U.S. Department of the Interior 

U.S. Geological Survey 

Source Identification and Fish Exposure for 

Polychlorinated Biphenyls Using Congener 

Analysis from Passive Water Samplers in the 

Millers River Basin, Massachusetts 

Water-Resources Investigations Report 00-4250 

Department of Environmental Protection 
Cover photos: 

Upper photo shows the confluence of the Millers River and the Otter River in the low-gradient reach 

upstream from the Birch Hill Dam taken 12/6/00 by John A. Colman.The other, taken 12/18/00 is the Millers 

River in the steep-gradient reach one mile downstream from the USGS surface-water discharge station at 

South Royalston, Massachusetts (01164000). Photo by Britt Stock. 
U.S. Department of the Interior 

U.S. Geological Survey 

Source Identification and Fish Exposure for 

Polychlorinated Biphenyls Using Congener 

Analysis from Passive Water Samplers in the 

Millers River Basin, Massachusetts 

By JOHN A. COLMAN 

Water-Resources Investigations Report 004250 

Prepared in cooperation with the 

MASSACHUSETTS DEPARTMENT OF ENVIRONMENTAL PROTECTION and the 

MASSACHUSETTS DEPARTMENT OF ENVIRONMENTAL MANAGEMENT 

Northborough, Massachusetts 

2001 
U.S. DEPARTMENT OF THE INTERIOR 

GALE A. NORTON, Secretary 

U.S. GEOLOGICAL SURVEY 

Charles G. Groat, Director 

The use of trade or product names in this report is for identification 

purposes only and does not constitute endorsement by the 

U.S. Government. 

For additional information write to: Copies of this report can be purchased from: 

Chief, Massachusetts-Rhode Island District U.S. Geological Survey 

U.S. Geological Survey Branch of Information Services 

Water Resources Division Box 25286 

10 Bear-foot Road Denver, CO 802250286 

Northborough, MA 01532 

or visit our web site at 

http://ma.water.usgs.gov 
CONTENTS 

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

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

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

Previous Investigations ................................................................................................................................................ 3 

Acknowledgments ....................................................................................................................................................... 6 

Sampling and Analysis .......................................................................................................................................................... 6 

Sampling Procedures ................................................................................................................................................... 7 

Analytical Laboratory Procedures ............................................................................................................................... 7 

Statistics for Evaluating Changes in Congener Patterns ............................................................................................. 10 

Polychlorinated Biphenyl Data ............................................................................................................................................. 10 

Data Quality ................................................................................................................................................................ 10 

Sampling Results ......................................................................................................................................................... 12 

Identification of Sources of Polychlorinated Biphenyl ......................................................................................................... 14 

Sources Upstream from Birch Hill Dam ..................................................................................................................... 15 

Conceptual Model of Source ....................................................................................................................................... 17 

Correspondence with Aroclors .................................................................................................................................... 18 

Congener Pattern Weathering and Sources Downstream from Birch Hill Dam ......................................................... 18 

Exposure of Fish to Polychlorinated Biphenyls in the Millers River Basin .......................................................................... 21 

Summary and Conclusions.. .................................................................................................................................................. 22 

References ............................................................................................................................................................................. 22 

Appendix A. Polychlorinated biphenyl congener names and International Union of Pure and Applied 

Chemistry (IUPAC) numbers in gas-chromatograph domain order ........................................................................ 25 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts ................. 29 

FIGURES 

1. Map showing Millers River Basin in Massachusetts and New Hampshire with town boundaries, town 

centers, and PCB passive-sampler stations displayed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 

2,3. Graphs showing: 

2. Correspondence of RMSD with mean ZPCB concentration for duplicate samples from 

the Millers River Basin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... 11 

3. Differences in congener patterns in duplicate samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 

4. Hydrographs showing daily mean discharge data for USGS stream gaging stations at Otter River 

at Otter River (station number 01163200), Millers River at South Royalston (station number 0116400), 

and Millers River at Erving (station number 01166500) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 

5-8. Graphs showing: 

5. (A) Streambed elevation profile of the Millers River from the Connecticut River to the 

confluence with the Otter River and of the Otter River to its source and (B) CPCB and 

between-station RMSD of congener concentrations in downstream order on the 

Otter River and the Millers River . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 

6. PCB congener patterns in the Otter River . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 

7. Relative PCB concentration congener patterns compared, average of three samples from station 

O-31.2 with patterns of Aroclor 1016 and 1242. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 

8. Ratio comparisons of normalized PCB congener concentrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 

Contents III 
TABLES 

1. Stations sampled for PCBs using passive samplers in the Millers River and Otter River, Massachusetts, 

during 1999 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..................................... 8 

2. Analyte ions monitored, surrogates used, and RRP determination for polychlorinated biphenyl Aroclors 

by HRGCLXMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................ 9 

3. Sums of congeners, Aroclor mixtures from passive samplers, and computed water-column concentrations 

at stations on the Millers River and the Otter River . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 

CONVERSION FACTORS, VERTICAL DATUM, AND ABBREVIATIONS 

CONVERSION FACTORS 

Multiply BY To obtain 

inch (in.) 25.4 millimeter 

foot (ft) 0.3048 meter 

quart (so 0.6636 liter 

mile (mi) 1.609 kilometer 

square mile (mi*) 2.590 square kilometer 

foot per mile (ft/mi) 0.1894 meter per kilometer 

cubic foot per second (ft3/s) 0.02832 cubic meter per second 

Temperature is given in degrees Celsius (“C), which can be converted to 

degrees Fahrenheit (“F) by use of the following equation: 

“F = 1.8(“(I) + 32 

VERTICAL DATUM 

Sea level: In this report, “sea level” refers to the National Geodetic Vertical Datum of 1929 (NGVD 

of 1929)-a geodetic datum derived from a general adjustment of the first-order level nets of the 

United States and Canada, formerly called Sea Level Datum of 1929. 

ABBREVIATIONS 

Abbreviated concentration units used in this report: Chemical concentrations in water solution are 

given in nanograms per liter (ng/L). Chemical concentrations in hexane solution are given in nanograms per hexane sample. One nanogram per liter is equivalent to one billionth of a gram per liter. 

Chemical concentration in fish tissue and sediment is given in micrograms per gram @g/g). One 

microgram per gram is equivalent to one millionth of a gram of chemical per gram of fish (or sediment). These concentrations are on a wet-weight basis for fish and a dry-weight basis for sediment. 

IV Contents 
Source Identification and Fish Exposure for 

Polychlorinated Biphenyls Using Congener 

Analysis from Passive Water Samplers in the 

Millers River Basin, Massachusetts 

f3y John A. Colman 

Abstract 

Measurements of elevated concentrations of 

polychlorinated biphenyls (PCBs) in fish and in 

streambed sediments of the Millers River Basin, 

Massachusetts and New Hampshire, have been 

reported without evidence of the PCB source. In 

1999, an investigation was initiated to determine 

the source(s) of the elevated PCB concentrations 

observed in fish and to establish the extent of fish 

exposure to PCBs along the entire main stems of 

the Millers River and one of its tributaries the 

Otter River. 

Passive samplers deployed for 2-week 

intervals in the water-column at 3 1 stations, during 

-summer and fall 1999, were used to assess PCB 

concentrations in the Millers River Basin. The 

samplers concentrate PCBs, which diffuse from 

the water column through a polyethylene membrane to hexane (0.200 liters) contained inside the 

samplers. Only dissolved PCBs (likely equivalent 

to the bioavailable fraction) are subject to diffusion through the membrane. The summed concentrations of all targeted PCB congeners (XPCB) 

retrieved from the samplers ranged from 1 to 8,000 

nanograms per hexane sample. Concentration and 

congener-pattern comparisons indicated that the 

historical release of PCBs in the Millers River 

Basin likely occurred on the Otter River at the 

upstream margin of Baldwinville, Mass. Elevated 

water-column concentrations measured in a wetland reach on the Otter River downstream from 

Baldwinville were compatible with a conceptual 

model for a present-day (1999) source in 

streambed sediments, to which the PCBs partitioned after their original introduction into the 

Otter River and from which PCBs are released to 

the water now that the original discharge has 

ceased or greatly decreased. 

Two four-fold decreases in ZPCB concentrations in the Millers River, by comparison with 

the highest concentration on the Otter River, likely 

were caused by (1) dilution with water from the 

relatively uncontaminated upstream Millers River 

and (2) volatilization of PCBs from the Millers 

River in steep-gradient reaches. A relatively constant concentration of CPCBs in the reach of the 

Millers River from river mile 20 to river mile 10 

was likely a consequence of a balance between 

decreased volatilization rates in that relatively 

low-gradient reach and resupply of PCBs to the 

water column from contaminated streambed sediments. A second high-gradient reach from river 

mile 10 to the confluence of the Millers River with 

the Connecticut River also was associated with a 

decrease in concentration of water-column 

CPCBs. Volatilization as a loss mechanism was 

supported by evidence in the form of slight 

changes of the congener pattern in the reaches 

where decreases occurred. 

Exposure of fish food webs to concentrations of dissolved PCBs exceeded the U.S. 

Environmental Protection Agency’s water-quality 

criterion for PCBs throughout most of the Millers 

Abstract 1 
River and Otter River main stems. Because the 

apparent source of PCBs discharged was upstream 

on the Otter River, a large number of river miles 

downstream (more than 30 mi) had summer watercolumn PCB concentrations that would likely lead 

to high concentrations of PCBs in fish. 

INTRODUCTION 

In 1985, elevated concentrations of polychlorinated biphenyls (PCBs) were reported for fish tissue 

samples collected from the Millers River downstream 

from the U.S. Army Corps of Engineers (USACE) 

Birch Hill Dam by the Massachusetts Division of 

Water Pollution Control (MDWPC). Subsequent studies by the MDWPC and the USACE confirmed initial 

findings (U.S. Army Corps of Engineers, 1993) and 

reported elevated concentrations of PCBs in streambed 

sediments and over-bank deposits along the Otter River 

in the wetlands upstream from the Birch Hill Dam 

(U.S. Army Corps of Engineers, 1995). Repeated measurements of PCBs in fish at concentrations above 

limits for fish consumption advisories (2 pglg wetweight basis), as well as in sediments at high concentrations, are concerns of the public as determined by 

public meetings of the Massachusetts Executive Office 

of Environmental Affairs Millers River Watershed 

Team. Thus, a priority for the Millers River Watershed 

Team is to determine when and where PCBs were 

introduced and how pervasive exposure of fish to PCBs 

might be in the Millers River Basin. 

In March 1999, a water-column investigation 

was initiated by the U.S. Geological Survey (USGS), 

in cooperation with the Massachusetts Department 

of Environmental Protection and the Massachusetts 

Department of Environmental Management, to determine the source(s) of the elevated PCB concentrations 

observed in fish and to establish the extent of fish 

exposure to PCBs along the entire main stem of the 

Millers River and of one of its tributaries, the Otter 

River. The USGS investigation of PCBs in the water 

column was complemented by a USACE study of 

water, fish, and sediment in the Birch Hill Dam area 

and by a U.S. Environmental Protection Agency 

(USEPA) on-site study at facilities bordering the Otter 

River. The water-column sampling employed passive 

samplers that respond to the dissolved fraction of 

PCBs, a fraction that is bioavailable for concentration 

through aquatic food webs. Reported here are the 

USGS results of comparisons among 31 sites of total 

PCBs and PCB-congener patterns that were used to 

assess sources of PCBs and exposure of fish to PCBs 

in the Millers River Basin. 

Description of the Study Area 

The Millers River drains a total area of about 

390 mi2 in Massachusetts and New Hampshire, of 

which 3 13 mi2 are in Massachusetts (fig. 1). The drainage basin is about 78 percent forested, 11 percent open 

land, 8 percent wetland, and 3 percent urban areas. 

Many wetlands in the basin indicate areas of former 

shallow lakes and ponds that have gradually filled 

through sedimentation. There are a total of 107 lakes 

and ponds in the basin. Seventy-two of these lakes are 

10 acres or more in area. Lake Monomonac, northeast 

of Winchendon, Mass. (592 acres), is the only lake 

larger than 500 acres in the watershed (Massachusetts 

Department of Environmental Management, Division 

of Water Resources, 1978; Massachusetts Department 

of Environmental Quality Engineering, Division of 

Water Pollution Control, 1976). 

The Millers River formed late in the last glacial 

period when several glacial lakes in the region coalesced and drained into the Connecticut River. The 

headwaters of the Millers River are in southern New 

Hampshire, in the towns of Fitzwilliam and Rindge, 

and in north-central Massachusetts, in the towns of 

Ashbumham and Winchendon. The North Branch and 

the main stem of the river join in Winchendon and then 

flow westward to the Connecticut River. Major tributaries of the Millers River are the Otter River, entering the 

Millers River in Winchendon, and the Tully River, 

entering the Millers River in Athol; both tributaries 

flow primarily through wetlands. The USACE Birch 

Hill Dam, located just downstream from the confluence 

of the Otter River with the Millers River, regulates a 

pool of 3,200 acres when full. Under normal flow conditions, water is not held back at the dam and the 

streams behind the dam are within their banks, which 

are bordered by extensive wetlands. 

Overall, the Millers River has a moderate gradient, averaging about 18 ft/mi from its headwaters area 

to the USGS streamflow-gaging station at Erving, 

Mass., a distance of about 43 river miles (Massachusetts Division of Water Pollution Control, 1980). 

However, a 5-mile reach of the Millers River that 

flows through a wooded area between South Royalston 

2 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
and Athol, Mass. has an average gradient of about 

43 ft/mi, which is about five times the average for 

rivers in Massachusetts (Massachusetts Department of 

Environmental Quality Engineering, Division of Water 

Pollution Control, 1974). Downstream from Athol, the 

stream gradient is almost flat in the reach extending to 

Orange, Mass. Downstream from Orange, the gradient 

gradually increases to Millers Falls, Mass., finally 

equaling the gradient of the Royalston-Athol reach. 

The gradient of the Otter River averages about 18 ft/mi 

for a distance of about 11.5 river mile; the steepest gradient occurs between Templeton, Mass., town center 

and Trout Brook (Wandle, 1984). 

Previous Investigations 

PCBs were first measured at elevated concentrations in fish from the Millers River through the 

Massachusetts Fish Toxics Monitoring Program. In 

1985, fish were collected at five locations for PCB 

analysis in response to a high concentration measured 

earlier (1972) in one white sucker (Cutostomus 

commersoni) from the Millers River. Samples were 

split and sent to two laboratories, the Mississippi State 

Chemical Laboratory available through the U.S. Fish 

and Wildlife Service, and the Massachusetts State 

Lawrence Experiment Station, resulting in two complete sets of data that corresponded well. Species collected varied among sites, but white suckers were 

obtained at four sites. Total PCBs determined in wholefish white sucker composites were 2.0,0.79,4.2 and 

0.2 pg/g (all concentrations in fish are in micrograms 

PCB per gram of fish, wet weight) for stations at river 

mile 7.45, 17.8, 28.4 and 39.5, respectively. (Approximate river mile, determined as distance upstream from 

the confluence of the Millers River and the Connecticut 

River, can be ascertained from the numbers associated 

with stations shown in fig. 1). At these stations and at 

an additional station at river mile 1.8, concentrations 

were variable in other species collected, including 

American eel (Anguih rostra&), fallfish (Semotilus 

corporulis), chain pickerel (&OX niger), and smallmouth bass (Micropterus dolomieu). The highest concentration of PCBs measured, 5.8 pg/g, was in a 

composite American eel sample, which also had the 

highest lipid content (11 percent). Concentrations were 

low in all species measured at the most upstream 

station (river mile 39.5) - 0.20 p.g/g, 0.18 pg/g, 

and not detected, in fallfish, white sucker, and chain 

pickerel, respectively (Robert Maietta, Massachusetts 

Department of Water Pollution Control, written 

commun., 1988). 

In 1987, more fish were sampled, and sediments 

also were included in a cooperative investigation by 

the MDWPC and USACE (U.S. Army Corps of 

Engineers, 1993, 1995). All fish were analyzed at the 

Massachusetts State Lawrence Experiment Station. 

PCB concentrations in fish fillets and whole fish composites from three stations on the Millers River 

upstream from the Otter River confluence (river mile 

34.9, 38.4 and 40) were all below 0.5 pg/g, except for 

one yellow bullhead (Ameiums natalis) from river 

mile 34.9; in which the concentration was 0.99 pg/g. 

Concentrations of the PCBs measured in 5 different 

species collected from the Otter River, upstream from 

Baldwinville (river mile 36.7), were also relatively low 

(co.12 to 0.88, median 0.25 pg/g), Six sites were investigated beginning 5 mi downstream from the Birch Hill 

Dam and continuing downstream to 7.4 mi upstream of 

the confluence with the Connecticut River. In composites of white sucker fillets, which were collected at all 

stations but one, concentrations were highest nearest 

Birch Hill Dam, (2.2 pg/g, river mile 24.6), decreased 

through the next two stations downstream (river mile 

21.1, 14.1), to 1.1 pg/g (river mile 10.9), and then 

increased to 1.6 pg/g at the most downstream station 

(river mile 7.4). The highest concentration of PCBs 

measured in the investigation, 5.5 pg/g, was that in a 

brown trout fillet collected at river mile 8.4. A large 

range in concentrations, from less than 0.1 to 5.5 pg/g, 

was measured in brown trout fillets. This variation may 

have been a result of the sampled fish consisting of a 

combination of recently stocked, presumably PCBfree, and longer resident fish, which had time to accumulate PCBs (Robert Maietta, oral commun., 2000). 

Total concentrations of PCBs in sediments collected during the 1987 investigation were highest at 

stations between the Birch Hill Dam and the confluence with the Otter River (river mile 29.5 and 30.7), 

ranging from 4 to 49 pg/g, dry-weight basis. All PCB 

concentrations in sediments are reported in micrograms 

PCBs per gram sediment, dry weight. At six stations 

downstream from the dam (river mile 0.1, 1.8, 10.9, 

19.3,28.0,29.5) PCB concentrations in the sediments 

were less than detection limits of 0.1 to 0.5 pg/g, 

except for station 10.9, where concentrations in the two 

samples collected were 1.7 and 7.3 p-g/g, respectively. 

Introduction 3 
--- 

$ 

EXPLANATION SWANZEY \ 

U.S. GEOLOGICAL SURVEY 

STREAM GAGING STATIONS 

01162500 Contmuous-record statlon and 

A number 

01162000 Continuous-record station with 

AiT telemetry and number 

M-$0 SAMPLING STATION +ND 

IDENTIFIER-Samplmg station 

numbers include the first letter of 

the river on which they are located 

and the number of miles that the 

statlon 1s upstream from the 

confluence of the Millers River 

with the Connecticut River 

42’3 - PRINCETON 

WINCHESTER 

Athoi 

+ SETTLEMENT CENTER I;(- ;y 

1 

I RICHMOND 

YEW HAMPSHIRE I I 

JSm--T----

\ 

I 

GILL ‘, 

42’3C 

5 10 KILOMETERS 

Figure 1. Millers River Basin in Massachusetts and New Hampshire with tow 

4 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
I 72'00 

TROY 

/ 

.-

-32 

‘\ 

/ / / / /’ \ 

\ 

\ 

: 

\ \ \ 

\ 

/ 

IIDoundaries, town centers, and PC6 passive-sampler stations displayed. 

Introduction 5 
In 1988, 16 more sediment samples were collected by USACE and MDWPC at various sediment 

depths in the Birch Hill Dam retention basin area. The 

highest PCB concentrations (180 pg/g) were measured 

in subsurface sediment (12 in. below the sedimentwater interface) at river mile 30.1 as well as in a subsediment layer (13.5 in. depth) at river mile 29.8 

between the dam and the confluence of the Millers 

River with the Otter River. Concentrations of 250 pglg 

were measured in subsurface sediment (14 in. deep) at 

a site on the Otter River (river mile 32.4). Low PCB 

concentrations (less than 0.5 pg/g) were measured in 

sediment of the Millers River upstream from the Otter 

River confluence and in the Otter River upstream from 

Baldwinville. 

Subsequent investigations were conducted in 

1989, 1990, and 1991 to determine within-site variability of the sediment analysis and to measure PCB concentrations in fish samples from the apparently 

contaminated reach upstream from the dam and in the 

Otter River downstream from Baldwinville. These 

investigations indicated that high concentrations of 

PCBs were not always measured in sediments sampled 

repeatedly at the same locations, but that high concentrations (14 to 58 p.g/g) continued to be measured in 

these reaches. High PCB concentrations (as high as 

29 pg/g) also were measured in overbank sediment 

locations where frequency of flooding was high (U.S. 

Army Corps of Engineers 1991,1993, 1995). 

PCB concentrations in fish fillets from the reach 

between the dam and downstream reaches of the Otter 

River ranged from 0.1 to 1 .O pg/g, not as high as those 

measured downstream from the dam (U.S. Army Corps 

of Engineers, 1991,1993, 1995). No trout, which had 

the highest PCB concentrations elsewhere, were collected in this reach. 

A regional investigation of organochlorines that 

included a Millers River Basin sample. was published 

by Coles (1998). A PCB concentration of 0.58 pglg 

was measured in a whole-fish composite white sucker 

sample collected in 1994 from the Otter River at the 

town center of Otter River (fig. 1). 

Acknowledgments 

The support of Alice Rojko, Millers River Basin 

team leader, Massachusetts Executive Office of Environmental Affairs, during planning and implementation 

of this investigation, is greatly appreciated. Simon 

Litten of the New York Department of Environmental 

Protection and John Hassett of the State University of 

New York-Syracuse provided valuable assistance in 

project design and sampling techniques. 

SAMPLING AND ANALYSIS 

The major objectives of this investigation were 

(1) to determine the source(s) of the elevated PCB concentrations observed in fish and (2) to establish the 

extent of fish exposure to PCBs along the entire main 

stem of the Millers River and of a tributary the Otter 

River. PCB concentrations were measured by means of 

passive samplers suspended in the water column at 

intervals along the Millers River and the Otter River. 

PISCES samplers were used, as described in detail by 

Litten and others (1993). The samplers, each containing 0.200 L of hexane and fitted with a polyethylene 

membrane, absorb PCBs during a 2-week deployment 

interval. (All hexane and acetone used in the project 

was pesticide analysis grade). This deployment interval 

results in PCB concentrations in hexane that reflect 

time-integrated dissolved concentrations of PCBs in 

river water passing the sampling point (Litten and 

others, 1993). 

Sampling of the water column rather than 

streambed sediment, another integrator of PCB concentrations, was selected because (1) water column samples generally require less laboratory-analysis cleanup 

than do sediment samples, so that detection limits are 

lower; (2) water-column results can give a better indication of PCB bioavailability, because dissolved PCBs 

cross cell membranes and are likely to get into the 

food web (Barron, 1990); and (3) water-column 

results are not subject to variability associated with 

sediments of grain size and organic carbon content. 

Passive samplers were chosen over grab-sample 

extraction because of (1) time integration of ambient 

PCB concentrations that occurs during sampler deployment, (2) ease of field deployment, and (3) sensitivity 

of the method (Litten and others, 1993). Hexane 

samplers were chosen over synthetic lipid-filled 

samplers (Rantalainen and others, 1998) to avoid 

extraction of PCBs from lipid and the additional 

laboratory cleanup necessary before analysis. 

An additional design feature of this project was 

quantification of PCBs in terms of congeners, the individual PCB compounds, of which about 100 (of a possible 209) have been detected in environmental 

6 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
samples (Schulz and others, 1989). The different PCB 

congeners result from the various numbers and positions of chlorine atoms possible that can attach to a 

biphenyl ring structure. Aroclors (with distinguishing 

numbers of 1016, 1232, 1242, 1254, etc.) are mixtures 

of PCB congeners that were produced commercially, 

which in some combination of environmental introduction and biogeochemical weathering, account for the 

congener pattern present in stream samples. Because 

relative concentrations of PCB congeners are unlikely 

to be exactly the same in samples from different 

sources, changes in congener pattern within a river 

reach can indicate new sources of PCBs (Litten and 

others, 1993). 

Sampling Procedures 

Sampling procedures followed the methods of 

Litten and others (1993). Samplers were cleaned in the 

laboratory with soap and water, a deionized water 

rinse, and air drying, followed by one acetone rinse and 

three hexane rinses. Low density polyethylene membranes (cut from Ziploc bags) and Viton O-rings were 

cleaned by 7-hour soxhlet extraction with hexane. 

Membranes were always new; O-rings were re-used 

after soap and water cleaning and four solvent rinses 

(as for samplers). After cleaning, the samplers were 

assembled and wrapped in hexane-rinsed aluminum 

foil. In the field, the assembled samplers were hexanerinsed just prior to deployment to remove any contamination associated with storage or transport. Finally, 

samplers were filled with 0.200 L of hexane and 

installed in the stream. The passive samplers were hung 

6 in. below the stream surface, membranes down, in 

pairs from plastic bottle buoys attached by nylon cord 

to cinder-block anchors. Sampling station locations 

were selected in pools, rather than in riffles, because 

slowly moving water was conducive to successful 

sampling. 

Samplers were deployed during four intervals in 

the spring through fall, 1999 (table 1). Deployments 

usually were for 14 days, although at 5 sampling stations in May and 4 stations in November, deployments 

were for 13 days. So that the relative positions of the 

stations could be determined easily, they were numbered by river mile preceded by the first letter of the 

river on which they were located. For example, O-31.2 

refers to the station on the Otter River 3 1.2 mi 

upstream from the confluence of the Millers River with 

the Connecticut River. The upper Millers River and the 

Otter River were sampled first (May-June) followed 

by the lower Millers River (July). Two follow-up 

samplings were conducted, primarily of Otter River 

stations (August-September and November). The station nearest Birch Hill Dam (M-29.1) was sampled four 

times, once during each deployment. Sampling stations 

were located upstream and downstream from settlement centers on the rivers to bracket potential sources, 

at intervals ranging from 0.6 to 6 mi initially and as 

close as 0.02 mi in follow-up samplings (fig. 1). 

Hydrographs of streamflow during the period of 

deployment were used to assess whether samplers 

remained suspended in the water column (not resting 

on the sediments) during the entire 2 weeks. Upon 

retrieval, samples were poured into 0.25 L precleaned 

I-Chem jars, and stored at -20°C until shipment by 

overnight courier to the analytical laboratory, Axys 

Analytical Services, Ltd., in Sidney, British Columbia, 

Canada. 

Analytical Laboratory Procedures 

Samples received at the laboratory were transferred to secure storage and maintained in the dark at 

4°C until preparation for analysis. The volume of each 

sample was determined using a graduated cylinder. 

Samples were prepared and analyzed for congeners 

using a modification of USEPA Method 8082A 

(U.S. Environmental Protection Agency, 1998). 

Principal modification of the technique was in means 

of detection/quantification, which was by lowresolution quadrupole mass selective detection, rather 

than by gas chromatography with electron-capture 

detection (ECD) and confirmation by mass 

spectrometer. A second modification was the use 

of carbon-13 labeled PCB congeners for the 

surrogate and internal standards, whereas Method 

8082A uses ECD standards-unlabeled PCB 209 and 

tetrachloro-meta-xylene. 

Samples were analyzed in batches of 10 to 

12 that included a procedural blank. Each hexane 

sample was spiked with an aliquot of a standard 

solution of five surrogate carbon-13 labeled PCBs, 

International Union of Pure and Applied Chemistry 

(IUPAC) congener numbers 101,105,118,180, 

and 209, and dried over anhydrous sodium sulfate. 

Sampling and Analysis 7 
Table 1. Stations sampled for PCBs using passive samplers in the Millers River and Otter River, Massachusetts during 1999 

[Latitude and longitude are in degrees, minutes, and seconds; dates arc month-day-year. No., number; USGS, U.S. Geological Survey] 

Station No. Latitude 

0 , N Longitude 0 , I 

Date 

deployed 

Date 

retrieved Comments 

O-41.8 42 33 36.0 72 00 38.0 5-26-99 6-08-99 

o-39.9 42 34 24.9 72 01 26.0 5-26-99 6-08-99 one sample lost 

O-36.9 42 35 35.8 72 02 44.5 5-26-99 6-08-99 

O-36.2 42 35 36.2 72 03 20.6 5-26-99 6-08-99 

o-35.4 42 35 56.4 72 03 58.5 1 l-10-99 1 l-24-99 one sample analyzed 

O-35.20 42 36 03.6 72 04 06.7 8-24-99 g-07-99 

o-35.17 42 36 04.5 72 04 08.0 1 l-10-99 1 l-24-99 one sample analyzed 

o-34.99 42 36 09.3 72 04 18.2 8-24-99 g-07-99 

o-34.97 42 36 10.6 72 04 19.1 8-24-99 g-07-99 

o-34.97 42 36 10.6 72 04 19.1 1 l-10-99 1 l-24-99 resampled, one sample analyzed 

o-34.93 42 36 11.9 72 04 20.1 8-24-99 g-07-99 

o-34.7 42 36 22.6 72 04 27.9 8-24-99 g-07-99 

o-34.5 42 36 22.9 72 04 42.0 8-24-99 g-07-99 

o-33.7 42 36 27.7 72 05 28.0 5-25-99 6-08-99 

o-33.1 42 36 46.8 72 05 33.8 8-19-99 g-02-99 

O-32.1 42 37 23.4 72 05 30.6 8-19-99 g-02-99 

O-31.2 42 38 04.2 72 05 39.9 5-25-99 6-08-99 one sample lost 

O-31.2 42 38 04.2 72 05 39.9 8-19-99 g-02-99 resampled 

M-33.8 42 41 03.0 72 05 02.0 5-25-99 6-08-99 

USGS station no. 

01162000 

M-31.2 42 38 17.7 72 05 36.0 5-25-99 6-08-99 one sample lost 

M-29.1 42 37 54.5 72 07 32.4 5-25-99 6-08-99 

M-29.1 42 37 54.5 72 07 32.4 7-02-99 7-16-99 resampled 

M-29.1 42 37 54.5 72 07 32.4 8-19-99 g-02-99 resampled 

M-29.1 42 37 54.5 72 07 32.4 1 l-10-99 1 l-24-99 resampled, one sample analyzed, and samplers 

resting on mud 

M-27.5 42 37 46.6 72 08 57.8 7-02-99 7-16-99 

USGS station no. 

01164000 

M-21.0 42 35 41.8 72 12 52.8 7-02-99 7-16-99 one sample lost 

M-18.1 42 34 50.0 72 15 00.5 7-02-99 7-16-99 

M-14.7 42 35 09.6 72 17 50.7 7-02-99 7-16-99 one sample lost 

M-12.8 42 35 48.5 72 19 36.8 7-02-99 7-16-99 samplers resting on mud 

M-12.8 42 35 48.5 72 19 36.8 1 l-10-99 1 l-23-99 resampled, one sample analyzed 

M-10.9 42 35 55.3 72 21 24.8 1 l-10-99 1 l-23-99 one sample analyzed 

M-10.4 42 35 43.4 72 21 48.4 1 l-10-99 1 l-23-99 one sample analyzed 

M-10.3 42 35 49.0 72 22 00.3 1 l-10-99 1 l-23-99 one sample analyzed 

M-9.8 42 35 57.2 72 22 29.8 7-02-99 7-16-99 

M-8.0 42 36 02.3 72 24 22.0 7-02-99 7-16-99 

M-2.6 42 34 45.5 72 28 56.4 7-02-99 7- 16-99 samplers on cobbles 

M-O. 1 42 35 42.0 72 29 46.0 7-02-99 7-16-99 one sample lost 

8 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
The dried extract was split gravimetrically; one half 

was reserved as backup sample, the other half was 

cleaned up on a Florisil column. After loading with the 

sample, the Florisil column was eluted with hexane 

followed by 15:85 dichloromethane:hexane. The latter 

fraction was treated with activated copper to remove 

sulfur, concentrated to a small volume, and transferred 

to an auto-sampler vial. Carbon- 13 PCB 153 was added 

to the vial as a recovery (internal) standard. 

High-resolution gas chromatography/lowresolution mass spectrometry analysis of the extract 

was carried out on a Finnigan Incas 50 mass spectrometer (MS) equipped with a Varian 3400 gas chromatograph, a CTC auto-sampler and a Prolab/Envirolink 

data system for MS control and data acquisition. A 

J&W DB-5 capillary column (60 m, 0.25 mm i.d., 

0.10 micron film thickness) was coupled directly to the 

MS source. The MS was operated at unit mass resolution in the electron ionization mode using multiple-ion 

detection, acquiring two characteristic ions for each 

target analyte and surrogate standard. Analyses of ten 

percent of samples (8 analyses) were confirmed on a 

high-resolution mass spectrometer. 

Initial calibration, to generate relative response 

factors (RRFs) of native PCB congeners with respect to 

carbon- 13 labeled PCB surrogate standards, was performed using a series of solutions that encompassed the 

working concentration range of the instrument. The 

multi-level initial calibration solutions contained the 

same suite of labeled surrogates as spiked in the samples, recovery standards, and the PCBs targeted for 

analysis. Calibration was verified at least once every 

12 hours by analysis of a mid-level calibration solution. 

PCB-congener concentrations were determined 

with respect to labeled surrogates by the internal standard quantitation method and all reported concentrations are recovery corrected. The recovery of labeled 

surrogates, added to the sample prior to clean up, was 

determined against the recovery standard (carbon- 13 

PCB 138) added to the final extract prior to GUMS 

analysis. The laboratory reported 99 peaks (domains) 

that included 128 target PCB congeners. Isomeric congeners that co-elute on the capillary column were 

reported as 2- or 3-congener combinations (Appendix 

A). The sums of the 128-congener concentrations were 

computed and reported as ZPCB values. 

Aroclor concentrations were estimated from the 

summed peak areas of a suite of “marker peaks” that 

are congeners characteristic of the particular Aroclor 

formulation (table 2). The summed peak areas of each 

marker peak set were converted to concentrations using 

RRFs derived from a calibration solution that contained 

equal concentrations of Aroclors 1242,1254, and 1260. 

This method uses these sets of marker peaks to express 

the undegraded Aroclor patterns. The method is especially useful in procedures that allow the congener data 

to be compared with historical Aroclor data. The congener analytical procedure used in this investigation, 

however, quantifies most of the congeners that are 

present in the major Aroclors: 96,90, 87, and 94 percent of Aroclors 1016, 1242, 1254, and 1260, respectively (Aroclor composition data from Schulz and 

others, 1989), so the CPCB values reported here would 

be within 4 to 13 percent of the total amount of PCBs 

present in the sample. 

Table 2. Analyte ions monitored, surrogates used, and RRF determination for polychlorinated biphenyl Aroclors by 

HRGC/LRMS 

[HRGULRMS, high resolution gas chromatography/low resolution mass spectrometry; RRF, relative response factor] 

Aroclor Characteristic congeners Surrogate RRF determined 

from Recovery standards 

1242/1016/1248 16132, 18, 17,28,31 13C-PCB-101 1242 13C-PCB 153 

1254 99,97, 87 13C-PCB-101 1254 13C-PCB 153 

1260 183,180,170 13C-PCB-180 1260 13C-PCB 153 

Sampling and Analysis 9 
Statistics for Evaluating Changes in 

Congener Patterns 

Differences in congener patterns between pairs 

of samples were quantified by comparing root mean 

square difference (RMSD) between normalized congener concentrations in the two samples. RMSD was 

determined as the square root of the sum of squared 

differences between normalized congener concentrations in the two samples divided by the number of 

congener pairs compared. Congener pairs were eliminated from compared sample data if the concentration 

of a congener was below the analytical detection limit 

in either sample. Congener concentrations were normalized by dividing by summed congener concentration for the sample. Sums of congeners used in 

normalization for the RMSD computation were based 

on congener pairs remaining after elimination of 

below-detection pairs. 

RMSD comparison statistics were computed for 

duplicate samples hung from one buoy, to determine 

congener variation at a station, and for samples from 

different stations, to determine variation between stations. These statistics can be used to determine whether 

the change in pattern between stations is significantly 

different (a = 0.05) from the change in pattern between 

duplicates by using a t-test (two-sample, assuming 

equal variances) to compare the mean of the RMSD 

statistics generated between sites with the mean of the 

RMSD statistics computed from duplicate comparisons. The means for the t-test were from pooled RMSD 

comparisons of samples at a station (sample 1 at a station compared to sample 2 at the same station) and 

from two RMSD comparisons between stations with 

duplicate sampling (sample 1 at one station compared 

to sample 1 of a second station and sample 2 of the first 

station compared to sample 2 of the second station). 

POLYCHLORINATED 

BIPHENYL DATA 

Data Quality 

Field quality-assurance procedures included two 

equipment blanks submitted blind to the laboratory, 

deployment of duplicate samplers at each station, and 

four resamplings at station M-29. l-one sampling 

during each of the four deployments. Laboratory 

10 Source Identification and Fish Exposure for Polychlorinated 

quality-assurance procedures included batch 

analytical runs with procedural blanks; opening, 

mid-run, and closing calibration checks; and 

confirmation of analysis of 10 percent of samples by 

high-resolution mass spectrometry. 

The equipment blanks were prepared by filling a 

sampler with 0.200 L of hexane in the field, which was 

poured into an I-Chem jar. None of the 128 congeners 

reported by the laboratory were detected in either 

equipment blank (method detection limits ranged 

from .2 to 0.5 ng per sample). 

During the project, 23 pairs of duplicate samples 

were obtained. The average difference between duplicate-pair CPCB concentrations (27 percent) indicates 

that the sampling rate of adjacent samplers was not 

exactly equal. Differences in sampling rate likely were 

caused by slightly different orientations of the samplers 

with respect to flow, resulting in different transport 

rates of water-column PCBs to the sampler membrane 

surface. Congener concentrations in procedural blanks 

from the laboratory were all less than detection. Other 

quality control parameters remained within control 

limits for all analyses. 

Even with a difference in overall sampling rate, 

the relative sampling rate among congeners would be 

expected to be the same for both samplers, so that the 

normalized congener patterns from duplicate samplers 

would be similar. In fact, the comparison statistic, 

RMSD, was very low, 0.1 to 0.3 percent, for duplicate 

sample pairs with CPCB amounts greater than 100 ng. 

RMSD values for hexane samples with XPCB amounts 

less than 100 ng were larger (fig. 2). The relation of 

RMSD with CPCB concentration for duplicate pairs is 

inversely correlated, because the relative precision of 

analysis decreases as concentrations approach the 

detection limit of the method. Slight differences in the 

bar-graph patterns of duplicates can be observed in 

plots of the duplicate samples (fig. 3). In these plots, 

as in all the congener plots and tables, congeners are 

in order of their retention time on the gas chromatograph. This order may correlate with the order of 

geochemical weathering because the lighter molecular 

weight, more volatile compounds are the first to 

emerge from the gas chromatograph followed by 

progressively heavier molecular weight, less volatile 

compounds. The plots indicate how the RMSD statistic 

can pick out differences in duplicates that appear 

quite similar. 

Biphenyls in the Millers River Basin, Mass. 
0.1 

0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 

MEAN ZPCB CONCENTRATION, IN MICROGRAMS PER HEXANE SAMPLE 

Figure 2. Correspondence of RMSD with mean ZPCB concentration for duplicate samples from the Millers River Basin. 

RMSD = 0.376 I O-31.2, SAMP 1 

0 O-31.2, SAMP 2 

RMSD = 0.119 I M-29.1, SAMP 1 

Cl M-29.1, SAMP 2 

POLYCHLORINATED BIPHENYL CONGENER IUPAC NUMBER 

Figure 3. Differences in congener patterns in duplicate samples. 

sample pairs with different RMSD values.] 

Results of the four repeated samplings at station 

M-29.1 were consistent (Appendix B). Average deviation of CPCB from the mean was 24 percent in the first 

6 samples (3 deployments) collected at the station. The 

CPCB concentration of the last sample collected at 

M-29.1, in November, was only one tenth the average 

of the previous values. 

Low concentrations of PCBs in hexane were 

obtained in all the November samples (Appendix B), 

and the November data were not used to interpret PCB 

[Two bars are plotted at each congener position for two 

source. Possible causes of the low response were lowtemperature water, which would reduce the efficiency 

of sampling by a factor of 3 (see “Exposure of Fish to 

Polychlorinated Biphenyls in the Millers River Basin” 

section), and low concentrations of PCBs in the water 

column because of dilution from higher flows that 

occurred in November as compared to the summer 

period (fig. 4). 

Polychlorinated Biphenyl Data 11 
--- MILLERS RIVER AT ERVING 01166500 

- OTTER RIVER AT OTTER RIVER 01 lS32W 

June July Aug. Sept. Oct. Nov. May 

1 ggg 

Figure 4. Daily mean discharge data for USGS stream gaging stations at Otter River at Otter River (station number 

01163200), Millers River at South Royalston (station number 0116400), and Millers River at Erving (station number 

01166500). [Data are provisional except for records May through September 1999 for Otter River at Otter River and 

Millers River at Erving, which are final. Arrows along the date axis indicate the 13- or 14-day periods of PISCES 

sampler deployment.] 

In some cases, the ratio of monitored ion molecular fragments recorded by the mass spectrometer did 

not pass the laboratory ratio criteria (20 percent of the 

theoretical) that was established for a congener 

expected at a particular retention time. Responses with 

ratios outside the criteria are indicated in the data 

reported in Appendix B. Generally, peaks that failed 

the ratio test were minor and did not comprise a substantial fraction of ZPCBs. Occasional large responses 

that did not meet the criterion-at station M-33.8, 

sample 2 (congeners 105/127), and station O-34.93, 

sample 1 (congeners 7/9)-and 2 large responses that 

did not fit PCB patterns observed in other samplesstation o-35.20, both samples (congeners 7/9)-were 

not included in CPCB or in RMSD calculations. 

Samples selected for analysis confirmation 

by high-resolution mass spectrometry were the 

low response samples-background samples and 

samples collected during November-and one highconcentration sample on the Otter River. The high resolution results (Appendix B) indicated more congener 

peaks could be identified in the low response samples 

with high resolution, compared to low resolution, mass 

spectrometry, and that qualitative and quantitative 

results were similar for the two methods in the 

high-concentration sample. 

Sampling Results 

The deployment of samplers was successful 

at most stations; however, on six occasions one 

sampler of a duplicate deployment was lost (table 1). 

Recoveries of the initial 0.200 L hexane from 

successful deployments averaged 0.173 L (66 samplers 

with a standard deviation of 0.017 L). Streamflow 

during deployment of samplers was constant or 

decreasing (fig. 4), so that samplers suspended in the 

water column (not resting on the streambed) at retrieval 

could be assumed to have remained suspended 

throughout the entire period of deployment. On three 

occasions, samplers had settled to the streambed by the 

end of deployment, once because of a punctured buoy. 

Depending on duration of sampler grounding (which is 

unknown), results from grounded samplers may not 

have represented water-column conditions accurately 

and were flagged where reported in figures and tables. 

A large range of ZPCB concentrations was 

measured through deployment of the passive 

samplers-from 1 to 8,000 ng/hexane sample (table 3). 

Units of PCB weight/hexane sample were used 

to avoid mistaking passive-sample results for 

concentrations in ambient water. The highest concentrations measured were more than 10 times greater 

than those reported in a previous PCB point-source 

investigation in the Black River, New York, in which 

passive samplers were used (Litten and others, 1993). 

12 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
Table 3. Sums of congeners, Aroclor mixtures from passive samplers, and computed water-column concentrations at stations 

on the Millers River and the Otter River, Massachusetts 

[Water temperatures used to compute water-column concentrations were averages of mean daily temperatures for the deployment period at the U.S. Geological 

Survey continuous-record gage on the Stillwater River near Sterling, Mass., 01095220: May deployment, 19.3”C; July deployment, 21.3-C; August deployment, 19.3’C; November deployment, 5.8’C; ND, below detection limit; No., number; EPCB, summed concentrations of all targeted polychlorinated biphenyl 

congeners; ngihexane sample, nanograms per hexane sample; q/L, nanograms per liter] 

Aroclor 

Station No. Date 

deployed Sample No. 

IPCB 

(nglhexane 

sample) 

1016 and 1242 

(ng/hexane 

sample) 

Aroclor 1254 

(nglhexane 

sample) 

Aroclor 1260 

(nglhexane 

sample) 

Water-column 

concentration 

OwW 

O-41.8 5-26-99 1 18 17 ND 7 0.8 

O-41.8 5-26-99 2 17 18 ND 8 .8 

o-39.9 5-26-99 1 19 17 ND 8 .9 

O-36.9 5-26-99 1 9 9 ND 5 .4 

O-36.9 5-26-99 2 11 ND ND ND .5 

O-36.2 5-26-99 1 10 7 ND 4 .5 

O-36.2 5-26-99 2 12 8 ND 7 .7 

o-35.4 1 l-10-99 1 ND ND ND ND ND 

o-35.20 8-24-99 1 29 33 11 ND 1.5 

O-35.20 8-24-99 2 15 21 11 2.6 1.1 

o-35.17 1 l-10-99 1 ND ND ND ND ND 

o-34.99 8-24-99 1 55 61 21 ND 2.2 

o-34.99 8-24-99 2 37 47 13 ND 1.5 

o-34.97 8-24-99 1 120 100 52 11 4.7 

o-34.97 8-24-99 2 56 61 20 ND 2.2 

o-34.97 11-10-99 1 ND ND ND ND ND 

o-34.93 8-24-99 1 78 77 27 5.2 3.6 

o-34.93 8-24-99 2 67 65 22 4.6 2.6 

o-34.7 8-24-99 1 130 160 27 ND 5.0 

o-34.7 8-24-99 2 160 220 28 ND 6.3 

o-34.5 8-24-99 1 190 260 31 3.8 7.7 

o-34.5 8-24-99 2 210 290 32 3.2 8.3 

o-33.7 5-25-99 1 1,200 1,800 99 9 43 

o-33.7 5-25-99 2 750 1,100 79 9 28 

o-33.1 8-19-99 1 1,860 3,200 130 3.6 77 

o-33.1 8-19-99 2 2,380 5,500 310 11 140 

O-32.1 8-19-99 1 2,200 3,700 140 2.7 94 

O-32.1 8-19-99 2 3,310 5,600 210 5.3 140 

O-31.2 s-25-99 1 8,000 12,000 640 ND 300 

O-31.2 8-19-99 1 7,310 12,000 430 7.2 300 

O-31.2 8-19-99 2 7,370 13,000 400 7.0 310 

M-33.8 5-25-99 1 4 ND ND ND .l 

M-33.8 5-25-99 2 1 ND ND ND .08 

M-31.2 5-25-99 1 9 9 8 ND .4 

M-29.1 5-25-99 1 1,900 2,800 160 ND 70 

M-29.1 5-25-99 2 1,500 2,100 170 6 55 

M-29.1 7-02-99 1 2,200 3,600 200 ND 72 

M-29.1 7-02-99 2 1,700 2,600 160 ND 54 

Polychlorinated Biphenyl Data 13 
Table 3. Sums of congeners, Aroclor mixtures from passive samplers, and computed water-column concentrations at stations 

on the Millers River and the Otter River, Massachusetts-Continued 

Station No. Date 

deployed Sample No. 

ZPCB 

(nglhexane 

sample) 

Aroclor 

8 1016 and 1242 

(ng/hexane 

sample) 

Aroclor 1254 

(ng/hexane 

sample) 

Aroclor 1260 

(nglhexane 

sample) 

Water-column 

concentration 

(ncW 

M-29.1 8-19-99 1 900 1,500 77 2.3 37 

M-29.1 8-19-99 2 1,150 1,900 .89 ND 48 

M-29.1 1 l-10-99 1 180 260 ND ND 20 

M-27.5 7-02-99 1 1,700 2,600 200 ND 56 

M-27.5 7-02-99 2 2,000 3,100 220 ND 65 

M-21.0 7-02-99 1 390 530 59 ND 13 

M-18.1 7-02-99 1 450 570 78 ND 15 

M-18.1 7-02-99 2 410 500 80 ND 13 

M-14.7 7-02-99 1 620 800 110 ND 20 

M-12.8 7-02-99 1 350 450 71 ND 12 

M-12.8 7-02-99 2 270 340 51 ND 8.7 

M-12.8 1 l-10-99 1 45 66 ND ND 5.1 

M-10.9 1 l-10-99 1 58 80 ND ND 6.4 

M-10.4 1 l-10-99 1 110 160 ND ND 14 

M-10.3 1 l-10-99 1 130 160 ND ND 12 

M-9.8 7-02-99 1 370 440 78 ND 15 

M-9.8 7-02-99 2 490 590 95 ND 20 

M-8.0 7-02-99 1 550 640 120 ND 23 

M-8.0 7-02-99 2 540 650 100 ND 22 

M-2.6 7-02-99 1 410 470 92 ND 17 

M-2.6 7-02-99 2 460 540 100 ND 19 

M-O. 1 7-02-99 1 260 280 70 ND 10 

The PCB concentrations in terms of Aroclors (table 3) indicates many of the samples have similar congener 

indicated Aroclor 1016/1242 dominated the high- patterns, as confirmed by statistical comparisons 

concentration samples, although small concentrations described in the following section. 

of 1254 and 1260 were also reported. IZPCB concentration often was less than the total concentration of the 

estimated Aroclors. These discrepancies may have 

been caused by unquantified congeners (as discussed in IDENTIFICATION OF SOURCES OF 

the Analytical Laboratory Procedures section), by POLYCHLORINATED BIPHENYLS 

‘altered environmental congener patterns caused by 

geochemical weathering, or analytical error in either Sources of PCBs can be inferred between 

the congener or the Aroclor determination. Generally, stations where there is a change in PCB concentration, PCB concentrations estimated by Aroclor are biased in PCB-congener patterns, or in both concentration high because of overlapping patterns of the Aroclor 

mixtures (Eganhouse, 1991). and pattern (Litten and others, 1993). These changes 

All sample congener concentration results are can be observed in a plot of average ZPCB concentraplotted as bar graphs in the Appendix B. Visual com- tion at a station and of RMSD between adjacent 

parison of the congener patterns in the bar graphs stations displayed in downstream order (fig. 5). 

14 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
II II III1 II I I I I I II I II II I -

I 

: 

1 

0 

MEAN PCB CONCENTRATION-In nanograms 

RMSD-In nyograms 2,000 6 : 

k? 

OW 

6,000 1,000 4 : 

gg 2 5,000 

g5o (0 4,000 

$923 3,000 

ti I 2,000 

2

W 1,000 

0 

Figure 5. (A) Streambed elevation profile of the Millers River from the Connecticut River to the 

confluence with the Otter River and of the Otter River to its source (Massachusetts Division of Water 

Pollution Control, 1980) and (6) ZPCB and between-station RMSD of congener concentrations in 

downstream order on the Otter River and the Millers River. [Data from stations sampled only in 

November are not displayed because of low response obtained during that sampling. Concentrations 

are means of two samples and RMSD are means of two sample comparisons unless indicated by (1) 

above the bars, where a sample was lost; * means t-test comparison showed between-station RMSD 

was significantly greater than within station RMSD; t means samplers were grounded on mud; 

tt means samplers were grounded on cobbles.] 

Sources Upstream from Birch Hill Dam Bar charts of the congener patterns from stations 

on the Otter River (fig. 6) show the nature of the pattern 

On the Otter River, ZPCB concentrations change coincident with the maximum RMSD between 

increased many fold in the downstream direction, O-36.2 and O-35.20. Generally the lower weight conbeginning at station o-35.20, with a maximum concen- geners (congeners containing fewer chlorine atoms) 

tration increase occurring between stations O-32.1 and increase from O-36.2 to O-35.2 relative to the higher- O-3 1.2 (fig. 5). Maximum pattern change, as indicated weight congeners (congeners containing more chlorine 

by RMSD, was computed farther upstream, between atoms). Of five groups of congeners that increase stations O-36.2 and o-35.20. Actually, a large ZPCB (marked by brackets below the axis for sample o-35.20 concentration change in percentage terms was measured coincident with the pattern change between sta- in figure 6), only one (group 4) is present in O-36.2 

tions O-36.2 and o-35.20 (table 3), but the absolute with essentially the same pattern (although 42/59 is 

concentrations involved were small. The progressive missing) as in station o-35.20. Downstream from 

increase of XPCB concentrations downstream from the o-35.20, the pattern in the five groups does not change 

maximum change in pattern is compatible with a from sample to sample, and the concentrations of the 

hypothesized PCB source that is distributed over a lower-weight congeners continue to increase relative to 

downstream reach between stations O-36.2 and O-31.2. higher-weight congeners. 

Identification of Sources of Polychlorinated Biphenyls 15 

ZPCB concentrations measured on the upper 

Millers River just upstream from the confluence with 

the Otter River, stations M-3 1.2 and M-33.8, were low 

(averages of 3 and 9 ng/hexane sample, which are too 

small to show in the inset, fig. 5) but increased to a high 

concentration (average 1,700 ng/hexane sample) downstream from the confluence with the Otter River at station M-29.1. Congener pattern change, as evaluated by 

RMSD, was high between stations M-33.8 and M-31.2 

and higher still between stations M-3 1.2 and M-29.1. 

These results reflect (1) the high relative error associated with congener analysis at low concentration, and 

(2) ZPCB concentration in the upper Millers River that 

was much lower upstream from the confluence with the 

Otter River than downstream and much different in 

congener pattern. The low CPCB concentrations at stations M-3 1.2 and M-33.8, indicate that there was not a 

PCB point source on the upper Millers River. 

Conceptual Model of Source 

Conceptually, a source distributed between stations O-36.2 and O-31.2 for the dissolved PCBs measured in the water column could be PCB-contaminated, 

fine-grained sediment on the stream bed. As noted in 

past investigations, high concentrations of PCBs (to 

250 pglg) have been measured in streambed sediments 

from the Millers River upstream from the Birch Hill 

Dam and from the lower Otter River (U.S. Army Corps 

of Engineers, 1995). Because PCBs have not been 

manufactured commercially in the United States since 

1977, active PCB discharge, such as that from industrial processing, has slowed or stopped in most locations. Current detections of PCBs in the dissolved 

phase are often from reservoirs of historical PCB discharge such as in ground water (for example, in the 

Housatonic River, Mass., S. Svirsky, U.S. Environmental Protection Agency, oral commun., 2000), landfills, 

or on stream sediments (for example, in the Fox River, 

Wis., William and others, 1997). Release from bed sediment distributed along a river reach would account for 

the progressive total PCB concentration increase and 

the congener-pattern change in the downstream direction measured in the Otter River-the greater the 

volume of contaminated sediment passed over by 

stream water, the greater the amount of PCBs picked 

up by the water. 

Exchange of PCBs between the water column 

and the sediments is commonly modeled as an equilibrium process with net transport direction depending on 

relative concentrations of PCBs adsorbed onto the sediments and dissolved in the water column (Mackay and 

others, 1992). During active discharge of PCBs into the 

water column, net transport would be from water to 

sediments, resulting in PCB loading of the solid phase. 

When discharge of PCBs into the stream is decreased 

or ended, the direction of PCB transport to achieve 

equilibrium would change to desorption from sediments to the water. Partition coefficients for PCBs 

between particulate organic carbon and water (I&,,) 

range from lo4 for PCB4 to lo* for PCB-209 

(Mackay and others, 1992). Large l$,, values mean that 

large amounts of PCBs could build up in sediments 

rich in organic matter during active PCB discharge. If 

active PCB discharge ceased or decreased, sorbed 

PCBs could move back into the water column from 

reworking of the contaminated sediments over a long 

period of time. 

Commonly, fine-grained sediments in the first 

depositional zone downstream from a PCB release 

point are highly contaminated with PCBs that have partitioned to the solid phase (Gay and Frimpter, 1985). 

The stream gradient in the Otter River decreases downstream from station O-36.2 as the stream enters an 

extensive zone of fine-grained wetland deposits associated with the Birch Hill Dam. Thus, progressive 

increase of PCB downstream from O-36.2 may be 

caused in part by an increasing fraction, in the downstream direction, of streambed sediment that is 

fine-grained and that contains sorbed PCBs. 

If the present water-column source of PCBs is 

historically contaminated streambed sediments, the 

point of historical active discharge for PCBs would be 

upstream from the point at which significant watercolumn PCB concentration increases and congener pattern changes occur. In the Otter River, the concentration increase (doubling) that occurs farthest upstream 

and the greatest congener pattern change occur 

between stations O-36.2 and o-35.20. Station o-35.20 

is upstream from pipe outfalls in the community of 

Baldwinville, including the waste-water treatment plant 

in Baldwinville that collects and treats waste from residences and industries in the community. However, 

sludge from the treatment plant is landfilled adjacent to 

the Otter River, upstream from the plant and upstream 

from station o-35.20. PCBs may have been discharged 

to the Otter River before the treatment plant went on 

Identification of Sources of Polychlorinated Biphenyls 17 
line (1979), existed in treatment plant effluent at some 

concentration after plant construction, and may have 

seeped into the river from the landfilled sludge. 

Correspondence with Aroclors 

The congener pattern least affected by PCBs 

from upstream of station o-35.20 and most strongly 

reflecting the source material is present in the three 

highest-concentration samples measured at station 

O-3 1.2 (Appendix B). Bar-graphs of congeners averaged from the three samples at O-3 1.2 compared with 

bar graphs of light Aroclors (1016 and 1242) (fig. 7), 

generally match well, although low-molecular weight 

congeners are slightly more prevalent in the O-3 1.2 

sample. Also, the prominent peak at 8/5 in the Aroclors 

is more than six times greater than the same peak in the 

O-3 1.2 sample. The statistical comparison, RMSD, 

between the light-weight Aroclors and the O-3 1.2 

sample is in the range of 1.2 to 1.3 percent-about five 

times greater than RMSD values for comparison of 

replicates at a station. The congener pattern is not 

inconsistent with a source of Aroclor 1016 or 1242. 

The hypothesized processes of sorption and desorption 

on the sediments before collection by the passive samplers might have altered the congener pattern so that an 

exact match would not be expected. 

Congener Pattern Weathering and 

Sources Downstream from 

Birch Hill Dam 

Downstream from the peak CPCB concentration 

at station O-3 1.2 (average of 7,560 ng/hexane sample), 

2=PCB concentrations decreased by a factor of four to 

the closely spaced stations of M-29.1 and M-27.5 and 

Aroclor 1016 

Aroclor 1242 

O-31.2, average 3 samples 

POLYCHLORINATED BIPHENYL CONGENER IUPAC NUMBER 

Figure 7. Relative PCB concentration congener patterns compared, average of three samples from station O-31.2 with 

patterns of Aroclor 1016 and 1242. 

18 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
then decreased again by a factor of four to the more 

distant station M-21 .O (fig. 5). From station M-21 .O 

downstream 13 mi to station M-8.0, concentrations 

were relatively constant, fluctuating between 3 10 and 

625 ng/hexane sample. Among the last three stations, 

M-8.0, M-2.6, and M-0.1, ZPCB concentrations 

decreased from 550 to 260 ng per sample. 

The initial decrease, between stations O-3 1.2 and 

M-29.1 likely was caused by streamflow dilution from 

the upper Millers River, in which EPCB concentrations 

were low. The ratio of streamflows during the 2-weeks 

of sampler deployment at the USGS gaging station 

01164000 (M-27.5) on the Millers River to USGS 

gaging station 01163200 on the Otter River, 6.1 mi 

upstream from the confluence, was approximately 5: 1 

(fig. 4). The ratio of flows likely would approach the 

PCB dilution ratio, 4: 1, if Otter River flow were measured at the confluence rather than 6.1 mi upstream. 

The second four-fold decrease, between stations M27.5 and M-21 .O, occurred in a reach where few tributaries enter the Millers River. This reach is high gradient, as noted in the basin description, and may be 

especially susceptible to PCB loss through volatilization to the atmosphere. The steep gradient also means 

that sedimentation of fine-grained suspended sediments 

and associated PCBs is unlikely, so that contaminated 

sediments would be relatively unavailable for PCB 

desorption into the water column in this reach. 

Changes in congener patterns associated with the 

PCB decreases between the two sets of stations can 

confirm possible causes of the decreases. T-test comparisons indicated change in pattern between stations 

was not significantly different (a = 0.05) from change 

in duplicates at a station for the first concentration 

decrease, between stations O-3 1.2 and M-29.1. Pattern 

change was significant, however, at the second 

decrease, between stations M-27.5 and M-21 .O (fig. 5). 

Dilution by the upper Millers River water, which was 

virtually devoid of PCBs, would not cause a pattern 

change, because all congeners would be reduced by the 

same amount and their relative abundance would be 

maintained. Decreased concentrations resulting from 

volatilization might cause a congener-pattern change 

because large molecular-weight congeners (those with 

many chlorine atoms) are volatilized less readily from 

water than are low molecular-weight congeners 

(Mackay, 1992). 

The nature of the pattern change can be 

expressed by ratios, R,,x, of normalized congener concentrations in successive samples downstream (stations 

M-29.1 through M-O. 1) to an upstream sample, O-3 1.2, 

defined, 

’ % contribution of congener IZ to total 

PCBs in sample x Rn,, = % contribution of congener IZ to total 

PCBs in sample O-3 1.2 

R,, values equal one where there was no change 

in the relative contribution of that congener to XPCBs 

of the sample by comparison with the contribution of 

the same congener to CPCBs at O-3 1.2. Congener 

ratios are greater than one for congeners that are 

enriched relative to O-3 1.2 and less than one for congeners that are depleted relative to O-3 1.2. When plotted 

in order of gas chromatograph retention time, a consistent congener-pattern change, such as from biogeochemical weathering, would be indicated by a 

progressive enrichment or depletion of congener along 

the retention-time axis. At the first two stations on the 

Millers River downstream from O-3 1.2, R,,, values 

were relatively constant and close to one (fig. 8A). 

Ratios for the next stations downstream, M-21 .O and 

M- 18.1, indicated enrichment of the higher molecular 

weight congeners and depletion of the lower molecular 

weight congeners (fig. S@. The same shift in congener 

pattern present for the M-21 .O and M-l 8.1 stations 

appeared in ratios for the next four stations downstream 

(fig. 8C and D). Finally, the shift was greatest at the last 

two stations before the confluence of the Millers River 

with the Connecticut River at stations M-2.6 and M-O. 1 

(fig. 8~9. 

These results are compatible with the hypothesized cause of decreases in CPCB in the steep-gradient 

reaches between stations M-27.5 and M-21 .O and 

between M-8.0 and M-0.1. Because of the steep 

gradient in these reaches, gas transfer increases across 

the air-water interface (Parker and Gay, 1987) and 

removal of the lower-molecular weight, more-volatile 

congeners might occur at a faster rate than for the 

higher-molecular weight, less-volatile congeners. Lack 

of pattern change and a lack of continued decrease in 

EPCB between M-21 .O and M-8.0 may reflect the flat 

gradient and low rates of volatilization in addition to 

replenishment of PCBs in the water column from 

fine-grained sediments deposited in these reaches. 

Identification of Sources of Polychlorinated Biphenyls 19 

These effects are consistent with a similar weathering 

of congener pattern observed among stations in lower 

Green Bay, Wise., with distance from the Fox River, a 

source of Aroclor 1242 (Willman and others, 1997). 

Passive-sampleresults do not lend support to a 

hypothesized additional source of PCBs to the Millers 

River below the Birch Hill Dam. CPCB concentrations 

were generally unchanging or decreasing in the downstream direction, and changes of the congener pattern 

appear to reflect weathering of the pattern from above 

Birch Hill Dam rather than the addition of new material. Also, the sampler results do not support introduction of new material to the lower river even from 

exactly the same type of source (and thus congener pattern) as hypothesized to have entered in Baldwinville. 

Unweathered PCBs from a similar source would 

“reset” the congener pattern to resemble more closely 

the concentrations observed at station O-31.2. In contrast, the trend of progressive weathering downstream 

from O-3 1.2 is not reset; the trend continues to the end 

of the Millers River. 

EXPOSURE OF FISH TO 

POLYCHLORINATED 

BIPHENYLS IN THE 

MILLERS RIVER BASIN 

Analytical results obtained from the PISCES 

samplers make possible the first survey of fish exposure 

to PCB concentration over the entire Millers River and 

its tributary, the Otter River. Fish receive much of their 

PCB burden from the food web, and food webs that 

start in bacteria or plant material receive PCBs initially 

by absorption through cell membranes from the dissolved phase. Since PISCES samplers concentrate 

PCBs from the dissolved phase, PISCES sampler 

results can be used to estimate dissolved-phase 

exposure. 

PCB concentrations in the PISCES samplers 

are related to PCB concentrations in the water by the 

formula: 

c, = MS /(St), (1> 

where C, is the concentration of the chemical in the 

water, M, is the mass of the chemical accumulated by 

the sampler over the exposure time (t), and S is the 

sampling rate term, a function of temperature and 

membrane size (Litten and others, 1993). For MS in 

units of nanograms, C, in units of nanograms per liter, 

t in days, and temperature in degrees Kelvin, the 

sampling rate (s) in units of liters per day is: 

s = Ae(- 6591/T + 19.269) 

whereA is surface area of membrane in centimeters, 

and Tis degrees Kelvin. This relationship was 

established by laboratory experiment and verified by 

comparing water-column grab samples to PISCES 

results in lakes and slow-moving streams (John 

Hassett, State University of New York-Syracuse, 

written commun., 2000). 

Equation 1 was used to estimate water-column 

1PCB concentrations from the PISCES results 

(table 3). The water temperatures used in the computation were averages of mean daily temperatures for the 

deployment period at USGS continuous-record stream 

gaging station 01095220 on the Stillwater River near 

Sterling, Mass., approximately 20 mi southeast of the 

study area. Computed CPCB water-column concentrations vary from less than 1 rig/L,, at upstream locations 

on the Millers River and the Otter River, to a maximum 

concentration of 310 rig/L,, on the Otter River just 

upstream from the confluence with the Millers River. 

Downstream from the confluence with the Otter River, 

computed water concentrations for the Millers River 

decreaseover several miles to 10 to 20 rig/L and remain 

approximately constant to the confluence with the 

Connecticut River. The USEPA water-quality criterion 

for PCBs in water promulgated in 1992 is 0.044 rig/L.. 

In March 1998, the Agency reassessed PCB cancer risk 

from eating fish derived from PCB contaminated water 

and proposed changing the criterion to 0.17 rig/L 

(Federal Register, 1998). Both standards are low concentrations-only the upstream stations in the Millers 

River and the Otter River approach these criteria. Concentrations of PCBs in all of the reaches downstream 

from the maximum pattern change (between O-36.2 

and O-35.2) are at levels that could lead to fish body 

burdens of PCBs that would be of concern for fish 

consumption. 

Exposure of Fish to Polychlorinated Biphenyls in the Millers River Basin 21 
SUMMARY AND CONCLUSIONS 

Passive samplers were used successfully in 

water-column deployment at 3 1 stations to define likely 

PCB source areas and exposure of fish to dissolved 

PCBs in the Millers River Basin. The rate of the PCB 

absorption by the samplers was greater during the 

summer than in the fall, when apparent dilution of 

water-column concentrations of PCBs by high flow and 

low water temperature decreased PCB transport across 

the semipermiable membranes of the samplers. 

Summer results yielded consistent concentration and 

congener-pattern data, from which a conceptual model 

of PCB contamination, transport, and partitioning in 

the Millers River Basin was developed. 

Comparison of PCB congener patterns indicated 

that a historical release point of PCBs in the Millers 

River Basin likely occurred on the Otter River at the 

upstream margin of Baldwinville, Mass. Increasing 

water-column concentrations with distance downstream from Baldwinville were compatible with a current (1999) source in streambed sediments in the 

wetland reach downstream from Baldwinville, to which 

the PCBs are hypothesized to have partitioned after 

their original introduction into the Otter River and from 

which PCBs are released to the water now that the original discharge has ceased or greatly decreased. 

Substantial decreases in total concentrations of 

all targeted PCB congeners (CPCB) in the Millers 

River downstream from the highest concentration station, on the Otter River, likely were caused by dilution 

with water from the relatively uncontaminated 

upstream Millers River, and by volatilization of PCBs 

in steep-gradient reaches. A relatively constant concentration of PCBs in the reach of the Millers River from 

river mile 20 to river mile 8 likely results from 

decreased volatilization rates in that relatively lowgradient reach. Resupply of PCBs to the water column 

from contaminated streambed sediments also may 

occur and tend to balance any loss to the atmosphere. 

A second high-gradient reach in the lower 8 miles of 

the Millers River before its confluence with the 

Connecticut River was also associated with decrease in 

dissolved PCB concentration. Volatilization as a loss 

mechanism was supported by weathering characteristics of the congener pattern in the reaches where 

concentration decreases occurred. Congener concentration and weathering-pattern data would not support 

22 Source Identification and Fish Exposure for Polychlorinated 

hypothesized additional PCB sources to the Millers 

River, other than streambed sediments, in the reach 

downstream from the Birch Hill Dam. 

Substantial exposure of fish food webs to dissolved PCB concentrations occurred throughout much 

of the Millers River Basin. Because the apparent source 

of PCBs discharged was upstream on the Otter River, 

fish in a large number of river miles downstream (more 

than 30 mi) had summer-time PCB exposures that may 

result in high concentrations of PCBs in fish. 

REFERENCES 

Barron, M.G., 1990, Bioconcentration: Environmental 

Science and Technology, v. 24, p. 1612-1618. 

Coles, J.F., 1998, Organochlorine compounds in fish tissue 

from the Connecticut, Housatonic, and Thames River 

Basin Study unit, 1992-94: U.S. Geological Survey 

Water-ResourcesInvestigations Report 9%4075,23 p. 

Eganhouse, R., and Gossett, R.W., 1991, Sources and 

magnitude of bias associated with determination of 

polychlorinated biphenyls in environmental samples: 

Analytical Chemistry, v. 63, p. 2130-2137. 

Federal Register, 1998, Water quality standards/ 

establishment of numeric criteria for priority toxic 

pollutants/states’ compliance-revision of 

polychlorinated biphenyls (PCBs) criteria: 

Environmental Protection Agency, v. 63, no. 63, p. 

16182-16188. 

Gay, F.B., and Frimpter, M.H., 1985, Distribution of 

polychlorinated biphenyls in the Housatonic River and 

adjacent aquifer, Massachusetts: U.S. Geological 

Survey Water-Supply Paper 2266,26 p. 

Litten, S., Mead, B., and Hassett, J., 1993, Application of 

passive samplers (PISCES) to locating a source of 

PCBs on the Black River, New York: Environmental 

Toxicology and Chemistry, v. 12, p. 639-647. 

Mackay, D., Wan-Ying Shiu, and Kuo-Ching Ma, 1992, 

Illustrated Handbook of Physical-Chemical Properties 

and Environmental fate for Organic Chemicals, v. 1, 

Monoaromatic Hydrocarbons, Chlorobenzenes and 

PCBs: Chelsea, Mich., Lewis Publishers, 697 p. 

MassachusettsDepartment of Environmental Management, 

Division of Water Resources, 1978 (updated March 

1983), A guide to public lakes, ponds and reservoirs of 

Massachusetts:MassachusettsDepartment of 

Environmental Management, 129 p. 

MassachusettsDepartment of Environmental Quality 

Engineering, Division of Water Pollution Control, 1974, 

Millers River 1973 Water Quality Analysis: 

Westborough, Mass., Massachusetts Deparhnent of 

Environmental Quality Engineering, 1 p. 

Biphenyls in the Millers River Basin, Mass. 
1976, Compilation of lakes, ponds, and reservoirs 

relative to the Massachusetts Lake Classification 

Program: Westborough, Mass., Massachusetts 

Department of Environmental Quality Engineering, 

124 p. 

Massachusetts Division of Water Pollution Control, 1980, 

The Millers River Basin 1979 water quality and time of 

travel survey data: Westborough Mass., Massachusetts 

Division of Water Pollution Control, 103 p. 

Parker, G.W., and Gay, EB ., 1987, A procedure for 

estimating reaeration coefficients for Massachusetts 

streams: U.S. Geological Survey Water-Resources 

Investigations Report 86-4111,34 p. 

Rantalainen, A.L., Ikonomou, M.G., and Rogers, I.H., 1998, 

Lipid-containing semipermeable membrane devices 

(SPMDs) as concentrators of toxic chemicals in the 

lower Fraser River, Vancouver, British Columbia: 

Chemosphere, v. 37, p. 1119-l 138. 

Safe, S., 1994, Polychlorinated biphenyls (PCBs)- 

Environmental impact, biochemical and toxic 

responses, and implications for risk assessment: Critical 

Reviews in Toxicology, v. 4, p. 87-149. 

Schulz, D.E., Petrick, G., and Duinker, J.C., 1989, Complete 

characterization of polychlorinated biphenyl congeners 

in commercial Aroclor and Clophen mixture by 

multidimensional gas chromatography-electron capture 

detection: Environmental Science and Technology, 

v. 23, p. 852-859. 

U.S. Army Corps of Engineers, 1991, Birch Hill Dam 

Reservoir PCB investigation, Phase I: Waltham, Mass., 

Department of the Army, New England Division, Corps 

of Engineers with support from the Waterways 

Experiment Station, variously paginated. 

-1993, Birch Hill Dam, Phase I-Limited Site 

Investigation Report: Waltham, Mass., Department of 

the Army, New England Division, Corps of Engineers, 

variously paginated, 10 appendixes. 

-1995, Birch Hill Reservoir PCB Investigation-Phase 

II: Waltham, Mass., Hydraulics and Water Quality 

Branch, Water Control Division, Engineering 

Directorate, Department of the Army, New England 

Division, Corps of Engineers, variously paginated. 

U.S. Environmental Protection Agency, 1998, Office of Solid 

Waste and Emergency Response: Test Methods for 

Solid Wastes, SW-846, variously paginated. 

Wandle, S.W., Jr., 1984, Gazetteer of hydrologic 

characteristics of streams in MassachusettsConnecticut River Basin: U.S. Geological Survey 

Water-Resources Investigations Report 84-4282, 110 p. 

Willman, E.J., Manchester-Neesvig, J.B., and Armstrong, 

D.E., 1997, Influence of ortho-substitution on patterns 

of PCB accumulation in sediment, plankton, and fish in 

a freshwater estuary: Environmental Science and 

Technology, v. 31, p. 3712-3718. 

References 23 
APPENDIX A: Polychlorinated Biphenyl Congener 

Names and International Union of Pure and Applied 

Chemistry (IUPAC) Numbers in Gas-Chromatograph 

Domain Order 
Appendix A. Polychlorinated biphenyl congener names and International Union of Pure and Applied Chemistry (IUPAC) 

numbers in gas-chromatograph domain order 

[No., number] 

Domain IUPAC No. Congener name Domain IUPAC No. Congener name 

1 4 2,2’-Dichlorobiphenyl 30 56 2,3,3’,4’-Tetrachlorobiphenyl 

1 10 2,6-Dichlorobiphenyl 30 60 2,3,4,4’-Tetrachlorobiphenyl 

2 7 2,4-Dichlorobiphenyl 31 77 3,3’,4,4’-Tetrachiorobiphenyl 

2 

3 

9 

6 

2,5-Dichlorobiphenyl 

2,3’-Dichlorobiphenyl 

32 

33 

91 

92 

2,2’,3,4’,6-Pentachlorobiphenyl 

2,2’,3,5,5’-Pentachlorobiphenyl 

4 5 2,3-Dichlorobiphenyl 34 84 2,2’,3,3’,6-Pentachlorobiphenyl 

4 8 2,4’-Dichlorobiphenyl 35 90 2,2’,3,4’,5-Pentachlorobiphenyl 

5 15 4,4’-Dichlorobiphenyl 35 101 2,2’,4,5,5’-Pentachlorobiphenyl 

6 19 2,2’,6-Trichlorobiphenyl 35 89 2,2’ ,3,4,6’ -Pentachlorobiphenyl 

I 18 2,2’,5-Trichlorobiphenyl 36 99 2,2’,4,4’,5-Pentachlorobiphenyl 

8 17 2,2’,4-Trichlorobiphenyl 37 83 2,2’,3,3’,5-Pentachlorobiphenyl 

9 24 2,3,6-Trichlorobiphenyl 37 108 2,3,3’,4,5’-Pentachlorobiphenyl 

9 27 2,3’,6-Trichlorobiphenyl 38 97 2,2’,3’,4,5-Pentachlorobiphenyl 

10 16 2,2’,3-Trichlorobiphenyl 38 86 2,2’,3,4,5-Pentachlorobiphenyl 

10 32 2,4’,6-Trichlorobiphenyl 39 87 2,2’,3,4,5’-Pentachlorobiphenyl 

11 26 2,3’,5-Trichlorobiphenyl 39 115 2,3,4,4’,6-Pentachlorobiphenyl 

12 

13 

25 

31 

2,3’,4-Trichlorobiphenyl 

2,4’,5-Trichlorobiphenyl 

39 

40 

116 

85 

2,3,4,5,6-Pentachlorobiphenyl 

2,2’,3,4,4’-Pentachlorobiphenyl 

14 28 2,4,4’-Trichlorobiphenyl 40 120 2,3’,4,5,5’-Pentachlorobiphenyl 

15 33 2’,3,4-Trichlorobiphenyl 41 110 2,3,3’,4’,6-Pentachlorobiphenyl 

15 20 2,3,3’-Trichlorobiphenyl 42 82 2,2’,3,3’,4-Pentachlorobiphenyl 

15 

16 

17 

21 

22 

37 

2,3,4-Trichlorobiphenyl 

2,3,4’-Trichlorobiphenyl 

3,4,4’-Trichlorobiphenyl 

43 

44 

45 

114 

122 

126 

2,3,4,4’,5-Pentachlorobiphenyl 

2’,3,3’4,5-Pentachlorobiphenyl 

3,3’,4,4’,5-Pentachlorobiphenyl 

18 53 2,2’,5,6’-Tetrachlorobiphenyl 46 136 2,2’,3,3’,6,6’-Hexachlorobiphenyl 

19 51 2,2’,4,6’-Tetrachlorobiphenyl 47 151 2,2’,3,5,5’,6-Hexachlorobiphenyl 

20 45 2,2’,3,6-Tetrachlorobiphenyl 48 144 2,2’,3,4,5’,6-Hexachlorobiphenyl 

21 46 2,2’,3,6’-Tetrachlorobiphenyl 48 135 2,2’,3,3’,5,6’-Hexachlorobiphenyl 

22 52 2,2’,5,5’-Tetrachlorobiphenyl 49 149 2,2’,3,4’,5’,6-Hexachlorobiphenyl 

22 73 2,3’,5’,6-Tetrachlorobiphenyl 49 139 2,2’,3,4,4’,6-Hexachlorobiphenyl 

23 49 2,2’,4,5’-Tetrachlorobiphenyl 50 134 2,2’,3,3’,5,6-Hexachlorobiphenyl 

23 43 2,2’,3,5-Tetrachlorobiphenyl 50 143 2,2’,3,4,5,6’-Hexachlorobiphenyl 

24 47 2,2’4,4’-Tetrachlorobiphenyl 51 131 2,2’,3,3’,4,6-Hexachlorobiphenyl 

24 48 2,2’,4,5-Tetrachlorobiphenyl 51 142 2,2’,3,4,5,6-Hexachlorobiphenyl 

24 75 2,4,4’ ,6-Tetrachlorobiphenyl 52 146 2,2’,3,4’,5,5’-Hexachlorobiphenyl 

25 44 2,2’,3,5’-Tetrachlorobiphenyl 53 123 2’,3,4,4’,5-Pentachlorobiphenyl 

26 42 2,2’,3,4’-Tetrachlorobiphenyl 54 118 2,3’ ,4,4’ ,5-Pentachlorobiphenyl 

26 59 2,3,3’,6-Tetrachlorobiphenyl 54 106 2,3,3’,4,5-Pentachlorobiphenyl 

27 41 2,2’,3,4-Tetrachlorobiphenyl 55 105 2,3,3’,4,4’-Pentachlorobiphenyl 

27 71 2.3’ ,4’ ,6-Tetrachlorobiphenyl 55 127 3,3’,4,5,5’-Pentachlorobiphenyl 

27 64 2,3,4’,6-Tetrachlorobiphenyl 56 153 2,2’,4,4’,5,5’-Hexachlorobiphenyl 

27 68 2,3’,4,5’-Tetrachlorobiphenyl 57 132 2,2’,3,3’,4,6’-Hexachlorobiphenyl 

28 40 2,2’,3,3’-Tetrachlorobiphenyl 57 168 2,3’,4,4’,5’,6-Hexachlorobiphenyl 

29 74 2,4,4’,5-Tetrachlorobiphenyl 58 141 2,2’,3,4,5,5’-Hexachlorobiphenyl 

29 61 2,3,4,5-Tetrachlorobiphenyl 59 137 2,2’,3,4,4’,5-Hexachlorobiphenyl 

26 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
Appendix A. Polychlorinated biphenyl congener names and International Union of Pure and Applied Chemistry (IUPAC) 

numbers in gas-chromatograph domain order-Continued 

Domain IUPAC No. Congener name Domain IUPAC No. Congener name 

60 138 2,2’,3,4,4’,5’-Hexachlorobiphenyl 75 171 2,2’,3,3’,4,4’,6-Heptachlorobiphenyl 

60 163 2,3,3’,4’,5,6-Hexachlorobiphenyl 76 173 2,2’,3,3’,4,5,6-Heptachlorobiphenyl 

60 164 2,3,3’,4’,5’,6-Hexachlorobiphenyl 77 172 2,2’,3,3’,4,5,5’-Heptachlorobiphenyl 

61 158 2,3,3’,4,4’,6-Hexachlorobiphenyl 77 192 2,3,3’,4,5,5’,6-Heptachlorobiphenyl 

61 160 2,3,3’,4,5,6-Hexachlorobiphenyl 78 180 2,2’,3,4,4’,5,5’-Heptachlorobiphenyl 

62 129 2,2’,3,3’,4,5-Hexachlorobiphenyl 79 193 2,3,3’,4’,5,5’,6-Heptachlorobiphenyl 

63 128 2,2’,3,3’,4,4’-Hexachlorobiphenyl 80 170 2,2’,3,3’,4,4’,5-Heptachlorobiphenyl 

64 156 2,3,3’,4,4’,5-Hexachlorobiphenyl 80 190 2,3,3’,4,4’,5,6-Heptachlorobiphenyl 

65 157 2,3,3’,4,4’,5’-Hexachlorobiphenyl 81 202 2,2’,3,3’,5,5’,6,6’-Octachlorobiphenyl 

66 179 2,2’,3,3’,5,6,6’-Heptachlorobiphenyl 82 201 2,2’,3,3’,4,5’,6,6’-Octachlorobiphenyl 

67 176 2,2’,3,3’,4,6,6’-Heptachlorobiphenyl 83 200 2,2’,3,3’,4,5,6,6’-Octachlorobiphenyl 

68 178 2,2’,3,3’,5,5’,6-Heptachlorobiphenyl 84 198 2,2’,3,3’,4,5,5’,6-Octachlorobiphenyl 

69 175 2,2’,3,3’,4,5’,6-Heptachlorobiphenyl 85 196 2,2’,3,3’,4,4’,5’,6-Octachlorobiphenyl 

70 187 2,2’,3,4’,5,5’,6-Heptachlorobiphenyl 8.5 203 2,2’,3,4,4’,5,5’,6-Octachlorobiphenyl 

70 182 2,2’,3,4,4’,5,6’-Heptachlorobiphenyl 86 195 2,2’,3,3’,4,4’,5,6-Octachlorobiphenyl 

71 183 2,2’,3,4,4’,5’,6-Heptachlorobiphenyl 87 194 2,2’,3,3’,4,4’,5,5’-Octachlorobiphenyl 

72 185 2,2’,3,4,5,5’,6-Heptachlorobiphenyl 88 205 2,3,3’,4,4’,5,5’,6-Octachlorobiphenyl 

73 174 2,2’,3,3’,4,5,6’-Heptachlorobiphenyl 89 208 2,2’ ,3,3’ ,4,5,5’ ,6,6’ -Nonachlorobiphenyl 

73 181 2,2’,3,4,4’,5,6-Heptachlorobiphenyl 

74 177 2,2’,3,3’,4’,5,6-Heptachlorobiphenyl 

Appendix A 27 
APPENDIX B: Polychlorinated Biphenyl 

Congeners from 31 Stations in the 

Millers River Basin, Massachusetts 
O-41.8 5/26/99 SAMP.1 

O-41.8 5126199 SAMP.2 

I,, I,, , , I I I I I I, I I I I ,,, ,,,,,,,,,,,J,,, 

0 .~,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,(,, 

3 2; 

O-39.9 5126199 SAMP.1 

z 15-

O-36.9 5/26/99 SAMP.1 

0-36.9 5126199 SAMP.2 7 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. [Samples 

are listed in downstream order and correspond in date order to the sample listing in table 2. When more than one 

congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars represent cases 

where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass the laboratory-ratio 

criterion that was established for a congener expected at a particular retention time. Designation (High Res) indicates 

sample was analyzed additionally by high-resolution mass spectrometry.] 

Appendix B 31 
POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

32 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
0-34.99, a/24/99 SAMP.1 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

Appendix B 33 
O-34.99, 0124199 SAMP.2 

O-34.97, 0124199 SAMP.1 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. [Samples are 

listed in downstream order and correspond in date order to the sample listing in table 2. When more than one congener is 

displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars represent cases where the ratio of 

monitored ion molecular fragments recorded by the mass spectrometer did not pass the laboratory-ratio criterion that was 

established for a congener expected at a particular retention time. Designation (High Res) indicates sample was analyzed 

additionally by high-resolution mass spectrometry.]-Continued. 

34 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
O-34.93, 8124199 SAMP.l 

O-34.93, 8124199 SAMP.2 

5~‘,,,,,“,,,,,,,,,,,,,,,,,,,,,,‘,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, I, 

O-34.93 8124199 SAMP.1 (High Res) j 

[I 4 

O-34.7, 8124199 SAMP.1 

0-34.7, 8124199 SAMP.2 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix 8. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. [Samples are 

listed in downstream order and correspond in date order to the sample listing in table 2. When more than one congener is 

displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars represent cases where the ratio of 

monitored ion molecular fragments recorded by the mass spectrometer did not pass the laboratory-ratio criterion that was 

established for a congener expected at a particular retention time. Designation (High Res) indicates sample was analyzed 

additionally by high-resolution mass spectrometry.]-Continued. 

Appendix B 35 

4 
32 O-34.5, 8124199 SAMP.2 

1261 

O-33.7, 5125199 SAMP.1 96 -

128- O-33.7 5125199 SAMP.2 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Pies) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

36 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
512 : O-33.1, 8/l 9199 SAMP.2 

384 7 

1,024 

768 O-31.2, 5/25/99 SAMP.1 

512 

256 

1,024 

768 

512 

256 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

Appendix B 37 
2 600- 1 

Iis 450 - O-31.2 8/19/99 SAMPl (High Res) : 

cn 

5 

% 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

38 Source identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
M-31.2 5125199 SAM!‘.1 

320 , , , , , , , , , ,, , I ,,,,(,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,(,,,,,,,,,,,,,,,,(,,,,,,,,,,, 3

G 256 -

M-29.1, 5125199 SAMP.1 

192 - % 

320~ I,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 

256 1 M-29.1, 5125199 SAMP.2 z 

0 320 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,~, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 

J 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

Appendix B 39 
256 = 

M-29.1, 8119199 SAMP 2 192 -

128-

40 ,,,,,,,,,,,,(,,,,,,,,,,,,,,,,,,,,,,,,,,,,(,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,~,,,,,,,~ 

32 -

M-29.1 1 l/10/99 SAMP.1 24 -

Sampler retrieved from mud 16 Z320 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, I I I, ,I I,, I, I, I I, I I I I I I I, I I I I I I I I I I I I I_ 

256 -

M-27.5, 712199 SAMP.1 192 -

128 -

320 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, I,, ,I I,, , , , , , , , , , I, I I I I I, I,, I I I,, I I ,_ 

256 -

M-27.5, - 712199 SAMP.2 192 -

128: 

64 -

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

40 Source Identification and Fish Exposure for Polychlorinated Biphenyls In the Millers River Basin, Mass. 
80_,,,,,,,,,,,,,,,,,,,~,,,,,,,,,,,,,,1,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,~,,,,,,,,,,,, 

64 : 

48 - M-21 .O - 712199 SAMP.1 

32 -

EOt,,,,,,,,,,,,,,l,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 

c 3 

64 - M-18.1 - 712199 SAMP.1 

48 -

80-l , , , , , I I I I I, I I I I, I I I I, I I, I, I I I I,, I ,,,,,,,,,,,,,,,,,,,,,,,,,I,, , I I I,, , , , , I I I I I,, , , , I I I,, ,_ 

M-18.1 - 712199 SAMP.2 48 -

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

Appendix B 41 
POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

42 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass. 
+ 64 - M-9.8, 712199 SAMP.1 

48 -

M-9.8, 712199 SAMP.2 

64 M-8.0, 712199 SAMP.1 

48 

32 

16 

M-8.0, 712199 SAMP.2 

POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

Appendix B 43 
POLYCHLORINATED BIPHENYL CONGENER NUMBER 

Appendix B. Polychlorinated biphenyl congeners from 31 stations in the Millers River Basin, Massachusetts. 

[Samples are listed in downstream order and correspond in date order to the sample listing in table 2. When more than 

one congener is displayed for one bar, multiple IUPAC numbers are given separated by a slash. Unfilled bars 

represent cases where the ratio of monitored ion molecular fragments recorded by the mass spectrometer did not pass 

the laboratory-ratio criterion that was established for a congener expected at a particular retention time. Designation 

(High Res) indicates sample was analyzed additionally by high-resolution mass spectrometry.]-Continued. 

“U.S. w - OFFIce: ZOOI-600-120/20002 

44 Source Identification and Fish Exposure for Polychlorinated Biphenyls in the Millers River Basin, Mass.