Distribution and Transport of Polychlorinated 

Biphenyls and Associated Particulates in the 

Milwaukee River System, Wisconsin, 1993–95

By Jeffrey S. Steuer, Sharon A. Fitzgerald, and David W. Hall

U.S. GEOLOGICAL SURVEY

Water-Resources Investigations Report 99–4100

Prepared in cooperation with the

WISCONSIN DEPARTMENT OF NATURAL RESOURCES

MILWAUKEE METROPOLITAN SEWAGE DISTRICT

Middleton, Wisconsin

1999
U.S. DEPARTMENT OF THE INTERIOR

BRUCE BABBITT, Secretary

U.S. GEOLOGICAL SURVEY

Charles G. Groat, Director

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

District Chief U.S. Geological Survey 

U.S. Geological Survey Branch of Information Services

8505 Research Way Box 25286

Middleton, WI 53562-3586 Denver, CO 80225-0286

The use of firm, trade, and brand names in this report is for identification purposes only and does

not constitute endorsement by the U.S. Geological Survey.
CONTENTS III

CONTENTS

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

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

Purpose and scope....................................................................................................................................................... 3

Environmental setting and hydrology ......................................................................................................................... 3

Site descriptions .......................................................................................................................................................... 4

Sampling and analytical methods ............................................................................................................................... 5

Distribution and transport of PCB’s and associated particulates .......................................................................................... 6

PCB congeners............................................................................................................................................................ 6

Phase partitioning of PCB’s ........................................................................................................................................ 12

Total suspended solids load and chlorophyll a concentrations ................................................................................... 13

Total suspended solids load......................................................................................................................................... 16

Concentrations and loads of transported PCB’s in the Milwaukee River system....................................................... 21

Summary ............................................................................................................................................................................... 26

References cited .................................................................................................................................................................... 28

Appendixes 1–2:

1. PCB congeners found during laboratory analysis of water and sediments in the Milwaukee River Basin 

and their respective limits of detection and quantification.............................................................................. 32

2a. Water column transport data for summed PCB congeners and related physical and water-quality 

characteristics at Cedar Creek at Columbia Avenue (USGS station 04086525), 1994–95 ............................. 33

2b. Water column transport data for summed PCB congeners and related physical and water-quality 

characteristics at Cedar Creek at Highland Road (USGS station 04086528), 1994–95.................................. 34

2c. Water column transport data for summed PCB congeners and related physical and water-quality 

characteristics at Milwaukee River at Highway T (USGS station 04086528), 1994–95 ................................ 34

2d. Water column transport data for summed PCB congeners and related physical and water-quality 

characteristics at Milwaukee River at Pioneer Road (USGS station 04086600), 1994–95............................. 35

2e. Water column transport data for summed PCB congeners and related physical and water-quality 

characteristics at Milwaukee River at Thiensville (USGS station 04086710), 1994–95 ................................ 36

2f. Water column transport data for summed PCB congeners and related physical and water-quality 

characteristics at Milwaukee River at Estabrook Park (USGS station 04087000), 1994–95.......................... 37

FIGURES

1. Map showing location of Cedar Creek and Milwaukee River sampling sites.......................................................... 2

2–7. Graphs showing:

2a. Dissolved PCB congener distributions from the two highest field-equipment-blank concentrations and 

two Milwaukee River field sites.................................................................................................................... 7

2b. Particulate PCB congener distributions from the two highest field-equipment-blank concentrations and 

two Milwaukee River field sites.................................................................................................................... 8

3a. Dissolved PCB congener distributions for Milwaukee River and Cedar Creek sites and one 

Aroclor mixture ............................................................................................................................................. 9

3b. Particulate PCB congener distributions for Milwaukee River and Cedar Creek sites and one 

Aroclor mixture ............................................................................................................................................. 10

3c. Bed-sediment PCB congener distributions for Milwaukee River and Cedar Creek sites and one 

Aroclor mixture ............................................................................................................................................. 11

4. Apparent distribution coefficients at two Milwaukee River Basin sites........................................................... 14

5. Correlation of point-sampled (POINT) and equal-width-increment (EWI) sampled suspended 

solids at four Milwaukee River and Cedar Creek sites ................................................................................. 15

6. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data 

from the Highland Road site on the Milwaukee River.................................................................................. 17

7. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data 

from the Pioneer site on the Milwaukee River.............................................................................................. 18
IV CONTENTS

CONTENTS—Continued

FIGURES—Continued

8–13. Graphs showing:

8. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data 

from the Thiensville site on the Milwaukee River...................................................................................... 19

9. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data

from the Estabrook Park site on the Milwaukee River ............................................................................... 20

10. Cumulative suspended solids-loads at three Milwaukee River sites and discharge at the 

Estabrook site.............................................................................................................................................. 22

11. Net suspended-solids loads for two Milwaukee River reaches and Estabrook discharge.............................. 22

12. Pioneer PCB concentration regression residuals ............................................................................................ 25

13. Cumulative summed PCB congener loads at three Milwaukee River sites and discharge at the 

Estabrook Park site...................................................................................................................................... 27

TABLES

1. Summed PCB congener concentration in bottom sediment and accumulated PCB mass estimates resulting

from the Wisconsin Department of Natural Resources bottom sediment surveys.............................................. 3

2. Calculated log KD and log KPOC values for selected PCB congeners and summed PCB congener 

concentrations at all sampling sites..................................................................................................................... 13

3. Total-suspended-solids loads computed for four Milwaukee River Basin sites..................................................... 21

4. Summed PCB congener concentration regression relations and characteristics at Highland Road 

(Cedar Creek) and three Milwaukee River sites ................................................................................................. 23

5. Computed total loads for the Milwaukee River Basin sites using PCB regression relations (RLOAD) ............... 26

6. Computed summed PCB congener loads based on three computation approaches for the Milwaukee 

River Basin sites.................................................................................................................................................. 28
CONVERSION FACTORS, VERTICAL DATUM, AND ABBREVIATIONS V

CONVERSION FACTORS, VERTICAL DATUM, AND ABBREVIATIONS

Multiply By To Obtain

acre 0.4048 hectare

mile (mi) 1.609 kilometer

square mile (mi2) 2.590 square kilometer

foot (ft) 0.3048 meter

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

micrometer (μm) 0.00003937 inch

millimeter (mm) 0.03937 inch

centimeter (cm) 0.3937 inch

meter (m) 3.281 foot

kilogram (kg) 2.205 pound

kilogram (kg) 0.00326 ton

gram (g) 1 x 109 nanogram

gram (g) 1 x 106 microgram

gram (g) 1 x 103 milligram

liter (L) 0.2642 gallon

ton 0.9072 megagram

Temperature in degrees Fahrenheit (°F) can be converted to degrees Celsius (°C) by use of the following equation:

°F = 1.8 (°C) + 32.

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

Abbreviated water-quality units used in this report: Chemical concentrations are given in metric units. Chemical concentration is given 

in milligrams per liter (mg/L), micrograms per liter (μg/L), or nanograms per liter (ng/L). Milligrams per liter is a unit expressing the concentration of chemical constituents in solution as weight (milligrams) of solute per unit volume (liter) of water. One thousand micrograms per 

liter is equivalent to one milligram per liter. For concentrations less than 7,000 mg/L, the numerical value is the same as for concentrations 

in parts per million. 

Miscellaneous abbreviations:

ΣPCB is a total PCB concentration obtained by summing all dissolved and particulate-phase congeners in a sample.

POINT samples are those water samples collected from a single point in a river, such as a sample obtained from the intake pipe of an 

automated sampler. 

EWI samples are water samples collected from equal-width-increments across a cross section of a river.

CHURN samples consist of four subsamples collected at equal-width-increments across a stream cross section that are subsequently

composited in a teflon churn splitter.

SLOH is the Wisconsin State Laboratory of Hygiene in Madison, Wisconsin.

MMSD is the Milwaukee Metropolitan Sewage District in Milwaukee, Wisconsin.
VI ACKNOWLEDGMENTS

ACKNOWLEDGMENTS

Technical Support

David E. Housner, Hydrologic Technician, U.S. Geological Survey, Middleton, Wis. 

Halward (Nick) L. Hanson, Hydrologic Technician, U.S. Geological Survey, Middleton, Wis.

Judy A. Wierl, Hydraulic Engineer, U.S. Geological Survey, Middleton, Wis.

William R. Selbig, (Student) Hydrology, U.S. Geological Survey, Middleton, Wis.

Peter E. Hughes, Chief Supervisory Hydrologist, U.S Geological Survey, Middleton, Wis.

Technical Reviewers

Robert P. Eganhouse, Research Chemist, U.S. Geological Survey, Reston, Va.

Dale J. Patterson (Deceased), Water Resources Engineer, Wisconsin Department of Natural Resources, Madison, Wis.

Xiaochun Zhang, Water Resources Engineer, Wisconsin Department of Natural Resources, Madison, Wis.

Editorial and Graphics

Michael Eberle, Technical Publications Editor, U.S. Geological Survey, Columbus, Ohio

Janice A. Fuller, Editorial Assistant, U.S. Geological Survey, Middleton, Wis.

Aaron T. Konkol, Cartographic Assistant, U.S. Geological Survey, Middleton, Wis.

Susan Z. Jones, Editorial Assistant, U.S. Geological Survey, Middleton, Wis.

Gail A. Moede, Writer/Editor Student Trainee, U.S. Geological Survey, Middleton, Wis.
Abstract 1

Abstract

The distribution and transport of polychlorinated biphenyl (PCB) congeners were determined 

at various sites on Cedar Creek and its receiving 

stream, the Milwaukee River. PCB congener distributions were determined in the operationally 

defined dissolved phase, suspended-particle phase, 

and surficial bed sediments (0–2 centimeters 

depth). At most sites, the relative abundances of 

PCB congeners in the suspended particles and surficial bed sediments were similar to each other, and 

in some cases, to known Aroclor mixtures (1242 

and 1260). Dissolved PCB congener distributions 

were higher in the less chlorinated congeners as 

predicted by their lower hydrophobicity and higher 

solubility. Log partition coefficients for the dissolved and the particle-associated organic carbon 

phases ranged from 5.0 to 5.8 and 6.5 to 7.5, 

respectively, for ΣPCB’s (congener summation). 

Particle-associated PCB’s exhibited two patterns: 

(1) a general increase in spring and summer associated with algal growth and, (2) episodic increases 

associated with resuspension of bed sediments during storms. Total suspended solids loads in water 

year 1994 ranged from 8,700 tons at Pioneer Road 

to 15,800 tons at Estabrook Park. PCB loads 

decreased from Highland Road (3.7 kilograms) to 

Pioneer Road (1.8 kilograms) from August 1994 to 

August 1995, indicating PCB deposition between 

those sites. PCB transport at Estabrook Park was 8 

to 16 kilograms during this same time period.

INTRODUCTION

Polychlorinated biphenyl (PCB) congener mixtures 

were used extensively in the United States from 1929 

until their manufacture was banned in the 1970’s. Each 

of the 209 possible PCB congeners consists of 1 to 10 

chlorine atoms attached to a biphenyl ring. The physical 

and chemical properties of the PCB congeners vary as a 

function of their structure. As a group, however, the 

congeners are substantially resistant to heat and degradation, properties that made them valuable for a wide 

variety of uses. Congener mixtures marketed under the 

trade names Aroclor (Monsanto, U.S.) and Askerel 

were extensively used in electrical equipment such as 

transformers, capacitors, switchgear, and manufacturing machinery. Aroclor mixtures also were used in 

printing inks, carbonless copy paper, heating coils, specialized cookware, fireproof panels, lubricating oils, 

resins, synthetic rubber, sealants and coatings, wax, 

waterproofing compounds, adhesives, and cutting oils 

(Cairns and others, 1986). Although manufacture of 

PCB’s was banned in the United States in the 1970’s, 

approximately 50 to 60 percent of all PCB’s ever manufactured are still in use, with an additional 20 to 30 percent of the manufactured PCB’s cycling in the 

environment from discarded waste materials (Anders 

Andren, University of Wisconsin-Madison, oral commun., September 1995).

PCB’s are known to bioaccumulate (Koslowski and 

others, 1994), to cause reproductive failure in birds 

(Yamashita and others, 1993), and to have negative 

effects on communities of fish (Evans and others, 

1990). Knowledge of the distribution and transport of 

PCB’s in the environment is important for protecting 

human drinking water supplies, ensuring the chemical 

integrity of fish and other food products, and providing 

healthful habitats for fish, birds, and other animals. 

PCB’s have been identified as a contaminant of 

concern in the Milwaukee River, Wis. (Marti and Armstrong, 1990; fig. 1), resulting in issuance of a fish consumption advisory. The bed sediments of Cedar Creek, 

a tributary to the Milwaukee River, have high concentrations of PCB’s. Results of the Cedar Creek Mass Balance Study (Westenbroek, 1993) indicated that Cedar 

Creek transported between 4 to 38 kilograms per year 

(kg/yr) of PCB’s to the Milwaukee River during 1990 

and 1991. The PCB’s entered Cedar Creek through floor 

drains and in cooling waters that were discharged from 

Distribution and Transport of Polychlorinated Biphenyls 

and Associated Particulates in the Milwaukee River 

System, Wisconsin, 1993–95

By Jeffrey S. Steuer, Sharon A. Fitzgerald, and David W. Hall
2 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin, 

1993–95

Figure 1. Location of Cedar Creek and Milwaukee River sampling sites.

43°23'

88°06' 87°48'

43°

0 2.5 5 MILES

0 2.5 5 KILOMETERS

0 .5 1 MILE

0 .5 1 KILOMETER

Ruck Pond

Whitefish

Bay

Pioneer Rd.

site

Columbia

Ave. site Highland

Rd. site

Hwy T site

Thiensville 

impoundment

Estabrook Park 

impoundment

Thiensville

site

Estabrook

Park site

Estabrook

Park site

Dam

L

a

k

e

M i c

h i g

a

n

Milwaukee

Milwauke

e

R

Cedar Cre

e

k

WISCONSIN

Location of

Milwaukee River

study sites

Normal PCB

sampling site

High-flow

sampling site

Lincoln Creek

Milwaukee R

High bottom

sediment PCB

concentrations

Base from U.S. Geological Survey

1:24,000, Milwaukee, Wisconsin, 1971
INTRODUCTION 3

several die-casting operations (Westenbroek, 1993). 

Results of a subsequent Wisconsin Department of Natural Resources survey of PCB contamination of Cedar 

Creek and Milwaukee River bottom sediments are summarized in table 1. 

Although some of the PCB’s at downstream sites 

may have originated from Cedar Creek, additional 

sources of PCB’s may also contribute to the contamination of Milwaukee River water, sediments, and biota. 

Lincoln Creek, which joins the Milwaukee River 

upstream from Estabrook Park, may have been, or still 

is, an additional source of PCB’s to the river. Additionally, river sediment-coring investigations done by the 

Wisconsin Department of Natural Resources located an 

area of PCB-contaminated sediments immediately 

downstream from the confluence of Lincoln Creek and 

the Estabrook impoundment (fig. 1).

In 1993, the U.S. Geological Survey (USGS), in 

cooperation with the Wisconsin Department of Natural 

Resources (WDNR) and the Milwaukee Metropolitan 

Sewage District, began this investigation to further 

understand the distribution and transport of PCB’s and 

associated particulates in the Milwaukee River system. 

The data collection and analysis efforts were designed 

to support WDNR construction of a deterministic PCB 

transport model.

Purpose and Scope

This report presents results of a USGS, WDNR, 

and Milwaukee Metropolitan Sewage District (MMSD) 

cooperative investigation into the occurrence and transport of PCB’s in the Milwaukee River system. Congener profiles in the operationally defined dissolved 

phase, suspended particles, and surficial bed sediments 

were determined. Total PCB congener loads and suspended-solid loads were computed at locations downstream from impoundments. Regression analysis on 

concentrations of summed PCB congeners (ΣPCB) as a 

function of total suspended solids, in addition to other 

environmental variables collected on a frequent basis, 

was used to compute the ΣPCB loads. 

Environmental Setting and Hydrology

The Milwaukee River drains an area of approximately 850 mi2

 in southeastern Wisconsin (fig. 1). 

Mean annual discharge of the Milwaukee River from 

80 years of record is 431 ft3/s. Mean discharge measured during the study period was less than the annual 

average; 378 and 303 ft3

/s in 1994 and 1995, respectively. The Milwaukee River Basin comprises six major 

subbasins: the East-West Branch, North Branch, South 

Branch, Cedar Creek, the Menomonee River, and the 

Table 1. Summed PCB congener concentration in bottom sediment and accumulated PCB mass estimates resulting from 

the Wisconsin Department of Natural Resources bottom-sediment surveys

[From Westenbroek (1993). μg/g, micrograms per gram; kg, kilograms; --, no data]

Reach

Surficial sediment

concentration

(μg/g)

Maximum sediment

concentration

(μg/g)

Accumulated PCB mass

(kg)

Cedar Creek

Upstream from Columbia Ave.

(10/7/94, postremediation) 8.3 to 280 280 Remediated

(formerly 743)

Columbia Ave. to Highland Rd. 

(8/11/95–8/14/95) 8.3 to 64 190 568

Highland Rd. to Milwaukee River 

confluence

Not recently sampled. Mass 

estimate based on historical data. -- 118

Milwaukee River

Confluence to Pioneer Rd. Surveys indicate minimal soft

sediment in this reach. -- <10

Pioneer Rd. to Thiensville

(10/26/93–10/29/93) 0.08 4.9 265

Thiensville to Trinity Creek (11/7/95) <0.05 to 0.21 .21 --

Estabrook impoundment “hot spot” 

(9/25/95–9/28/95) 2.3 to 100 870 --

Estabrook impoundment (11/2/93) 0.26 to 3.3 380 5,276

(Thiensville to Estabrook)
4 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin, 

1993–95

Kinickinnic River. Average annual precipitation is 

about 30 in., and two-thirds of the precipitation falls as 

rain during the growing season. Average annual snowfall is about 46 in., and average annual air temperature 

is 46°F (Wisconsin Department of Natural Resources, 

1992).

The geology of the Milwaukee River Basin consists of unconsolidated, clay-rich glacial deposits resting on Silurian dolomite bedrock. Basin altitude ranges 

from about 1,360 ft above sea level in the northwest to 

about 580 ft above sea level at Milwaukee Harbor in the 

southeast. Surface drainage channels are generally well 

connected, and relatively few areas of the basin drain 

predominantly to ground water (Sullivan and others, 

1995). The basin contains approximately 430 mi of 

perennial streams and 87 lakes and ponds with surface 

areas greater than 5 acres. The basin has long been predominantly urban and industrial in southern areas proximate to the city of Milwaukee (1990 population was 

about 636,000). Urban land, including residential areas 

and land used for transportation and utilities, occupies 

about 11 percent of the total basin area (Sullivan and 

others, 1995). About 75 percent of the basin is agricultural, about 8 percent is forested, about 5 percent is wetland, and less than 1 percent is barren. 

Site Descriptions

Six sites (fig. 1) on Cedar Creek and on the Milwaukee River were sampled:

1. The Columbia Avenue dam site (USGS station 

04086525) on Cedar Creek drains 121 mi2

 of 

the Milwaukee River Basin and is downstream 

from Ruck Pond impoundment, which was 

remediated in 1994. No monitoring equipment 

was onsite, and only a few samples were collected immediately downstream from the dam.

2. The Highland Road site (USGS station 

04086528), 50 ft downstream from the Columbia impoundment on Cedar Creek, has a drainage area of 123 mi2

. This site was instrumented 

with a shore-based automated suspended-solids 

sampler and a continuous water-temperature 

probe. The sampler was fitted with a 3/8-in. 

propylene suction line and was set up to 

include purge and rinse cycles. Discharge data 

for Cedar Creek were collected downstream 

from this site at USGS station 04086500. The 

Wire/Nail and Hamilton ponds are two Cedar 

Creek PCB-contaminated impoundments 

located between the Highland Road site and its 

confluence with the Milwaukee River. These 

sites, however, were not sampled as part of this 

investigation.

3. The Highway T site (USGS station 04086416) 

was on the Milwaukee River immediately 

upstream from the confluence of Cedar Creek 

and the Milwaukee River (fig. 1) and has a 

drainage area of approximately 479 mi2. No 

equipment was installed at this site. Limited 

PCB samples were collected in the vicinity of 

the Highway T bridge to document PCB transport upstream from the Cedar Creek confluence with the Milwaukee River.

4. Milwaukee River flow at the Pioneer Road site 

(USGS station 04086600) originates from 

about 607 mi2 of the basin. Samples were collected either about 60 ft downstream from the 

Pioneer Road bridge during base flow or from 

the bridge during high flow. The site was 

instrumented with an automated sampler activated by a stage sensor and with river-stage 

recorders for discharge computation. There 

was no impoundment at this site, so soft bed 

sediment suitable for sampling was collected 

from small, discontinuous pockets located 

mainly downstream from islands and along 

some sections of the bank.

5. The Thiensville site (USGS station 04086710) 

was downstream from Pioneer Road, a location 

representing discharge from about 643 mi2 of 

the basin.Water samples were collected 50 ft 

upstream from the Highway 167 bridge at 

Thiensville during base flow or from the bridge 

during high flow. The site was instrumented 

with an automated sampler triggered by a stage 

sensor. Discharge was not measured at the site 

but rather was estimated from the measured 

discharge at the Pioneer site multiplied by the 

basin area ratio (1.06). Samples of soft bed sediment were collected from an impoundment 

upstream from the bridge. 

6. The Estabrook Park site (USGS station 

04087000) was in a Milwaukee County park, 

downstream from Thiensville, and about 6.6 mi 

upstream from the Milwaukee Harbor. Samples 
INTRODUCTION 5

during low to medium flow were collected 

approximately 2,000 ft downstream from the 

Port Washington Road bridge. At high flow, 

samples were collected from the downstream 

railroad bridge. Discharge data were collected 

continuously, and the site was instrumented 

with an automated sampler triggered by a stage 

sensor. Bed-sediment samples were collected 

from behind the dam and upstream from the 

water-sampling site.

Sampling and Analytical Methods

General methods of sample collection and field 

preparation are discussed in detail in Fitzgerald and 

Steuer (1997) and in House and others (1993). Water 

samples were collected by dipping 20-L stainless steel 

canisters through the water column at four locations 

across the creek or river. These samples were composited and processed as one 80-L sample. The particulate 

and operationally defined dissolved phases were separated onsite immediately after sample collection (particulate and operationally defined dissolved phase are 

defined for the purposes of this study by the filter pore 

size, 0.7 μm). Field filtering of the 80-L water samples 

involved a parallel stack of up to five 293-mm stainless 

steel filter plates with precombusted 0.7-μm glass fiber 

filters inserted between the plates. The filtrate was then 

pumped at a rate not exceeding 1-L/min through 

Amberlite XAD-2 resin columns to concentrate the 

operationally defined dissolved hydrophobic contaminants. The filters and XAD-2 resins were subsequently 

analyzed at the State Laboratory of Hygiene (SLOH) in 

Madison, Wis., by use of methods described in Fitzgerald and Steuer (1997). 

Water samples analyzed for ancillary constituents 

such as particulate organic carbon (POC), dissolved 

organic carbon (DOC), chlorophyll a, chloride, volatile 

suspended solids (VSS), and total suspended solids 

(TSS) were collected in 1-L glass bottles submerged 

through the water column in the same manner and at the 

same locations as those used for PCB sampling. The 

four cross-section samples were composited in a teflon 

churn splitter (referred to as “CHURN samples”) to 

obtain the final representative sample (Ward and Harr, 

1990). Subsequently, samples analyzed for particulate 

organic carbon (POC) and dissolved organic carbon 

(DOC) were processed through a stainless steel Gelman 

filter apparatus with a 0.45-μm silver filter. Chlorophyll 

a samples were processed through a 5.0-μm mixed acetate and nitrate cellulose filter.

For comparison with results from this water-collection method—necessitated by the large water volume 

required for the PCB sample—a second suspended-solids sample was collected and analyzed separately. This 

suspended-solids sample was collected with a 470-mL 

glass bottle and plastic nozzle that was sequentially submerged at four equally spaced locations along a cross 

section, either manually at wadable sites or by use of a 

D-77 USGS sampler at nonwadable sites. Samples from 

the cross section (referred to as “equal-width-increment 

(EWI) samples”) were poured directly into the laboratory bottles themselves. No churn was used for splitting.

The automated suspended-solids samplers were 

used to collect point samples daily at 1200 hours and 

more frequently during storm events. When the river 

was frozen, sampling was reduced to once every 2 or 3 

days at all sites and was often done manually with a 

1-L plastic bottle. Additionally, the automated samplers 

were triggered at the time of EWI sample collection to 

assess the ability of the automated samples obtained at 

one point in the cross section to represent water quality 

in the entire cross section, as represented by the EWI 

samples. Automated and manual grab samples are 

referred to as “POINT samples.”

EWI samples collected for TSS determinations 

were placed in 1-L plastic bottles and chilled to 4°C 

during shipment to the SLOH. Automatically collected 

samples for TSS determination were removed from the 

automated sampler and kept chilled (4°C) during shipment to the MMSD. Samples sent to SLOH and MMSD 

were analyzed for TSS with the identical pipette method 

(State Laboratory of Hygiene, Madison, Wis., Method 

340.1). A known volume of water was filtered through 

pre-weighed glass fiber filters, which were subsequently dried at 103–105°C for 1 hour, cooled, and 

reweighed. Based upon duplicate samples (appendixes 

2a–2f), overall sampling precision (field and laboratory) was 6 percent.

Samples analyzed for PCB congeners and ancillary 

constituents were collected from June 1993 through 

August 1995. At Estabrook Park, 15 of 29 samples were 

collected when discharge was above the mean annual 

discharge of 431 ft3/s, and 24 of the samples were collected when the river was above the 50-percent exceedance discharge of 223 ft3

/s. Sediment and PCB 

contaminant loading are greatest during high flow. 

Thus, to optimize the project data set for load estima-
6 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin, 

1993–95

tion, sampling was emphasized during high flow (Richards, 1994; Dolan and others, 1981). 

All PCB samples were analyzed on a congenerspecific basis by use of capillary column gas chromatography with electron capture detection (gas chromatograph with a 60-m DB5 column) at SLOH (Degenhardt, 

1996). This method allows the determination of as 

many as 85 congeners (with 26 co-elutions). Details on 

quantitation, generation of response factors, surrogate 

standards, matrix spikes, retention time reference peaks, 

and internal standards are contained in Degenhardt 

(1996). The average recovery of surrogate and matrix 

spikes for all samples analyzed during the period coincident with the analysis of the samples from the study 

reported here can be found in table 1 of Fitzgerald and 

Steuer (1997). Congener concentrations were not corrected for percent recovery of either the surrogates or 

the matrix spikes. Detection limits, limits of quantification, IUPAC numbers, and congener descriptions used 

in sample analysis are reported in appendix 1.

Four samples of surficial bottom sediment (0–2 cm 

depth), one per season, were collected at the Pioneer, 

Thiensville, and Estabrook sites. Most samples were 

collected by means of an Ekman dredge, although some 

samples were collected with a simple hollow tube at the 

wadable site (Pioneer Road). Field and laboratory methods for bed-sediment constituents are described in detail 

in Fitzgerald and Steuer (1997). 

The USGS computer program CLOAD was used to 

estimate TSS and PCB loads. CLOAD employs a flowintegration approach to estimate loads whereby concentration data are estimated by linear interpolation 

between existing data points and are subsequently multiplied by 15-minute discharge values (daily in winter) 

to obtain loads (Porterfield, 1972). 

Field quality control consisted of analysis of fieldequipment blanks and replicates. Congener distributions representative of the Highway T site (upstream 

control site), the Pioneer site (which had the lowest 

PCB concentration of the contaminated sites), and the 

two highest field-equipment blank samples are compared in figures 2a and 2b. Appendix 1 contains a complete listing of the plotted congeners. Numerous 

congeners (IUPAC nos. 5/8, 16/32, 28/31, 26, 33, 49, 

44, 37/42, 41/64, 70/76, 66/95, 84/92, 101, 99, 87, 

77/110, 149, 132/152) were detected in the field-equipment blanks but were not detected in the upstream-control-site samples. Therefore, contamination observed in 

the field blanks was most likely from the field-blank 

water and is not indicative of compromised samples. 

Finally, overall sampling precision (including field and 

laboratory) based on five sets of duplicate samples of 

dissolved PCB’s and particle-associated PCB’s was 11 

percent and 14 percent, respectively (1 standard deviation). A more detailed discussion on quality-assurance 

sample results can be found in Fitzgerald and Steuer 

(1997).

DISTRIBUTION AND TRANSPORT OF 

PCB’S AND ASSOCIATED PARTICULATES

PCB Congeners

Operationally defined dissolved and particle-associated PCB congener data from water-column and bedsediment samples collected at the Columbia, Highland, 

Pioneer, Thiensville, and Estabrook sites are shown in 

figures 3a–3c. Congener data are represented as a percentage of the sums of all congeners. Data from samples 

collected at a given site were averaged together. PCB 

congener distributions in water and bed sediments were 

similar at the Highland, Pioneer, and Thiensville sites. 

In addition, the particle-associated PCB congener pattern appears nearly identical to the surficial-sediment 

core data, a relation that indicates interaction between 

the two media.

The congener pattern changes as one progresses 

downstream to the Estabrook site. The Estabrook congener distribution has a higher percentage of less chlorinated congeners than those observed at the upstream 

sites. This shift is especially noticeable in the suspended-particle-associated PCB and the bed-sediment 

distributions (figs. 3b and 3c). Unlike those for the 

upstream sites, the suspended-particle-associated PCB 

distribution at the Estabrook site is not solely reflective 

of the bed-sediment PCB profile. Rather, PCB distributions of suspended particles at Estabrook appear to be a 

mixture of those present in the Estabrook bed sediments 

and congeners transported from the upstream water column. 

Historical records indicate the use of PCB Aroclor 

1254 and 1260 at waste discharges into Cedar Creek 

and the Milwaukee River upstream from the Pioneer 

and Thiensville sites (Westenbroek, 1993). A comparison of PCB congener distributions of these two Aroclor 

mixtures with bed-sediment PCB distribution at Pioneer 

and Thiensville indicate marked similarities (fig. 3c). In 

contrast, bed-sediment PCB distributions at Estabrook 

more closely resemble a third Aroclor mixture (1242; 
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 7

Figure 2a. Dissolved PCB congener distributions from the two highest field-equipment-blank concentrations and two Milwaukee 

River field sites. (“ΣPCB” denotes summed PCB congeners.)

 Field-Equipment Blanks

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

‘

Pioneer Road 

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

Highway T - Upstream boundary

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

CONCENTRATION, IN NANOGRAMS PER LITER (ng/L)

IUPAC CONGENER NUMBER (ELUTION ORDER)

4/13/95 (ΣPCB = 0.09 ng/L)

4/27/95 (ΣPCB = 0.15 ng/L)

median concentration (ΣPCB = 2.93 ng/L; 8/3/93)

minimum concentration (ΣPCB 0.50 ng/L; 1/19/95)

8/26/96 (ΣPCB =0.67 ng/L)

5/11/96 (ΣPCB = 1.30 ng/L)
8 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin, 

1993–95

Figure 2b. Particulate PCB congener distributions from the two highest field-equipment-blank concentrations and two 

Milwaukee River field sites. (“ΣPCB” denotes summed PCB congeners.)

 Field-Equipment Blanks

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

(PCB’s detected in only one sample)

Pioneer Road

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

0.53 0.42

Highway T - Upstream boundary

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

CONCENTRATION, IN NANOGRAMS PER LITER (ng/L)

8/26/96 (ΣPCB = 0.45 ng/L)

4/13/95 (ΣPCB = 0.04 ng/L)

4/27/95 (ΣPCB = 0.26 ng/L)

IUPAC CONGENER NUMBER (ELUTION ORDER)

median concentration (ΣPCB = 4.73 ng/L; 4/13/95)

minimum concentration (ΣPCB = 1.12 ng/L; 1/19/95)
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 9

Figure 3a. Dissolved PCB congener distributions for Milwaukee River and Cedar Creek sites and one Aroclor mixture. 

(Error bars represent 1 standard deviation.) CONGENER FRACTION OFDISSOLVED PCB

IUPAC CONGENER NUMBER (ELUTION ORDER)

Thiensville

0%

2%

4%

6%

8%

10%

12%

14%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=16

Pioneer Road

0%

2%

4%

6%

8%

10%

12%

14%

16%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=26

Columbia Avenue

0%

5%

10%

15%

20%

25%

30%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=11

Highland Road

0%

2%

4%

6%

8%

10%

12%

14%

16%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=13 Estabrook Park

0%

2%

4%

6%

8%

10%

12%

14%

16%

18%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=31

0%

2%

4%

6%

8%

10%

12%

14%

16%

7

17334940

56/60

87

151

132/153182/187171/202

201128

Aroclor 1242
10 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Figure 3b. Particulate PCB congener distributions for Milwaukee River and Cedar Creek sites and one Aroclor mixture. 

(Error bars represent 1 standard deviation.)

IUPAC CONGENER NUMBER (ELUTION ORDER)

CONGENER FRACTION OF PARTICULATE PCB

Columbia Avenue

0%

2%

4%

6%

8%

10%

12%

14%

16%

18%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=11 Thiensville

0%

2%

4%

6%

8%

10%

12%

14%

16%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=16

Highland Road

0%

2%

4%

6%

8%

10%

12%

14%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=13 Estabrook Park

0%

2%

4%

6%

8%

10%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=31

Pioneer Road

0%

2%

4%

6%

8%

10%

12%

14%

7 

17 33 49 40 

56/60

87 

151 

132/153182/187171/202

201 128 

n=26

0%

2%

4%

6%

8%

10%

7

17334940

56/60

87

151

132/153182/187171/202

201128

Aroclor 1254
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 11Figure 3c. Bed-sediment PCB congener distributions for Milwaukee River and Cedar Creek sites and one Aroclor mixture.

Estabrook Park

0%2%4%6%8%

10%12%14%

#7

#18

#26

#45

#47/48

#40

#91

#99

#136

#135/144

#132/153

Pioneer Road

0%2%4%6%8%

10%

#7

#18

#26

#45

#47/48

#40

#91

#99

#136

#135/144

#132/153

#178

#174

#180

#196/203

#128

n=4

Aroclor 1260

02468

101214

#7

#18

#26

#45

#47/48

#40

#91

#99

#136

#135/144

#132/153

Thiensville

0%2%4%6%8%

10%12%

#7

#18

#26

#45

#47/48

#40

#91

#99

#136

#135/144

#132/153

#178

#174

#180

#196/203

#128

Ponar coresGravity cores

n=4

CONGENER FRACTION OF TOTAL BED-SEDIMENT PCB

IUPAC CONGENER NUMBER (ELUTION ORDER)

7

19

24/27

28/31

45

49

37/42

74

91

101

87

77/110

135/144

146

137/176

182/187

174

172/197

170/190

195/208

128

7

19

24/27

28/31

45

49

37/42

74

91

101

87

77/110

135/144

146

7

19

24/27

28/31

45

49

37/42

74

91

101

87

77/110

135/144

146

7

19

24/27

28/31

45

49

37/42

74

91

101

87

77/110

135/144

146

137/176

182/187

174

172/197

170/190

195/208
12 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin, 

1993–95

fig. 3a) with the addition of a relatively small percentage of some of the higher chlorinated congeners contained in Aroclor 1260 (fig. 3c). A possible source of 

Aroclor 1242 is the Lincoln Creek subbasin (fig. 1), 

which contains a mixture of industrial, commercial, and 

residential land use.

Phase Partitioning of PCB’s

Physiochemical associations of PCB’s in rivers are 

generally controlled by the interplay between the character (organic carbon content, surface area, mass) of 

sorbing phases (DOC, colloids, and POC) and the 

hydrophobicity of the PCB molecules themselves, usually approximated by the octanol-water partition coefficient (KOW) (Karickhoff and others, 1979). A theoretical, thermodynamically based partitioning of PCB’s 

between the truly dissolved phase, the DOC-bound 

phase (KDOC), and the POC-bound phase (KPOC) can be 

computed as follows (assuming equilibrium conditions), solved here for KPOC (Karickhoff and others, 

1979):

KPOC = CPAR/[(CDIS + CDOC )(POC) -

(KDOC /KPOC)(DOC)(CPAR)], (1)

where

CPAR is concentration of particle-associated PCB

(mass per volume),

CDIS is concentration of “dissolved” PCB

 (mass per volume),

CDOC is concentration of DOC-associated PCB

(mass per volume),

POC is concentration of particle-associated

organic carbon (mass per volume),

DOC is concentration of dissolved organic 

carbon (mass per volume),

KDOC is partition coefficient for DOC-associated

PCB (volume per mass).

For each sample, all term values in the above equation were measured except KDOC and KPOC. These two 

partition coefficients cannot be determined from field 

measurements but must be computed from theory and 

other measured parameters, owing to the inability to 

accurately separate PCB’s associated with the various 

phases. On the basis of a literature search, however, 

Bierman and others (1992) noted that the ratio between 

KPOC and KDOC could be approximated as follows:

KPOC /KDOC = 0.01,

where both unknowns have been defined previously. 

Therefore, this approximation reduces the problem to 

one equation and one unknown, allowing a unique 

solution. The KPOC value is based upon PCB partitioning to organic carbon; however, KPOC tends to have a 

relatively large error associated with the variability of 

the several terms in the equation. Another caveat is that 

although the PCB concentration of the operationally 

defined dissolved phase (CDIS) is based on the mass of 

PCB’s passing through a 0.7-μm glass fiber filter, the 

DOC mass is determined by that which passes through 

a 0.45-μm silver membrane filter. Thus, the mass of 

sorbing medium (DOC) is underestimated with respect 

to the operationally observed PCB concentration associated with DOC, resulting in an underestimate of the 

second denominator term (eq. 1) and therefore an 

underestimate of KPOC. 

Alternately, an empirically determined, two-phase 

apparent distribution coefficient (KD) can be computed 

from the measured parameters and is defined as 

follows:

KD = CPAR /(TSS x CDIS ), (2)

where all unknowns have been previously defined. As 

mentioned, the operationally defined dissolved phase 

was analyzed from the filtrate that passed through a 

0.7-μm glass fiber filter. Although the apparent KD

value is empirical and does not rise directly from partitioning theory, is mainly useful as a way to compare 

PCB distributions among several samples on a relative 

basis. 

Computed apparent KD and KPOC values, averaged 

from all data for each sampling site, are given in table 2. 

At all sites, KD and KPOC for the summed PCB congeners was intermediate between those values for IUPAC 

congeners 28/31 (both trichlorobiphenyls) and 180 

(a heptachlorobiphenyl). A negative KPOC resulted 

from the second term in the denominator in equation 1 

being larger than the first, possibly a result of the 

assumed KDOC/KPOC ratio of 0.01. 

The apparent distribution and organic-carbon-normalized partition coefficients compare favorably 

between the Fox River site at De Pere, Wis., as computed in the Lower Fox River Model Study (Steuer and 

others, 1995) and the Milwaukee River sites. Although 

KPOC is often used in PCB transport modeling, KPOC

was more variable than KD in both the Lower Fox River 

Model study and this investigation. In the Fox River 

study, POC was determined by the difference between 

TOC and DOC; thus KPOC variability was thought to be 
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 13

the result of that computation. However, KPOC values 

computed in the present study from directly measured 

POC concentrations also were more variable than the 

KD values (table 2). 

At all sites, the distribution of particle-associated 

PCB’s is a substantially different distribution from that 

of the operationally defined dissolved phase (figs. 3a 

and 3b). The sediment/water partition coefficients 

(fig. 4) indicate that the more chlorinated congeners 

have a much greater affinity for particulate matter than 

the less chlorinated congeners. In some cases, such as 

IUPAC congener 7 (a less chlorinated congener) and 

congener 194 (a more chlorinated congener), estimated 

partition coefficients differ by an order of magnitude. 

At equilibrium or near-equilibrium conditions, the more 

chlorinated congeners have a greater affinity for particulate matter. Thus, partitioning could explain the differences in PCB distribution observed in the operationally 

defined dissolved phase and the particulate phase 

(figs. 3a and 3b). 

Total Suspended Solids and Chlorophyll a

Concentrations

PCB’s and other hydrophobic, lipophilic compounds are typically found sorbed to riverine biotic 

material, sediments, and other solids. Thus, 

chlorophyll a (surrogate for algae) and TSS data were 

collected at each site in addition to discharge data to 

facilitate interpretation of PCB concentrations and 

loads. Data from all sites indicate that the automated 

POINT sample TSS data, which were collected from a 

single location in the river, provided a reasonable 

approximation of the more representative EWI samples 

(fig. 5). Reasonable correlations of POINT and EWI 

data may result when the river being sampled is well 

mixed with respect to a constituent of interest, in this 

case, suspended solids. Occasionally, the POINT sample was collected manually rather than automatically, 

often during the winter when sample tubing was frozen. 

On two occasions at Thiensville (12/14/93 and 1/19/95) 

and once at Estabrook (8/31/94), the POINT sample 

yielded TSS concentrations that were much higher than 

the EWI or CHURN samples (appendixes 2e and 2f). 

These three samples are not included in figure 5. It is 

likely the manual sampling inadvertently collected 

resuspended bottom material. The river-discharge data 

or samples collected at the same time at other Milwaukee sites do not support the elevated TSS concentrations 

(appendix 2).

TSS, chlorophyll a, and discharge data from the 

Highland, Pioneer, Thiensville, and Estabrook sites 

(figs. 6a–6d) indicate that TSS concentrations during 

some intervals are not directly related to discharge. 

Although sediments and other solids, including detritus, 

are frequently mobilized during periods of snowmelt or 

storm discharge, biotic material can increase exponenTable 2. Calculated log KD and log KPOC values for selected PCB congeners and summed PCB 

congener concentrations at all sampling sites

[ΣPCB, summed PCB congeners; () indicates coefficient of variation; %, percent]

Log KD Log KPOC

Site 28/31 ΣPCB 180 28/31 ΣPCB 180

Milwaukee River Basin

Columbia Ave. 4.5

(41%)

5.7

(62%)

6.1

(53%)

5.4

(45%)

6.8

(113%)

7.5

(118%)

Highland Rd. 4.8

(105%)

5.8

(117%)

6.4

(94%)

5.9

(100%)

7.5

(239%) Negative

Pioneer Rd. 4.5

(73%)

5.2

(58%)

5.6

(58%)

5.7

(58%)

6.5

(67%)

7.1

(292%)

Thiensville 4.5

(72%)

5.2

(48%)

5.6

(47%)

5.7

(77%)

6.7

(141%)

6.3

(1,646%)

Estabrook Park 4.7

(78%)

5.0

(70%)

5.7

(36%)

6.1

(119%)

6.8

(209%) Negative

Other studies—Fox River, Wis.

Fox River at De Pere1

1From Steuer and others (1995).

5.1 5.1 5.6 6.2 6.2 6.8
14 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Figure 4. Apparent distribution coefficients (KD) at two Milwaukee River Basin sites. (Error bars represent 1 standard deviation.)

Highland Road

0

200,000

400,000

600,000

800,000

1,000,000

1,200,000

1,400,000

1,600,000

1,800,000

2,000,000

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

Estabrook Park

0

200,000

400,000

600,000

800,000

1,000,000

1,200,000

1,400,000

1,600,000

1,800,000

2,000,000

7 

19 

24/2728/31

45 49 

37/42

74 91 

101 

87 

77/110

135/144

146 

137/176182/187

174 

172/197170/190195/208

128 

APPARENT 

KD, IN LITERS PER KILOGRAM 

IUPAC CONGENER NUMBER
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 15

Figure 5. Correlation of point-sampled (POINT) and equal-width-increment (EWI) sampled suspended solids at four Milwaukee 

River and Cedar Creek sites. EWI SUSPENDED-SOLIDS CONCENTRATION, IN MILLIGRAMS PER LITER

POINT SUSPENDED-SOLIDS CONCENTRATION, IN MILLIGRAMS PER LITER

Highland Road

0

5

10

15

20

25

0 5 10 15 20 25

EWI = 0.82 POINT

(R2 = 0.67)

Pioneer Road

0

10

20

30

40

50

60

70

80

0 10 20 30 40 50 60 70 80

EWI = 0.86 POINT

(R2 = 0.83)

Thiensville

EWI = 0.91 POINT

(R2 = 0.93)

0

10

20

30

40

50

60

70

80

90

0 10 20 30 40 50 60 70 80 90

Estabrook Park

0

100

200

300

400

500

600

0 100 200 300 400 500 600

EWI = 1.17 POINT

(R2 = 0.59)
16 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

tially with the availability of sunlight and resultant 

warmwater conditions. Therefore, factors in addition to 

discharge may be needed to represent suspended-solids 

transport and PCB transport in the Cedar Creek/Milwaukee River system. In general, concentrations of TSS 

and discharge increase sequentially from Highland 

Road to Estabrook Park. (Note the sequentially increasing y-axes scales on some of the graphs in figs. 6–9.)

At the Highland site, TSS concentrations did not 

exceed 40 mg/L except during late December 1994, 

when TSS concentrations exceeded 70 mg/L. This TSS 

spike was also observed at the downstream sites and 

may have been reflective of an algal bloom; no chlorophyll a data are available to confirm this. Some small 

TSS concentration increases correspond to the rising 

hydrograph limb (April through May 1995); but, in general, the impoundment did not generate high TSS concentrations. The overall cyclical TSS concentration 

pattern reflects the chlorophyll a (biotic growth) concentration data. This growth pattern is also observed at 

the three downstream sites. 

At the Pioneer site, below the confluence of Cedar 

Creek and the Milwaukee River, TSS concentration 

increased greatly on the rising hydrograph limb during 

numerous events (fig. 7). Yet, during spring 1995, 

increased discharge did not generate high TSS concentrations at the Pioneer site. A late December 1994 

increase in TSS similar to that noted at the Highland site 

(fig. 6) is readily observable in the Pioneer data (fig. 7). 

At Pioneer Road, Thiensville, and other sites downstream, however, the December 1994 increase that was 

so pronounced at the upstream Highland site is overshadowed by much larger solids concentrations associated with high-flow events and warm-weather 

conditions that occur annually. 

The Thiensville site is immediately downstream 

from an impoundment, and TSS peaks increased 

slightly relative to those measured upstream at Pioneer 

Road. TSS and chlorophyll a concentrations are notably 

elevated during warm-weather periods of 1993 and 

1994 (fig. 8). Elevated discharges in early spring of 

1994 and 1995 were associated with low concentrations 

of TSS. This may have resulted from low availability of 

a flocculent, resuspendable bottom-sediment layer during that time of year or from reduced sediment inputs 

from the surrounding subbasin.

Estabrook Park, with its impervious urban basin 

contributions, is a hydraulically variable site compared 

to Thiensville and the other upstream sites. The rapid 

fluctuations in TSS concentration measured at 

Estabrook necessitated use of a log scale for displaying 

the data (fig. 9). Although the Estabrook site is, like 

Thiensville, immediately downstream from an 

impoundment, Estabrook is also downstream from the 

urbanized Lincoln Creek tributary. Lincoln Creek 

drains a 9.6-mi2 urban basin that includes industrial 

inputs and urban stormwater discharges. Estabrook had 

maximum chlorophyll a concentrations of greater than 

250 mg/L (fig. 9), demonstrating the substantial contribution that biotic material can make to the TSS concentration during an algal growth period. Increased TSS 

concentrations are again observed on the rising 

hydrograph limb. As is the case with the two upstream 

sites, this response is not readily observed during the 

early spring periods.

Total Suspended Solids Load

Suspended-solids loads for the Highland, Pioneer, 

Thiensville, and Estabrook sites were estimated by the 

CLOAD procedure (table 3). Loads increased from Pioneer Road to Estabrook Park; however, as figure 10 and 

table 3 indicate, solids suspension and deposition are 

variable with time and river reach. For example, the 

cumulative TSS load at Thiensville was less than at Pioneer Road from about March through November 1994, 

an indication that material advected past the Pioneer site 

was being deposited in the Thiensville impoundment. 

By the end of the study period, in summer of 1995, the 

cumulative TSS load at Thiensville substantially 

exceeded loads advected at Pioneer Road, signifying 

net scour or substantial biotic growth or both in the 

Thiensville impoundment. Substantially larger TSS 

loads measured at Estabrook Park than at Thiensville 

resulted from sediment influx from the Lincoln Creek 

tributary and other urban sources, along with substantial 

biotic growth or scour in the Estabrook impoundment. 

During water year 1994, TSS input from Lincoln Creek 

was 2,300 tons (Corsi and others, 1997) upstream from 

the Estabrook site. Thus, more than 25 percent of the 

8,100-ton TSS increase from Thiensville to Estabrook 

Park (table 3) can be attributed to Lincoln Creek input. 

A controlled dam release from the Estabrook impoundment on October 12, 1994, moved an estimated 103 tons 

of solids, which is represented as a short vertical segment of the Estabrook cumulative TSS load curve 

(fig. 10). 

Comparison of discharge to TSS loads (fig. 10) 

also illustrates that although biotic material can substan-
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 17

Figure 6. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data from the Highland 

Road site on the Milwaukee River.

ΣPCB

0

50

100

150

200

250

300

350

400

7/25/94 9/13/94 11/2/94 12/22/94 2/10/95 4/1/95 5/21/95 7/10/95 8/29/95

1440 ng/L 528 ng/L

0

50

100

150

200

250

300

7/25/94 9/13/94 11/2/94 12/22/94 2/10/95 4/1/95 5/21/95 7/10/95 8/29/95

Discharge

ΣPCB CONCENTRATION, IN NANOGRAMS 

PER LITER

DISCHARGE, IN CUBIC FEET 

PER SECOND

TSS CONCENTRATION, IN MILLIGRAMS PER LITER; 

CHLOROPHYLL 

A CONCENTRATION, IN MICROGRAMS 

Regressed ΣPCB

ΣPCB sample

0

5

10

15

20

25

30

35

40

7/25/94 9/13/94 11/2/94 12/22/94 2/10/95 4/1/95 5/21/95 7/10/95 8/29/95

TSS sample

Chlorophyll-a sample

Total suspended solids and

 Chlorophyll a 77 mg/L

TSS Sample

Chlorophyll a sample
18 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Figure 7. Total suspended solids (TSS), summed PCB congener ( ΣPCB) concentration, and discharge data from the Pioneer 

site on the Milwaukee River. 

0

20

40

60

80

100

120

140

6/10/93 9/18/93 12/27/93 4/6/94 7/15/94 10/23/94 1/31/95 5/11/95 8/19/95

176 ng/L 214 ng/L

ΣPCB CONCENTRATION, IN NANOGRAMS 

PER LITER

TSS CONCENTRATION IN MILLIGRAMS PER LITER; 

CHLOROPHYLL 

A CONCENTRATION, IN MICROGRAMS 

PER LITER

DISCHARGE, IN CUBIC FEET 

PER SECOND

Discharge

0

500

1,000

1,500

2,000

6/10/93 9/18/93 12/27/93 4/6/94 7/15/94 10/23/94 1/31/95 5/11/95 8/19/95

Regressed ΣPCB

ΣPCB sample

ΣPCB

Total suspended solids and

 Chlorophyll a

0

50

100

150

200

250

6/10/93 9/18/93 12/27/93 4/6/94 7/15/94 10/23/94 1/31/95 5/11/95 8/19/95

TSS sample

Chlorophyll a sample

302 mg/L 342 mg/L

TSS sample

Chlorophyll a sample
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 19

Figure 8. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data from the Thiensville 

site on the Milwaukee River.

Total suspended solids

and Chlorophyll a

0

50

100

150

200

250

6/10/93 9/18/93 12/27/93 4/6/94 7/15/94 10/23/94 1/31/95 5/11/95 8/19/95

TSS

Chl a

576 mg/L 394 mg/L 361 mg/L

ΣPCB

0

10

20

30

40

50

60

70

6/10/93 9/18/93 12/27/93 4/6/94 7/15/94 10/23/94 1/31/95 5/11/95 8/19/95

ΣPCB CONCENTRATION, IN NANOGRAMS 

PER LITER

DISCHARGE, IN CUBIC FEET 

Discharge

0

500

1000

1500

2000

2500

6/10/93 9/18/93 12/27/93 4/6/94 7/15/94 10/23/94 1/31/95 5/11/95 8/19/95

TSS CONCENTRATION IN MILLIGRAMS PER LITER; 

CHLOROPHYLL A CONCENTRATION, IN MICROGRAMS 

 PER LITER

TSS sample

Chlorophyll a sample

Regressed ΣPCB

ΣPCB sample
20 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Figure 9. Total suspended solids (TSS), summed PCB congener (ΣPCB) concentration, and discharge data from the Estabrook 

Park site on the Milwaukee River.

ΣPCB 

1

10

100

1000

10000

06/10/93 09/18/93 12/27/93 04/06/94 07/15/94 10/23/94 01/31/95 05/11/95 08/19/95

TSS CONCENTRATION IN MILLIGRAMS PER LITER; 

CHLOROPHYLL-A CONCENTRATION, IN MICROGRAMS 

PER LITER

ΣPCB CONCENTRATION, IN NANOGRAMS 

PER LITER

DISCHARGE, IN CUBIC FEET 

PER SECOND

Discharge

0

500

1000

1500

2000

2500

06/10/93 09/18/93 12/27/93 04/06/94 07/15/94 10/23/94 01/31/95 05/11/95 08/19/95

Regressed ΣPCB

ΣPCB sample

Total suspended solids and

Chlorophyll a

1

10

100

1000

06/10/93 09/18/93 12/27/93 04/06/94 07/15/94 10/23/94 01/31/95 05/11/95 08/19/95

TSS sample

Chl a

TSS sample

Chlorophyll a sample
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 21

tially increase TSS concentrations during times of low 

flow, most TSS is transported on the main stem of the 

Milwaukee River during high flow. In addition to the 

cumulative TSS load (fig. 10), TSS passing the Thiensville and Estabrook sites was analyzed on a reach basis 

(fig. 11) to illustrate the dynamic nature and complexity 

of TSS transport on the Milwaukee River. Intervals 

where the “Pioneer to Thiensville” line is positive indicates that solids loads were greater at Thiensville than 

upstream at Pioneer Road; however, in numerous cases, 

the line is negative, indicating deposition and accumulation of solids in the Thiensville impoundment. Similarly, a positive “Thiensville to Estabrook” line indicates greater solids transport at Estabrook Park than 

upstream at Thiensville, and a negative line indicates 

that solids are accumulating in the Estabrook impoundment.

Comparison of the two stream reaches produced 

some interesting results, such as during spring 1994 

when sediments were being deposited at Thiensville 

(negative line) but being scoured at Estabrook Park 

(positive line). Net solids loading on the Thiensville to 

Estabrook reach is complicated by Lincoln Creek input. 

During this interval of positive net load (February and 

March 1994), 6,200 tons more TSS passed the 

Estabrook site than the Thiensville site, whereas input 

from Lincoln Creek was about 170 tons of TSS 

upstream from the Estabrook site (Corsi and others, 

1997). Clearly, much of the solids passing the Estabrook 

site were resuspended from the bottom sediments 

upstream from the Estabrook Park. In contrast, during 

the end of the March to May 1995 event (which was 

much smaller than the spring of 1994 event), the opposite occurred: net load in the Pioneer to Thiensville 

reach was positive (scour), whereas deposition occurred 

behind the Estabrook dam.

Concentrations and Loads of Transported 

PCB’s in the Milwaukee River System

Data detailed in appendixes 2a–2f indicate that 

PCB concentration and load increase as one progresses 

down the Milwaukee River Basin. PCB samples from 

the Columbia site on Cedar Creek, immediately downstream from the remediated Ruck Pond impoundment, 

resulted in loads less than 3 grams per day (g/d) (appendix 2a). In contrast, PCB samples collected from the 

Highland site on Cedar Creek, downstream from the 

contaminated Columbia impoundment, resulted in 

ΣPCB loads as high as 20 g/d.

At the Highway T site, 4 out of 5 PCB samples 

result in a ΣPCB load of less than 1 g/d. After Cedar 

Creek joins the Milwaukee River, downstream from 

Highway T, ΣPCB loads increased such that the median 

sampled summed PCB congener load at Estabrook was 

26 g/d, and the maximum sampled load was 221 g/d.

At the four downstream sites, the fraction of PCB 

found in the particle phase ranged from 61 percent to 74 

percent (median values; appendixes 2b, 2d, 2e, 2f). 

Thus, TSS formed the basis of the ΣPCB regression 

equations. All PCB congeners present in a sample were 

summed to obtain the reported ΣPCB concentrations for 

each sample. 

Congener-specific PCB data have been published 

(Holmstrom and others, 1995, 1996, and 1997) and are 

stored in the USGS QWDATA data base. Concentrations of the operationally defined dissolved phase, particle-associated phase, and total ΣPCB’s (both phases), 

Table 3. Total-suspended-solids loads computed for four Milwaukee River Basin sites

[The irregular load intervals are necessary to accomodate comparison with the Highland Road data, which were collected for a limited 

time interval; --, no data]

Site

Sampling 

interval

(No. of samples)

Load (tons)

7/1/93–7/31/93

(1 month)

8/1/93–7/31/94

(1 year)

8/1/94–7/31/95

(1 year)

Water year 1994

10/1/93–9/30/94

(1 year)

Highland Road 7/29/94–9/4/95

(158)

-- -- 630 --

Pioneer Road 6/16/93–8/29/95

(401)

2,800 9,600 4,400 8,700

Thiensville 7/22/93–8/17/95

(351)

3,000 9,100 8,200 7,700

Estabrook Park 6/22/93–8/3/95

(447)

2,800 16,800 11,200 15,800
22 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Figure 10. Cumulative suspended solids-loads at three Milwaukee River sites and discharge at the Estabrook site.

Figure 11. Net suspended-solids loads for two Milwaukee River reaches and Estabrook discharge.

0

5,000

10,000

15,000

20,000

25,000

30,000

35,000

06/29/93 10/07/93 01/15/94 04/25/94 08/03/94 11/11/94 02/19/95 05/30/95

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

CUMULATIVE SUSPENDED-SOLIDS LOAD, IN TONS

 DISCHARGE, IN CUBIC FEET PER SECOND

Estabrook Park

Thiensville

Pioneer Road 

Discharge (Estabrook Park)

-600

-400

-200

0

200

400

600

06/29/93 10/07/93 01/15/94 04/25/94 08/03/94 11/11/94 02/19/95 05/30/95

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

Pioneer to Thiensville

Thiensville to Estabrook

Estabrook discharge

Discharge (Estabrook Park)

Estabrook scour or 

Lincoln Creek input

Thiensville deposition

SUSPENDED-SOLIDS LOAD, IN TONS

DISCHARGE, IN CUBIC FEET PER SECOND

06/29/93 10/07/93 01/15/94 04/25/94 08/03/94 11/11/94 02/19/95 05/30/95
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 23

along with the ancillary constituents are given in appendix 2.

PCB’s and other hydrophobic compounds typically 

sorb to riverine biotic material, sediments, and other 

solids; thus, the ΣPCB regressions initially focused on 

the TSS variable. POINT TSS samples, instead of 

CHURN or EWI samples, were used in the ΣPCB loading regression analyses because of the greater data density and more complete event coverage afforded by the 

frequency of POINT sample collection. In addition to 

TSS, regression was used to examine ΣPCB concentration as a function of discharge, time of year, temperature, and precipitation. Depending on the site, some of 

these variables were used to transform the TSS variable. 

The site-specific environmental settings, impoundment 

hydrodynamics, surrounding subbasin and tributary 

inputs, and channel morphology required that the form 

of the regression equations be site specific (table 4). The 

dependent and independent variables were log10 transformed to normalize the distributions; thus, it was necessary to apply the bias correction factor (table 4) as 

detailed in Gilroy and others (1998).

For the Highland site (fig. 6), a simple linear 

regression of log ΣPCB and log TSS resulted in a correlation coefficient (r2) of 0.88. Without the log tranformations of the variables, r2 equaled 0.67. At this site, in 

addition to the positive ΣPCB-TSS correlation, ΣPCB 

was found to be negatively correlated with discharge 

(appendix 2b). This ΣPCB-discharge relation had the 

form of the transformation equation in table 4 with the 

slope (-0.67) and intercept (2) selected as to maximize 

r

2

. An example of the importance of Qc transformation 

on TSS is on April 27, 1995, and August 17, 1995, when 

POINT TSS was 14 mg/L on both sample days but the 

discharge was 253 ft3

/s and 63 ft3/s, respectively. On the 

high-flow day, April 27, 1995, the ΣPCB concentration 

was one-sixth of that on the low-flow day. Thus, the 

TSS variable was transformed (decreased) with increasing discharge (table 4).

At the Pioneer site (fig. 7), PCB-laden water from 

Cedar Creek is diluted by the relatively PCB-free Milwaukee River upstream (appendix 2c). The Cedar 

Creek/Milwaukee River flow ratio effectively transformed the TSS variable to reflect the decreased ΣPCB 

concentration during periods of low Cedar Creek disTable 4. Summed PCB congener concentration regression relations and characteristics at Highland Road (Cedar Creek) and 

three Milwaukee River sites

[TSS, total suspended solids, in milligrams per liter; r2, correlation coefficient; SE, standard error; μ log[PCB], mean of the log (ΣPCB); %, percent;

 = bias correction factor]

Site Regression equation r2 p-value 1.96 • 

Highland Road H1: Log (ΣPCB) = 1.56 log X + 0.29

X = (-0.67 Log Qc +2) TSS

Qc is instantaneous Cedar Creek discharge 

in cubic feet per second, at the time of the 

TSS sample

0.93 1.0 x 10-7 18.0% 1.03

Pioneer Road P1: Log (ΣPCB) = 1.02 log X - 0.05 

applied on or before August 24, 1994

P2: Log (ΣPCB) = 1.08 log X - 0.26

applied after August 24, 1994

.88

.70

3.4 x 10-8

5.0 x 10-3

30.0%

54.9%

1.03

1.05

Thiensville T1: Log (ΣPCB) = 0.53 log (TSS) + 0.34 .83 2.7 x 10-6 21.2% 1.01

Estabrook Park E1: Log (ΣPCB) = 0.78 log X + 0.45

X = (0.006QL

2

 - 0.02QL + 0.06) TSS

QL is instantaneous Lincoln Creek 

discharge, in cubic feet per second

E2: Log (ΣPCB) = 0.81 log TSS + 0.21

.85

.74

8.9 x 10-12

8.0 x 10-9

20.0%

26.1%

1.02

1.04

10 SE2

2

---------    

SE

μlog PCB [ ]

--------------------    

10

S E2

2

---------    

X DailyCedarCreekDisch e arg

DailyPioneerDisch e arg -----------------------------------------------------------------------------     =

0.3

• TSS
24 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

charge relative to Milwaukee River discharge. For 

example, on July 7, 1994, and August 16, 1995, the TSS 

concentrations were nearly identical. However, the fraction of Milwaukee River flow that originated from 

Cedar Creek was nearly 3 times greater on July 7, 1994, 

resulting in a higher ΣPCB concentration. 

On August 24, 1994, flow was diverted around the 

PCB-contaminated Ruck Pond impoundment on Cedar 

Creek to enable removal of contaminated sediment 

from Ruck Pond. Regression residuals—the difference 

between the regressed ΣPCB value and the sample 

ΣPCB data point—for the Pioneer site are shown in figure 12. If one regression equation is used for the entire 

Pioneer-site sampling period, 75 percent of the regression residuals after the Ruck Pond diversion are negative (fig. 12), signifying that the regression model 

overpredicted the data after August 24, 1994. If two 

regression equations are used, one before and one after 

the Ruck Pond flow diversion (remediation), the postremediation residuals are less biased. Apparently 

ΣPCB concentration was at least partially affected by 

the Ruck Pond remediation; thus, the two regression 

equations were used to separate the data into before and 

after the diversion date (table 4). 

At the Thiensville site (fig. 8), flow, temperature or 

precipitation transformation of TSS did not improve the 

linear correlation with ΣPCB; thus, the ΣPCB regression was based solely on TSS with no transformation. 

All PCB data were collected prior to the Ruck Pond 

flow diversion, thus, it was not possible to examine the 

Thiensville data in light of the Ruck Pond remediation.

At the Estabrook site, Lincoln Creek and the surrounding urban basin contribute significant discharge 

and suspended solids, as shown in figure 9. The substantial discharges may resuspend soft sediments at the 

Lincoln Creek confluence, an area in the Milwaukee 

River where strong eddies and distinct elevation 

changes of soft-sediment deposits have been observed 

(William Wawrzyn, Wisconsin Department of Natural 

Resources, oral commun., 1996). This is also an area of 

increased PCB concentrations in the bottom sediments 

(fig. 1; table 1). Transforming the TSS variable with 

Lincoln Creek instantaneous discharge (QL) appropriately increased the resulting PCB concentrations for the 

two PCB samples obtained during high Lincoln Creek 

inflow (appendix 2f) and improved the regression relation (r2 = 0.85, table 4). Without the TSS variable transformation, the PCB regression equation had a lower 

linear correlation coefficient (r2 = 0.74). 

During the study period, QL rose to 2,500 ft3

/s, 

much greater than the maximum discharge during 

which PCB samples were collected at the Estabrook site 

(95 ft3/s). Thus, it is unclear what the transformation 

relation should be when QL is greater than 95 ft3/s. For 

QL greater than 95 ft3/s, a linear extension (X = 

0.036Q - 0.32 in equation E1 in table 4) was used to estimate the PCB concentration. The complex physical setting upstream from Estabrook Park—including a large 

vertical PCB gradient in the bottom sediment in the 

vicinity of Lincoln Creek (fig. 1), significant sedimentation from urban inputs, and resuspension from a range 

of soft sediment deposits under specific flow—may 

require a deterministic model to obtain more accurate 

PCB loads at the Estabrook site.

The regression relation, regression statistics, and 

the log10 bias correction factors are detailed in table 4. 

By comparing the POINT TSS concentrations (appendixes 2b–2f), which form the basis of the independent 

variable in the regression equations, to the full range of 

monitored TSS (figs. 6–9), it is apparent that the regression relations were based largely on the data range for 

which they are ultimately applied. The standard error 

multiplied by 1.96 and normalized by the dependent 

variable (log PCB), provides some indication of a confidence interval, although the actual 95-percent confidence interval is a function of the specific independent 

variable.

In general, over an extended period of time, total 

water-column PCB concentrations will decrease as 

PCB is transported out of the bottom sediments. The 

equations in table 4 do not contain time as an independent variable; thus, the regressions will not reflect this 

expected PCB concentration decrease. If these PCB 

regressions are compared to data collected in subsequent years, one would expect to see a negative trend in 

the residuals; the regression will be overpredicting the 

actual water-column concentrations. Limited data collection 5 to 7 years after this initial effort could be used 

to incorporate a time-decay function in the relation.

To compute ΣPCB loads, PCB concentrations computed from the frequent POINT TSS samples and the 

regression relations in table 4 were used in combination 

with 15-minute discharge data and the flow-integration 

method (CLOAD). This regression approach will be 

referred to as “RLOAD.”

Over the course of the investigation, it appeared 

that part of the Cedar Creek PCB load was deposited 

between the Highland and Pioneer sites; 1.9 kg more 

ΣPCB was advected past Highland Road than Pioneer 
DISTRIBUTION AND TRANSPORT OF PCB’S AND ASSOCIATED PARTICULATES 25

Figure 12. Pioneer PCB concentration regression residuals.

 ̋

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

5/11/93 8/19/93 11/27/93 3/7/94 6/15/94 9/23/94 1/1/95 4/11/95 7/20/95 10/28/95

Ruck Pond flow diverted

 PCB RESIDUALS, FIELD DATA MINUS REGRESSION VALUE, IN PERCENT

Separate regression equations before (P1) and after (P2) Ruck Pond remediation

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

5/11/93 8/19/93 11/27/93 3/7/94 6/15/94 9/23/94 1/1/95 4/11/95 7/20/95 10/28/95

Ruck Pond flow diverted

One regression equation for entire period
26 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Road. In the Fox River system, volatilization losses 

were approximately 15 percent of advection (Steuer and 

others, 1995). Applying this rough approximation for 

volatization loss (15 percent of 3.7 kg = 0.6 kg), it 

appeared that approximately 1.3 kg of PCB (3.7 - 1.8 - 

0.6 = 1.3) may have been deposited upstream from Pioneer Road, possibly in the lower Cedar Creek impoundments (table 5).

Net annual ΣPCB loading in the Pioneer to Thiensville reach was inconsistent; one year it was less at 

Thiensville (by 1.7 kg), whereas the following year it 

was 0.9 kg greater at Thiensville. The Estabrook Park 

ΣPCB loads were computed using both regression relations. Estabrook ΣPCB advection was consistently 

greater than that at Thiensville (5 to 16 kg greater per 

year) an indication of ΣPCB flux from the Estabrook 

impoundment or surrounding watershed.

Cumulative ΣPCB loading as affected by time of 

year, discharge, and Estabrook dam releases is detailed 

in figure 13. Between June 29, 1993, and July 31, 1995, 

38 kg of ΣPCB were advected past Estabrook (21 kg 

if one uses equation E2, the regression that does not 

include the Lincoln Creek discharge transformation of 

TSS). The lowering of the Estabrook pool on 

October 12, 1994, released 51 g of ΣPCB (55 g if 

regression equation E2 from table 4 is used).

For the purpose of load-computation comparison, 

ΣPCB loads were calculated by means of two additional 

approaches. In a second approach, the total integration 

method (CLOAD) was applied to the limited number of 

individual ΣPCB sample concentrations listed in appendix 2. These results will be referred to as SLOAD. The 

third load-computation approach, the Stratified Beale 

Ratio Estimator (SBRE), involved time-based strata 

defined by minimizing loading error over specific time 

intervals (Richards, 1994; Preston and others, 1989). 

The SBRE estimates both a load and an associated confidence interval based on the root mean square error of 

the load computations. The RLOAD approach, which 

used the frequent POINT TSS data, in most instances 

resulted in larger loads than the SLOAD or SBRE methods that used solely the PCB concentration data. Intensive manual collection of PCB samples before and after 

event peaks was often impossible, whereas the automated TSS samplers did capture data during the peak 

load intervals. In one instance at the Estabrook site for 

the period June 29, 1993 to June 28, 1994, the regression approach based on TSS resulted in lower PCB 

loads than the SBRE approach did (table 6). Few PCB 

samples were collected during the low-TSS- and lowPCB-concentration winter period; thus, the SBRE loads 

encompassing this interval are probably too high.

SUMMARY

Concentrations of PCB congeners in the operationally dissolved, suspended-particle-associated, and surficial-bed-sediment (0–2 cm depth) phases at four sites 

on Cedar Creek and the Milwaukee River in Wisconsin 

were studied to determine the distribution and loads of 

total PCB’s in the river. For three of the four sites, the 

PCB congener pattern in the particle-associated phase 

was similar to that in the bed sediment, indicating interaction between the two media. At the fourth site 

(Estabrook Park), the PCB congener distributions of 

suspended particles seemed to reflect a mixture originating from the Estabrook surficial bed sediments and 

suspended particles from the upstream sites. PCB distributions in the surficial bed sediments from all sites were 

generally recognizable as either one or both of PCB 

Aroclor 1242 and 1260. As expected, PCB distributions 

in the operationally defined dissolved phase generally 

showed higher abundances of the more soluble, less 

chlorinated congeners compared to both the suspended 

particles and surficial bed sediments. Variability in 

Table 5. Computed total loads for the Milwaukee River Basin sites using PCB regression relations (RLOAD)

[Estabrook Park load computed with regression equation E2; ( ), load values calculated with regression equation E1; kg, kilogram; --, no data]

Site PCB sampling interval

(No. of samples)

Loads (kg)

7/1/93–7/31/93 8/1/93–7/31/94 8/1/94–7/31/95 Water year 1994

Highland Road 8/11/94–8/17/95

(13)

-- -- 3.7 --

Pioneer Road 6/30/93–8/16/95

(26)

1.2 5.3 1.8 4.8

Thiensville 6/29/93–7/8/94

(16)

1.0 3.6 2.7 3.2

Estabrook Road 6/29/93–8/29/95

(27)

1.9 (1.8) 11.6 (20.3) 7.6 (16.3) 10.9 (17.5)
SUMMARY 27

computed distribution coefficients (KD) was less than 

that for organic normalized carbon partition coefficients 

(KPOC). Combining congener-specific PCB data from 

the five sites, log KD and log KPOC ranged from 5.0 to 

5.8 and 6.5 to 7.5 units, respectively. Particle-associated 

PCB’s exhibited two patterns: (1) a general increase in 

spring and summer associated with algal growth and (2) 

episodic increases associated with resuspension of bed 

sediments during storms. Calculated total suspended 

solids (TSS) and total PCB (ΣPCB) loads at each site 

were dependent on site-specific characteristics, including the tributary inflow and presence and operation of 

dams. 

TSS loads during water year 1994 ranged from 

8,700 tons at Pioneer to 15,800 tons at Estabrook. 

Regression relations based on single-point, automated 

sampler TSS measurements in addition to other environmental variables collected on a frequent basis were 

used to compute total ΣPCB concentrations. The regression-generated ΣPCB (total PCB concentration derived 

by summation of all dissolved and particulate congeners) concentrations were subsequently multiplied by 

15-minute-discharge data to obtain loads. ΣPCB loads 

decreased from Highland (3.7 kg/yr) to Pioneer 

(1.8 kg/yr), indicating PCB deposition between those 

sites. Computed loads of total ΣPCB’s (operationally 

defined dissolved plus particle-associated phases) were 

an order of magnitude higher at the Estabrook site as 

compared to the three upstream sites and were likely 

due to a large reservoir of resuspendable PCB-laden 

sediment behind the dam. Uncertainty in the Estabrook 

ΣPCB loads is attributed to the limited PCB data collected during peak Lincoln Creek discharges, a period 

when PCB-laden bottom sediment may be resuspended 

in the confluence area. The lowering of the Estabrook 

impoundment in October 1994 released 0.05 kg of 

ΣPCB. A ΣPCB load comparison was done using two 

additional approaches: the Stratified Beale Ratio Estimator (SBRE) and the total-flow-integration method 

applied to individual sample concentrations (SLOAD). 

Results were comparable to ΣPCB loads based on 

regressed ΣPCB concentration values, but the SBRE 

and SLOAD commonly resulted in lower loads. This 

low bias was probably due to limited manual-sample 

collection during peak flows. This was not an issue with 

the regression approach that was based on automated 

TSS sampling.

Figure 13. Cumulative summed PCB congener loads at three Milwaukee River sites and discharge at the Estabrook Park site. SUMMED PCB CONGENER LOAD, GRAMS

0

5,000

10,000

15,000

20,000

25,000

30,000

35,000

40,000

07/01/93 10/09/93 01/17/94 04/27/94 08/05/94 11/13/94 02/21/95 06/01/95

Discharge (Estabrook Park)

Estabrook Park (eq. 1)

Estabrook Park (eq. 2)

Pioneer Road

Thiensville
28 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

REFERENCES CITED

Bierman, V.J., DePinto, J.V., Young, T.C., Rogers, P.W., Martin, S.C., and Raghunathan, R.K., 1992, Development 

and validation of an integrated exposure model for toxic 

chemicals in Green Bay, Lake Michigan: U.S. Environmental Protection Agency, Cooperative Agreement CR814885.

Cairns, T., Doose, G.M., Froberg, J.E., Jacobson, R.A., and 

Siegmund, E.G., 1986, Analytical chemistry of PCBs, in

Waid, J.S., ed., PCBs and the environment: Boca Roton, 

Fla., CRC Press, v. 1, p. 2.

Corsi, S.R., Graczyk, D.J., Owens, D.W., and Bannerman, 

R.T., 1997, Unit-area loads of suspended sediment, suspended solids, and total phosphorus from small watersheds in Wisconsin: U.S. Geological Survey Fact Sheet 

FS–195–97, 4 p.

Degenhardt, D.E., 1996, Methods and quality control for the 

organic chemistry unit of the Wisconsin State Laboratory of Hygiene: Madison, Wis., Wisconsin State Laboratory of Hygiene, 1,910 p.

Dolan, D.M., Yui, A.K., and Geist, R.D., 1981, Evaluation of 

river load estimation methods for total phosphorus: 

Journal of Great Lakes Research, v. 7, no. 3, p. 207–214.

Evans, D.O., Warren, G.J., and Cairns, V.W., 1990, Assessment and management of fish community health in the 

Great Lakes— synthesis and recommendations: Journal 

of Great Lakes Research, v. 16, p. 639–669.

Fitzgerald, S.A., and Steuer, J.J., 1997, Polychlorinated 

biphenyls as probes of biogeochemical processes in rivers, in Eganhouse, R.P., ed., Molecular markers in environmental geochemistry: American Chemical Society 

Symposium Series 671, p. 382–397.

Gilroy, E.J., Hirsch, R.M., and Cohn, T.A., 1998, Mean 

square of regression-based constituent transport estimates: Water Resources Research, v. 26, no. 9, p. 2069–

2077.

Holmstrom, B.K., and others, 1995, Water resources data, 

Wisconsin, water year 1994: U.S. Geological Survey 

Water-Data Report WI–94–2, 388 p.

____1996, Water resources data, Wisconsin, water year 1995: 

U.S. Geological Survey Water-Data Report WI–95–1, 

562 p.

____1997, Water resources data, Wisconsin, water year 1996: 

U.S. Geological Survey Water-Data Report WI–96–1, 

464 p.

House, L.B., Hughes, P.E., and Waschbusch, R.J., 1993, Concentrations and loads of polychlorinated biphenyls in 

major tributaries entering Green Bay, Lake Michigan, 

1989–90: U.S. Geological Survey Open-File Report 

93–132, 41 p.

Karickhoff, S.W., Brown, D.S., and Scott, T.A., 1979, Sorption of hydrophobic pollutants on natural sediments: 

Water Resources Research, v. 13, p. 241–248.

Koslowski, S.E., Metcalfe, C.D., Lazar, R., and Haffner, 

G.D., 1994, The distribution of 42 PCBs, including three 

coplanar congeners, in the food web of the Western 

Basin of Lake Erie: Journal of Great Lakes Research, 

v. 20, no. 1, p. 260–270.

Marti, E.A., and Armstrong, D.E., 1990, Polychlorinated 

biphenyls in 16 Lake Michigan tributaries: Journal of 

Great Lakes Research, v. 16, no. 3, p. 396–405.

Porterfield, G., 1972, Computation of fluvial sediments discharge: techniques of water resources investigations of 

the U.S. Geological Survey, book 3, chap. C3, 66 p.

Preston, S.D., Bierman, V.J., Jr., and Sullivan, S.E., 1989, An 

evaluation of methods for the estimation of tributary 

mass loads: Water Resources Research, v. 25(c), 

p. 1379–1389.

Richards, R.P., 1994, Tributary loading estimated for selected 

herbicides in Lake Erie tributaries of Michigan and 

Ohio: Report submitted to the U.S. Environmental Protection Agency Great Lakes National Program Officer 

for Grant # 6L 995453-01, 30 p.

Steuer, J.J., Jaeger, S.R., and Patterson, D.A., 1995, A deterministic PCB transport model for the lower Fox River 

between Lake Winnebago and De Pere, Wisconsin: Wisconsin Department of Natural Resources WR–389–95, 

p. 283.

Sullivan, D.L., Peterson, E.M., and Richards, K.D., 1995, 

Environmental setting of fixed sites in the Western Lake 

Table 6. Computed summed PCB congener loads based on three computation approaches for the Milwaukee River Basin 

sites

[All loads in kilograms; SLOAD, integration method using sample PCB concentrations; RLOAD, integration method using regressed PCB values; SBRE, 

Stratified Beale Ratio Estimation; +, indicates 95 percent confidence interval]

Computation 

approach

Highland Rd.

8/8/94–8/7/95

Pioneer Rd.

6/30/93–6/29/94

Pioneer Rd.

7/1/94–6/30/95

Thiensville

6/29/93–6/28/94

Estabrook Pk.

6/29/93–6/28/94

Estabrook Pk.

6/30/94–6/29/95

SLOAD 2.0 3.8 2.4 4.2 13.2 6.4

RLOAD 3.7 5.9 2.5 4.2 1

19.8

212.4

1

Using equation E1 from table 4.

2Using equation E2 from table 4.

1

17.0 

28.3 

SBRE 2.3 + 0.5 4.6 + 1.7 1.3 + 0.6 3.9 + 1.1 17.6 + 4.8 5.5 + 1.6
REFERENCES CITED 29

Michigan Drainages, Michigan and Wisconsin: U.S. 

Geological Survey Water-Resources Investigations 

Report 95–4211–A, 30 p.

Ward, J.R., and Harr, C.A, 1990, Methods for collection and 

processing of surface-water and bed-material samples 

for physical and chemical analyses: U.S. Geological 

Survey Open-File Report 90–140, 71 p.

Westenbroek, S., 1993, Cedar Creek polychlorinated 

biphenyls mass balance, Phase I—Data summary and 

analysis, final draft: Wisconsin Department of Natural 

Resources, 156 p.

Yamashita, N., Tanabe, S., Ludwig, J.P., Kurita, H., Ludwig, 

M.E., and Tatsukawa, R., 1993, Embryonic abnormalities and organochlorine contamination in double-crested 

cormorants (Phalacrocorax auritus) and caspian terns 

(Hydroprogne caspian) from the Upper Great Lakes in 

1988: Environmental Pollution, v. 79, p. 163–173.

Wisconsin Department of Natural Resources, 1992 [June], 

Milwaukee River Basin Integrated Management Plan: 

v. 4, 241 p.
30 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95
APPENDIXES 1–2 31

APPENDIXES 1–2
32 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin, 

1993–95

Appendix 1. PCB congeners found during laboratory analysis of water and sediments in the Milwaukee River Basin and their 

respective limits of detection and quantification in nanograms per liter

[From Degenhardt (1996). LOD; limit of detection, LOQ, limit of quantification; () indicates positions of chlorine substitution on biphenyl nucleus]

LOD LOQ Congener number and

chlorine substitution position LOD LOQ Congener number and

chlorine substitution position

0.020 0.060 7 (2, 4) 0.035 0.11 85 (2, 2’, 3, 4, 4’)

.080 .27 6 (2, 3’) .030 .10 136 (2, 2’, 3, 3’, 6, 6’)

.090 .30 5/8 (2, 3/2, 4’) .035 .11 77/110 (3, 3’, 4, 4’ /2, 3, 3’, 4’, 6)

.025 .070 19 (2, 2’, 6) .035 .11 82 (2, 2’, 3, 3’, 4)

.030 .090 18 (2, 2’, 5) .020 .070 151 (2, 2’, 3, 5, 5’, 6)

.030 .10 17 (2, 2’, 4) .025 .070 135/144 (2, 2’, 3, 3’, 5, 6’ /2, 2’, 3, 4, 5’, 6)

.025 .070 24/27 (2, 3, 6/2, 3’, 6) .025 .070 149 (2, 2’, 3, 4’, 5’, 6)

.035 .11 16/32 (2, 2’, 3/2, 4’, 6) .030 .090 118 (2, 3’, 4, 4’, 5)

.035 .11 26 (2, 3’, 5) .030 .11 146 (2, 2’, 3, 4’, 5, 5’)

.080 .27 28/31 (2, 4, 4’ /2, 4’, 5) .030 .11 132/153 (2, 2’, 3, 3’, 4, 6’ /2, 2’, 4, 4’, 5, 5’)

.035 .11 33 (2’, 3, 4) .020 .070 141 (2, 2’, 3, 4, 5, 5’)

.055 .18 22 (2, 3, 4’) .030 .090 137/176 (2, 2’, 3, 4, 4’, 5/2, 2’, 3, 3’, 4, 6, 6’)

.025 .070 45 (2, 2’, 3, 6) .035 .11 138/163 (2, 2’, 3, 4, 4’, 5’ /2, 3, 3’, 4’, 5, 6)

.030 .090 46 (2, 2’, 3, 6’) .040 .12 178 (2, 2’, 3, 3’, 5, 5’, 6)

.025 .070 52 (2, 2’, 5, 5) .020 .070 182/187 (2, 2’, 3, 4, 4’, 5, 6’ /2, 3, 4’, 5, 5’, 6)

.025 .070 49 (2, 2’, 4, 5’) .035 .12 183 (2, 2’, 3, 4, 4’, 5’, 6)

.035 .11 47/48 (2, 2’, 4, 4’ /2, 2’, 4, 5) .030 .11 185 (2, 2’, 3, 4, 5, 5’, 6)

.025 .070 44 (2, 2’, 3, 5’) .025 .090 174 (2, 2’, 3, 3’, 4, 5, 6’)

.035 .11 37/42 (3, 4, 4’ /2, 2’, 3, 4’) .030 .11 177 (2, 2’, 3, 3’, 4’, 5, 6)

.040 .12 41/64/71 (2, 2’, 3, 4/2, 3, 4’, 6/2, 3’, 4’, 6) .035 .11 171/202 (2, 2’, 3, 3’, 4, 4’, 6/2, 2’, 3, 3’, 5, 5’, 6, 6’)

.030 .090 40 (2, 2’, 3, 3’) .045 .14 172/197 (2, 2’, 3, 3’, 4, 5, 5’ /2, 2’, 3, 3’, 4, 4’. 6, 6’)

.030 .090 74 (2, 4, 4’, 5) .030 .11 180 (2, 2’, 3, 4, 4’, 5, 5’)

.040 .12 70/76 (2, 3’, 4’, 5/2’, 3, 4, 5) .020 .070 199 (2, 2’, 3, 3’, 4, 5, 6, 6’)

.050 .16 66/95 (2, 3, 4, 4’/2, 2’, 3, 5’, 6) .080 .27 170/190 (2, 2’, 3, 3’, 4, 4’, 5/2, 3, 3’, 4, 4’, 5, 6)

.030 .090 91 (2, 2', 3’, 4', 6) .040 .14 201 (2, 2', 3, 3', 4, 5, 5', 6)

.050 .16 56/60 (2, 3, 3', 4' /2, 3, 4, 4') .080 .27 196/203 (2, 2', 3, 3', 4, 4', 5, 6' /2, 2', 3, 4, 4', 5, 5', 6)

.050 .16 84/92 (2, 2', 3, 3', 6/2, 2', 3, 5, 5') .080 .27 195/208 (2, 2', 3, 3', 4, 4', 5, 6/2, 2', 3, 3', 4, 5, 5', 6, 6')

.025 .070 101 (2, 2', 4, 5, 5') .030 .11 194 (2, 2', 3, 3', 4, 4', 5, 5')

.025 .070 99 (2, 2', 4, 4', 5) .040 .14 206 (2, 2', 3, 3', 4, 4', 5, 5', 6)

.030 .090 97 (2, 2', 3', 4, 5) .035 .11 128 (2, 2', 3, 3', 4, 4')

.035 .11 87 (2, 2', 3, 4, 5') .080 .27 167 (2, 3', 4, 4', 5, 5')
Appendix 2 33

Appendix 2a. Water column transport data for summed PCB congeners and related physical and water-quality characteristics at Ced

Avenue (USGS station 04086525), 1994–95

[Qc, Cedar Creek instantaneous streamflow at Cedarburg; ft3/s, cubic feet per second; μg/g, micrograms per gram; ng/L, nanograms per liter; mg/L, milligrams per li

%, percent; POINT, collected with point sampler; CHURN, processed from churn splitter; EWI, equal-width-increment sample; DOC, dissolved organic carbon; SOCFOC, fraction organic carbon; --, no data; <, less than; ΣPCB, summed congeners]

Total suspended solids Carbon ΣPCB

Date of 

sampling

Time of 

sampling

Qc

(ft3/s)

POINT(mg/L)

CHURN

(mg/L)

EWI

(mg/L)

Chlorophyll a

(μg/L)

SOC

(mg/L)

DOC

(mg/L)

FOC

(%)

Particulate

(ng/L)

Particulate

(μg/g)

Dissolved

(ng/L)

12/02/94 1430 39 -- 3 6 1.60 0.50 9.0 16.7 1.55 0.52 0.97 

1/12/95 1320 45 -- <5 <5 .87 .40 5.2 16.0 1.65 .66 .68 1/24/95 1240 50 -- <5 <5 -- .50 8.4 20.0 1.94 .78 .84 3/16/95 1730 102 -- 4 4 7.10 .60 9.7 15.0 2.57 .64 4.7 3/22/95 1045 127 -- 4 6 3.35 .70 11 17.5 2.23 .56 .67 4/14/95 0715 163 -- 8 8 10.7 .60 11 7.5 5.62 .70 1.4 4/27/95 1430 267 -- 8 8 13.1 1.2 8.7 15.0 2.00 .25 .97 6/28/95 0700 15 -- 8 8 5.41 1.1 7.9 13.8 31.91 3.99 17.1 8/08/95 1000 11 -- 8 8 13.0 1.0 5.6 12.5 44.91 5.61 10.5 8/08/95 1001 11 -- 10 9 11.8 1.3 5.5 13.0 31.77 3.18 11.5 8/17/95 1315 63 -- 12 16 7.53 1.3 7.1 10.8 6.62 .55 2.9 Median 50 -- 8 8 7.00 .70 8.4 15.0 2.57 .66 1.4 
34 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Appendix 2b. Water column transport data for summed PCB congeners and related physical and water-quality characteristics at Ceda(USGS station 04086528), 1994–95[Qc, Cedar Creek instantaneous streamflow at Cedarburg; ft3/s, cubic feet per second; ng/L, nanograms per liter; mg/L, milligrams per liter; μg/g, micrograms per gr

dissolved organic carbon; SOC, suspended organic carbon; FOC, fraction organic carbon; POINT, collected with point sampler; CHURN, processed from churn splitincrement sample; %, percent; --, no data; <, less than; 

ΣPCB, summed PCB congeners]

Total suspended solids Carbon ΣPCB

Date of 

sampling

Time of 

sampling

Qc

(ft3/s)

POINT(mg/L)

CHURN

(mg/L)

EWI

(mg/L)

Chlorophyll a

(μg/L)

SOC

(mg/L)

DOC

(mg/L)

FOC

(%)

Particulate

(ng/L)

Particulate

(μg/g)

Dissolved

(ng/L)

8/11/94 0745 26 10 22 18 6.17 0.7 9.0 3.2 227.75 10.35 44.96 

8/31/94 0800 19 18 18 11.6 1.2 6.6 6.7 173.83 9.66 43.74 9/21/94 1335 9.2 11 8 -- 9.2 1.0 5.8 12 78.24 9.78 38.27 

10/11/94 1020 19 9 8 10 3.09 .60 4.8 7.5 118.42 14.80 21.21 

1/24/95 1030 50 2 <5 <5 1.43 .60 8.2 24 1.40 2.56 1.03 3/16/95 1510 105 6 6 5 5.27 .80 9.4 13 15.50 2.58 4.60 3/22/95 0700 132 6 5 4 3.94 .60 11 12 18.56 3.71 1.23 4/14/95 0940 158 12 8 8 5.75 .70 11 8.8 29.91 3.74 6.07 4/14/95 0942 158 -- 8 8 4.97 -- -- 8.8 28.16 3.52 5.06 4/27/95 1220 253 14 12 10 11.4 .70 9.0 5.8 20.70 1.73 2.77 6/27/95 1530 14 20 8 10 7.99 1.2 8.6 15 118.48 14.81 48.81 

8/8/95 1230 12 16 15 16 32.8 2.0 5.9 13 148.18 9.88 45.51 

8/17/95 0845 63 14 18 18 9.50 1.8 5.8 10 107.52 5.97 23.35 Median 50 11 8 10 6.17 .70 8.6 10 78.24 5.97 21.21 

Appendix 2c. Water column transport data for summed PCB congeners and related physical and water-quality characteristics at Milw

(USGS station 04086416), 1994–95

[Qp, Milwaukee River instantaneous streamflow at Pioneer Road; ft3/s, cubic feet per second; ng/L, nanograms per liter; mg/L, milligrams per liter; μg/g, microgram

DOC, dissolved organic carbon; SOC, suspended organic carbon; FOC, fraction organic carbon; POINT, collected with point sampler; CHURN, processed from churinterval sample; %, percent; --, no data; 

ΣPCB, summed PCB congeners]

Total suspended solids Carbon ΣPCB

Date of 

sampling

Time of 

sampling

Qp

(ft3/s)

POINT(mg/L)

CHURN

(mg/L)

EWI

(mg/L)

Chlorophyll a

(μg/L)

SOC

(mg/L)

DOC

(mg/L)

FOC

(%)

Particulate

(ng/L)

Particulate

(μg/g)

Dissolved

(ng/L)

4/13/95 1530 772 -- 14 13 16.9 1.0 7.7 7.1 0.04 0.00 0.09 4/27/95 1700 879 -- 20 18 25.3 1.5 9.5 7.5 .26 .01 .15 6/27/95 1140 57 -- 32 26 165 3.7 9.2 11.6 1.94 .06 1.50 

8/8/95 1500 120 -- 52 45 171 7.3 6.6 14.0 1.55 .03 1.25 

8/17/95 0745 560 -- 60 64 85.0 4.0 9.0 6.7 1.66 .03 1.21 Median 560 -- 32 26 85.0 3.7 9.0 7.5 1.55 .03 1.21 
Appendix 2 35

Appendix 2d. Water column transport data for summed PCB congeners and related physical and water-quality characteristics at Milwauke

(USGS station 04086600), 1994–95

[Qp, Milwaukee River instantaneous streamflow at Pioneer Road; ft3/s, cubic feet per second; ng/L, nanograms per liter; mg/L, milligrams per liter; μg/g, micrograms per g

Cedar Creek daily mean streamflow/Milwaukee River daily mean streamflow (at Pioneer Road); n, sample collected at noon; DOC, dissolved organic carbon; SOC, suspendorganic carbon; POINT, collected with point sampler; CHURN, processed from churn splitter; EWI, equal-width-increment sample; %, percent; --, no data; ΣPCB, summed 

Total suspended solids Carbon ΣPCB

Date of 

sampling

Time of 

sampling

Qp

(ft3/s)

POINT(mg/L)

CHURN

(mg/L)

EWI

(mg/L)

Chlorophyll a

(μg/L)

SOC

(mg/L)

DOC

(mg/L)

FOC

(%)

Particulate

(ng/L)

Particulate

(μg/g)

Dis

(n

6/30/93 1315 285 0.19 20n 22 20 21.6 1.1 13 5.0 8.97 0.41 6

7/11/93 1345 1,870 .11 55n 62 -- 10.3 4.6 14 7.4 17.10 .28 6

8/3/93 1000 300 .12 -- 14 14 3.60 .5 12 3.6 3.48 .25 2

8/24/93 1515 250 .13 15n 10 8 8.60 .6 8.9 6.0 3.89 .39 39/14/93 1520 646 .26 51 44 40 17.7 -- -- -- 53.25 1.21 69/28/93 1415 614 .18 16 11 18 3.60 .4 14 3.6 5.13 .47 3

10/20/93 0915 290 .15 14 13 22 45.0 .8 9.2 6.2 2.33 .18 1

11/16/93 0745 322 .19 6 5 7 29.0 .8 7.8 16.0 3.23 .65 2

12/14/93 1445 265 .18 32 4 3 9.85 .3 8.1 7.5 1.43 .36 1

2/16/94 0745 110 .25 4 3 2 3.38 .5 4.6 16.7 1.17 .39 13/10/94 1200 1,300 .27 -- 32 31 7.27 2.6 9.7 8.1 16.70 .52 13/16/94 900 1,100 .26 -- 9 6 2.47 .4 8.4 4.4 2.44 .27 15/17/94 1600 250 .16 17 8 8 19.5 1.1 9.2 13.8 3.47 .43 26/22/94 1400 67 .28 42 28 32 24.4 1.8 7.6 6.4 12.31 .44 3

7/7/94 1430 224 .22 71 59 60 105 3.9 6.8 6.6 32.76 .56 57/8/94 1515 410 .45 77 59 59 83 2.6 8.8 4.4 76.30 1.29 17

8/11/94 1050 169 .18 20 19 29 41.2 1.0 8.6 5.3 7.58 .40 4

8/31/94 0945 150 .13 26 26 24 55.4 1.9 6.3 7.3 7.33 .28 49/21/94 1150 112 .13 14 16 8 25.1 .8 6.0 5.0 2.90 .18 1

10/11/94 1150 99 .10 10 5 5 5.49 .3 6.0 6.0 1.16 .23 1

1/19/95 1445 190 .19 30 10 8 8.89 1.3 10 13.0 1.12 .11 3/17/95 0740 774 .12 8 18 17 15.5 1.2 9.0 6.7 3.86 .21 3/21/95 1430 626 .24 6 6 6 10.1 .6 8.8 10.0 1.82 .30 4/13/95 1200 772 .26 14 12 12 17.9 1.0 9.0 8.3 4.73 .39 14/28/95 1420 945 .31 18 19 20 24.7 1.3 10 6.8 8.62 .72 28/16/95 1615 392 .08 69 79 75 116 7.3 8.2 9.2 20.79 .26 28/29/95 1730 1,320 .17 72 77 71 34.4 5.2 8.4 6.8 -- -- -- Median 300 .18 19 16 18 17.9 1.1 8.8 6.7 4.31 .39 2

Qc Qp ------
36 Distribution and Transport of Polychlorinated Biphenyls and Associated Particulates in the Milwaukee River System, Wisconsin,

1993–95

Appendix 2e. Water column transport data for summed PCB congeners and related physical and water-quality characteristics at Milw(USGS station 04086710), 1994–95[ft3/s, cubic feet per second; ng/L, nanograms per liter; mg/L, milligrams per liter; μg/g, micrograms per gram; g/d, gram per day; Qt, estimated discharge at Thiensv

DOC, dissolved organic carbon; SOC, suspended organic carbon; FOC, fraction organic carbon; POINT, collected with point sampler; CHURN, processed from churincrement sample; %, percent; --, no data; <, less than; 

ΣPCB, summed PCB congeners]

Total suspended solids Carbon ΣPCB

Date of 

sampling

Time of 

sampling

Qt

(ft3/s)

POINT(mg/L)

CHURN

(mg/L)

EWI

(mg/L)

Chlorophyll a

(μg/L)

SOC

(mg/L)

DOC

(mg/L)

FOC

(%)

Particulate

(ng/L)

Particulate

(μg/g)

Dissolved

(ng/L)

6/29/93 1430 342 -- 23 24 43.0 1.8 13 7.8 11.38 0.49 2.57 

7/11/93 1140 1834 -- 63 -- 12.8 4.0 14 6.3 23.88 .38 22.63 

8/3/93 1330 298 17n 23 22 9.6 .8 12 3.5 8.94 .39 2.37 

8/25/93 0745 249 20n 16 20 25.3 .7 8.9 4.4 6.94 .43 3.38 9/14/93 1300 432 -- 22 24 21.1 -- -- -- 11.13 .51 1.91 9/28/93 1215 652 19 18 16 4.00 .4 13 2.2 8.78 .49 3.73 

10/20/93 1140 301 22/13 12 14 14.7 .5 8.8 4.2 5.07 .42 3.80 

11/15/93 1000 331 6 11 9 29.2 .8 7.2 7.3 3.93 .36 2.13 

12/14/93 1250 291 86 3 3 6.65 .2 7.5 6.7 . 1.01 .34 2.66 

2/15/94 1500 760 -- <2 2 2.23 .4 4.4 20.0 1.07 .53 2.58 3/10/94 1500 2605 -- 20 19 5.34 -- -- -- 7.25 .36 1.12 3/16/94 1200 1926 -- 10 9 2.96 .5 7.6 5.0 1.94 .19 1.47 5/17/94 1400 257 25 24 24 59.2 2.2 9.6 9.2 10.57 .44 2.57 6/22/94 1145 74 -- 42 45 108 3.8 8.3 9.0 18.03 .43 2.84 

7/7/94 1245 232 76 59 62 205 4.9 7.2 8.3 16.38 .28 2.88 7/8/94 1315 452 68 60 61 75.1 2.3 8.0 3.8 12.42 .21 3.61 

Median 336 20 21 19 17.9 .8 8.6 6.5 8.86 .41 2.62 
Appendix 2 37

Appendix 2f. Water column transport data for summed PCB congeners and related physical and water-quality characteristics at Milwaukee (USGS station 04087000), 1994–95

[ft3/s, cubic feet per second; ng/L, nanograms per liter; mg/L, milligrams per liter; μg/g, micrograms per gram; g/d, grams per day; QE, Milwaukee daily mean streamflow a

instantaneous streamflow; TOC, total organic carbon; DOC, dissolved organic carbon; SOC, suspended organic carbon; FOC, fraction organic carbon; POINT, collected wiprocessed from churn splitter; EWI, equal-width-increment sample; %, percent; --, no data; ΣPCB, summed PCB congeners]

Total suspended solids Carbon ΣPCB

Date of 

sampling

Time of 

sampling

QE

(ft3/s)

(QL)

(ft3/s)

POINT(mg/L)

CHURN

(mg/L)

EWI

(mg/L)

Chlorophyll a

(μg/L)

SOC

(mg/L)

DOC

(mg/L)

FOC

(%)

Particulate

(ng/L)

Particulate

(μg/g)

Dis

(n

6/29/93 0930 400 3.8 79/41

1Rapidly changing discharge, sample collected before and after PCB sample.

26 24 64.0 2.1 13 8.1 20.77 0.80 1

7/11/93 0930 1750 6.3 72n 70 -- 27.0 3.4 13 4.9 37.67 .54 1

8/4/93 0900 305 4.1 35 21 21 20.9 1.2 12 5.7 16.38 .78 1

8/25/93 1100 248 3.5 19 17 18 53.2 1.1 8.3 6.5 16.74 .98 19/14/93 0945 511 95 76/371 33 32 25.5 -- -- -- 101.32 3.07 19/28/93 0915 715 6.5 17 21 20 4.60 .5 12 2.4 12.21 .58 

10/20/93 1400 316 3.4 46 59 61 36.2 1.5 8.9 2.5 22.65 .38 

11/15/93 1400 360 5.0 -- 17 20 19.7 1.0 7.2 5.9 12.91 .76 

12/14/93 1010 321 3.1 7 8 6 6.39 .2 7.6 2.5 . 3.14 .39 

2/15/94 1045 180 4.8 8 3 4 2.12 .3 4.6 10.0 1.34 .45 

3/11/94 1000 1,400 5.2 -- 43 45 6.36 -- -- -- 49.10 1.14 

3/16/94 1415 1,300 7.2 61 44 49 7.17 .8 7.9 1.8 30.10 .68 5/17/94 0900 268 3.6 28n 30 30 83.6 1.2 9.3 4.0 29.88 1.00 15/17/94 1045 268 3.6 28n 28 29 86.8 2.2 9.4 7.9 23.37 .83 16/22/94 0915 78 3.2 33 32 35 97.8 2.1 8.7 6.6 22.85 .71 1

7/7/94 0945 268 4.8 64 49 48 275 1.3 7.2 2.7 24.36 .50 7/8/94 1045 1,090 14 86 88 83 213 5.3 6.8 6.0 28.77 .33 

8/11/94 1330 219 6.8 33 40 39 115 1.0 9.0 2.5 17.93 .45 

8/31/94 1215 173 4.8 360 28 30 82.4 2.2 6.6 7.9 18.99 .68 19/21/94 0915 85 2.4 18 17 18 44.2 1.4 6.2 8.2 19.25 1.13 1

10/11/94 1445 124 3.4 13 14 13 25.8 1.0 6.1 7.1 9.64 .69 

10/12/94 1000 530 2.8 450 436 576 90.8 7.8 6.6 1.8 160.43 .37 10/12/94 1315 191 3.2 68 99 100 43.3 2.3 6.4 2.3 46.94 .47 

1/19/95 0930 220 4.0 55 13 12 6.03 1.1 7.2 8.5 4.88 .38 3/17/95 1045 858 3.4 29 28 22 14.6 2.0 8.8 7.1 10.25 .37 3/17/95 1050 858 3.4 44 28 24 13.9 1.6 9.1 5.7 13.75 .49 3/21/95 0845 647 6.1 14 21 18 10.8 .8 9.4 3.8 8.01 .38 4/13/95 0830 849 11 25 38 47 10.8 1.3 8.3 3.4 11.88 .31 4/28/95 0930 1,260 11 37 48 44 25.7 2.1 8.8 4.4 17.77 .37 8/16/95 1330 557 30 106 42 50 120 4.0 5.6 9.5 31.46 .75 8/29/95 1230 1,180 3.0 99 67 65 40.0 3.8 10 5.7 22.66 .34 Median 360 4.1 35 30 30 27.0 1.4 8.3 5.7 19.25 .54