U.S. Department of the Interior

U.S. Geological Survey

Open-File Report 07–1272

Estimation of Freely-Dissolved Concentrations of 

Polychlorinated Biphenyls, 2,3,7,8-Substituted Congeners 

and Homologs of Polychlorinated Dibenzo-p-dioxins and 

Dibenzofurans in Water for Development of Total Maximum 

Daily Loadings for the Bluestone River Watershed, Virginia 

and West Virginia

Estimation of Freely-Dissolved 

Concentrations of Polychlorinated 

Biphenyls, 2,3,7,8-Substituted Congeners 

and Homologs of Polychlorinated Dibenzop-dioxins and Dibenzofurans in Water 

for Development of Total Maximum 

Daily Loadings for the Bluestone River 

Watershed, Virginia and West Virginia

By Robert W. Gale

Open-File Report 2007–1272

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: 2007

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Suggested citation:

Gale, R.W., 2007, Estimation of freely-dissolved concentrations of polychlorinatedbiphenyls, 2,3,7,8-substituted 

congeners and homologs of polychlorinated dibenzo-p-dioxins and dibenzofurans in water for development of total 

maximum daily loadings for the Bluestone River watershed, Virginia and West Virginia: U.S. Geological Survey OpenFile Report 2007–1272, 27 p. 
iii

Contents

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

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

Experimental Method....................................................................................................................................2

SPMD Preparation................................................................................................................................2

SPMD Performance Reference Compounds (PRCs) .............................................................2

Native PCB and PCDD/DF Fortification ....................................................................................3

Field Collection......................................................................................................................................3

Initial Sample Processing...........................................................................................................3

Procedural Internal Standard Fortification and Dialytic Recovery of Contaminants.......3

Sample Preparation..............................................................................................................................4

Secondary Reactive Column Cleanup......................................................................................4

High Performance Size-Exclusion Chromatographic (HP-SEC) Fractionation..................4

High Performance Porous Graphitic Carbon Chromatographic (HP-PGC)

Fractionation ...................................................................................................................4

Low Pressure Basic Alumina Chromatographic (LP-BAC) Fractionation ..........................4

Congener-Specific Polychlorinated Biphenyl Analysis.........................................................4

Polychlorinated Dibenzo-p-Dioxin and Dibenzofuran Analysis ...........................................5

Secondary Sample Preparation—Additional QC Samples...................................................5

Confirmatory Congener-Specific Polychlorinated Biphenyl Analysis ................................5

Quality Assurance and Quality Control .............................................................................................6

Results and Discussion.................................................................................................................................6

SPMD Accumulation of Selected Congeners of Polychlorinated Biphenyls .............................6

SPMD Accumulation of 2,3,7,8-Substituted Congeners and Homologs of Polychlorinated

Dibenzo-p-Dioxins and Dibenzofurans ................................................................................9

SPMD Release of Performance Reference Compounds (PRCs) ................................................10

Calculation of Estimated Concentrations of PCBs, PCDDs, and PCDFs in Water....................11

Concentrations of Selected Congeners of Polychlorinated Biphenyls in Water............11

Concentrations of 2,3,7,8-Substituted Congeners and Homologs of Polychlorinated

Dibenzo-p-Dioxins and Dibenzofurans in Water.....................................................11

Acknowledgments.......................................................................................................................................13

References Cited..........................................................................................................................................13

Tables.............................................................................................................................................................15
iv

Tables

1. SPMD samples deployed and collected from the Bluestone River watershed, 

Tazewell County, Virginia, and Mercer County, West Virginia (Waterbody 

VAS-N36/N37R) .............................................................................................................................7

2. Amounts of total polychlorinated biphenyls (PCBs), total polychlorinated 

dibenzo-p-dioxins (PCDDs) and total polychlorinated dibenzofurans (PCDFs) 

per semipermeable membrane device (SPMD) composite sample for the 

Bluestone River watershed sample set, fall 2005....................................................................8

3. Percentages of performance reference compounds (PRCs) remaining in 

semipermeable membrane device (SPMD) composite samples from the 

Bluestone River watershed sample set, fall 2005..................................................................10

4. Average aOPRC intercept values of performance reference compounds (PRCs), 

maximum and minimum volumes of water sampled, and estimated uncertainties 

in sampling rates for semipermeable membrane device composite samples from 

the Bluestone River watershed sample set, fall 2005...........................................................12

5. Estimated concentrations of selected congeners of polychlorinated biphenyls 

(PCBs) in water from the Bluestone River watershed sample set, fall 2005.....................16

6. Estimated total concentrations in water of polychlorinated biphenyls (PCBs), 

polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans 

(PCDFs) from the Bluestone River watershed sample set, fall 2005 ..................................13

7. Estimated concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins 

(PCDDs) and dibenzofurans (PCDFs), and homologs of dioxins and furans in water 

from the Bluestone River watershed sample set, fall 2005..................................................24
v

Conversion Factors and Datum

Multiply By To obtain

Length

micrometer (μm) 0.00003937 inch (in.)

centimeter (cm) 0.3937 inch (in.)

meter (m) 3.281 foot (ft) 

Area

square meter (m2) 10.76 square foot (ft2) 

square centimeter (cm2) 0.1550 square inch (ft2) 

Volume

microliter (μL) 0.0000002642 gallon (gal)

milliliter (mL) 0.0002642 gallon (gal)

liter (L) 0.2642 gallon (gal)

cubic meter (m3) 264.2 gallon (gal) 

Flow rate

liter per day (L·d-1) 0.2642 gallon per day (gal·d-1) 

Mass

femtogram (fg) 3.527 x 10-17 ounce, avoirdupois (oz)

picogram (pg) 3.527 x 10-14 ounce, avoirdupois (oz)

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

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

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

gram (g) 0.03527 ounce, avoirdupois (oz)

kilogram (kg) 2.205 pound avoirdupois (lb)

Density

gram per cubic centimeter (g/cm3) 62.4220 pound per cubic foot (lb/ft3) 

Concentration

nanogram per gram (ng·g-1) = part per billion (ppb; 109)

milligram per liter (mg·L-1) = part per million (ppm; 106)

microgram per liter (μg·L-1) = part per billion (ppb; 109)

nanogram per liter (ng·L-1) = part per trillion (pptr; 1012)

picogram per liter (pg·L-1) = part per quadrillion (ppq; 1015)

nanogram per milliliter (ng·mL-1) = part per billion (ppb; 109)

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

 °F=(1.8×°C)+32

Concentrations of chemical constituents in water are given in milligrams per liter (mg·L-1). 

micrograms per liter (μg·L-1), nanograms per liter (ng·L-1), picograms per liter (pg·L-1), or 

femtograms per liter (fg·L-1).
vi
Abstract

The Commonwealth of Virginia Department of Environmental Quality, working closely with the State of West 

Virginia Department of Environmental Protection and the U.S. 

Environmental Protection Agency is undertaking a polychlorinated biphenyl source assessment study for the Bluestone 

River watershed. The study area extends from the Bluefield 

area of Virginia and West Virginia, targets the Bluestone River 

and tributaries suspected of contributing to polychlorinated 

biphenyl, polychlorinated dibenzo-p-dioxin and dibenzofuran 

contamination, and includes sites near confluences of Big 

Branch, Brush Fork, and Beaver Pond Creek. 

The objectives of this study were to gather information 

about the concentrations, patterns, and distribution of these 

contaminants at specific study sites to expand current knowledge about polychlorinated biphenyl impacts and to identify 

potential new sources of contamination. Semipermeable 

membrane devices were used to integratively accumulate the 

dissolved fraction of the contaminants at each site. Performance reference compounds were added prior to deployment 

and used to determine site-specific sampling rates, enabling 

estimations of time-weighted average water concentrations 

during the deployed period.

Minimum estimated concentrations of polychlorinated 

biphenyl congeners in water were about 1 picogram per liter 

per congener, and total concentrations at study sites ranged 

from 130 to 18,000 picograms per liter. The lowest concentration was 130 picograms per liter, about threefold greater 

than total hypothetical concentrations from background levels 

in field blanks. Polychlorinated biphenyl concentrations in 

water fell into three groups of sites: low (130–350 picogram 

per liter); medium (640–3,500 picogram per liter; and high 

(11,000–18,000 picogram per liter). Concentrations at the high 

sites, Beacon Cave and Beaverpond Branch at the Resurgence, 

were about four- to sixfold higher than concentrations estimated for the medium group of sites. 

Minimum estimated concentrations of polychlorinated 

dibenzo-p-dioxin and dibenzofuran congeners in water were 

about 0.2 to 1 femtograms per liter. Estimated total concentrations of 2,3,7,8-substituted congeners in water at study sites 

ranged from less than 1 to 22,000 femtograms per liter and 

less than 1 to 2,300 femtograms per liter for polychlorinated 

dibenzo-p-dioxin and dibenzofuran congeners, respectively. 

Total concentrations of 2,3,7,8-substituted congeners in water 

were comprised largely of octachlorodibenzo-p-dioxin and 

dibenzofuran, with less than 10 percent of the total contributed 

by concentrations of other congeners, mainly 2,3,7,8-heptachlorodibenzo-p-dioxin and dibenzofuran.

Of special interest for this study was 2,3,7,8-tetrachlorodibenzo-p-dioxin with a regulatory surface water-quality criterion of 1,200 femtograms per liter. Estimated concentrations in 

water ranged from 0.5 to 41 femtograms per liter. Concentrations in water were less than 5 femtograms per liter at all study 

sites, except the Bluefield Westside Sewage Treatment Plan, 

with an estimated concentration of 41 femtograms per liter.

Estimated total concentrations of homologs of polychlorinated dibenzo-p-dioxins and dibenzofurans in water at 

the study sites ranged from 3,200 to 36,000 femtograms per 

liter and 210–4,800 femtograms per liter, respectively. Again, 

homologs of polychlorinated dibenzo-p-dioxins and dibenzofurans in water were comprised largely of octachlorodibenzop-dioxin and dibenzofuran.

Introduction

The Commonwealth of Virginia Department of Environmental Quality (VADEQ), working closely with the State 

of West Virginia Department of Environmental Protection 

Estimation of Freely-Dissolved Concentrations of 

Polychlorinated Biphenyls, 2,3,7,8-Substituted Congeners 

and Homologs of Polychlorinated Dibenzo-p-dioxins 

and Dibenzofurans in Water for Development of Total 

Maximum Daily Loadings for the Bluestone River 

Watershed, Virginia and West Virginia

By Robert W. Gale
2 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

(WVDEP) and the U.S. Environmental Protection Agency 

(USEPA) is undertaking a polychlorinated biphenyl (PCB) 

source assessment study for the Bluestone River watershed.

This watershed is located in the coalfields of Virginia 

and West Virginia, where historically, over 300 mining 

industry related facilities existed, many of which employed 

PCB-containing oils. Many of these operations have [since] 

closed. Some facilities were located in the remote valleys and 

ridges of the watershed, and other, smaller facilities, were 

home-based operations. The goals of the proposed source 

assessment are to ensure that no site is actively contributing PCBs to the watershed and to provide a baseline for the 

PCB Total Maximum Daily Load (TMDL) study required 

by the Clean Water Act. In the United States, commercially 

used technical mixtures of PCBs are commonly referred to as 

Aroclors® (Mosanto, St. Louis, Mo.) with a naming convention using a four-digit number denoting, first, the ring system 

(12 for biphenyl) and then the average percent chlorination 

(for example, 42 percent) (Frame and others, 1996); PCBs 

are referred to as Aroclors® in many State regulations. Currently, the calculated total PCB surface water-quality criteria 

(SWQC), based on the weight percent of each homolog group 

of the technical PCBs are 1,700 pg·L-1 and 47 pg·L-1 for the 

Commonwealth of Virginia and for West Virginia, respectively 

(Virginia State Water Control Board, 1997; Virginia Water 

Quality Standards, 2006; West Virginia Environmental Quality 

Board, 2000). 

The Bluestone River watershed study is complicated by 

several factors (Lott and Newman, 2005). Most PCB misuse 

and improper disposal occurred decades ago and over a wide 

area. The karst geology of the region moves water from the 

surface through underground pathways near known or suspected PCB contaminated sites. Because of differential loadings of PCBs, differing exposure scenarios, and different target 

organisms, the transport mechanisms and bioaccumulation 

potential for PCBs are different in each watershed and even 

within a sub-watershed. The watershed crosses the Virginia–

West Virginia State Line; tributaries from industrial areas in 

West Virginia enter Virginia and ultimately the Bluestone 

exits Virginia into West Virginia, thus requiring a cooperative 

assessment and TMDL approach to be developed by the Commonwealth of Virginia and the State of West Virginia.

Existing records of PCB related activities of State and 

Federal agencies and previous PCB sampling schemes, PCB 

environmental data, and reports of activity, cleanups, and site 

closures in the watershed have been compiled by the VADEQ. 

Potential PCB sources were identified by personal contacts 

and results of survey forms to gain information about historic 

PCB usage in the watershed; leading to locations of several 

contaminated sites.

The objectives of this study were to gather information 

about the concentrations, patterns, and distribution of selected 

congeners of PCBs, polychlorinated dibenzo-p-dioxins 

(PCDDs), and polychlorinated dibenzofurans (PCDFs) at 

specific study sites to expand current knowledge about PCB 

impacts and to identify potential new sources of contamination. Semipermeable membrane devices (SPMDs) were used 

to integratively accumulate the dissolved fraction of PCBs and 

PCDDs/DFs at each site. Performance reference compounds 

were added to the SPMDs prior to deployment and used to 

determine site-specific sampling rates of SPMDs, enabling 

estimations of time-weighted average (TWA) water concentrations of PCBs and PCDDs/DFs during the deployed period. 

This information will be used by the VADEQ, WVDEP, and 

USEPA to compare TWA concentrations with the SWQC for 

each analyte to determine those analytes potentially exceeding 

the proposed TMDLs being developed for the Bluestone River 

watershed.

Experimental Method

SPMD Preparation

Standard SPMDs (1 m x 2.5 cm x ~70–80 μm thickness, 

1.00 mL 2,3-bis[[(E)-octadec-9-enoyl]oxy]propyl (E)-octadec9-enoate (triolein), each) were deployed and composited for 

this work. Performance reference compound (PRC) loss rates 

equivalent to sampling rates of 2–4 L·d-1 were used to predict 

sampling rates for this study and the compositing required 

to attain these detection limits. The use of six standard 

SPMDs per site was calculated to provide sufficient sampling, 

once composited, to achieve the lowest quantification limit 

required; approximately tenfold less than targeted quantification SWQC for 2,3,7,8-TCDD of 1.2 pg·L-1. 

Semipermeable membrane devices were prepared for the 

VADEQ for deployment at 15 selected sites in the Virginia 

portion of the Bluestone River watershed, two of these sites 

were replicated (n=2) for a total of 17 sampling points. Three 

field blank SPMD composite samples, three fortified field 

blank SPMD composite samples, one fabrication blank SPMD 

composite sample, and one fortified field blank composite 

sample also were prepared. This required preparation and 

addition of PRCs to 150 standard SPMDs. Semipermeable 

membrane device composites also were prepared for the 

WVDEP for deployment at three selected sites in the West 

Virginia portion of the Bluestone River watershed along with 

three field blank samples. The number and configuration 

of the devices necessary to achieve the specified detection 

limits was the same as for VADEQ, six standard SPMDs per 

composite. No fortified field blank SPMD composite samples 

or other quality control (QC) samples were prepared for the 

WVDEP deployment. This required the additional preparation 

and addition of PRCs to 36 standard SPMDs. 

SPMD Performance Reference Compounds 

(PRCs)

Suitable PRCs for the target analytes were selected for 

calibration (Huckins and others, 1999, 2002, 2006). The 
Experimental Method 3

previous deployment used only perdeuterated polycyclic 

aromatic hydrocarbons (PAH-d) (Lott and Newman, 2005), 

which were not considered completely acceptable as PRCs in 

this study because of their potential for photolytic degradation and dissimilarity to the analytes; rather, selected PCB 

congeners (PCB-014, PCB-029, and PCB-050) not found at 

any appreciable level in commercial Aroclors® were used 

here. However, the perdeuterated polycyclic aromatic hydrocarbons (acenaphthylene-d, acenaphthene-d, fluorene-d, 

phenanthrene-d, and pyrene-d) were included here as PRCs for 

comparative purposes.

A volume of 200 mL of purified triolein was required for 

this sample set, allowing enough residual triolein for anticipated SPMD losses and for preparing various QC samples. 

The 200 mL triolein was fortified with a 1,000 ng of each PCB 

and 200 μg of each PAH-d by addition of isooctane solutions 

of the PRC-PCBs and the PRC-PAH-d to triolein and removal 

of the residual isooctane by rotary-evaporation. The PRCPCBs were added at 5.0 ng·SPMD-1 and the PRC-PAH-d were 

added at 1.0 μg·SPMD-1; or 30.0 ng and 6.00 μg per composite, respectively.

Native PCB and PCDD/DF Fortification

Composites of six SPMDs, representing the one fortified 

fabrication blank and the three fortified field blanks were fortified with a mixture of native PCBs and PCDDs/DFs at levels 

near the quantification limits to determine the recovery efficiencies of the overall method. The native PCBs were added as a 

1:1:1:1 mixture of Aroclors® 1242:1248:1254:1260. Current 

estimates of total PCB method background concentrations (as 

the sum of selected congeners) are about 7.5 ng·SPMD-1, or 

45 ng per composite. Therefore, 1,200 ng of Aroclor®1:1:1:1 

was added, to allow quantification above potential background 

levels of PCBs. The PCDDs/DFs were added as a native 

standard solution of the tetra- through octa- chlorinated 2,3,7,8-

substituted congeners. There are no current estimates of PCDD/

DF method background concentrations for SPMDs; however, 

the 1997 Columbia River Study (McCarthy and Gale, 1999) 

reported levels for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) 

of about 1–3 pg·SPMD-1, which would be equivalent to about 

6–20 pg in procedural blanks and in field blanks. Therefore, 240 

pg of 2,3,7,8-TCDD were added; and because the native PCDD/

DF standard solution contains levels of congeners that increase 

with degree of chlorination, the amounts of individual PCDD 

and PCDF congeners added were: Cl4–240 pg; Cl5-7–1,200 pg; 

and Cl8–2,400 pg, respectively.

Field Collection

The extent of the Bluestone River watershed to be sampled was in the Bluefield area of Virginia and West Virginia, 

targeting the Bluestone River and tributaries suspected of contributing to PCB and PCDD and PCDF contamination; including sites near confluences of Big Branch, Brush Fork, and 

Beaver Pond Creek. Fifteen deployment sites were selected by 

the VADEQ and three additional sites selected by the WVDEP. 

Site selection was based on considerations of appropriate site 

availability for SPMD deployment and specific stream conditions at each site. The design of the study required SPMD 

deployments at points where lateral mixing in the flow regime 

of each site was optimized, providing the most representative 

sampling of the stream at both high and low flow periods. The 

coordinates for each sampling point were documented by a 

geographic positioning system. Locations of these points were 

also described relative to existing landmarks, and all pertinent 

information concerning target analytes was compiled by the 

VADEQ as part of this study.

The deployment and collection of SPMDs for this project 

were accomplished by the VADEQ, WVDEP, and USGS 

personnel. These field personnel developed a sampling plan in 

accordance with USGS, VADEQ, and USEPA requirements 

(Standard Operating Procedures Manual, 2003; Water Quality Monitoring Consolidated Guidance, 2004). All deployed 

samples consisted of six standard SPMDs per site. Samples 

were transported to and from the site in precleaned sealed cans 

placed on ice. Field blanks were shipped, transported, and handled in the field in a manner consistent with the actual samples 

(for example, cans were opened and SPMDs were handled). 

All sampling equipment was cleaned prior to sampling and 

cleaned after each use. All samples were stored at -20 °C in 

sealed cans placed in coolers, and were handled under chain 

of custody. The samples were shipped overnight to the USGS 

Columbia Environmental Research Center, where they were 

logged, and stored at -20 °C.

Initial Sample Processing

Processing of SPMD samples consisted of inspection of 

the devices; all observations were noted and discussed with 

the principal investigator. Any punctures or leaking seals were 

resealed and documented. The exterior surface of the each 

SPMD was cleaned to remove any adhering particulates and 

the biofilm.

Procedural Internal Standard Fortification and 

Dialytic Recovery of Contaminants

The Procedural Internal Standard (PIS) solution was 

prepared by combining stock solutions to prepare 12.00 mL 

of a fortification solution containing PCB-155 (2,2’,4,4’,6,6’-

hexachlorobiphenyl) and PCB-204 (2,2’,3,4,4’,5,6,6’-octachlorobiphenyl) at 133 pg·μL-1 and 13C 2,3,7,8- substituted 

PCDDs/DFs at concentrations ranging from 3.33–6.67 pg·μL-1. 

Each SPMD in each composite sample (and in each field 

blank, fortified field blank, fabrication blank, and fortified 

fabrication blank) was opened, fortified with one-sixth (50 μL) 

of the total specified amount of procedural internal standards, 
4 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

and resealed as was performed for the native PCB and PCDD/

DF fortification in the previous section. 

After fortification with PIS or PIS and native analytes and 

resealing, each SPMD was individually dialyzed according to 

established procedures. Hexane dialysis through the low density polyethylene membrane recovers small molecular weight 

target analytes (<1,000 Da) from the triolein reservoir and the 

membrane itself with greater than 99 percent efficiency. All 

dialysates from the individual SPMDs comprising one composited sample were combined, and concentrated in volume to 

6.0 mL (1.0 SPMD-equivalents·mL-1, or SPMD-eq·mL-1). 

Sample Preparation

Secondary Reactive Column Cleanup

Interfering anthropogenic and biogenic compounds in 

dialysates were removed by reaction in a layered sulfuric acidtreated silica gel/potassium hydroxide treated silica gel/silica 

gel column (SASG/KS/SG). The secondary reactive cleanup 

columns were calibrated for the collection of the appropriate 

target analyte fraction (c-PCBs/PCDDs/DFs) using a dichloromethane/hexane solvent scheme. The collected fractions 

were solvent-exchanged to dichloromethane and concentrated 

in volume to 1.00 mL.

High Performance Size-Exclusion 

Chromatographic (HP-SEC) Fractionation

HP-SEC was used to separate the analytes from residual 

higher molecular weight compounds in the reactive cleanup 

fractions. Higher molecular weight compounds are only 

slightly retained and elute prior to most target analytes; also, 

any elemental sulfur, a problematic interference during analysis, is more highly retained than the analytes, and elutes after 

the analyte fraction is collected. The HP-SEC was calibrated 

for the collection of the appropriate analyte fraction (c-PCBs/

PCDDs/DFs). The reactive cleanup fractions were then fractionated by HP-SEC at the rate of six SPMD-equivalents per 

HP-SEC cycle. The collected HP-SEC fractions were solventexchanged to isooctane and concentrated in volume to 1.0 mL.

High Performance Porous Graphitic Carbon 

Chromatographic (HP-PGC) Fractionation

Separation of the PCDDs and PCDFs from PCBs and 

other polyhalogenated hydrocarbons was necessary to remove 

potentially interfering chemicals that typically may be present at concentrations several orders of magnitude greater than 

those of the dioxins and furans, and to thereby achieve the 

required detection limits. The extended-pi systems of planar 

aromatic chemicals (PCDDs/DFs, and non-ortho-substituted 

PCBs) interact very strongly and very specifically with pisystem in the graphitic planes of the porous graphitic carbon, providing a highly selective and efficient fractionation 

mechanism. The HP-PGC was calibrated for the collection of 

the appropriate analytes: (fraction 1) weakly retained monoortho – tetra-ortho-substituted PCBs (c-PCBs); (fraction 2) 

non-ortho-substituted PCBs (not collected); and (fraction 3) 

PCDDs/DFs. The collected c-PCB fractions were concentrated, 

solvent-exchanged to isooctane, and concentrated in volume to 

6.0 SPMD-eq·mL-1 for dual-column gas chromatography with 

electron-capture detection (GC-ECD) analysis. The collected 

PCDD/DF fractions were solvent exchanged to isooctane and 

concentrated in volume to about 0.5 mL for further fractionation by low pressure basic alumina chromatography.

Low Pressure Basic Alumina Chromatographic 

(LP-BAC) Fractionation

Residual PCBs and other polyhalogenated hydrocarbons 

that potentially interfere with the high-resolution mass-spectrometric analysis for PCDDs and PCDFs were minimized by 

chromatographic separation of the resulting HP-PGC PCDD/

DF fractions by LP-BAC. Most polyhalogenated hydrocarbon 

interferences are only slightly retained and elute prior to most 

analytes; also, any remaining biogenic materials may be more 

highly retained than the analytes, and elute after the analyte fraction is collected. The LP-BAC columns were calibrated for the 

collection of the appropriate analyte fraction (PCDDs/DFs) using 

a dichloromethane/cyclohexane solvent scheme. The collected 

LP-BAC fractions were concentrated in volume to about 0.5 mL.

Congener-Specific Polychlorinated Biphenyl 

Analysis

Instrumental internal standards (IIS) were added to each 

c-PCB fraction and the final volume adjusted to 6.0 SPMDeq⋅mL-1. Individual PCB congeners were measured in sample 

fractions by dual-column GC-ECD. Analyses were performed 

using cool on-column capillary injection onto retention gaps 

connected to a 60 m x 0.25 mm x 0.25-μm film thickness 5 

percent phenyl-, 95 percent methylsilicone capillary column, 

and a 60 m x 0.25 mm x 0.25-μm film thickness 50 percent 

phenyl-, 50 percent methylsilicone capillary column, respectively. Potential peaks for PCB congeners were matched and 

identified on one or both GC capillary columns with individual congener standards comprised of two IIS (PCB-030, 

-207), two PIS (PCB-155, -204), 128 PCB congeners found 

in Aroclors® at levels greater then 0.05 weight percent, and 

16 PCB congeners found at less than this level. The capillary 

GC-ECD data were collected, archived in digital form, and 

processed using chromatography data-system software. Up to 

nine levels of calibration for each individual congener were 

used to quantify the targeted congeners. The calibration curve 

covers a concentration range of 0.01–0.03 to 100 ng·mL-1 of 

each congener.
Experimental Method 5

Polychlorinated Dibenzo-p-Dioxin and 

Dibenzofuran Analysis

Instrumental internal standards were added to each 

PCDD/DF fraction and the final volume adjusted to about 

25–50 μL. PCDFs and PCDDs were determined by gas 

chromatography with high-resolution mass spectrometric 

detection (GC-HRMS) by monitoring five sequential mass 

windows of selected ions for the Cl4-8 PCDFs and PCDDs during the chromatographic separation. Analyses were performed 

using heated direct on-column injection onto a retention gap 

connected to a 30 m x 0.15 mm x 0.1-μm film thickness 5 

percent phenyl-, 95 percent methylsilicone capillary column. 

The analytical column was directly interfaced to the MS. The 

HRMS system was tuned to a mass resolution of 10,000 and 

calibrated using perfluorotetradecahydrophenanthrene, and 

mass windows were established for five ion groups and monitored sequentially during the temperature program. Within 

each mass window, the two most abundant ions were measured 

for positive identification and quantification of each analyte; additional ions were monitored for any responses from 

potentially interfering chemicals (for example, Cl5-9 polychlorinated diphenyl ethers, Cl5-7 polychlorinated terphenyls, Cl6-7

polychlorinated naphthalenes, and others), for Cl3-8 dibenzothiophenes, and Cl3-8 phenanthrenes and anthracenes. Isotope 

dilution calibration curves describing the response of each 

native congener (from 0.1 to 1,000 pg·μL-1) to that of a labeled 

procedural internal standard congener were used.

Window switching times were established using a 

window-defining PCDF/PCDD standard mixture; relative 

retention times were then established for polychlorinated 

dibenzothiophenes and other compounds of interest. Chromatographic columns were selected and temperature programmed on the basis that they must resolve 2,3,7,8-TCDD 

from 1,2,3,7/1,2,3,8-TCDD (and from 1,2,3,4-TCDD) by a 

resolution factor of at least 0.5. Column performance was 

verified by analyzing standards of individual components, 

and observing the chromatographic resolution of the TCDDs, 

hexachlorodibenzo-p-dioxins and dibenzofurans (HxCDDs 

and HxCDFs). Similarly, relative retention times for all other 

congeners of interest were evaluated with respect to labeled 

analogs. 

Calibration curves describing the response of each native 

congener to that of a labeled procedural internal standard 

congener were used directly in the calculations, and their 

ranges of values were determined in the calibration procedure. 

Each calibration curve was matched to the range of analyte 

responses in the sample set.

Secondary Sample Preparation—Additional QC 

Samples

Because of the very low concentrations of PCBs that 

were anticipated in these samples, the cleanliness of all equipment was verified prior to any application of the extracts to a 

preparation step. The automated, multi-sample fractionation 

systems, HP-SEC and HP-PGC, were of special concern 

because they could be likely sources of sample carryover 

in preparation work. To minimize the potential for this to 

occur, the following checks were performed and the fractions 

analyzed prior to sample preparation; also, QC samples were 

added to the sample set to demonstrate the [low] levels of carryover throughout the preparation scheme.

The HP-SEC and the HP-PGC systems were demonstrated to be free of PCB background. All injector lines were 

thoroughly cleaned or replaced as necessary. Multiple solvent 

injection cycles were processed to equilibrate each system. 

Then, triplicate solvent blanks were collected and analyzed 

for PCBs. Each system was considered acceptably clean if 

levels of PCBs are less than 50 ng (total) with no single c-PCB 

contributing greater than 1 ng; otherwise, the systems were 

recleaned and further blanks evaluated.

Three separate procedural blanks were incorporated into 

the secondary portion of the sample preparation scheme to 

demonstrate the cleanliness of the post-dialysis part of the 

overall sample preparation plan. These procedural blanks were 

in addition to the procedural blanks previously prepared for 

the field and dialysis portions of this study. These procedural 

blanks were prepared and interspersed throughout the sample 

set, and then processed through the entire secondary scheme: 

secondary reactive cleanup, HP-SEC, HP-PGC, and LP-BAC 

for the PCDD/DF fractions. In addition, individual blanks 

were prepared for each discrete step of the scheme: a) secondary reactive cleanup, b) HP-SEC, c) HP-PGC, and d) LP-BAC; 

these blanks were used to assess and document the relative 

contributions of background PCBs (and PCDDs/DFs) from 

each step of the preparation scheme.

Confirmatory Congener-Specific Polychlorinated 

Biphenyl Analysis

Sample chromatography by dual-column GC-ECD exhibited high levels of interferences by coeluting peaks, which 

limited quantification of PCB-014, PCB-029, and PCB-050, 

the polychlorinated biphenyl congeners selected for use as 

PRCs in this study. All sample and field blank extracts were 

reanalyzed by gas chromatography with quadrupole mass 

spectrometric detection (GC-QMS) using both full-scan and 

selected-ion recording (SIR) for quantification of these congeners. Polychlorinated biphenyl congeners were determined by 

GC-QMS by monitoring selected ions for the Cl1-10 PCBs during the chromatographic separation. Analyses were performed 

using cool on-column injection onto a retention gap connected 

to a 40 m x 0.18 mm x 0.1-μm film thickness 5 percent phenyl-, 95 percent methylsilicone capillary column. The analytical column was directly interfaced to the MS. The MS system 

was tuned to a mass resolution of 1,000 and calibrated using 

perfluorotributylamine, and the mass window was established 

for one ion group encompassing the two most abundant Cl1-10

PCBs and monitored during the temperature program. Within 
6 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

the mass window, the two most abundant ions were measured 

for positive identification and quantification of each analyte. 

Internal standard calibration curves describing the response 

of each congener to that of a procedural internal standard 

congener were used. Additional full-scan mass spectrometric 

analyses were conducted to confirm suspected interferences.

Quality Assurance and Quality Control

An operational QC system of checks was used to control 

and assess the quality of measurements. This system of checks 

was managed by a quality assurance (QA) system that ensures 

that defined standards of quality are being met (at stated levels 

of confidence). The accuracy and precision of environmental 

methods were assessed by utilizing appropriate checks for 

sample preparation and instrumental analysis. The appropriate 

QC sample types were selected on the basis of applicability to 

the objectives of this study and incorporated into the analysis 

plans.

Replicates, fortified field blanks, field blanks, fortified 

fabrication blanks, and fabrication blanks were prepared during the manufacture of SPMDs for deployment. The fortified 

field blanks and the fortified fabrication blanks were fortified 

with native analytes during fabrication. In addition to these 

QC samples, three procedural blanks were prepared to evaluate laboratory background levels of an analyte or background 

interferences with an analyte signal from the preparation 

method; and two fortification verification solutions were prepared to confirm analyte fortification levels.

Results and Discussion

Semipermeable membrane devices for the VADEQ and 

WVDEP parts of this study were prepared together and the 

samplers were shipped to VADEQ on September 13, 2005. 

Sampling began on September 15, 2005, for all VADEQ sites; 

October 1, 2005, for WVDEP Sites 1 and 2, Beacon Cave; 

and October 5, 2005, for WVDEP Site 3, Morris Spring. All 

deployed samples consisted of six standard SPMDs per site. 

Samples were transported to and from the site in precleaned 

sealed cans placed on ice. Field blanks were shipped, transported, and handled in the field in a manner consistent with the 

actual samples. All sampling equipment was cleaned prior to 

sampling and cleaned after each use. Most VADEQ samples 

were collected on November 1, 2005, with VADEQ Site-11, 

Cross-tributary to Beaverpond Branch collected on November 

14, 2005. WVDEP samples for Sites 1 and 2, Beacon Cave, 

were collected on October 29, 2005; WVDEP Site-3, Morris 

Spring was collected on November 14, 2005. All sampling 

devices were retrieved without losses. All samples were stored 

at -20 °C in sealed cans placed in coolers, and were handled 

under chain of custody. Samplers were shipped overnight and 

received at the Columbia Environmental Research Center on 

November 15, 2005. The samples were inventoried, checked, 

and stored at -20°C. The SPMD samples deployed and collected from the Bluestone River watershed, Tazewell County, 

Virginia, and Mercer County, West Virginia (Waterbody VASN36/N37R) are listed in table 1.

The SPMDs from VADEQ and WVDEP were treated 

as one set throughout sample preparation, analysis, and data 

reduction. Initial sample preparation entailed fortifying all 

samples with procedural internal standards, sample dialysis, compositing and concentration, along with preparation 

of quality control samples. Secondary sample preparation 

involved enrichment and purification of the SPMD dialysates 

through a series of cleanup and fractionation steps: secondary 

reactive cleanup, HP-SEC, HP-PGC, and an additional LPBAC step for the PCDD/DF fractions from HP-PGC.

The instrumental analysis plan initially required only two 

analyses: congener-specific PCB analysis by dual-column GCECD, and 2,3,7,8-PCDD/DF/homolog analysis by GC-HRMS. 

However, additional perdeuterated PAH PRCs were incorporated into the study for comparison with the c-PCB PRCs, 

and required a separate analysis. Significant chromatographic 

interferences with the c-PCB PRC results required further 

GC-QMS analyses to obtain more reliable PRC information. 

In addition to unidentified chromatographic interferences, high 

levels of OCPs and PBDEs prompted semiquantitative analysis of the pesticides in these samples. 

SPMD Accumulation of Selected Congeners 

of Polychlorinated Biphenyls

Amounts of total PCBs, PCDDs, and PCDFs accumulated 

by SPMDs at study sites are summarized in table 2. Amounts 

of PCB congeners in the composite samples were adjusted for 

recoveries of procedural internal standards and then corrected 

for background by subtraction of average field blank levels 

of PCBs. Low molecular weight congeners (PCB-001–PCB035) are typically adjusted using PCB-029; however, in this 

study PCB-029 was used as a PRC and therefore its use as a 

PIS was precluded and these congeners were adjusted using 

PCB-155. A reporting limit of 0.03 ng per 6-SPMD composite was established for PCB congeners, with the exception of 

PCB-001, 002, and 003, wherein, a reporting limit of 0.3 ng 

was established. Congeners with coeluting chromatographic 

interferences were flagged, omitted from the final tabulations, 

and were not included in the summations for total amounts of 

PCBs, or in the calculation of PCB concentrations in water. 

Concentrations for chromatographically unresolved PCB 

congeners were calculated from the 5 percent phenyl and the 

50 percent phenyl column information. Concentrations were 

averaged for PCB congeners resolved on both the 5 percent 

phenyl and the 50 percent phenyl columns. High levels of four 

organochlorine pesticides were determined to coelute, each 

with a specific PCB congener: PCB-063–heptachlor epoxide; 

PCB-090–cis-chlordane; PCB-093–trans-nonachlor; and PCB196–methoxychlor. Therefore, these values were omitted. 

High levels of tetrabrominated diphenyl ether congener 047 
Results and Discussion 7

Table 1. SPMD samples deployed and collected from the Bluestone River watershed, Tazewell County, Virginia, and Mercer County, 

West Virginia (Waterbody VAS-N36/N37R).

Columbia Environmental 

Research Center 

sample name

Station field 

identification

number 

Latitude, 

longitude

Deployment Collection

State Station name Date Time Date Time

WVDEP 2005 Study

1. Site #1 WV WVDEP-1 Beacon Cave # 1 -- 10/1/2005 12:00 10/29/2005 11:00

2. Site #1 Field Blank WV WVDEP-FB-1 Beacon Cave # 1

3. Site #2 WV WVDEP-2 Beacon Cave # 2 -- 10/1/2005 14:00 10/29/2005 12:15

4. Site #2 Field Blank WV WVDEP-FB-2 Beacon Cave # 2

5. Site #3 WV WVDEP-3 Morris Spring -- 10/5/2005 n/a 11/14/2005 13:15

6. Site #3 Field Blank WV WVDEP-FB-3 Morris Spring -- -- -- -- --

VADEQ RARE 2005 Study

1. Site #1 WV 9-LRR000.03 Laurel Fork Confluence 37° 18.89’N, 

81° 19.60’W

9/15/2005 17:45 11/1/2005 16:00

2. Site #2 WV 9-ABB000.02, 

Replicate 1

Abbs Valley River 37° 18.41’N, 

81° 18.88’W

9/15/2005 18:30 11/1/2005 15:30

3. Site #3 WV 9-ABB000.02, 

Replicate 2

Abbs Valley River 37° 18.41’N, 

81° 18.88’W

9/15/2005 18:45 11/1/2005 15:40

4. Field Blank #3 WV 9-ABB000.02 Abbs Valley River -- -- -- -- --

5. Fortified Field Blank #3 WV 9-ABB000.02 Abbs Valley River -- -- -- -- --

6. Site #4 VA 9-BST022.43 Bluestone River below Yards 37° 18.17’N, 

81° 17.84’W

9/15/2005 16:15 11/1/2005 15:00

7. Site #5 VA 9-BFK000.02 Brush Fork 37° 16.58’N, 

81° 18.30’W

9/15/2005 14:45 11/1/2005 14:30

8. Site #6 WV 9-BFK003.14 Brush Fork, below Armory 37° 17.30’N, 

81° 15.77’W

9/15/2005 14:51 11/1/2005 16:30

9. Site #7 WV 9-XRD000.43 Neal’s Hollow 37° 16.11’N, 

81° 16.45’W

9/15/2005 19:45 11/1/2005 17:00

10. Site #8 VA VA0025054-001 Bluefield Westside STP 37° 15.64’N, 

81° 16.92’W

9/15/2005 14:15 11/1/2005 14:10

11. Site #9 VA 9-BPB000.02 Beaverpond Creek 37° 15.31’N, 

81° 16.55’W

9/15/2005 7:45 11/1/2005 13:40

12. Site #10 VA 9-WHI000.03 Whitley Creek 37° 15.14’N, 

81° 16.25’W

9/15/2005 13:15 11/1/2005 12:05

13. Site #11 WV 9-XEF000.10 Cross-tributary to Beaverpond 

Branch

37° 14.84’N, 

81° 14.41’W

9/15/2005 11:45 11/1/2005 14:23

14. Site #12 VA 9-BPB001.51, 

Replicate 1

Beaverpond Branch below 

Bluefield City Park

37° 14.65’N, 

81° 15.46’W

9/15/2005 12:30 11/1/2005 11:30

15. Site #13 VA 9-BPB001.51, 

Replicate 2

Beaverpond Branch below 

Bluefield City Park

37° 14.65’N, 

81° 15.46’W

9/15/2005 12:45 11/1/2005 11:40

16. Field Blank #2 VA 9-BPB001.51 Beaverpond Branch below 

Bluefield City Park

-- -- -- -- --

17. Fortified Field Blank #2 VA 9-BPB001.51 Beaverpond Branch below 

Bluefield City Park

-- -- -- -- --

18. Site #14 WV 9-BPB000.17 Beaverpond Branch at resurgence37° 14.48’N, 

81° 14.07’W

9/15/2005 10:45 11/1/2005 10:30

19. Site #15 VA 9-BST025.23 Bluestone River above Beaverpond Branch37° 15.30’N, 

81° 16.57’W

9/15/2005 8:05 11/1/2005 13:50

20. Site #16 VA 9-WVC000.05 Wright Valley Creek 37° 14.95’N, 

81° 17.29’W

9/15/2005 10:00 11/1/2005 13:20

21. Site #17 VA 9-BST028.90 Bluestone River below water 

treatment plant

37° 14.38’N, 

81° 16.66’W

9/15/2005 8:50 11/1/2005 9:55

22. Field Blank #1 VA 9-BST028.90 Bluestone River below water 

treatment plant

-- -- -- -- --

23. Fortified Field Blank #1 VA 9-BST028.90 Bluestone River below water 

treatment plant

-- -- -- -- --
8 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

coeluted with PCB-180, which also was omitted. Unidentified 

chemicals were found to coelute with three additional PCB 

congeners (PCB-003, PCB-025, and PCB-101), again, these 

values were omitted. 

Total amounts of PCBs in field samples ranged from 

130 to 20,000 ng, much greater than field blank amounts 

(40–53 ng). Three groups of sites are apparent: low (130–530 

ng); medium (550–2,500 ng); and high (11,000–20,000 ng). 

Amounts of PCBs determined in the three high sites: Beacon 

Cave #1 and #2, and Beaverpond Branch at resurgence #14, 

are about seven- to tenfold higher than the amounts determined for the medium group of sites. 

Procedural internal standard recoveries for all samples 

ranged from 62 to 125 percent for PCB-155 and from 71 to 

111 percent for PCB-204, excluding VADEQ Site-10, Whitley 

Creek, and WVDEP Site-3, Morris Spring. Whitley Creek 

recoveries ranged from 18 to 24 percent as a result of sample 

preparatory losses. Morris Spring recoveries were 175 percent 

and 140 percent, respectively; no explanation for this discrepancy was found.

As anticipated, background amounts of PCB congeners 

in quality-control samples incrementally increased for each 

additional sample preparation step in the sample processing 

scheme. The PIS solution used for recovery determination 

had amounts of only five congeners greater than the reporting 

limits. Four of these congeners (PCB-001, 006, 100, and 197) 

ranged from the reporting limits to less than threefold greater 

than these limits. 

Values for all congeners in preparatory blanks for each 

cleanup or fractionation step were less than or very close to 

the reporting limits, with total amounts of PCBs ranging from 

2.6 to 5.0 ng. Average total amounts of PCBs in procedural 

blanks were 11 ng, and average total amounts of PCBs in 

dialysis processing blanks were 21 ng. The contribution from 

the fabrication blank (materials for a six-SPMD composite 

plus all sample preparation) was 54 ng of total PCBs. The total 

amounts of PCBs in all six field blanks ranged from 40 to 53 

ng (average 44 ng).

Analytical precision for the native PCB fortification 

solution (Aroclor® 1242:1248:1254:1260, 1,000 ng nominal 

amount fortified) averaged 6.6 percent, and the total PCB 

recovery for the solution was 870 ± 10 ng; the measured 

amounts of the congeners were used in the subsequent recovery calculations for fortified samples. Recoveries of individual 

Table 2. Amounts of total polychlorinated biphenyls (PCBs), total polychlorinated dibenzo-p-dioxins (PCDDs) and total 

polychlorinated dibenzofurans (PCDFs) per semipermeable membrane device (SPMD) composite sample for the Bluestone River 

watershed sample set, fall 2005.

[Total PCBs are reported in ng per composite, and total PCDDs and total PCDFs are reported in pg per composite]

Sample name

Field identification 

number Field sample label Total PCBs Total PCDDs Total PCDFs

VADEQ

Site #1 9-LRR000.03 Laurel Fork Confluence 530 700 380

Site #2 9-ABB000.02, 

Replicate 1

Abbs Valley River 140 340 110

Site #3 9-ABB000.02, 

Replicate 2

Abbs Valley River 130 370 130

Site #4 9-BST022.43 Bluestone River below Yards 1,400 2,200 690

Site #5 9-BFK000.02 Brush Fork 2,500 670 300

Site #6 9-BFK003.14 Brush Fork, below Armory 190 580 260

Site #7 9-XRD000.43 Neal’s Hollow 280 980 450

Site #8 VA0025054-001 Bluefield Westside STP 1,300 1,900 740

Site #9 9-BPB000.02 Beaverpond Creek 1,300 2,700 920

Site #10 9-WHI000.03 Whitley Creek 1,000 1,000 920

Site #11 9-XEF000.10 Cross-tributary to Beaverpond Branch 1,500 6,600 1,500

Site #12 9-BPB001.51, 

Replicate 1

Beaverpond Branch below Bluefield City Park 1,500 2,500 470

Site #13 9-BPB001.51, 

Replicate 2

Beaverpond Branch below Bluefield City Park 2,100 3,100 530

Site #14 9-BPB000.17 Beaverpond Branch at resurgence 15,000 1,800 550

Site #15 9-BST025.23 Bluestone River above Beaverpond Branch 780 1,000 370

Site #16 9-WVC000.05 Wright Valley Creek 290 750 400

Site #17 9-BST028.90 Bluestone River below water treatment plant 140 810 150

WVDEP

Site #1 WVDEP-1 Beacon Cave # 1 20,000 1,600 630

Site #2 WVDEP-2 Beacon Cave # 2 11,000 1,400 460

Site #3 WVDEP-3 Morris Spring 550 335 140
Results and Discussion 9

congeners ranged from 53 to 118 percent and averaged 102 ± 

21 percent. Recoveries of individual congeners in the fortified field blank samples ranged from 41 to 173 percent and 

averaged 100 ± 16 percent. It should be noted that the mixed 

Aroclor® standard used for fortification had very low concentrations of some PCB congeners, which biased the reported 

recovery ranges for analytes near the reporting limit; the 

majority of congeners, with amounts several-fold greater than 

the reporting limits, were quantitatively recovered.

Precision, calculated as relative difference between site 

replicates, generally was excellent. Relative differences varied 

more for those replicates with greater total amounts of PCBs 

(24 percent, VADEQ Site #12 and #13 samples) than for 

the replicates with lesser total amounts of PCBs (5 percent, 

VADEQ Site #2 and #3 samples).

SPMD Accumulation of 2,3,7,8-Substituted 

Congeners and Homologs of Polychlorinated 

Dibenzo-p-Dioxins and Dibenzofurans

Total amounts of PCDDs and of PCDFs for the Bluestone River watershed sample set are summarized in table 2. 

Amounts of 2,3,7,8-substituted congeners and homologs of 

PCDDs and PCDFs in the six-SPMD composite samples from 

the Bluestone River watershed (inherently adjusted for recoveries of PIS) were corrected for background by subtraction of 

average field blank levels of PCDDs and PCDFs. 

The site groupings for PCDDs and PCDFs do not parallel 

those for PCBs; the three very high-level PCB sites corresponded to sites with only mid-range total amounts of PCDDs 

and PCDFs. Total amounts of PCDDs and PCDFs were found 

at very high levels at only one site: VADEQ Site-11, Crosstributary to Beaverpond Branch. At this site PCDDs were twofold greater than average, and PCDFs were about 50 percent 

greater than the next highest group of sites (VADEQ Site-9, 

Beaverpond Creek; VADEQ Site-10, Whitley Creek; and 

VADEQ Sites-12 and 13, Beaverpond Branch below Bluefield 

City Park). The remaining sites exhibited a gradual increase in 

amounts of PCDDs and PCDFs with no significant site groupings into low, medium, or high levels of PCDDs/DFs.

Of the 2,3,7,8-substituted congeners, octachlorodibenzofuran (OCDF) and 1,2,3,4,6,7,8-heptachlorodibenzofuran 

(HpCDF) contributed largely to total amounts of PCDFs; 

only OCDD contributed significantly to the total amount 

of PCDDs. Amounts of homologs (summed amounts of 

2,3,7,8-substituted plus non-2,3,7,8-substituted congeners) 

were correlated differently with total amounts of PCDDs or 

PCDFs than were the 2,3,7,8-substituted congeners. Homolog 

amounts of TCDFs contributed most significantly to the total 

amount of PCDFs. All PCDF homolog groups were similarly 

correlated with total amounts of PCDFs. Amounts of TCDD 

and OCDD homologs contributed largely and about equally to 

the total amount of PCDDs, and as with the PCDFs, all PCDD 

homolog groups were similarly correlated with total amounts 

of PCDDs. 

The TCDF homologs were comprised of complex mixtures of TCDF congeners, the profiles of which did not change 

significantly among sites. The TCDD homolog series were 

found to be very different in composition compared with the 

TCDF homolog series. Of special note was that one specific 

non-2,3,7,8-substituted congener of PCDDs contributed to the 

majority of TCDD homologs and to total PCDDs. This congener has been tentatively identified as either 1,2,3,7-TCDD or 

1,2,3,8-TCDD, members of an unresolved chromatographic 

pair on the 5 percent phenyl-, 95 percent methylsilicone capillary column.

Procedural internal standard recoveries for all samples 

ranged from 48 to 114 percent (average 70 ± 19 percent), 

excluding VADEQ Site-10, Whitley Creek because of sample 

preparatory losses (average recovery 14 percent). The analytical isotopic dilution method used here, inherently corrected for 

these preparatory losses. No inconsistencies in recoveries for 

the WVDEP Site-3 sample were found, indicating that only 

the post HP-PGC c-PCB fraction of the sample was compromised.

Preparatory blanks for the HP-PGC and LP-BAC steps 

were less than or very close to the reporting limits for all congeners, with total amounts of PCDDs and total PCDFs ranging 

from 2 to 4 pg. Average total amounts of PCDDs and PCDFs 

in procedural blanks ranged from 4 to 7 pg, and average total 

amounts of PCDDs and PCDFs in dialysis processing blanks 

ranged from 6 to 11 pg. The total amounts of PCDDs and 

PCDFs contributed from the fabrication blank were 24 pg and 

14 pg, respectively. The average total amounts of PCDDs and 

PCDFs in VADEQ field blanks ranged from 14 to 17 pg and 

from 9 to 12 pg, and average total amounts in WVDEP field 

blanks ranged from 13 to 17 pg and from 4 to 5 pg, respectively. Average recoveries of native PCDD and PCDF congeners in the fortified field blank samples ranged from 69 to 104 

percent. 

Analytical precision for the native PCDD/DF fortification 

solution (fortified at 8,640 pg PCDDs and 12,240 pg PCDFs) 

averaged 3 percent. Recoveries of total amounts of PCDDs and 

PCDFs for the solution were 8,300 ± 100 pg and 12,000 ± 100 

pg, respectively. Individual congener recoveries ranged from 93 

to 100 percent (average 95 ± 3 percent) for PCDDs and from 

86 to 105 percent (average 97 ± 5 percent) for PCDFs. These 

measured amounts of the congeners were used in the subsequent 

recovery calculations for fortified samples. Individual congener 

recoveries in the fortified fabrication blank sample ranged from 

102 to 108 percent; however, recoveries of individual congeners 

in the fortified field blank samples ranged from 56 to 104 percent. Recoveries of all PCDD congeners in these samples were 

consistently 97–105 percent. 

Precision of PCDD/DF accumulation between site replicates was generally excellent with differences of less than 20 

percent for between total amounts of PCDDs and PCDFs in 

both replicate samples. As discussed for replication between 

sites for total amounts of PCBs, relative differences between 

replicate samples were found to be inversely related to the 

total amounts of PCDDs and PCDFs. 
10 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

SPMD Release of Performance Reference 

Compounds (PRCs)

Initial amounts of PRCs in the six-SPMD composite samples before exposure were defined as the average of amounts 

determined in PRC-fortified field blank samples associated 

with VADEQ or with WVDEP sites (samplers not undergoing release of PRCs by environmental exposure). Overall 

average values from both sets of field blanks were not used 

because of small yet significant differences in averaged values 

between each set of sites. Final amounts of PRCs in SPMDs 

were defined as the amounts determined in field samples after 

exposure. 

The c-PCB PRC amounts were adjusted for recoveries of PIS PCB-155. The PAH-d PRCs were quantified after 

dialysis and were not adjusted for recovery; however, values 

for the PAH-d PRCs were included in this study to enable 

comparisons of PCB and PAH-d release rates. Amounts of 

c-PCB and PAH-d PRCs in the associated blank samples were 

less than the reporting limits, therefore, neither the c-PCB nor 

the PAH-d PRC values were corrected for background. The 

dual-column GC-ECD values indicated positive biases for the 

c-PCB PRCs resulting from interfering compounds, therefore, 

subsequent SIR GC-QMS confirmations of the c-PCB PRCs 

were performed. Percentages of PRCs remaining in field 

samples at the end of exposures were determined by comparing the final amounts of PRCs measured in the samples to the 

initial amounts of PRC and are summarized in table 3.

Amounts of PRCs remaining in SPMDs after exposure 

ranged from <0.1 percent (not detectable) to much greater 

than 100 percent. Significant interferences in the quantification of some PRCs in some samples were indicated by 

recoveries of amounts in SPMDs greater than those initially 

fortified. Interferences in quantifying c-PCB PRCs are 

most evident in samples from Site-5 (Brush Fork), Site-14 

(Beaverpond Branch at resurgence), and WVDEP-1 and 2 

(Beacon Cave #1 and #2). These samples contained high 

total amounts of PCBs (2,500–20,000 ng), including amounts 

of PCB-014, PCB-029, and PCB-050 that, when accumulated in SPMDs, approached those amounts added initially 

as PRCs for monitoring release. No coeluting or interfering 

congeners for the confirmatory SIR GC-QMS analysis were 

noted. However, finding [of] high amounts of PCB congeners 

previously not considered to be present in the environment 

at significant levels, suggests that additional caution must 

be employed for the selection of candidate PRCs and for 

the selection of subsequent analytical methods for PRCs, as 

environmental levels of these compounds or analytical interferences with these compounds were much more prevalent 

than first assumed. 

Table 3. Percentages of performance reference compounds (PRCs) remaining in semipermeable membrane device (SPMD) 

composite samples from the Bluestone River watershed sample set, fall 2005.

Performance Reference Compounds

Sample name Acenaphthylene-d Acenaphthene-d Fluorene-d Phenanthrene-d PCB-014 Pyrene-d PCB-029 PCB-050

VADEQ

Site #1 22 < 0.1 20 32 72 72 88 94

Site #2 21 39 32 27 85 45 86 88

Site #3 5.5 29 32 40 80 61 87 86

Site #4 4.1 19 35 31 74 86 85 84

Site #5 29 46 28 30 90 78 100 100

Site #6 23 49 37 98 67 86 79 80

Site #7 12 < 0.1 25 23 64 65 76 80

Site #8 32 8.6 33 70 99 96 97 100

Site #9 18 11 37 40 60 51 75 89

Site #10 14 < 0.1 83 50 33 56 49 57

Site #11 18 14 41 41 40 100 55 83

Site #12 18 6.5 49 61 48 100 63 78

Site #13 19 5.4 27 65 42 130 58 75

Site #14 12 1.1 32 12 87 55 110 180

Site #15 6.8 1.1 25 41 58 86 72 79

Site #16 14 1.1 27 18 54 65 66 71

Site #17 9.6 9.7 30 36 59 77 70 72

WVDEP

Site #1 13 20 29 24 91 75 120 220

Site #2 16 14 40 30 92 78 110 160

Site #3 19 23 50 27 14 100 31 50
Results and Discussion 11

Calculation of Estimated Concentrations 

of PCBs, PCDDs, and PCDFs in Water

Concentrations of PCBs, PCDDs, and PCDFs in water 

were estimated using the PRC-adjusted empirical uptake rate 

model incorporated into a spreadsheet calculator program 

(Huckins and others, 2006). Because of the availability of 

c-PCB and PAH-d PRC information, all PRC values were 

investigated for use in calculating estimates of the concentrations of target compounds in water. The final PRC amounts 

for PCB-014, PCB-029, and PCB-050 were determined by 

GC-QMS and were corrected for PCB-PIS recovery; final 

PRC amounts for acenaphthylene-d, acenaphthene-d, fluorene-d, phenanthrene-d, and pyrene-d were determined by gas 

chromatography with flame ionization detection of dialysates 

and were not corrected for recovery. Initial PRC amounts were 

determined from the average of SPMD field blank samples 

associated with VADEQ or with WVDEP sites using the 

methods just described. Overall average values from both sets 

of field blanks were not used because of differences between 

each set of sites. Final PRC amounts were determined in each 

SPMD field sample. PRC intercepts (a0PRC) within each site 

and among sites were calculated using PRC-adjusted empirical uptake rate model and represent a measure of the sampling rate. The a0PRC values were reviewed; data were omitted 

for PRCs at sites in which the final PRC amounts were not 

detectable (<0.01 μg for PAH-d) and in which the final PRC 

amounts were greater than the initial amounts (interferences 

or accumulation of PRC compounds from the site). Comparison of a0PRC values among and between all sites was used to 

establish an acceptable range of PRC ratios (final amount/initial amount) for selecting a0PRC values and for omitting outliers 

prior to averaging values at each site. Calculations provided 

similar values of a0PRC over a broad range of releases, from 

PRC releases of only a few percent to those that were nearly 

quantitative. After data review, accepted values of a0PRC were 

averaged for use and are summarized in table 4.

The total volumes of water sampled ranged from 40 to 

2,300 L. At each site, sampling rates were maximum for Cl2-3

PCBs, which ranged from 690 to 2,300 L of water sampled, 

and decreased about 17-fold to 40–140 L for Cl7-8 PCDDs/

DFs. Across sites, sampling rates for the same analytes varied 

by only about three- to fourfold. This indicated that average 

water flows encountered by the deployed SPMDs were somewhat similar, possibly because the deployment structures had 

a greater effect on mediating flow to the SPMD surfaces more 

than differences in bulk streamflows outside the structures had 

in directly affecting flow at the SPMD surfaces.

The uncertainty factor for estimating concentrations of 

compounds in water from SPMD accumulation using PRC 

release data was calculated from the antilog of the standard 

deviation of the log-based a0PRC values (table 4). Using these 

estimates of uncertainty, the uncertainties of most estimated 

concentrations in water were less than about ± twofold, with 

the exception of Sites-12 and 13 (Beaverpond Branch below 

Bluefield City Park) which were about twofold and Site 

WVDEP-3 (Morris Spring) which was about threefold.

Concentrations of Selected Congeners 

of Polychlorinated Biphenyls in Water

Amounts of PCB congeners in SPMDs were adjusted for 

recoveries of PIS and were corrected for background amounts 

of c-PCBs in the associated field blank samples prior to 

calculation of the estimated concentrations in water. Specific 

PCB congeners with interferences from high levels of OCPs 

or PBDEs were omitted from the concentration calculations, 

as were congeners with unidentified co-eluting compounds. 

For PCB congeners less than the reporting limit, the reporting 

limit value was used in the calculation of the concentration of 

the congener in water. This resulted in minimum concentrations of congeners in water of about 1 pg·L-1. Congener values 

less than the reporting limit were not included in total PCB 

concentrations.

Estimated concentrations of PCB congeners in water and 

estimated total concentrations of PCBs in water, calculated 

as the sum of all detectable concentrations of PCB congeners 

in water, are presented in table 5, at the end of this report. 

Estimated total concentrations of PCBs at study sites ranged 

from 130 to 18,000 pg·L-1 (table 6) and were found to be 

linearly related to the relative amounts of PCBs accumulated 

by SPMDs.

The lowest estimated PCB concentration in water (130 

pg·L-1) is almost threefold greater than total hypothetical 

concentrations of field blank amounts of PCBs (about 50 

pg·L-1). As discussed previously for amounts of PCBs, three 

groups of sites are apparent for PCB concentrations in water: 

low (130–350 pg·L-1); medium (640–3,500 pg·L-1); and high 

(11,000–18,000 pg·L-1). Concentrations of PCBs in water 

estimated at the three high sites: Beacon Cave #1 and #2, 

and Beaverpond Branch at resurgence #14, are about four- to 

sixfold higher than concentrations estimated for the medium 

group of sites. 

Concentrations of 2,3,7,8-Substituted Congeners 

and Homologs of Polychlorinated Dibenzo-pDioxins and Dibenzofurans in Water

Amounts of 2,3,7,8-substituted congeners and homologs 

of PCDDs and PCDFs in the six-SPMD composite samples 

from the Bluestone River watershed were inherently adjusted 

for recoveries of PIS by the isotopic dilution mass spectrometric technique used, and were corrected for background 

amounts of c-PCBs in the associated field blank samples 

prior to calculation of the estimated concentrations in water. 

Concentrations of PCDD and PCDF congeners with levels 

less than the reporting limit were derived from the reporting 

limit of the congeners in water. This resulted in minimum 

estimated concentrations of congeners in water of about 0.2 
12 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

to about 1 fg·L-1. Qualifiers for PCDD and PCDF congeners 

(or homologs) not meeting the quality-control criteria were 

propagated throughout the calculations and remain associated with their respective congener concentration in water. 

For analytes exceeding ± 15 percent tolerance in the ratio 

of the primary and secondary ions used for quantification, 

the lesser value is reported as the quantification limit and 

denoted LQ; for analytes not detected in the sample, the 

specified detection limit is reported and denoted ND. Analytes with recovery of the associated 13C-labelled surrogate 

exceeding the quality control limits set by the method were 

reported and denoted LR. Total concentrations of PCDDs 

and PCDFs were derived from the summation of detectable 

concentrations of each homolog group; therefore, congeners 

that were undetectable or unquantifiable were not included 

in concentrations in water of either the homologs or the total 

PCDDs or PCDFs. Estimated concentrations of 2,3,7,8-substituted congeners, homologs, and total PCDDs and PCDFs 

in water, calculated as the sum of all detectable concentrations of congeners in water (table 7, at the end of this report).

Estimated concentrations of 2,3,7,8-substituted congeners 

in water at study sites ranged from <1 to 22,000 fg·L-1 and 

<1 to 2,300 fg·L-1 for PCDDs and PCDFs, respectively. Total 

concentrations of 2,3,7,8-substituted congeners in water were 

comprised largely of OCDD and OCDF, with less than 10 percent of the total contributed by concentrations of other, mainly 

2,3,7,8-heptachloro-congeners.

Of special interest for this study was 2,3,7,8-TCDD, 

the only PCDD/DF congener with a regulatory SWQC value 

(1.2 pg·L-1 or 1,200 fg·L-1; Virginia Water Quality Standards, 

2006). Estimated concentrations of 2,3,7,8-TCDD in water 

ranged from 0.5 to 41 fg·L-1, as calculated from quantifiable amounts of 2,3,7,8-TCDD in SPMDs at the study sites. 

Concentrations of 2,3,7,8-TCDD in water were <5 fg·L-1 at all 

study sites, except Site #8 (Bluefield Westside STP) with an 

estimated concentration of 2,3,7,8-TCDD in water of 41 fg·L-1. 

Concentrations of 2,3,7,8-sustituted PCDD and PCDF congeners in water followed the same trends as previously described 

for amounts of 2,3,7,8-sustituted PCDD and PCDF congeners 

in SPMDs.

Table 4. Average aOPRC intercept values of performance reference compounds (PRCs), maximum and minimum volumes of 

water sampled, and estimated uncertainties in sampling rates for semipermeable membrane device composite samples from 

the Bluestone River watershed sample set, fall 2005.

[Volumes of water for PCB are reported in L and are calculated for log Kow 5.3 (maximum) and log Kow 7.8 (minimum). Volumes of water for 

PCDDs and PCDFs are reported in L and are calculated for log Kow 6.8 (maximum) and log Kow 9.8 (minimum). Relative uncertainties are reported 

as multipliers/divisors of estimated concentrations]

Sample name aOPRC

Polychlorinated biphenyls Polychlorinated dibenzo-p-dioxins 

and dibenzofurans

Relative 

Maximum Minimum Maximum Minimum uncertainty

VADEQ

Site #1 -3.51 1,200 250 730 71 1.29

Site #2 -3.54 1,100 240 680 66 1.67

Site #3 -3.54 1,100 230 680 66 1.33

Site #4 -3.55 1,100 230 660 64 1.27

Site #5 -3.65 860 180 520 51 1.56

Site #6 -3.58 1,000 220 620 61 1.51

Site #7 -3.38 1,600 340 980 95 1.13

Site #8 -3.75 690 150 420 41 1.67

Site #9 -3.44 1,400 300 870 84 1.55

Site #10 -3.37 1,700 350 1,000 98 1.24

Site #11 -3.39 1,600 340 970 95 1.85

Site #12 -3.46 1,400 290 830 81 2.00 

Site #13 -3.39 1,600 330 960 94 2.10

Site #14 -3.44 1,400 300 860 84 1.83

Site #15 -3.45 1,400 290 840 82 1.59

Site #16 -3.31 1,900 400 1,200 110 1.35

Site #17 -3.38 1,600 340 980 85 1.42

WVDEP

Site #1 -3.24 1,300 280 800 78 1.15

Site #2 -3.29 1,200 250 720 70 1.24

Site #3 -3.16 2,300 480 1,400 136 2.70
References Cited 13

Estimated total concentrations of PCDDs and PCDFs in 

water at the study sites ranged from 3,200 to 36,000 fg·L-1 and 

210–4,800 fg·L-1, respectively. Total PCDD and PCDF concentrations were calculated as the sum of homolog concentrations in water. Homologs of PCDDs and PCDFs in water were 

comprised largely of OCDD and OCDF.

Generally, homolog contributions decreased from 

octa- > hepta- > tetra- > penta- > hexa-chlorodibenzo-pdioxin and from octa- > tetra- > penta- > hepta- > hexachlorodibenzofuran. SPMDs accumulated significantly 

greater amounts of Cl4-5 homologs comprising non-2,3,7,8-

substituted congeners than those comprising only 2,3,7,8-

substituted congeners. The lesser chlorinated congeners 

contributed very much to the overall PCDD and PCDF 

concentrations in water. 

Acknowledgments

This study was supported through cooperative agreements with the U.S. Environmental Protection Agency (Interagency Agreement Number 14922025) and the West Virginia 

Department of Environmental Protection (Agreement Number 

06C3WV833500004).

References Cited

Frame, G.M., Cochran, J.W., and Boewadt, S.S., 1996, Complete PCB congener distributions for 17 Aroclor mixtures 

determined by 3 HRGC systems optimized for comprehenTable 6. Estimated total concentrations in water of polychlorinated biphenyls (PCBs), polychlorinated dibenzop-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the Bluestone River watershed sample set, 

fall 2005.

[Total PCBs are reported in pg ·L-1, and total PCDDs and total PCDFs are reported in fg ·L-1]

Sample 

name

Field identification 

number Field sample label PCBs PCDDs PCDFs 

VADEQ

Site #1 9-LRR000.03 Laurel Fork Confluence 640 4,900 980

Site #2 9-ABB000.02, 

Replicate 1

Abbs Valley River 180 3,200 210

Site #3 9-ABB000.02, 

Replicate 2

Abbs Valley River 180 3,700 270

Site #4 9-BST022.43 Bluestone River below Yards 1,800 10,000 1,500

Site #5 9-BFK000.02 Brush Fork 3,500 9,300 820

Site #6 9-BFK003.14 Brush Fork, below Armory 260 6,900 630

Site #7 9-XRD000.43 Neal’s Hollow 260 7,200 720

Site #8 VA0025054-001 Bluefield Westside STP 2,300 11,000 2,300

Site #9 9-BPB000.02 Beaverpond Creek 1,300 13,000 1,900

Site #10 9-WHI000.03 Whitley Creek 910 7,100 1,600

Site #11 9-XEF000.10 Cross-tributary to Beaverpond Branch 1,300 36,000 4,800

Site #12 9-BPB001.51, 

Replicate 1

Beaverpond Branch below Bluefield City Park 1,500 15,000 1,000

Site #13 9-BPB001.51, 

Replicate 2

Beaverpond Branch below Bluefield City Park 1,700 16,000 940

Site #14 9-BPB000.17 Beaverpond Branch at resurgence 13,000 17,000 2,000

Site #15 9-BST025.23 Bluestone River above Beaverpond Branch 800 9,100 850

Site #16 9-WVC000.05 Wright Valley Creek 260 5,100 770

Site #17 9-BST028.90 Bluestone River below water treatment plant 130 6,500 230

WVDEP

Site #1 WVDEP-1 Beacon Cave #1 18,000 17,000 3,500

Site #2 WVDEP-2 Beacon Cave #2 11,000 17,000 3,000

Site #3 WVDEP-3 Morris Spring 350 1,600 160
14 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

sive, quantitative, congener-specific analysis: Journal of 

High Resolution Chromatography, 19:657–668.

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

R.C., Gibson, V.L., Gala, W.R., Echols, K.R., 1999, 

Determination of uptake kinetics (sampling rates) by lipidcontaining Semipermeable Membrane Devices (SPMDs) 

for Polycyclic Aromatic Hydrocarbons (PAHs) in water: 

Environmental Science and Technology, 33: 3,918–3,923.

Huckins, J.N., Petty, J.D., Lebo, J.A., Almeida, F.V., Booij, 

K., Alvarez, D.A., Cranor, W.L., Clark, R.C., Mogensen, 

B.B., 2002, Development of the permeability/performance 

reference compound approach for in situ calibration of 

semipermeable membrane devices: Environmental Science 

and Technology, 36:85–91.

Huckins, J.N., Petty, J.D., Booij, K., 2006, Monitors of organic 

chemicals in the environment—Semipermeable membrane 

devices: New York, Springer.

Lott, C,R,, Newman, A., 2005, PCBs in the Bluestone River: 

Virginia Department of Environmental Quality, web publication, accessed on April 21, 2005, at http://www.deq.

virginia.gov/tmdl/pptpdf/blstpcb1.pdf.

McCarthy, K.A., Gale, R.W., 1999, Investigation of the distribution of organochlorine and polycyclic aromatic hydrocarbon compounds in the Lower Columbia River using 

semipermeable membrane devices: U.S. Geological Survey 

Water-Resources Investigation Report 99–4051, 136 p.

Standard Operation Procedures Manual for the (Virginia) 

Department of Environmental Quality, 2003, Office of 

Water Quality Monitoring Programs (revision No. 10).

Virginia State Water Control Board, 1997, Water Quality 

Standards, 9VAC 25–260–5 et seq. Statutory Authority: 

62.1–44.15 )3a) of the Code of Virginia.

Virginia Water Quality Standards: 9 VAC 25–260, January, 

2006.

West Virginia Environmental Quality Board, 2000, Requirements Governing Water Quality Standards.

Water Quality Monitoring Consolidated Guidance Memorandum, 2004, DEQ Guidance Memo: 04–2005, Legislative 

Rule 46CSRI.
Tables 15

Tables
16 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

Table 5. Estimated concentrations of selected congeners of polychlorinated biphenyls (PCBs) in water from the Bluestone River 

watershed sample set, fall 2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and others, 1996]

RARE Study Field Samples—Fall 2005

Sample name Site #1 SPMDs Site #2 SPMDs Site #3 SPMDs Site #4 SPMDs Site #5 SPMDs Site #6 SPMDs

Field indentification 9-LRR000.03 9-ABB000.02, Rep 1 9-ABB000.02, Rep 2 9-BST022.43 9-BFK000.02 9-BFK003.14

Field sample label

Laurel Fork 

Confluence Abbs Valley River Abbs Valley River

Bluestone River 

below Yards Brush Fork

Brush Fork, 

below Armory

PCB congener(s)

001 3.9 9.5 2.6 5.0 15 7.5

002 < 1 < 1 < 1 < 1 < 1 < 1

004 4.9 4.2 3.0 19 250 4.6

005 0.06 0.07 0.1 0.2 0.3 0.1

006 1.4 0.9 1.0 3.9 22 1.3

007 < 1 < 1 < 1 2.5 3.4 < 1

008 1.6 0.6 1.2 9.1 160 1.5

009 0.3 0.2 0.2 1.9 5.4 0.1

010 0.8 1.2 1.1 1.8 7.9 0.9

012,013 5.3 1.3 1.0 20 4.3 1.8

015 1.4 0.04 0.2 5.7 73 1.8

016 4.0 0.5 0.7 15 71 2.0

017 7.5 0.8 0.8 26 170 3.5

018 12 1.2 1.4 41 170 6.6

019 3.9 0.4 0.4 19 94 2.4

020 0.5 < 1 < 1 5.1 9.4 0.3

022 3.4 0.5 0.4 9.5 67 1.5

024,027 1.9 < 1 < 1 6.3 41 0.7

026 1.6 0.2 0.1 6.5 39 0.9

028 9.3 1.0 1.0 35 270 5.0

031 7.1 4.0 3.5 49 200 4.7

032 3.8 0.03 < 1 18 140 2.0

033 8.5 4.4 3.6 31 27 4.3

034 < 1 < 1 < 1 0.2 1.7 0.10

035 0.9 < 1 < 1 1.2 3.8 0.5

037,059 1.4 0.09 0.2 5.6 25 0.8

040 2.8 0.2 0.1 9.4 35 1.2

041 2.3 0.7 0.7 5.1 17 1.0

042 3.7 0.3 0.2 12 46 1.5

044 17 1.2 1.3 46 150 5.8

045 4.2 1.0 0.8 12 49 1.6

046 1.1 < 1 < 1 7.4 19 0.7

047 9.9 2.5 2.4 46 68 4.0

048 2.4 0.1 0.2 6.7 35 1.1

049 12 1.7 1.6 32 110 3.9

051 1.3 0.1 0.09 2.5 14 0.4

052 37 18 17 94 160 14

053 7.7 1.6 1.2 21 51 3.0

054 6.6 5.3 4.9 15 4.7 3.0

056,060 2.8 0.9 0.8 15 83 0.7

064 7.6 1.0 0.9 20 82 2.9

066 7.3 1.5 1.7 33 110 3.8

067 1.1 0.2 0.4 1.2 5.2 0.1

069 0.6 0.2 0.1 1.3 0.4 0.04

070 14 2.7 2.4 36 85 5.5

071 4.4 0.3 0.6 13 53 1.5

073 0.3 0.1 0.09 0.9 < 1 0.1

074 5.3 1.1 1.2 13 61 2.3

075 4.9 1.2 1.1 56 19 5.5

077 8.6 1.4 1.9 21 11 3.0

081,117 1.7 0.3 0.3 2.7 1.8 0.6

082 5.4 0.6 1.3 11 6.7 1.8

083 2.6 0.6 0.6 6.2 3.0 0.9

084 12 1.9 2.1 29 13 3.7

085 2.3 1.1 0.7 < 1 0.5 < 1

087 15 2.8 3.3 26 13 1.6

091 6.8 1.2 1.4 14 7.1 2.1

092 7.4 2.0 2.3 19 6.5 2.2

095 30 5.4 5.7 79 26 9.4

097 11 2.0 2.1 21 12 2.8

099 18 3.9 4.0 32 16 4.4

100 < 1 < 1 < 1 0.1 2.0 0.3

103 1.3 2.1 1.8 3.4 0.6 0.8

104 0.5 0.2 0.1 1.7 1.2 0.1

105 10 2.5 2.7 17 9.4 2.4

109 2.9 0.8 0.8 4.4 2.6 0.9

110 40 9.4 9.8 94 31 11

114 0.7 0.1 0.1 0.9 0.4 0.06

115 1.6 0.4 0.5 1.5 1.2 0.6

118 27 7.3 7.9 48 22 7.2
 17

Table 5. Estimated concentrations of selected congeners of polychlorinated biphenyls (PCBs) in water from the Bluestone River 

watershed sample set, fall 2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and others, 1996]

RARE Study Field Samples—Fall 2005

Sample name Site #1 SPMDs Site #2 SPMDs Site #3 SPMDs Site #4 SPMDs Site #5 SPMDs Site #6 SPMDs

Field indentification 9-LRR000.03 9-ABB000.02, Rep 1 9-ABB000.02, Rep 2 9-BST022.43 9-BFK000.02 9-BFK003.14

Field sample label

Laurel Fork 

Confluence Abbs Valley River Abbs Valley River

Bluestone River 

below Yards Brush Fork

Brush Fork, 

below Armory

119 2.5 1.6 1.3 5.8 2.0 0.8

122 2.3 0.4 0.3 12 1.5 0.5

123 0.9 0.1 0.2 1.7 0.6 0.2

124 1.7 0.5 0.6 3.3 2.0 0.5

128 7.1 2.0 2.2 13 3.4 2.3

129 2.0 0.3 0.5 3.8 0.8 0.5

130 3.1 0.8 0.8 5.9 1.6 1.0

131 0.7 0.1 0.1 1.3 0.4 0.2

132 < 1 < 1 < 1 25 6.4 4.9

134 3.1 0.8 1.0 8.8 1.6 1.2

135 4.5 1.2 1.3 9.4 2.1 1.3

136 4.1 1.2 1.3 15 3.2 2.1

137 8.8 1.1 0.5 3.5 1.0 0.5

138 < 1 7.8 8.4 50 15 8.1

141 4.8 1.5 1.5 13 3.1 1.8

144 1.4 0.6 0.6 3.8 0.8 0.5

146 5.1 1.9 1.9 13 4.1 2.4

147 1.4 0.6 0.6 2.2 0.9 0.8

149 22 5.9 6.7 61 14 8.8

151 5.5 1.3 1.9 21 5.4 2.8

153 27 10.0 10 67 22 9.7

154 0.6 < 1 0.09 1.1 0.6 0.2

156 3.2 0.8 0.8 3.6 1.8 0.9

157 1.1 0.2 0.2 2.5 0.5 0.4

158 4.1 1.1 1.3 7.7 2.6 1.4

163 7.6 2.5 2.7 18 5.6 3.3

164 3.3 1.1 1.3 5.8 1.4 0.8

165 < 1 < 1 < 1 < 1 < 1 < 1

167 1.8 0.4 0.7 4.2 1.4 0.7

170 4.3 1.3 1.3 11 4.2 2.8

171 1.8 0.8 1.0 4.8 1.3 1.3

172 0.8 0.2 0.2 2.8 0.9 0.5

173 < 1 < 1 < 1 0.1 < 1 < 1

174 5.3 1.6 1.6 17 4.3 3.2

175 1.1 0.2 0.1 0.8 0.2 0.1

176 1.0 0.1 0.1 1.6 0.8 0.2

177 3.0 0.8 1.0 9.4 2.5 1.9

178 1.5 0.6 0.6 4.7 1.5 1.1

179 2.2 0.6 0.5 8.5 2.2 1.3

183 3.3 1.2 1.2 9.4 3.2 2.2

185 0.5 0.1 0.2 2.2 0.5 0.4

187 7.6 2.4 2.7 21 7.6 4.8

189 < 1 < 1 0.1 0.3 < 1 < 1

190 0.9 0.2 0.2 3.1 1.0 0.5

191 0.2 < 1 < 1 0.5 < 1 0.1

193 1.9 0.5 0.2 4.5 1.0 0.3

194 2.1 0.6 0.3 4.6 3.3 1.4

195 0.8 0.5 0.5 2.5 1.0 0.6

197 < 1 < 1 < 1 0.09 < 1 < 1

199 3.1 0.8 0.8 6.0 2.9 1.8

200 0.8 0.4 0.9 3.8 1.1 0.2

201 1.0 0.8 0.8 0.9 2.2 1.5

202 1.2 0.6 1.1 2.6 1.1 0.7

203 2.4 0.6 0.9 5.0 2.6 1.6

205 0.7 < 1 < 1 0.8 0.2 0.2

206 5.2 1.6 1.6 3.7 3.1 1.7

208 2.0 0.9 0.9 1.2 0.8 0.7

209 4.4 1.3 1.7 1.8 1.1 0.9

Sum of c-PCB water 

concentrations

640 180 180 1,800 3,500 260
18 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

Table 5. Estimated concentrations of selected congeners of polychlorinated biphenyls (PCBs) in water from the Bluestone River 

watershed sample set, fall 2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and others, 1996]

RARE Study Field Samples—Fall 2005

Sample name Site #7 SPMDs Site #8 SPMDs Site #9 SPMDs Site #10 SPMDs Site #11 SPMDs Site #12 SPMDs

Field identification 9-XRD000.43 VA0025054-001 9-BPB000.02 9-WHI000.03 9-XEF000.10 9-BPB001.51, Rep 1

Field sample label Neal’s Hollow

Bluefield Westside 

STP (g) Beaverpond Creek Whitley Creek

Cross-tributary to 

Beaverpond Branch

Beaverpond Branch 

below Bluefield 

City Park

PCB congener(s)

001 2.4 5.6 < 1 6.1 < 1 0.4

002 < 1 < 1 < 1 0.9 < 1 < 1

004 1.6 210 12 11 5.1 8.6

005 0.2 4.3 0.09 0.3 0.3 0.6

006 0.9 11 2.1 4.5 1.0 0.8

007 0.3 5.2 0.3 0.4 0.9 0.3

008 1.8 41 3.6 3.9 3.5 2.9

009 0.3 10 0.6 0.5 1.6 0.6

010 0.3 26 6.3 1.7 1.0 11

012,013 2.7 82 14 4.2 60 22

015 1.1 30 4.7 4.1 6.2 6.3

016 1.3 37 11 6.5 6.0 19

017 1.7 38 9.2 9.7 6.2 5.9

018 3.6 74 16 16 12 13

019 1.7 33 32 11 7.5 59

020 0.2 21 0.9 0.9 2.0 1.7

022 1.6 19 5.7 4.6 6.4 7.3

024,027 0.4 15 12 3.3 3.8 25

026 0.8 13 3.2 2.2 2.5 3.9

028 4.9 45 16 14 20 24

031 6.7 110 16 10 16 16

032 0.8 16 26 7.9 4.7 54

033 6.3 94 15 10 44 19

034 0.3 0.8 < 1 < 1 0.7 0.5

035 0.3 3.5 1.8 1.0 1.6 3.3

037,059 0.8 2.9 11 4.4 4.4 20

040 1.0 6.9 13 6.7 21 20

041 0.9 9.2 5.4 3.0 9.7 7.4

042 1.3 7.7 14 6.7 4.4 27

044 4.7 41 46 20 100 95

045 2.1 11 24 12 14 48

046 0.5 9.8 9.0 4.7 3.2 14

047 3.4 100 28 14 60 34

048 1.0 8.8 4.4 2.5 2.3 7.0

049 3.9 25 35 16 9.1 66

051 0.3 4.1 5.8 4.3 2.2 7.8

052 20 110 100 46 150 150

053 3.0 76 29 16 39 46

054 5.5 25 28 12 100 38

056,060 2.4 16 14 6.4 7.9 26

064 2.9 19 26 11 6.4 51

066 4.4 24 38 11 10 42

067 0.2 1.5 1.7 0.7 1.9 2.5

069 0.08 4.4 1.3 0.5 5.6 2.0

070 5.9 47 20 15 13 20

071 1.1 11 16 7.6 5.0 28

073 0.3 4.8 0.7 0.3 1.8 0.9

074 2.3 14 10 4.8 6.9 16

075 8.8 88 16 9.3 22 12

077 3.6 0.2 14 14 18 13

081,117 0.5 4.5 1.6 1.2 2.8 2.6

082 1.6 8.8 6.9 5.5 5.6 7.4

083 0.9 6.0 3.9 3.3 6.5 4.3

084 3.2 25 18 16 11 15

085 < 1 15 < 1 0.03 < 1 0.1

087 3.4 23 8.8 11 8.4 12

091 1.8 8.0 9.1 8.7 5.2 7.7

092 2.8 14 11 9.5 11 7.6

095 8.7 56 44 44 29 33

097 2.9 21 13 10 11 11

099 4.1 20 17 16 13 15

100 0.07 < 1 < 1 0.03 0.9 < 1

103 0.8 3.6 6.0 4.8 32 11

104 0.2 1.8 2.5 1.0 0.7 1.7

105 3.0 26 8.6 6.2 8.5 8.1

109 0.8 6.0 2.7 2.2 4.7 3.3

110 11 90 50 40 34 40
 19

Table 5. Estimated concentrations of selected congeners of polychlorinated biphenyls (PCBs) in water from the Bluestone River 

watershed sample set, fall 2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and others, 1996]

RARE Study Field Samples—Fall 2005

Sample name Site #7 SPMDs Site #8 SPMDs Site #9 SPMDs Site #10 SPMDs Site #11 SPMDs Site #12 SPMDs

Field identification 9-XRD000.43 VA0025054-001 9-BPB000.02 9-WHI000.03 9-XEF000.10 9-BPB001.51, Rep 1

Field sample label Neal’s Hollow

Bluefield Westside 

STP (g) Beaverpond Creek Whitley Creek

Cross-tributary to 

Beaverpond Branch

Beaverpond Branch 

below Bluefield 

City Park

114 0.1 0.7 0.3 0.5 0.3 0.5

115 0.10 1.5 1.5 0.5 1.4 1.4

118 8.5 54 24 18 24 20

119 0.9 6.7 4.8 2.8 16 3.3

122 0.09 26 1.3 1.4 5.1 2.4

123 0.2 0.7 1.2 0.5 1.1 1.1

124 0.9 3.4 1.8 1.0 1.7 1.4

128 2.2 9.1 6.6 5.9 4.4 4.1

129 0.5 2.7 2.1 1.7 1.6 1.3

130 1.1 3.8 3.2 2.8 2.3 1.8

131 0.2 0.9 0.8 0.7 0.3 0.3

132 3.8 20 15 14 8.5 7.6

134 0.9 7.1 4.5 4.2 2.1 1.4

135 1.6 < 1 6.8 4.6 < 1 < 1

136 1.7 30 7.5 11 13 8.2

137 0.6 2.3 1.9 1.7 1.7 1.3

138 7.9 31 26 26 17 15

141 1.8 6.7 7.7 7.8 5.7 4.1

144 0.5 1.9 2.5 2.4 2.9 2.0

146 2.5 5.4 7.2 7.5 5.0 4.0

147 0.5 0.9 2.3 2.5 3.2 2.0

149 8.3 26 34 37 22 17

151 2.6 14 12 14 10 6.0

153 10 44 34 35 25 18

154 0.2 1.7 1.0 1.1 0.3 1.0

156 1.6 2.9 4.0 2.5 1.6 1.2

157 0.7 1.0 2.6 0.8 1.2 2.0

158 1.3 4.7 4.3 4.0 3.4 2.6

163 3.3 10 10 11 6.6 5.6

164 0.8 3.8 3.2 3.4 1.7 2.0

165 < 1 < 1 < 1 0.1 < 1 < 1

167 1.4 2.8 3.6 2.1 2.3 2.5

170 1.8 4.5 7.5 11 4.4 3.2

171 0.7 1.6 3.7 3.8 1.6 1.0

172 0.5 0.7 2.0 2.0 1.1 0.7

173 < 1 < 1 0.3 0.1 0.08 < 1

174 2.2 7.2 11 15 8.0 5.0

175 0.09 1.0 0.6 0.8 1.6 0.7

176 0.1 0.5 1.1 1.4 1.2 0.4

177 1.3 3.1 6.2 7.9 4.0 2.7

178 0.7 2.5 3.4 3.9 3.8 1.8

179 0.9 2.7 4.2 6.5 6.2 2.8

183 2.3 3.0 8.8 9.0 5.5 4.9

185 0.3 0.2 1.5 1.9 1.2 0.6

187 3.7 5.8 15 18 10 7.2

189 < 1 0.1 0.2 0.4 0.08 < 1

190 0.3 0.8 2.2 2.0 1.1 1.0

191 0.07 < 1 0.6 0.4 0.2 0.2

193 0.2 1.2 1.8 3.5 2.7 1.3

194 0.7 5.7 3.0 4.6 2.9 1.6

195 0.2 < 1 2.1 2.2 2.4 1.5

197 < 1 < 1 0.1 0.3 0.1 < 1

199 1.3 1.7 4.6 4.8 3.4 2.6

200 0.2 5.6 0.9 1.0 0.6 0.9

201 0.4 7.6 1.3 1.0 6.7 2.5

202 0.4 < 1 1.8 2.2 4.3 1.4

203 0.8 1.8 3.4 3.7 2.6 1.7

205 0.3 0.3 1.5 0.8 1.6 0.9

206 1.1 1.9 2.8 2.7 4.2 3.0

208 0.4 0.5 0.9 1.4 1.5 1.0

209 0.3 0.3 1.7 7.3 4.5 2.5

Sum of c-PCB water 

concentrations

260 2,300 1,300 910 1,300 1,500
20 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

Table 5. Estimated concentrations of selected congeners of polychlorinated biphenyls (PCBs) in water from the Bluestone River 

watershed sample set, fall 2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and others, 1996]

RARE Study Field Samples—Fall 2005

Sample name Site #13 SPMDs Site #14 SPMDs Site #15 SPMDs Site #16 SPMDs Site #17 SPMDs

Field identification 9-BPB001.51, Rep 2 9-BPB000.17 9-BST025.23 9-WVC000.05 9-BST028.90

Field sample label

Beaverpond Branch 

below Bluefield 

City Park

Beaverpond Branch 

at resurgence (h)

Bluestone River 

above 

Beaverpond Branch

Wright Valley 

Creek

Bluestone River below 

water treatment plant

PCB congener(s)

001 0.8 < 1 0.9 < 1 < 1

002 < 1 < 1 < 1 < 1 < 1

004 10 41 9.3 1.9 0.5

005 0.2 1.2 0.10 0.08 0.08

006 1.0 3.1 1.0 0.3 0.6

007 0.3 0.2 0.09 < 1 < 1

008 3.0 8.9 3.9 0.9 0.2

009 0.7 0.7 0.4 0.4 0.08

010 12 150 0.7 0.2 0.2

012,013 24 6.6 2.3 1.4 1.4

015 7.6 35 5.9 0.5 0.2

016 23 340 4.3 0.8 0.6

017 6.6 23 24 1.6 0.8

018 15 58 10 2.1 1.2

019 71 820 9.3 1.1 0.5

020 2.1 16 0.4 0.06 0.05

022 9.0 73 2.4 0.6 0.4

024,027 31 360 4.0 0.3 0.1

026 4.6 24 1.4 0.3 0.1

028 28 120 11 2.0 1.3

031 21 110 11 1.6 2.7

032 68 1,200 10 0.7 0.2

033 21 9.9 4.7 1.5 2.4

034 0.6 6.5 0.05 < 1 < 1

035 4.4 63 1.4 0.06 < 1

037,059 24 250 1.3 0.4 0.2

040 28 280 2.3 0.6 0.3

041 9.0 49 1.4 0.5 0.4

042 33 380 5.5 0.7 0.4

044 110 1,300 20 2.8 1.6

045 56 570 3.3 1.0 0.5

046 16 170 2.8 0.3 < 1

047 43 330 30 3.8 3.6

048 8.4 77 1.8 0.3 0.2

049 85 940 23 2.2 1.4

051 9.7 120 8.4 0.6 0.3

052 190 1,400 38 7.8 5.9

053 56 500 19 1.8 1.6

054 47 25 4.8 2.2 2.4

056,060 31 320 4.0 0.3 0.6

064 65 700 6.9 1.6 1.0

066 49 470 12 1.8 1.6

067 2.8 9.5 0.7 < 1 < 1

069 2.4 4.7 0.3 0.1 0.08

070 23 120 18 3.0 2.3

071 35 430 7.9 0.7 0.2

073 1.1 4.7 0.6 0.07 0.05

074 19 170 5.9 1.1 1.0

075 14 30 17 2.4 15

077 13 52 14 3.7 2.0

081,117 2.8 8.4 2.4 0.5 0.4

082 8.1 43 5.1 1.3 0.8

083 4.5 18 3.2 0.7 0.5

084 17 120 12 2.6 1.3

085 0.8 20 < 1 < 1 < 1

087 11 89 15 3.0 1.8

091 8.3 53 7.8 1.7 0.9

092 10.0 38 9.3 2.3 1.3

095 38 210 30 8.1 3.6

097 12 74 12 2.3 1.4

099 16 92 19 3.2 2.2

100 < 1 16 0.5 0.3 0.2

103 13 15 2.5 1.4 1.5

104 1.9 4.5 0.5 0.1 0.02

105 8.7 39 11 1.9 1.4

109 3.8 8.1 2.9 0.6 0.6

110 43 200 43 8.8 5.0

114 0.4 2.6 0.5 0.09 0.09

115 1.9 3.2 1.2 0.08 0.09
 21

Table 5. Estimated concentrations of selected congeners of polychlorinated biphenyls (PCBs) in water from the Bluestone River 

watershed sample set, fall 2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and others, 1996]

RARE Study Field Samples—Fall 2005

Sample name Site #13 SPMDs Site #14 SPMDs Site #15 SPMDs Site #16 SPMDs Site #17 SPMDs

Field identification 9-BPB001.51, Rep 2 9-BPB000.17 9-BST025.23 9-WVC000.05 9-BST028.90

Field sample label

Beaverpond Branch 

below Bluefield 

City Park

Beaverpond Branch 

at resurgence (h)

Bluestone River 

above 

Beaverpond Branch

Wright Valley 

Creek

Bluestone River below 

water treatment plant

118 22 86 33 5.8 4.3

119 8.7 21 2.5 0.7 0.8

122 2.1 3.6 0.8 0.2 0.5

123 1.3 2.6 0.5 0.2 0.1

124 1.5 6.0 2.0 0.4 0.2

128 4.3 4.9 6.1 1.7 1.0

129 1.3 1.3 1.9 0.5 0.2

130 1.9 2.0 2.6 1.0 0.4

131 0.4 0.6 0.6 0.2 0.08

132 7.7 10 10 3.5 2.3

134 1.7 2.5 3.1 1.2 0.6

135 0.4 9.1 4.3 2.8 0.5

136 6.4 4.8 4.7 2.8 1.1

137 1.5 1.8 2.0 0.6 0.2

138 15 17 24 9.6 4.2

141 4.3 4.4 5.4 3.1 0.9

144 1.8 1.9 1.3 0.8 0.3

146 4.1 4.6 5.5 3.6 1.3

147 2.3 3.1 1.7 0.7 0.4

149 17 21 23 16 4.4

151 6.4 6.7 7.7 7.0 1.7

153 20 22 28 17 5.7

154 1.0 1.1 0.5 0.2 0.1

156 2.3 1.9 3.6 0.8 0.4

157 2.0 0.6 1.3 0.2 0.1

158 2.6 2.9 4.2 1.4 0.6

163 5.6 5.9 8.8 5.2 1.8

164 2.0 2.2 2.8 1.6 0.5

165 < 1 < 1 < 1 < 1 < 1

167 2.5 1.6 2.1 0.6 0.3

170 3.3 1.9 5.8 5.4 1.1

171 1.0 0.8 2.4 2.3 0.5

172 0.8 0.4 0.7 1.6 0.2

173 < 1 < 1 0.07 0.1 < 1

174 4.9 2.5 7.1 8.9 1.6

175 0.7 1.5 0.3 0.5 < 1

176 0.3 0.1 0.6 1.0 0.1

177 2.6 1.5 4.5 5.4 1.1

178 1.7 1.1 2.4 3.3 0.7

179 2.6 1.6 3.6 5.1 0.9

183 3.8 3.6 5.0 5.0 1.3

185 0.6 0.3 0.9 1.3 0.1

187 6.8 3.5 11 14 2.8

189 < 1 < 1 0.1 0.1 < 1

190 0.7 0.4 1.4 1.6 0.3

191 0.4 1.3 0.4 0.3 < 1

193 1.7 1.0 1.5 1.7 0.4

194 1.6 0.5 2.6 2.8 0.7

195 1.7 0.6 1.1 1.4 0.4

197 < 1 < 1 0.09 0.1 < 1

199 2.4 1.3 3.2 3.8 0.9

200 0.5 0.3 0.2 0.4 0.06

201 3.0 7.3 1.1 1.0 0.8

202 1.7 1.7 1.2 1.6 0.4

203 1.6 0.9 2.6 3.1 0.6

205 1.1 1.5 0.6 0.7 0.1

206 2.9 1.9 2.0 1.7 0.8

208 0.9 0.7 0.7 0.5 0.2

209 3.1 1.0 0.3 0.3 < 1

Sum of c-PCB water 

concentrations

1,700 13,000 800 260 130
22 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

Table 5. Estimated concentrations of selected congeners of polychlorinated 

biphenyls (PCBs) in water from the Bluestone River watershed sample set, fall 

2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and 

others, 1996]

WVDEP Study Field Samples—Fall 2005

Sample name Site #1 SPMDs Site #2 SPMDs Site #3 SPMDs (*)

Field identification WVDEP-1 WVDEP-2 WVDEP-3

Field sample label Beacon Cave #1 (h) Beacon Cave #2 (h) Morris Spring

PCB congener(s)

001 0.4 0.8 < 1

002 < 1 < 1 < 1

004 72 47 0.5

005 0.8 0.2 0.1

006 5.3 2.9 0.4

007 0.7 0.3 0.6

008 13 7.0 < 1

009 1.4 0.7 0.4

010 240 160 0.2

012,013 6.4 4.8 5.5

015 44 29 1.6

016 490 330 1.1

017 41 22 < 1

018 80 49 0.6

019 1,200 790 1.3

020 29 15 0.1

022 110 64 0.3

024,027 530 320 0.5

026 36 20 0.04

028 160 98 1.3

031 110 55 24

032 2,000 1,200 0.8

033 12 8.2 12

034 12 6.3 0.1

035 110 66 2.6

037,059 340 200 1.2

040 390 230 1.1

041 75 42 2.1

042 540 310 1.0

044 1,600 990 1.5

045 770 470 4.0

046 230 140 2.2

047 440 240 8.2

048 120 63 < 1

049 1,300 740 1.6

051 190 110 0.8

052 1,600 1,000 60

053 690 430 9.2

054 31 27 21

056,060 440 260 0.8

064 930 550 1.4

066 630 360 1.4

067 18 9.9 0.4

069 6.3 3.7 0.2

070 120 72 0.5

071 620 360 1.7

073 5.3 3.5 0.5

074 210 130 0.2

075 39 22 1.5

077 53 32 4.1

081,117 8.4 5.8 0.3

082 53 33 1.7

083 22 14 1.8

084 150 92 7.4

085 26 19 < 1

087 110 65 1.9

091 64 40 3.8

092 41 27 2.0

095 260 160 18

097 90 55 2.0

099 99 62 5.3

100 17 11 0.04

103 13 9.8 4.4

104 1.1 1.8 0.6

105 43 28 1.1

109 8.6 5.7 1.6

110 230 140 13

114 2.0 1.4 0.1

115 7.8 2.2 0.6
 23

Table 5. Estimated concentrations of selected congeners of polychlorinated 

biphenyls (PCBs) in water from the Bluestone River watershed sample set, fall 

2005.—Continued

[Concentrations of PCBs are reported in pg·L-1 water. PCB congener numbering is follows Frame and 

others, 1996]

WVDEP Study Field Samples—Fall 2005

Sample name Site #1 SPMDs Site #2 SPMDs Site #3 SPMDs (*)

Field identification WVDEP-1 WVDEP-2 WVDEP-3

Field sample label Beacon Cave #1 (h) Beacon Cave #2 (h) Morris Spring

118 83 57 3.0

119 22 16 5.5

122 4.1 2.6 0.4

123 3.4 2.2 0.4

124 6.2 3.9 0.4

128 3.3 2.6 2.5

129 1.1 0.7 0.7

130 1.6 1.1 1.4

131 0.5 0.3 0.3

132 8.9 7.4 6.1

134 2.1 1.6 1.4

135 6.0 4.8 < 1

136 5.0 4.2 5.6

137 1.4 0.9 0.7

138 12 8.9 5.9

141 3.3 2.6 1.7

144 1.0 0.8 1.0

146 3.2 2.6 2.0

147 2.4 1.4 1.0

149 16 11 13

151 5.9 4.1 4.0

153 18 13 6.8

154 1.3 0.9 0.2

156 1.2 1.2 0.7

157 0.3 0.4 0.7

158 2.2 1.7 1.1

163 4.3 3.2 2.9

164 1.7 1.2 1.5

165 < 1 < 1 < 1

167 0.9 0.8 1.0

170 1.1 0.8 2.3

171 0.5 0.4 0.9

172 0.2 0.2 0.6

173 < 1 < 1 0.04

174 1.8 1.3 3.4

175 0.5 0.6 0.3

176 0.1 0.09 0.3

177 1.1 0.7 1.9

178 0.8 0.6 1.1

179 1.4 0.7 1.7

183 2.5 1.2 2.4

185 0.2 0.1 0.4

187 2.8 2.1 4.3

189 < 1 < 1 < 1

190 0.2 0.2 0.5

191 < 1 < 1 0.1

193 0.7 0.2 0.5

194 0.5 0.3 0.9

195 0.5 0.3 0.9

197 < 1 < 1 < 1

199 0.7 0.6 1.2

200 0.4 0.1 0.2

201 3.3 2.9 0.7

202 0.7 0.4 0.4

203 0.5 0.3 0.8

205 1.6 1.4 0.4

206 0.3 0.3 0.8

208 < 1 < 1 0.1

209 < 1 < 1 < 1

Sum of c-PCB water 

concentrations

18,000 11,000 350
24 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia Table 7. Estimated concentrations of 2,3,7,8-substituted polychlorinated dibenzop-dioxins (PCDDs) and dibenzofurans (PCDFs), and homologs of dioxins and furans in water from the Bluestone River watershed sample set, fall 2005. [Concentrations of PCDDs and PCDFs are reported in fg·L-1 water; ND, not detected at specified detection limit; LR, denotes recovery of 13C-labelled surrogate below 25% but above 10%: relative stan- dard deviation estimated as about 25%; LQ, ion ratio outside of ±15% tolerances: analyte is either less than the method quantification limit or is subject to interference] RARE Study Field Sample—Fall 2005 Sample name Site #1 SPMDs Site #2 SPMDs Site #3 SPMDs Site #4 SPMDs Site #5 SPMDs Site #6 SPMDs Field identification 9-LRR000.03 9-ABB000.02, Rep 1 9-ABB000.02, Rep 2 9-BST022.43 9-BFK000.02 9-BFK003.14 Field sample label Laurel Fork Conflence Abbs Valley River Abbs Valley River Bluestone River below Yards Brush Fork Brush Fork, below Armory Dioxins/Furans PCDDs 2,3,7,8-Tetrachloro 1.3 0.6 LQ 0.6 LQ 4.6 LQ 4.3 3.3 TOTAL TETRA-PCDDs 430 110 93 2,500 150 78 1,2,3,7,8-Pentachloro 11 2.2 LQ 4.5 37 16 LQ 8.1 TOTAL PENTA-PCDDs 330 100 82 1,700 290 160 1,2,3,4,7,8-Hexachloro 16 4.5 LQ 4.5 LQ 27 19 15 1,2,3,6,7,8-Hexachloro 44 10 12 94 49 43 1,2,3,7,8,9-Hexachloro 24 7.9 LQ 15 52 29 26 TOTAL HEXA-PCDDs 470 160 110 810 450 400 1,2,3,4,6,7,8-Heptachloro 610 220 270 860 710 620 TOTAL HEPTA-PCDDs 1,100 560 610 1,800 1,500 1,200 Octachloro 2,600 2,300 2,800 3,700 6,900 5,100 TOTAL PCDDs 4,900 3,200 3,700 10,000 9,300 6,900 PCDFs 2,3,7,8-Tetrachloro 8.0 5.1 5.5 22 11 7.7 TOTAL TETRA-PCDFs 280 110 120 620 350 250 1,2,3,7,8-Pentachloro 3.6 1.2 1.9 7.3 4.3 2.6 2,3,4,7,8-Pentachloro 9.4 2.1 3.6 34 14 11 TOTAL PENTA-PCDFs 150 45 50 390 160 150 1,2,3,4,7,8-Hexachloro 6.1 0.6 1.8 11 5.0 3.6 1,2,3,6,7,8-Hexachloro 4.7 LQ 0.6 1.8 8.6 5.0 3.9 2,3,4,6,7,8-Hexachloro 8.3 1.2 LQ 2.4 14 8.8 6.5 1,2,3,7,8,9-Hexachloro 0.3 ND 0.3 ND 0.3 ND 0.3 ND 0.4 ND 0.3 ND TOTAL HEXA-PCDFs 120 26 30 200 120 100 1,2,3,4,6,7,8-Heptachloro 62 7.1 13 LQ 83 42 33 1,2,3,4,7,8,9-Heptachloro 2.2 0.5 0.5 LQ 1.9 LQ 1.2 0.5 TOTAL HEPTA-PCDFs 150 18 30 160 91 72 Octachloro 280 10 42 180 95 60 

TOTAL PCDFs 980 210 270 1,500 820 630 
 25

Table 7. Estimated concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and homologs of dioxins and furans in water from the Bluestone River watershed sample set, fall 2005.—Continued[Concentrations of PCDDs and PCDFs are reported in fg·L-1 water; ND, not detected at specified detection limit; LR, denotes recovery of 13C-labelled surrogate below 25% but above 10%: relative standard deviation estimated as about 25%; LQ, ion ratio outside of ±15% tolerances: analyte is either less than the method quantification limit or is subject to interference]

RARE Study Field Samples—Fall 2005

Sample name Site #7 SPMDs Site #8 SPMDs Site #9 SPMDs Site #10 SPMDs Site #11 SPMDs Site #12 SPMDs

Field identification 9-XRD000.43 VA0025054-001 9-BPB000.02 9-WHI000.03 9-XEF000.10 9-BPB001.51, Rep 1

Field sample label Neal’s Hollow

Bluefield 

Westside 

STP (g)

Beaverpond 

Creek Whitley Creek

Cross-tributary to 

Beaverpond 

Branch

Beaverpond Branch 

below Bluefield 

City Park

Dioxins/Furans

PCDDs

2,3,7,8-Tetrachloro 4.2 41 2.1 1.4 LQ, LR 5.0 1.7 TOTAL TETRA-PCDDs 180 3,600 1,900 250 LR 3,300 1,500 1,2,3,7,8-Pentachloro 12 LQ 630 37 30 LR 58 19 TOTAL PENTA-PCDDs 180 4,400 570 290 LR 940 800 1,2,3,4,7,8-Hexachloro 20 13 47 44 LQ, LR 79 32 1,2,3,6,7,8-Hexachloro 45 50 120 100 LR 230 72 1,2,3,7,8,9-Hexachloro 29 23 81 77 LQ, LR 150 58 TOTAL HEXA-PCDDs 450 470 1,100 920 LR 1,700 1,100 1,2,3,4,6,7,8-Heptachloro 690 430 1,600 1,300 LR 4,800 1,300 TOTAL HEPTA-PCDDs 1,500 850 3,200 2,300 LR 8,200 3,400 Octachloro 4,900 1,400 6,700 3,400 LR 22,000 8,200 TOTAL PCDDs 7,200 11,000 13,000 7,100 36,000 15,000 

PCDFs

2,3,7,8-Tetrachloro 14 84 23 19 LR 19 9.7 TOTAL TETRA-PCDFs 280 1,200 620 500 LR 500 320 1,2,3,7,8-Pentachloro 2.8 3.8 6.8 7.0 LR 8.2 3.3 LQ 2,3,4,7,8-Pentachloro 13 19 24 18 LR 30 13 TOTAL PENTA-PCDFs 160 800 340 310 LR 390 170 1,2,3,4,7,8-Hexachloro 3.1 2.9 9.1 7.3 LR 21 5.4 1,2,3,6,7,8-Hexachloro 4.2 3.3 11 10 LR 23 6.9 2,3,4,6,7,8-Hexachloro 7.3 7.1 LQ 18 18 LR 29 5.1 1,2,3,7,8,9-Hexachloro 0.2 ND 0.5 ND 0.2 ND 0.2 ND, LR 0.2 ND 0.2 ND TOTAL HEXA-PCDFs 100 130 260 220 LR 560 140 1,2,3,4,6,7,8-Heptachloro 36 43 130 120 LR 430 74 1,2,3,4,7,8,9-Heptachloro 1.3 0.8 5.6 5.1 LQ, LR 22 2.3 TOTAL HEPTA-PCDFs 86 83 260 240 LR 1,000 150 Octachloro 100 95 420 370 LR 2,300 220 TOTAL PCDFs 720 2,300 1,900 1,600 4,800 1,000 
26 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia Table 7. Estimated concentrations of 2,3,7,8-substituted polychlorinated dibenzop-dioxins (PCDDs) and dibenzofurans (PCDFs), and homologs of dioxins and furans in water from the Bluestone River watershed sample set, fall 2005.—Continued [Concentrations of PCDDs and PCDFs are reported in fg·L-1 water; ND, not detected at specified detection limit; LR, denotes recovery of 13C-labelled surrogate below 25% but above 10%: relative standard deviation estimated as about 25%; LQ, ion ratio outside of ±15% tolerances: analyte is either less than the method quantification limit or is subject to interference] RARE Study Field Samples—Fall 2005 Sample name Site #13 SPMDs Site #14 SPMDs Site #15 SPMDs Site #16 SPMDs Site #17 SPMDs Field identification 9-BPB001.51, Rep 2 9-BPB000.17 9-BST025.23 9-WVC000.05 9-BST028.90 Field sample label Beaverpond Branch below Bluefield City Park Beaver- pond Branch at resurgence (h) Bluestone River above Beaverpond Branch Wright Valley Creek Bluestone River below water treatment plant Dioxins/Furans PCDDs 2,3,7,8-Tetrachloro 1.3 0.9 2.7 1.8 2.5 TOTAL TETRA-PCDDs 1,700 36 180 62 71 1,2,3,7,8-Pentachloro 19 29 LQ 18 11 6.8 TOTAL PENTA-PCDDs 800 210 210 170 83 1,2,3,4,7,8-Hexachloro 27 46 28 19 12 1,2,3,6,7,8-Hexachloro 61 120 80 58 26 1,2,3,7,8,9-Hexachloro 52 85 53 30 19 LQ TOTAL HEXA-PCDDs 1,100 880 640 450 320 1,2,3,4,6,7,8-Heptachloro 1,300 2,000 1,000 710 540 TOTAL HEPTA-PCDDs 3,600 3,700 2,100 1,500 1,200 Octachloro 8,300 12,000 6,000 3,000 4,800 TOTAL PCDDs 16,000 17,000 9,100 5,100 6,500 PCDFs 2,3,7,8-Tetrachloro 11 7.6 12 6.5 4.6 TOTAL TETRA-PCDFs 350 230 210 140 81 1,2,3,7,8-Pentachloro 3.1 2.1 3.9 3.0 1.2 2,3,4,7,8-Pentachloro 11 3.6 12 8.6 3.3 TOTAL PENTA-PCDFs 160 70 130 110 45 1,2,3,4,7,8-Hexachloro 4.4 6.6 5.8 3.5 1.0 1,2,3,6,7,8-Hexachloro 6.1 7.3 6.0 4.4 LQ 1.2 2,3,4,6,7,8-Hexachloro 4.0 4.7 5.5 2.8 LQ 1.0 LQ 1,2,3,7,8,9-Hexachloro 0.2 ND 0.2 ND 0.2 ND 0.2 ND 0.2 ND TOTAL HEXA-PCDFs 120 220 160 120 42 1,2,3,4,6,7,8-Heptachloro 60 190 73 64 15 1,2,3,4,7,8,9-Heptachloro 2.0 13 2.3 LQ 1.7 0.3 ND TOTAL HEPTA-PCDFs 120 490 160 170 32 

Octachloro 200 1,000 200 230 27 LQ TOTAL PCDFs 940 2,000 850 770 230 
 27

Table 7. Estimated concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and homologs of dioxins and furans in water from the Bluestone River watershed sample set, fall 2005.—Continued[Concentrations of PCDDs and PCDFs are reported in fg·L-1 water; ND, not detected at specified detection limit; LR, denotes recovery of 13C-labelled surrogate below 25% but above 10%: relative standard deviation estimated as about 25%; LQ, ion ratio outside of ±15% tolerances: analyte is either less than the method quantification limit or is subject to interference]

WVDEP Study Field Samples—Fall 2005

Sample name Site #1 SPMDs Site #2 SPMDs Site #3 SPMDs (*)

Field identification WVDEP-1 WVDEP-2 WVDEP-3

Field sample label Beacon Cave #1 (h) Beacon Cave #2 (h) Morris Spring

Dioxins/Furans

PCDDs

2,3,7,8-Tetrachloro 0.7 0.5 1.8 TOTAL TETRA-PCDDs 15 11 52 1,2,3,7,8-Pentachloro 31 23 24 TOTAL PENTA-PCDDs 130 110 180 1,2,3,4,7,8-Hexachloro 50 39 2.8 LQ 1,2,3,6,7,8-Hexachloro 140 110 11 1,2,3,7,8,9-Hexachloro 84 69 7.3 LQ TOTAL HEXA-PCDDs 820 650 130 1,2,3,4,6,7,8-Heptachloro 2,300 2,000 160 TOTAL HEPTA-PCDDs 3,800 3,300 420 Octachloro 12,000 12,000 780 TOTAL PCDDs 17,000 17,000 1,600 

PCDFs

2,3,7,8-Tetrachloro 1.9 LQ 1.3 1.9 TOTAL TETRA-PCDFs 59 37 56 1,2,3,7,8-Pentachloro 1.6 0.9 0.6 2,3,4,7,8-Pentachloro 4.7 2.9 2.8 TOTAL PENTA-PCDFs 59 41 36 1,2,3,4,7,8-Hexachloro 10 8.2 0.7 1,2,3,6,7,8-Hexachloro 9.9 7.9 0.9 LQ 2,3,4,6,7,8-Hexachloro 15 12 1.2 1,2,3,7,8,9-Hexachloro 0.8 0.3 ND 0.1 ND TOTAL HEXA-PCDFs 380 280 28 1,2,3,4,6,7,8-Heptachloro 290 250 9.5 1,2,3,4,7,8,9-Heptachloro 20 17 0.2 ND TOTAL HEPTA-PCDFs 930 760 20 Octachloro 2,100 1,900 22 TOTAL PCDFs 3,500 3,000 160 
28 Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia

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Gale—Development of Total Maximum Daily Loadings for the Bluestone River Watershed, Virginia and West Virginia—Open-File Report 07–1272

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