SERA
United States
Environmental Protection
Agency
                      Great Lakes
                      National Program Office
                      77 West Jackson Boulevard
                      Chicago, Illinois 60604
EPA 905-R94-024
October 1994
Assessment and
Remediation of
Contaminated Sediments
(ARCS) Program
HAZARD RANKING OF CONTAMINATED SEDI-
MENTS BASED ON CHEMICAL ANALYSIS,
LABORATORY TOXICITY TESTS, AND BENTHIC
COMMUNITY STRUCTURE: METHOD OF PRIORI-
TIZING SITES FOR REMEDIAL ACTION
                      United States Areas of Concern

                      ARCS Priority Areas of Concern

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Hazard Ranking of Contaminated Sediments Based on



  Chemical Analysis,  Laboratory Toxicity Tests, and



 Benthic Community Structure: Method of Prioritizing



                Sites for Remedial Action
               M. L. Wildhaber and C. J. Schmitt




                   National Biological Survey




                   Midwest Science Center




                   4200 New Haven Road




                  Columbia, Missouri 65201








                      September 22, 1994








                         Prepared for:



     Assessment and Remediation of Contaminated Sediments Program



                Great Lakes National Program Office



                U.S. Environmental Protection Agency



                       77 West Jackson



                     Chicago, Illinois 60604



  U..S. Fish and Wildlife Service/National Biological Survey Contract Number



                       DW14933874-1

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                              DISCLAIMER




    Mention of trade names or commercial products does not constitute




endorsement or recommendation for use.

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                           TABLE OF CONTENTS

                                                                  Page


INTRODUCTION                                                       1

OVERALL HAZARD RANKING                                           2

      Ranking Sites Based on Toxicity Estimated from Chemistry            3

           -Toxic units model                                          5

           -Estimated pore-water concentrations                          6

           -Water quality standards                                     9

           -Other information                                        12

      Ranking Sites Based on Toxicity as Measured by
      Laboratory Toxicity Tests                                        12

      Ranking Sites Based on Toxicity as Measured by
      Benthic Community Structure                                    14

      Final Ranking                                                  15

      Objectives                                                    16

MATERIALS AND METHODS                                          16

      Sediment  Sampling Locations                                    16

      Sampling and Biological Measures                                16

      Chemical Analyses                                             17

      Detection  Limits                                                18

      Toxic Units Model Evaluation                                     19

      Ranking Evaluation                                             20

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                     TABLE OF CONTENTS (continued)




                                                                 Page




RESULTS                                                          21




     Toxic Units Model                                             21




           -Laboratory toxicity                                       21




           -Benthic community structure                              23




     Final Ranking                                                  25




DISCUSSION AND CONCLUSIONS                                     26




     Effectiveness  of the Toxic Unit Model                             26




           -Laboratory toxicity                                       26




           -Benthic community structure                              30




           -Data quality                                            32




           -Potential for model enhancements                          33




     Ranking Approach                                             35




ACKNOWLEDGMENTS                                               38




REFERENCES                                                       39




TABLES                                                           50




FIGURES                                                          74

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                              INTRODUCTION




    Contaminated sediments have become a major focus of environmental concern




and research, particularly in the Great Lakes (USEPA 1990). The concern is that




even with elimination of current and future sources of contamination, those




contaminants already present in sediments are a threat to aquatic life and human




health.  The Assessment and Remediation of Contaminated Sediments (ARCS)




program was managed by the Great Lakes National Program Office  of the United




States Environmental Protection Agency (USEPA) specifically to address




contaminated sediment issues in the Great Lakes and to examine new and




innovative ways to both assess and treat contaminated sediments (USEPA 1990).




    One goal of the ARCS program was to develop a method by which the  relative




risks associated with contaminated sediment from different sites can be evaluated.




A general method of ranking contaminated sediments based upon direct sediment




analyses and tests proposed by Kreis (1989)  and was used to proportionally scale




sediment variables so that they could be compared and combined.  The ranking




method developed for ARCS was modified and enhanced from the version




proposed by Kreis (1989) by incorporating bioavailability, control-adjusted




laboratory toxicity tests, and mean tolerance  to pollution of the benthic community




for  the sediments of concern.




    The numerical ranking system developed by Kreis (1989) was intended  as a




guide, to be used in  evaluating regulatory and remediation alternatives for




contaminated Great  Lakes sediments.  Kreis (1988) previously showed that the
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ranking process can be an effective tool for determining which sites, of a set of




contaminated sites, have the highest concentrations of total contaminants and




associated parameters.  The results of the ranking process can then be used to




prioritize sites for remediation; this prioritization is necessary due to the high cost




of sediment remediation. As resources and technologies become available, the




sediments needing remediation could each be "cleaned-up" in the order of their




ranking.  The remediation procedure or combination of procedures chosen is site-




specific and would depend on ecological, chemical, economic, and engineering




considerations.








                        OVERALL HAZARD RANKING




   In this report, we used the process of proportional scaling from 1 to 100 (Kreis




1989) to scale different types of information (i.e., sediment chemistry, laboratory




toxicity, and benthic community structure) in a way that they can be evaluated




equivalently.  As suggested by Kreis (1989), once all the information was on the




same scale, the data were combined by averaging (i.e., arithmetic mean)  the




information from all three categories. The site mean of the proportionally scaled




values was then  considered to be the best estimate of relative hazard, among




sites, of sediment contaminants to aquatic life.




   The primary difference between this relative ranking process  and the earlier




process (Kreis 1989) is that this one incorporates more information, including: 1)




adjustment of the bulk sediment chemistry concentrations for estimated

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bioavailability and cumulative chronic toxicity through the use of "toxic units"

(defined in the next section); 2) incorporating of control-adjusted laboratory toxicity

test results;  and 3) incorporating of benthic community information, in the form of

mean tolerance to pollution per organism for each site.



Ranking Sites Based on Toxicity Estimated from Chemistry Data

   In the ranking system developed by Kreis (1989), each chemical or group of

chemicals (e.g., metals,  dioxins, etc.) analyzed was ranked independently.  For

each analyte or group of analytes, the measured values or totals, respectively,

representing each site under consideration were scaled from 1 to 100, relative to

each other (i.e., the minimum measured value became  1, the maximum, 100). The

equation used to calculate the ranks for each chemical or  group of chemicals was:
               Rank = 1      S/te value - Minimum value
                           Maximum value - Minimum value
The independent ranks calculated for each chemical or group of chemicals was

then combined by averaging (arithmetic mean) for each site, yielding a mean rank

for each site based on chemical concentrations. In this ranking process the

chemicals analyzed are scaled relative to each other based only on the

concentrations present; the process does not scale those chemicals based on the

true measure of concern, which is hazard. In  addition to analyte concentration.

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hazard also includes a toxicity component.




   The approach we present for evaluating the hazard associated with chemicals




in sediments includes toxicologies!, ecological, and bioavailability information.  In




contrast to the earlier method (Kreis 1989), in our approach the "toxic units"




(Sprague and Ramsay 1965)  for each contaminant measured are calculated.




Sprague and Ramsay (1965)  defined a toxic unit as the ratio of observed water




concentration  of a contaminant to the incipient lethal concentration of that




contaminant.  Our definition of a toxic unit is similar, but based on the USEPA




Ambient Water Quality Criteria (AWQC); we define a toxic unit as the ratio  of the




estimated bioavailable component of the contaminant to the chronic toxicity water




quality criteria (e.g. USEPA 1986a) for that contaminant. We estimate




contaminant bioavailability by assuming that concentrations of the water-soluble,




bioavailable fractions of organic chemicals are controlled by equilibrium partitioning




(DiToro et al. 1991), and that acid volatile sulfides control the  solubility and




bioavailability of metals (DiToro et al. 1990).  Our estimates of chronic toxicity are




based heavily  on the AWQC for chronic toxicity (e.g., USEPA 1986a), which




incorporate laboratory-measured chronic toxicity—which  indirectly incorporates




bioaccumulation and measured bioaccumulation.




   In our approach, total potential toxicity is calculated  by summing toxic units




over all contaminants measured for each site.  This total potential toxicity is then




ranked among sites using the ranking equation described earlier (Kreis 1989).  The




result is a relative ranking of  the sites  under investigation based on the cumulative

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knowledge of what is known about the potential bioavailability and toxicity of the



contaminants found in the sediments at each site.  In our approach the analytes



present in sediments are scaled for toxicity and bioavailability and combined



(summed). These sums are then ranked.






Toxic units model



    To estimate toxicity of a complex mixture of chemicals, we used an additive



model based  on toxic units. A toxic unit is defined here as the ratio of the



estimated concentration of a contaminant in the pore water of a test sediment to



an estimate of chronic toxicity of that contaminant in water. The equation for



toxic units is:
                                           Q

                               Toxic unit = —^~
                   r   = Estimated pore-water concentration
                   ^wp

                   C   = Water quality standard
The toxic units for the contaminants in a sediment are then summed to produce a



total toxicity estimate for that sediment.

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Estimated pore-water concentrations




    Pore-water concentrations of the contaminants are estimated on the basis of



equilibrium partitioning and organic carbon control for organic compounds (DiToro



et al. 1991) and AVS and sulfide control for metals (DiToro et al. 1990).  The




estimated pore-water concentrations are considered estimates of the bioavailable



portions of the total concentrations of each contaminant measured in the




sediments (i.e., the concentration to which sediment-dwelling organisms would be



exposed at equilibrium).




    Pore-water concentrations of organic compounds were estimated from the




total sediment concentration in two  ways: 1). by assuming complete bioavailability




of bulk sediment concentrations; and 2). by correcting for organic carbon using



equilibrium partitioning  (DiToro et al. 1991).  The intent of using both methods




was to evaluate how well the toxic units model predicted toxicity of sediments as



measured by control-adjusted laboratory toxicity tests and mean tolerance to




pollution of the benthic community and how the ranking of hazard among sites



compared with and without accounting for bioavailability through equilibrium




partitioning. In the bulk-sediment approach, organic analytes are considered



completely bioavailable; that is, the pore-water concentration was estimated by




multiplying the dry weight concentration of each analyte by the dry weight to




moisture  content ratio of  the sediment. In the equilibrium partitioning method, the




pore-water concentration for organic contaminants and, hence, the bioavailability,



of each analyte is assumed to be controlled  by organic carbon content of the

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sediment, and is consequently a function of the organic carbon partition coefficient
(K^) of the analyte.  We used equilibrium partitioning modeling to estimate the
pore-water concentration of each analyte on the basis of the bulk (i.e., dry-weight)
sediment concentration, the arithmetic mean log octanol/water partition coefficient
(Table 1), and the proportion of organic carbon in the sediment sample associated
with that analyte, as follows:
                                           oc
            Where:
            CWP = Pore-water analyte concentration,
            Cs = Bulk-sediment analyte concentration;
            LogtfJ = 0.983 x Log(Kov) + 0.00028 (Ditoro et al. 1991)
            KQW = Octanoti water partition coefficient,
            ^ = Sediment organic carbon partition coefficient, and
            POC = Proportion of organic carbon in the sediment


   The main source of Kow values was USEPA (1987a); however, this document
did not contain Kow values for all analytes.  For those organic analytes lacking a
Kow, the following substitutions were made: Chlorodioxins and chlorodibenzofurans
lacking Kow values were assumed to have the same Kow as a  chlorodioxin with the
same  number of chlorines for which a value was available;  for endrin ketone (a

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polar metabolite of endrin) the Kow of endrin aldehyde (another polar metabolite)




was substituted; and for cis- and trans-chlordane. the Kow for technical chlordane,




a complex mixture containing these and other constituents, was used.




    Analogous to the methods used for organic contaminants, pore-water




concentrations of metals were also estimated from the bulk sediment  concentration




in two ways: 1). by assuming complete bioavailability of bulk sediment




concentrations; and 2). by correcting for AVS by using the concentrations of




metals simultaneously extracted with AVS (i.e., simultaneously extracted metals-




SEMs) adjusted for AVS (DiToro 1990).  In both methods, the estimated pore-




water concentration was the estimated bioavailable concentration (entire sediment




concentrations in  the first method) multiplied by the dry weight to moisture




content  ratio of the sediment. In the first method, the full concentration of each




metal present  in the sediment is considered bioavailable. In the second, only those




metals extractable with a weak acid (1-IM  HCI) and adjusted for the potential sulfide




salts that could be formed by the extracted metals are considered bioavailable. As




described for organic contaminants and organic carbon, the intent of using these




two methods was to evaluate how well the toxic units model predicted the toxicity




of sediments based on control-adjusted laboratory toxicity tests and mean




tolerance to pollution of the benthic community and how the ranking of hazard




among sites compared with and without AVS limitation.




    The AVS model is based on the assumption that under the reducing conditions




present  within sediments, sulfides control the pore-water concentrations and,
                                      8

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hence, bioavailability of divalent metals. The sulfide salts of the metals are




relatively insoluble; the formation of these salts thereby renders the divalent metals




unavailable. AVS modeling of pore-water concentrations therefore adjusts the




maximum potential pore-water concentrations of metals downward based on the




amount of AVS present.




    In the ARCS sediments, the total molar concentrations metals simultaneously




extracted with AVS frequently exceeded the molar sulfide concentration.




Consequently, it was necessary to  apportion the sulfide among the divalent metals




and arsenic present.  We allocated  AVS to metals and arsenic based on the




solubility product constants,  K,p, of their sulfide salts (Weast et al. 1988).




Accordingly, AVS was allotted to metals in  the following order:  mercury, silver,




copper, cadmium, lead, zinc, nickel, arsenic, iron, manganese, and chromium (i.e.,




mercuric sulfide is the least soluble and chromium sulfide the most soluble sulfide).




An equimolar amount of AVS was allotted to each metal in the order of their K.p




until either all AVS was allotted or  all metals were sulfide-bound. For selenium,




which is not controlled by AVS, we used  the bulk-sediment concentration and the




sediment quality standard proposed by  Lemly et al. (1993).








Water quality standards




   Relative potential toxicity was estimated from  chronic toxicity information for




each analyte (Table 2), the primary source of which was the series of AWQC




documents.  The calculation of chronic  toxicity AWQC incorporates information

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both on chronic toxicity of a contaminant to various forms of aquatic life and the



bioconcentration factor of the contaminant in aquatic ecosystems.  Thus, this




estimate of chronic toxicity is also more indicative of the severity of long-term



exposure to a contaminant for aquatic organisms than would  be a direct measure




of toxicity. In addition, many of the so-called "short-term"  tests performed under




the  ARCS Program, and against which we compare the results of the toxic units




model, are in  fact longer in duration than 96 h and include sublethal endpoints



such as growth and behavior.  Hence, they are more appropriately compared to the




chronic criteria.



    For those  analytes without AWQC, chronic toxicity values were obtained from




other sources (Table 2).  We used the chronic toxicity values of the Michigan



Department of Natural Resources 1993 Water Quality Standards (unpublished data)




for  the dichlorobenzenes, naphthalene, silver, and tributyltin.  For dibenzofuran,



bis(2-ethylhexyl)phthalate, and dimethyl phthalate, we estimated a value by




proportionally adjusting the Michigan  DNR chronic toxicity standard for 1,2-



dichlorobenzene on the basis of the ratio of 1,2-dichlorobenzene toxicity to that of



the  other compounds (LeBlanc 1980). For the chlorodioxins, chlorodibenzofurans,



and polychorinated biphenyls  (PCBs), we estimated a value by proportionally




adjusting the  Aroclor8 1254 AWQC (USEPA 1980a) in two steps: First, we




determined the  ratio of the aryl hydrocarbon hydroxylase (AHH) activity of Aroclor8



1254 to that  of TCDD and the ratio of the AHH  activity  of Aroclor8 1254 to that of




each compound (Smith et al. 1990). For some isomers and  congeners, the ratio
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of AHH activity of Aroclor8 1254 to that of TEF of each compound {Safe 1990)




was used.  We then used the ratio of these two values as a proportionation factor




to adjusted Aroclor8 1254 values. For most polycyclic aromatic hydrocarbons




(PAHs), a chronic toxicity estimate was back-calculated using equilibrium




partitioning from a sediment threshold (USEPA 1985a) by assuming 4% organic




carbon (the value used to generate the threshold concentrations) and the K,,,. values




used in the model presented here; for benzo(
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values used in the calculations for individual sediments were those measured in the




14-d flow-through sediment toxicity test with Chironomous riparius. one of the



ARCS laboratory toxicity tests, for that sediment (Nelson et al. 1993).




   Lack of available information precluded the use of several of the  compounds




measured in the example data set in the ranking process. These included: the a, 13,



and 6 isomers of hexachlorocyclohexane; dimethyl butyl phthalate; di-n-




octalphthalate; 2-methyl naphthalene; 4-methyl naphthalene; and




benzo(b)flouranthene, for which toxicity information was lacking; and monobutyl-




and dibutyl-tin, for which Kow values were not available.








Other information




   The potential toxicity of ammonia in the ARCS sediments prompted the




inclusion  of the unionized ammonia levels associated with the 14-d  Chironomous



riparius sediment toxicity test  for each sediment (Nelson et al 1993).  The toxicity




of ammonia and, hence, the AWQC for ammonia (USEPA 1985b) are  pH-



dependent. Consequently, we used the pH values measured during the same



toxicity tests  to estimate the AWQC for unionized ammonia.








Ranking Sites Based on Toxicity as Measured by Laboratory Toxicity Tests




   When the results  of multiple laboratory sediment toxicity tests and multiple




endpoints measured within some tests are to be used  together, the data from each




toxicity test and  multiple endpoints measured within some tests had to  be scaled
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equivalently (analogous to the toxic units scaling performed on the suite of

chemistry measures).  This was accomplished by normalizing the measured

response associated with an endpoint to the control sediment response for that

endpoint:
       Control-adjusted laboratory =  ..     Endpoint value for test sediment
            toxicity response            Endpoint value for control sediment
Adjusting a test response to its control scales that measure as a proportion of its

control, and it also adjusts the responses for the conditions present at the time of

the test. The latter accounts for variation attributable to the tests being run at

different times, in different locations, by different investigators, or combinations of

these factors. So that the control-adjust laboratory toxicity response ordered the

sites in the same fashion with respect to toxicity as the toxic units model (i.e.,

lowest value  = least toxic and highest value = most toxic), the ratio of the

endpoint value for the test sedimentiendpoint value for the control sediment was

subtracted from one, as shown in the last equation.  The estimates of hazard—the

control-adjusted laboratory toxicity responses for each endpoint—were then

averaged (i.e., arithmetic mean) over all measured endpoints for a site to estimate

the mean hazard for each site based  on laboratory toxicity. This mean estimated

hazard was then ranked among sites.
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   In some tests (e.g., 48-hour Daphnia magna survival-Table 3), multiple




concentrations of the test medium were used to estimate LCSOs, which yield little




information compared to the actual response at individual concentrations, and




which are not scalable to the control.  For such tests, a response was first




multiplied by  the proportion of the full concentration of the medium at which the



test was run  (i.e., 50%  elutriate response  was multiplied by 0.5) before the




proportional laboratory toxicity response was  calculated.  This "proportionation



factor" gave  the observed response for each concentration an equivalency to




100% (i.e., the concentration at which the other tests were run) and enabled



scaling of the responses relative to controls.








Ranking Sites Based  on  Toxicity as Measured by Benthic Community Structure




   As we described  for laboratory toxicity tests, when different measures of



benthic  community structure and  well-being are measured, they must be uniformly




scaled for evaluation. The measure we used was Lenat's (1993) biotic index (i.e.



mean tolerance-to-pollution per organism). Lenat (1993) presents a  extensive list




of tolerance to pollution values for all the organisms considered in his estimates of



mean tolerance per organism.  The mean  tolerance is calculated  by  first assigning




each species  a relative tolerance value to pollution; the set of tolerance to pollution




values for each species  presented by Lenat (1993) was based on correlations




between water quality and abundance data for each species.  Once  the tolerance




value for each species is obtained, the mean tolerance (T) is calculated by
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summing the product of the abundance (IM,) and tolerance value for each species at




a site (Tj) and then dividing that total by the total number of organisms at a site:
                                       E N,
Calculating the mean tolerance to pollution of the benthic community assures that




the presence of less tolerant orders influences the ranking of a site (i.e., the site is




considered less toxic). Here, it is this mean tolerance to pollution per organism at




a site that is ranked among sites.  Because Lenat's values were derived for flowing




waters in the southeast,  tolerance values for some taxa had to be obtained from




other sources.  Table 4 gives the list of organisms observed in the ARCS




sediments, their associated tolerance values, and the source of the value; a few of




the tolerance values had  to be obtained from another source.








Final Ranking




   The rankings that result from the different types of information discussed (i.e.




chemistry, laboratory toxicity tests, and benthic community structure) can be




combined to produce a final ranking for each site. At this point each type of




information has been scaled from 1 to  100.  The estimate of relative hazard for the




sites under investigation, based on all three types of information, is the arithmetic
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mean of the three ranks.








Objectives




   In this report, we focus on two main aspects of the just mentioned ranking




procedure.  The first goal of this report was to evaluate the effectiveness of the




toxic units approach at predicting biological endpoints (i.e., laboratory toxicity and




benthic community structure). The second goal was to evaluate how site ranking




changed as the level of information collected at a site declined.








                        MATERIALS AND METHODS




Sediment Sampling Locations




   Sediment samples were collected at 19 different sites for the ARCS program




(Ingersoll et al. 1993). Samples were obtained from the lower reaches of two




rivers and one harbor complex: in the Buffalo River, samples from five sites were




collected in October, 1989; in the Saginaw River, three sites were sampled in




December,  1989,  and seven were sampled in June, 1990 (only  one of which had




been sampled in December); and four Indiana Harbor sites were  sampled in August,




1989.








Sampling and Biological Measures




   Grab samples of sediment were collected with a 23- x 23-cm Ponar sampler




and brought into the laboratory for analysis.  At each site, one sample was
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collected for chemical analysis and laboratory toxicity tests and five samples were




collected for benthic community analyses. Those samples designated for both




chemical analysis and laboratory toxicity testing were split into two portions; one




portion of each sample was analyzed for contaminants and the other portion was




used in laboratory toxicity tests. Those samples designated for benthic community




analysis were sieved with a 500-um screen and organisms were  identified to the




lowest possible taxonomic level. Table 3 gives a list of laboratory toxicity tests




carried out on the set of sediment samples modeled in this paper and the endpoints




measured.  Table 4 gives a list of the taxa observed in the set of sediment samples




modeled in this paper, the tolerance value used for each taxon, and the reference




from which the tolerance value  was obtained.  Further details of  sample collection,




handling, preparation, and testing are presented elsewhere (Ingersoll et at. 1993).








Chemical Analyses




    A variety of methods were  used to measure contaminant concentrations in the




ARCS sediment samples.  A subsample of the analytical portion of each sediment




was freeze-dried to  gravimetrically estimate percent solids. A second subsample




was analyzed with a carbon determinator to estimate total organic carbon.  A third




subsample  was used to estimate acid volatile sulfides (AVS) by leaching with 1-N




HCL; simultaneously extracted metals (SEM) were determined by analyzing the




resulting HCL solutions by atomic absorption spectroscopy.  A fourth subsample




was completely digested with acids and analyzed for total metals by atomic
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absorption. Crustal elements were estimated from a fifth, freeze-dried subsample




of sediment analyzed by x-ray fluorescence. Methylmercury was estimated from a




sixth subsample of sediment digested in potassium hydroxide and analyzed by




atomic fluorescence.  Organotins were quantified by gas chromatography from a




seventh subsample after extraction with 0.2% tropolone. Organic chemical




residues (i.e., PAHs, PCBs, chlorinated pesticides, PCDDs, and PCDFs) were




extracted with methylene chloride (all but PCDDs and PCDFs) or benzene (PCDDs




and PCDFs) from subsamples eight and nine, respectively, and analyzed by gas




chromatography and mass spectrometry. Further details of these chemical




analyses can be found elsewhere (Ingersoll  et al. 1993).








Detection Limits




   To complete this study, we had to account for differences in analytical




sensitivity among samples by defining for each analyte one censoring level to be




applied to all samples. We needed to ensure that an analyte measured with low




sensitivity (i.e., high detection limit) did not control the toxic units estimate for any




sample only because of that analyte's high  detection limit.  To eliminate this




possibility, we censored at the highest detection limit among samples for each




analyte; i.e., any concentrations, detected or not,  that were at or below this




censoring level were assumed to be zero. The censoring process we used for the




ARCS chemistry data was the most appropriate alternative because the data had




been collected prior to the development of the model; preliminary analyses revealed
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that many of the toxic units values derived from the ARCS sediment chemistry




data were defined by the analytical sensitivity (i.e., detection limits) of the




methods used to measure the various analytes.  The detection limits for one set of




Saginaw River sediments were so high that they completely dominated the hazard




assessment.  Consequently, data from the seven Saginaw River sites sampled in




June of 1990 were not included in the analyses presented here; our analyses are




based on samples from the other 12 ARCS sites, all of which had much lower and



more consistent detection limits.








Toxic Units Model Evaluation




    Model predictions were analyzed by simple regression and correlation. We




assessed the ability of various forms of the toxic units model (e.g., with and



without certain variables) to predict mean control-adjusted laboratory toxicity




and/or mean tolerance to pollution of the benthic community on the basis of




regression results, which were evaluated in terms of R2- and P- values. A model




was considered a better predictor of toxicity than other models if it  accounted for a




larger percentage of the variability observed in the measured response (i.e., mean



control-adjusted laboratory toxicity or mean tolerance to pollution of the benthic



community).
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Ranking Evaluation




   In the ARCS program, there were three categories of collection sites for



sediments: Priority Master Stations, Master Stations, and Reconnaissance




Stations. The difference between the categories of stations was in the number of




parameters measured.  At Priority Master Stations, all chemistry (Table 2),




laboratory toxicity (Table 3), and  benthic community (Table 4) measurements were




made.  At Master Stations, all chemistry, a shortened list of laboratory toxicity ('*'



tests in Table 3), and all benthic community measurements were made.  At




Reconnaissance Stations, only  a short list of contaminants (i.e. cadmium,




chromium, copper, iron, nickel, lead, zinc, unionized ammonia, and total AroclorRs)



and Microtox" were measured.  The intent of this gradient of information collected



at each site was designed to determine how much information was actually needed




to effectively evaluate the relative contaminant hazard among a group of sites.




   As  directed under the ARCS program, we evaluated the effect of different




amounts of information on the  resultant final  ranking of the sites.  We compared



and contrasted the final ranking among sites when Priority Master Station




indicators were used as opposed  to when: 1). Master Station indicators were used;



2). Reconnaissance indicators were used; and, 3). only the contaminants




considered bioaccumulative were used in the  toxic units model with the full bulk



sediment concentration of each contaminant considered bioavailable.  The latter




question was added on our part based upon our review of the draft Great Lakes




Water Quality Initiative (USEPA 1993) (Table 5).  We wanted to know the extent
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to which the relative ranking of sites changed when the set of information used in



the process was reduced. In other words, what is the minimal, most cost-effective




suite of measurements required to accurately rank the sites?  The assessment of



the extent to which the ranking changed was measured by the change in the




amount of variation explained by the full model rankings when reduced sets of data




were used to rank the sites (i.e., change in R2).  The fact that comparisons were




limited to pairs of ranks allowed us to  use simple correlation analysis.  We used the




Statistical Analysis System (SAS Institute 1990) for all  data management,




computations, and statistical analyses.








                                  RESULTS




Toxic Units Model




Laboratory toxicity



    The best predictor of laboratory toxicity was the full model of bioavailable




contaminants, which included  both organic carbon control for organic



contaminants and AVS control for inorganics (Figure  1). This model accounted for



more than 89% of the variability present in mean laboratory toxicity.  When bulk



contaminant concentrations were substituted for bioavailable fractions, the model




accounted  for only 68%  of the variability (Figure 2).  Among the ARCS sites,



predicted toxicity of Indiana Harbor site 3 was the most greatly affected  when



equilibrium partitioning and AVS  were excluded  from the model; toxicity  at this site




was accurately estimated by the full model, but greatly underestimated by the bulk
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chemistry model (cf. Figures 1 and 2).




   Tables 6-8 give the list of individual contaminants that were estimated to be




present at at least one toxic unit at one or more sites within an area of concern




(e.g., Saginaw River), based on bioavailability chronic toxicity. These lists are




shorter than the full list of contaminants measured because not all PCB mixtures,




dibenzodioxins, dibenzofurans, etc. were present at toxic concentrations at all




sites.  The contaminants  that contributed the most to the toxic units estimate for a



sediment, including iron and ammonia, varied among sites;  no single contaminant




dominated at all sites (Tables 6-8). In general, only a few contaminants accounted




for the greatest percentage of estimated toxicity at each site.  For example,




endosulfan, endrin, methylmercury, and iron contributed most in the Buffalo River;



chromium, dieldrin, endosulfan, endrin, heptachlor, iron, methylmercury, PCBs, and




tributyl tin the most in Indiana Harbor; and chlordane, heptachlor, iron, and PCBs



the most in the Saginaw  River.




   The full model indicated that unionized ammonia, chromium, and iron were



present at potentially toxic concentrations and accounted for much observed




variability at most sites (Tables 6-8).  Although  it probably influenced many



laboratory toxicity  test results, unionized ammonia alone did not explain all the




toxic effects of the sediments observed in the laboratory; alone it accounted for




more than 60% of the variability (Figure 3), substantially less than the full model.




The relative toxicity of Saginaw River  site 6 was much higher than predicted when




ammonia alone was used in the model (cf. Figures 1 and 3). Although iron is only
                                     22

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toxic at relatively high concentrations—1 mg/l (USEPA 1976)—it was also important




in the prediction of laboratory toxicity from sediment chemistry. Without iron, the




toxic units model (including ammonia) accounted for just over 52% of the




variability of the laboratory toxicity test  (Figure 4) as compared to 89% with both




iron  and ammonia included (Figure 1). Without iron, the site with the highest




relative toxicity (i.e., Indiana  Harbor site 7) was predicted to have about half its




measured toxicity (cf. Figures 1 and 4).  And finally, replacing the bioavailable




fractions with whole-sediment concentrations of those contaminants that are




considered Bioaccumulative Contaminants of Concern by USEPA (1993-Table 5),




and  assuming them to be completely bioavailable, also reduced  the model's ability




to predict laboratory toxicity. Using only the bioaccumulatives  in this fashion, the




model accounted for less than 70% of the variability in the laboratory toxicity tests




(Figure 5).








Benthic community structure




   As described for laboratory toxicity,  the best predictor of the mean tolerance




value for the  benthic community was the full model of bioavailable contaminants,




which included both equilibrium partitioning for organics and AVS for metals .  This




model accounted for 40% of the variability present in  the mean tolerance value




(Figure 6). When bulk contaminant concentrations were substituted for




bioavailable fractions, the model accounted for  only 34% of the variability (Figure




7).  If only contaminants considered Bioaccumulative Contaminants of Concern by
                                     23

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USEPA (Table 5) are used in the toxic units model, the model accounted for 40%




of the variability in the mean tolerance value for the benthic community (Figure 8).




    The variability of the mean tolerance value of the benthic community had a




different set of relationships with ammonia and iron than did the laboratory toxicity




results. In contrast to what was observed for the laboratory toxicity tests,




unionized ammonia did not explain a significant amount of the variability in the




mean tolerance value of the benthic organisms (R2 = 0.04, P =0.56).  Moreover,




without iron, the full model no longer accounted for a significant percentage of the




variability in the tolerance value (R2 = 0.11, P =0.31); for laboratory toxicity




tests, the level of significance declined but the full model could  still predict the




response without iron (Figure 4).  In fact, when iron is the only contaminant




considered, the model accounted for 40% of the variability in benthic community




structure, as  it did when all contaminants  were considered  (Figure 9).




    Two other important observations must be noted. First, when only the




taxonomic order of each organism, instead of the  lowest  level of taxonomic




identification  possible (i.e. mostly genera and  species), were used to  calculate the




mean tolerance value for the benthic community, there were no significant




relationships with toxic units in any form.  Second, even  though we can predict




laboratory toxicity and benthic community mean tolerance using the toxic  units




model, there was no correlation between laboratory toxicity and benthic




community mean tolerance (R2 =  0.21, P  = 0.13).
                                     24

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Final Rankings




   The shortened list of laboratory toxicity indicators (i.e., from Priority Master




Station to Master Station indicators), in general, produced the same results as the



full set of data (R2 = 0.99, P  = 0.0001; Figure 10).  Further exclusion of




laboratory toxicity (except MicrotoxR) and benthic community data, and using only



the short list of sediment contaminant  measures (i.e., reducing the Priority Master




Stations to Reconnaissance stations) resulted in both increases and decreases in




relative toxicity estimates within the set of sites (R2  = 0.75, P =0.0003; Figure




11).  Eight sites, as opposed to only five for the Priority Master Station indicators,




had relative toxicity rankings greater than 40 when only Reconnaissance data were




used.  Also, some sites switched position relative to  other sites; for example,



Saginaw River site 3 was least toxic with only the Reconnaissance indicators




whereas it was sixth most toxic based on all Priority Master Station data.




     Using only the data on  bioaccumulative contaminants (i.e., ignoring laboratory




toxicity and benthic community measures) and  assuming the complete




bioavailability of all bioaccumulative  contaminants (by use of measured bulk



sediment concentrations found in the sediment) produced the most dramatic



change in relative toxicity of the sites (R2 = 0.75, P  = 0.0003; Figure 12).



Relative to the most toxic site (i.e., Indiana Harbor site 7), the estimated  toxicity of



all other sites decreased greatly.  All but three sites that had relative hazard values




between 40 and 60 in  the case of Priority Master Station data (including Indiana




Harbor site 3) had relative toxicities less than 12 when only bioaccumulatives were
                                      25

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used. As a final note, even though we tried different measures to rank the relative




toxicity of sites, Indiana Harbor site 7  was always the most toxic, followed by




Saginaw  River site 6.








                       DISCUSSION AND CONCLUSIONS




Effectiveness of the Toxic Units Model




Laboratory toxicity




   Based upon our comparisons of different model permutations, the best estimate




of toxicity was produced by the model that incorporated bioavailability calculations




and included the fullest list of potential contaminants.   Without estimates of




bioavailability, comparisons with toxicity data inherently assumed that all




contaminants are completely bioavailable, which greatly reduced model fit.




Conversely, without consideration of the toxic effects of contaminants that are




only toxic at relatively high concentrations, such as iron, it is inherently assumed




that such contaminants  are completely nontoxic. The chronic AWQC for iron, for




example, is  1 mg/L (USEPA 1976); nevertheless, when  iron was excluded the




estimated toxicity was also less effective than the full model at  predicting observed




laboratory effects. Collectively, these findings corroborate previous studies




reporting that sediment  toxicity, as defined by short-term tests such as those




incorporated in the ARCS program, is  mediated by pore-water concentrations




(Hamelink et al. 1971, Ditoro et al. 1991), and that this toxicity is additive (Safe




1990).
                                      26

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   One possible reason for a lack of concordance between the bioaccumulatives



and toxicity test results may lie with the PCB component of the ARCS chemistry



data set, which is inherently weak. Analyses based on Aroclor8 mixtures, as



performed for the ARCS program, may not accurately represent the distribution or




abundance of toxic PCB congeners in weathered environmental mixtures (Tillitt et




al. 1992).  Consequently, the TEF approach we used to estimate the toxicity of the




PCBs in ARCS sediments, which  was based on the dioxin equivalency of



unweathered mixtures, may not have been accurate.  Better estimates would be



obtained through instrumental analyses of individual AHH-active congeners (Kuehl



et al. 1991) or, for reconnaissance activities such as those conducted under the



ARCS program, through the use of biologically based measurements of dioxin-like




activity, as measured by the H4IIE in vitro assay (Tillitt et al. 1991).




   Kinetic factors may also greatly affect the sensitivity of sediment toxicity tests



to bioaccumulative contaminants. Implicit in the comparison of toxicity test results



with equilibrium-based toxic units estimates is the assumption that the equilibrium




{or, at least, steady-state) conditions of the site from which the sediment was



collected are re-established at the time of the test. No measure of the degree to



which this assumption was satisfied was included in the ARCS data set, however,




and the rates of such processes may be relatively slow. For this and other



reasons, the uptake of sediment-bound, hydrophobic contaminants such as PCBs




and dioxins is also slow (Pruell et al. 1993). Moreover, delayed mortality may



occur (Mehrle et al.  1988).  Collectively, these kinetic factors would tend to make
                                     27

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short-term tests less responsive to contaminants controlled by partitioning and




other relatively slow processes than to others. Nevertheless, our modeling results




indicate a contribution by RGBs and other hydrophobic contaminants to laboratory-




measured toxicity.




   Many of the environmental chemistry variables measured in the ARCS




sediments were highly intercorrelated, as were the toxicity test results. Such




intercorrelation impedes the assessment of causality. This was particularly true for




assessing the effects of iron in sediments.  Because iron is soluble only in the




absence of oxygen {Drever 1982), it could be argued that toxicity attributable to




iron is actually caused by a lack of oxygen. In the ARCS study, however, and




contrary to our original suspicions, toxicity attributable to the high concentrations




of iron in many sediments appeared to be more than just an artifact or surrogate




measure of low dissolved oxygen concentrations. Most of the laboratory toxicity




tests  were performed with reconstituted water, and the  dissolved oxygen levels of




waters overlying the test sediments were monitored regularly and found to be




acceptable  in most tests {Nelson et al. 1993).  Thus, the improved relationship




between  laboratory toxicity and toxic units estimates with  the inclusion of iron




seemed to be directly related to the actual toxicity of the iron which, at the high




concentrations present in some ARCS sediments (Tables 6-8), is not surprising.




    Although ammonia was  present at potentially toxic concentrations at most




sites, the contribution to total toxicity of ammonia in the toxic units model was




assessed on the basis of unionized ammonia concentrations and pH measured
                                     28

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regularly during the conduct of laboratory toxicity tests.  In these tests, the




overlying water was reconstituted water and not ambient water.  We are not sure




how accurately the measurements of ammonia and pH incorporated into the toxic




units model represent the ammonia actually present in the natural system prior to




sediment collection.  To make the estimates of toxicity attributable to ammonia




representative of the natural system, the ammonia and pH concentrations in the




water overlying the sediment within the natural system should be measured.  The




same is true for dissolved oxygen, which should also  be  measured under ambient




conditions. Despite the presence of ammonia at potentially toxic levels and its




potential to influence the results of the laboratory toxicity tests, ammonia alone




was not able  to effectively predict the toxicity of the  sediments, as noted earlier.




      Our findings  support the hypothesis that benthic toxicity, as measured by




short-term toxicity tests, is mediated by pore-water contaminant concentrations, as




has been suggested by others for some time (e.g.,  Hamelink et al. 1971; DiToro et




al. 1990, DiToro et al.  1991).  Ecosystem  risk, however, has much broader




implications, especially for bioaccumulative contaminants, where trophic transfers




predominate.   With our findings, we have shown that the short-term laboratory




toxicity tests  are sensitive to iron and ammonia, responses to which  may mask the




effects of slow-acting,  bioaccumulative contaminants. The short-term laboratory




toxicity tests,  by themselves, appear to reflect toxicity of the sediments in the




immediate vicinity  from which they are collected, but not necessarily the




ecosystem risk represented by the transfer of the contaminants they contain
                                     29

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through the food chain.








Benthic community structure




   In the ARCS data, the benthic community structure of contaminated sediments




was  related to the toxicity of the contaminants present as defined by the toxic




units approach. As the estimated toxic units of a sediment increased the mean




tolerance to pollution of the benthos community increased.  Like the relationship




between toxic units and laboratory toxicity test results, the strength of the




relationship between toxic units estimates and mean tolerance to pollution declined




when, instead of estimated bioavailable concentrations, bulk sediment




concentrations of contaminants were used in the toxic units estimates.  Unlike the




work with laboratory toxicity and toxic units, bioavailable iron toxic units alone had




as strong a relationship with mean tolerance to pollution as any other toxic units




estimates.




   The differences in the observed strength of the relationships among sediment




community tolerance, laboratory toxicity test results, and toxic units estimates




seems to be an indicator of an information short fall.  The much  stronger




relationship observed between laboratory toxicity  and toxic units than between




sediment community tolerance and toxic units, seems to  indicate an information




short fall related to sediment community identification. The observed increased




strength of the relationship between toxic units and benthic community tolerance




with a finer scale of resolution in taxa identification is an indicator  of one possible
                                      30

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way to improve the strength of the relationship.  In the ARCS data, the greatest




percentage of organisms fell into the category of unidentifiable Tubificidae (i.e.




family level identification) (Canfield et al. 1993). From Lenat's (1993) tolerance




values, it is apparent that there is a wide range of tolerances among Tubificidae




species.  It is possible that a finer level of identification (i.e.  genera and/or species)




would have strengthened the relationship between toxic units estimates and




benthic community tolerance.




    Another possible contributing factor to the differences in the strength of the




relationships among sediment community tolerance, laboratory toxicity test results,




and toxic units estimates is that the sediment community tolerance measures a




different aspect of contamination than the other two measures.  The much




stronger relationship between laboratory toxicity and toxic units than between




sediment community tolerance and toxic units may be that the sediment




community tolerance is  more of a long-term measure of effect than the other two




measures. This is speculation but  it requires  further evaluation before it can either




be accepted or reject as a cause.




    Overall, our results are an indication that the toxic units model is an effective




tool for understanding benthic community  structure in relationship to complex




contaminant mixtures, and that Lenat's  (1993) biotic index is a  good measure of




the effects of pollution,  in general, on benthic community structure.
                                     31

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Data quality




   Important in the application of a toxic units approach is the consistency and




quality of the data.  To make accurate environmental-chemistry based comparisons



of sediment samples, based on environmental chemistry, the concentrations of any




given analyte must be measured with the same sensitivity among the samples to




be compared; the censoring level (i.e., detection limit) for any given analyte must




be consistent (preferably constant) among samples.  If this is not the situation,



differences among samples or sites may be controlled by analytical sensitivity




rather than true differences among the samples (e.g., two identical samples may



appear different if represented by differing detection limit values) which




necessitated our elimination of most of the Saginaw River ARCS data from




consideration. The best way to avoid the influence of detection  limits on toxic




units estimates is to define a minimum level of sensitivity for each analyte (i.e., a



performance-based criterion).  Moreover, this minimum level of acceptable




sensitivity should be determined by the level  of concern for the analyte. Defining  a



minimum level of sensitivity for contaminant  measurements  is only the first step in



addressing the problem of detection limits associated with contaminant



measurements, the second being how to treat those censored values that




inevitably occur. The most environmentally conservative approach would  use all




values, including censored values in the toxic units model.  Because of the expense




associated with remediation, the high toxic units estimated using this approach




would encourage consistently high sensitivity.
                                     32

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Potential for mode! enhancements




   The methods we used to estimate the bioavailable portions of measured




contaminants assume  solid-phase control by organic carbon for organic compounds




and sulfide for metals  and arsenic (DiToro et al. 1990, DiToro et at. 1991).  We




made no attempt to account for other mechanisms, such as sorption or




complexation by other organic or inorganic ligands that might be present in the




pore waters.  We also assumed  complete insolubility of sulfides, an obvious over




simplification.  Consequently, the models do not predict toxicity of all




contaminants at all times {Ankley et al.  1993); nevertheless, they represent the




current best estimate  of the potential toxicity of sediment contaminants.  The toxic




units approach incorporated into the model is also versatile; as better methods for




estimating the bioavailability of sediment contaminants are developed and water




quality standards are revised, such  refinements can be incorporated into the




modeling process.




   It is important to note that if chronic toxicity standards for sediment quality




were available, they and actual measured sediment concentrations would be used




in the toxic units model instead  of AWQC and estimates of pore-water




concentrations, respectively.  In fact, the proposed Sediment Quality Thresholds




for organic chemicals  (USEPA 1985a) are founded on estimated pore-water




concentrations, equilibrium partitioning, and the AWQC.   In the absence of




published sediment criteria for all contaminants, however, AWQC and estimation of




the pore-water concentration  of individual analytes remains the best available
                                     33

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method for estimating toxic units.




   The toxic units approach assumes that each contaminant is independent of all




other contaminants--!.e., effects are strictly additive. The model does not account




for synergistic or antagonist interactions that may occur among contaminants in




complex mixtures, even though such interactions are well documented (e.g.




Warren 1971, de  March 1988, Parrott and Sprague 1993, Schmitt et al. 1993).




As information becomes available on the  nature of the contradictions to this




assumption, quantifiable interactions can be incorporated into the  model, along




with improvements in the bioavailability estimates. As noted earlier, the model




also presently assumes that the bioavailability of divalent metals and arsenic is




controlled by AVS.  Future model improvements should also include incorporation




of other inorganic and organic ligands, perhaps through speciation modeling, to




estimate the pore-water concentrations of the divalent ions.




   Yet another assumption inherent in our approach is that all endpoints in all




toxicity tests conducted for the ARCS  program are equivalent.  We used this




approach because it is analogous to the procedure used by USEPA (1986a) to




derive the AWQC-upon which the toxic units are based-wherein toxicity test




results from a broad suite of taxa are averaged to  obtain mean acute and chronic




values for individual contaminants.  Given the equally broad array  of contaminants




present in the ARCS sediments, we felt that such  an unbiased approach was




prudent. We recognize, however, that subsequent evaluation of the model may




suggest that certain test results should  be weighted more heavily  than others.
                                     34

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    The toxic units approach needs further validation with other data sets spanning




a broader range of conditions. The ARCS data set from which the approach was




developed contained no sediments that were not toxic to some degree to all the




organisms tested.  In this current evaluation of the toxic units approach, the lack




of sediments containing only background contaminant levels and little to no




observed toxicity allows  us to state only that the approach  is a good measure of




relative toxicity among sediment samples. Full evaluation of the  effectiveness of




the toxic units approach  to predict sediment toxicity will require a sediment data




base containing sediments with a full range of toxicity (i.e., nontoxic to extremely




toxic) resulting from a wide variety of contaminants.








Ranking Approach




    From our analysis, we found that it is very important how much and what type




of information is included in the hazard ranking of a site.  As the  amount of




information incorporated  into the ranking process declined (i.e.. Priority Master




Station  indicators to Master Station  indicators to Reconnaissance Station




indicators) the hazard ranking of the sites changed.  As the  information used to




rank the sites changed so did both the relative hazard of the sites to the most




hazardous site and the order of the sites based on relative hazard.  More




dramatically, when the information used to estimate the relative hazards of the




sites included only the bioaccumulative compounds, only three  of the six sites




estimated to be the most hazardous sites using the full  set of information  (i.e.,
                                     35

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relative ranks over 30) still had relative ranks above 30.  The most dramatic




change occurred in the relative ranking of site 3 in Indiana Harbor; it went from a




relative hazard rank greater than 57 using the full set of information to less than




12 using only bioaccumulatives.




   The minimal amount of information necessary for an appropriate assessment of




the relative hazard among a set of sites seems to be the  Master Station level (i.e.,




chemistry, moderate range of laboratory toxicity data, and benthic community




structure). The information gained by the inclusion of macrophytes and toxicity




tests with more species of invertebrates (i.e.. Priority Master Stations) had little to




no effect on relative hazard ranking of the sites. If only Microtox and a short list of




contaminants (i.e.. Reconnaissance Station data) are used to produce the relative




hazard ranking for a set of sites, the relative ranking of the sites becomes




confused.




   Not only the amount of information, as discussed, but also the type of




information used to construct the relative  hazard ranking of a set of sites may




dramatically affect the resulting hazard ranking.  If the intent of using the ranking




process is to determine overall relative  toxicity, the set of information used should




include all the types of information collected at Master Stations in this study (i.e.,




chemistry, laboratory toxicity,  and benthic community structure). If the intent of




using the ranking process is to determine hazard to organisms on the upper end of




the aquatic food chain, including wildlife, the set of information would be similar to




the bioaccumulatives  tested in this study.  Thus, it is crucial that the question of
                                      36

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concern for a set of sites be correctly formulated before such a relative ranking




process is employed.




     The purpose of the described ranking process is to allow different types of




data, measured on different scales, to be combined into one overall estimate of




relative hazard for the set of contaminated sites under investigation.  The scaling




done for each class of data (i.e., chemistry, laboratory toxicity, benthic




community) allows for the incorporation into the estimates of relative hazard as




much information as  is available in the scientific literature. The result is a current




best estimate of relative hazard for the sites under investigation.  This approach




enables the comparison  and combination of sediment contamination information,




measured on different scales, on one relative scale that has a foundation in




environmental chemistry, toxicology, and ecology. The process is alsp dynamic; as




more information becomes available about sediment processes, chemical fates,




toxicity,  etc., new information can be incorporated into the ranking model.  Thus,




the estimates of relative hazard become more accurate as the base of knowledge




increases.  It can also become a planning tool by pointing out where information is




most needed.




     If not already apparent, the relative site rankings generated in this study are




based on contaminant levels at one point in space. The next step would be to




adjust (i.e., weight) the toxicity of each  site based on an estimate of the area (or




volume) of contaminated sediment at each site. Thus, the single point relative




hazard ranking of sites may change dramatically if less toxic sites represent a
                                     37

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greater proportional area (or volume).




    Finally, the ranking process need not be limited to the types of data described




here. Other classes of information (i.e., potential for resuspension, aesthetics,




recreational potential, etc.) can also be incorporated by scaling the observed values




from 1 to 100 as was done with the information presented in this report. The




model can also be extended to other quantifiable hazards, such as carcinogenicity,




by defining a toxic unit to be the level of concern for such hazards.  Again, this




demonstrates the general utility of the ranking process as one way of assessing




the relative hazard  among many sites when limited resources require prioritization.








                            ACKNOWLEDGMENTS




   This study was jointly undertaken by the USEPA, Great  Lakes Program Office




(GLNPO) and the U.S Department of the Interior, Fish and Wildlife Service, National




Fisheries Contaminant Research Center (NFCRC),  now part of the National




Biological Survey.  We thank  M. Tuchman and R. Fox of GLNPO, W. Lick and J.




DePinto of the ARCS modeling workgroup, R. Kreis  and J.  Rathbun of the USEPA




Large Lakes Research Station, P. Landrum of the National Oceanic and




Atmospheric Administration, G. Hurlburt of the Michigan Department of Natural




Resources, M. Miah and J. Boyd of Lockheed Engineering and Sciences Company,




B. Schumacher of USEPA Environmental Monitoring Laboratory-Las Vegas, and J.




Huckins, L. Jacobs, D. Tillitt, C. Ingersoll, and  T. Canfield of the NFCRC for their




assistance.
                                     38

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      for the USEPA GLNPO Assessment and Remediation of Contaminated




      Sediments (ARCS) project: biological and chemical assessment of




      contaminated Great Lakes sediment. C. G.  Ingersoll, D. R. Buckler, E. A.




      Crecelius, and T. W. La Point (eds). U.S. Fish and Wildlife Service,




      Columbia, Missouri.
                                     42

-------
Newsted, J.L. and J.P. Giesy, 1987. Predictive models for photoinduced acute




      toxicity of polycyclic aromatic hydrocarbons to Daphnia magna. Strauss




      (Cladocera, Crustacea). Environ. Toxicol. Chem. 6(6):445-461.








Parrott, J.L., and J.B.  Sprague. 1993. Patterns of toxicity of sublethal mixtures of




      metals and organic chemicals determined by Microtox8 and by DIMA, RNA,




      and protein content of fathead minnows (Pimephales promelas). Can. J.




      Fish. Aquat. Sci. 50:2245-2253.








Pruell, R.J., N.I. Rubinstein, B.K. Taplin, J.A. Livolsi, and R.D. Bowen. 1993.




      Accumulation of polychlorinated organic contaminants from sediment by




      three benthic marine species. Arch. Environ. Contam. Toxicol. 24:290-297.








Safe, S.,  1990. Polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs),




      dibenzofurans (PCDFs), and related compounds: environmental and




      mechanistic considerations which support the development of toxic




      equivalency factors (TEFs). CRC Crit. Rev. Toxicol.  21, 51-88.
                                    43

-------
Schmitt, C. J., M. L. Wildhaber, J. B. Hunn, T. Nash, M. N. Tieger, and B. L.




      Steadman. 1993. Biomonitoring of lead-contaminated Missouri streams with




      an assay for erythrocyte d-aminolevulinic acid dehydratase activity  in fish




      blood. Archives of Environmental Contamination and Toxicology 25:464-




      475.








Sijm, D.T.H.M., H. Wever and P.J. DeVries, 1989. Octan-1-ol/water partition




      coefficients of polychlorinated dibenzo-p-dioxins and dibenzofurans:




      experimental values determined with a stirring method. Chemosphere




      19:263-266.








Smith, L.M., T.R. Schwartz and K. Feltz, 1990. Determination and occurrence of




      AHH-active polychlorinated  biphenyls, 2,3,7,8-tetrachloro-p-dioxin and




      2,3,7,8-tetrachlorodibenzofuran in Lake Michigan sediment and biota. The




      question of their relative toxicological significance. Chemosphere




      21(9):1063-1085.








Sprague, J. B. and  B. A. Ramsay.  1965. Lethal levels of mixed copper-zinc




      solutions for juvenile salmon. J. Fish. Res. Bd.  Canada 22(2):425-432.








Statistical Analysis System. 1990. Version 6.08 for OS/2. SAS Institute




      Incorporated, Gary, IMC.
                                     44

-------
Tillitt, D.E., G.T. Ankley, and J.P. Giesy. 1991. Characterization of the H4IIE rat




      hepatoma cell bioassay as a tool for assessing toxic potency of planar




      halogenated hydrocarbons in environmental samples. Environ.  Sci. Technol.




      25:87-92.








Tillitt, D.E., G.T. Ankley, J.P.  Giesy, J.P. Ludwig, H. Kurita-Matsuba, D.V.




      Weseloh, P.S. Ross, C. Bishop, L. Sileo, K.L. Stromberg, J. Larson, and T.J.




      Kubiak. 1992. Polychlorinated biphenyl residues and egg mortality in double-




      crested cormorants from the Great Lakes. Environ. Toxicol. Chem. 11:1281-




      1288.








U.S. Environmental Protection Agency. 1993. ASTER data base. ERL-Duluth,




      Duluth, Minnesota.








U.S. Environmental Protection Agency. 1976. Quality criteria for water. EPA




      440/9-76-023. Washington  DC.








U.S. Environmental Protection Agency. 1980a. Ambient water quality criteria for:




      polychlorinated biphenyls (PCBs). EPA 440/5-80-068. Washington DC.








U.S. Environmental Protection Agency. 1980b. ambient water quality criteria for:




      Aldrin/Dieldrin. EPA 440/5-80-019. Washington DC.
                                    45

-------
U.S. Environmental Protection Agency. 1980c. Ambient water quality criteria for:




      chlordane. EPA 440/5-80-027. Washington DC.








U.S. Environmental Protection Agency. 1980d. Ambient water quality criteria for:




      DDT. EPA 440/5-80-038. Washington DC.









U.S. Environmental Protection Agency. 1980e. Ambient water quality criteria for:




      endosulfan. EPA 440/5-80-046. Washington DC.








U.S. Environmental Protection Agency. 1980f. Ambient water quality criteria for:




      endrin. EPA 440/5-80-047. Washington DC.









U.S. Environmental Protection Agency. 1980g. Ambient water quality criteria for:




      heptachlor. EPA 440/5-80-052. Washington DC.








U.S. Environmental Protection Agency. 1980h. Ambient water quality criteria for:




      hexachlorocyclohexane. EPA 440/5-80-054. Washington DC.








U.S. Environmental Protection Agency. 1980i. Ambient water quality criteria for:




      phthalate esters. EPA 440/5-80-067. Washington DC.
                                    46

-------
U.S. Environmental Protection Agency. 1980J. Ambient water quality criteria for:




      copper. EPA 440/5-80-036.  Washington DC.









U.S. Environmental Protection Agency. 1980k. Ambient water quality criteria for:




      mercury. EPA 440/5-80-058. Washington DC.









 U.S. Environmental Protection Agency. 1984a. Ambient water quality criteria for:




      arsenic. EPA 440/5-84-037.  Washington DC.









U.S. Environmental Protection Agency. 1984b. Ambient water quality criteria for:




      cadmium. EPA 440/5-84-032. Washington DC.









U.S. Environmental Protection Agency. 1984c. Ambient water quality criteria for:




      chromium. EPA 440/5-84-029. Washington DC.









U.S. Environmental Protection Agency. 1984d. Ambient water quality criteria for:




      lead. EPA 440/5-84-027. Washington DC.









U.S. Environmental Protection Agency. 1984e. Ambient water quality criteria for:




      mercury. EPA 440/5-80-058. Washington DC
                                    47

-------
U.S. Environmental Protection Agency.  1985a. National prospective on sediment




      quality. Office of Water, Washington D.C.









U.S. Environmental Protection Agency. 1985b. Ambient water quality criteria for




      ammonia. EPA 440/5-85-001.









U.S. Environmental Protection Agency. 1986a. Ambient water quality criteria. EPA




      440/5-86-001. Washington DC.









U.S. Environmental Protection Agency. 1986b. Ambient water quality criteria for:




      toxaphene. EPA 440/5-86-006. Washington DC.









U.S. Environmental Protection Agency. 1986c. Ambient water quality criteria for:




      nickel. EPA 440/5-86-004. Washington DC.









U.S. Environmental Protection Agency, 1987a. Processes, coefficients, and models




      for simulating toxic organics and heavy metals in surface waters. EPA




      600/3-87-015. Washington DC.









U.S. Environmental Protection Agency, 1987b. Ambient water quality criteria for:




      zinc. EPA 440/5-87-003. Washington DC.
                                    48

-------
U.S. Environmental Protection Agency. 1989. Rapid bioassessment protocols for




      use in streams and rivers: benthic macroinvertebrates and fish. EPA 440/4-




      89-001. Washington, DC.








U.S. Environmental Protection Agency. 1990. Assessment and Remediation of




      Contaminated Sediments (ARCS) work plan. U.S. Environmental Protection




      Agency, Great Lakes Program Office, Chicago, IL. 59 p.








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Warren, C.  E. 1971. Biology and  water pollution control. W. B. Saunders




      Company, Philadelphia, PA.








Weast, R. C., M. J. Astle, and W. H. Beyer. 1988. CRC handbook of chemistry




      and physics. CRC Press, Inc.,  Boca Raton, FL.
                                   49

-------
Table 1.  Octanol/water partition coefficients used in the toxic units model for the

contaminants measured in ARCS sediments.
          Contaminant
Octanol/water
   Partition
 Coefficient
  (Log(K0J)
Reference
 Organochlorine compounds

  Chlorodioxins

    2,3,7,8-                     6.42
    Tetrachlorodibenzodioxin

    1,2,3,7,8-                   6.64
    Pentachlorodibenzodioxin

    1,2,3,4,7,8-                 7.80
    Hexachlorodibenzodioxin

    1,2,3,6,7,8-                 7.80
    Hexachlorodibenzodioxin


    1,2,3,7,8,9-                 7.80
    Hexachlorodibenzodioxin


    1,2,3,4,6,7,8-               8.00
    Heptachlorodibenzodioxin

    Octachlorodibenzodioxin      8.00

  Chlorodibenzofurans

    2,3,7,8-                     6.53
    Tetrachlorodibenzofuran

    1,2,3,7,8-                   6.79
    Pentachlorodibenzofuran

    2,3,4,7,8-                   6.92
    Pentachlorodibenzofuran

    1,2,3,4,7,8-                 7.80
    Hexachlorodibenzofuran
                 Sijm et al. 1989

                 Sijm et al. 1989

                 Sijm et al. 1989

                 1,2,3,4,7,8-Hexachlorodi-
                 benzodioxin-Sijm et al.
                 1989
                 1,2,3,4,7,8-Hexachlorodi-
                 benzodioxin-Sijm et al.
                 1989
                 Sijm et al. 1989

                 Sijm et al. 1989


                 Sijm et al. 1989

                 Sijm et al. 1989

                 Sijm et al. 1989

                 1,2,3,4,7,8-Hexachlorodi-
                 benzodioxin—Sijm et al.
                 1989
                                     50

-------
        Contaminant
   Octanol/water
     Partition
    Coefficient
     (Log(K0J)
         Reference
   1,2,3,6,7,8-
   Hexachlorodibenzofuran

   2,3,4,6,7,8-
   Hexachlorodibenzofuran

   1,2,3,7,8,9-
   Hexachlorodibenzofuran
   1,2,3,4,6,7,8-
   Heptachlorodibenzofuran
   1,2,3,4,7,8,9-
   Heptachlorodibenzofuran
   Octachlorodibenzofuran
Chlorobenzenes
   1,2-Dichlorobenzene
   1,3-Dichlorobenzene
   1,4-Dichlorobenzene
 Polychlorinated biphenyls
   Aroclor6 1016
   Aroclor6 1221
   Aroclor6 1232
   Aroclor6 1242
   Aroclor6 1248
   Aroclor6 1254
   Aroclor6 1260
 Pesticides
   Aldrin
   xis-chlordane
7.80

7.80

7.80

7.92

7.92

7.97

3.483 (n = 6)
3.507 (n = 6)
3.455 (n = 8)

5.58 (n  = 3)
4.045 (n = 2)
3.87 (n  = 2)
4.845 (n = 2}
5.933 (n = 4)
6.123 (n - 3)
6.80 (n  = 3)

5.30
4.13 (n  = 2)
1,2,3,4,7,8-Hexachlorodi-
benzodioxin—Sijm et al.
1989
1,2,3,4,7,8-Hexachlorodi-
benzodioxin--Sijm et al.
1989
1,2,3,4,7,8-Hexachlorodi-
benzodioxin-Sijm et al.
1989
Sijm et al. 1989

Sijm et al. 1989

Sijm et al. 1989

USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA
USEPA
USEPA
USEPA
USEPA
USEPA
USEPA
1987a
1987a
1987a
1987a
1987a
1987a
1987a
USEPA 1987a
Chlordane USEPA 1987a
                                   51

-------
        Contaminant
   Octanol/water
     Partition
    Coefficient
    (Log(K0J)
        Reference
   Trans-chlordane
   P_,p_-DDD
   p.,fi-DDE
   Dieldrin
   a-Endosulfan
   yff-Endosulfan
   Endosulfan-sulfate
   Endrin
   Endrin aldehyde
   Endrin ketone

   Heptachlor
   Heptachlor epoxide
   K-Hexachlorocyclohexane
   (Lindane)
   Methyoxychlor
   Toxaphene
Polycyclic aromatic
Compounds
   Acenaphthylene
   Anthracene
   Benz(a)anthracene
   Benzo(a)pyrene
   Benzo(cj,h,j)perylene
   Benzo(k)fluoranthene
   Chrysene
4.13 (n = 2}
6.11 (n = 2)
6.013 (n  = 4)
5.695 (n  = 6)
3.54
-1.70
-1.70
-1.30
4.827 (n  = 3)
3.15
3.15

4.41
2.65
3.573 (n  = 3)

4.24 (n - 2)
3.30 (n = 2)
3.895 (n = 2)
4.477 (n = 6)
5.61 (n = 2)
5.383 (n = 3)
6.863 (n = 3)
6.45 (n = 2)
5.71 (n = 3)
Chlordane USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a
Endrin aldehyde USEPA
1987a
USEPA 1987a
USEPA 1987a
USEPA 1987a

USEPA 1987a
USEPA 1987a
USEPA
USEPA
USEPA
USEPA
USEPA
USEPA
USEPA
1987a
1987a
1987a
1987a
1987a
1987a
1987a
                                 52

-------
         Contaminant
  Octanol/water
     Partition
    Coefficient
    (Log(K0J)
         Reference
Dibenzofuran
Fluoranthene
Fluorene
lndeno(1,2,3-c,d)pyrene
Napthalene
Phenanthrene
Pyrene
4
5
4
7
3
4
5
.09
.150
.118
.085
.341
.524
.119

(n
(n
(D
(n
(n
(n

= 3)
= 4)
= 2)
= 7)
= 5)
= 8)
USEPA
1993
USEPA
USEPA
USEPA
USEPA
USEPA
USEPA
ASTER database
1
1
1
1
1
1
987a
987a
987a
987a
987a
987a
 Phthalate esters
    Bis(2-ethylhexyl)phthalate
    Butyl benzyl phthalate
    Dimethyl phthalate
 Organo-metals
    Tributyltin
9.17 (n  = 2)
5.556 (n = 4)
1.763 (n = 3)

3.2
USEPA 1987a
USEPA 1987a
USEPA 1987a

Maguire et al. 1983
*N equals number of values averaged (arithmetic mean) to produce the indicated
value.
                                    53

-------
Table 2.  Estimation of the chronically toxic pore-water concentration defining a toxic unit for each contaminant

used in the toxic units model. "MT" minimal or no observed toxicity.
              Contaminant
     Toxic Unit Calculations (ug/L)
         Reference
 Organochlorine Compounds

  Chlorodioxins

    2,3,7,8-Tetrachlorodibenzodioxin


    1,2,3,7,8-Pentachlorodibenzodioxin


    1,2,3,4,7,8-Hexachlorodibenzodioxin


    1,2,3,6,7,8-Hexachlorodibenzodioxin


    1,2,3,7,8,9-Hexachlorodibenzodioxin


    1,2,3,4,6,7,8-Heptachlorodibenzodioxin


    Octachlorodibenzodioxin


  Chlorodibenzofurans

    2,3,7,8-Tetrachlorodibenzofuran
0.0141 x 0.00000992 = 0.0000376


0.0141 x (0.0000099/0.0087)3
= 0.0000160

0.0141 x (0.0000099/0.045)3
= 0.00000308

0.0141 x (0.0000099/0.004)3
= 0.0000348

0.0141 x (0.0000099/0.0037)3
= 0.0000376

0.0141 x (0.0000099/0.0028)3
= 0.0000495

0.0141 x (0.0000099/0.1)4
= 0.00000139
0.0141 x (0.0000099/0.025)3
=  0.00000556
USEPA 1980a and Smith et
al. 1990

USEPA 1980a and Smith et
al. 1990

USEPA 1980a and Smith et
al. 1990

USEPA 1980a and Smith et
al. 1990

USEPA 1980a and Smith et
al. 1990

USEPA 1980a and Smith et
al. 1990

USEPA 1980a, Smith et al.
1990, and Safe 1990
USEPA 1980a and Smith et
al. 1990
                                                 54

-------
             Contaminant
    Toxic Unit Calculations (ug/L)
        Reference
   1,2,3,7,8-Pentachlorodibenzofuran


   2,3,4,7,8-Pentachlorodibenzofuran


   1,2,3,4,7,8-Hexachlorodibenzofuran


   1,2,3,6,7,8-Hexachlorodibenzofuran


   1,2,3,7,8,9-Hexachlorodibenzofuran


   2,3,4,6,7,8-Hexachlorodibenzofuran


   1,2,3,4,6,7,8-Heptachlorodibenzofuran


   1,2,3,4,7,8,9-Heptachlorodibenzofuran


   Octachlorodibenzofuran


Chlorobenzenes

   1,2-Dichlorobenzene

   1,3-Dichlorobenzene

   1,4-Dichlorobenzene
0.0141 x (0.0000099/0.038)3
= 0.00000366

0.0141 x (0.0000099/0.38)3
= 0.000000366

0.0141 x (0.0000099/0.27)3
= 0.000000515

0.0141 x (0.0000099/0.065)3
= 0.00000214

0.0141 x (0.0000099/0.1)
= 0.00000139

0.0141 x (0.0000099/0.14)3
= 0.000000993

0.0141 x (0.0000099/0.1 )4
= 0.00000139

0.0141 x (0.0000099/0.1)4
= 0.00000139

0.0141 x (0.0000099/0.1)4
= 0.00000139
    7.0

   180.0

   43.0
USEPA 1980a and Smith et
al. 1990

USEPA 1980a and Smith et
al. 1990
USEPA 1980a and Smith et
al. 1990
USEPA 1980a and Smith et
al. 1990
USEPA 1980a, Smith et al.
1990, and Safe 1990
USEPA 1980a and Smith et
al. 1990
USEPA 1980a, Smith et al.
1990, and Safe 1990
USEPA 1980a, Smith et al.
1990, and Safe 1990

USEPA 1980a, Smith et al.
1990, and Safe 1990
Michigan DNR 1993

Michigan DNR 1993

Michigan DNR 1993
                                               55

-------
             Contaminant
    Toxic Unit Calculations (ug/L)
        Reference
 Polychlorinated byphenyls (PCBs)
  Aroclor6 1016
  Aroclor6 1221
  Aroclor6 1232

  Aroclor6 1242

  Aroclor6 1248

  Aroclor6 1254
  Aroclor6 1260
Pesticides
  Aldrin
  cis-Chlordane
  trans-Chlordane
  p.,p/-DDE
  fi,fi'-DDT
  Dieldrin
  a-Endosulfan
   MT
   MT
0.0141 x (0.0000099/ 0.001934)3
=  0.0000717
0.0141 x (0.0000099/0.0000137)3
=  0.0101
0.0141 x (0.0000099/0.0000173)3
=  0.00801
   0.014
   MT
  0.0019
  0.0043
  0.0043
  0.001
  0.001
  0.001
  0.0019
  0.056
Smith et al. 1990
Smith et al. 1990
USEPA 1980a and Smith et
al. 1990
USEPA 1980a and Smith et
al. 1990
USEPA 1980a and Smith et
al. 1990
USEPA 1980a
Smith et al. 1990
Dieldrin USEPA 1980b
Chlordane USEPA 1980c
Chlordane USEPA 1980c
DDT USEPA 1980d
DDT USEPA 1980d
USEPA 1980d
USEPA 1980b
Endosulfan USEPA 1980e
                                              56

-------
             Contaminant
    Toxic Unit Calculations (ug/L)
        Reference
  /ff-Endosulfan
  Endosulfan sulfate
  Endrin
  Endrin aldehyde
  Endrin ketone
  Heptachlor
  Heptachlor epoxide
  K-Hexachlorocyclohexane (Lindane)
  Methyoxychlor
  Toxaphene
Polycyclic aromatic hydrocarbons (PAHs)
  Acenaphthylene

  Anthracene

  Benz(a)anthracene

  Benzo(a)pyrene
  0.056
  0.056
  0.0023
  0.0023
  0.0023
  0.0038
  0.0038
  0.08
  0.03
  0.0002

24000 ug/kg5/(0.046 x Koc7}

44000 ug/kg5/(0.046 x Koc7)

220000 ug/kg5/(0.046 x Koc7)

1800000 ug/kg5/(0.046 x Koc7)
Endosulfan USEPA 1980e
Endosulfan USEPA 1980e
USEPA 1980f
Endrin USEPA 1980f
Endrin USEPA 1980f
USEPA 1980g
Heptechlor USEPA 1980g
USEPA 1980h
USEPA 1976
USEPA 1986b
USEPA 1985a and DiToro et
al. 1991
USEPA 1985a and DiToro et
al. 1991
USEPA 1985a and DiToro et
al. 1991
USEPA 1985a and DiToro et
al. 1991
                                               57

-------
           Contaminant
     Toxic Unit Calculations (ug/L)
         Reference
Benzo(c[,h,j)perylene



Benzo(k)fluoranthene


Chrysene


Dibenzofuran



Fluoranthene



Fluorene



Indenod ,2,3-c,d)pyrene


Napthalene

Phenanthrene


Pyrene
(1800000 ug/kg5/(0.046 x Koc7))
x 3.118
5000000 ug/kg5/(0.046 x Koc7)


460000 ug/kg5/(0.046 x Koc7)
   x 0.70810 = 4.956
(1800000 ug/kg5/(0.046 x Koc7))
x 2.438
28000 ug/kg5/(0.046 x Koc7)



24000000 ug/kg5/(0.046 x Koc7)


   29.0

56000 ug/kg5/(0.046 x Koc7)


198000 ug/kg5/(0.046 x Koc7)
USEPA 1985a, DiToro et al.
1991, and Newsted and
Giesy 1987

USEPA 1985a and DiToro et
al. 1991

USEPA 1985a and DiToro et
al. 1991

1,2-Dichlorobenzene
Michigan DNR 1993 and
LeBlanc 1980

USEPA 1985a, DiToro et al.
1991, and Newsted and
Giesy 1987

USEPA 1985a and DiToro et
al. 1991
USEPA 1985a and DiToro et
al. 1991

Michigan DNR 1993

USEPA 1985a and DiToro et
al. 1991

USEPA 1985a and DiToro et
al. 1991
                                             58

-------
             Contaminant
    Toxic Unit Calculations (ug/L)
        Reference
Phthalate esters
   Bis(2-ethylhexyl)phthalate

   Butyl benzyl phthalate
   Dimethyl phthalate

Metals, organo-metals, and metaloids
   Arsenic
   Cadmium
   Chromium
   Copper
   Iron
   Lead
   Manganese
   Mercury
   Methyl mercury

   Nickel
   Selenium
79x4.58310 = 32.081

    3.0
79x 13.7510 = 96.25
   190.0
e (0.7852 x In(hardness) - 3.49)
_(0.81 9 x In(hardness) + 1.561)
\2
    5.6
    1000
_(1.273 x In(hardness) - 4.705)

 not toxic
  0.012
0.01211/1012 = 0.0012

-(0.846 x In(hardness) + 1.1645)

1.0 (ug/g dry weight sediment)
1,2-Dichlorobenzene
Michigan DNR 1993 and
LeBlanc 1980
USEPA 1980i
1,2-Dichlorobenzene
Michigan DNR 1993 and
LeBlanc 1980
USEPA 1984a
USEPA 1984b
USEPA 1984c
USEPA 1980J
USEPA 1976
USEPA 1984d
USEPA 1976
USEPA 1984e
Mercury USEPA 1980k and
USEPA 1984e
USEPA 1986c
Lemly et al. 1993
                                                 59

-------
               Contaminant
    Toxic Unit Calculations (ug/L)
         Reference
    Silver

    Tributyl tin
    Zinc
 Other compounds
    Ammonia
    29.0

   0.009
s (0.8473 x In(hardness) + 0.7614)
((0.8/FT13)/FPH14)/RATI015
Michigan DNR 1993
Michigan DNR 1993
USEPA 1987b


USEPA 1985b
1Aroclore 1254 chronic AWQC (USEPA 1980a).
2AHH activity of Aroclor6 1254 relative to that of 2,3,7,8-Tetrachlorodibenzodioxin (Smith et al. 1990).
3The ratio AHH activity of Aroclor8 1254 relative to 2,3,7,8-Tetrachlorodibenzodioxin:AHH activity of listed
contaminant relative to 2,3,7,8-Tetrachlorodibenzodioxin (Smith et al. 1990).
4The ratio AHH activity of Aroclor6 1254 relative to 2,3,7,8-Tetrachlorodibenzodioxin (Smith et al. 1990):Toxic
Equivalency Factor (TEF) of listed contaminant relative to 2,3,7,8-Tetrachlorodibenzodioxin (Safe  1990).
Estimated sediment threshold concentration for listed contaminant (USEPA 1985a).
6Proportion of organic carbon in sediment used to estimate sediment threshold concentrations (USEPA 1985a).
7KOC = 10(0-00028 + osaa-iooiKow^ KOW js octano|/water partition coefficient (DiToro et al. 1991).
8Relative toxicity of listed contaminant to Benzo(a)pyrene (Newstead and Giesy 1987).
91,2-Dichlorobenzen 1993 water quality standard from Michigan Department of Natural Resources.
10Relative toxicity of listed contaminat to1,2-Dichlorobenzene (LeBlanc 1980).
11AWQC for mercury (USEPA 1984e).
12Relative toxicity of methyl  mercury to mercury (USEPA 1980k).
13py _ 1Q(0.03 x (20- 15))
14FPH =  1, IF pH < = 8 THEN FPH = (1 + 10(74-pH))/1.25.
15RATIO  = 16,  IF pH  < = 7.7 THEN  RATIO = 24 x 10'7 7-pH)/(1 + 10(74-pH|).
                                                    60

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Table 3. Laboratory toxicity tests included in the assessment of sediment toxicity.

Laboratory toxicity tests used in evaluation of Master Station data are denoted by
Test Organism
Fishes
*Pimephales promelas
embryo larvae
*Pimephales promelas
larvae
Zooplankters
Ceriodaphnia dubia






Length Sediment
of Test Phase

7 d Whole
sediment
7 d Whole
sediment

7 d Sediment
elutriate
(6.25, 12.5,
25, 50,
100%) and
whole
sediment
Endpoints

Survival, length,
and terata
Survival and
weight

Reproduction and
survival





  *Daphnia maqna
  *Daphnia magna


 Benthic invertebrate

  Chironomous riparius


  *Chironomous tentans
48 h      Sediment
          elutriate
          (3.125, 6.25,
          12.5, 25, 50,
          and 100%)
          and whole
          sediment

7 d       Whole
          sediment
14 d      Whole
          sediment

10 d      Whole
          sediment
Survival
Survival and
reproduction
Survival and length
Survival and length
                                    61

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Test Organism
*Hexagenia bilineata
*Hvalella azteca
*Hvalella azteca
Pontoporeia hoyi
Pontoporeia hoyi
Length
of Test
10 d
14 d,
28 d
7 d
5 d
20 d
Sediment
Phase
Sediment
elutriate and
whole
sediment
Whole
sediment
Whole
sediment
Whole
sediment
Whole
sediment
Endpoints
Survival and
molting frequency
Survival, length,
antenna length,
and sexual
maturation
Survival
Preference
Survival
Phytoplankters
 *Selenastrum capricornutum
24 h
 *Selenastrum capricornutum    48 h
 * Selenastrum capricornutum    96 h
Macrophytes

 Hvdrilla verticillata
Sediment
elutriate
(6.25, 10.2,
12.5, 25,
28.6, 50, 57,
71.4%)

Sediment
elutriate
(6.25, 12.5,
25, 50,
100%)

Sediment
elutriate
(6.25, 12.5,
25, 50,
100%)
          Whole
          sediment
                         14
C uptake
                         Growth
                         Growth
               Root length, shoot
               length, chlorophyll,
               dehydrogenase,
               and peroxidase
                                   62

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       Test Organism
 Length
 of Test
  Sediment
    Phase
    Endpoints
                             4d
          Whole
          sediment
               Biomass,
               chlorophyll a, and
               frond number
Microbes

 *Photobacterium
 phosphoreum
5 min,
15 min
Sediment
elutriate
(5.65, 6.25,
11.25, 12.5,
22.5,  25, 45,
50, 100%)
Luminescence
                                  63

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Table 4. Tolerance to pollution values for taxa identified in the full group of
sediment samples used in the analyses. Also included is the associated reference
from which each tolerance value was taken.  Those tolerance values with  an 'n'
value were estimated because no value was available from any reference.  An
estimate was either calculated from the mean of values for the species found in
the sediments (i.e. family or high taxon tolerance) or from the mean of members of
the same genera with tolerance values. The values for the hemiptera were based
on educated guess.
Scientific Name
Amphipoda
Crustacea
Gammarus lacustris
Annelida
Hirudinea
Helobdella elongata
Helobdella stagnalis
Batracobdella phalera
Placobdella ornata
Naididae
Dero digitata
Oligocheata
Tubificidae
Aulodrilus pigueti
Aulodrilus limnobius
Aulodrilus plureseta
llvodrilus templetoni
Limnodrilus cervix
Limnodrilus claparedianus
Limnodrilus hoffmeisteri
Limnodrilus maumeensis
Tolerance Value
6.0

6.9

7.9 (n = 3)
9.9
6.7
7.1
7.8 (n = 2)

10
8.2
8.55 (n = 8)
4.7
5.2
4.95 (n = 2)
9.4
10
9.78 (n = 4)
9.8
9.78 (n = 4)
Reference
Hilsenhoff 1988

Lenat 1993

Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993

Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
                                     64

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Scientific Name
Limnodrilus undedemianus
Limnodrilus sp.
Quistadrilus multisetosus
Tubifex tubifex
Bivalvia
Sphaeriidae
Musculium sp.
Pisidium sp.
Sphaerium sp.
Unionidae
Anodonta imbecillis
Anodonta grandis
Eliptio complanata
Coleoptera
Pshenidae
Haliplus
Decapoda
Diptera
Ceratopogonidae
Plapomyia sp.
Chaoboridae
Chaoborus sp.
Tolerance Value
9.7
9.6
8.55 (n = 8)
10

7.25 (n = 2)
7.25 (n = 2)
6.8
7.7

5.4
5.4
5.4

2.5
5.7
6.0


6.9

8.5
Reference
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993

Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993

Lenat 1993
Lenat 1993
Lenat 1993

Lenat 1993
Lenat 1993
USEPA 1989


Lenat 1993

Lenat 1993
Chironomidae
5.7
Lenat 1993
                                65

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Scientific Name
Chironomous sp.
Cladopelma sp.
Coelotanypus sp.
Cricotopus sp.
Cryptochironomous sp.
Dicrotendipes sp.
Glyptotendipes sp.
Microchironomous sp.
Polypedilum sp.
Procladius sp.
Tanypus sp.
Ephemeroptera
Caenis sp.
Tolerance Value
9.8
2.5
7.7
8.12 (n - 5)
7.35 (n - 2)
7.9
8.5
7.79 (n - 6)
6.67 (n - 7)
9.3
9.6
2.7
7.6
Reference
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Lenat 1993
Gastropoda
 Ancylida
   Laevapex fucus
 Bithyniidae
   Bithynia tentaculata

 Hydrobiidae
   Cincinnatia cincinnatiensis
7.3
6.1
6.1
Lenat 1993
Lenat 1993
(Mullusca)
Lenat 1993
(Mullusca)
                                    66

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           Scientific Name
Tolerance Value
     Reference
 Valvatidae
   Valvata lewisi

   Valvata tricarinata
6.1

6.1
Lenat 1993
(Mollusca)
Lenat 1993
(Mollusca)
Hemiptera
   Sigara sp.
6.0
6.0
(estimate)
(estimate)
Odanata
   Gomphus sp.
6.9
6.2
Lenat 1993
Lenat 1993
Trichoptera
   Oecetis sp.
5.7
Lenat 1993
                                   67

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Table 5.  Bioaccumulative Contaminants of Concern1 used in toxic units model
 Organochlorine compounds

 Chlorodioxins and furans
  2,3,7,8-Tetrachlorodibenzodioxin
  1,2,3,7,8-Pentachlorodibenzodioxin
  1,2,3,4,7,8-
  Hexachlorodibenzodioxin
  1,2,3,6,7,8-
  Hexachlorodibenzodioxin
  1,2,3,7,8,9-
  Hexachlorodibenzodioxin
  1,2,3,4,6,7,8-
  Heptachlorodibenzodioxin
  Octachlorodibenzodioxin
  2,3,7,8-Tetrachlorodibenzofuran

  1,2,3,7,8-Pentachlorodibenzofuran
  2,3,4,7,8-Pentachlorodibenzofuran
  1,2,3,4,7,8-
  Hexachlorodibenzofuran
  1,2,3,6,7,8-
  Hexachlorodibenzofuran
  1,2,3,7,8,9-
  Hexachlorodibenzofuran
  2,3,4,6,7,8-
  Hexachlorodibenzofuran
  1,2,3,4,6,7,8-
  Heptachlorodibenzofuran
  1,2,3,4,7,8,9-
  Heptachlorodibenzofuran
  Octachlorodibenzofuran
 Polychlorinated
 biphenyls
 Aroclor6 1016
 Aroclor8 1221
 Aroclor6 1232
 Aroclor6 1242

 Aroclor6 1248

 Aroclor6 1254

 Aroclor6 1260

Pesticides
 Aldrin

 cis-Chlordane
 trans-Chlordan
 p.,fi-DDD

 S,fi-DDE
 Dieldrin

 a-Endosulfan

 /ff-Endosulfan

 Endosulfan
 sulfate
Polycyclic aromatic
hydrocarbons (PAHs)
 Benzo(a)pyrene
 Benzo(cj,h,j)perylene
 Benzo(k)fluoranthene
 Endrin

 Endrin aldehyde

 Endrin ketone

 Heptachlor

 Heptachlor epoxide
 K-Hexachlorocyclo-
 hexane (Lindane)
 Methyoxychlor
 Toxaphene
Metals, organo-
metals, and metaloids
 Arsenic

 Methyl mercury

 Mercury

 Selenium
'Modified from USEPA (1993). Draft GLWQI.
                                     68

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Table 6. Toxic units, based on the estimated  bioavailable fraction, for individual
contaminants in Buffalo River sediments.  Only contaminants given are those for
which toxic units were one or greater at one or more sites; all contaminants
included in total.
Contaminant
Ammonia
(unionized)
Chromium
p_,p.-DDT
yff-Endosulfan
Endrin aldehyde
Iron
Methyl mercury
Naphthalene
Octachlorodibenz
o-dioxin
Aroclor6 1248
Aroclor6 1254
Selenium
Tributyl tin
Total
BR 1
5.31
NT1
2.06
NT
NT
NT
581.59
4.01
1.33
1.05
NT
3.80
23.12
623.97
BR 3
1.56
11.13
8.24
NT
1033.58
984.36
NT
NT
NT
NT
11.50
NT
NT
2051.75
Site
BR 7
2.25
3.11
14.74
1128.38
NT
701.8
NT
NT
NT
NT
NT
NT
NT
1851.03
BR 8
2.32
1.77
NT
NT
NT
514.56
NT
NT
NT
NT
NT
NT
NT
518.94
BR9
4.12
2.39
NT
NT
NT
449.76
NT
NT
NT
NT
NT
NT
NT
456.44
1NT stands for not toxic (i.e., the estimated pore-water concentration for the

individual contaminant was less than the level of concern).
                                     69

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Table 7. Toxic units, based on the estimated bioavailable fraction, for individual



contaminants in Indiana Harbor sediments.  Only contaminants given are those for




which toxic units were one or greater at one or more sites; all contaminants



included in total.
Contaminant
Aldrin
Ammonia
(unionized)
Anthracene
trans-Chlordane
Chromium
BL,EL-DDE
fi,fi-DDT
Dibenzofuran
Dieldrin
/?-Endosulfan
Endrin aldehyde
Heptachlor
Heptachlor
epoxide
Iron
Methyl mercury
Naphthalene
Octachlorodibenz
o-dioxin
Octachlorodibenz
o-furan
Aroclor6 1242

IH 3
3.56
7.93
NT
17.47
97.97
NT
NT
NT
637.74
675.76
NT
NT
NT
4719.95
NT
1.71
NT
NT
223.04

Site
IH 4
NT1
8.70
NT
NT
63.91
NT
NT
NT
NT
NT
NT
NT
NT
3681.06
1350.47
1.14
NT
NT
90.76
70
IH 6
5.32
12.75
NT
26.23
85.06
1.06
2.18
NT
496.54
NT
195.32
10.50
1804.79
1335.52
NT
1.31
3.66
NT
353.63

IH 7
12.21
16.06
1.35
39.26
779.21
2.94
NT
11.63
NT
NT
NT
44.37
2010.72
10712.79
364.63
1.02
5.17
3.85
836.59


-------
Contaminant
Aroclor6 1254
Selenium
Tributyl tin
Total
IH 3
NT
2.60
249.13
6645.32
Site
IH4
11.50
2.30
154.88
5354.88
IH 6
NT
3.80
1028.63
5369.41
IH
NT
3.10
NT
14848.
7



66
1NT stands for not toxic (i.e., the estimated pore-water concentration for the




individual contaminant was less than the level of concern).
                                     71

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Table 8. Toxic units, based on the estimated bioavailable fraction, for individual

contaminants in Saginaw River sediments. Only contaminants given are those for

which toxic units were one or greater at one or more sites; all contaminants

included in total.
Contaminant
Aldrin
Ammonia
(unionized)
trans-Chlordane
Chromium
B..B.-DDE
Heptachlor
Heptachlor
epoxide
1234678-
Heptachlorodi-
benzofuran
Iron
Octachlorodibenz
o-dioxin
Octachlorodibenz
o-furan
Aroclor8 1242
Aroclor8 1254
12378-
Pentachlorodi-
benzofuran
SR 3
NT1
1.67
NT
2.98
NT
NT
NT
NT
648.96
1.35
NT
223.04
NT
NT
Site
SR 6
56.14
1.93
136.31
90.73
8.26
81.84
5965.91
1.08
27.36
4.41
1.37
4921.87
25.96
1.76
SR 10
NT
NT
NT
2.31
NT
NT
NT
NT
661.99
1.32
NT
NT
16.20
NT
 23478-            2.17               11.21              1.29
 Pentachlorodi-
 benzofuran
                                     72

-------
                                            Site
   Contaminant          SR 3               SR 6              SR 10
 Tetrachlorodi-      NT                 6.94              NT
 benzofuran
 Tributyl tin        39.84              NT                NT

 Total	699.97	11344.15	685.84
1NT stands for not toxic (i.e., the estimated pore-water concentration for the
individual contaminant was less than the level of concern).
                                    73

-------
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  Figure 2. Observed relative sediment toxicity versus total toxic units based on

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-------
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ndiana H
 agjnaw
 aqinaw
 irbor
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River site 6
        0              20000000          40000000          60000000

            Bulk Chemistry Toxic Units for Bioaccumulatives


Figure 5. Observed relative sediment toxicity versus total toxic units based on

bulk sediment concentrations of bioaccumulative contaminants. Line represents

the relation Y = 0.32 - 0.0000000089X (R-squared - 0.68, n = 12, P = 0.001).

-------
   0
  i         i        i         i         i         i        i         I
2,000    4,000    6,000    8,000   10,000   12,000   14,000   16,000
                   Total Toxic Units
Figure 6. Benthic community mean tolerance to pollution versus total toxic units
based on bioavailable fractions of all contaminants. The line represents the
relation Y = 8.71 - 0.000018X (R-squared - 0.40, n - 12, P = 0.0278).

-------
    0
 10       20        30        40        50
Bulk Sediment Chemistry Toxic Units (millions)
60
Figure 7. Benthic community mean tolerance to pollution versus total toxic units
based on bulk sediment concentrations of all contaminants. The line represents
the relation Y = 8.74 - 0.000000005X (R-squared = 0.34, n - 12, P - 0.0463).

-------
0
60
                10        20        30        40       50
                  Toxic Units of Bioaccumulatives (millions)
Figure 8. Benthic community mean tolerance to pollution versus total toxic units
based on bulk sediment concentrations of only bioaccumulative contaminants. The
line represents the relation Y = 8.74 - 0.000000005X (R-squared = 0.34,
n = 12, P = 0.0466).

-------
    0
2,000
4,000       6,000
 Iron Toxic Units
8,000      10,000
Figure 9. Benthic community mean tolerance to pollution versus total toxic units
based on bioavailable fractions of iron only. The line represents the relation
Y = 8.73 - 0.000027X (R-squared = 0.40, n = 12, P = 0.0261).

-------
    120
      0
            T   I   I    I
              BUFFALO RIVER
INDIANA HARBOR
SAGINAW RIVER
                       AREA OF CONCERN
            PRIORITY MASTER VARIABLES
       MASTER VARIABLES
Figure 10. Comparison of the overall ranking of sites based on Priority Master
Stations (shaded bars) versus Master Stations (crosshatched bars). Bars
represent the average of the relative ranking among sites of toxic units,
control-adjusted laboratory toxicity, and mean tolerance to pollution of the
benthic community for both Priority Master Stations and Master Stations.

-------
      120
                 BUFFALO RIVER
INDIANA HARBOR
I    I
  SAGINAW RIVER
                          AREA OF CONCERN
            PRIORITY MASTER VARIABLES
   RECONNAISANCE VARIABLES
Figure 11. Comparison of the overall ranking of sites based on Priority Master
Stations (shaded bars) versus Reconnaissance Stations (crosshatched bars). Bars
represent the average of the relative ranking among sites of toxic units,
control-adjusted laboratory toxicity, and mean tolerance to pollution of the
benthic community for Priority Master Stations. For Reconnaissance Stations,
bars represent the average of the relative ranking among sites of toxic units,
which were base only a short list of contaminants, and Microtox.

-------
  LJU
  LU
  CC
      120
      100
       80
       60
       40
       20
                 BUFFALO RIVER
INDIANA HARBOR
SAGINAW RIVER
                          AREA OF CONCERN
         PRIORITY MASTER VARIABLES
BIOACCUMULATIVE CONTAMINANTS
Figure 12. Comparison of the overall ranking of sites based on Priority Master
Stations (shaded bars) versus bioaccumulative contaminants (crosshatched bars).
Bars represent the average of the relative ranking among sites of toxic units,
control-adjusted laboratory toxicity, and mean tolerance to pollution of the
benthic community for Priority Master Stations. For bioaccumulative
contaminants, bars represent the toxic units based on bulk concentrations of
those contaminants listed as bioaccumulative  contaminants of concern (Table 5).

-------