PB84-153196
Derivation of Site-Specific Water Quality
Criteria for Cadmium and the St. Louis
River Basin, Duluth, Minnesota
(U.S.) Environmental Research Lab.
Duluth, MN
Feb 84
U.S. Department of
TedsEcai
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EPA-600/3-84-029
February 1984
DERIVATION' OF SITE-SPECIFIC WATER QUALITY CRITERIA
FOR CADMIUM AND THE ST. LOUIS RIVER BASIN,
DULUTH, MINNESOTA
R. L. Spehar and A. R. Carlson
U.S. Environmental Protection Agency
Environmental Research Laboratory-Duluth
6201 Congdon Boulevard
Duluth, MN 55804
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TECHNICAL REPORT DATA
(Pleats read Instructions onthe reverse before completing)
\. REPORT NO.
EPA-600/3-84-029
3. RECIPJENT-S ACCESSION NO
4. TITLc AND SUBTITLE
Derivation of Site-Specific Water Quality Criteria for
Cadmium and the St. Louis River Basin, Duluth, Minnesota
5. REPORT DATE
Fphruarv 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R.L. Spehar and A.R. Carison
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Duluth, MN 55804
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Same as above
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-600/03
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Several freshwater aquatic species were exposed to cadmium In site and laboratory
water to evaluate an "organism testing" protocol proposed by the U.S. Environmental
Protection Agency for deriving site-specific, water quality criteria. The procedures of
recalculation. Indicator species, and resident species were used In this protocol to
modify the national maximum and 30-day average cadmium criteria, i These procedures were
used to account for differences In species sensitivity and In the biological
availability and/or toxlclty of cadmium due to physical and/or chemical characteristics
of the site water.
..The site-spec'lfIc, maximum concentration derived from the recalculation procedure
was slightly lower (1.3 as compered to 2.2 pg/l) tnen the national criterion value. The
maximum concentration derived from ttie Indicator species procedure was 7.0 pg/l and wns
calculated by using a water effect ratio frcrn tests conducted In both site and
laboratory water.. Acute tests with several species demonstrated that cadmium was less
toxic In site water .than In laboratory water. The site-specific, maximum concentration
derived from the resident species procedure (from eight species exposed to cadmium In
site water) was 1.9 M9/I. The 30-day average concentrations were the same as the
maximum concentrations In alI procedures where the national acute-chronic ratio was used
In the calculation. These concentrations were much lower when the site-specific,
acute-chronic ratio was applled.
- Acute tests conducted monthly In site water showed that cadmium toxlclty varied by
more than a factor of three over the year. This Indicates the need for considering
seasonal changes In physical and chemical characteristics of ttie site water when
deriving criteria to protect aquatic life.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.tDENTIFIERS/OPE^ ENDED TERMS C. COSATI Field/Croup
IB. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (Thti Report)
unclassified
21. NO. OF PAGES
61
20. SECURI r Y CLASS (This page)
unclassified
22. PRICE
EPA Form 2220-1 (R»». 4-77) PREVIOUS EDISON is OBSOLETE
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
11
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TABLE OF CONTENTS
SECTION
PAGE
INTRODUCTION 1
Study site 2
PRODECURES AND T2ST METHODS
Procedures for calculating criteria 8
Water characteristics 9
Exposure systems 10
Toxicant solution 10
Biological procedures 11
Statistical analysis 14
RESULTS 15
DISCUSSION 24
CRITERIA CALCULATION
Recalculation procedure 26
Indicator species procedure 27
Resident species procedure . . 31
Summary of criteria calculations 32
OVERALL ASSESSMENT 34
ACKNOWLEDGEMENTS . .35
REFERENCES 36
APPENDIX A. Biological survey of aquatic species resident to the St.
Louis River and river basin 40
APPENDIX B. Ambient water quality parameters obtained for the St.
Louis River site at Cloquet, Minnesota during Che months
of April through December 1981 45
APPENDIX C. Recalculation Procedure. Minimum data set for cadmium
from the national criterion document for species and
families resident to the St. Louis River 46
APPENDIX D. Indicator Species Procedure. Acute values (LC50) for
indicator species exposed to cadmium in St. Louis River
and reconstituted water 48
111
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APPENDIX E. Acute (LC50) and chronic values for aquatic organisms
exposed to cadmium in Ct. Louis River water 49
APPENDIX F. Chronic toxicity values of two species exposed to
cadmium in St. Louis River and Lake Superior water .... 50
APPENDIX G. Resident Species Procedure. Minimum data set of
resident aquatic species exposed to cadnium in St.
Louis River water 51
APPENDIX H. Cadmium water quality criteria derived fron the
national and site specific procedures 52
IV
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LIST OF TABLES
TABLE PAGF.
1 Size, temperature, and source of aquatic species exposed to
cadmium in St. Louis River and reconstituted water 12
2 Monthly averages in water quality parameters for cadmium tests
conducted in St. Louis River, reconstituted and Lake Superior
water 16
3 Correlation coefficients for St. Louis River cadmium toxicity
tests with fathead .a'.nnows and corresponding water quality
parameters for the months April through December 1981 1C
4 Acute values (LC50, ys/1) for aquatic species exposed to cadnu-.-vi
in St. Louis River and reconstituted water 20
5 Survival and growth of fathead minnows exposed to various
concentrations of cadmium in St. Louis River water for 32 days . . 21
6 Survival and young production of Ceriodaphnia reticulata exposed
to various cadmium concentrations in St. Louis River vat'i for
9 davs 23
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LIST OF FIGURES
.-. .;?-;.««S%e-' . " . -V?
FIGURE . PAGI
1 St. Louis River Basin 4
2 Ihiluth aid Superior Estuary 5
3 St. Louis River site at the State Highway 33 crossing in Cloquet,
Minnesota 7
4 Monthly LC50 values (+_ 95% confidence limits) for tests with
one-day-old fathead rainbows exposed to cadmium in St. Louis
River and reconstituted water 17
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ABSTRACT
Several freshwater aquatic species were exposed to cadmium in site and
laboratory water to evaluate an "organism testing" protocol proposed by the
U.S. Environmental Protection Agency for deriving site-specific, water
qvlity criteria. The procedures of recalculation, indicator species, and
resident species were used in this protocol to modify the national maximum
and 30-day average cadmium criteria. These procedures were used to account
for differences in species sensitivity and ''. the biological availability
and/or toxicity of cadmium due to physical and/or chemical characteristics of
the site water.
The site-specific, maximum concentration derived frotfrthe recalculation
procedure was slightly lower (1.3 as compared to 2.2 fjg/1) than the national
criterion value. The maximum concentration derived from the indicator
species procedure was 7.0 y?/l and was calculated by using a water effect
ratio from tests conducted in both site and laboratory water. Acute tests
with several species demonstrated that cadmium was less toxic in site water
than in laboratory water. The site-specific, maximum concentration derived
from the resident species procedure (from eight species exposed to cadmium in
site water) was 1.9 jjg/1. The 30-day average concentrations were the same as
the maximum concentrations in all procedures where the national acute-chronic
ratio was used in the calculation. These concentrations were much lower when
the site-specific, acute-chronic ratio was applied.
Acute tests conducted monthly in site water showed that cadmium toxicity
varied by more than a factor of three over the year. This indicates the need
for considering seasonal changes in physical and chemical characteristics of
the site water when deriving criteria to protect aquatic life.
VII
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INTRODUCTION
Under the Clean Water Act of 1977 [Sec. 304(a)(D] the U.S. Environ-
mental Protection Agency (U.S. EPA) is required to review and publish
criteria for water quality necessary to protect public water supplies and the
propagation of shellfish, fish and wildlife. Criteria present scientific
data and guidance on the environmental effects of pollutants which can be
useful to derive water quality-based regulatory requirements such as effluent
limitations, water quality standards or toxic pollutant effluent standards
(U.S. EPA, 1980a).
National water quality criteria have been derived by applying a set of
guidelines (U.S. EPA, 1983a) to data for certain pollutants designated as
toxic under Section 307(a)(l) of the Clean Water Act of 1977 persuant to an
agreement in the case of Natural Resourses Defense Council et al. vs. Train,
1976. Tnese guidelines specify that criteria shouM be based on an array of
data from species, both plant and animal, occupying various trophic levels.
Based on these data, criteria can be derived which should adequately protect
the type of species necessary to support an aquatic community. Although
criteria~"represent a reasonable estimate of pollutant concentrations
consistent with the maintainance of designated uses, each state may
appropriately modify these values to reflect local conditions.
Since national criteria may be either underprotective or oyerprotective,
t.\\e Office of Research and Development and the Office of Water Regulations
and Standards of U.S. EPA are currently developing guidelines (U.S. EPA,
I983b) for modifying national water quality criteria to local conditions or
to site-specific criteria. National criteria are based on information
obtained from toxicity and bioconcentration tests conducted in laboratory
sources of water. However, toxicological information obtained for laboratory
1
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tested aquatic species, however, may not be applicable to species in specific
water bodies because: 1) the species at a particular site may be more or
less sensitive than Lhose included in the national criteria data base or 2)
the physical and/or chemical charateristics of the water at the site may
alter the biological availability and/or toxi>_ ity of the material.
The main purpose of this research was to test procedures that might be
useful for deriving site-specific water quality criteria. Tha specific
objective of the study was to conduct tests to evaluate an "organism testing"
protocol for deriving site-specific criteria utilizing toxicity tests with
several species of aquatic organisms in site and laboratory water. The type
of tests and/or exercises that were performed in this study were designed to
correlate with the site-specific guidelines as they are now proposed (U.S.
EPA, 1983b). This study was designed to help identify problems that one
might encounter when using the guidelines and to provide an example for a
site-specific criteria derivation for a chemical at an actual site.
Tests were conducted with cadmium because this chemical is highly toxic
to aquatic organisms (National Academy of Sciences, 1973), it is commonly
found in the environment due to its presence in treated municipal wastes
(U.S. EPA, 1980b) , and its chemistry in water is such that it may be
influenced by changes in water quality (Giesy et al. 1977; Calamari et al.
1980; Reid and McDuffie, 1981), which would be a major consideration for
modifying the present national criteria.
Study site
The St. TXJUIS River system near Duluth, Minnesota was chosen as the site
for study because: 1) Water quality monitoring data and hydrodynamic and
water quality models were available (DeVore, 1983). 2) It provided both
clean and dirty water characteristics needed for biological testing and for
2
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deriving a site-specific water quality criteria. 3) Resident aquatic species
for this river system were already known (State of Minnesota, 1941; National
Biocentric Inc. 1973; University of Wisconsin, 1976; DeVore, 1978; State of
Wisconsin, 1982; U.S. EPA, 1983o; Mary Balcer, personal communication)
(Appendix A).
The St. Louis River basin is a large area totaling 3,584 square miles in
northeastern Minnesota (Figure 1) (Waters, 1977). It is located primarily in
southern St. Louis County with small portions in adjoining counties and in
Douglas County, Wisconsin. The St. Louis River system includes approximately
1,400 miles of streams, 815 miles of which are the St. Louis River and its
tributaries (State of Minnesota, 1941). From source to mouth, the St. Louis
River has a total length of 164 miles, flows in a general northeast-southwest
direction and forms a drainage pattern roughly parallel to the north shore of
Lake Superior. Vearly all water received by the $'. . Louis River is from
surface drainage, bog seepage and overflow from lakes. Bog drainage and high
humic content give the river its brown color. The water of the St. Louis
River system is of moderate chemical fertility.
The mouth of the St. Louis River is an estuary containing approximately
11,500 acres of water. It has been developed into a major industrial port
which serves as the economic base for the cities of'Dulath, Minnesota and
Superior, Wisconsin (Figure 2). Dredging and the discharge of municipal
sewage, paper mill waste, wash water and other industrial wastes hive
degraded water quality in the St. Louis River below Cloijuet, Minnesota since
the turn of the century. Since 1979, however, domestic as well as industrial
wastes from Duluth and the surrounding communities have been treated by the
Western Lake Superior Sanitary District Treatment Plant (WLSSD). This has
greatly improved water quality in a very short period of time. The WLSSD
3
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MINNESOTA [WISCONSIN
Figure 1. St. Louis River Basin (Waters, 1977),
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0 1.6
Kilomeierj
DUCOTH
LAKE SUPERIOR
Superior Entry
Figure 2. Duluth and Superior estuary.
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plant treats an average of 160 million liners per day and removes over 300
metric tons of pollutants per day (Ducette, 1980). The effluent ftom this
treatment plant is discharged into the estuary (Figure 2) and is the major
point discharge of treated waste in this area.
The site chosen for a source of dilution water in this study was located
approximately 34 miles upstream from the mouth of the Duluth-Superior estuary
at the Stat^ Highway 33 crossing in the city of Cloquet, Minnesota (Figure
3). Water samples were taken from the north channel to represent the river's
quality immediately before the influence of the Cloquet area. This site on
the river was considered to have the highest water quality closest to the
impacted Duluth-Superioi" estuary (Western Lake Superior Sanitary District,
personal communication). Water at this site was also judged to be of high
quality because several species of aquatic organisms were able to survive,
grow and reproduce in it under laboratory conditions with no apparent adverse
effects. No industrial point discharges existed'upstream of this site.
Ambient water quality parameters including metal analyses for this site
obtained during the tests (from April to December 1981) are included in
Appendix B.
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Figure 3. St. Louis River site at the State Highway 33 crossing in
Cloquet, Minnesota.
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PROCEDURES AND TEST METHODS .
Procedures for calculating c: ?ria
Three procedures were used in this study to modify the national maximum
and 30-day average concentration criteria for cadmium. They were used for
illustrative purposes only because all three procedures would not necessarily
be used in an actual site modification. In addition, procedures to determine
a Final Residue Value or a Final Plant Value (which are required in the
National Guidelines for deriving water quality criteria; U.S. EPA, 1983a)
were not included in this study because cadmium is not a lipid-soluble
material and plants have not been shown to be as sensitive to cadmium as
aquatic animals. Thus, the site-specific, Final Chronic Value for cadmium
was the same as the site-specific, 30-day average concentration for all
procedures conducted in this study.
The three procedures used to calculate a site-specific, criteria for
cadmium in the St. Louis River were as follows:
1) the recalculation procedure was used to account for differences in
cadmium sensitivity between species resident in the St. Louis River and those
species contained in the national cadmium criteria document (U.S. EPA,
1983d). 2) The indicator species procedure was used to account for
differences in the biological availability and/or toxicity of cadmium due to
physical and/or chemical characteristics of the St. Louis River water and
laboratory water by deriving a water effect ratio (toxicity in site water
divided by the toxicity in laboratory water). 3) The resident species
procedure was used to account simultaneously for differences in both resident
species sensitivity and differences that nay be attributed to water quality.
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In addition to the above procedures, acute tests were conducted monthly
on one-day-old fathead minnows to determine if seasonal changes in water
quality affected the toxicity of cadmium in the St. Lcuis River.
A detailed description of defining a site, the rationale, assumptions
and limitations of the site-specific procedures and their relationship to
those used for deriving national water quality criteria are included in the
proposed site-specific guidelines (U.S. EPA, 1983b).
Water characteristics
Water samples for preliminary and acute toxicity tests in St. Louis
River water were taken below the water surface with 19 liter polyethylene
jugs and immediately brought back to the laboratory for testing. Large
quantities of water needed for cr.jonic tests were obtained by pumping river
water through a 30 meter, 5 cm diameter collapsible PVC hose to a 3,800 liter
steel truck tank.. Site water was then transferred to the laboratory and
pumped into two 1,900 liter Teflon coated head tanks where it was stored and
vigorously aerated prior to use. Both reconstituted and Lake Superior water
were used as laboratory dilution water in comparative toxicity tests.
Reconstituted vater was made according to procedures described, by the
American Society for Testing and Materials (ASTM, 1980) for soft water.
Unfiltered Lake Superior water was obtained directly from Lake Superior.
Both waters were heated (if necessary) to the appropriate test temperature
for each test.
Chemical characteristics of the site water were determined after^each
collection by the Western Lake Superior Sanitary District located in Duluth,
Minnesota. In addition, chemical characteristics for all dilution waters
were measured just prior to or during all toxicity tests at the Environmental
9
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Research Laboratory, Duluth, Minnesota and were conducted according to
procedures of the American Public Health Association et al. (1980).
Exposure systems
Static tests with larval fish were conducted in 600 ml glass beakers
containing 500 ml of solution. Glass beakers containing 200 ml of solution
were used for static tests with invertebrates. Wide mouth glass jars
containing five to 10 liters of test solution were used for static tests with
juvenile fish. Duplicate test chambers were used in all tests for each of
five toxicant concentrations and a control. All test chambers used for these
tests were contained in a water bath for temperature control. Fluorescent
light bulbs provided a light intensity of 80 to 100 lux during a 16-b.
photoperiod.
Flow-through acute and chronic exposures with fish were conducted using
a diluter system (Benoit et al. 1982) which delivered five toxicant concen-
trations and a control to four replicate chambers per treatment. Glass test
chambers measured 7 cm wide x 19 cm long x 9 cm high with a water c*epLh of
4.5 cm. The flow to each chamber was 12.5 +_ 1 ml/min. Fluorescent bulbs
provided a light intensity of 200 to 500 lux it the water surface during a
16-h photoperiod.
Toxicant solution
Stock solutions for static tests were prepared by dissolving reagent
grade cadmium chloride (CdC^) in distilled water. After ttst
concentrations were calculated, measured amounts of stock solution were
diluted with the dilution water to provide for various toxicant concentra-
tions. For flow-through tests, cadmium stock was dissolved ir. 19 liters of
distilled water and pumped to the diluter via a fluid metering pump to
produce the desired test concentrations. Water samples from each test
10
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concentration and control were collected in 250 ml Nalgene LPE bottles at the
beginning of each acute static test and once a week during flow-through
tests. They were acidified with concentrated nitric acid (0.5% v/v) for
analyses. Preliminary analysis indicated that no metal was lost in the water
after 96 hours, therefore, water measurements for cadmium were made only at
the beginning of the tests. Water samples were analyzed with a Perkin Elmer
atomic absorption spectrophotoraeter equipped with either a HGA 500 graphite
furnace or an automatic burner control. All measurements are expressed as
total cadmium and not as the compound. The limits of detection for these
procedures were 0.25 and 35 fjg/l, respectively. To verify the accuracy of
the method of analysis, known amounts of the metal were added to control
water to obtain percentage recoveries. Percentage recoveries ranged from 91
to 110% for 76 spiked samples. In addition, one set of samples was
periodically filtered through a 0.45 fjmillipore filter to characterize the
portion of dissolved metal. The mean percentages, standard deviation and
number of samples of dissolved cadmium for individual tests (including five
cadmium concentrations per test) w^re 84 +_ 1.0 (8), 84 +_ 1.0 (4), 96 +_ 2.0 v
(9) for St. Louis River, Lake Superior and reconstituted water,,
respectively.
Biological procedures
Size, temperature and source of aquatic species exposed to cadmium in
the St. Louis River and reconstituted water are shown in Table I. Tests to
determine a water effect ratio were conducted in both waters with each
species at the same tine and under the same test conditions. Tests with
different species were conducted throughout the year as they became available
from their respective sources. Procedures for conducting acute tests
11
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Table 1. Size, temperature, and source of aquatic species exposed to cadmium in
St. Louis River, and reconstituted water.
Species
Cladoceran,
(Daphnia raagna)
Cladocpran,
(Simocephalus vetulus)
Cladoceran,
(Simocephalus serrulatus)
Cladoceran,
(Ceriodaphnia reticulata)
Amphipod,
(Gammarus pseudol imnaeus)
Amphipod,
(Hyalella azteca)
Mayfly,
(Paraleptophlebia praepedita)
Rainbow trout ,
(Salmo gairdneri)
Brown trout,
(Salmo trutta)
Fathead minnow,
(Pimephales promelas)
Channel catfish,
(Ictalurus punctatus)
Age(d)
Li f e or
Stage Wa\ght(g)
Young
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followed those described by the nmerican Society for Testing and Materials
(ASTM, 1980).
Tests wer-i conducted monthly beginning in April and ending in December
1981 to determine the effect of seasonality ->n the physical and chemical
characteristics of the site water and the subsequent effects on biological
availability and/or toxicity of cadmium on fathead minnows. These tests were
initiated by incubating fathead minnow embryos that were <24 hours old in St.
Louis River water, reconstituted and/or Lake Superior water for four to five
days, or until they hatched. Ten one-day-old larvae were then transferred to
each dupliate test chamber and exposed for 96 hours for the calculation of
LC50 values. Other acute tests with juvenile animals were initiated by first
acclimating each species in site or laboratory dilution water at the test
temperature for at least two days prior to testing. All cladocerans were
reared in the dilution water for a sufficient amount of time to produce young
before being tested. After acclimation, 10 or 20 animals of each species
were transferred to each test concentration and control. Acute tests lasted
for 96 hours for all species except cladocerans, which lasted 48 hours, and
LC50 values were calculated as the response variable.
Chronic tests lasted for 32 days for fathead minnows and nine days for
cladocerans. These tests were done according to procedures similar to those
described by ASTM (1983) and Mount and Norberg (1982), respectively.
Survival, growth and/or reproduction were used as the response variable in
these tests. All animals obtained from outside sources were held in the
dilution water for at least two weeks before testing. During the holding
period, fish were treated for disease, if needed, according to procedures
described by ASTM (1980).
13
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Statistical analysis
The computerized, modified, trimmed Spearman-Karber method described by
Hamilton et al. (1977) was used to determine 48- and 96-h LC50 values. Daily
mortality data of replicate exposure tanks were combined before LC50 values
were calculated.
For chronic tests, survival and embryo hatchability data were trans-
formed to arcsin % (Dixon and Massey, 1957) for variance stabilization.
Individual weights frora fish in replicate chambers wore pooled before the
data was subjected to a one way analysis of variance (P = 0.05) and to
Dunnett's one-sided comparison of treatment means to control means (P = 0.05)
(Steel and Torrie, 1960).
14
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RESULTS
Water parameters measured for tests conducted monthly in St. Louis
River, reconstituted, and Lake Superior water are shown in Table 2.
Dissolved oxygen concentrations in ail tests were maintained between 60 and
100% of saturation. Tests were not continued with reconstituted water during
the months of November and December because of unexplained mortality of
animals cultured in this water during October. Lake Superior water was used
to replace reconstituted water as a representative of laboratory water in the
months of November and December.
No particular trend was observed for any water quality parameter with
time and most values were relatively constant [<25% relative standard
deviation (RSD)]. Values for turbidity and dissolved solids, however, were
highly variable (100 and 129% RSD, respectively).
Monthly LC50 values for tests with one-day-old fath~ead minnows exposed
to cadmium in St. Louis River and reconstituted water are shown in Figure 4.
The mean acute value for cadmium obtained from Lake Superior water tests in
November and December was 42 /jg/l. Acute values calculated from exposures in
river water varied by a factor of three, whereas values obtained from tests
conducted in reconstituted and Lake Superior water varied by less than a
factor of two. The average acute values for St. Louis River water were
approximately five and two times higher than those obtained for reconstituted
and Lake Superior water, respectively. Linear regression correlation
coefficients obtained for acute toxicity and seasonal water quality
parameters are shown in Table 3. Values ranged from R = 0.21 for pH to 0.77
for dissolved solids. Correlations between acute LC50 values for fathead
minnows exposed in St. Louis River and reconstituted waters on a monthly
basis were significant (R = 0.75), indicating that there may have been slight
15
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Table 2. Monthly averages in water quality parameters for cadmium tests with fathead minnows conducted in
St. Louis River, reconstituted and Lake Superior water.
Parameter
Hardness
Acidity
Alkalinity
PH
Conductivity
TC
TIC
DIC
TOC
DOC
Turbidity
Color (CU)
CL-
SOA2-
Susp. Solids
Diss. Solids
April
63.0
2.9
54.0
7.6
146
_a
-
-
-
3.0
120
6.5
11.0
6.8
97
May
55.0
2.6
41.0
7.2
104
24.0
7.5
-
16.5
-
2.0
150
5.0
10.0
2.8
104
June
St.
59.0
4.0
50.0
7.4
134
31.7
12.7
12.5
19.0
18.8
6.0
190
4.0
9.0
9.2
104
July
August
Sept
Oct
Nov
Dec
Louis River Water
66.0
2.3
55.0
7.6
138
33.2
11.1
11.0
22.2
22.6
20.0
230
4.5
10.0
27.0
142
Reconstituted
Hardness
Alkalinity
Acidity
PH
Conductivity
Hardness
Alkalinity
Acidity
PH
Conductivity
40.0
30.0
. -
7.5
136
»
-
-
-
48.0
42.0
2.1
7.9
155
45.0
40.0
2.1
7.4
100
41.0
29.0
2.3
7.4
167
Lake
mm
-
-
-
42.0
30.0
1.9
7.3
165
Superior
_
-
-
-
65.0
4.2
52.0
7.3
155
34.7
11.7
6.6
23.0
24.4
10.0
210
5.0
15.0
14.4
147
Water
41.0
29.0
5.7
7.0
136
Water
-
-
-
74.0
3.6
65.0
7.8
165
28.7
14.2
14.3
14.6
14.0
3.0
180
5.5
12.0
0.4
144
39.0
26.0
4.1
7.7
160
_
-
-
-
79.0
2.0
42.0
7.6
115
31.7
10.3
9.2
21.4
22.8
5.0
280
6.0
12.0
0.4
114
^m
-
-
-
_
-
-
-
62.0
2.9
46.0
7.3
129
28.2
10.1
10.3
18.1
18.6
2.0
195
5.0
18.0
0.4
136
_
-
-
-
47.0
42.0
2.2
7.4
95.0
60.0
3.7
49.0
7.4
132
28.9
9.9
-
19.0
-
2.0
120
5.0
13.0
1.2
125
__
-
-
-
44.0
41.0
3.4
7.4
9.30
a No measurement made
-------
180
160
I4O
120
o>
100
in so
3
60
20
St. Louis River water
Reconstituted water
.1
j.
M
J A
MONTH
N
Figure 4. Monthly LC50 values (+95% confidence limits) for tests with
one-day-old fathead minnows exposed to cadmium in St. Louis
River and reconstituted water.
17
-------
Table 3. Correlation coefficients for St. Louis River cadmium toxicity
tests with fathead minnows and corresponding water quality
parameters for the months April through December 1981.
Mater quality Linear regression
parameter correlation coefficient
Ha'rdness 0.34
Alkalinity 0.34
pH 0.21
Total organic carbon 0.60
Turbidity 0.68
Suspended solids 0. 58
Dissolved solids 0.77
18
-------
differences in the sensitivity of various batches of fish over time. All
fathead minnows were obtained from the sane culture unit at our laboratory
throughout the testing period.
Acute values for 12 species of aquatic species exposed to St. Louis
River and reconstituted water are shown in Table 4. Comparative data showed
that cadmium was less toxic to four out of five species in St. Louis River
water than it was in reconstituted water. Values for G. pseudolirnnaeus were
nearly the satne in both waters, resulting in a water effect ratio (relating
LC50 values in river water over those in reconstituted water) of one. It is
not clear why this species responded differently than the others; however,
this test may reflect very little or no difference in cadmiinr binding
capacity in the test waters at the time of sampling. Water effect ratios for
fathead minnows, cladocerans (j5. serrulatus), rainbow trout and brown trout
ringed from 2.6 to 10.8.
Chronic effects of cadmium on fathead minnows exposed in St. Louis River
water are presented in Table 5. Cadmium significantly reduced embryo
hatchability and survival and caused larval deformity at concentrations of
51.6 and 98.3 jjg/1. All larvae exposed to 98.3 yg/1 were dead immediately
after hatch and only 13% remained alive after this period at 51.6 yg/1.
After four days post hatch, survival of larvae exposed to the next lower
concentration of 26.7 ^g/1 was reduced to 60%. Mortality continued at this
concentration throughout the test period, resulting in a significant
reduction in survival by the end of the 32-day test. Significant reductions
in survival were not observed in fish exposed to 13.4 yg/1 and below. Growth
was not decreased at any ot the concentrations where fish survived. Based on
these results, the upper chronic limit (lowest tested concentration which
caused significant decreases from the control) fcr cadmium in St. Louis River
19
-------
Table 4. Acute values (LC50, yg/l) for aquatic species exposed to cadmium in
St. Louis River and reconstituted water.
Species
Daphnia ma^na
Ceriodaphnia reticulata
Simocephalus vetulus
Siraocephalus serrulatus
Gancnarus pseudolimnaeus
Hyalella azteca
Paraleotophlebia praepedila
Salmo ^airdneri
Salmo trutta
Pimeohales oromelas
Lepomis macrochirus
Ictalurus punctatus
Endpoint
48-h
48-h
48-h
48-h
48-h
96-h
96-h
96-h
96-h
96-h
96-h
96-h
Exposure
St. Louis River
166
(124-221)
129
(104-160)
89.3
(73.6-108)
123
(106-141)
54.4
(35.7-82.9)
285
(232-350)
449
(166-1217)
10.2
(7.9-13.1)
15.1
_c
3390
(2710-4240)
8810
(8200-9450)
7940
(7080-8910)
Water
Reconstituted
_a
24.5
(18.6-32.1)
68.3
(38.7-121)
2.3
(1.6-3.3)
1.4
(1.1-1.8)
1280
(1100-1470)
a No test was conducted
k 95% confidence limits
c 95% confidence limits could not be calculated using this method
20
-------
Table 5. Survival and growth of fathead minnows exposed to various
concentrations of cadmium in St. Louis River water for 32
days.
Measured
water
concentration
(ug/1)
<0
6
13
26
51
98
.25 (control)
.4 + 0.7a(9)b
.4 + 1.8(9)
.7 + 3.1(9)
.6 + 1.5(3)
.3 f_ 3.8(2)
Embryo Normal Mean
hatchability larvae at Survival weight
hatch (%) (%) (mg)
100+0.0 100+0.0 93 + 0.0 107 +_ 24(28)b
97+4.9 97+4.9 94+9.2 110+20(28)
100 + 0.0 100 + 0.0 94 + 9.2 103 + 30(28)
97 + 4.9 97 + 4.9 30+4.2* 105+47(9)
73 + 0* 0* 0*
83 + 14* 0* 0* -
a aiean +_ standard deviation
b number of fish weighed
* asterisk denotes values significantly different from the controls
(P = 0.05)
21
-------
water was 26.7 yg/1 and the lower chronic limit (the highest tested
concentration which did not cause significant decreases from the control) was
13.4 ng/1. The chronic value (geometric mean of the chronic limits) for this
species was 18.9 ng/1.
Chronic effects of cadmium on cladocerans (Ceriodaphnia reticulata)
exposed in St. Louis River water are shown in Table 6. After six days of
exposure, survival of daphnids was reduced tc S0% at 15.2 yg/1. Only one
animal remained alive (10%) at this concentration by the end of the nine-day
test. Young production occurred at all concentrations after six days of
exposure. However, the mean number of young produced was significantly
reduced after six days at 15.2 (ig/1 and nine days at 7.2 j/g/1. The chronic
value for this species based on the chronic limits of 3.4-7.2 yg/l calculated
froni these results was 4.9 jjg/l.
22
-------
Table 6. Survival and young production of Ceriodaphnia reticulaca exposed
to various cadmium concentrations In St. Louis River water for
9 days.
Measured water
concentration (ag/1)
<0.25 (control)
0.9 + O.la
1.8 + 0.2
3.4 + 0.2
7.2 + 0.6
15.2 + 0.6
Survival
(%)
80 + 42
90 + 32
80 + 42
80 + 42
60 + 52
10 + 32*
Mean number
of young
5.2 + 5.3
4.0 + 3.6
3.8 + 1.8
2. A + 2.5
2.1 + 2.0*
0.4 + 1.0*
a mean and standard deviation of four samples
* asterisk denotes values significantly different from the control (P = 0.05)
23
-------
DISCUSSION
Seasonality (96-h) acute tests with one-day-old fathead minnows
conducted in St. Louis River water indicated that cadmium toxicity was
significantly correlated to turbidity and dissolved solids concentration in
the water. The LC50 values varied by more than a factor of three and
increased with increased turbidity and dissolved solids concentration. The
variation in LC50 values for tests conducted in reconstituted water was less
"* " *
»
than a factor of two. The larger variation in values obtained from tests
conducted in site water was attributed to high and low stream flows which
influenced turbidity and dissolved solids concentrations throughout the year.
The direct proportionality found between toxicity and these parameters
suggests that the large degree of binding or complexing of cadmium that
occurred during times when concentrations of part, iculates in this water were
the highest resulted in reduced cadmium toxicity. Although this effect on
toxicity was not dramatic in the present tests, larger variations in toxicity
may occur in streams where particulate loads change significantly during
different times of the year. The frequency of testing needed to determine
seasonal toxicity differences will dr.pend on this variability. The frequency
will have to coincide with the waste treatment facilities design flow or with
NPDES permits issuance.
The acute toxicity tests demonstrated that cadmium was less toxic in St.
Louis River water than in reconstituted or Lake Superior water. The
difference was observed in seasonality tests with fathead minnow larvae and
in tests utilizing juveniles of five species including both v.ivertebrates and
fish. These findings indicate that physical and/or chemical characteristics
of the St. Louis River water reduced the biological availability and/or
toxicity of cadmium from that observed in reconstituted or Lake Superior
24
-------
water. This result co.nfirras the basic assumption underlying the indicator
species approach for criteria modification which this study was designed to
verify in a field situation. Although certain factors such as pH, hardness,
alkalinity and carbon dioxide have been the most studied and quantified with
respect to their effects on heavy metal toxicity, the literature indicates
that organic solutes, inorganic and organic colloids, and suspended
particulates play a major role in affecting the toxicity of heavy metals to
aquatic life (Spoor, personal communication). Recent work by Benoit
(personal communication) has shown that hardness alone has relatively no
effect on cadmium toxicity in Lake Superior water, but that suspended solids
(clay) and dissolved solids (humic acid) greatly reduce c'.aiul-^ toxicity to
fathead minnows.
25
-------
CRITERIA CALCULATION
Based on the results of the tests described above, site-specific, water
quality criteria for cadmium in the St. Louis River were derived using the
following procedures.
Recalculation procedure
This procedure allows for modification of the national maximum
concentration, by eliminating data for non-resident species from the national
data base.
Values for the minimum data set for cadmium from the national criteria
document for species and families resident to this site are provided in
Appendix 0. These data were sufficient to meet the minimum data set
requirements of the National Guidelines (U.S. EPA, 198?a). No additional
acute tests in laboratory water were needed to calculate a site-specific,
criterion using this procedure. The Species Mean Acute Values (SMAV's) are
listed in order of the highest to the lowest. Family Mean Acute Values
(FMAV's) are similarity listed and were used to calculate the site-specific,
Final Acute Value (FAV). Family Mean Acute Values differed in some cases
from the SMAV's when a family was represented by more than one species.
The site-specific, FAV for this procedure and cadmium was calculated to
be 2.4 yg/1. The site-specific, maximum concentration was derived by the
following equation:
Site-Specific, Maximum Concentration = Site-Specific, Final Acute Value
2
26
-------
Because the toxicity of cadmium has been related to the hardness of the
water, this relationship was taken into account before the site-specific,
maximum concentration was calculated. The site-specific, maximum
concentration for cadmium from the above equation, adjusted for hardness of
the St. Louis River ("55 rag/1 as CaCO-j; the lowest hardness measured in
this water over a years' time) was 1.3 wg/1 using the recalculation procedure
(Appendix C).
No testing was required to determine a site-specific, 30-day average
concentration using this procedure. A site-specific, Final Chronic Value
(FCV) can be derived from this procedure by dividing the site-specific, FAV
by the national acute-chronic ratio. Since the national acute-chronic ratio
for cadmium is 2.0 (U.S. EPA, 1983d), the site-specific, FCV for cadmium is
the same as the site-specific, maximum concentration, 1.3 /Jg/l. Since a
site-specific, Final Residue Value or a Final Plant Value was not available,
the sice-specific, 30-day average concentration for cadmium in St. Louis
River, using the recalculation procedure, was 1.3 /jg/1.
Indicator species procedure
This procedure is based on the determination of a water effect ratio to
account for the differences in the toxicity of cadmium in St. Louis River and
laboratory water due to physical and/or chemical characteristics of these
waters. Tests for each species were conducted in each water, at the same
time, and under similar test conditions. A water effect ratio was calculated
as:
Water Effect Ratio = Site Water LC50
Lab Water LC50
27
-------
Measured LC50 values for a. toxicant must be significantly different in
thfi two waters for this procedure to be valid. (If the values are not
different, then the national, maximum concentration is the site-specific,
maximum concentration.)
VJater effect ratios were obtained from tests with several fish and
invertebrate species (Appendix D). Although only tests with one fish and one
invertebrate species were required for this procedure, tests were conducted
with several species to provide additional information for this study. A
filter feeder (cladoceran) was included because it is on<» of the most
sensitive species to cadmium in the national criteria document. Because it
ingests particulate matter for food, this type of species also provided a
good example to discern differences in the biological availability and/or
toxicity for cadmium. Two species of trout, fathead minnows, and amphipods
were also tested because they are examples of both cold and warm water
species and are dissimilar taxonomically.
The results of these tests indicated that cadmium was generally less
toxic in site water than in reconstituted water. An exception to this
occurred in tests with amphipods where the toxicity of cadmium was the same
in both waters, resulting in a water effect ratio of 1.0. Tests with brown
trout, on the other hand, showed that"there was a large toxicity difference
resulting in a water effect ratio of 10.2. Since these ratios were
statistically different from water effect ratios obtained for the other
species, they were not used in the calculation of a site-specific, maximum
concentration for the purposes of this study. If water effect ratios from
tests with only these two species were available, additional tests would have
been needed to confirm or refute the differences in ratios found between
these species.
28
-------
The 96-h LC50 values for cladocerans, rainbow trout and fathead minnows
were statistically different in both site and laboratory water and their
water effect ratios were similar, allowing them to be used for the calcula-
tion of a site-specific, maximum concentration in the following equation:
Site-Specific, = Geometric Mean x National, Maximum
Maximum Concentration Water Effect Ratio Concentration
(7.0 fjg/1) (3.9) (1.8 yg/l)
The national, maximum concentration of 1.8 yg/1 was adjusted for the
hardness of the laboratory water (45 mg/1 as CaCC^) before the
site-specific, maximum concentration was calculated. The site-specific,
maximum concentration for cadmium for the St. Louis- River was 7.0 >jg/1 using
the indicator species procedure.
The site-specific, 10-day average concentration for the indicator
species procedure can be derived by 1) ca.culation (no testing required)
using the national acute-chronic ratio and applying it to the site-specific,
FAV, by 2>-performing two pairs of acute and chronic tests which include
tests with both a fish and an invertebrate species conducted in site water
and by applying the resulting acute-chronic-ratio to the site-specific, FAV,
and by 3) conducting chronic tests with both a fish and an invertebrate
species in site and laboratory water and then applying the chronic water
effect ratio to the national FCV.
Since the national acute-chronic ratio for cadmium is 2.0 the site-
specific, 30-day average concentration using the first method was the same as
the site-specific, maximum concentration of 7.0 j/g/1. The following equation
was used for the calculation:
20
-------
Site-Specific, Final Chronic Value = Site-Specific, Final Acute Value
National Final Acute-chronic Ratio
The site-specific, 30-day average concentration using the second method
was calculated to be 0.3 tie./1 based on a geometric mean acute-chronic ratio
of 50 (from present tests performed in the St. Louis River water, Appendix E)
and the following equation:
Site-Specific, Final Chronic Value = Site-Specific, Final Acute Value
Site-Specific, Final Acute-Chronic Ratio
The site-specific, chronic value was obtained for both of these methods
by using a site-specific, FAV of 14 (two times the site-specific, maximum
concentration obtained from this procedure).
Although tests were not conducted specifically to obtain a site-specific,
chronic value using the third method, due to the time constraints of this
study, comparisons were made between present chronic tests in St. Louis River
water and recent tests conducted with the sane species in Lake Superior water
at the Environmental Research Laboratory-Duluth, Duluth, Minnesota for use as
an example for providing a chronic water effect ratio for this method
(Appendix F) . The mean, chronic, water effect ratio from these studies for
two species (fathead minnows and cladocerans) was determined to be 1.0
because the chronic values obtained from tests in site and laboratory water
were not significantly different (the chronic limits overlapped) (U.S. EPA,
1983b). Since the mean, chronic, water effect ratio was not different from
30
-------
1.0, the site-specific, FCV is the same as the national FCV adjusted for the
hardness of the St. Louis River or 2.2 fig/1 using this method (Appendix H).
Resident species procedure
This procedure allowed for modification of the cadnium national criteria
on the basis of tests conducted in site water with a set of species resident
in St. Louis River (Appendix G), Because the minimum data set requirements
for resident species were met at the St. Louis River site, substitute
families were not needed for testing under this procedure. Furthermore, a
family in a phylum other than arthropoda or chordata (i.e. Rotifera,
Annelida, Molluska, etc.), was not included in this aqta set because it was
not a requirement of the National Guidelines at the time that these tests
were conducted.
The site-specific, FAV calculated using the prescribed method (U.S.
EPA, 1983a) for resilient species was 3.8 ug/l. The site-specific, maximum
concentration was calculated as:
Site-Specific, Maximum Concentration = Site-Specific, Final Acute Value
2
The resulting site-specific, maximum concentration for cadmium using the
resident species procedure was 1.9 &f I.
The 30-day average concentrations for the resident species procedure
were obtained by the same methods (I and 2) described earlier under the
indicator species procedure using 3.8 isi./1 as the site-specific FAV. The
site-specific FCV's for these methods were 1.9 and 0.1 jig/l, respectively.
The third method was the same as that for the indicator species procedure and
resulted in a site-specific FCV of 2.2 ug/l (Appendix H).
31
-------
Summary of criteria calculation
Cadmium water quality criteria derived from the national and
site-specific procedures are compared in Appendix H. Criteria derived from
the recalculation procedure were slightly lower than those of the national
criteria. The lower recalculated criteria were attrihuted to the lower
number of families used to calculate the site-specific FAV's (10 as compared
to 21) and to the use of the same sensitive families in both procedures. The
maximum concentration criterion obtained from this procedure will usually be
lower than national value because the smaller "N" is, the lower the FAV will
be (National Guidelines, U.S. EPA, 1983a). Site-specific criteria for
cadmium derived from tha indicator species procedure were higher than those
derived from the national and the recalculation procedure. This result was
expected because criteria derived from this procedure were based on a water
effect ratio which was attributed to site water characterisitics that
decreased the bioavailability and/or toxicity of cadmium. Cadmium was found
to be less toxic to several species in St. Louis River water than in
laboratory water. The site-specific, maximum concentration derived from the
resident species procedure was slightly higher than the criterion derived from
the recalculation procedure but less than that obtained from the indicator
species procedure. This result was .also expected and attributed to the
combination of using a limited data base (N = 8) (which resulted in a lower
criteria) and the use of site water tests (which resulted in higher criteria
due to the mitigating effects of the site water characteristics). In
addition, the site-specific, 30-day average concentrations derived from the
chronic, water effect ratio method in the present example were the sanu; as the
national FCV (adjusted for the hardness of our laboratory water) because the
mean, chronic water effect ratio was not significantly different from
37
-------
1.0. The low, 30-day average concentration obtained from the second method
of both the indicator and resident species procedures was attributed to the
large, site-specific, acute-chronic ratio used in the calculation of the site
specific PCV. The large acute-chronic ratio obtained from the present tests
was obtained for commonly tested species (one fish and one invertebrate)
which were different from the species used to calculate the national Final
Acute-Chronic Ratio of 2.0. The low acute-chronic ratio used in the national
water quality criteria document for cadmium (U.S. EPA, 1983d) was determined
for chinook salmon. Because the Final Acute Value for cadmium was based on
rainbow trout, a species in the same family as the chinook salmon, higher
ratios were not used.
33
-------
OVERALL ASSESSMENT
Although all of the above procedures were tested in this study, only one
of these approaches would most likely be used in an actual site criteria
nodification. If species sensitivity was the important factor, the
recalculation procedure would be the least costly approach because it would
require no testing. When water quality at a site may mitigate the toxicity
of a chemical, the indicator species procedure is encouraged. This is
especially true for metals like cadmium where biological availability and/or
toxicity are significantly effected by variations in water quality
characteristics of the site water. When both species sensitivity and water
quality are important considerations for a particular site, the resident
species procedure would be the best approach because it is designed to
account for differences due to both of these factors. This approach,
however, would be the most costly because at least eight acute tests are
required to be conducted in site water.
The above procedures were designed for deriving site-specific water
quality criteria by allowing substantial flexibility with respect to the
methodology used. This should permit regulatory agencies to choose the most
efficient means of obtaining the information needed to modify national
criteria for each particular site. Site-specific, water quality criteria for
cadmium and the St. Louis River obtained from the site specific guidelines
appear to be logical, taking into account the national cadmium criteria and
physical, chemical and biological characteristics of this site water. Using
these procedures to derive site-specific water quality criteria for toxic
materials at different sites should provide additional input to the
development of effective, site-specific guidelines.
34
-------
ACKNOWLECEMENTS
We wish to thank J. E. Poldoskl, J. W. Penoos and F. A. Puglisi for
conducting analytical measurements of cadmium and T. J. Nelson a.id M. K. Ege
for routine analyses. We also wish to sincerely thank J. J. Stepun and his
laboratory staff at the Western Lake Superior Sanitary District plant in
Duluth, Minnesota for providing water quality monitoring data, extensive
analyses of water samples of the St. Louis River, and for their valuable
assistance with water sampling throughout this study.
35
-------
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pp.
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39
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Appendix A. Biological survey of aquatic species resident to the St.
river basin.
PLANKTON
Louis River and
PHYTOPLANKTON
Baclllarlophyceae (diatoms)
Achnanthes lanceolata var. rostrata
Asterlonella formosa
Cocconels spp.
Cosclnodlscus spp.
Cyclotella meneghlnlana
Cymbella spp.
Diatonia himenale
Dlatoma spp.
Eunotia pectlnalis
Fragilaria capuclna
Fragllaria crotonensls
Fragilaria spp.
Gomphonema spp.
Melosira distans
Melosira granulata
Meloelra varians
Melosira spp.
Meridlon circulare
Navicula cuspidata
Navlcula exlgua
Navicula gastrum
Navicula hungarica
Navicula pupula
Navicula radlosa
Navicula viridula
Naviculi spp.
Nltzschla palea
Nir.zschia tryblionella
Nltzschia spp.
Pinnularla spp.
Rholcosphenla curvata
Stauroneis crucicula
Stephanodiscus spp.
Synecra actlnastroldes
Synedra ulna
Synedra spp.
Tabellaria fenestratc
unidentified diatoms 40
Chlorophyta (green algae)
Actinastruai spp.
Ankistrodesmus
Cosmarlum
Crucigenia quadrata
Elaktothrix viridis
Klrchneriella lunaris
Pandorina morim
Pediastrum duplex
Scenedesmus spp.
unidentified unicells
unidentified colonies
unidentified filaments
Cyanophyta (bluegreen algae)
Anabaena spp.
Anacystis spp.
Aphanocapsa spp.
Euglenophyta
Euglena spp.
Phacus longicauda
Pyrrophyta
Ceratium hirudinella
Cryptomonadaler
Cryptomonas erosa
-------
Appendix A. (Continued)
ROTOTARIA
Conochllus sp.
Synchaeta sp.
Keratella cochlearls
Keratella quadrata
Kelllcottla longlsptna
Polyarthra sp.
Agplanchla priodonta
Pleosoma hudsonla
Brachlonus sp.
Cupelopagls sp.
Tetramastlx sp.
Trichocerca sp.
Fillnla sp.
Monostyla sp.
ZOOPLANKTON
Cladocera
Cerlodaphnia raegalops
Cerlodaphnla reticulata
Slmocephalus vetulus
Simocephalus serrulatus
Eubosmina coregoni
Bosmina longlroscris
Bosraina coregoni
Daphnla pulex
Daphnla retrocurva
Daphnia ambigua
Daphnia galeata mendotae
Leptodora klndtll
Diaphanosoraa blrgel
Alona guttata
Alona sp.
Chydorus sp.
Latona setlfera
Campcocercus sp.
Pleuroxus sp.
Slda sp.
Copepoda
Diaptomus ashlandi
Dlaptonsus slcllls
Diaptomus minutes
Diaptomus oregonensls
Diaptomid copepodids
Eurytemora afflnls
Eplschura lacustrls
Llmnocalnus macrurus
Leptodiaptomls mlnutus
Leptodlaptomus slcllls
Leptodlaptomis slclloldes
Leptodiaptomus ashlandi
Eplschura lacustrls
Skistodiaptomus oregonensis
Cyclopoid copepodids
Cyclops blcuspldatus
Cyclops vernalls
Eucy lops agilis
Mesocyclops leukartl
Mesocyclops edax
Paracyclops ftmbrlatus
Dlacyclops thjmasl
Macrocyclops albldls
Acanthocyclops vernalis
Tropocyclops prasinus
Halocyclops sp.
Orthocyclops modestus
llarpacticolda sp.
Osphrantlcum sp.
-------
Appendix A. (Continued)
ANNELIDA
Oligochaeta
Tubifex sp.
Pblychaeta
Helobdella stagnalis
Helobdella elongata
Manayunkia sp.
Hirudlnae
BENTHIC ORGANISMS
Illinobdella alba
MOLLUSCA
Pelecypoda
Sphaeriurn transversum
Sphaerium sltnlli
Sphaerium lacustra
Sphaerium nitidium
Sphaerium securis
Sphaeriura partumium
Sphaerium rhoraboideum
Sphaerium favale
Sphaerium striatinuni
Sphaeriura occidintale
Pisidiura fallax
Campeloma sp.
Musculium sp.
Gastropoda
Amnicola limnosa
Valvata sincera
Valvata tricarinata
Promentus exacuous megas
Proraentus unbilicatellus
Gyraulus deflectus
Helisoma anceps
Physa sp.
Isopoda
Asellus iutermedius
Asellus racovitzae
Ephemoroptera
Paraleptophlebia praepedita
Hexagenia sp.
Caenis sp.
Ephemerella sp.
Trtcoptera
Phylocentropis sp.
Oecetis sp.
Glossosoma sp.
Neureclipsis sp.
Molanna sp.
Leptccella sp.
Wormaldia sp.
Diptera
Microspecta sp.
Tribelos sp.
Chaoborus sp.
Cricotopus sp.
Procladius sp.
Parachironomus sp.
Cryptochironoraus sylifera
Cryptochironomus nais
Xenochironomus sp.
Chironomus sp.
Polypedilua sp.
Clinotanypus sp.
Coelotanypus sp.
Ablabesmyia sp.
Glyptotendipes sp.
Tanytarsus sp.
Palporaia sp.
ANTRHOPODA
Amphipoda
Gararaarus pseudolironaeus
Gammarus fasciatus
Ganncarus lacustris
Hyalella aztcca
Pontoporeia affinis
42
-------
Appendix A. (Continued)
FISH
Petroinyzontidae
Silver lamprey (Ichthyomyzon unlcuspis)
Angutllidae
American eel (Angullla rostrata)
Clupeidae
Alewlfe (Alosa pseudoharengus)
Salmonidae
Pink salmon (Oncorhynchus gorbuscha)
Chinook salmon (Oncorhynchus tshawytscha)
Rainbow troat (Salmo gairdnerl)
Brovm trout (Salmo trutta)
Lake herring (Coregonus arcedl)
Osmerldae
Rainbow smelt (Osmerus mordax)
Unbrldae
Central raudminnow (Umbra llml)
Esocidae
Northern pike (Esox luclus)
Muskellunge (Esox masqutnongy)
Cyprlnldae
Lake chub (Couesius plumbeus)
Creek chub (Semotilus atromac-ulatus)
Carp (Cyprlnus carplo)
Goldfish (Carasslus auratus)
Golden shiner (Notemlgonus crysoleucas)
Emerald shiner (Notropis atherinoldes)
Common shiner (Notropis cornutus)
Spottall shiner (Notropis hudsonius)
Mimic shiner (Notropis volucellus)
Fathead minnow (Plmephales promelas)
Bluntnose minnow (Plmephales nota^us)
Longnose dace (Rhinichthys cataractae)
Catostomtdae
Longnose sucker (Catostomus catostonius)
White sucker (Catostomus commersoni)
Silver redhorse (Moxostoma anisurum)
Shorthead redhorse (Moxostoma macrolepidotum)
-------
Appendix A. (Continued)
Ictalurldae
Black bullhead (Ictalurus melas)
Yellow bullhead (Ictalurus natalis)
Brown bullhead (Ictalurus nebulosus)
Channel catfish (Ictalurus punctatus)
Stonecat (Noturus flavuo)
Tadpole mad torn (Noturus gyrlnus)
Percopsidae
Trout-perch (Percopsis omiscoiaaycus)
Gadidae
Burbot (Lota lota)
Gasterosteidae
Brook stickleback (Culaea inconstans)
Percichthydae
White bass (Morone chrysops)
Centrarchidae
Rock bass (Ambloplites rupestrls)
Pumpklnseed (Lepomis glbbosus)
Blueglll (Leponis macrochirus)
Smalliaouth bass (Klcropterus dolomieul)
White crapple (Pbmoxis annularls)
Black crappie (Pbmoxis nigro-naculatus)
Percidae
Johnny darter (Etheostoaa nigrum)
Yellow perch (Perca flavescens)
Logperch (Percina caprodes)
Walleye (Stizostedion vitreum vitreum)
Sciaenidae
Freshwater drum (Aplodinotus grunniens)
44
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Appendix B. Ambient water quality parameters obtained for ulie St. Louis River site «t Cloquet, Minnesota
during the months of April through December 1981a.
Date
81/C4/14
81/05/13
81/07/01
81/07/08
81/03/05
81/09/09
81/10/20
81/11/04
81/12/09
Date
81/04/14
81/05/13
81/07/01
31/07/08
81/08/05
81/09/09
81/10/20
81/11/04
81/12/09
Date
81/04/14
31/05/13
81/07/01
31/07/08
81/OS/05
81/09/09
81/10/20
81/11/04
81/12/09
Water Water
Depth Temp
(°C)
50 6
05 12
03 19
05 26
20 22
10 20
50 7
17 6
04 0
NI!3+NH4-
N Total
(a^/D
0.04
0.02
0.04
0,01
0.02
0.10
0.03
0.02
0.03
Copper
Cu, Tot
(ug/D
18
12
15
11
<10
13
<10
20
14
DO pH
(mg/1)
9.9 7.9
S.5 7.7
5.6 7.5
5.1 7.1
5.6 7.5
6.9 8.1
9.1 7.7
10.0 7.5
12.1 7.3
N03-N
Total
(ag/D
0.22
0.09
0.10
0.10
0.13
0.05
0.09
0.12
0.20
Zinc
Zn, Tot
(Vg/D
20
23
30
27
18
19
18
20
13
T Alk.
CaC03
(mg/1)
39
31
37
44
57
:7
40
42
52
Chloride
Total
(mg/1)
7
5
4
5
5
5
6
6
5
Nickel
Ni, Tot
-------
Appendix C. RECALCULATION PROCEDURE. Minimum data set for cadmium from the national
Rank
10
9
8
7
6
5
4
3
2
criterion document for species
River.
Family Mean
Acute Value
Family (ug/1)
Blthynlldae 8,400
Centrarchidae 3,174
Epheaerellldae 2,319
Cyprinldae 1,743
Chironomidae 1,200
Angulllldae 734
Physldae 150
Gamma r id ae 70
Daphnidae 27.8
and families resident
Species
Snail,
Amnicola sp.
Bluegill,
Lepomis macrochirus
Pumpkinseed,
Lepomis gibbosus
Mayfly,
Ephenierella sp.
Goldfish,
Carassius a-^ratus
Common carp,
Cyprinus carpio
Fathead minnow,
Pimephales promelaa
Midge,
Chironotaus sp.
American ael,a
Anguilla rostrata
Snail,
Physa sp.
Scud,
Gamma r as sp.
Cladoceran,
Daphnla pulex
Cladoceran,
to the St. Louis
Species Meaa
Acute Value
(^g/D
8,400
4,775
1,343
2,319
8,397
215
2,080
1,200
734
150
70
40.4
62; 3
Siciocephalus serrulatus
46
-------
Appendix C. (Continued)
Family Mean
Acute Value
Rank Family (ng/D
1 Saltnonidae 5.1
Species
Chinook salraon,
Oncorhynchus tswhawytscha
Rainbow trout ,
Salmo gairdneri
Species Mean
Acute Value
(Ug/1)
4.9
3.9
a Uncommon species
Site-Specific Final Acute Value a 2.4 ug/1 (calculated for a hardness of 50 ng/1 from
site-specific Family Mean Acute Values)
Site-Specific Criterion Maximum Concentration = (2.4 ug/1) / 2 = 1.2 ug/1 (for a
hardness of *iO mg/1)
In (Site Specific Criterion Maxiraira Intercept = In (1.2) - [slope x In (50)]
° 0.182 - 4.533 = -4.356
Site-Specific Criterion Maximum Concentration = e(1'16 Iln hardness] - 4.356
=1.3 ug/1 adjusted for a hardness of
55 ag/1.
47
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Appendix D. INDICATOR SPECIES PROCEDURE. Acute values (LC50) for indicator
species exposed to cadmium in St. Louis River and reconstituted
water.
Species
St. Louis
River Water
Reconstituted
Water
Water Effect
Ratio
Cladoceran (Simocephalus serrulatus) 123
Amphipod (Gamnarus psuedolimnaeus) 54.5
Rainbow trout (Salmo gairdneri) 10.2
Brown trout (Salmo trutta) 15.1
Fathead minnow (Plmephales promelas) 3,390
24.5
68.3
2.3
1.4
1,280
5.0
1.0
4.4
10.8
2.6
48
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Appendix E. Acute (LC50) and chronic values for aquatic organisms exposed
to cadmium in St. Louis River water.
Acute Chronic
Value Value Acute-Chronic
Species (:^g/l) (ng/1) Ratio
Fathead minnow (Plrncphales promelas) 1,830 18.9 97
Cladoceran (Ceriodaphnla reticulata) 129 5.0 26
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Appendix F. Chronic toxicity values of two species exposed to cadmium in
St. Louis River and Lake Superior water.
Species
Fathead minnow
(Pimephales promelas)
Chronic
Sti Louie Ri
Water
18.9
(13-26)
Value ((jg/l)
ver L. Superior
Water
13C
b (9-18)
Chronic3
Water F.ffect
Ratio
1.0
Cladoceran 5.0 4.2d
(Cerodaphnia reticulata) (3.4-7.2) (3-6) 1.0
a Chronic water effect ratios are 1.0 since values in site and laboratory
water are not different (chronic limits overlap).
Chronic limits
c Benoit (personal consnunicat ion)
" Mount (personal communication)
50
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Appendix G. RESIDENT SPECIES PROCEDURE. Minimum data set of resident
aquatic species exposed to cadmium in St. Louis River water.
LC50
Rank Species (yg/1)
8 Bluegill (Lepomis macrochirus) 8,300
7 Channel catfish (ictalurus punctatus) 7,900
6 Fathead minnow (PimephaLes promelas) 3,390
5 Mayfly (Paraleptophlehia praepedita) 449
4 Amphipod (Hyalella azteca) 285
3 Cladoceran (Si-nocephalus serrulatus) 123
2 Amphipod (ftammarus psuedolimnaeus) 54.4
1 Rainbow trout (Salmo gairdneri) '. 10.2
51
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Appendix H. Cadmium water quality criteria derived from the national and
site specific procedures.
Criterion
Derivation
Procedure
N'ational
Site-Specific
Recalculation
Indicator
Resident
Number of
Families Used
21
8
21b
8
Maximum
Concentration
('ig/D
2.2a
1.3a
7.0C
1.9
30-day Average
Concentration
(ug/D
2.2a
1.3a
7.0
0.3
2.2a
1.9
0.1
2.2a
a Adjusted for a water hardness of the St. Louis River of 55 mg/1
as CaCOj.
b The national data base containing 21 families was used in this
calculation.
c A national criterion of 1.8 ug Cd/1 (adjusted for a hardness of 45 mg/1
hardness (as CaCOj)) was used in this procedure.
52
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