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
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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

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    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

-------
                                 REFERENCES




American Public Health Association, American Water Works Association and




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     pp.




American Society for Testing and Materials.  1983.  Proposed standard




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     fishes.  Draft No. 5, February 1983.  Steven C. Schimmel, U.S. EPA,




     Narragansett, RI.  E-47.01.




American Society for Testing and Materials.  1980.  Standard practice for




     conducting acute toxltity tests wo.th fishes, macroinverte.brates, and




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Balcer, M. D.  1983.  Personal communcation.  University of




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Calamari, D., R. Marchetti, and G. Vailati.  1950.  Influence of water




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DeVore, P. W.  1983.  An annotated bibliography of environmental research




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DeVore, P. W.  19/8.  Fishery resources of the Superior-Duluth estuary.  For




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                                     36

-------
     Superior Environmental Studies, University of Wisconsin-Superior,




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Dixon, W. J. and F. J. Massey, Jr.  1957.  Introduction to statistical




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Ducette, W.J.  1980.  Monitoring of chloro-organics in the St. Louis River:




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     of Minnesota-Duiuth, Duluth, MN  55812.




Giesy, J. P., Jr., G. J. Leversee, and D. R. Williams.  1977.  Effects of




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Hamilton, M. A., R. C. Russo, and R. V. Thurston.  1977.  Trimmed Spearman




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Mount, 0. I.  1983.  Personal communication.  U.S. EPA, Environmental




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Mount, D. I. and T. J. Norberg.  1982.  A seven-day life-cycle cladoceran




     toxicity test.  Presented at the Society of Environmental Toxicology and




     Chfiaistry, 3rd Annual meeting, November 1982, Arlington, VA.




National Academy of Sciences and National Academy of Engineering.  1973.




     Water quality criteria 1972.  U.S. Environmental Protection Agency, U.S.




     Government Printing Office, Washington, DC  20402




National Biocentric, Inc.  1973.  Appendix for environmental impact




     assessment for Duluth-Superior harbor.  Sponsored by the U.S. Army




     Engineer District, St. Paul under Contract Mo. DACW 37-73-C-0074 by




     National Biocentric, Inc., St. Paul, MN  55113



                                     37

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Reid, J. D. and 3. McDuffle.  1981.  Sorptlon of trace cadmium on clay




     minerals and river sediments: Effects of pH and Cd(II) concentrations in




     a synthetic river water.  Water Air Soil Pollut. 15: 375-386.




Spoor, W.  198?.  Personal communication.  U.S. EPA, Environmental Research




     Laboratory-Duluth, Duluth, MN  55804




State of Minnesota.  1941.  A biological survey and fishery management plan




     for the streams of the St. Louis River basin.  Minnesota Department of




     Conservation, Division of Game and Fish, St. Paul, MN.




State of Wisconsin.  1982.  1981 Superior harbor index station report.




     Memorandum from S. T. Schrara to T. L. Margenau, February 15, 1982.  File




     Ref. 3600.




Steel, R. G. D. and J. H., Torrie.  1960.  Principles and procedures of




     statistics with special reference to the biological sciences.




     McGraw-Hill, New York.  481 pp.




University of Wisconsin-Superior.  1976.  Environmental  inventory of lower




     St. Louis River covering proposed improvements to Duluth-Superior




     harbor, Minnesota and Wisconsin.  Submitted to Knvironnentai Resources




     Branch, St. Paul District, St. Paul, MN  55101 by the Center for Lake




     Superior Environmental Studies, University of Wisconsin, Superior, WI




     54880.  Contract Mo. DACW-37-75-C-0202.




U.S. Environmental Protection Agency.  1980a.  Water quality criteria




     documents availability.  Federal Register Vol.  45  No. 231.  Washington.




     DC  20460.




U.S, Environmental Protection Agency.  1980b.  Treatability manual. Vol. 11.




     Industrial description.  Center Environmental research Information,




     Cincinnati, Oil.

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U.S. Environmental Protection Agency.  1983a.  Guidelines for deriving




     numerical national water quality criteria for the protection of aquatic




     life and its uses.  Draft July 5, 1983.  U.S. EPA, Environmental




     Research Laboratories at Duluth, MM; Gulf Breeze, FL; Narragansett,  RI;




     and Corvallis, OR.




U.S. Environmental Protection Agency.  1983b.  C-iideliiies for deriving




     numerical aquatic site-specific water quality criteria by modifying




     national criteria (Draft January 31, 1983).  U.S. EPA,  Environmental




     Research Laboratories in Athens, GA; Corvallis, OR; Duluth, MN; Gulf




     Breeze, FL; and Narragansett,  XI, Office of Water Regulations and




     Standards, and Office of Research and Development, Washington, DC




     20460.




U.S. Environmental Protection Agency.  1983c.  Chemical and biological




     studies related to th<'. water quality of St. Louis Bay of Lake Superior.




     Draft report.  Environmental Research Laboratory-Duluth, Duluth, Mil




     55804




U.S. Environmental Protection Agency.  1983d.  Revised section B of Ambient




     Water Quality Criteria for Cadmium, Draft August 19, 1983.  U.S. EPA,




     Environmental Research Laboratories at Duluth, MN and Narragansett, RI.




Waters, T. F.  1977.  The streams and rivers of Minnesota.  University of




     Minnesota Press, Minneapolis, MN  55455.




Western Lake Superior Sanitary Dl&trict.  1983.  Personal communication, J.




     Stepun.  Water quality monitoring data program, SL336M.  Duluth, MN




     55806.
                                     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 (blue—green algae)
     Anabaena spp.
     Anacystis spp.
     Aphanocapsa spp.

Euglenophyta
     Euglena spp.
     Phacus longicauda

Pyrrophyta
     Ceratium hirudinella

Cryptomonadaler
     Cryptomonas erosa

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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.

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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

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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)

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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

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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

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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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