.gov/owow/monitoring/

rbp/

Barrick, R.C., Furlong, E.T., and Carpenter, Roy, 1984, Hydrocarbon and azaarene markers of coal transport to aquatic sediments: Environmental Science and Technology, vol. 18, no. 

11, p. 846-854.

Baumann, P.C., Mac, M.J., Smith, S.B., and Harshbarger, J.C., 

1991, Tumor frequencies in walleye (Stizostedian vitreum) 

and brown bullhead (Ictalurus nebulosus) and sediment contaminants in tributaries of the Laurentian Great Lakes: Canadian Journal of Fisheries and Aquatic Science, vol. 48, no. 9, 

p. 1804-1810.

Canadian Council of Ministers of the Environment, 1999, 

Canadian sediment quality guidelines for the protection of 

aquatic life: Winnipeg, Publication 1299, 4 p.

Chambers, D.B., and Messinger, Terence, 2001, Benthic macroinvertebrate communities and their response to selected 

environmental factors in the Kanawha River Basin, West 

Virginia, Virginia, and North Carolina: U.S. Geological 

Survey Water-Resources Investigations Report 01-4021, 52 

p.

Chapman, P.M., Downie, J., Maynard, A., 1996, Coal and 

deodorizer residues in marine sediment, contaminants or pollutants: Environmental Toxicology and Chemistry, vol. 15, 

no. 5, p. 638-642.

Ehlke, T.A., Runner, G.S., and Downs, S.C., 1982, Hydrology 

of Area 9, Eastern Coal Province, West Virginia: U.S. Geological Survey Open-File Report 81-803, 63 p.

Furlong, E.T., Vaught, D.G., Merten, L.M., Foreman, W.T., 

and Gates, P.M., 1996, Methods of analysis by the U.S. Geological Survey National Water-Quality Laboratory; determination of semivolatile organic compounds in bottom sediment by solvent extraction, gel permeation chromatographic 

fractionation, and capillary-column gas chromatography/

mass spectrometry: U.S. Geological Survey Open-File 

Report 95-719, 67 p.

Germain, Andre, Perron, Francine, and Van Coillie, Raymond, 

1993, PAH in the environment— fate, ecotoxicty and regulations, supporting document no. 3: Environment Canada, 

Montreal, Quebec.

Hostettler, F.D., Kvenvolden, K.A., Rosenbauer, R.J., and 

Short, J.W., 1999, Aspects of the Exxon Valdez oil spill--A 

forensic study and a toxics controversy, in Morganwalp, 

D.W., and Buxton, H.T., eds., U.S. Geological Survey Toxic 

Substances Hydrology Program--Proceedings of the Technical Meeting, Charleston, South Carolina, March 8-12, 1999-

-Volume 2 of 3--Contamination of Hydrologic Systems and 

Related Ecosystems: U.S. Geological Survey WaterResources Investigations Report 99-4018B, p. 135-144.

Huckins, J.N., Petty, J.D., Lebo, J.A., Orazio, C.E., Prest, H.F., 

Tillitt, D.E., Ellis, G.S., Johnson, B.T., and Manuweera, 

G.K., 1996, Semipermeable membrane devices (SPMDs) for 

the concentration and assessment of bioavailable organic 

contaminants in aquatic environments, in Ostrander, G., ed., 

Techniques in aquatic toxicology: Boca Raton, FL, CRCLewis Publishers, p. 625-655.

Huckins, J.N., Petty, J.D., Orazio, C.E., Lebo, J.A., Clark, R.C., 

Gibson, V.L., Gala, W.R., and Echols, K.R, 1999, Determination of uptake kinetics (sampling rates) by lipid-containing 

semipermeable membrane devices (SPMDs) for polycyclic 

aromatic hydrocarbons (PAHs) in water: Environmental Science and Technology vol. 33, p. 3918-3923.

Huckins, J.N., Tubergen, M.W., and Manuweera, G.K., 1990, 

Semipermeable membrane devices containing model lipid— 

a new approach to monitoring the availability of lipophilic 

contaminants and estimating their bioconcentration potential: Chemosphere vol. 20, p. 533-552.

Irwin, R.J., Van Mouwerik, Mark, Stevens, Lynette, Seese, 

M.D., and Basham, Wendy, 1998, Environmental contaminants encyclopedia: National Park Service, Water Resources 

Division, Fort Collins, Colo., accessed August 25, 2003, at 

URL http://www.nature.nps.gov/toxic/.

Luellen, D.A., and Shea, Damian, 2002, Calibration and field 

verification of semipermeable membrane devices for measuring polycyclic aromatic hydrocarbons in water: Environmental Science and Technology vol. 36, p. 1791-1797.

Messinger, Terence, and Chambers, D. B., 1998, Selected contaminants in bed sediment in the Kanawha River Basin [abs]: 

Proceedings of the West Virginia Academy of Science, v. 70 

no. 1, p. 20.

Messinger, Terence, and Chambers, D.B., 2001, Fish communities and their relation to environmental factors in the 

Kanawha River Basin, West Virginia, Virginia, and North 

Carolina, 1997-98: U. S. Geological Survey Water Resources 

Investigation Report 01-4048, 51 p.

Messinger, Terence, and Hughes, C.A., 2000, Environmental 

setting and its effects on water quality, Kanawha-New River 

Basin--West Virginia, Virginia, North Carolina: U S. Geological Survey Water Resources Investigation Report 00-

4020, 75 p.
14 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

Moore, J.W. and Ramamoorthy, S., 1984, Aromatic hydrocarbons-polycyclics, in Organic Chemicals in Natural 

Waters—Applied Monitoring and Impact Assessment: 

Springer-Verlag, New York, p. 67-87.

 Paybins, K.A., Messinger, Terence, Eychaner, J.H., Chambers, 

D.B., and Kozar, M.D., 2001, Water quality in the KanawhaNew River Basin, West Virginia, Virginia, and North Carolina, 1996-98: U.S. Geological Survey Circular 1202, 36 p. 

Sander, L. C. and Wise, S.A., 1997, Polycyclic aromatic hydrocarbon structure index: National Institute of Standards and 

Technology Special Publication 922, accessed July 30, 2003 

at http://ois.nist.gov/pah/. 

Shelton, L. R., and Capel, P. D., 1993, Guidelines for the collecting and processing samples of stream bed sediment for 

analysis of trace elements and organic contaminants for the 

National Water-Quality Assessment Program: U S. Geological Survey Open-File Report 94-458, 20 p.

Short, J.W., Kvenvolden, K.A., Carlson, P.R., Hostettler, F.D., 

Rosenbauer, R.J., and Wright, B.A., 1999, Natural hydrocarbon background in benthic sediment of Prince William 

Sound—coal vs. oil: Environmental Science and Technology, vol. 33, no. 1, p. 34-42.

Smith, S.B., Blouin, M.A., and Mac, M.J., 1994, Ecological 

comparisons of Lake Erie tributaries with elevated incidence 

of fish tumors: Journal of Great Lakes Research, vol. 20, no. 

4, p. 701-716.

Stark, Allen, Abrajano, Teofilo Jr., Hellou, Jocelyne, and Metcalf-Smith, J.L., 2003, Molecular and isotopic characterization of polycyclic aromatic hydrocarbon distribution and 

sources at the international segment of the St. Lawrence 

River: Organic Geochemistry, vol. 34, no. 1, p. 225-237. 

Streitweiser, Andrew, Heathcock, C.H., and Kosower, E.M., 

1992, Introduction to organic chemistry: MacMillan Publishing Company, New York, 1256 p.

U.S. Environmental Protection Agency, 2003, Water quality 

standards: accessed July 21, 2003, at URL http://

www.epa.gov/waterscience/standards/.

Ward, S.M., Taylor, B.C., and Crosby, G.R., 1998, Water 

resources data, West Virginia, water year 1997: U.S. Geological Survey Water-Data Report WV-97-1, 392 p.

Ward, S.M., Taylor, B.C., and Crosby, G.R., 1999, Water 

resources data, West Virginia, water year 1998: U.S. Geological Survey Water-Data Report WV-98-1, 476 p.

Wiley, J.B., and Brogan, F.D., 2003, Comparison of peak discharges among sites with and without valley fills for the July 

8-9, 2001, flood in the headwaters of Clear Fork, Coal River 

Basin, mountaintop coal-mining region, Southern West Virginia: U.S. Geological Survey Open-File Report 03-133, 12 

p.

Yunker, M.B., Macdonald, R.W., Vingarzan, Roxanne, Mitchell, R.D., Goyette, Darcy, and Sylvestre, Stephanie, 2002, 

PAHs in the Fraser River basin—a critical appraisal of PAH 

ratios as indicators of PAH source and composition: Organic 

Geochemistry, vol. 33, no. 4, p. 489-515.
Table 4 15

Table 4. Polycyclic aromatic hydrocarbon concentrations measured in fine bottom sediment at selected sites in coal-mining areas in the Kanawha River Basin in West Virginia, in July 1998[All concentrations are in g/kg; E, estimated; <, less than; bold type, exceeding the Probable Effects Level1; italic type, between the Threshold Effects Level1 and Probable Effects Level1]

1Canadian Council of Ministers of the Environment (1999)

Site Sampling date Acenaph- thene Acenaph- thylene Anthracene Benz[a]- Anthracene Benzo[a]- pyrene Chrysene Dibenz[a,h]- anthracene Fluoran- thene

Camp Creek upstream from Mash Fork near Camp Creek

7/20/98 E0.84 E1.5 E3.2 10 10 19 E2.3 22

Mill Creek near Hopewell 7/28/98 E1.2 11 19 54 45 54 7.5 74North Fork Cherry River at Highway 39 Bridge

7/23/98 5.0 E1.6 E1.9 6.5 6.3 14 E1.5 9.7

Sewell Creek at East Rainelle 7/22/98 E3.4 E4.1 13 38 35 58 6.7 98Miller Creek at Nallen 7/23/98 E2.3 E1.4 5.0 6.1 6.5 20 E3.1 7.2Kellys Creek at Cedar Grove 7/13/98 12 25 64 190 195 284 57 243Cabin Creek at Dry Branch 7/13/98 27 46 108 242 198 400 56 278Davis Creek upstream from Trace Fork at Davis Creek

7/13/98 E1.6 E3.6 7.2 32 33 42 5.6 80

Laurel Fork at Hacker Valley 7/14/98 E2.1 14 12 44 53 62 11 70Left Fork Holly River near Replete 7/14/98 5.0 E1.7 E2 6.5 6.0 16 E1.5 11Birch River at Boggs 7/16/98 E1.6 E3.7 5.6 31 26 64 7.6 44Sandlick Creek near Arnett 7/23/98 E4.5 24 43 163 100 239 31 306Laurel Creek below Hopkins Fork at Hopkins Fork

7/21/98 15 24 32 131 148 188 30 192

Spruce Laurel Fork at Clothier 7/29/98 5.8 5.0 8.9 56 38 118 13 48Hewitt Creek at Jeffrey 7/14/98 5.2 11 25 82 93 119 29 130Big Horse Creek at Altman 7/14/98 E0.82 5.0 5.0 19 22 20 E4 25
16 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River Table 4. Polycyclic aromatic hydrocarbon concentrations measured in fine bottom sediment at selected sites in coal-mining areas in the Kanawha River Basin in West Virginia, in July 1998 [All concentrations are in g/kg; E, estimated; <, less than; bold type, exceeding the Probable Effects Level; italic type, between the Threshold Effects Level and Probable Effects Level] Site Fluorene Naphtha- lene Phen- anthrene Pyrene 1,2- dimethyl- naphthalene 1,6-dimethyl- naphthalene 1- methyl- 9H- fluorene 1-methyl- phenanth- rene 1- methyl- pyrene 2,3,6- trimethyl- naphthalene Camp Creek upstream from Mash Fork near Camp Creek E2.8 E3.1 26 19 5.0 E2.3 5.0 E3.6 E1.6 E1.5 Mill Creek near Hopewell E4.8 E3.7 51 58 E0.94 E2.9 E3.1 5.9 E3 E3.0 North Fork Cherry River at Highway 39 Bridge E0.87 E3.4 19 9.4 E0.7 E3.0 E2.0 6.9 E1.3 E2.3 Sewell Creek at East Rainelle 7.0 9.8 65 75 E1.1 5.0 E3.4 7.8 E3.8 E3.2 Miller Creek at Nallen 7.6 63 56 12 16 54 10 27 9.4 24 Kellys Creek at Cedar Grove 51 633 701 252 146 479 75 182 69 206 Cabin Creek at Dry Branch 105 432 836 300 202 606 155 302 89 291 Davis Creek upstream from Trace Fork at Davis Creek E3.3 20 43 67 E4.2 11 E2.6 7.9 5.1 E4.6 Laurel Fork at Hacker Valley E4.3 18 71 76 8.7 11 E3 17 8.2 6.5 Left Fork Holly River near Replete E2.2 8.1 23 14 E2.5 8.9 E2.6 9.3 E2.8 5.4 Birch River at Boggs 11 71 134 44 22 77 16 50 11 36 Sandlick Creek near Arnett 19 15 181 252 5.9 37 21 66 22 21 Laurel Creek below Hopkins Fork at Hop- kins Fork 36 385 575 155 118 329 67 167 90 152 Spruce Laurel Fork at Clothier 27 173 278 63 64 253 48 105 45 94

Hewitt Creek at Jeffrey 19 199 280 116 56 157 29 87 29 61Big Horse Creek at Altman E1.9 19 28 23 E4.9 12 E1.9 6.2 E3.0 5.4
Table 4 17

Table 4. Polycyclic aromatic hydrocarbon concentrations measured in fine bottom sediment at selected sites in coal-mining areas in the Kanawha River Basin in West Virginia, in July 

1998—Continued

[All concentrations are in g/kg; E, estimated; <, less than; bold type, exceeding the Probable Effects Level; italic type, between the Threshold Effects Level and Probable Effects Level]

Site 2,6-dimethyl- naphthalene 2-methyl- anthracene 4,5-methylene- phenanthrene Benzo[b]- fluoranthene Benzo[g,h,i]- perylene Benzo[k]- fluoranthene Coronene Indeno- [1,2,3-c,d]- pyrene

Camp Creek upstream from Mash Fork near Camp Creek

6.0 E1.2 E2.2 13 5.9 8.4 E1.5 7.4

Mill Creek near Hopewell 5.8 5.1 9.6 38 21 34 E3.1 28North Fork Cherry River at Highway 39 Bridge

E4.3 5.0 5.0 8.6 E4.7 5.1 <5 E4.4

Sewell Creek at East Rainelle 8.8 E3.4 7.7 40 20 32 E2.2 26Miller Creek at Nallen 58 E1.6 5.0 8.5 12 E2.7 E2.8 E2.8Kellys Creek at Cedar Grove 385 42 60 186 337 123 E74.6 119Cabin Creek at Dry Branch 567 45 5.0 235 180 132 E38.0 127Davis Creek upstream from Trace Fork at Davis Creek

15 E2.9 5.7 32 22 28 E3.0 25

Laurel Fork at Hacker Valley 13 E4.1 9.6 44 37 35 E7.7 39Left Fork Holly River near Replete 9.8 E1.1 E2.5 7.9 6.6 E4.8 E2.3 E4.1Birch River at Boggs 75 E4.2 5.0 32 31 13 E7.8 17Sandlick Creek near Arnett 58 14 33 114 86 93 E11.4 96Laurel Creek below Hopkins Fork at Hopkins Fork 281 31 35 173 132 102 E23.9 68Spruce Laurel Fork at Clothier 191 26 5.0 43 77 18 25 18Hewitt Creek at Jeffrey 137 18 50 84 228 55 E56.0 66Big Horse Creek at Altman 13 E2.1 E2.8 20 20 14 E2.8 15
18 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River Table 5. Polycyclic aromatic hydrocarbon concentrations in fine stream-bottom sediment at selected sites in the New River Gorge National River and Gauley River National Recreation Area, West Virginia, in 1996 and July 2002 [All concentrations are in g/kg; <, less than; E, estimated; --, not measured; bold type, exceeding the Probable Effects Level1; italic type, between the Threshold Effects Level1 and the Probable Effects Level] Site Sampling date Acenaphthene Acenaphthylene Anthracene Benzo[a]- Anthracene Benzo[a]- pyrene Chrysene Dibenz[a,h]- anthracene Fluoranthene Piney Creek near McCreery 9/24/96 <50 <50 E17.2 64.3 51.6 210 <50 136 Piney Creek near McCreery 7/18/02 28.9 12.0 25.3 74.8 66.2 124 13 129 New River at Thurmond 10/4/96 <50 E45 74.0 200 160 240 56 370 New River at Thurmond 7/22/02 50.2 82.2 190 334 252 336 50.6 820 Dunloup Creek near Thur- mond 7/22/02 35.6 54.6 76.7 169 138 276 35.8 332 Manns Creek near Cunard 7/19/02 15.0 11.3 15.5 44.2 37.4 89.2 8.5 110 Peters Creek near Lockwood 9/25/96 100 39.7 371 822 754 1,570 <50 1,630 Peters Creek near Lyonsville 8/7/02 14.4 39.8 55 268 166 249 26 282

1Canadian Council of Ministers of the Environment (1999)

Site Fluorene Naphthalene Phenanthrene Pyrene

1,2-

dimethylnaphthalene 1,6-dimethyl- naphthalene 1-methyl- 9H- Fluorene 1-methyl- phenanthrene 1-methyl- pyrene

Piney Creek near McCreery E37.4 85 320 137 <50 E45.6 E47.8 114 E24.9Piney Creek near McCreery 37.7 72 242 114 10.3 87.3 62.1 55.7 11.9New River at Thurmond 57.0 74 290 310 E18 78 59 84 64New River at Thurmond 101 111 764 603 23.9 102 65.5 101 45.9Dunloup Creek near Thurmond 50.5 93.8 420 282 25.6 107 74.4 130 39.4Manns Creek near Cunard 19.4 35 144 87.4 12.2 80 37.2 54.8 11Peters Creek near Lockwood 120 419 2,270 1,570 E41.5 188 73.2 684 206Peters Creek near Lyonsville 23 140 242 316 62.3 214 40.3 99.8 52.1
Table 5 19

Table 5. Polycyclic aromatic hydrocarbon concentrations in fine stream-bottom sediment at selected sites in the New River Gorge National River and Gauley River National Recreation Area, West Virginia, in 1996 and July 2002 —Continued[All concentrations are in g/kg; <, less than; E, estimated; --, not measured; bold type, exceeding the Probable Effects Level; italic type, between the Threshold Effects Level and the Probable Effects Level]

Site

2,3,6-

trimethylnaphthalene 2,6-dimethyl- naphthalene 2-methyl- anthracene 4,5- methylene- phenanthrene Benzo[b]- fluoranthene Benzo[g,h,i]- perylene Benzo[k]- fluoranthene Coronene Indeno- [1,2,3-c,d]- pyrene

Piney Creek near McCreery E47.2 123 <50 <50 79.4 60.7 61 -- E43Piney Creek near McCreery 49.8 168 8 10.3 110 48.9 57.9 E16.2 56.8New River at Thurmond 62 140 59 E44 190 97 150 -- 170New River at Thurmond 83.5 156 55 109 338 140 150 E36.2 191Dunloup Creek near Thurmond 87.7 169 27.6 29.8 199 90.7 109 E33.5 115Manns Creek near Cunard 46.4 102 6.2 9.4 60.8 27.9 28 E10.4 29.9Peters Creek near Lockwood 75.3 206 66.8 400 564 238 451 -- 176Peters Creek near Lyonsville 79.3 154 21.3 10.7 260 98.2 121 E26.3 99.4
20 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

Table 6. Polycyclic aromatic hydrocarbon concentrations measured in semipermeable membrane devices in streams in the New River 

Gorge National River and Gauley River National Recreation Area, 2002

[wk, week; E, estimated; <, less than]

Site Deployment 

time Naphthalene 2-ethylnaphthalene 

2,6-dimethylnaphthalene1,6-dimethylnaphthaleneAcenaphthylene 

Piney Creek near McCreery 1 wk E3.2 E1.1 E1.6 E1.7 <25

Piney Creek near McCreery 1 wk blank <25 <25 <25 <25 <25

Piney Creek near McCreery 2wk 54.2 E1.8 E1.7 E1.6 E4.3

Piney Creek near McCreery 2wk blank <25 <25 <25 <25 <25

Piney Creek near McCreery 5 wk E1.9 E1.0 E1.6 E1.6 E1.2

Piney Creek near McCreery 5 wk blank <25 <25 <25 <25 <25

New River at Thurmond 1 wk 31.9 E1.5 E1.5 E1.3 E2.4

New River at Thurmond 1 wk blank E9.6 <25 E1.4 E1.3 <25

Dunloup Creek near Thurmond 1 wk E3.2 E1.0 E1.9 E2.1 <25

Dunloup Creek near Thurmond 1 wk blank E9.8 E1.2 E1.4 E1.3 <25

Dunloup Creek near Thurmond 2wk E2.5 E1.1 E1.7 E1.8 E1.2

Dunloup Creek near Thurmond 2wk blank E6.3 <25 E1.3 E1.2 <25

Dunloup Creek near Thurmond 5 wk E2.4 E1.1 E1.7 E1.7 E1.2

Dunloup Creek near Thurmond 5 wk blank 97.5 E1.7 E1.7 E1.4 E8.3

Manns Creek near Cunard 1 wk E1.9 E1.1 E1.3 E1.2 <25

Manns Creek near Cunard 1 wk blank E10.1 E1.1 E1.4 E1.4 <25

Manns Creek near Cunard 2wk E1.3 E1.0 E1.3 E1.1 <25

Manns Creek near Cunard 2wk blank 102 E1.8 E1.5 E1.1 E23.7

Manns Creek near Cunard 5 wk E1.0 <25 E1.2 E1.3 <25

Manns Creek near Cunard 5 wk blank E8.5 <25 E1.2 E1.2 <25

Peters Creek near Lyonsville 1 wk E2.1 E1.1 E1.5 E1.4 <25

Peters Creek near Lyonsville 1 wk blank E11.4 E1.1 E1.4 E1.4 <25

Peters Creek near Lyonsville 2wk E0.96 E1.1 E1.5 E1.6 <25

Peters Creek near Lyonsville 2wk blank E12.8 E1.2 E1.4 E1.4 <25

Peters Creek near Lyonsville 5 wk E0.96 <25 E1.5 E1.6 <25

Peters Creek near Lyonsville 5 wk blank E11.6 E1.2 E1.4 E1.4 <25
Table 6 21

Table 6. Polycyclic aromatic hydrocarbon concentrations measured in semipermeable membrane devices in streams in the New River 

Gorge National River and Gauley River National Recreation Area, 2002—Continued

[wk, week; E, estimated; <, less than]

Site

1,2-

dimethylnaphthalene

Acenaphthene

2,3,6-

trimethylnaphthalene

Fluorene 1-methyl-9HFluorene Phenanthrene 

Piney Creek near McCreery <25 E3.8 E1.4 E3.5 E1.8 E9.2

Piney Creek near McCreery <25 <25 <25 E1.0 E1.4 E1.8

Piney Creek near McCreery E1.0 E4.3 E1.5 E4.7 E2.0 E19.2

Piney Creek near McCreery <25 <25 <25 <25 E1.5 E2.0

Piney Creek near McCreery E1.0 E3.6 E1.6 E4.0 E2.0 E17.9

Piney Creek near McCreery <25 <25 <25 <25 E1.4 E1.8

New River at Thurmond E0.9 E2.1 E1.3 E3.0 E1.7 E10.2

New River at Thurmond E0.8 E0.5 E1.2 E1.1 <25 E1.9

Dunloup Creek near Thurmond E0.8 E6.2 E1.4 E4.9 E1.9 E15.9

Dunloup Creek near Thurmond <25 E0.6 E1.2 E1.2 E1.5 E2.0

Dunloup Creek near Thurmond <25 E5.8 E1.5 E4.5 E1.8 E18.3

Dunloup Creek near Thurmond <25 E0.5 E1.2 E1.2 E1.8 E2.2

Dunloup Creek near Thurmond E0.9 E5.2 E1.6 E4.2 E2.0 E24.0

Dunloup Creek near Thurmond E0.9 E1.5 E1.2 E3.5 E1.7 E13.4

Manns Creek near Cunard E0.9 E0.6 E1.2 E1.2 E1.5 E2.5

Manns Creek near Cunard E1.0 <25 E1.2 E1.1 E1.5 E1.9

Manns Creek near Cunard E1.0 E0.7 E1.3 E1.2 E1.5 E2.9

Manns Creek near Cunard <25 E1.4 E1.2 E4.1 E1.7 E18.5

Manns Creek near Cunard <25 E0.7 E1.3 E1.4 E1.6 E4.2

Manns Creek near Cunard <25 <25 E1.2 E1.1 E1.4 E1.6

Peters Creek near Lyonsville <25 E2.3 E1.4 E2.2 E1.6 E6.9

Peters Creek near Lyonsville <25 <25 <25 E1.1 E1.4 E1.7

Peters Creek near Lyonsville <25 E1.8 E1.7 E2.1 E1.9 E7.9

Peters Creek near Lyonsville E0.8 E0.5 E1.2 E1.2 E1.5 E1.9

Peters Creek near Lyonsville <25 E2.2 E1.8 E2.4 E2.0 E10.7

Peters Creek near Lyonsville <25 <25 E1.2 E1.2 E1.6 E2.2
22 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

Table 6. Polycyclic aromatic hydrocarbon concentrations measured in semipermeable membrane devices in streams in the New River 

Gorge National River and Gauley River National Recreation Area, 2002—Continued

[wk, week; E, estimated; <, less than]

Site Anthracene 2-methylanthracene 

4,5-

methylenephenanthrene

1-methylphenanthrene Fluoranthene Pyrene 

Piney Creek near McCreery E1.6 <25 E2.3 E1.8 E8.4 E8.0

Piney Creek near McCreery <25 <25 <25 E1.6 E1.8 E1.7

Piney Creek near McCreery E2.4 E2.3 E4.0 E2.4 E21.8 E22.3

Piney Creek near McCreery <25 <25 <25 E1.6 E1.8 E1.6

Piney Creek near McCreery E2.6 E6.1 E5.6 E2.9 41.3 45.5

Piney Creek near McCreery <25 <25 <25 E1.5 E1.8 E1.7

New River at Thurmond E1.7 <25 E2.5 E1.9 E11.2 E5.9

New River at Thurmond <25 <25 <25 E1.5 E1.7 E1.6

Dunloup Creek near Thurmond E2.2 <25 E2.9 E2.2 E12.4 E8.6

Dunloup Creek near Thurmond <25 <25 <25 <25 E1.7 E1.6

Dunloup Creek near Thurmond E2.1 <25 E3.7 E2.5 E19.7 E14.3

Dunloup Creek near Thurmond <25 <25 <25 E1.6 E1.7 E1.7

Dunloup Creek near Thurmond E2.2 <25 E5.5 E3.2 43.1 31.9

Dunloup Creek near Thurmond E2.3 <25 E2.0 E1.8 E4.6 E4.4

Manns Creek near Cunard <25 <25 <25 E1.6 E2.9 E2.1

Manns Creek near Cunard <25 <25 <25 E1.6 E1.6 E1.6

Manns Creek near Cunard <25 <25 <25 E1.6 E3.7 E2.6

Manns Creek near Cunard E2.7 <25 E3.8 E1.8 E11.8 E12.9

Manns Creek near Cunard <25 <25 E1.9 E1.8 E6.3 E4.1

Manns Creek near Cunard <25 <25 <25 E1.5 E1.6 E1.5

Peters Creek near Lyonsville E1.5 <25 E2.1 E1.8 E5.8 E4.3

Peters Creek near Lyonsville <25 <25 <25 E1.5 E1.7 E1.6

Peters Creek near Lyonsville E1.6 <25 E2.4 E2.4 E9.1 E7.5

Peters Creek near Lyonsville <25 <25 <25 E1.6 E1.8 E1.6

Peters Creek near Lyonsville E1.7 <25 E3.0 E3.0 E17.3 E14.5

Peters Creek near Lyonsville <25 <25 <25 E1.6 E1.7 E1.6
Table 6 23

Table 6. Polycyclic aromatic hydrocarbon concentrations measured in semipermeable membrane devices in streams in the New River 

Gorge National River and Gauley River National Recreation Area, 2002—Continued

[wk, week; E, estimated; <, less than]

Site

1-

methylpyrene 

Benz[a]-

anthracene Chrysene Benzo[b]-fluoranthene 

Benzo[k]-

fluoranthene 

Benzo[e]-

pyrene 

Piney Creek near McCreery E1.6 E2.0 E2.4 E2.5 E1.7 E1.6

Piney Creek near McCreery <25 <25 <25 <25 <25 <25

Piney Creek near McCreery E2.0 E3.2 E6.5 E4.2 E2.9 E2.8

Piney Creek near McCreery <25 <25 <25 <25 <25 <25

Piney Creek near McCreery E2.8 E5.4 E13.6 E7.4 E3.3 E4.8

Piney Creek near McCreery <25 <25 <25 <25 <25 <25

New River at Thurmond E1.5 E2.9 E1.7 E2.1 E1.5 E1.3

New River at Thurmond <25 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond E1.5 <25 E2.0 E2.1 E1.5 E1.4

Dunloup Creek near Thurmond <25 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond E1.7 E2.2 E3.3 E2.8 E1.9 E1.7

Dunloup Creek near Thurmond <25 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond E2.1 E3.4 E8.2 E4.5 E2.5 E2.9

Dunloup Creek near Thurmond E1.6 E2.2 E1.1 E2.0 E1.7 E1.3

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard E1.8 E2.5 E1.7 E2.9 E2.2 E2.1

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville E1.5 <25 <25 <25 <25 <25

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville E1.8 E2.0 E1.6 E2.1 E1.5 E1.4

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville E2.8 E2.8 E3.4 E2.9 E1.8 E1.9

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25
24 PAHs in Bottom Sediment and Bioavailability in Streams in the New River Gorge National River

Table 6. Polycyclic aromatic hydrocarbon concentrations measured in semipermeable membrane devices in streams in the New River 

Gorge National River and Gauley River National Recreation Area, 2002—Continued

[wk, week; E, estimated; <, less than]

Site Benzo[a]-

pyrene Perylene Benzo[g,h,i]-perylene

Indeno 

[1,2,3-c,d] 

pyrene

Dibenzo[a,h]

anthracene Coronene 

Piney Creek near McCreery E2.4 <25 <25 <25 <25 E0.76

Piney Creek near McCreery <25 <25 <25 <25 <25 <25

Piney Creek near McCreery E2.7 E1.2 E1.2 E2.4 <25 E0.86

Piney Creek near McCreery <25 <25 <25 <25 <25 <25

Piney Creek near McCreery E3.2 E1.5 E1.7 E2.7 E1.6 E0.59

Piney Creek near McCreery <25 <25 <25 <25 <25 <25

New River at Thurmond E2.4 <25 <25 <25 <25 E0.97

New River at Thurmond <25 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond E2.3 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond <25 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond E2.4 <25 E1.0 E2.2 <25 <25

Dunloup Creek near Thurmond <25 <25 <25 <25 <25 <25

Dunloup Creek near Thurmond E2.7 <25 E1.2 E2.4 <25 <25

Dunloup Creek near Thurmond E2.4 <25 E0.98 E2.2 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard E3.7 E1.2 E2.9 E3.5 <25 E1.2

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Manns Creek near Cunard <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25

Peters Creek near Lyonsville E2.4 <25 <25 <25 <25 <25

Peters Creek near Lyonsville <25 <25 <25 <25 <25 <25


Literature Cited 27