Sheboygan River Food Chain
and
Sediment Contaminant Assessment
Final Project Report
U.S. Environmental Protection Agency
Grant #GL-995681
Submitted To:
Dr. Marc Tuchman
U.S. Environmental Protection Agency
Great Lakes National Program Office
Chicago, Illinois
Submitted by:
Marsha Burzynski
Wisconsin Deparement of Natural Resources
Southeast Region - Milwaukee, WI
April 2000
-------
TABLE OF CONTENTS
INTRODUCTION 1
CONTAMINANTS OF CONCERN 2
FOOD CHAIN STUDY OBJECTIVES 4
HISTORICAL SOURCES OF CONTAMINATION 5
Kohler Landfill Superfund Site 5
Sheboygan River and Harbor Superfund Site 6
Coal Gasification Facility 7
METHODS AND MATERIALS 8
STUDY AREA 8
SAMPLING PROCEDURES 11
Schedule 11
Tissue Collections 11
Larval Invertebrates 11
Emergent Invertebrates 12
Crayfish 12
Fish 13
Sediment 14
Semi-permeable Polymeric Membrane Devices (SPMD) 14
Analytical Procedures 15
RESULTS AND DISCUSSION 18
POLYCHLORINATED BIPHENYLS (PCBS) 18
Total PCB Concentrations 18
Sediments 19
Invertebrates 21
Fish Species 24
Total PCB Accumulation in Food Chain Study Components 27
PCB Homolog Distribution 31
Semi-permeable Polymeric Membrane Devices (SPMDs) 35
Biota-sediment Accumulation Factors (BSAFs) for PCB Homolog Groups 38
POLYCYCLIC AROMATIC HYDROCARBONS (PAH S) 42
HEAVY METALS 48
CONCLUSIONS AND QUESTIONS 50
REFERENCES 52
-------
LIST OF TABLES
Table 1. Food Chain Study Segment Descriptions 8
Table 2. Sampling Dates for Food Chain Study Components 11
Table 3. Food Chain Study Analytical Summary Table for all Samples 17
Table 4. Non-coplanar (routine) PCB Congeners Analyzed for all Sheboygan River Samples 19
Table 5. Total Sediment PCB and Total Organic Carbon Concentrations at all Sites 21
Table 6. Larval Invertebrates Identified for teh Sheboygan River Food Chain Study 22
Table 7. Emergent Invertebrate Orders and Families Identified 22
Table 8. Total PCB Concentrations and Percent Lipid Measured at all Sites for Invertebrates 24
Table 9. Fish Species Collected, Number of Fish and Average Length for Each Composite
Collected by Stream Segment 25
Table 10. Total PCB Concentrations and Percent Lipid Content in Sheboygan River Fish 26
Table 11. Average PCB H omolog Concentrations by Site and Food Chain Component 33
Table 12. Average Water Temperatures During Both SPMD Deployments 36
Table 13. BSAFs by Homolog Group for Food Chain Study Biota 40
Table 14. PAH Compound Concentrations for Sediment 46
Table 15. Comparison of Sheboygan River Camp Marina Area Total PAH Concentrations with Other
Urban Streams 47
Table 16. Average Total PAH Concentrations in Benthic Macroinvertebrates 47
Table 17. Average SPMD Total PAH Concentrations for Both Deployment Periods 47
Table 18. Average Sediment Heavy Metal Concentrations 48
Table 19. Average Macroinvertebrate Heavy Metals Concentrations 49
LIST OF FIGURES
Figure 1. Sheboygan River Basin 9
Figure 2. Food Chain Study Area 10
Figure 3. Total PCB Concentrations in Sediment 21
Figure 4. Average Total Invertebrate PCB Concentrations 24
Figure 5. Average Total PCB Concentrations for Fish Species 27
Figure 6. Total PCB Accumulation in Different Food Chain Study Components at Each Site 28
Figure 7. Toxic PCB Congener Accumulation in all Food Chain Study Components at Each Site 30
Figure 8. PCB Homolog Concentrations for Each Food Chain Component at Each Site 32
Figure 9. Percent PCB Homolog Composition for all Food Chain Components 34
Figure 10. PCB Homolog Concentrations in SPMDs 36
Figure 11. Sheboygan River Discharge for Both SPMD Deployment Periods 38
Figure 12. BSAFs by Homolog Group for Food Chain Study Biota 41
-------
INTRODUCTION
The purpose of this report is to document the results of the Sheboygan River Food Chain and Sediment
Contaminant Assessment. This project was completed by the Wisconsin Department of Natural
Resources (WDNR) with funding assistance from the U.S. EPA Great Lakes National Program Office
(Grant #GL-995681).
The International Joint Commission, in response to the 1987 Amendments to the Great Lakes Water
Quality Agreement identified the lower 14-mile section of the Sheboygan River as a Great Lakes Area of
Concern (AOC). This means that the Sheboygan River AOC is considered one of the 43 most
contaminated areas in the Great Lakes drainage basin. In response to this designation, the WDNR in
conjunction with area citizens developed Remedial Action Plans (RAPs). The first Sheboygan River
RAP document (WDNR, 1989) outlined the sources of contaminants to the AOC. The second RAP
document (WDNR, 1995a) refined the source information and recommended actions to clean up the
contaminated areas and evaluate the results. Through the RAP process, guidelines required the advisory
committees to evaluate potential impairments to the 14 beneficial uses of waterways identified by the
International Joint Commission (IJC). For the Sheboygan AOC, nine of the 14 beneficial uses were
considered impaired. Contaminated sediments directly or indirectly contribute to seven of the impaired
uses. This study combines many recommendations contained in the RAP documents to determine the
contribution, composition and distribution of contaminants within the AOC.
Contaminated sediment is a major contributor of pollutants to the Sheboygan River AOC and Lake
Michigan. Several programs including U.S. EPA's Superfund and WDNR's Environmental Repair
Program (ERP) have initiated actions within the AOC that are beginning to address contaminated
sediment. These individual programs have narrowly defined, program specific objectives. On the other
hand, RAP committees determined that an ecosystem approach was necessary to achieve long-term goals.
The focus should encompass the processes and progress achieved through the Superfund and ERP
-------
programs, yet go beyond their limitations to benefit the entire lower section of the river from the
Sheboygan Falls dam to the harbor.
In order to design an effective and comprehensive restoration strategy for the Sheboygan River,
ecosystem impacts from contaminants must be understood. Corrective actions to eliminate ecosystem
impacts associated with contaminated sediment will also achieve significant progress towards delisting
impaired uses in the AOC. Many recommendations put forth by the RAP committees reflect the need to
determine baseline conditions in the AOC by identifying the contribution, composition and distribution of
contaminants associated with river sediments. This project implemented several recommendations
identified by the RAP committees through an integrated, coordinated and collaborative effort to establish
needed baseline conditions for the food chain from which to evaluate the performance of future clean up
actions.
CONTAMINANTS OF CONCERN
The primary contaminants of concern in the Sheboygan River AOC are poly chlorinated biphenyls
(PCBs), polynuclear aromatic hydrocarbons (PAHs) and heavy metals. Because of their stability and
persistence in the environment, PCBs are still with us today. Their hydrophobic and lipophilic properties
allow for rapid accumulation in organisms through the food chain. Fish and waterfowl consumption
advisories are in effect for the Sheboygan River. A do not eat advisory for all resident fish species
(including carp, walleye, smallmouth bass, catfish, northern pike, rock bass, bluegill and crappie) is in
effect for the Sheboygan River Area of Concern (WDOH & WDNR, 1998). In 1987, the WDNR
suspended stocking of trout and salmon after it was discovered that the stocked fish were accumulating
high levels of PCBs before leaving the river. WDNR staff completed an experimental stocking study of
trout and salmon (Eggold et al., 1994) which concluded that trout and salmon stocked in the spring
migrate to Lake Michigan soon after stocking. Since these fish spend little time in the river, PCB
accumulation concentrations of returning fish were not different from those in reference streams.
Conversely, the fish stocked in the fall over winter in the river and accumulate high amounts of PCBs in
-2-
-------
their tissues. The returning fish had tissue PCB concentrations higher than fish stocked in reference
streams. In response to the study, the WDNR resumed stocking trout and salmon in the Sheboygan River
only in the spring.
Populations of mink within the Sheboygan River AOC are well below what normally would be expected
given the available habitat. Small mammal trapping by the WDNR in 1993 recovered no mink within the
AOC. Occasional mink are seen in this area. However, they are suspected as transients that are not
breeding in the area (Katsma, 1994). Mink depend on a diet offish and invertebrates, and may be
accumulating contaminants from these food sources through the food chain (Patnode, 1995).
Reproductive problems in mink are suspected because of their low population levels and the high quality
of available habitat. Studies have shown that reproduction has been severely reduced when mink are
exposed to PCBs (Aulerich et al., 1971; 1973; Aulerich & Ringer, 1977).
A consumption advisory for waterfowl with PCB tissue contamination is in effect for portions of the
Sheboygan River and Harbor. The advisory states that no one should eat mallard ducks using the
Sheboygan River from the Sheboygan Falls dam downstream to the river's mouth at Lake Michigan. In
addition no one should eat lesser scaup (bluebills) using the Sheboygan Harbor (WDNR, 1996).
PAHs are also accumulated by organisms somewhat, but tend to be more volatile and are readily
metabolized by higher vertebrates. Schrank, et al. (1997) found that white suckers residing in the lower
Sheboygan River accumulated significant amounts of PAHs and PCBs. These fish also exhibited some
blood and tissue alterations suggesting impaired fish condition.
Heavy metals are also a concern from an accumulation and toxicity standpoint, but their presence in
AOC sediments and biota is less understood than the organic contaminants.
-3-
-------
FOOD CHAIN STUDY OBJECTIVES
The overall goal of this study is to establish baseline contaminant concentrations associated with
sediments, water column and the biota within the Sheboygan River AOC, and to identify potential
bioaccumulation factors between sediment, water column and biota. This project was designed to:
1. Provide baseline information for the Sheboygan River RAP's long-term trend monitoring strategy to
evaluate the performance of future remedial actions and to delist impaired uses.
2. Determine the bioavaJability of toxic substances and bioaccumulation of PCBs through the food
chain in the AOC.
3. Evaluate spatial distribution of PCB congeners in AOC sediment and availability to aquatic
organisms.
4. Provide needed information on PAH distribution and bioavailability in the Sheboygan River.
5. Provide information about the distribution and uptake of heavy metals in the Sheboygan River.
Each of these objectives includes evaluations of the:
1. Focus on the presence or absence of compounds between food chain elements (bioaccumulation
objectives) or river segments (source or distribution objectives).
2. Differences (concentrations or mass) between food chain elements or river segments.
Review of the historical data relating to aquatic community composition provided the basis to identify a
simplistic food chain for the Sheboygan River comprising resident species for use in this study. Each of
the biotic components was carefully chosen to reflect food chain links to the contaminants available from
the sediments and water column. Larval benthic macroinvertebrates were chosen to establish a primary
link between sediments and water column contaminants to insectivorous fish. Adult macroinvertebrates
were chosen to evaluate a potential link to the terrestrial community. Crayfish were chosen as an
intermediate link to predator fish. Longnose dace are insectivorous and a potential food source to
smallmouth bass. White suckers are omnivorous and were chosen (year 1+ and adults) as an intermediate
-4-
-------
food chain link. The young white suckers are also potential prey for smallmouth bass. Smallmouth bass
are the highest link in the food chain chosen for this study. Year 1+ smallmouth bass feed on insects and
small crayfish, while the adults are primarily piscivorous (Becker, 1983).
HISTORICAL SOURCES OF CONTAMINATION
The Sheboygan River RAP committees identified contaminated sediment as a significant source of
PCBs, PAHs and heavy metals to the AOC and Lake Michigan. The study area contains two Federal
Superfund Sites (Sheboygan River and Harbor and Kohler Landfill), that have contributed pollutants of
concern to the Sheboygan River. A former coal gasification facility site in the City of Sheboygan is under
investigation through WDNR's Environmental Repair Program. The following sections describe the
known suspected sources of pollutants of concern to the Sheboygan River Food Chain and Sediment
Contaminant Assessment study area.
Kohler Landfill Superfund Site
The Kohler Company Landfill was declared a Superfund site in 1984 after contaminated surface water
runoff was detected. Kohler Company has operated this landfill since 1950 for foundry sand, core and
pottery waste disposal. Certain cells were used for disposal of chrome plating sludges, enamel powder,
hydraulic oils, solvents and paint wastes. The Remedial Investigation (RI) for this site was completed in
1990 (Blasland & Bouck, 1991). Wastes found in the landfill include volatile organic compounds
(VOCs) including vinyl chloride, trichlorethane (TCE) and 1,2-dichlorethane (DCE), PAHs, phenolic
compounds, and heavy metals including chromium, cadmium, lead, copper, antimony and zinc.
Groundwater in the shallow aquifer beneath the site is also contaminated with these compounds and flows
into the Sheboygan River rather than underneath it (Geraghty and Miller, 1992).
A Record of Decision (ROD) was issued in 1996 for landfill closure and the groundwater element.
Construction of the remedy began in 1997 and was completed during the summer of 1998. The slope
adjacent to the Sheboygan River and side slopes were capped and planted with vegetation (accounting for
-5-
-------
about one-half of the landfill). The north side of the landfill is currently operating and accepting foundry
sands and pottery clays.
A perimeter drain along the south and east portion of the landfill (>2000 linear feet) was constructed to
collect leachate from the shallow aquifer. The leachate is being collected in the drain and pumped to the
City of Sheboygan Wastewater Treatment Facility for treatment. Long-term care of the collection system,
groundwater and leachate monitoring will be provided by Kohler Company (Fauble, 1998).
Sheboygan River and Harbor Superfund Site
The Sheboygan River and Harbor was designated a Federal Superfund site in 1985 because of suspected
PCB contamination in the river and floodplain. Results of the Remedial Investigation (RI) conducted for
this site showed presence of PCBs, metals and several VOCs in the sediment and water column, and
PCBs and heavy metals in floodplain soils (Blasland & Bouck, 1990). Sediment PCB concentrations in
the river sediments between the Sheboygan Falls dam and the Waelderhaus dam ranged from no detect
(ND) to 4500 ppm. Downstream of the Waelderhaus Dam PCB concentrations ranged from 1.9-220 ppm.
Concentrations of metals in sediments were variable, but generally increased from upstream to
downstream. Samples collected from floodplain soils generally followed the same patterns as the river
sediments.
The sediments in the river section from the Sheboygan Falls Dam to the Waelderhaus dam were
considered highly contaminated with PCBs and a threat to human health. Tecumseh Products Company (a
responsible party for this Superfund Site) and the U.S. EPA cooperated to remove about 5000 cubic yards
of contaminated sediment from the Sheboygan River. About 2500 cubic yards of sediments were placed
in a confined treatment facility as part of U.S. EPA's Assessment and Remediation of Contaminated
Sediment (ARCS) program. The remaining 2500 cubic yards were placed in a confined disposal facility
located on Tecumseh property until final site remediation decisions are made through the Superfund
process. Some additional sediment areas were "armored" in place using an experimental design
-6-
-------
developed by Blasland & Bouck Engineers. River monitoring to gauge the performance of removal
actions included water column, sediment and caged fish sampling. Fourteen of the 18 areas excavated
had post-removal sediment PCB concentrations below 40 ppm with an average of 13 ppm (Blasland &
Bouck, 1992).
Coal Gasification Facility
The Wisconsin Public Service Corporation (WPSC) is the responsible party identified for a
manufactured gas plant site under investigation by WDNR's Environmental Repair program. The former
facility was located in the City of Sheboygan and operated between 1880 and 1930. During construction
of a floating pier along the east bank of the Sheboygan River in 1990, builders found coal tar in the soil.
Sources of pollution from this site include runoff from the gas plant (tars), contaminated groundwater and
tar tanks which were previously underground but are now under water due to shoreline recession. WPSC
conducted an environmental investigation of the site and concluded that both soil and groundwater
contamination existed (Simon Hydro-Search, 1992). Groundwater at the site showed levels of arsenic,
total cyanide and benzene above the state of Wisconsin enforcement standard. The coal gasification plant
is the suspected source of PAHs found in downstream sediments near the Pennsylvania Avenue Bridge
(Blasland & Bouck, 1990) and the Eighth Street Bridge (RMT, 1993).
-7-
-------
METHODS AND MATERIALS
STUDY AREA
The Sheboygan River AOC is located in east central Wisconsin, about 55 miles north of the City of
Milwaukee. The Sheboygan River headwaters are located in Fond du Lac County and the river flows
east, southeast approximately 80 river miles before reaching the western shore of Lake Michigan in the
City of Sheboygan (Figure 1). The river has an annual mean discharge of 250 cubic feet per second (cfs)
and drains a 432 square mile area. The Sheboygan River has a diverse resident fishery and is classified as
supporting a warmwater sport fish community with seasonal runs of Lake Michigan trout and salmon in
the lower 10 miles of river. The study area consists of the reference site located above the Sheboygan
Falls dam (segment 1), and five consecutive segments over 14 miles of river extending from below the
Sheboygan Falls dam to the Sheboygan Harbor (Figure 2). The selected study segments and rationale are
described in Table 1.
Table 1. Food Chain Study Segment Descriptions
Segment
Description
1
Reference site. No known sources of PCB, PAH or metals contamination. Most samples taken from the area near
Meadowlark Road, 4.5 river miles upstream of Sheboygan Falls Dam. Mainly rural land uses adjacent to the
stream. A good mix of pools, riffles and runs.
Rochester Park area. River mile 13.9 to 11.2. Area from Sheboygan Falls Dam in Sheboygan Falls downstream to
Riverbend Dam in the Village of Kohler. Primary contaminants of concern are PCBs. This segment includes the
upstream most source of PCBs in the Sheboygan River AOC, and the highest sediment PCB concentrations
(WDNR, 1995; Blasland & Bouck, 1992). Adjacent land uses are park land and private ownership (natural riparian
area). Dynamic river section. Contains a large riffle area, many deposition zones and pools.
Between Dams area. River mile 11.2 to 9.9. Between Riverbend and Waelderhaus Dams. Significant depositional
zone downstream from Segment 2. Primarily PCB contamination. Contains a small riffle area.
River mile 9.9 to 5.0. From Waelderhaus Dam downstream to discharge from Kohler Company settling ponds.
This section of the river runs through the Kohler Company River wildlife area and is not readily accessible from the
road. This segment is similar to segment 5 and was not sampled.
Esslingen Park area. River mile 5.0 to 1.6. From Kohler Company settling pond discharge to Camp marina in the
city of Sheboygan. This river section includes sediment contaminated with heavy metals, PAHs and PCBs. Has
fast moving water with large rocks and deposition areas typical of streams this size.
Camp Marina area. River mile 1.6 to river mouth at Sheboygan Harbor. Surface PCB concentrations lower than
upstream segments. Heavy metals present with high PAH concentrations suspected from historic coal gasification
facility. Significant deposition zones with slow moving water. Historic navigation channel.
-8-
-------
Figure 1. Sheboygan River Basin
-v '*t
14SOHD
-------
Figure 2. Food Chain Study Area
o-
-------
SAMPLING PROCEDURES
Schedule
Table 2 shows the sample collection schedule for the Food Chain Study. Larval and emergent aquatic
macroinvertebrates were collected throughout July and August 1994. Semi-permeable polymeric
membrane devices (SPMDs) to measure uptake of PCBs and PAHs from the water column were deployed
twice in the study segments. Fish were collected in the fall of 1994. Most sediment samples were
collected through the ice during February 1995, with the exception of the reference site cores, which were
collected in April 1995.
Table 2. Sampling Dates for Food Chain Study Components
Sample Type
Larval inverts
Larval inverts
Larval inverts
Larval inverts
Emergent inverts
Emergent inverts
Emergent inverts
Emergent inverts
Crayfish
Fish collections
SPMDs
Sediment
Segment 1
01 August 1994
08 August 1994
15 August 1994
22 August 1994
18 July 1994
01 August 1994
15 August 1994
Segment 2
02 August 1994
09 August 1994
16 August 1994
23 August 1994
02 August 1994
09 August 1994
16 August 1994
Segments
04 August 1994
11 August 1994
18 August 1994
25 August 1994
04 August 1994
11 August 1994
18 August 1994
Segments
03 August 1994
12 August 1994
17 August 1994
24 August 1994
20 July 1994
12 August 1994
17 August 1994
22 August 1994 23 August 1994 25 August 1994 24 August 1994
20 Sept. 1994 22 Sept. 1994 22 Sept. 1994 20 Sept. 1994
1 3 Oct. 1 994 24 Oct. and 25 Oct. and 1 9 Oct. 1 994
01 Nov. 1994 02 Nov. 1994
First deployment: 29 July 1994 to 12 August 1994 (14 days)
Second deployment: 24 August 1 994 to 21 September 1 994 (28 days)
04 April 1995 24 Feb. 1995 23 Feb. 1995 22 Feb. 1995
Segments
No tissue
samples were
collected in this
segment.
21 Feb. 1995
Tissue Collections
Larval Invertebrates
Larval benthic macroinvertebrates were collected from cobble sized rocks in riffle areas at segments 1,
2, 3 and 5 on four different dates (Table 2). Using latex gloves and pre-cleaned forceps, rocks were
picked up, and large bodied larvae (mayfly and caddisfly) were hand picked from the rocks and deposited
into pre-cleaned glass jars rinsed with site water (Figure A.1, Appendk A). The jars were kept in coolers
with ice for transport to the WDNR Southeast Region Biology Laboratory. After arriving at the SER
- 1 1 -
-------
laboratory, larvae were separated from small rocks, algae and other extraneous material that may have
been introduced in the field. A small sub-sample of larvae were preserved in alcohol and identified to
family or genus level. A minimum of 20 g of larval invertebrates was collected and stored frozen for each
sample.
Emergent Invertebrates
Emergent aquatic macroinvertebrates were collected using terrestrial light traps manufactured by Bio
Quip, Inc. (Gardena, CA) at segments 1, 2, 3, and 5. The traps consist of a 3-gallon plastic bucket fitted
with a funnel and fluorescent light source. The bucket was lined with aluminum foil to prevent cross
contamination of the samples between sites and sampling dates. The foil also made extraction of the
invertebrates from the bucket easier. The adult insects are attracted to the fluorescent light suspended
above the bucket and fall through the funnel into the bucket. The traps were placed in areas
representative of riffle and depositional zones for each segment on four different dates (Table 2, page 11).
To ensure adequate sample, four traps were used at each site. Two of the traps were placed on rocks on
the streambanks and two were suspended from overhanging tree branches (Figure A. 2). The traps were
placed at dusk and were left on for about two hours after dark. Traps were retrieved and placed into a
large cooler containing ice for 1 to 2 hr to immobilize the insects. The traps were then opened and the
aluminum foil containing the insects was removed, sealed and labeled. Emergent invertebrates were
collected from the traps and stored frozen until they were sorted to exclude terrestrial invertebrates. Sub-
samples of the invertebrates were taken from each sample site and identified to determine orders and
families.
Crayfish
Crayfish were collected during September 1994 from riffles in segments 1, 2, 3, and 5 by disturbing
cobble substrates (by kicking) upstream of a standard d-frame net. (Table 2, page 11; Figure A. 3).
Individuals between 38 and 44 mm long were placed in a pre-cleaned glass mason jar rinsed with site
water at the collection site. After returning to the SER laboratory, the crayfish collected from each site
- 12-
-------
were divided into three replicate samples, wrapped in aluminum foil and stored frozen until they were
transported to the laboratories for analysis.
Fish
Longnose dace (insectivore), white suckers (omnivore) and smallmouth bass (predator) were collected
from segments 1, 2, 3 and 5 by electroshocking with a direct current stream shocker in September and
October 1994 (Figure A.4). PCB congeners were the only contaminants of concern analyzed in fish for
this study. Fish tend to readily metabolize PAHs and do not appreciably accumulate heavy metals.
Longnose dace (Rhinichthys cataractae) were selected as representative of forage and insectivorous fish
species for this study. The longnose dace is generally found in riffle areas in small and mid-sized fast
moving streams throughout Wisconsin. These fish are primarily insectivorous, with Diptera (81%),
Ephemeroptera (10%) and Trichoptera (9%) comprising their diet (Becker, 1983). Three composites of
25 similar size fish were collected, packaged in foil and frozen until they were analyzed for PCB
congeners.
White suckers (Catostomus commersonii) were collected in two sizes to represent two distinct life
stages, young (age 1+) and adult. White suckers were chosen because they are omnivorous, taking
whatever food may be available including insects, crustaceans, plants, fish and fish eggs. Suckers are
found in streams throughout Wisconsin and are important forage for sport fish (Becker 1983). For adults,
three composites of 3 to 6 similar size fish each were collected. Three composites of 6 to 8 similar sized
young fish were also collected.
Smallmouth bass (Micropterus dolomieui) were collected in young and adult sizes. Smallmouth bass
are carnivorous and begin to feed on Daphnia and small midge larvae 6 to 15 days from hatching. Once
they reach 38 mm in length smallmouth bass feed mainly on small fishes and insects, and begin to feed on
small crayfish at about 75 mm long. Fish, crayfish and adult macroinvertebrates make up the bulk of the
- 13-
-------
adult smallmouth bass diet (Becker, 1983). Three composites of 6 to 8 similar sized young fish were
collected, and three composites of 3 to 4 similar sized adult fish were collected.
Sediment
Sediment samples were collected from segments 1, 2, 3, 5, and 6. Five core samples were collected
from segments 1, 2, 3 and 6 and four samples were collected from segment 5 because of a lack of
appropriate depositional sites. A 7.6-cm diameter push-coring device was used to collect the sediment
samples (Figure A. 5). The top 15 cm from each core, representing the zone where most biological
activity takes place, were homogenized in the field and transferred to clean sample containers. The
samples were stored at the WDNR Southeast Region laboratory at 4°C prior to delivery to the State
Laboratory of Hygiene for analysis.
Semi-permeable Polymeric Membrane Devices (SPMD)
Semi-permeable polymeric membrane devices (SPMDs) were used in this study to determine water
column bioavailability of PAHs and PCBs in segments 1, 2, 5 and 6. The SPMDs were purchased from
CIA Laboratories (St. Joseph, MO), the laboratory holding the exclusive license. Each SPMD contained
1 ml (0.91 g) triolein, a neutral lipid similar to fish lipid, spread into a thin film inside a heat sealed 34
inch long by 1 inch wide low density polyethylene (LPDE) layflat tube twisted into a 17 inch long mobius
strip. Prior to sealing, the lipid was spiked with an internal standard (d10 phenanthrene) for permeability
evaluation. Detailed information regarding SPMD preparation methods and quality assurance are located
in Appendix A of the Sheboygan River Food Chain Study Work Plan (WDNR, 1995b).
Three sets of four SPMDs were placed in segments 1, 2, 5 and 6 during two different sampling periods.
The SPMDs were inserted into 3.5 inch by 24 inch tubing constructed from electrical conduit to protect
them from being torn by debris washing downstream (Figure A. 6). The time of SPMD exposure to the air
was noted for each replicate at each site. In all cases the SPMD deployment devices were secured with
cable ties attached to concrete half-blocks, and placed perpendicular to the shoreline. The tubes were
- 14-
-------
oriented on the blocks parallel to stream flow. The SPMDs were left in place for 14 days for the first
deployment, and 28 days for the second deployment.
After the first deployment the deployment devices were modified slightly. Several of the SPMDs at the
reference site were punctured during the first deployment and appeared chewed, presumably by a turtle.
We were able to retrieve adequate sample for analysis however. This is the only site that received any
damage to the SPMDs. For the second deployment we fashioned end caps from galvanized hardware
cloth for each deployment device to deter animals from coming in contact with the SPMDs (Figure A. 7).
After the second deployment no SPMDs were damaged.
Trip blanks consisting of two SPMDs were exposed to the air to correspond to the longest air exposure
time of the SPMDs that were deployed. Four SPMDs were also deployed by hanging in trees at two
separate locations (segment 1 and segment 5) for the entire period of aquatic deployment to measure
atmospheric contribution of contaminants to the surface waters.
After the SPMDs were collected, they were stored frozen at SER in airtight containers until they were
shipped to the ETF Laboratory for extraction. Following extraction the material recovered from the
SPMDs was split. Half of the material was analyzed at the ETF Laboratory in Stevens Point for PAHs,
while the other half was shipped to the SLOH for PCB congener analysis.
Analytical Procedures
All samples collected for this study were analyzed by the SLOH, the Environmental Task Force Trace
Organics Laboratory (ETF) or the UW-Extension Soil and Plant Analysis Laboratory. The SLOH
analyzed all tissue samples and SPMDs for PCB congeners, heavy metals and percent lipid, and sediment
samples for PCB congeners, PAHs, heavy metals and total organic carbon (TOC). The ETF Laboratory
analyzed all macroinvertebrate samples for PAHs, and SPMD samples for PAHs. The UW-Extension
Soil and Plant Analysis Laboratory analyzed sediment samples for particle size. Specific analytical
- 15-
-------
procedures employed for this project are described in detail in the Work Plan Appendices and the QAPP
(WDNR, 1995c). Table 3 shows the analyses conducted for each sample type by segment.
- 16-
-------
Table 3. Food Chain Study Analytical Summary Table for all Samples.
Sample Type
Larval invertebrates
Adult invertebrates
Crayfish
Longnose dace
White suckers (young and adult)
Smallmouth bass (young and adult)
Sediment
SPMDs
Reference
(# samples)
Routine PCBs (4)
Coplanar PCBs (3)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (4)
Coplanar PCBs (4)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (3)
Coplanar PCBs (2)
PAHs (3)
Heavy metals (3)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (5)
Coplanar PCBs (5)
PAHs (3)
Heavy metals (5)
TOC (5)
Particle size (5)
Routine PCBs (3)
Coplanar PCBs (2)
Percent lipid (3)
Rochester
(#samples)
Routine PCBs (4)
Coplanar PCBs (3)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (4)
Coplanar PCBs (4)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (3)
Coplanar PCBs (2)
PAHs (3)
Heavy metals (3)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (5)
Coplanar PCBs (5)
PAHs (3)
Heavy metals (5)
TOC (5)
Particle size (5)
Routine PCBs (3)
Coplanar PCBs (2)
Percent lipid (3)
Between Dams
(# samples)
Routine PCBs (4)
Coplanar PCBs (3)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (4)
Coplanar PCBs (4)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (3)
Coplanar PCBs (2)
PAHs (3)
Heavy metals (3)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs(1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (5)
Coplanar PCBs (5)
PAHs (4)
Heavy metals (5)
TOC (5)
Particle size (4)
No SPMDs
deployed at this
site
Esslingen
(# samples)
Routine PCBs (4)
Coplanar PCBs (3)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (4)
Coplanar PCBs (4)
PAHs (4)
Heavy metals (4)
Percent lipid (4)
Routine PCBs (3)
Coplanar PCBs (2)
PAHs (3)
Heavy metals (3)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (3)
Coplanar PCBs (1)
Percent lipid (3)
Routine PCBs (4)
Coplanar PCBs (4)
PAHs (4)
Heavy metals (4)
TOC (4)
Particle size (4)
Routine PCBs (3)
Coplanar PCBs (2)
Percent lipid (3)
Camp Marina
(# samples)
Routine PCBs (5)
Coplanar PCBs (5)
PAHs (4)
Heavy metals (5)
TOC (5)
Particle size (5)
Routine PCBs (3)
Coplanar PCBs (2)
Percent lipid (3)
7-
-------
RESULTS AND DISCUSSION
POLYCHLORINATED BIPHENYLS (PCBs)
Sixty-nine PCB congeners (62 non-coplanar, 7 coplanar) were analyzed for all food chain study
components. Analyzing the PCBs by congener provides more information than reporting Aroclor or total
PCB concentrations. The most bioaccumulative PCB congeners contain five (penta) to seven (hepta)
chlorine molecules per atom. These isomer groups make up over half (112) of the 209 PCB congeners.
The penta through hepta chlorinated congeners are also some of the most toxic PCB congeners in the
environment because of their bioavailability and chronic toxicity (McFarland and Clarke, 1989). The 62
routine (non-coplanar) PCB congeners analyzed are listed in Table 4. These congeners were analyzed in
every sample collected for this study. Seven coplanar congeners (77, 105, 123, 126, 156, 157, and 169)
were analyzed for at least one replicate for each food chain component sampled at each site. Of all the
PCB congeners in existence, the coplanar congeners are considered the most toxic. These congeners are
structurally similar to 2,3,7,8-TCDD, the most potent synthetic environmental toxicant known, and
display similar properties. The non-ortho substituted coplanar congeners (77, 126, 169) mostly resemble
2,3,7,8-TCDD and are considered the most toxic of all congeners produced (McFarland and Clarke, 1989;
Safe, 1990). In addition, 15 of the "routine" PCB congeners (18, 44, 49, 52, 74, 87, 99, 101, 118, 128,
151, 157, 167, 177, 177, 180, 183, 194, and 201) are considered more toxicologically active to varying
degrees (McFarland and Clarke, 1989).
Analyses of total PCB concentrations, PCB homolog groups, toxic PCB congeners, and biota-sediment
accumulation factors are presented in the following sections.
Total PCB Concentrations
Total PCB concentrations were estimated by summing the concentrations of 62 routine (non-coplanar)
congeners that were resolved as 40 individual and 22 pairs (or triplets) of co-eluting congeners (Table 4).
Seven coplanar congeners were also analyzed but not added to the total since they were not analyzed for
- 18-
-------
all samples. These will be discussed in a later section on toxic congeners. Only the congeners giving a
positive result were summed to obtain the total. Concentrations measured at less than the level of
detection (LOD) or between the LOD and level of quantitation (LOQ) were assumed to be zero.
Table 4. Non-coplanar (routine) PCB Congeners Analyzed
for all Sheboygan River Samples
PCB Congener
(IUPAC) Number
5/8
6
7
16/32
17
18
19
22
24/27
26
28/31
33
37/42
40
41/64/71
44
45
46
47/48
49
52
56/60
66/95
70/76
74
77/110
82
84/92
85
87
91
Number of
Chlorines per
atom
2
2
2
3
3
3
3
3
3
3
3
3
3/4
4
4
4
4
4
4
4
4
4
4/5
4
4
4/5
5
5
5
5
5
PCB Congener
(IUPAC) Number
97
99
101
118
128
132/153
135/144
136
137/176
138/163
141
146
149
151
157
167
170/190
171/202
172/197
174
177
178
180
182/187
183
185
194
195/208
196/203
199
201
206
Number of
Chlorines per atom
5
5
5
6
6
6
6
6
6/7
6
6
6
6
6
6
7
7/8
7/8
7
7
7
7
7
7
7
8
8/9
8
8
8
9
Sediments
PCB congeners and sediment particle size were measured in sediment composites taken at five locations
in each study segment with the exception of the Esslingen segment. This segment has a fast-moving
current with more sand and gravel than the other segments, so four composites were collected at this site
- 19-
-------
(Table 5). Composites consisted of mixing the top 15-cm of sediment taken from two different but
adjacent cores. Letters A through E identified the five composites in each segment.
Table 5. Sediment Texture Characteristics for Food Chain Study Samples
Field ID
1A
1B
1C
1D
1E
2A
2B
2C
2D
2E
3A
3B
3C
3D
3E
5A
5B
5C
5D
6A
6B
6C
6D
6E
% Solids
57
60
57
44
50
62
48
61
74
58
66
63
77
55
47
51
74
73
68
67
55
46
57
74.5
% Sand
85
55
51
24
42
60
60
66
82
82
52
62
85
47
51
20
76
78
74
52
60
26
31
84
% Silt
7
31
26
56
43
30
23
21
12
10
36
25
10
38
35
58
17
14
17
35
28
56
50
9
% Clay
8
14
13
20
15
10
17
13
6
8
12
13
5
15
14
22
7
8
9
13
12
18
19
7
Soil Texture
LOAMY SAND (B)
SANDY LOAM (C)
SANDY LOAM (C)
SILT LOAM (E)
LOAM (D)
SANDY LOAM (C)
SANDY LOAM (C)
SANDY LOAM (C)
LOAMY SAND (B)
LOAMY SAND (B)
LOAM (D)
SANDY LOAM (C)
LOAMY SAND (B)
LOAM (D)
LOAM (D)
SILT LOAM (E)
LOAM (D)
LOAMY SAND (B)
SANDY LOAM (C)
LOAM (D)
LOAM (D)
SILT LOAM (E)
LOAM (D)
LOAMY SAND (B)
Total PCB concentrations in sediment ranged from 0.002 mg/kg at the reference site to 14.63 mg/kg at
the Rochester site (Table 6, Figure 3). Total PCB concentrations in sediment generally decreased
downstream from the Rochester site. PCB concentrations at the Reference site were detectable (0.002-
0.007 mg/kg) but were two to three orders of magnitude lower than at the contaminated sites downstream.
Average total PCB concentrations followed a similar pattern.
The Rochester site is closest to the original source of PCBs in the lower Sheboygan River, so the
longitudinal decrease in PCBs downstream is most likely due to sediment dispersion and dilution
downstream with uncontaminated sediments originating in the watershed. Since no known sources of
PCBs exist above the Sheboygan Falls dam, the detectable concentrations at the Reference site are most
-2O-
-------
likely caused by atmospheric deposition. Although PCBs were detected in low concentrations at the
Reference site, the concentrations are far below the 0.05-0.06 mg/kg average total PCB concentrations
measured as background upstream of the Sheboygan Falls Dam (Schuettpelz, 1992; David, 1990).
Table 6. Total Sediment PCB and Total Organic Carbon Concentrations at all
Sites.
Reference
Rochester
Betw. Dams
Esslingen
Camp Marina
Total PCBs (mg/kg)
Average (n)
Minimum
Maximum
Std. Deviation
0.005 (5)
0.002
0.007
0.002
7.21 (5)
2.59
14.63
5.13
3.40 (5)
2.01
4.54
1.05
1 .68 (4)
1.05
2.05
0.47
1 .58 (5)
1.01
1.83
0.34
Total Organic Carbon (jig/g)
Average
Minimum
Maximum
Std. Deviation
28620 (5)
22100
40900
8532
21300(5)
14100
33600
7695
23000 (5)
10200
33100
9219
16635 (4)
8740
35100
12407
24740 (5)
9300
35900
10570
Figure 3. Total PCB Concentrations in Sediment
16
"
..
14
"ra
-§ 12
o 10
*=
I 8
§ 6
8 4H.
S 2
CL
OH
0.000.01 0.000.01 0.01 0.00
Reference
Rochester Betw. Dams Esslingen Camp Marina
Sample Site
|DComp. A Comp. B DComp. C DComp. D Comp. E DAverage
Invertebrates
PCB congeners were measured for larval macroinvertebrates and emergent macroinvertebrates collected
at the Reference, Rochester, Between Dams and Esslingen sites. Collections were made weekly at each
site for a total of four weeks (Table 2, page 11). Crayfish were collected in a single day at each site and
-21 -
-------
separated into three similar size samples. Larval invertebrates collected were identified to genera, and are
listed in Table 7). Emergent invertebrates collected were identified to family and are listed in Table 8.
Table 7. Larval Invertebrates Identified for the Sheboygan River Food Chain
Study.
Order
Ephemeroptera
Trichoptera
Family
Heptageniidae
Caenidae
Hydropsychidae
Polycentropodidae
Limnephilidae
Genus
Stenacron
Stenonema
Caenis
Cheumatopsyche
Macrostemum
Ceratopsche
Hydropsyche
Polycentropus
Pycnopsyche
Segment Number
1
X
X
X
X
X
X
X
X
X
2
X
X
X
X
X
X
X
3
X
X
X
X
X
X
X
X
5
X
X
X
X
X
X
X
X
Table 8. Emergent Invertebrate Orders and Families Identified.
Order
Diptera
Hemiptera
Trichoptera
Ephemeroptera
Lepidoptera
Coleoptera
Family
Chironomidae
Tipulidae
Corixidae
Helicopsychidae
Hydropsychidae
Leptoceridae
Philopotamidae
Limnephilidae
Polycontropodidae
Hydroptilidae
Phryganeidae
Ephemeridae
Heptageniidae
Polymitarcidae
Caenidae
Pyralidae
Elmidae
Segment
1
X
X
X
X
X
X
X
X
X
X
X
X
X
2
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
3
X
X
X
X
X
X
X
X
X
X
X
X
5
X
X
X
X
X
X
X
X
X
X
X
X
Total PCB concentrations in larval invertebrates ranged from 0.006 |jg/g at the Reference site to 8.90
Hg/g at the Rochester site (Table 9). Average total PCB concentrations for larval invertebrates decreased
downstream from Rochester Park. Emergent invertebrates followed the same pattern. Total PCB
concentrations ranged from 0.032 |jg/g at the Reference site to 20.99 |jg/g at Rochester. Average total
PCB concentrations decreased downstream from Rochester. Emergent invertebrate total PCB
-22-
-------
concentrations were much higher than the larval invertebrates at all sites. A couple scenarios may
account for these differences. All the larval invertebrates were collected from rocks in faster flowing
riffle areas. In these areas PCB exposure is primarily through the water column and food sources
collected from the water column. Most of the emergent invertebrates collected were from families more
closely associated with sediments and detritus. In the larval and emergent invertebrate collections,
caddisflies comprised 75 to 95 percent of the invertebrates collected with mayflies comprising most of the
remainder. The hydropsy chid caddisflies were the dominant family of larval caddisflies collected. These
caddisflies are net filter feeders, collecting their food from particles suspended in the water column. The
dominant emergent caddisflies collected were from families that feed by grazing or scraping. They have
direct contact with the substrate and feed on detritus, algae, very small invertebrates and fungi. The other
emergent invertebrate orders collected (Diptera, Hemiptera, Lepidoptera and Coleoptera) comprised less
than one percent of total invertebrates collected at any site.
Additionally, when larval macroinvertebrates go through metamorphosis to the adult stage, PCB
concentrations could increase. The mass of emergent adults is less than larvae. Larsson (1984) found
that in chironomid adults, weights post metamorphosis were reduced by a factor of 3.8. The exuviae
retained only 17 percent of PCBs. Therefore, weight reduction combined with PCB retention could help
explain the increase in PCB concentration from larvae to adult stages.
-23-
-------
Table 9. Total PCB Concentrations and Percent Lipid Measured at all Sites for
Invertebrates.
Reference
Total
PCBs*
Percent
Lipid
Rochester
Total
PCBs*
Percent
Lipid
Between Dams
Total
PCBs*
Percent
Lipid
Esslingen
Total
PCBs*
Percent
Lipid
Larval invertebrates
Average (n)
Minimum
Maximum
Std. Dev.
0.016(4)
0.006
0.038
0.015
4.53(4)
0.30
8.70
3.75
7.99(4)
6.71
8.90
1.04
4.58(4)
4.10
5.80
0.82
7.89(4)
7.03
8.71
0.79
3.53(4)
1.20
5.40
1.73
5.54(3)
5.16
5.73
0.33
4.40(3)
3.40
5.10
0.89
Emergent invertebrates
Average (n)
Minimum
Maximum
Std. Dev.
0.075(4)
0.032
0.153
0.054
6.05(4)
4.80
7.20
1.18
14.95(4)
11.85
20.99
4.14
4.03(4)
2.90
5.10
1.88
11.98(4)
7.31
17.43
4.92
3.68(4)
2.00
4.90
1.24
8.00(4)
7.09
8.93
0.82
4.80(3)
4.20
5.40
0.55
Crayfish
Average (n)
Minimum
Maximum
Std. Dev.
0.009(3)
0.001
0.026
0.015
0.87(3)
0.70
1.00
0.15
1.81 (3)
1.72
1.90
0.09
0.95(3)
0.70
1.20
2.25
2.33
2.18
2.48
0.15
1.67(3)
1.40
1.80
0.23
1.75(3)
1.59
1.88
0.15
1.90(3)
1.70
2.10
0.20
*all concentrations are reported as fj^/g wet weight.
Figure 4. Average Total Invertebrate PCB Concentrations
O)
o
'-4'
CO
-II
I
o
O
DO
o
CL
16
14
12
10
8
6
4
2
0
Reference
Rochester
Between Dams
Esslingen
Site
n Emergent
I Larval n Crayfish
Fish Species
Longnose dace (insectivores), young and adult white suckers (omnivores) and young and adult
smallmouth bass (predators) were collected from the Reference, Rochester, Between Dams and Esslingen
Sites (Table 2, page 11). Three composites offish were collected and analyzed for routine PCB
-24-
-------
congeners. The numbers offish in each composite and average length for each species collected are
shown in Table 10 below.
Table 10. Fish Species Collected, Number of Fish and Average Length for Each
Composite Collected by Stream Segment.
Species
Longnose dace
Reference
Com
p(#
fish)
1(25)
2(25)
3(25)
Avg.
length
(mm)
108
94
60
Rochester
Com
p(#
fish)
1(25)
2(25)
3(25)
Avg.
length
(mm)
58
71
91
Between Dams
Com
p(#
fish)
1(25)
2(25)
3(25)
Avg.
length
(mm)
53
63
70
Esslingen
Com
p(#
fish)
1(25)
2(25)
3(25)
Avg. length
(mm)
116
98
68
Young white suckers
1(6)
2(6)
3(6)
103
119
133
1(8)
2(8)
3(8)
78
97
106
1(7)
2(7)
3(7)
88
110
126
1(9)
2(9)
3(9)
87
108
131
Adult white suckers
1(4)
2(4)
3(4)
286
254
236
1(3)
2(3)
3(3)
254
278
310
1(6)
2(6)
3(6)
279
299
347
1(3)
2(3)
3(3)
250
289
348
Young smallmouth bass
1(7)
2(7)
3(7)
82
88
98
1(8)
2(8)
3(8)
61
73
88
1(6)
2(6)
3(6)
64
74
90
1(8)
2(8)
3(8)
78
90
100
Adult smallmouth bass
1(3)
2(3)
3(3)
216
293
266
1(3)
2(3)
3(3)
243
274
292
1(4)
2(4)
3(4)
292
256
217
1 (4)
2(4)
3(4)
192
225
255
PCB concentrations for all species were lowest at the Reference site (0.008-0.551 |Jg/g). The highest
PCB concentrations measured for longnose dace (19.70 |Jg/g), young white suckers (15.90 |Jg/g) and
young smallmouth bass (29.84 |Jg/g) were found at the Between Dams site (Table 11). Because longnose
dace and young fish generally migrate less than an adult fish, a common food source that is enriched with
PCBs at the Between Dams site could be responsible for the higher concentrations. Larval insects could
be this common food source because the dace and young fish are primarily insectivorous or omnivorous
(Becker, 1983). The highest PCB concentrations for adult white suckers (16.50 |Jg/g) and adult
smallmouth bass (35.41 |Jg/g) were measured in fish taken from the Rochester site (Table 11).
Average total PCB concentrations decreased downstream from Rochester for adult white suckers and
adult smallmouth bass, while the average total PCB concentrations for young white suckers and young
-25-
-------
smallmouth bass followed the pattern: Between Dams>Rochester>Esslingen (Figure 5). Average total
PCB concentrations for longnose dace increase downstream from Rochester to Esslingen.
Table 11. Total PCB Concentrations and Percent Lipid Content in Sheboygan
River Fish.
Reference
Total
PCBs*
Percent
Lipid
Rochester
Total
PCBs*
Percent
Lipid
Between Dams
Total
PCBs*
Percent
Lipid
Esslingen
Total
PCBs*
Percent
Lipid
Lonanose dace
Average (n)
Minimum
Maximum
Std. Dev.
0.175(3)
0.041
0.401
0.196
3.00(3)
2.20
3.40
0.70
11.46(3)
7.98
17.30
5.09
6.87(3)
5.10
10.00
2.72
16.67(3)
13.43
19.70
3.14
5.53
4.80
6.20
0.70
17.06(3)
13.65
19.19
2.98
8.83(3)
6.80
10.00
1.77
Young White Suckers
Average (n)
Minimum
Maximum
Std. Dev.
0.058(3)
0.011
0.152
0.081
1.67(3)
1.50
1.90
0.21
10.04(3)
9.74
10.49
0.40
3.03(3)
2.50
3.90
0.76
11.07(3)
8.39
15.90
4.20
3.13
2.40
3.90
.043
4.66(3)
4.01
5.62
0.86
3.30(3)
2.50
3.90
0.72
Adult White Suckers
Average (n)
Minimum
Maximum
Std. Dev.
0.040(3)
0.008
0.096
0.049
0.83(3)
0.60
1.20
0.32
10.21 (3)
6.22
16.50
5.52
0.87(3)
0.70
1.00
0.15
9.54(3)
7.42
12.29
2.50
1.30(3)
1.10
1.60
0.26
7.66(3)
3.29
14.43
5.95
1.90(3)
1.60
2.50
0.52
Young Smallmouth Bass
Average (n)
Minimum
Maximum
Std. Dev.
0.055(3)
0.028
0.101
0.040
3.10(3)
2.60
3.40
0.44
18.27(3)
17.17
19.57
1.21
4.20(3)
3.90
4.40
0.26
23.50
17.96
29.84
5.98
3.77(3)
3.40
4.00
0.32
12.63(3)
9.81
14.14
2.44
4.63(3)
3.80
5.30
0.76
Adult Smallmouth Bass
Average (n)
Minimum
Maximum
Std. Dev.
0.276(3)
0.095
0.551
0.242
3.33(3)
2.00
4.90
1.46
30.39(3)
21.70
35.41
7.56
2.80(3)
2.50
3.10
0.30
21.57(3)
15.08
28.46
6.70
2.83(3)
2.40
3.20
0.40
16.91 (3)
16.19
18.21
1.13
3.57(3)
3.10
4.10
0.50
*all units for PCBs expressed as ub/g
**only one sample analyzed for coplanar PCBs
-------
Figure 5. Average Total PCB Concentrations for Fish Species
Qadult smallmouth bass
yoy smallmouth bass
Dadult white sucker
Dyoy white sucker
longnose dace
reference
Rochester
Betw. Dams
Esslingen
Site
Total PCB Accumulation
Bioaccumulation of PCBs in the Sheboygan River is evident at all sites (Figure 6). Total PCB
concentrations generally increased from sediments to macroinvertebrates to fish at each site. With the
exception of crayfish, mean macroinvertebrate PCB concentrations were higher than mean sediment
concentrations. Crayfish have much lower mean lipid content (0.87-1.90%) compared to larval (3.53-
4.58%) and emergent (3.68-6.05%) macroinvertebrates which could account for the lower PCB tissue
concentrations (Table 9, page 24).
-27-
-------
Figure 6. Total PCB Accumulation in Different Food Chain Study Components at Each Site.
Q_
.D..
0 0.1 50 .
to
(j
-3
i
.=: ~*
Reference
n
,, .-. ||
"^ v £
Food Chain
Site
0.040 °'°"
n n n
3 3 « i
| 3 S t
MM
^ b
Component
r\
S
^
J
"5
E
_s
_
Rochester Site
oc _________________^^
o
o
LL.
o T-'
1-
Z 5 -
30.39
1 8.27
n n
1 1 ^ 1
~£ "t V
* £ &
L X n
4.95
1.46
0.04
j ? -^
^ 1 1
e. 3
^ X
>.
Food Chain Component
0.2
3 j
' ;
1 1
J , = -f
1 I
Between Dams Site
w
1
O . .
o I I
o 1-°7
d. 1 1 3-54
O . .
1
^ l~~l rn 1
"£ "t * 'e y S ^
"* M £ ^ -i ~5 ^
c 3
D
Food Chain Component
Esslingen Site
O , ,
g It)
i ^Q 8.00 766
^ '" r^i n 4" n
^ g 1 1 1 1 II II
cJ t? £ v* fj ^i
0 ;x ^
o "5
Food Chain Component
...»
t
E
i
E J
O
_e
E
0
1 .5
?
1
'
O
_£
E
"5
-------
Longnose dace accumulated higher concentrations of PCBs than young and adult white suckers and
young smallmouth bass. The longnose dace collected were adults, with longer exposure times to PCB
contaminated materials than the young white suckers and young smallmouth bass, which were probably
in the river less than one year. The longnose dace mean lipid content (3.0-8,83%) was about 3 to 8 times
higher than mean lipid content of adult white suckers (0.83-1.90%) (Table 11, page 26). In addition,
longnose dace on average were much smaller than the adult white suckers (60-116 mm for dace; 236-348
mm for white suckers) (Table 10, page 25); so the ratio of PCBs to body weight would be greater in
longnose dace. The smallmouth bass generally accumulated higher concentrations of PCBs than the other
fish species studied with the exception of young smallmouth bass at the reference and Esslingen sites.
The very low average PCB concentrations at the Reference site could explain more variation in
accumulation between food chain components. At the Esslingen site, longnose dace (68-116 mm average
length) were of similar size to young smallmouth bass (78-116 mm average length), but mean longnose
dace lipid content (8.83%) was nearly twice the mean young smallmouth bass lipid content (4.63%). The
mean adult smallmouth bass lipid content (3.57%) was less than half the mean lipid content of longnose
dace at the Esslingen site.
Toxic Congener Accumulation
The 22 PCB congeners considered most toxic to biota were summed for all food chain components
(Figure 7). Overall, the toxic congeners represented about 23 to 34 percent of the total PCB concentration
at the contaminated sites. Accumulation of these congeners followed the same general patterns as with
total PCBs (sediment
-------
Figure 7. Toxic PCB Congener Accumulation in all Food Chain Study Components at Each Site.
Reference
Rochester
Between Dams
Esslingen
Food Chain Component
Food Chain Component
-3O-
-------
PCB Homolog Distribution
PCB congeners were summed into homolog groups for all study components and averaged (Figure 8,
Table 12). Average PCB homolog concentrations in all study components at the reference site were
either below detection limits or at very low concentrations. Average sediment homolog concentrations
were the least for all components, and above detection only for the terra (0.58 ng/g), penta (2.19 ng/g) and
hexachlorobiphenyls (2.15 ng/g). Adult smallmouth bass had the highest average homolog concentrations
for most homolog groups at the reference site (with the exception of trichloropiphenyls), but still at very
low concentration.
Average concentrations for all homologs at the downstream sites generally increased from sediment to
increasingly higher biological components according to the following pattern: crayfish
-------
Figure 8. PCB Homolog Concentrations for Each Food Chain Component at Each Site.
0 Concentration (ng/g)
3 _j. _
2 ro -t>. en co o N
1 OOOOOOC
ouuu
ynnn -
.. (UUU
D)
p bOOO
~~^ cnnn -
g ouuu
ro 4000
o 2000
-i nnn -
1 UUU
o
8000
-3 700°
°> 6000
§" 5000
'§ 4000
| 3000
§ 2000
° 1000
0
.0
ro 4000
O
1 000
rJ
1 1 1
1
Rl
rl H1H , jJ
2345678
r
Ii r
Its
t
i r
234
Q 19R ^
_
h
i-m
1 1 1 1 rl n_
nn-rfh-B IT 1 1 II I II H
* 12,555
3
nn
H
1
RjlJ
m-Hl_^J _ _
5678
^ 8.212
Between Darns
|
Jt
~
n-J _
2345678
_
rll
fnfll
_rw^« J n HI IT
bssimgen
nl
llll
IT
1 11
1 _i-H MINI _j-i_i-n-B
2345678
Homolog
n sediment Crayfish d Larval Insects
d Emergent Insects young white sucker dyoung smallmouth
D longnose dace D adult white sucker adult smallmouth
-32-
-------
Table 12. Average PCB Homolog Concentrations by Site and Food Chain Component
Site
Reference
Reference
Reference
Reference
Reference
Reference
Reference
Reference
Reference
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Type (n)
Sediment (5)
Crayfish (3)
Larval Insects (4)
Emergent Insects (4)
longnose dace (3)
young white sucker (3)
adult white sucker (3)
young smallmouth (3)
adult smallmouth (3)
Sediment (5)
Crayfish (3)
Larval Insects (4)
Emergent Insects (4)
longnose dace (3)
young white sucker (3)
adult white sucker (3)
young smallmouth (3)
adult smallmouth (3)
Sediment (5)
Crayfish (3)
Larval Insects (4)
Emergent Insects (4)
longnose dace (3)
young white sucker (3)
adult white sucker (3)
young smallmouth (3)
adult smallmouth (3)
Sediment (5)
Crayfish (3)
Larval Insects (3)
Emergent Insects (4)
longnose dace (3)
young white sucker (3)
adult white sucker (3)
young smallmouth (3)
adult smallmouth (3)
Homolog totals
2
0.00
0.00
0.00
0.00
7.99
0.00
0.00
0.00
0.00
634.46
16.00
294.75
214.03
222.43
243.77
123.20
642.90
404.87
367.56
32.67
669.65
371.05
420.47
440.83
187.04
810.03
569.83
87.41
11.33
332.37
164.60
357.80
190.63
131.00
474.93
414.87
3
0.00
6.00
7.10
7.80
19.45
7.60
5.10
5.83
16.82
1900.60
334.27
1606.55
2342.25
2037.67
1819.00
1302.67
3317.33
3630.00
841.00
459.30
2007.50
2378.00
3455.00
2505.67
1470.67
4353.67
3348.33
376.45
270.83
1271.67
1369.50
2818.33
901.67
1062.27
2435.00
2650.33
4
0.58
11.00
12.90
26.00
55.97
68.50
30.50
32.80
92.11
2664.20
839.07
3654.03
6685.75
5017.17
4379.67
4333.73
7295.00
12555.00
1239.00
1051.67
3047.98
5011.50
7001.53
4572.03
3847.23
9128.00
8212.00
689.45
785.30
2242.87
3326.85
7165.67
1909.47
3270.40
5519.33
7029.70
5
2.19
2.74
5.39
28.25
59.92
21.46
14.91
22.66
99.87
1474.20
408.80
1821.75
4114.75
3020.67
2490.00
2919.67
4803.00
9700.40
667.97
494.33
1522.25
2864.50
3809.67
2420.67
2602.67
6114.67
5961.27
392.18
418.70
1216.33
2141.00
4494.00
1087.00
2104.00
2974.33
4690.00
6
2.15
1.90
5.63
21.03
41.70
12.77
13.00
18.80
60.10
531.42
184.03
574.53
1516.50
1011.10
899.67
1232.70
1887.33
3995.00
264.58
243.00
561.25
1174.75
1656.33
944.40
1182.00
2662.00
3158.67
141.53
217.87
424.63
867.23
1905.00
468.47
857.30
1051.03
1954.67
7
0.00
0.00
0.00
3.90
9.40
0.00
2.50
2.40
13.37
100.52
44.53
127.58
330.43
219.00
212.37
281.10
398.27
907.23
54.62
62.93
120.55
273.10
342.43
194.17
254.33
543.43
692.83
28.66
59.33
98.83
214.65
371.87
108.80
207.03
212.47
400.90
8
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.10
20.56
4.73
22.68
64.75
32.70
43.33
55.97
67.33
179.92
15.28
6.70
21.40
58.90
58.80
29.97
47.67
85.84
121.00
6.56
7.67
18.07
41.33
59.60
18.03
40.23
34.27
69.10
-33-
-------
Figure 9. Percent PCB Homolog Composition for all Food Chain Components.
60
m 50
o
16 40
?30
o
120
£ 10
Reference
I
n
60
| 50
| 30
| 20
I 10
Rochester
1
60
-------
Semi-permeable Polymeric Membrane Devices (SPMDs)
Individual PCB congeners were summed for homolog mass for each study site and deployment period.
Homolog group PCB concentrations were calculated by dividing homolog PCB masses by the mass of the
lipid recovered from SPMDs in each deployment device. The homolog concentrations from the three
deployment devices at each site were then averaged. SPMDs were not deployed at the Between Dams
site but were deployed upstream and downstream of a site near the Sheboygan Harbor called Camp
Marina. Habitat at the Camp Marina site was not suitable for collecting invertebrate and fish species, so
SPMDs were used as a fish surrogate to determine organic pollutant bioconcentration (or bioavailability)
at this site.
Homolog concentrations at the reference site were very low to undetectable for all groups during both
deployments (Figure 10). Concentrations for the lower chlorinated homolog groups (di-
tetrachlorobiphenyls) at the Rochester and Esslingen sites were nearly double during the first deployment
than during the second. PCB homolog concentrations at the two Camp Marina sites were similar between
both deployment periods. Hepta- and octa-chlorinated biphenyls were generally below detection at all
sites during both deployment periods.
Average water temperatures during the first and second deployments were similar for each site (Table
13). Observed temperature differences were probably too small to account for any differences in PCB
uptake during the two deployments. Moreover, the slightly higher average temperature combined with
the longer exposure of the second deployment (28 days vs. 14 days) should have resulted in higher
concentrations of PCBs detected. These marked differences between deployments were only observed at
the two upstream contaminated sites, and only for the di-tetra-chlorobiphenyl homolog groups.
-35-
-------
Table 13. Average Water Temperatures During Both SPMD Deployments
Site
Reference
Rochester
Esslingen
Camp Marina (upstream)
Camp Marina (downstream)
First Deployment
22.1
21.5
20.8
19.7
21.1
Second Deployment
25.0
21.3
24.3
21.7
22.9
Figure 10. PCB Homolog Concentrations in SPMDs
3000
First Deployment (14 days)
456
Homolog (# Cl)
a
'5.
ro
^>
c
o
c
HI
o
o
m 500
a.
Second SPMD Deployment (28 days)
i
0
2
f-
3
-
1-1
|
II rTHl
45678
Homolog Group (#CI)
preference Rochester DEsslingen DCamp Marina (up) DCamp Marina (down)
One possible explanation for the higher PCB concentrations detected during the first SPMD deployment
is a decrease in the sampling rate due to biofouling. Sampling rate decreases can be calculated using the
-36-
-------
loss of a permeability reference compound (PRC). For this study, d10phenanthrene was spiked into each
SPMD for permeability evaluation. It is assumed net uptake of native and deuterated forms of
compounds by SPMDs occur at nearly identical rates. Further, it is assumed that factors affecting
phenanthrene uptake and loss affect PCB congeners similarly. Deuterated phenanthrene was spiked into
all SPMDs prior to deployment. Losses of this compound relative to levels in trip blanks (exposed only
during field deployment and retrieval) were used to calculate the percent decrease in sampling rate due to
biofouling (Table 14).
Table 14. Average Percent Decrease in the Loss of d10 Phenanthrene spikes in
field-deployed SPMDs vs. Trip Blank SPMDS.
Site
Rochester
Esslingen
First Deployment
17.8
25.9
Second Deployment
80.7
67.9
It does make sense that increased biofouling during a longer deployment period would decrease the
SPMD contaminant uptake during the second deployment. Therefore, less biofouling probably accounted
for the higher levels of di-tetrachlorinated biphenyls at Rochester and Esslingen during the first
deployment. It is unclear however why decreased biofouling during the first deployment period did not
translate into higher concentrations of the other homolog groups.
Since the SPMDs were not deployed for a long enough period to be in equilibrium with the surrounding
water column, they were sampling integratively (Huckins et al., 1990). Some type of episodic event
could have caused the ambient water column concentration of PCBs to increase during the first
deployment period. During this time, over 3.5 inches of rain fell, with 2.7 inches falling over a three-day
period (0.82" 7/30/94 and 1.87" 8/01/94). Conversely, during the second deployment period, only one
inch of rain fell during the entire time. The water discharge rate of the Sheboygan River increased nearly
three fold following the rainfall events during the first deployment period and remained elevated for about
five days (Figure 11).
-37-
-------
The higher flows in the river could have caused contaminated sediment or floodplain soil disturbance.
Since lower chlorinated PCB congeners are more water soluble (e.g. 4 Cl congeners are 10 times more
soluble than 6 Cl congeners) ambient water column concentrations of lower chlorinated PCBs could have
become elevated during the first deployment period. By contrast, higher chlorinated congeners are less
water-soluble and are more likely to be bound to organic particles. Since SPMDs only sample dissolved
pollutants, lower chlorinated congeners would be sampled more readily.
Figure 11. Sheboygan River Discharge for Both SPMD Deployment Periods.
250
-. 200
8
7 150
S>
Jl 100
8
Q 50
0
Sheboygan River Discharge
First Deployment
Date
f
0)
S>
u
250
200
150
1 nn -
en _
ou
0.
Sheboygan River Discharge
Second Deployment
*
* * * \*^~ *^H 1^| f. j. t »
^^^* *
g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g
Date
-------
Biota-sediment Accumulation Factors (BSAFs) for PCB Homolog Groups
Average BSAFs for PCB homolog groups and the most toxic PCB congeners were calculated for all
trophic groups by dividing the average lipid-normalized tissue PCB concentration by the average TOC
normalized sediment PCB concentration.
At the reference site, BSAFs were calculated for homolog groups 4, 5 and 6 only because sediment PCB
concentrations for the remaining homolog groups were below detectable levels (Table 15, Figure 12).
BSAFs for PCB homologs at this site were generally 10 to 50 times greater than the other sites, probably
because of the very low measured PCB concentrations in the sediment and tissue. BSAFs generally
increased with increasing trophic level (with the exception of emergent invertebrates). For the highest
trophic groups (adult white suckers and adult smallmouth bass), BSAFs increased with increasing
chlorination (except octachlorobiphenyls). BSAFs were higher for the trichloro through
heptachlorobiphenyls for all trophic groups at the Between Dams site, even though measured sediment
PCB concentrations were less than half of the Rochester average (3.4 mg/kg, Between Dams; 7.21 mg/kg
Rochester).
Average BSAFs were calculated for the 22 PCB congeners measured that are considered most
toxicologically active (McFarland and Clarke, 1989). Only three of the congeners were detected at the
Reference site (IUPAC# 87,105,118). At the downstream sites, BSAFs ranged from <1 to 16.36 (Table
16). Adult smallmouth bass and adult white suckers (the highest trophic levels) had the highest calculated
BSAFs. The highest BSAFs for most congeners were found at the Between Dams site. BSAF values
generally increased with increasing trophic levels at all sites. There was not a distinct relationship
apparent between BSAF and extent of chlorination for individual congeners.
-------
Table 15. BSAFs by Homolog Group for Food Chain Study Biota
Site
Reference
Reference
Reference
Reference
Reference
Reference
Reference
Reference
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Between Dams
Between Dams
Between Dams
Between Dams
Between Dams
Between Dams
Between Dams
Between Dams
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Tissue type (n)
Crayfish (3)
Larval invertebrates (4)
Emergent invertebrates (4)
Longnose dace (3)
Young white suckers (3)
Adult white suckers (3)
Young smallmouth bass (3)
Adult smallmouth bass (3)
Crayfish (3)
Larval invertebrates (4)
Emergent invertebrates (4)
Longnose dace (3)
Young white suckers (3)
Adult white suckers (3)
Young smallmouth bass (3)
Adult smallmouth bass (3)
Crayfish (3)
Larval invertebrates (4)
Emergent invertebrates (4)
Longnose dace (3)
Young white suckers (3)
Adult white suckers (3)
Young smallmouth bass (3)
Adult smallmouth bass (3)
Crayfish (3)
Larval invertebrates (4)
Emergent invertebrates (4)
Longnose dace (3)
Young white suckers (3)
Adult white suckers (3)
Young smallmouth bass (3)
Adult smallmouth bass (3)
PCB Homolog Group (# chlorines)
Dichloro
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.05
0.19
0.16
0.10
0.23
0.39
0.43
0.41
0.12
1.68
0.70
0.46
0.84
0.81
1.29
1.21
0.10
1.25
0.56
0.68
0.95
0.67
1.67
1.91
Trichloro
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.33
0.60
0.28
0.57
1.33
0.72
1.21
0.73
2.12
1.99
1.63
2.06
2.89
3.02
3.10
0.51
10.50
1.02
1.19
0.99
1.13
1.87
2.66
Tetrachloro
15.78
1.52
110.20
49.81
36.21
25.53
12.67
121.48
0.60
0.53
1.22
0.47
0.98
3.17
1.13
2.99
1.13
2.18
2.80
2.22
2.54
5.24
4.27
5.10
0.80
1.00
1.34
1.64
1.14
1.84
2.28
3.83
Pentachloro
4.94
5.94
6.56
23.74
15.36
19.07
10.26
55.06
0.52
0.48
1.35
0.50
1.01
3.92
1.35
4.17
0.97
2.01
2.88
2.23
2.49
6.57
5.25
6.80
0.74
0.95
1.50
1.80
1.13
2.09
2.15
4.45
Hexachloro
1.23
7.13
4.96
17.73
9.83
19.76
8.57
31.03
0.64
0.42
1.36
0.47
1.00
4.60
1.45
4.71
1.21
1.89
3.00
2.46
2.48
7.58
5.79
9.15
1.07
0.92
1.68
2.13
1.36
2.37
2.10
5.13
Heptachloro
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.82
0.49
1.56
0.57
1.27
5.58
1.63
5.72
1.49
1.94
3.25
2.43
2.43
7.69
5.61
9.52
Octachloro
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.43
0.44
1.54
0.43
1.31
5.61
1.39
5.72
0.55
1.22
2.44
1.48
1.32
5.13
3.15
5.91
1.48
1.09
2.10
2.09
1.61
2.88
2.15
5.30
0.91
0.96
1.94
1.62
1.28
2.66
1.68
4.38
-4O-
-------
Figure 12. BSAFs by Homolog Group for Food Chain Study Biota.
CO
120 -
-i nn -
sn -
fin -
40
20 -
0 -I
Reference
1
h
H"
rfT
jfj-
n-
i
i
1
iz -
10 -
8.
CO R
4.
2 -
0_
H
Rochester
^^m ^rvJKl rrfHl
D hi t hi T t hi
n
rrftl
rrfk
ri
1
-i
rrftl
ri
'
-I r
rrlH
|-|
1
Homolog Group (#CI)
Homolog Group (#cl)
Homolog Group (#CI)
D Crayfish Larval D Emergent
DLongnose dace BYoung white suckers DAdult white suckers
Young smallmouth bass D Adult smallmouth bass
12
10
S 6
m
Esslingen
rr
Homolog Group (#CI)
-41 -
-------
Table 16. BSAFs for the Most Toxic PCB Congeners.
Site
reference
reference
reference
reference
reference
reference
reference
reference
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Rochester
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Betw. Dams
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Esslingen
Tissue Type
Crayfish
Larval Insects
Emergent Insects
longnose dace
yoy white sucker
yoy smallmouth bass
adult white sucker
adult smallmouth bass
Crayfish
Larval Insects
Emergent Insects
longnose dace
yoy white sucker
yoy smallmouth bass
adult white sucker
adult smallmouth bass
Crayfish
Larval Insects
Emergent Insects
longnose dace
yoy white sucker
yoy smallmouth bass
adult white sucker
adult smallmouth bass
Crayfish
Larval Insects
Emergent Insects
longnose dace
yoy white sucker
yoy smallmouth bass
adult white sucker
adult smallmouth bass
18
0.07
0.28
0.44
0.16
0.39
0.41
0.58
0.60
0.14
1.51
1.30
0.79
1.07
1.79
1.34
1.76
0.07
0.55
0.52
0.58
0.53
1.27
0.94
1.45
44
0.09
0.40
1.04
0.39
0.78
0.81
2.39
1.93
0.16
1.79
2.43
2.05
2.16
3.59
4.06
3.66
0.10
0.69
1.02
1.72
1.01
2.15
2.59
2.99
49
0.70
0.50
1.19
0.54
1.02
1.21
3.30
3.07
1.25
2.20
2.81
2.60
2.85
4.55
5.63
5.50
0.91
1.05
1.35
1.97
1.33
2.65
3.24
4.37
52
0.58
0.49
1.21
0.52
0.65
1.08
1.91
2.67
1.01
2.16
2.79
2.56
2.12
4.18
3.82
5.18
0.77
1.04
1.37
2.01
0.92
2.70
2.89
4.40
74
1.13
0.74
1.72
0.61
1.28
1.67
5.01
4.86
1.87
2.86
3.35
2.48
2.97
5.56
8.02
7.41
1.25
1.18
1.50
1.81
1.22
2.16
3.76
4.90
77
0.54
0.48
1.00
0.16
0.29
0.76
0.45
2.89
0.00
0.00
2.34
0.68
0.63
2.62
1.16
3.03
0.26
0.31
0.45
0.60
0.37
0.59
0.29
0.89
87
0.00
0.00
1.53
5.91
8.75
2.67
9.35
14.35
0.62
0.55
1.39
0.54
1.06
1.30
4.11
4.09
1.26
2.12
2.97
2.51
2.61
5.76
7.45
8.18
0.93
0.93
1.33
1.85
1.13
2.08
3.55
4.69
99
1.08
0.58
1.60
0.62
1.27
1.83
5.67
5.75
1.97
2.61
3.69
3.16
3.37
7.29
10.12
10.78
1.55
1.17
1.87
2.27
1.60
2.66
5.05
6.74
101
0.92
0.56
1.57
0.68
1.21
1.71
4.83
5.31
1.87
2.39
3.64
3.26
3.35
6.72
9.12
9.87
1.41
1.08
1.92
2.53
1.54
3.08
4.84
6.42
105
0.00
0.00
3.79
31.84
18.96
6.06
26.26
23.33
0.63
0.50
1.42
0.54
0.76
1.98
3.28
5.94
0.81
1.98
1.92
1.71
1.67
6.87
6.23
7.32
0.51
0.53
0.94
1.80
0.82
1.66
1.17
3.09
118
9.98
7.80
4.85
16.61
11.88
8.38
18.18
38.43
0.99
0.61
1.82
0.67
1.32
2.14
6.14
6.41
1.86
2.48
3.69
2.83
3.00
7.19
10.29
11.29
1.18
1.09
1.83
2.06
1.33
2.09
3.87
5.96
126
3.82
5.00
128
0.67
0.46
1.22
0.45
1.08
1.54
4.79
5.12
1.39
1.90
2.80
2.14
2.61
5.97
8.23
9.03
1.04
0.85
1.42
1.57
1.25
1.63
3.33
4.36
151
0.39
0.26
0.38
0.33
0.76
1.16
2.53
3.36
0.75
1.40
0.94
1.56
2.17
4.12
4.48
5.43
0.74
0.73
0.83
1.54
1.22
1.88
2.41
3.68
156
0.73
0.51
1.57
0.52
0.66
1.62
3.52
6.44
1.10
1.67
3.00
2.01
2.01
8.31
6.00
10.43
0.67
0.52
1.22
2.47
1.15
1.49
2.14
4.22
157
0.81
0.68
1.87
0.43
0.59
1.59
2.75
6.29
0.85
1.67
2.51
3.34
2.53
10.05
9.07
14.60
1.13
0.95
1.33
3.94
1.62
1.46
1.67
3.11
167
1.11
0.61
1.82
0.67
1.36
2.40
6.62
7.12
1.98
2.33
3.98
3.09
2.69
8.62
10.30
16.36
1.65
1.26
2.11
2.27
1.42
2.22
4.67
5.91
177
0.81
0.39
1.26
0.39
0.99
1.24
4.30
4.61
1.40
1.70
2.81
1.94
2.03
4.24
6.05
7.40
1.50
1.01
1.97
1.77
1.31
1.86
4.02
4.60
180
1.15
0.58
1.81
0.69
1.49
1.85
6.80
6.67
1.79
2.11
3.48
2.75
2.50
5.95
8.48
11.00
1.70
1.10
2.15
2.19
1.38
2.34
5.01
5.48
183
0.62
0.49
1.54
1.29
1.58
5.61
5.76
1.07
1.93
3.15
2.47
5.73
7.94
9.09
1.00
0.99
2.01
1.39
2.04
4.45
4.95
194
0.99
0.56
1.96
0.61
1.56
1.74
7.12
7.33
1.04
1.48
3.03
1.82
1.63
3.86
6.05
7.37
1.37
1.05
1.96
1.66
1.20
1.73
4.73
4.34
201
1.09
0.48
1.64
0.44
1.39
1.48
5.67
5.98
1.37
1.37
2.68
1.64
1.69
3.75
5.64
7.33
1.60
0.91
1.80
1.50
1.37
1.45
4.19
4.29
-42-
-------
BSAFs for PCB homolgs and congeners are generally consistent with published reports (Ankley et al.,
1992; Lake et al., 1990; Ferraro et al., 1991). With the exception of the highest trophic levels at the
Between Dams site, most BSAFs fell into the range of 1 to 4 as previously published.
The higher BSAFs for all organisms at the Between Dams site compared to the Rochester site is
somewhat puzzling. One explanation may be that organisms at the Between Dams site had more direct
contact with sediment than the other two contaminated sites. The Between Dams site is much shorter (1.3
miles) than the other contaminated sites (2.7 mi, Rochester; 3.4 mi, Esslingen). The Waelderhaus Dam
may serve to hold contaminated sediments in this river segment. Instead of being transported further
downstream, sediments are deposited behind the dam. The river is also less dynamic at the Between
Dams site because of the ponding effect of the dam. Water moves slower and sediment has more
opportunity to deposit in this area. Additionally, fish species have a more restricted range in this area of
the river because the dams restrict migration.
Alternatively, water column transport of PCBs from the more contaminated Rochester site may be
having an influence at the Between Dams site. Many of the larval invertebrates collected were filter and
suspension feeders. The action of feeding and respiring allow these organisms to filter suspended PCB
particles from the water column. The higher trophic level organisms probably accumulate PCBs through
the food chain as well as the water column. The higher BSAFs for fish at the Between Dams site may be
more of a function of prey concentration and respiration than to direct contact with sediments.
Another explanation may lie with the number of sediment samples collected. Only five samples were
collected at each site (4 at Esslingen) and averaged for calculating BSAFs. This is relatively few samples
to characterize one to 3 mile-long river segments. It is possible that we missed some areas of higher
contamination. Because we sampled through the ice, we did not have the opportunity to characterize the
size of each sediment deposit.
-43-
-------
POLYCYCLIC AROMATIC HYDROCARBONS (PAHS)
Seventeen poly cyclic aromatic hydrocarbon compounds (PAH) were analyzed in sediment, SPMDs and
macroinvertebrates. Fish tissue was not analyzed for PAHs because they readily metabolize these
compounds. The 17 compounds were summed to calculate a total PAH concentration. Eight of the 17
compounds are considered carcinogenic and were summed to estimate the most toxic fraction of the
compounds analyzed.
Three sediment samples were analyzed for PAHs from segments 1, 2, 3, 5 and 6 (Table 17). One deeper
sample (the lower 20 cm of a 96 cm core) was taken near the site of a former coal gasification facility
adjacent to the Camp Marina overnight area in the city of Sheboygan.
All samples at the reference site were below the limit of detection for all PAH compounds. This is a
primarily agricultural area with few known sources of these compounds, so very low to undetectable
concentrations were expected at this site.
Sediment PAH concentrations at the Rochester site ranged from 0.28 mg/kg to 23.51 mg/kg. PAH
concentrations at the Between Dams site ranged from 0.12-1.19 mg/kg, while concentrations at the
Esslingen site ranged from 0.13-9.81 mg/kg. The two higher samples at Rochester (23.51 mg/kg) and
Esslingen (9.81 mg/kg), while elevated, are within ranges typical of urban runoff (Table 18). These
concentrations may be due to their locations near storm sewer outfalls that drain urban areas in the City of
Sheboygan Falls and the City of Sheboygan respectively.
Sediment concentrations at the Camp Marina site ranged from 5.35-15.10 mg/kg. These concentrations
are similar to other surface sediment samples taken in the Sheboygan River, and are far less than surface
sediment samples taken in Milwaukee area streams (Table 18).
The deeper sediment sample in segment 6 (near the former coal gasification facility at Camp Marina), at
3452 mg/kg has a total PAH concentration 150 to 28,000 times higher than any of the surface samples
-44-
-------
taken from the Sheboygan River for this study. This one sample was extracted from a 96 cm long core.
Upon examination of the core, the lower 20 cm appeared oil soaked and revealed a very strong odor. This
portion of the core was homogenized and analyzed for PAHs. As part of an Emergency Repair Fund
investigation, several cores were taken at varying depths near this site, with total PAH concentrations
taken from depths of 11-119 inches ranging from 0.09 to 9294 mg/kg (NRT, 1998).
Individual PAH compound concentrations for each sample were compared to sediment quality criteria
developed by the Ontario Ministry of the Environment (1993). The samples at the Rochester and
Esslingen sites with elevated PAH concentrations, and the three surface samples at Camp Marina had
individual compound concentrations between the lowest effects level (LEL) and the severe effects level
(SEL) (Table 17). This indicates these samples are marginally to significantly polluted have the potential
to affect sediment use by some benthic organisms.
The deeper core at the Camp Marina site greatly exceeded the SEL for all compounds for which there
are guidelines. This indicates that the sediments are grossly polluted and are detrimental to the majority
of benthic species.
Average total PAH concentrations in larval and emergent macroinvertebrate tissues increased with
increasing urbanization throughout the watershed (Table 19). No PAH compounds were measured above
the limit of detection in any crayfish sample at any site even though detectable levels of PAHs were found
in sediments at the Rochester, Between Dams and Esslingen sites.
Average total PAH concentrations in SPMDs increased from upstream to downstream for both SPMD
deployment periods (Table 20). The second deployment should have yielded higher concentrations of
PAHs than the first deployment (28 days vs 14 days). Excessive biofouling may have decreased the
permeability of the membrane during the second deployment (see biofouling discussion on page 37).
-45-
-------
Table 17. PAH Compound Concentrations for Sediment.
PAH Compound
ACENAPHTHENE
ACENAPHTHYLENE
ANTHRACENE
BENZO (A)
ANTHRACENE
BENZO (A) PYRENE
BENZO (B)
FLUORANTHENE
BENZO (E) PYRENE
BENZO (G H I)
PERYLENE
BENZO (K)
FLUORANTHENE
CHRYSENE
DIBENZO (A H)
ANTHRACENE
FLUORANTHENE
FLUORENE
INDENO (1 2 3-C D)
PYRENE
PERYLENE
PHENANTHRENE
PYRENE
sum all PAH
sum cPAH
Sample Sites
Reference
1B
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
1D
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
1E
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
**
Rochester
2A
**
**
**
**
**
**
**
**
**
**
0.16
**
**
**
**
0.12
0.28
**
2C
**
**
**
**
**
0.13
**
**
**
**
0.16
**
**
**
**
0.12
0.41
0.13
2D
**
**
1.00
0.92
**
**
9.14
Between Dams
3A
**
**
**
**
**
**
**
**
**
**
0.12
**
**
**
**
**
0.12
0.00
3D
**
**
**
0.12
0.11
0.18
**
**
**
0.10
0.30
**
**
**
0.16
0.22
1.19
0.51
3E
**
**
**
**
0.17
**
0.18
**
**
0.13
**
0.24
**
**
0.12
0.13
0.20
1.17
0.30
Esslingen
5A
**
**
0.13
0.48
0.32
**
**
0.15
3.61
SB
**
**
**
**
**
**
**
**
**
**
**
0.19
**
**
**
0.16
0.14
0.49
0.00
5C
**
**
**
**
**
**
**
**
**
**
**
0.13
**
**
**
**
**
0.13
0.00
Camp Marina
6A
**
**
0.11
0.21
0.16
0.22
**
**
0.14
0.11
0.56
2.16
6C
0.22
**
0.48
**
0.38
**
0.17
0.17
3.39
6D
0.22
0.22
0.79
0.48
**
0.19
0.26
6.72
6deep
400.00
16.00
330.00
180.00
210.00
170.00
90.00
43.00
67.00
130.00
13.00
290.00
250.00
56.00
27.00
840.00
340.00
3452.00
869.00
LEL
(ppm)
*
0.22
0.32
0.37
0.24
0.17
0.34
0.6
0.75
0.19
0.2
0.56
0.49
4
SEL
(ppm)
*
370
1480
1440
1340
320
460
130
1020
160
320
95C
85C
10000
*from Ontario Guidelines (1993)
**below LOD
Exceeds Severe Effects Level
-46-
-------
Table 18. Comparison of Sheboygan River Camp Marina Area Total PAH
Concentrations with Other Urban Streams
Streams (Reference)
Sheboygan River Near Camp Marina (this study)
Sample ID
6A
6C
6D
Sample Depth
0-6"
0-6"
0-6"
Total PAH
Concentration (mg/kg)
5.35
9.67
15.10
Sheboygan River Near Camp Marina (NRT, 1998)
Milwaukee River Basin Streams
(Masterson and Bannerman, 1995)
Beaver Creek
Lincoln Creek
SD-701B
SD-702A
SD-702B
SD-704B
SD-706C
0-10"
0-16.75"
0-15.25"
0-23"
0-11"
0.08
0.16
0.83
443.60
1.24
BV-05
BV-01
LC-09
LC-10
LC-11
LC-12
0-10 cm
0-10 cm
0-10 cm
0-10 cm
0-10 cm
0-10 cm
28.52
79.45
14.33
34.04
21.23
42.43
Table 19. Average Total PAH Concentrations in Benthic Macroinvertebrates.
Sample Site
Reference
Rochester
Between Dams
Esslingen
Larval
6.50
37.10
32.95
104.15
Emergent
15.05
30.98
42.58
89.1
Crayfish
**
**
**
**
Table 20. Average SPMD Total PAH Concentrations for Both Deployment Periods.
Site
Reference
Rochester
Esslingen
Camp Marina up
Camp Marina down
Total PAH Concentrations (ng/g
First Deployment
179.13
827.17
1696.90
2914.70
2894.20
Second
lipid)
Deployment
198.85
333.37
822.10
2313.05
1754.13
-47-
-------
HEAVY METALS
Heavy metal concentrations (As, Cr, Cu, Pb, Hg, Se, Cd, Ag) were analyzed for sediment at segments 1,
2, 3, 5 and 6 and for macroinvertebrates at segments 1, 2, 3 and 5 (Tables 21 and 22). Average heavy
metal sediment concentrations were generally similar to sediment concentrations in urban streams studied
in Milwaukee County (Masterson and Bannerman, 1995). Cadmium concentrations exceeded the
Ontario Guideline's lowest effects level threshold (LEL) at the four downstream sites. Copper
concentrations exceeded the LEL at the Rochester, Esslingen and Camp Marina sites, while lead exceeded
the LEL at the Esslingen and Camp Marina sites. With the exception of copper (for crayfish) and lead,
most of the heavy metal tissue concentrations in benthic macroinvertebrates were similar to the reference
site. Emergent invertebrate tissue lead concentrations, however, were two to six times greater at the
reference site than the downstream sites. The higher copper concentrations in crayfish are not surprising.
Arthropods have hemocyanin for transporting oxygen through their blood (Pennak, 1978). This protein
contains copper as the oxygen binding agent.
Table 21. Average Sediment Heavy Metal Concentrations.
Metal
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Selenium
Silver
Reference
Cone.
1.16
**
14.60
13.72
9.60
0.07
0.48
**
n
5
5
5
5
5
5
5
Rochester
Cone.
0.88
1.60
13.26
33.44
19.40
0.09
0.26
6.00
n
5
2
5
5
5
5
5
1
Between Dams
Cone.
0.85
0.80
13.08
14.16
12.20
0.05
0.25
**
n
5
2
5
5
5
5
5
-
Esslingen
Cone.
1.00
1.45
18.00
27.50
40.00
0.04
0.31
**
n
4
2
4
4
4
4
4
-
Camp Marina
Cone.
1.35
1.30
22.40
32.20
53.20
0.08
0.35
**
n
5
1
5
5
5
5
5
-
-48-
-------
Table 22. Average Macroinvertebrate Heavy Metals Concentrations.
Site
Reference
Rochester
Betw. Dams
Esslingen
Tissue
type
Larval
Emergent
Crayfish
Larval
Emergent
Crayfish
Larval
Emergent
Crayfish
Larval
Emergent
Crayfish
n
4
4
3
4
4
3
4
4
3
4
4
3
Metal
As
0.18
0.10
0.60
0.18
0.15
0.50
0.13
**
0.53
0.10
0.10
0.57
Cd
0.018
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.05
0.02
0.01
Cr
0.68
0.13
0.37
0.75
0.10
0.30
0.75
0.13
0.50
0.95
0.15
0.33
Cu
3.38
9.30
16.67
3.90
7.83
23.67
3.98
7.30
22.67
4.85
8.88
28.67
Pb
0.46
0.76
0.14
0.74
0.13
0.22
0.55
0.32
0.27
1.07
0.31
0.45
Hg
0.03
0.06
0.04
0.02
0.05
0.02
0.02
0.03
0.02
0.02
0.04
0.03
Se
0.49
0.86
0.29
0.45
1.05
0.39
0.31
1.07
0.37
0.41
1.11
0.34
Ag
0.01
0.02
0.07
0.01
0.02
0.07
**
**
0.05
**
0.01
0.03
-49-
-------
CONCLUSIONS
Average total PCB concentrations in sediment, macroinvertebrates and some fish species were
higher near the siource of PCB contamination ad decreasaed downstream. It is unclear why
longnose dace, young smallmouth bass and young white suckers had higher PCB tissue
concentrations at the Between Dams site.
PCBs bioaccumulate significantly through the food chain in the Shebogyan River, even at the
Esslingen site, with average sediment concentrations of less than 2.0 mg/kg. PCBs accumulate
with increasing concentrations from sediment to macroinvertebrates to fish.
The 22 most toxic PCB congeners accumulate through the food chain following the same
pattern a the "routine" congeners. These toxic congeners account for 23-34 percent of the total
at the contaminated sites.
Average PCB concentrations for all homolog groups at the contaminated sites increased from
sediment with increasing trophic levels as follows: crayfish
-------
Average total PAH concentrations in SPMDs incrased from upstream to downstream for both
deployment periods. This is consistent with the pattern of increasing PAH concentrations with
increasing urbanization.
Heavy metal concentrations in sediment were similar to sediment concentrations in Milwaukee
County streams. Cadmium concentrations exceeded the lowest effects level at all downstream
sites. Copper and lead exceeded the LEL at some sites.
Heavy metal tissue concentrations for most macroinvertebrates were similar at all sites with the
exception of copper (in crayfish) and lead. Since crayfish contain copper as hemocyanin
(blood protein with copper as the oxygen carrier), this is not suprising.
-5'
-------
REFERENCES
Ankley, G.T., P.M. Cook, A.R. Carlson, D.J. Call, J.A. Swenson, H.F. Corcoran, and R.A. Hoke. 1992.
Bioaccumulation of PCBs from sediments by oligochaetes and fishes: comparison of laboratory and
field studies. Can. J. Fish. Aquat. Sci. 49:2080-2085.
Aulerich, R.J., R.K. Ringer, H.L. Seagran and W.G. Youatt. 1971. Effects of feeding coho salmon and
other Great Lakes fish on mink reproduction. Can. J. Zoo. 49:611-616.
Auerich, R.K., R.K. Ringer and S. Iwanoto. 1973. Reproductive failure and mortality of mink fed on
Great Lakes fish. Journal of Reprod. Pert., Suppl. 19, 365-376.
Aulerich, RJ. and RK. Ringer. 1977. Current status of PCB toxicity to mink and effect on their
reproduction. Env. Cont. and Tox. pp 279-292.
Becker, GC. 1983. Fishes of Wisconsin. The University of Wisconsin Press. Madison, WI. 1052 pp.
Blasland & Bouck Engineers, P.C. 1990. Remedial investigation/enhanced screening report; Sheboygan
River and Harbor. Syracuse, New York.
Blasland & Bouck Engineers, P.C. 1992. Removal action-construction documentation report. Sheboygan
River and Harbor Project. Syracuse, New York Two Volumes.
David, M.M. 1990. PCB congener distribution in Sheboygan River sediment, fish and water. MS Thesis,
U.W. Madison. 158 pp.
Eggold, B.T., J.F. Amrhein and M.A. Coshun. 1994. PCB accumulation by salmonid smolts and adults
and its effect on stocking policies. WDNR files.
Fauble, P. 1998. Personal communication. WDNR Waste Management Program, Madison, WI.
Ferraro, S.P., H. Lee, L.M. Smith, RJ. Ozretich, and D.T. Specht. 1991. Accumulation factors for eleven
polychlorinated biphenyl congeners. Bull. Environ. Contain. Toxicol. 46:276-283.
Geraghty and Miller. 1992. Environmental contamination assessment and groundwater remedial action
alternatives report. Kohler Company Landfill Superfund Site.
Huckins, J.M., M.W. Tubergen and GK. Manuweera. 1990. Semipermeable membrane devices
containing model lipid: A new approach to monitoring the bioavailibility of lipophilic contaminants
and estimating their bioconcentration potential. Chemosphere. 20(5):533-552.
Katsma, D. 1994. Personal communication. WDNR Wildlife Management Program, Plymouth, WI.
Lake, J.L., N.I. Rubinstein, H.Lee, C.A. Lake, J. Heltsche and S. Pavignano. 1990. Equilibrium
partitioning and bioaccumulation of sediment-associated contaminants by infaunal organisms.
Environ. Toxicol. Chem. 9:1095-1106.
Larsson, P. 1984. Transport of PCBs from aquatic to terrestrial environments by emerging chironomids.
Environ. Pollut. Ser. A. 34:283-289.
-52-
-------
Masterson, J.P. and R.T. Bannerman. 1995. Impacts of stormwater runoff on urban streams in Milwuakee
County, Wisconsin. WDNR Report in files.
McFarland, V.A. and J.U. Clarke. 1989. Environmental occurrence, abundance and potential toxicity of
polychlorinated biphenyl congeners: Considerations for a congener-specific analysis. Environ.
Health Perspect. 81:225-239.
Natural Resource Technology, Inc. 1998. Sediment investigation report. Former manufactured gas plant
site, Sheboygan, Wisconsin. For Wisconsin Public Service Corporation, Green Bay, Wisconsin.
Oliver, E.G. and A.J. Niimi. 1988. Trophodynamic analysis of polychlorinated biphenyl congeners and
other chlorinated hydrocarbons in the Lake Ontario ecosystem. Environ. Sci. Technol. 22:388-397.
Ontario Ministry of Environment. 1993. Guidelines for the protection and management of aquatic
sediment quality in Ontario. Ontario, Canada.
Patnode, K. 1995. Personal communication. WDNR Wildlife Toxicology Program, Madison, WI.
Pennak, R.W. Fresh-water invertebrates of the United States. Second Edition. John Wiley & Sons, New
York. 803 pp.
RMT, Inc. 1993. Subsurface investigation summary report and workplan, Wisconsin DOT ID #4996-00-
40; 8th Street Bridge, Sheboygan, Wisconsin.
Safe, S. 1990. Polychlorinated biphenyls (PCBs), dibenzo-/?-dioxin (PCDD), dibenzofurans (PCDF) and
related compounds: Environmental and mechanistic considerations which support the development
of toxic equivalency factors (TEFs). Crit. Rev. Toxicol. 21:51-88.
Schrank, C.S., S.M. Cormier, and V.S. Blazer. 1997. Contaminant exposure, biochemical, and
histopathological biomarkers in white suckers from contaminated and reference sites in the
Sheboygan River, Wisconsin. J. Great Lakes Res. 23(2): 119-130.
Schuettpelz, D. 1992. Water quality and sediment quality criteria for the Sheboygan River Superfund
Site. Correspondence/Memorandum to Mark Giesfeldt, SW/3, July 10, 1992.
Simon Hydro-Search. 1992. Phase I environmental investigation, manufactured gas plant site, Sheboygan,
WI. Prepared for Wisconsin Public Service Corporation, Green Bay, WI.
STS Consultants. 1992. Phase II subsurface contamination assessment. C. Reiss Coal Company Facility,
Sheboygan, WI. Prepared for Koch Carbon, Inc. Project No. 19419XF.
STS Consultants. 1993. Phase III contamination assessment and remedial Action Plan, C. Reiss Coal
Company Facility, Sheboygan, WI. Prepared for Koch Carbon, Inc. Project No. 19419XF.
Willman, E.J., J.B. Manchester-Neesvig, and D.E. Armstrong. 1997. Influence of ortho-substitution on
paterns of PCB accumulation in sediment, plankton, and fish in a freshwater estuary. Environ. Sci.
Technol. 31:3712-3718.
Wisconsin Division of Health and Wisconsin Department of Natural Resources. 1998. Important health
information for people eating fish from Wisconsin waters. Pub. No. FH824 98REV.
-53-
-------
Wisconsin Department of Natural Resources. 1989. The Shebogyan River remedial action plan. PUBL-
WR-211-99. 128pp.
Wisconsin Department of Natural Resources. 1995a. The Sheboygan river remedial action plan update.
October, 1995.
Wisconsin Department of Natural Resources. 1995b. Sheboygan River food chain and sediment
contaminant assessment work plan. GLNPO Grant #GL-995681.
Wisconsin Department of Natural Resources. 1995c. Sheboygan River food chain and sediment
contaminant assessment quality assurance project plan. Grant#GL-995681.
Wisconsin Department of Natural Resources. 1996. Waterfowl Health Advisory in 1996 Wisconsin
hunting regulations.
-54-
-------
APPENDIX A
Photographs Depicting
Sampling Activities
for
Sheboygan River Food Chain Study
-55-
-------
Figure A.1.
Collecting larvae from rocks in riffle
areas of Sheboygan River.
Figure A.2.
Emergent light trap at streamside
(above).
Right: Light trap hanging above
river.
-56-
-------
Figure A.3.
Kick net technique for
collecting crayfish.
Figure A.4.
Collecting fish using
stream electroshocker.
-57-
-------
Figure A.5.
Sediment sampling
device.
Figure A.6.
Semi-permeable polymeric
membrane devices (SPMDs) in
deployment device during first
deployment period.
Figure A.7.
Modified SPMD deployment device
to prevent damage during second
deployment period.
------- |