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Full text of "Identification of toxic substances in the upper Illinois River : final report"

ILENR/RE-WR-92/07 



IDENTIFICATION OF 
TOXIC SUBSTANCE! 
IN THE UPPER .O ^ 

ILLINOIS RIVER 






^i^r--^ 7olo£i: 



(sertraline HO) 




Illinois Department of 
Energy and Natural Resources 



Jim Edgar, Governor 
John S. Moore, Director 



John S. Moore, Director 



' — UUfSois Department of Energy and Natural Resources 



325 West Adams Street. Room 300 

Springfield. IL 62704-1892 

217/785-2800 

Telefax 217/785-2618 



Identification of Toxic Substances in the Upper Illinois River 

ILENR/RE-WR-92/07 



Dr. Frank S. Dillon was the Project Manager for this research endeavor, and made a 
substantial creative contribution to the drafting of the final report. His efforts were 
left unacknowledged inadvertently. 

A corrected title page and NTIS form are attached. ENR regrets the error. 



Printfid on Bervcied Paoer 



ILENR/RE-WR-92/07 
Printed: October 1992 
Reprinted: November 1992 
Contract: WR 3691 
Project: 89/215 



Identification of Toxic Substances in the Upper Illinois River 

Final Report 



Prepared by: 

River Research Laboratory 

Forbes Biological Station 

Illinois Natural History Survey 

P.O. Box 599 

Havana, IL. 62644 



Principal Investigators: 

Richard E. Sparks 
Philippe E. Ross 



Project Manager: 
Frank S. Dillon 



Prepared for: 

Illinois Department of 

Energy and Natural Resources 

Office of Research and Planning 

325 W. Adams, Room 300 

Springfield, IL 62704-1892 



Jim Edgar, Governor John S. Moore, Director 

State of Illinois Illinois Department of 

Energy and Natural Resources 



REPORT DOCUMENTATION -"T^ ^ ....g./O; 



, Tttl» »nd SuMHU *• •'•oort 0*t« 

Identification of Toxic Substances in the Upper Illinois River October 1992 



Philippe E. Ross and Frank S. Dillon 



ng Organization Rapt. No 



River Research Laboratory 
Forbes Biological Station 
Illinois Natural History Survey 
P.O. Box 599 
Havana, IL 62644 



la Proiact/Taak/Worti Un)t No 

89/215 



11. Cantract(C) or GranKC) 
(C) 

,n, WR3691 



12. Sponaonna Orsanxation Nama and Addr««t 

Illinois Department of Energy and Natural Resources 

Office of Research and Planning 

325 West Adams Street 

Springfield, IL 62704-1892 



11. Typa of Rapon & Pariod Covarao 



It. AbMTKt (Umtt .aOO worm) 

Between 1955 and 1958, several abundant species of acquatic 
nail clams practically disappeared from the upper Illinois 
equally drastic repercussions on the populations of ducks a 
invertebrates. The situation changed very little into the 
in water quality. This research found that porewater from 
contains a toxic factor that inhibits the filtering ability 
also negatively effects the water flea, while stimulating a 
All evidence points to ammonia as the toxic agent. Also, a 
contained toxic oil products, including polycyclic aromatic 
naphthalene. A three phase Toxicity Identification and Eva 
utilized in reaching these conclusions. 



insects, snails and finger- 
River. These declines had 
nd fish that fed upon tnese 
1980s, despite improvements 
relevant river sediments 

of fingernail clams and 
Iga and bacteria growth. 
t two sites, the porewater 

hydrocarbons , such as 
luation methodology was 



Water Pollution, Toxicity, Water Pollution Effects (Animals) 
Sedimants, Sedimentation, Suspended Sediments 











Sedimentation - Illinois River 








Toxicity - Illinois River 








Water Pollution - Illinois River 








c. cosATi naid/GcuB Bioloqical and Medical Sciences; 


Environmental Bioloqv 






IS. AvaiiaMiity stMamant jjq restriction on distribution. 


1 19. Sacurtty Claat (Thli Raport) 


21. No. o« Pagai 




Available at IL Depository Libraries or from 
National Technical Information Service, 
SnrinnfiPlh — ]il 


llnclassi f ipii 


7? 




; 20. S«cuntv Claai Ohli Pafa) 

Unc lassi f iea 


22. Pnca 





(Sm ANSt-239.18) 



S— Inatruetiona on Aovaraa 



OPTIONAL FORM 272 ( 

'Formariv NTIS-35) 
Dapartmant of Con>mar 



ILENR/RE-WR-92/07 
Printed: October 1992 
Reprinted: November 1 992 
Contract: WR 3691 
Project: 89/215 



Identification of Toxic Substances in the Upper Illinois River 
Final Report 



Prepared by: 

River Research Laboratory 

Forbes Biological Station 

linois Natural History Survey 

P.O. Box 599 

Havana, IL. 62644 



Principal Investigators: 

Richard E. Sparks 
Philippe E. Ross 



Prepared for: 

Illinois Department of 

Energy and Natural Resources 

Office of Research and Planning 

325 W. Adams, Room 300 

Springfield, IL 62704-1892 



Jim Edgar, Governor John S. Moore, Director 

State of Illinois Illinois Department of 

Energy and Natural Resources 



This report has been reviewed by the Illinois Department of Energy and Natural Resources (ENR) and 
approved for publication. Statements made by the author may or may not represent the views of 
the Department. Additional copies of this report are available through the ENR Clearinghouse at 
800/252-8955 (within Illinois) or 217/785-2800 (outside Illinois). 



Printed by the Authority of the State of Illinois. 
Date Printed: 

Quantity Printed: 

Referenced Printing Order: 



October 1992 

Reprinted: November 1992 



250 

200 reprints 



One of a series of research publications published since 1975. This series includes the following 
categories and are color coded as follows: 



Energy Resources 
Water Resources 
Air Quality 
Environmental Health 
Insect Pests 
Information Services 
Economic Analysis 



-RE-ER 

-RE-WR 

-RE-AQ 

-RE-EH 

-RE-IP 

-RE-IS 

-RE-EA 



-Red 

-Blue 

-Green 

-Grey 

-Purple 

-Yellow 

-Brown 



Illinois Department of Energy and Natural Resources 
Office of Research and Planning 

325 West Adams, Room 300 

Springfield, Illinois 62704-1892 

217/785-2800 



Printed on Recycled Paper 



ACKNOWLEDGEMENTS 

This research was administered and partially funded by the Illi- 
nois Department of Energy and Natural Resources (IDENR), with the bal- 
ance of funding from the Illinois Environmental Protection Trust Fund. 
The development of the fingernail clam bioassay, one of five bioassays 
used in this project, was funded separately by grant F-94-R from the 
Federal Aid in Fish Restoration Program (Wallop-Breaux Act), adminis- 
tered by the Illinois Department of Conservation. 

Many people contributed to this project. Dr. Anthony A. Paparo, 
Department of Zoology and School of Medicine, Southern Illinois Univer- 
sity at Carbondale, did much of the early development of a variety of 
methods for assessing responses of clams and mussels to contaminants. 
Ms. Diane Dillon and Mr. Jeffrey Arnold provided valuable technical 
assistance at Western Illinois University, as did Ms. Louann Burnett at 
the Natural History Survey in Champaign, and Mr. K. Douglas Blodgett at 
the Natural History Survey's Long Term Resource Monitoring Station in 
Havana. Ms. Camilla Smith provided secretarial assistance at the River 
Research Laboratory of the Stephen A. Forbes Biological Station in 
Havana. The research could not have been done without the laboratory 
facilities, office space, and equipment provided by Dr. Richard V. 
Anderson and the Department of Biological Sciences at Western Illinois 
University--to both we express our great appreciation. This project 
would not have come into being without the sustained interest of Dr. 
John Marl in, Director of the Illinois Pollution Control Board, in the 
mysterious die-off of fingernail clams in the Illinois River and the 
widespread ecological repercussions of their failure to recolonize. 
Finally, we thank our project officers at DENR, Ms. Linda Vogt and Mr. 
Will iam Denham. 



TABLE OF CONTENTS 

Executive Summary xi 

1.0. Introduction 1 

2.0. Project Goals and General Approach 9 

3.0. Methods 11 

3.1. Site Description 11 

3.2. Sampling Design 12 

3.2. Sample Collection Procedures 12 

3.3. Chemical analysis 15 

3.4. Bioassays 16 

3.5. Toxicity identification and evaluation procedures 20 

3.5.1. Phase 1 20 

3.5.2. Phase II 21 

3.5.3. Phase III 24 

4.0. Results 25 

4.1. Relative toxicity 25 

4.2. Toxicity Identification Evaluation - Phase 1 29 

4.2.1. 1990 29 

4.2.2. 1991 32 

4.3. Toxicity Identification Evaluation - Phase II 32 

4.4. Toxicity Identification Evaluation - Phase III 40 

4.5. Sensitivity of Recolonizing Clams 42 

5.0. Discussion. 45 

6.0. Li terature C i ted 53 



LIST OF FIGURES 

Figure 1.1. Sampling stations on the Illinois Waterway 2 

Figure 1.2. Sampling stations in the Chicago area 3 

Figure 1.3. TIE procedures 7 

Figure 1.4. Phase I procedures 8 

Figure 4.1. Results of toxicity tests with five test species 26 

Figure 4.2. Fingernail clam response to porewaters 28 

Figure 4.3. Correlation of toxicity with ammonia 41 



LIST OF TABLES 

Table 3.1. Location of sampling stations 13 

Table 4.1. Toxicity of porewater to Ceriodaphnia dubi'a 30 

Table 4.2. Results of treating sediment porewater 1990 31 

Table 4.3. Toxicity and ammonia concentrations 33 

Table 4.4. Results of treating sediment porewater 1991 34 

Table 4.5. Results of treating sediment porewater with zeolite... 35 

Table 4.6. Toxicity of sediment porewater 37 

Table 4.7. Toxicity of extracts from sediment porewater 38 

Table 4.8. Constituents of elutriates 39 



EXECUTIVE SUMMARY 

In a brief span of 3 years, 1955-1958, several abundant species of aquatic 
insects, snails, and fingernail clams practically disappeared from a 170-km reach 
of the Illinois River, from Hennepin on the north to the mouth of the Sangamon 
River on the south. The declines of the fingernail clam, Musculium transversum, 
were particularly spectacular: from average densities of 21,000 animals per square 
meter to zero in Peoria Lake and backwater lakes near Havana. The declines had 
drastic repercussions on the ducks and fish that fed upon the invertebrates. The 
lesser scaup duck, or bluebill, virtually stopped using the Illinois River as a major 
migration route, and there was a decline in the condition and growth of bottom- 
feeding fish, including sport fish, -such as channel catfish, and commercially 
important species, such as common carp. 

The situation changed very little into the 1980s, despite improvements in 
water quality (e.g., higher disolved oxygen levels attributable to improved waste 
treatment in the Chicago-Joliet area and Peoria). This lack of recovery was espe- 
cially puzzling because the- invertebrates are capable of rapidly recolonizing 
barren areas; seed populations are available in spring-fed areas of Peoria Lake and 
in tributaries and these organisms have short, rapid life cycles. 

We found that porewater from Illinois River sediments contains a toxic 
factor that inhibits the filtering ability of the clam, and the toxicity increases 
upstream, peaking near Lockport. We observed the same pattern of sediment 
toxicity with a different test organism, also representing a class of important food 
organisms for fish and waterfowl: the water flea, Ceriodaphnia dubia. In contrast, 
the porewater actually stimulates an alga and bacteria, but this is not surprising 
because of the great physiological differences among plants, bacteria and animals. 

Toxicity greatly decreased when the porewater was made slightly more acid 
and porewater became nontoxic when filtered through a resin that removed 
ammonia. Removal of heavy metals with a chelating agent had no effect on toxic- 
ity. All the evidence points to ammonia as the culprit, especially since toxicity in 
all tests correlated highly with the concentration of ammonia, which is known to 
be toxic to aquatic animals. Since ammonia is a nutrient for plants and certain 
types of bacteria, the presence of ammonia likewise could explain the stimulation 
of these organisms. 

Although ammonia appears responsible for the major upstream-downstream 
pattern in toxicity, there were two sites where the porewater contained visible 
signs of oil and the toxicity was associated with petroleum hydrocarbons, includ- 
ing PAHs (polycyclic aromatic hydrocarbons) such as naphthalene. 

During the course of this study, several species of fingernail clams, includ- 
ing M. transversum, reappeared in the Chicago area waterways and in the Illinois 
River at Peoria and Havana. There are at least four possible explanations for this 
surprising reappearance of clams in the same general areas where the porewaters 
tested toxic. First, we found that clams recolonizing the upper Illinois are more 
resistant to ammonia than the clams from the lower Illinois, where the organisms 
were obtained for all of the early bioassays. Second, our previous research demon- 
strated that the surface layers of sediment in some areas are less toxic than layers 
a few centimeters deeper. Toxicity may have been overestimated in tests where 
surface and deep layers of sediment were mixed prior to testing. Third, toxic 
episodes may be brief and infrequent, allowing organisms to colonize in between 
episodes. Fourth, the distribution of toxicity in sediments may be extremely 
patchy, so that healthy organisms are found adjacent to barren areas. If the latter 
two hypotheses prove to be true, acute toxicity in the Illinois River has changed 
recently from a widespread problem to a more localized or episodic problem. 
Reduction of toxicity in surface sediments may reflect recent reductions in 
ammonia loading from sewage treatment plants in the Chicago area, although it is 
not clear whether the sources of ammonia in the porewaters are effluents, the 
deeper layers of sediments, or both. 



1.0 INTRODUCTION 

The quality of sediments is critical to the ecological health of 
aquatic ecosystems. Benthic organisms that live in sediments are key 
links in food chains that lead from nutrients in water and sediment to 
higher level consumers, such as fish and ducks. Sediments in aquatic 
systems can be both sinks and sources for inorganic and organic contami- 
nants. At present,. the extent of the sediment contamination problem is 
largely unknown. Comprehensive assessments of the accumulation of 
contaminants from agricultural, municipal, and industrial sources in 
sediments of our rivers, lakes and estuaries have not been completed. 
Currently, the U.S. Environmental Protection Agency has identified 134 
sites with serious sediment contamination problems (USEPA 1988). In 
addition, 41 areas in the Great Lakes (IJC 1988), 50 coastal sites, and 
85 wildlife refuges have been identified where contaminated sediments 
pose a problem (USEPA 1988). 

In Illinois, contaminants have been identified in sediments 
throughout much of the Illinois River and its associated tributaries and 
waterways (Figures 1.1 and 1.2; Cahill and Steele 1986; Cahill and 
Autrey 1987; Blodgett et al . 1984; Mathis et al . 1973; Polls et al . 
1985; Harrison et al . 1981; Coleman and Sanzolone 1991; Bhowmik and 
Demissie 1989; Sparks and Blodgett 1984; and Fitzpatrick and Bhowmik 
1990). Two-thirds of the population of the state lives in the Illinois 
River basin which drains approximately half the state (Talkington 1991). 
The river historically has been one of the most productive rivers in 
North America in terms of fish and wildlife populations. In 1908, 



Des Plaines 
River 



•^•-) Detailed Map 




Ohio River 



Figure 1.1. Location of sediment sampling stations on the Illinois Waterway. 
Stations are identified according to river miles: Illinois River miles (IR) 
start at Grafton at mile 0.0 and proceed upstream to Chicago. A reference 
station was established on the Mississippi River (MR), 377 miles above the 
confluence with the Ohio River. ^ 




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a 320-km (200-mile) reach from the great bend at Hennepin to the conflu- 
ence with the Mississippi River at Grafton (Figure 1.1) produced 10% of 
the total U.S. harvest of freshwater fish and two thousand commercial 
fisherman made a living from the river (U.S. Department of Commerce and 
Labor 1911). The commercial yield was 24 million pounds annually, or 
about 178 pounds per acre of permanent water (Lubinski et al . 1981). By 
the 1950s the yield had dropped to 38 pounds per acre; since the 1970s 
the yield has been a low 4 pounds per acre, totaling only 0.32% of the 
total U.S. catch (Sparks 1984). Similar downward trends were recorded 
over the same period for two other indicators of biological 
productivity: waterfowl and sport fish populations (Bellrose et al . 
1979; Sparks 1977; Sparks 1992). Major commercial fish species and the 
diving ducks feed on bottom-dwelling invertebrates such as clams, 
snails, aquatic worms, and aquatic insects. In the early 1900's a 
healthy benthic community contributed to the tremendous production of 
fish and waterfowl. A major component of that benthic community was a 
small clam, Musculium transversum (Family Sphaeriidae) . Now, this clam 
as well as other small mollusks, mayflies, midges, and other burrowing 
aquatic insects has been virtually eliminated from certain reaches of 
the Illinois River (Starrett 1972, Anderson 1977, Sparks et al . 1986). 

Declines in the benthic invertebrates of the Illinois River system 
have been linked to sediment-associated toxicity (Sparks et al . 1981; 
Blodgett et al . 1983; Sparks 1984). Aquatic sediments can accumulate 
both inorganic and organic chemicals that are absorbed to particulate 
matter or are in solution in sediment porewater (Salomons et al . 1987, 
Tessier and Campbell 1987). Porewater (also called interstitial water) 
is the water occupying the spaces between the sediment particles. These 



contaminants can have acute toxic effects on benthic organisms, or 
accumulate slowly in the organisms until some toxic threshold is 
reached. 

The toxicity to aquatic organisms is known for only a fraction 
(<1%) of the approximately 50,000 compounds manufactured in the U.S. 
(Martell et al . 1990). This situation is further complicated by the fact 
that organisms usually are simultaneously exposed to a number of chemi- 
cals (Giesy et al . 1990). The toxic responses associated with these 
mixtures of compounds depends on their bioavailability--some contami- 
nants are bound to sediment particles or otherwise unavailable to organ- 
isms. For instance, the bioavailability of non-ionic organic compounds 
depends on the total organic carbon content (TOC) of the sediment 
(Nebeker et al . 1989, Swartz et al . 1990, Di Toro et al . 1991) and the 
bioavailability of certain cationic metals depends on the acid-volatile 
sulfide (AVS) content of the sediment (Di Toro et al . 1990, Ankley et 
al. 1991, Carlson et al . 1991). Due to the complex mixtures of contami- 
nants present in most toxic sediments, as well as the effects that 
sediment matrices may have on the bioavailability of compounds, it has 
been difficult to link specific compounds with toxicity. The tradition- 
al approach to identifying toxic agents has been to correlate toxicity 
with the concentrations of chemicals in the bulk sediment sample (Carr 
et al . 1989). This approach does not work well with complex mixtures 
and does not address the question of bioavailability. The dose response 
curve for biological effects from certain chemicals is not correlated to 
the bulk sediment concentration but rather to the porewater concentra- 
tion (Di Toro et al . 1991). The recent development of Toxicity Identi- 
fication and Evaluation (TIE) methodology has made it possible to iden- 



tify specific toxic compounds in complex mixtures (Figure 1.3; Mount and 
Anderson-Carnahan 1988; Mount and Anderson-Carnahan 1989; Mount 1988). 

TIE procedures use toxicity-based fractionation schemes to charac- 
terize and identify compounds in aqueous samples that exhibit toxicity 
to aquatic organisms. Although TIE cannot be used on bulk sediments, it 
can be applied to the aqueous fraction (porewater). Previous studies 
(Adams et al . 1985; Swartz et al . 1985; Knezovich and Harrison 1988; 
Connell et al . 1988; Swartz et al . 1988, Di Toro et al . 1992) have shown 
a correlation between toxicity or bioaccumulation of a number of contam- 
inants by benthic macroinvertebrates, on the one hand, and porewater 
concentrations on the other. The TIE procedures are designed to address 
multiple toxicant interactions as well as matrix effects on bioavail- 
ability. The major strength of TIE is that it allows direct relation- 
ships to be established between toxicity and chemical analyses. TIE is 
a phased approach that is designed to isolate, identify and confirm the 
presence of acutely toxic compounds. TIE methodology for identification 
of chronically toxic compounds is currently under development (USEPA 
1992). Phase I of TIE consists of a series of chemical and physical 
manipulations designed to remove or render biologically unavailable 
generic classes of compounds (Figure 1.4). Phase II uses information 
from Phase I to focus appropriate analytical methods on toxic fractions. 
Phase III consists of methods designed to verify that the suspected 
toxicant is the actual toxicant. TIE methodology has been applied to 
sediments from the Great Lakes (Ankley et al . 1990) and the Calumet Sag 
Channel of the Illinois River system (Schubauer-Berigan and Ankley 
1991). We applied these techniques to sediments from the Illinois River 
System in an effort to identify the substance or substances responsible 
for the declines of the benthic invertebrates. 



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2.0 PROJECT GOALS AND GENERAL APPROACH 

The primary goal was to identify the toxicants in the sediments of 
the Illinois Waterway. In addition, we hoped to identify upstream- 
downstream patterns in toxicity and follow toxicity gradients upstream 
to sources. 

We tested the toxicity of sediments taken widely along the entire 
length of the Illinois Waterway, and from one reference site on the 
Upper Mississippi River (Figures 1.1 and 1.2). Next, sediments that 
exhibited toxicity were subjected to Phase I Toxicity Identification and 
Evaluation (TIE) procedures (pH adjustment, addition of a chelating 
agent, etc.), to characterize the toxicants (see Figures 1.3 and 1.4). 
If the toxicity at all sites varied the same way in response to the 
Phase I treatments, we would know we were dealing with one class of 
toxicants, or perhaps even one major toxicant, and we could focus 
additional sampling on the most toxic reach in the hope of identifying 
the major source. At the same time. Phase II and Phase III TIE 
procedures would confirm the identity of the toxicant or at least narrow 
the range of suspect chemicals. However, if Phase I testing indicated 
that different classes of toxicants occurred in different reaches of 
the waterway, then we would have a much more complex task of identifying 
multiple toxicants and multiple sources--a task that might extend well 
beyond the budget and time limitations of this research. 



3.0 METHODS 

3.1 Site Description 

Today's Illinois Waterway is approximately 327 miles (526 km) long 
connecting Lake Michigan and the Chicago-Joliet metropolitan area with 
the Mississippi River and the agricultural heartland, near Grafton, 
Illinois (Figure 1.1). The headwaters are in the highly industrialized 
Chicago area where the flow of the Chicago River was reversed to carry 
wastes away from Lake Michigan into the Illinois River via the Chicago 
Sanitary and Ship Canal and the downstream portion of the Des Plaines 
River (Figure 1.2). The Calumet Sag Channel enters the Sanitary and 
Ship Canal near Lemont. The Illinois River proper begins with the 
confluence of the Des Plaines and Kankakee rivers, and flows through a 
predominantly agricultural drainage, although the industrial city of 
Peoria is situated approximately mid-way along the waterway. 

Locations on the waterways are designated by river mile as record- 
ed in river charts prepared by the U.S. Army Corps of Engineers (1987) 
and by markers along the waterways, starting with mile 0.0 at the con- 
fluence with the Mississippi and proceeding upstream to Chicago. The 
following abbreviations are used in the text, figures, and tables to 
identify reaches of the waterway, and stations are identified by reach 
abbreviation and river mile: 

IR Illinois River proper 

DP Des Plaines River 

CS Calumet Sag Channel 

SS Chicago Sanitary and Ship Canal 

CR Chicago River 



11 



The one reference station on the Upper Mississippi River is located 
377.0 miles above the confluence with the Ohio River and is designated 
MR 377.0. The locations of the sample stations are given in Table 3.1 
and Figures 1.1 and 1.2. In accordance with Corps of Engineers termi- 
nology, the designation "left bank" or "right bank" assumes the observer 
is facing downstream. 

3.2 Sampling Design 

Nineteen sampling stations were established throughout the 
Illinois Waterway (Figures 1.1 and 1.2). Samples were collected from 15 
stations from November 1989 to June 1990, and from all 19 stations from 
November 1990 to June 1991 (Table 3.1). 

3.2 Sample Collection Procedures 

It is important to limit the disruption of the sediment so that 
toxicity evaluations are conducted under conditions that closely match 
the in situ conditions (ASTM 1991). The most appropriate sediment 
sampling device is study specific. Sediment corers generally disrupt 
the sediment little but collect a limited sample volume (ASTM 1991). 
This study employed a battery of bioassays as well as the TIE proce- 
dures, all of which used sediment porewater. The volume of porewater 
needed for this work made the use of sediment corers impractical. We 
used a 25.4 cm (10-inch) Ekman dredge that works well in the soft to 
semi-soft sediments that characterize the Illinois Waterway and collects 
a relatively large sample volume (ASTM 1991). 



12 



Table 3.1. Location of sampling stations. 



River Mile Description 



North Branch of Chicago River at Michigan Avenue Bridge 
South Branch of the Chicago River at Harrison Street Bridge 

Upstream of Division Street Bridge on Calumet Sag Channel 
Upstream of 104th Street Bridge on Calumet Sag Channel 

-5 m from left bank 

-25 m from left bank 

-2 m from right bank downstream of Route 171 Bridge 

-10 m from left bank upstream from Justice Navigation Light 

10 m upstream of sunken barge and 30 m from right bank 

Left bank -300 m upstream of Brandon Road Lock and Dam 

-30 m from left bank across from 01 in Chemical 

Upstream of Du Page River Daymark -500 m from right bank 

-100 m upstream of Bal lards Island 

Center of Turner Lake 

Upper Peoria Lake, south of Chill icothe 

SE Corner of Lake Chautauqua 

Center of Meredosia Lake 

Entrance to Swan Lake 

MR 377.0 Montrose Flats, Pool 19, Mississippi River 



Note: The Illinois Waterway includes the Illinois River (IR), Des 
Plaines River (DP), Chicago Sanitary and Ship Canal (SS), Chicago river 
(CR), and Calumet Sag Channel (CS). The mileages start at IR 0.0 at the 
confluence with the Mississippi and proceed upstream to Chicago. Mile- 
ages on the Upper Mississippi River (MR) start at the confluence with 
the Ohio. "Right" and "left" assume the observer is facing downstream. 
m = meters. 



CR 


326 


.4 


CR 


324 


.8 


CS 


318 


.5 


CS 


307 


.4 


SS 


317 





SS 


315 


3 


SS 


313 





SS 


310 





SS 


292 


2 


DP 


286 


3 


DP 


281 


1 


DP 


277 





IR 


248 


2 


IR 


215 





IR 


180 





IR 


125 


5 


IR 


72 





IR 


6 






13 



The sampler was rinsed with river water at the site prior to 
sediment collection. The sample was placed in prewashed (Biosoap wash, 
ultrapure water rinse) high density polyethylene containers. High 
density polyethylene containers are relatively inert and are optimal for 
samples contaminated with a variety of chemicals (ASTM 1991). The con- 
tainers were filled completely to achieve zero sample head space. 
Sample containers were placed on ice as soon as possible following 
collection (never exceeding 2 hours). Samples were transported to the 
laboratory and stored at 4°C for no more than two weeks as recommended 
by Anderson et al . (1984). 

We used sediment porewater in our toxicity tests. Numerous stud- 
ies (Adams et al . 1985; Swartz et al . 1985; Knezovich and Harrison 1988; 
Connell et al . 1988; Swartz et al . 1988, Di Toro et al 1992) have shown 
that porewater is an appropriate surrogate for bulk sediment. Porewater 
can be collected from sediment samples by several methods: 
centrifugation, squeezing, suction, and equilibrium dialysis (ASTM 
1991). Centrifugation is generally used if large volumes of porewater 
are required (Edmunds and Bath 1976). Constituents such as salinity, 
dissolved inorganic carbon, ammonia, sulfide, and sulfate are generally 
not affected as long as oxidation is prevented; however, dissolved 
organic carbon (DOC) and dimethyl sufide may be significantly reduced 
using this method (Howes et al . 1985). Sediment porewater was extracted 
by centrifugation at 4000 g (g = the acceleration due to gravity) at 4°C 
for 45 minutes. Sample porewater was stored with zero head space at 4°C 
in a decontaminated cubitainer for a maximum of 1 week. The time from 
collection to testing ranged from 1 to 6 days, and averaged 2.6 days for 



14 



all sediments. 

Surface water samples were collected just prior to collection of 
sediment. Surface water was collected from approximately mid-depth in 
the water column using a Van Dorn sampler. Samples were placed in pre- 
cleaned cubitainers and immediately placed on ice. Surface water sam- 
ples were stored at 4°C for a maximum of one week. 

3.3 Chemical Analysis 

Routine chemical measurements were taken on both surface water and 
porewater samples. Samples were brought to ambient temperature (20- 
24°C) prior to making the following measurements: 

SURFACE WATER PORE WATER 

Dissolved Oxygen Dissolved Oxygen 

pH (negative log of the hydronium pH 

ion concentration (minus {H''"))) Conductivity 

Alkalinity 

Conductivity Hardness 

Alkalinity Total Ammonia-N 

Hardness Total CI (chlorine) 

Total Ammonia-N (ammonia measured H2S (hydrogen sulfide) 

as nitrogen, N) Sulfide 

Dissolved oxygen was measured using a standard Y.S.I. Model 57 
oxygen meter with a Y.S.I. Model 5739 probe. Temperature and pH were 
measured using a Jenco Microcomputer pH-Vision 6071 pH meter with a 
temperature-compensating Ross electrode. Specific conductance was 
measured using a Y.S.I. Model 35 Conductance Meter with a Y.S.I. Model 
3401 probe. Total alkalinity was measured using the ASTM (1982) stand- 
ard titration method. Total hardness was measured using the EDTA titra- 
metric method (APHA 1989). Total ammonia nitrogen was determined using 
the Nesslerization method (APHA 1989), total residual chlorine by the 
DPD colorimetric method (APHA 1989), sulfide by the methylene blue 



15 



method (APHA 1989) and hydrogen sulfide by the lead sufide method. All 
instrumentation was calibrated prior to testing. 

We intended to calculate the fraction of the total ammonia that 
existed in the un-ionized state during the toxicity tests (see below). 
In aqueous ammonia solutions an equilibrium exists between ammonia in 
the highly toxic un-ionized form (NH3) and ammonia in the relatively 
nontoxic ionized form {NH4"''). The dominant factor regulating the 
equilibrium between the two forms is pH, with the temperature having a 
lesser effect. We were not able to calculate un-ionized ammonia 
concentrations in the toxicity tests because the pH of the porewater 
drifted slightly during the tests. Temperature was held constant. 
However, our subsequent analysis of the correlation between toxicity and 
total ammonia is justified because the initial pHs of the samples were 
similar (6.5-7.25) and all drifted in a similar manner, so the un-ion- 
ized ammonia concentrations were some consistent fraction of the total 
ammonia concentrations in all the test chambers. 

Measurements of total organic carbon (TOC) were performed on bulk 
sediment samples. The results are expressed in percent organic 
carbon. 

3.4 Bioassays 

Burton (1991) described several components that should be consid- 
ered in selecting a bioassay for toxicity assessment: 

Components of an Optimal Toxicity Assay 

1. Verification components 

Ecosystem relevance 

Species sensitivity patterns 

Appropriate test phase 

Short or long exposure period 

Definitive response dynamics 

16 



2. Resource components 

Organism availability 
Laboratory availability 
Expertise required 
Expense and time required 

3. Standardization components 

Approved standard methods 

Reference data base 

Interlaboratory validation 

Quality assurance and control criteria 



Verification components such as ecosystem relevance, sensitivity, and 
discriminatory ability are so critical that multiple species and end- 
points should be incorporated in testing programs for sediment toxicity 
assessments, according to Burton (1991). Therefore we measured the 
relative toxicity of the sediment porewater with a battery of bioassays 
that included the following test organisms: the marine bacterium, Photo- 
bacterium phosphoreum (Microtox''^), the freshwater alga, Selenastrum 
capricornutum, the rotifer, Branchionus calyciflorus, the daphnid, 
Ceriodaphm'a dubia, and the sphaerid clam, Musculium transversum. The 
Microtox''^ assay measures the luminescence of P. phosphoreum (Bulich et 
al . 1981). Inhibition of this luminescence is considered a toxic re- 
sponse. The 5. capricornutum assay measures the inhibition of photosyn- 
thetic activity of an algal culture as a measure of toxicity (Ross et 
al . 1988). The rotifer assay is a mortality test (Snell and Personne 
1989). The C. dubia assay was the standard USEPA (1985) acute assay 
(48-hour mortality). The sphaerid or fingernail clam assay is based on 
measuring changes in filtering rates. The dilution water used in the 
toxicity tests and for maintaining the organisms was Perrier'^ bottled 
water. 



17 



The fingernail clam filtering assay used in this study is based on 
observations by Aldridge et al . (1987), Sparks and Sandusky (1983), 
Sparks et al . (1981), and Anderson et al . (1978) that stresses, includ- 
ing toxicants, impair the ability of bivalves to filter particles from 
water (including the food particles on which the clams feed). The assay 
is outlined below and a detailed description is given in Sparks et al . 
(1992). Filtering rates are determined by measuring the fingernail 
clams' -ability to filter yeast from a suspension of known concentration. 
Fingernail clams are first exposed to the porewater sample for one hour. 
They are then placed in a yeast suspension and allowed to filter for one 
hour. Two controls are used: the first consists of the yeast suspen- 
sion alone and is used to determine the change in concentration due to 
settling of the yeast. The second control determines the baseline 
filtering rate of clams exposed for 1 hour in clean, uncontaminated 
water. The yeast concentrations are measured at the beginning and end 
of the filtering period. The filtering rates of the exposure and 
control tests are then determined by taking the initial yeast 
concentration minus the final concentration minus the amount settled 
divided by the weight of the test organisms. Filtering rates are 
expressed as the concentration of yeast filtered per unit weight of 
organism per unit time. 

C^ = initial concentration of yeast 

Cf = final concentration of yeast 

W = wet weight of clams, in g (grams) 

C3 = change in yeast concentration due to settling 

- Cr - C- 

filtering rate in mg (milligrams) yeast/g clam/hour 



18 



The exposure filtering rate is then compared to the control. The test 
result is a sublethal response (percent reduction in filtering rate, 
relative to the control) as opposed to an "all or none" (death or sur- 
vival, toxic or nontoxic) type of response. The inhibition of the 
filtering performance of the clams is proportional to the severity of 
the stress (Sparks et al . 1992). For purposes of evaluating sediments 
for toxicity, it is useful to be able to rank sites based on relative 
toxicity. Only the 1990-1991 porewater samples were evaluated using 
this assay because it was not fully developed until late 1990. 

The results of the various assays were standardized for easier 
comparisons. The treatment results were divided by the control results 
and then 1 was subtracted from the quotient. A negative value indicates 
inhibition (toxicity), a positive value indicates stimulation, and 
indicates no response (no difference with respect to the control). If 
we use the fingernail clam filtering bioassay as an example: 

T = test response to sample of sediment porewater 

C = control response to uncontaminated dilution water 

T = 3.4 mg yeast/g clam/hour 

C = 6.5 mg yeast/g clam/hour 

T/C = 3.4/5.5 = .52 

.52 - 1.00 = -.48 A decline of 48% from the 

control value, a marked inhibition of the filtering 

ability of the clams. 
Results of the C. dubi'a bioassay are expressed in toxicity units, 
as well as 48-hour LC50s, where toxicity units = 100/(48-hour LC50). 
The 48-hour LC50 is the percent dilution of porewater (or treated pore- 
water) that kills 50% of the test organisms in 48 hours. For example, 

19 



if a 7% solution (by volume) of porewater in dilution water is the LC50 
(see site CS307.4, Table 4.1), 

7% = 48-hour LC50 

100/LC50 = 100/7 = 14.3 toxic units 
meaning that the toxicity in the porewater is more than 14 times the 
lethal dose. 

3.5 Toxicity Identification and Evaluation Procedures 

Samples exhibiting acute toxicity to C. dubia were subjected to 
Toxicity Identification and Evaluation (TIE) procedures developed at the 
USEPA's National Effluent Toxicity Assessment Center (NETAC). The goal 
is to separate toxicants from nontoxic compounds, using sample fraction- 
ation techniques in combination with bioassays to determine which frac- 
tions contain most of the toxicity. We used C. dubia as the TIE test 
organism, because it is a widely-accepted reference species. The TIE 
approach consists of three phases outlined in Figure 1.3. 

3.5.1 Phase I characterizes the physical and chemical properties of the 
sample toxicants by altering or rendering biologically unavailable 
generic classes of compounds (Mount and Anderson-Carnahan 1988). After 
Phase I the toxicants are classified as having characteristics of ca- 
tionic metals, non-polar organics, volatiles, oxidants, or substances 
not affected by Phase I methods. Phase I manipulations are outlined in 
Figure 1.4. The primary tool of Phase I is manipulation of sample pH. 
The questions asked are: (1) Is toxicity different at different pHs? 
(2) Does sample manipulation at different pHs affect toxicity? (3) Is 
toxicity attributable to cationic metals, such as copper or lead? (4) 
Is toxicity associated with oxidizing agents, such as chlorine or 



20 



chloramines? The graduated pH test answers the first question and is 
designed to indicate a pH-dependent toxicant such as un-ionized ammonia. 
The second question is answered by performing the following tests at 
different pHs: aeration, filtration and reverse-phase solid phase ex- 
traction (SPE). Aeration tests determine whether toxicity is attributa- 
ble to volatile or oxidizable compounds. The filtration tests indicate 
whether toxicity is associated with filterable components. Reverse- 
phase SPE indicates whether toxicity is attributable to non-polar com- 
pounds. Presence of toxic cationic metals is indicated if addition of a 
chelating agent, ethylenediaminetetraacetic acid (EDTA), diminishes 
toxicity. Presence of chlorine or other oxidizing agents is indicated 
by a reduction in toxicity following addition of the reducing agent, 
sodium thiosulfate. 

3.5.2 Phase II uses chemical fractionation techniques in parallel with 
toxicity tests to isolate suspected toxicants (Mount and Anderson-Carna- 
han 1989). Our Phase I results strongly implicated ammonia as a toxi- 
cant, so we retested the samples after selectively removing ammonia 
using a zeolite ion exchange resin, following the methods of Mount and 
Anderson-Canaragan (1989), Ankley et al . (1990), and Schubauer-Berigan 
and Ankley (1991). Zeolites are naturally-occurring or synthetically- 
created crystalline hydrated alkali -aluminum silicates. A column was 
prepared by packing a glass tube with a commercially available zeolite 
product. The sample was passed over the zeolite column using a metering 
pump, at a flow rate of approximately 10 ml/min (milliliters per minute). 
Post column samples were analyzed for total ammonia and screened for 
acute toxicity. 



21 



In addition to implicating ammonia, Phase I testing also indicated 
that toxicity in some samples was associated with non-polar organic 
materials and with material that was retained on the filters. We 
applied the following Phase II isolation techniques that were used in a 
similar situation by Schubauer-Berigan and Ankley (1991). To verify 
that toxicity was due in part to material retained on the filters, the 
filters were extracted with methylene chloride. Filters used in Phase I 
for samples from the Des Plaines River site DP277.0 and the Calumet Sag 
Channel site CS307.4 were soaked in 10 ml of methylene chloride for 1 
hour. The solvent was evaporated from the beakers and dilution water 
was added to the same volume as the original filtered sample. The 
extracts then were screened for acute toxicity. 

Having checked the toxicity of the material on the filters, we 
next investigated the nonpolar organics using solid phase Cjg absorption 
columns and subsequent chromatography. To maximize the extraction of 
possible toxicants, filtration was omitted and porewater was centrifuged 
at 10,000 g for 30 minutes to remove particles that would clog the Cjg 
column. The supernatant from the centrifugation step was checked for 
toxicity. If toxicity was present, a 200-ml sample of the supernatant 
was passed over a 6-ml Cjg column that had been conditioned with 25 ml 
of methanol followed by 25 ml of Millipore^^ ultrapure water. Post 
column aliquots were collected after passage of 25 ml and 100 ml of 
methanol and tested for toxicity. 

Toxicity was not recovered from the DP277.0 sample using 100% 
methanol elutions of the C^g columns as suggested by Mount and Anderson- 
Carnahan (1989), so we eluted the columns with increasingly nonpolar 
mixtures of methylene chloride in methanol (1, 5, 10, 15, 20, 25, 30, 
35, 40, 45, 50, and 100%) as suggested by Schubaurer-Berigan and Ankley 

22 



(1991). The elutriates were collected in hexane-rinsed scintillation 
vials. Toxicity may not have been recovered by methanol extractions 
because either the toxic compounds or the oil and grease they are sorbed 
to are highly nonpolar. The methylene chloride was evaporated and the 
sample restored to volume using methanol. The fractions were tested for 
toxicity using 150 u^ (microliters), 75 ul , and 37.5 ul of the fraction 
in 10 ml of dilution water. The methanol concentrations were below the 
48-hour LC50 for C. dubia, so toxicity was attributed to the nonpolar 
organic solutes, rather than to the methanol solvent. 

The toxic fractions were sent to Daily Analytical Laboratories in 
Peoria, Illinois for analysis on a Hewlett-Packard 5890A gas chromato- 
graph with a 5970A Series mass selective detector along with a 7673A 
autosampler. The methanol concentrate was injected into a 30-m (meter) 
x 0.25-mm (millimeter)-i .d. DB-5 J&W capillary column. The temperature 
program was 40°C for 4 minutes followed by an increase at a rate of 10° 
C per minute to a peak of 300° C for 10 minutes. Run time was 40 
minutes with a scan start time at 3 minutes. The peak detection 
threshold was 10,000 counts, with a threshold at 100 counts. A 
splitless injection mode was used along with a linear scanning method 
from 40-450 mhz (megahertz). The samples had 40 ug (micrograms)/ml of 
internal standards of the following compounds; l,4-Dichlorobenzene-d4, 
Naphthalene-dS, Acenaphthene-dlO, Phenanthrene-dlO, Chrysene-dl2 and 
Perylene-dl2. After the sample was analyzed by the mass selective 
detector, they were compared to library searches using the NIH (National 
Institutes of Health) EPA (U.S. Environmental Protection Agency) Mass 
Spectral Database. Identifications were based on the best fit with a 
minimum search fit of 70%. 



23 



3.5.3 Phase III confirms the identity of toxicants that are provision- 
ally identified in Phases I and II. We employed two methods from the 
suite of Phase III techniques suggested by Mount (1988): (1) We corre- 
lated toxicity with measured concentrations of suspect chemicals in our 
test solutions, and (2) we compared the relative sensitivity of our test 
species to known toxicants and to our samples. The correlation analy- 
sis was performed on the toxicity tests which used the standard refer- 
ence animal, C. dubia. As mentioned earlier, the correlation analyses 
used total ammonia concentrations, rather than un-ionized ammonia con- 
centrations. The drift in pH during the toxicity tests made it impossi- 
ble to calculate un-ionized ammonia concentrations based on measurements 
of total ammonia and the pH of the test solutions. 



24 



4.0 RESULTS 

4.1 Relative Toxicity 

There were marked differences in the responses of the five test 
organisms to sediment porewater from the same sites (Figure 4.1). 
Luminescence of the marine bacterium, Photobacterium phosphoreum, 
(Microtox test) was inhibited by 34% at SS313.0 on the Sanitary and Ship 
Canal and 32% at CS307.4 on the Calumet Sag Channel. Maximum stimula- 
tion of approximately 50% occurred at the next site upstream on the 
Calumet Sag Channel, CS318.5. Responses to porewaters from other sites 
were slight and variable, sometimes mildly inhibitory and sometimes 
mildly stimulatory. 

Photosynthesis by the freshwater alga, Selenastrum capricornutum, 
was markedly stimulated, by a factor of nearly 2, by sediment porewaters 
from the mouth of Swan Lake, IR6.0, and the Sanitary and Ship Canal, 
SS310.0. Stimulation is an indication of nutrient enrichment; e.g., by 
nitrogen and phosphorus (Ross et al . 1988). The greatest inhibition, 
-86%, was caused by sediment porewater from Lake Chautauqua, IR125.5, 
although inhibition also occurred at IR72.0, IR281.1, SS313.0, SS315.3, 
and CS307.4. 

A large percentage of the rotifers, Branchionus caTciflorus, died 
in porewaters from Meredosia Lake (IR72) and Lake Chautauqua (IR125.5), 
but the rotifers exhibited no significant responses to samples taken 
anywhere else (Figure 4.1). 

In contrast to the microorganisms (bacterium, alga, and rotifer), 
the macroinvertebrates C. dubi'a and M. transversum were remarkably 



25 



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itZM 








-O Q. O <4- 
















fco rs Q) II 


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26 



consistent in their responses to the sediment porewaters. Both organ- 
isms exhibited no inhibitory response to porewaters from the lower 
Illinois River or from the reference site in the Upper Mississippi River 
(Figure 4.1). The stimulation of filtering performance in the finger- 
nail clam, M. transversum, may have been caused by favorable ratios of 
dissolved sodium, potassium, calcium, and magnesium salts in porewaters 
from the lower river. Anderson, Sparks and Paparo (1978) demonstrated 
the importance of these salts in regulating the beating of the cilia on 
the gills of the clams. Salts that affect the cilia are likely to 
affect filtering performance because the lateral cilia produce the water 
currents that bring food into the clam and the latero-frontal cilia act 
as filters. Also, the presence of organic matter in the sediment pore- 
waters may have stimulated a feeding response in the clams, which are 
deposit feeders, as well as water column filterers. The clam and the 
water flea likewise are consistent in indicating toxicity in the upper 
waterway. Filtering performance in the clam was inhibited starting with 
sediment porewaters from IR248.2 near Marseilles and water flea mortali- 
ty started at DP277.0, just above the mouth of the Du Page River near 
the Interstate 55 bridge. Sediment porewaters from 7 of the 13 upstream 
sites were toxic to C. dubia, and 12 of 13 inhibited the fingernail clam 
(Figure 4.1). 

Since the fingernail clam is the organism of main interest in this 
study, the response of the clams is extracted from Figure 4.1 and 
presented separately in Figure 4.2. With the exception of a stimulatory 
response to porewater from one station in the Sanitary and Ship Canal, 
SS315.3, all the upper waterway stations exhibited some degree of 



27 




esuodsay 



e . 



I 5 
- i 

•S i 



28 



M 

a 
s 

1 J 

■■^ s 

ti 
11 



toxicity to the fingernail clam, with the most toxic stations located in 
the reach between the mouth of the Du Page River, DP277.0, and the 
Summit-Stickney area, SS313.0. 

4.2 Toxicity Identification Evaluation - Phase I 

Standard toxicity identification evaluations (TIE) use C. dubia to 
determine whether various treatments reduce the toxicity of porewater. 
We felt it was unnecessary to use the nonstandard clam bioassay in TIE 
because the fingernail clams and C. Dubia responded similarly to the 
sediment porewaters, and C. dubia appeared to be an adequate surrogate 
for the clam. 

Seven sites were acutely toxic to C. dubia in 1990 and 1991, with 
six sites in common between the two years (Table 4.1). One site on the 
upper Calumet Sag Channel, CS318.5, was acutely toxic in 1990 but not in 
1991. The mouth of the Du Page River, DP277.0, was not sampled in 1990. 
The level of toxicity ranged from 1.1 to 14.3 times the lethal dose, 
with the greatest toxicity observed in the Calumet Sag Channel (CS307.4) 
in 1991. The second greatest toxicity (7 times the lethal dose) was 
also observed in 1991 near the mouth of the Du Page River (DP277.0). 
The following discussion of the TIE Phase I results is summarized by 
year, 1990 and 1991. 

4.2.1 1990. The only sample manipulation that consistently 
reduced toxicity in the 1990 samples of sediment porewater was the 
graduated pH test (Table 4.2). Toxicity at pH 8.5 was greater than at 
pH 7.5 and pH 6.5 indicating a pH-dependent toxicant. Some ionic 
compounds, e.g., cationic metals, can be more toxic at a higher pH; 
however, EDTA chelation tests did not remove toxicity. Another common 

29 



Table 4.1. Toxicity of porewater to Ceriodaphnia dubia (48-hour LC50, 
reported as a % of porewater in test solution, and as toxic units, 
100/LC50). 







] 


1990 






1991 




Site 


LC50 


Toxic Units 
1.5 


LC50 


lo 


xic Units 


CR 325.4 


65 


(48-79) 


66 


(48-79) 


1.5 


CR 324.8 


71 




1.4 


89 






1.1 


CS 318.5 


67 


(44.91) 


. 1.5 


>100 









CS 307.4 


62 


(47-80) 


1.6 


7 


(5-12) 




14.3 


SS 317.0 


>100 







>100 









SS 315.3 


NS 






>100 









SS 313.0 


51 


(25-80) 


2.0 


95 






1.1 


SS 310.0 


NS 







>100 









SS 292.2 


71 




1.4 


35 






2.8 


DP 285.3 


71 




1.4 


71 






1.4 


DP 281.1 


NS 







>100 









DP 277.0 


NS 







14 


(10-23) 




7.1 


IR 248.2 


>100 







>100 









IR 215.0 


>100 







>100 









IR 180.0 


>100 







>100 









IR 125.5 


>100 







>100 









IR 72.0 


>100 







>100 









IR 6.0 


>100 




.... 


>100 









Notes: 

a. >100 indicates that 100% porewater did not kill at least half the 
test organisms in 48 hours. 

b. Dashes ( ) indicate that toxic units could not be calculated 

because porewater was not lethal within the 48-hour exposure period. 

c. Numbers in parentheses indicate range of dilutions that caused 50% 
mortality in 48 hours (48-hour LC50s). 

NS=not sampled 



30 



Table 4.2. Results of treating sediment porewater to reduce 
toxicity and characterize the toxicant. Porewater was 
obtained from acutely toxic Illinois Waterway sediments in 
1990. 









Sample 


Si 


ite 








Phase I Treatments 


DP 


286.3 


SS 292. 


2 




SS 


313.0 


CS 307.4 


pH adjustment 




NR 


NR 








NR 


NR 


Aeration 




NR 


NR 








NR 


NR 


Filtration 




NR 


NR 








NR 


NR 


Reverse-phase SPE 




NR 


NR 








NR 


NR 


Oxidation reduction 




NR 


NR 








NR 


NR 


EDTA chelation 




NR 


NR 








NR 


NR 


Graduated pH 




R 


R 








R 


R 








Sample 


"si 


ite 








Phase I Treatments 


CS 


318.5 


CR 324. 


8 




CR 


326.4 




pH adjustment 




NR 


NR 








NR 




Aeration 




NR 


NR 








NR 




Filtration 




NR 


NR 








NR 




Reverse-phase SPE 




NR 


NR 








NR 




Oxidation reduction 




NR 


NR 








NR 




EDTA chelation 




NR 


NR 








NR 




Graduated pH 




R 


R 








R 





NR= No reduction in toxicity 
R= Reduction in toxicity 
SPE= solid phase extraction 



31 



aquatic toxicant that is strongly pH-dependent is ammonia. Total ammo- 
nia concentrations in the acutely toxic samples ranged from 32.7 mg/1 
(milligrams per liter) to 59.8 mg/1 (Table 4.3). 

4.2.2 1991. Five of the seven sites evaluated in 1991 had the same 
characterization pattern as in 1990 (Table 4.4). The only manipulation 
to consistently reduce toxicity was the graduated pH test, again 
indicating a pH-dependent toxicant such as ammonia (Table 4.3). Total 
ammonia concentrations in the 1991 samples ranged from 28.6 mg/1 to 51.2 
mg/1 (Table 4.3). The characterization pattern differed for porewaters 
from DP277.0 on the Des Plaines River and CS307.4 on the Calumet Sag 
Channel (Table 4.4). Toxicity in these porewaters was reduced by 
filtration and solid phase extraction with a Cjg column, indicating that 
toxicity is due to non-polar organic compounds associated with 
filterable particles. These samples contained visible quantities of 
oil. 

In summary, Phase I results from 1990 and 1991 indicate that acute 
toxicity in most sediment porewaters from the Upper Illinois Waterway is 
attributable to a pH-dependent toxicant, most likely ammonia. Porewater 
from one location in the lower Des Plaines River and one location in the 
lower Calumet Sag Channel contained toxicity attributable to non-polar 
organics associated with oil or grease. 

4.3 Toxicity Identification Evaluation - Phase II 

Phase II techniques were used to isolate toxicants in porewaters 
from the seven sites where ammonia was suspect and the two sites where 
non-polar organics were suspect. The zeolite columns completely removed 
acute toxicity from porewaters where ammonia was suspect (Table 4.5). 



32 



Table 4.3. Toxicity and ammonia concentrations in sediment 
porewater in 1990 and 1991. Toxic units = 100/LC50, where 
LC50 is the % dilution that kills 50% of the exposed Cerio- 
daphnia dubia in 48 hours. Ammonia concentrations in the 
porewater are expressed as total ammonia nitrogen, N, in 
mg/1. 



1990 



Site 


Toxic Units 


CR 324.8 
CR 326.4 


1.4 
1.5 


CS 307.4 
CS 318.5 


1.6 
1.5 


SS 292.2 
SS 313.0 


1.4 
2.0 



Total Ammonia-N 

mn 

37.8 
25.6 

35.4 
42.7 



41.5 
59.8 

DP 286.3 1.4 23.8 



1991 



CR 324.8 1.1 34.2 

CR 326.4 1.5 51.2 

SS 292.2 2.8 33.5 

SS 313.0 1.1 28.6 

DP 286.3 1.4 30.5 



33 



Table 4.4. Results of treating sediment porewater to reduce 
toxicity and characterize the toxicant. Porewater was 
obtained from acutely toxic Illinois Waterway sediments in 
1991. 







Sample S- 


ite 






Phase I Treatments 


DP 277.0 


DP 286. 


.3 


SS 292.2 


CS 307.4 


pH adjustment 


NR 


NR 




NR 


NR 


Aeration 


NR 


NR 




NR 


NR 


Filtration 


R 


NR 




NR 


R 


Reverse-phase SPE 


R 


NR 




NR 


R 


Oxidation reduction 


NR 


NR 




NR 


NR 


EDTA chelation 


NR 


NR 




NR 


NR 


Graduated pH 


NR 


R 




R 


NR 






Sample S- 


ite 






Phase I Treatments 


CS 313.0 


CR 324, 


.6 


CR 326.4 




pH adjustment 


NR 


NR 




NR 




Aeration 


NR 


NR 




NR 




Filtration 


NR 


NR 




NR 




Reverse-phase SPE 


NR 


NR 




NR 




Oxidation reduction 


NR 


NR 




NR 




EDTA chelation 


NR 


NR 




NR 




Graduated pH 


R 


R 




R 





NR= No reduction in toxicity 
R= Reduction in toxicity 
SPE= solid phase extraction 



34 



Table 4.5. Results of treating sediment porewater with zeolite to 
remove ammonia. Porewater was obtained from acutely toxic Illinois 
Waterway sediments. 



1990 




Pre- 


Zeolite 


Post 


Zeolite 


Site 


Ammonia-N 

(mg/i) 


Toxicity 


Ammonia-N 
(mg/1) 


Toxicity 


CR 326.4 
CR 324.8 


25.62 
37.82 


T 
T 


1.70 
1.46 


NT 
NT 


CS 318.5 
CS 307.4 


42.70 
35.38 


T 
T 


1.98 
2.24 


NT 
NT 


SS 313.0 
SS 292.2 


- 59.78 
41.48 


T 
T 


2.58 
1.22 


NT 
NT 


DP 286.3 


23.67 


T 

1991 


4.88 


NT 


CR 326.4 
CR 324.8 


51.29 
34.16 


T 
T 


1.86 
1.70 


NT 
NT 


SS 313.0 
SS 292.2 


28.60 
33.55 


T 

T 


3.05 
1.95 


NT 

NT 


DP 286.3 


30.50 


T 


1.70 


NT 



T = Acute toxicity was present, as determined by toxicity tests with 

Ceriodaphnia dubia. 
NT = No acute toxicity 



35 



Since the zeolite selectively removes ammonia, these results support 
identification of ammonia as the toxicant. 

The suspect nonpolar organics at sites CS307.4 and DP281.1 seemed 
to have different chemical and physical properties because no toxicity 
could be obtained from DP281.1 by column absorption and elution with 
methanol alone, whereas CS307.4 did yield toxicity with the methanol 
extraction (Table 4.6). Moreover, toxic materials were eluted by a wider 
range of methylene chloride/methanol mixtures (20-50%) from the CS307.4 
sample than from the DP277.0 sample (25-40%, Table 4.7). Also, the 
greatest toxicity in porewater sample DP281.1 was associated with resi- 
due left on the filters after passage of porewater, whereas the greatest 
toxicity in sample CS307.4 was in supernatant left after centrifuging 
out most of the particles (Table 4.6). The DP277.0 elutriate contained 
no organics detectable by gc-mass spectrography, whereas 34 organic 
compounds were detected in the CS307.4 elutriate (Table 4.8). This was 
surprising because the DP277.0 elutriates contained toxicity (Table 
4.7), but perhaps there were undetectable quantities of nonpolar organ- 
ics that were highly toxic. 

The elutriates from sample CS307.4 contained different combina- 
tions of nonpolar organics (Table 4.8). No compounds were found above 
the detection limits in the 20% fraction. The 25% fraction contained 
the polycyclic aromatic hydrocarbon (PAH) naphthalene. The 30% fraction 
contained primarily cyclic and branched hydrocarbons (cyclohexane, 
octane) and PAHs. The 35-50% fractions contained numerous long chain 
hydrocarbons such as heptadecane, undecane and dodecane. The 40 and 45% 
fractions also contained the alkenes, eicosene and dotriacontanol . In 
general, toxicity in these samples appears to be primarily due to 
petroleum hydrocarbons and PAHs. Scubauer-Berigan and Ankley (1991) 



36 



Table 4.6. Toxicity of sediment porewater following fractionation by 
filtration, centrifugation, and column absorption and extraction. 
Fractions were tested for toxicity using Ceriodaphnia dubia. Toxicity 
is expressed as the 48-hour LC50, reported as % of sample fraction in 
test solution, and as toxic units, (100/LC50). Numbers in parentheses 
indicate a range of dilutions that caused 50% mortality in 48 hours. 





DP 


277, 


.0 


CS 


307, 


.4 




LC50 




Toxic 
Units 


LC50 




Toxic 
Units 


^Filter 
extraction 


27 
(18-40) 




3.7 


62 
(48-71) 




1.6 


^Centrifugation 
whole sample 


71 




1.4 


9 




11.1 


cpost Ci8 
(25ml)'" 


>100 







18 




5.6 


^POSt Cio 

(100 ml) 


>100 







18 




5.6 



^Porewater was filtered, then the filters were extracted with methylene 
chloride. Extracts tested for toxicity. 

'^Centrifugation at 10,000 g for 30 minutes to settle the particles in 
the porewater. Supernatant tested for toxicity. 

^200-ml samples of supernatants from b were passed through absorption 
columns, then aliquots were taken after passage of 25 ml and 100 ml of 
methanol through the columns. Aliquots tested for toxicity. 

>100 indicates that the undiluted fraction did not kill at least half 
the test organisms in 48 hours. 

indicates that toxic units could not be calculated because the 

undiluted fraction was not lethal within the 48-hour exposure period. 



37 



Table 4.7 Toxicity of extracts from sediment porewater. The porewater 
was obtained from sediments at site CS 307.4 and site DP 277.0 where 
nonpolar organic chemicals were suspected of contributing to toxicity. 
The porewater was passed through Cjo absorption columns and then the 
columns were eluted with increasingly nonpolar mixtures of methylene 
chloride in methanol (1%-100% methylene chloride). The elutriates were 
tested for toxicity on Ceriodaphm'a dubia. 



Fraction of Site Site 

Methylene Chloride DP 277.0 CS 307.4 

in Methanol 

100% NT NT 

50% NT T 

45% - NT T 

40% T T 

35% T T 

30% T T 

25% T T 

20% NT T 

15% NT NT 

10% NT NT 

5% NT NT 

1% NT NT 



T = Toxic 
NT = Not Toxic 



38 



Table 4.8 Constituents of elutriates from solid phase Cjg absorption 
columns. Toxic sediment porewaters from sites CS 307.4 and DP 277.0 
were passed through the columns, which then were elutriated with mix- 
tures of methylene chloride in methanol. The elutriates were analyzed 
with a gas chromatograph. Values in table are concentrations, in mg/1 , 
calculated from areas under the peaks in the chromatographs. 



Chemical 



cyclohexadecane 
cyclohexane, dimethyl 
cyclohexane, trimethyl 
cyclohexane, methyl propyl 
cyclopentane, 1-methyl- 

3-4-(l-methylethyl) 
cyclopentane, methyl propenyl 
decane, trimethyl 
dodecane, trimethyl 
1-dotriacontanol 
3-eicosene 
5-eicosene 

heneicosan, ethylpropyl 
heptacosane 
heptadecane 
heptadecane, trimethyl 
heptadecane, tetramethyl 
heptane, 3-ethyl -5-methyl 
1-heptanol, 2-propyl 
nonadecane 

nonahexacontanoic acid 
nonane, dimethyl 
octane, trimethyl 
octane, dimethyl 
octadecane, chloro 
3-octadecanol 

naphthalene, decahydro-2-methyl 
tetratetracontane 
tritetracontane 
tridecane, methyl 
tritetracontane 
undecane, dimethyl 
undecane, 2,5-dimethyl 
undecane, 3,6-dimethyl 
undecane, 6-methyl 





CS 


307.4 




DP 277.0 


Methylene 


chloride/methanol % 




30 35 


40 


45 


50 










11 


No peaks 


38 


-- 


61 


48 
32 


above 

detection 

limits 


-- 


26 


12 


-- 




10 


54 


50 


18 




.. 


22 


-- 


-- 




-- 


21 


32 
13 
18 

76 


44 
16 




18 


44 


49 


46 




15 


-- 


38 


-- 




13 


-- 


-- 


-- 




-- 


21 


-- 


12 




-- 


16 


29 


-- 




10 


-- 


17 
13 


-- 




10 28 


-- 


36 


48 




-. 


22 


-- 


11 




- 


14 


13 
16 
19 


-- 




23 


-- 


-- 


-- 




_- 


36 


-- 


-- 




21 


-- 


-- 


-- 





-- = not detected 



39 



identifed non-polar organics associated with oil and grease as a source 
of toxicity in sediments in the upstream portions of the Calumet Sag 
Channel and Lake Calumet. 

4.4 Toxicity Identification Evaluation - Phase III 

Toxicity in sediment porewaters from the upper Illinois Waterway 
is correlated with total ammonia concentrations (r = 0.85, Figure 4.3). 
Jones and Lee (1988) found that of more than 30 contaminants measured in 
sediments from New York Harbor, only ammonia concentrations correlated to 
observed toxicity in grass shrimp. Ankley et al . (1990) identified 
ammonia as a major toxicant in sediments from the lower Fox River and 
Green Bay, Wisconsin. 

The fingernail clam, Musculium transversum, is sensitive to ammo- 
nia. Anderson, Sparks and Paparo (1978) found that un-ionized ammonia 
concentrations of 0.08-0.09 mg/1 inhibited the cilia on the gills of the 
clams, and the growth of the clams in the laboratory was reduced at 
concentrations between 0.20 and 0.34 mg/1 NH3-N. Un-ionized ammonia 
concentrations greater than these are likely to occur in sediment pore- 
waters of the upper Illinois Waterway, based on total ammonia concentra- 
tions we measured (23.8-59.8 mg/1 NH3-N) and pH ranges known to occur in 
the water column. The clams must draw oxygenated water from the water 
column down their burrows to survive, and in doing so, they might shift 
the pH from the low levels characteristic of anaerobic sediments to 
higher levels characteristic of the water column, thereby increasing the 
fraction of the total ammonia that exists in the toxic un-ionized form. 

In summary, several lines of evidence lead to the conclusion that 
ammonia in sediment porewater was limiting macroinvertebrate populations 
in the Illinois Waterway at the time this study was conducted. First, 

40 



"c 
o 
E 
E 
< 

IB 
o 



o 
x 

o 



c 
o 

CD 

o 
O 




o 


c t 


in 


^ '^ 




2 .i 




■- -D 




a o 








£ - 




1! 


_J 


o "-^ 




^ O) 


c c 


E^ 










o l! 


C3 






c u 


"c 


^ 


BO 




E 


1 ^ 


< 


11 






-% 


li 


h- 


1- 01 

1 ^ 




g g 




o « 




<o "o 




i •- 


O 


1 !^ 



(0901/001.) siiun 01X01 



g .:2 



0> -I 

i 2: 



41 



o> o 
— o 



the porewater contains a pH-sensitive toxicant that is not affected by 
chelation with EDTA, as heavy metals would be (Tables 4.2 and 4.4). 
Second, toxicity to both C. dubia and the fingernail clam M. transversum 
is associated with total ammonia concentrations in sediment porewater 
(Table 4.3, and Figures 4.1, 4.2, and 4.3). Third, removal of ammonia 
by treatment with zeolite removes the toxicity (Table 4.5). Finally, H. 
transversum is known to be sensitive to un-ionized ammonia at levels 
that are likely to occur in the porewaters. 

Not all the toxicity found in the upper Illinois Waterway was 
associated with ammonia. Porewaters from the Calumet Sag Channel 
(CS307.4) and the lower Des Plaines River (DP277.0) contained visible 
signs of oil and grease and toxicity associated with PAHs (including 
naphthalene) and other compounds found in petroleum. 

4.5 Sensitivity of Recolonizing Clams 

Much to our surprise, we found several species of fingernail 
clams, including Muscuh'um transversum, at several sites in the upper 
Illinois Waterway: the Chicago Sanitary and Ship Canal (SS317.0), the 
North Branch of the Chicago River (CR325.4), and the Calumet Sag Channel 
(CS318.5). Biologists from the Long Term Resource Monitoring (LTRM) 
Station at Havana also reported finding fingernail clams in mud they 
happened to bring up on their sampling nets and boat anchors. 

We wondered if these clams had acquired some resistance to the 
toxicants in the sediments, so we tested their responses to a sediment 
sample from the Chicago Sanitary and Ship Canal (SS317.0) and another 
from the Calumet Sag Channel (CS318.5). At the same time, we tested 
clams from Swan Lake on the lower Illinois River, where we had obtained 

42 



all the clams used in our previous bioassays. This work was done 
outside the scope of our original research proposal and is of a very 
prel iminary nature. 

The preliminary results support the hypothesis of differential 
resistance. The clams from the Sanitary and Ship Canal showed virtually 
no impairment of filtering performance in response to porewater from the 
place where they where taken or to the Calumet Sag porewater (see 
below). The clams from Swan Lake were sensitive (36% decline in filter- 
ing performance) to porewater from the Sanitary and Ship Canal, while 
they had only a slight negative response, comparable to the Cal-Sag 
clams, to the Cal-Sag porewater. The Ship Canal porewater was not 
tested on the Cal-Sag clams. 



SOURCE OF CLAMS 
CS318.5 
SS317.0 
Swan Lake 



SOURCE OF POREWATER 

SS317.0 CS318.5 

-0.17 

-0.08 0.00 

-0.36 -0.13 



43 



5.0 DISCUSSION 

Two different patterns of toxicity occur in the sediment 
porewaters of the Illinois Waterway. There is a gradient of increasing 
toxicity in the upstream direction, associated with increasing 
concentrations of total ammonia in the sediments. The second pattern is 
characterized by patches of toxicity associated with polycyclic aromatic 
hydrocarbons (PAHs), such as naphthalene, and long-chain hydrocarbons, 
both evidently derived from petroleum. One of the latter sites was 
located on the lower Pes Plaines River section of the waterway, near 
several refineries. Previous studies have measured elevated levels of 
metals, pesticides, PAHs, and PCBs in the sediments of the upper Illi- 
nois Waterway (lEPA 1990) and demonstrated that sediments are toxic 
(Sparks et al . 1981; Blodgett et al . 1984; Schubauer-Berigan and Ankley 
1991). The two toxicity problems might even be related: Ankley et al . 
(1991) suggested that natural microbial processes in aquatic ecosystems 
may be compromised by organic loading or selective toxicity. The alter- 
ation of microbial processes could play a role in the incidence of 
ammonia accumulation and subsequent toxicity in sediments in the Upper 
Illinois Waterway. 

It is well established that certain sediments can contain high 
concentrations of ammonia (Keeney 1973, Berner 1980). Nitrogen-contain- 
ing organic matter is decomposed in sediments by heterotrophic bacteria. 
The amount of ammonifi cation that takes place depends in part on oxygen 
availability (Kleerekoper 1953). Ammonia can accumulate to toxic levels 
under anaerobic conditions (Berner 1980). Serruya (1974) found that 
ammonia formation is greatest about 10 cm (centimeters) below the 
sediment-water interface. In this situation, ammonia probably diffuses 

45 



from the deeper sediments to surficial sediments, and perhaps even to 
the overlying water, especially if sediments are resuspended by currents 
or boat- or wind-driven waves. The fingernail clam, Musculium 
transversum, the organism of primary interest in this study, makes 
shallow burrows in the sediment and may be exposed to much higher levels 
of ammonia than organisms living in the water column, at the mud-water 
interface, or on plants, rocks, and woody debris. 

Ammonia toxicity is due to the un-ionized (NH3) form (USEPA 1985). 
The proportion of total ammonia existing in the un-ionized form is 
controlled primarily by pH and temperature (Emerson et al . 1975). The 
pH of sediments can fluctuate dramatically on a seasonal basis, and the 
pH of the overlying water can fluctuate daily, so that episodes of 
toxicity may occur even if the total ammonia concentration remains 
relatively constant. Ammonia loading of rivers tends to increase during 
winter because the microorganism-mediated conversion of ammonia to 
nitrate stops at cold temperatures. Also, aquatic vegetation does not 
remove ammonia (a plant nutrient) during winter dormancy. Water quality 
standards frequently allow higher levels of ammonia in the winter be- 
cause the proportion of total ammonia existing in the toxic, un-ionized 
form is less at cold temperatures. However, the sensitivity of fish to 
ammonia increases at cold temperatures, so even though there may be less 
un-ionized ammonia, acute toxicity may still occur (Reinbold and Pesci- 
telli 1990). Research is needed to determine the effect of cold temper- 
atures on the sensitivity of invertebrates, as well as fish, to ammonia. 

Musculium transversum is sensitive to ammonia. Anderson, Sparks 
and Paparo (1978) found that un-ionized ammonia concentrations of 0.08- 
0.09 mg/1 (expressed as un-ionized ammonia nitrogen, NH3-N, in mg/1) 

46 



inhibited the cilia on the gills of the clams, and the growth of the 
clams in the laboratory was reduced at concentrations between 0.20 and 
0.34 mg/1 NH3-N. The C. dubia acute LC50 for ammonia is 1.04 mg/1 NH3-N 
(Ankley et al . 1990). Arthur et al . (1987) reported un-ionized ammonia 
toxicity to 5 invertebrates ranged from 1.95 to 18.3 mg/1 NH3-N and 
mollusks (snails) were most sensitive. 



iPECIES 

Snail 

Physa gyn'na - adult 
Hell soma trivolvis - adult 


LC50 (mg/1) 

1.95 
2.17 


Amphipod 
Crangonyx pseudogracih's - adult 


3.12 


Mayfly 
Callibaetis skokianus - nymph 


3.12 


Isopod 
Asellus racovitzai - adult 


5.02 


Caddisfly 
Phi Tardus giaeris - larvae 


10.1 


Crayfish 
Orconectes immunis - adult 


18.3 



Concentrations of this magnitude (1.0-8.0 mg/1 NH3-N) are commonly found 
in the sediments in the Upper Illinois Waterway, based on total ammonia 
concentrations (23.8-59.8 mg/1) and naturally occurring pHs. Ammonia 
places organisms in double jeopardy because it exerts an oxygen demand 
in the process of nitrification (conversion to nitrites and then ni- 
trates) and low oxygen levels place organisms under additional stress 
(USEPA 1985). Ammonification may be occurring in the deep, anaerobic 
zones of the sediments and nitrification in the shallower, aerobic 



47 



zones, or in the boundary water at the sediment surface, so benthic 
invertebrates are exposed to the worst of both worlds. They are exposed 
to ammonia and to low oxygen at the same time. 

The highest ammonia concentrations in sediments are associated 
with nitrogen-enriched sediments or high organic loading, as from sewage 
treatment plants (Brezonik 1973; Ankley et al . 1990; and Schubauer- 
Berigan and Ankley 1991). Although most sewage treatment plants remove 
a substantial portion of carbon in municipal waste, most do not remove 
nitrogen, but convert it from ammonia into nitrate. It is possible that 
nitrate is carried down into the sediments where it is converted back 
into ammonia in the anaerobic zones. If this is the case, ammonia 
toxicity in the sediments might be reduced by reducing the nitrogen 
loading of the river. 

During the course of this study, several species of fingernail 
clams, including M. transversum, reappeared in the Chicago area water- 
ways and in the Illinois River at Peoria and Havana. There are at least 
four possible explanations for this surprising reappearance of clams in 
the same general areas where the porewaters tested toxic. First, we 
found that clams recolonizing the upper Illinois were more resistant to 
ammonia than the clams from the lower Illinois, where the organisms were 
obtained for all of the early bioassays. Second, our previous research 
demonstrated that the surface layers of sediment in some areas were less 
toxic than layers a few centimeters deeper (Sparks, Sandusky and Paparo 
1981; Blodgett et al . 1984). Toxicity may have been overestimated in 
tests where surface and deep layers of sediment were mixed prior to 
testing. Third, toxic episodes may be brief and infrequent, allowing 
organisms to colonize in between episodes. Fourth, the distribution of 



48 



toxicity in sediments may be extremely patchy, so that healthy organisms 
are found adjacent to barren areas. If the latter two hypotheses prove 
to be true, toxicity in the Illinois River has changed recently from a 
widespread, chronic problem to a more localized or episodic problem. 
Reduction of toxicity in surface sediments may reflect recent reductions 
in ammonia loading from sewage treatment plants in the Chicago area, 
although it is not clear whether the sources of ammonia in the pore- 
waters are effluents, the deeper layers of sediments (as described 
above) , or both. 

We remind the reader that all the toxicity tests we conducted were 
short-term, acute tests. The fingernail clams, MuscuTium transversum, 
were exposed to sediment porewater for only 1 hour and then their fil- 
tering performance was tested in clean dilution water. The water flea, 
Ceriodaphm'a dubia, was exposed to porewater for just 48 hours. The 
organisms in the waterways are exposed to contaminants for their entire 
life spans. In the past, more sensitive tests with fingernail clams 
have demonstrated toxicity even in downriver sediments, including Peoria 
Lake and Quiver Lake (Sparks, Sandusky and Paparo 1981). 

In addition to being a problem for the benthic invertebrates that 
fish feed upon, ammonia in the Illinois Waterway may be a problem for 
the fish themselves. In 1987, the U.S. Fish and Wildlife Service simu- 
lated resuspension of bottom sediments by boat- or wind-driven waves by 
stirring sediments in clean water, allowing the sediment to settle for 
24 to 48 hours, then exposing larval fathead minnows, Piwephales prome- 
las, to the water. Water mixed with surface sediments from the Chicago 
River and the Des Plaines River killed all the fish within 24 hours. 
Surface sediments from Lake Chautauqua, a bottomland lake and federal 



49 



wildlife refuge along the Illinois River at Havana, killed 15% of the 
test fish in 96 hours; deeper sediments, taken at the 30,5-45.7 cm (12- 
to 18-inch) depth, killed 25%. Fish mortality correlated (R = 0.71, P < 
0.01) with the concentration of un-ionized ammonia released from the 
sediment and both ammonia and fish mortality increased upstream toward 
Chicago. The Long Term Research Monitoring Station (LTRM) at Havana 
started measuring ammonia concentrations in Anderson Lake, a floodplain 
lake of the Illinois River and a state fish and wildlife area, on 1 May 
1990, 2 days after a fish kill. The total ammonia nitrogen 
concentration was 0.90 mg/1 and the un-ionized ammonia nitrogen was 
calculated to be 0.36 mg/1 at the temperature of 16.6° C and pH of 9.34. 
NH3-N concentrations of 0.32 mg/1 at 3-5° C and 1.35 mg/1 at 24-25° C 
were acutely lethal to bluegill sunfish, Lepomis macrochirus (Reinbold 
and Pescitelli 1990). The fish kill might have been caused by ammonia, 
if the un-ionized ammonia had peaked at higher concentrations before our 
samples were taken. 

Elevated un-ionized ammonia concentrations might be triggered by 
resuspension of sediments or episodes of elevated pH resulting from 
phytoplankton blooms. Plants remove carbon dioxide from the water, in 
the form of carbonic acid and bicarbonate, and thereby elevate the pH of 
the water, which in turn increases the proportion of ammonia existing in 
the toxic, un-ionized form. The Havana LTRM station (unpublished data) 
measured pHs as high as 10.12 in backwater lakes of the Illinois River 
in July 1990 and values between 9.0 and 10.0 occur fairly often. 
Episodes of acute ammonia toxicity thus may be occurring sporadically in 
places other than just the upper Illinois River, and it takes only one 
brief episode per year to kill or reduce populations of invertebrates or 



50 



fish that take many months or years to build up. Potential sources of 
ammonia or nitrogen, besides sewage plants and anaerobic sediments, 
include industrial plants (especially refineries and munitions plants), 
feedlots, and agricultural fields. 

Although a general recovery does seem to be beginning in the 
Illinois River, with the return of fingernail clams in some areas where 
they have been absent at least 30 years and appearance of largemouth 
bass throughout the Illinos River proper, the pace and permanence of 
recovery still appears to be threatened by ammonia, even if the problem 
now turns out to be episodic instead of chronic. Reports of fingernail 
clam and mussel die-offs in the Upper Mississippi River and other rivers 
(Wilson et al . submitted; Blodgett and Sparks 1987; Neves 1987) indicate 
that drastic population declines in macroinvertebrates that burrow in 
sediments are not unique to the Illinois River. 



51 



6.0 LITERATURE CITED 

Adams, W.J., R.A. Kimerle, and R.G. Mosher. 1985. Aquatic safety 

assessment of chemicals sorbed to sediments. Pages 429-453 in R.D. 
Cardwell, R. Purdy, and R.C. Bahner, eds. Aquatic Toxicity and 
Hazard Assessment: Seventh Symposium, ASTM 854, American Society 
for Testing and Materials, Philadelphia, PA. 

Aldridge, D.W., B.S. Payne, and A.C. Miller. 1987. The effects of 
intermittent exposure to suspended solids and turbulence on three 
species of freshwater mussels. Environmental Pollution 45:17-28. 

Anderson, K.B. 1977. Musculium transversum in the Illinois River and 
an acute potassium bioassay method for the species. M.S. Thesis, 
Western Illinois University, Macomb, IL. 79 pp. 

Anderson, K.B., R.E. Sparks, and A. A. Paparo. 1978. Rapid assessment 
of water quality using the fingernail clam, Musculium transversum. 
University of Illinois Water Resources Center, Center Research 
Report No. 133. 

Anderson, R.V., D.M. Day, M. Demissie, F.S. Dillon, J.W. Grubaugh, M.S. 
Henebry, K.S. Lubinski, and R.E. Sparks. 1984. Flows, equations 
and input values for the nine state-vaiable biological model. Pool 
19, Mississippi River--second generation. A computer-modelling 
project of the Large-River, Long-Term Ecological Research Project 
(LTER). Unpublished report. 106 pp. 

Ankley, G.T., A. Katko, and J. Arthur. 1990. Identification of ammonia 
as an important sediment-associated toxicant in the lower Fox River 
and Green Bay, Wisconsin. Environmental Toxicology and Chemistry 
9:313-322. 

Ankley, G.T., K. Lodge, D.J. Call, M.D. Balcer, L.T. Brooke, P.M. Cook, 
R.G. Kreis, Jr., A.R. Carlson, R.D. Johnson, G.J. Niemi, R.A. Hoke, 
C.W. West, J. P. Giesy, P.D. Jones, and Z.C. Fuying. 1991. 
Integrated assessment of contaminated sediments in the lower Fox 
River and Green Bay, Wisconsin. Ecotoxicology and Environmental 
Safety 23:46-63. 

APHA. 1989. Standard methods for the examination of water and 

wastewater. 17th Edition, American Public Health Association, 
Washington, D.C. 

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59 



REPORT O0CUMENT.T,ON | .. «- ~ .„„.gj^„, 



1. RcclpMiTf 1 Accasuon No 



4. TItto and SuMltIa 

Identification of Toxic Substances in the Upper niinois River 



5. Report Oat* 

nrtnher 1992 



7. Apthortt) , . ^ 

Richard E. Sparks and Philippe E. 



Ross 



Parformmt Or«anliation Rapt. 



I. Parforminc Orsanlxatton Nama and Addraa* 

River Research Laboratory 
Forbes Biological Station 
Illinois Natural History Survey 
P.O. Box 599 
Havana, IL 62644 



la Pro|act/Ta»k/Wor* Unit 

89/215 



II. ContracKC) or Grant(C) No 



WR3691 



12. Sponaofinc Organization Nama and Addraas 

Illinois Department of Energy and Natural Resources 

Office of Research and Planning 

325 West Adams Street 

Springfield. IL 62704-1892 



13. Typa of Raport & Pariod Covarad 



Between 1955 and 1958, several abundant species of acquatic 
nail clams practically disappeared from the upper Illinois 
equally drastic repercussions on the populations of ducks a 
invertebrates. The situation changed very little into the 
in water quality. This research found that porewater from 
contains a toxic factor that inhibits the filtering ability 
also negatively effects the water flea, while stimulating a 
All evidence points to ammonia as the toxic agent. Also, a 
contained toxic oil products, including polycyclic aromatic 
naphthalene. A three phase Toxicity Identification and Eva 
utilized in reaching these conclusions. 



insects, snails and finger- 
River. These declines had 
nd fish that fed upon these 
1980s, despite improvements 
relevant river sediments 

of fingernail clams and 

ga and bacteria growth, 
t two sites, the porewater 

hydrocarbons, such as 
luation methodology was 



Water Pollution, Toxicity, Water Pollution Effects (Animals] 
Sedimants, Sedimentation, Suspended Sediments 



b. M«ntlfi«rs/09«n-End«d Tarmt 

Sedimentation - Illinois River 

Toxicity - Illinois River 

Water Pollution - Illinois River 



c. COSATI Flald/Group 



Biol ogical and Medical Sciences; Environmental Biology 



i«. Avaiiabiirty statamant fjQ restriction on distribution. 
Available at IL Depository Libraries or from 
National Technical Information Service, 

■^pr-i nr|f-io1H yA 



19. Sacurtty Clait (This Raport) 

llnclassi fipu 



21. No. of Pagai 

11 



3. Sacuhty Clait (This Paga) 

Unclassi f led 



(Saa ANSI- 



39.18) 



Saa Inttructiont on Ktimn* 



OPTIONAL FORM 272 (1-77) 
(Formerly NTIS-35) 
Dapartmant of Commarca 



Printed by the Authority of the State of Illinois 
Printed on Recycled Paper