United States
                     Environmental Protection
                     Agency
Environmental Research
Laboratory
Duluth MN 55804
                    Research and Development
EPA-600/S3-84-064 June 1984
&EPA         Project  Summary
                    Chemical  and  Biological  Studies
                    Related  to  the  Water  Quality
                    of  St. Louis  Bay of  Lake  Superior
                    Anthony R. Carlson and Nelson Thomas
                      This study was a cooperative effort
                    among the University  of Wisconsin-
                    Superior,  University  of  Minnesota-
                    Duluth,  and U.S. EPA  Environmental
                    Research Laboratory-Duluth to develop
                    and evaluate effluent toxicity screening
                    methods  and  test  methods and
                    protocols  for  deriving  site-specific
                    water quality criteria.  The  principal
                    components of the study   were  to
                    include: (1) a chemical characterization
                    of the main discharges to the St. Louis
                    River and Harbor, (2)  persistence of
                    toxic pollutants in the St. Louis River
                    and  Harbor, (3) a description  of the
                    exposure times for various components
                    of the ecosystem, (4) bioassays with St.
                    Louis River water ad resident species,
                    (5) an assessment as to the degradation
                    of the biologic community of St. Louis
                    Harbor, and (6) a modeling framework
                    to address items 1 through 5.
                      Because  persistent toxic   pollutant
                    concentrations were  not found in the
                    Western Lake Superior Sanitary District
                    (WLSSD) effluent and no  persistent
                    open water pollutant problems were
                    apparent,  this  study  was  ended.
                    Following  are a series of reports  on
                    work completed.

                      This Project Summary was developed
                    by  EPA's  Environmental  Research
                    Laboratory, Duluth. MN. to  announce
                    ke y findings of the research project that
                    is fully documented in a separate report
                    of the same title (see Project Report
                    ordering information at back).

                    Introduction
                      St. Louis Bay of Lake Superior provides
                    a unique opportunity to study a natural
ecosystem  and  related  observed
response  to  pollutants to laboratory
testing  effect  endpoints  and
observations. To understand a pollutant's
cause and effect relationship in such a
system, it must be studied in sufficient
depth to understand  the  controlling
factors To this end, several on site (field)
and laboratory studies were  undertaken
to quantify possible pollutant impacts and
resulting biotic responses  of the bay
ecosystem
  Such research is needed to provide a
basis for  the U.S   Environmental
Protection Agency's (EPA) Office of Water
to provide guidance to the states on the
modification of national water quality
criteria to site-specific situations, and the
control of complex effluents through the
National Pollution Discharge System. The
EPA Great Lakes National Program Office
also needs information on the causes of
pollution of St. Louis Bay and the impact
of the bay on western Lake Superior
  The primary objectives of this research
project were:  (1)  field test the  EPA
guidelines for deriving site-specific water
quality criteria, (2) obtain data on the
relationship between toxicity testing of a
complex  effluent and  receiving water
biotic response, and  (3) evaluate the
usefulness of  water  quality criteria  to
protect a Great Lakes ecosystem.
  To  meet  the above  objectives, three
conditions must have existed. The first is
that a point source discharge to the bay
had to be at least chronically toxic, the
toxic components of the effluent had to be
identified, and the bay biota had to  be
impacted by the effluent. Because the
Western  Lake Superior  Sanitary District
(WLSSD)  discharge,   containing  both

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treated domestic and industrial wastes,
appeared to meet the above conditions, it
was selected for  initial  study. It is the
largest single point discharger to the bay,
its final effluents had exhibited toxicity in
the past and some fish kills had occurred
in the embayment near its discharge pipe
During 1982 studies to chemically char-
acterize the WLSSD effluent, determine
its toxicity and trace its movement in and
out  of the  bay were  initiated  Other
studies were  initiated to provide a water
chemistry and biological  baseline for the
bay  from  which   present  and  future
pollutant impacts on the bay, and the
bay's impact on Lake Superior, could be
determined  A  literature search of all
studies relevant to St. Louis Bay was also
begun. Information  gained from these
first-year  efforts  were  necessary to
determine if the primary objectives of this
research project were achievable and, if
achievable, to plan subsequent studies.
  This project was undertaken as a coop-
erative effort of the U.S. EPA Environ-
mental   Research  Laboratory-Duluth,
University  of  Minnesota-Duluth,  and
University of Wisconsin-Superior.
Following  are  reports  on  individual
research tasks undertaken in 1982.


Results and Conclusions--
St.  Louis Bay

Water Chemistry Surveys
  At the six sites, in the small embayment
near the WLSSD wastewater treatment
plant, ammonia, alkalinity,  total  phos-
phorus, and chloride were higher than in
the control embayments.
  The  fraction  of  WLSSD  effluent,
estimated from chloride  concentration
was 0.20-0.25 in the three sites closest to
the discharge pipe and 0.05-0 10 in the
three sites farthest from the discharge
pipe.  Ammonia and total  phosphorus
appear to have a substantial sediment
source m the  small embayment near
WLSSD.
  Nutrient input budgets for St. Louis Bay
revealed  that 90%  of  the  alkalinity,
ammonia and total phosphorus loadings
were derived from the St. Louis River with
the remainder originating from WLSSD.
However, high chloride concentrations in
the WLSSD effluent contribute 43% of
the Cl  loading to St.  Louis Bay, compared
to 57% from the St.  Louis River.
  Comparison of  the  total  phosphorus
input budget for  1982  with a similar
budget for 1972 revealed that the WLSSD
sewage treatment plant  released one-
fifth the  total  phosphorus  that  was
 released by the  nine sewage treatment
 plants operating  in 1972
  Phenol concentrations decreased from
 8 to 9 fjg L'1 in the mid-1970s to 3//g L '
 in 1982.
  The mean total phosphorus  at site L
 (downstream from the present WLSSD
 plant) decreased from 110 /ug LH between
 1972 to 1979 to 75 fjg L ' for 1979 to 1982.
  The mean ammonia concentration at
 site L decreased  from 0.259 mg L~1 (pre-
 1979) to 0.116 mg L'1 after 1979.

 Benthic Invertebrate Surveys
  The   benthic   invertebrate  surveys
 demonstrated   noticeable  differences
 between the WLSSD discharge bay and
 two  bays  (controls)  upstream.   The
 discharge bay contained fewer types of
 organisms and  these are considered
 more tolerant of  domestic effluents. The
 differences between the bays were less
 noticeable in October  than in June or
 August.

 Phytoplankton andZooplankton
 Surveys
  The   Duluth-Supenor  Harbor  is  a
 complex system for pelagic sampling. Not
 only is the bathymetry complex, with the
 extensive  shallows  plus   the  deep
 dredged  ship   channels,  but  the
 interactive flows of the St. Louis  River
 and seiche currents from Lake Superior
 make point samples a function of many
 variables. In the shallows,  particularly,
 the range of seasonal change can be
 extreme Within  this context, examina-
 tion of the plankton data  from Summer
 1982 shows no adverse influence of the
 effluent from the WLSSD plant.

 WLSSD Effluent Toxicity and
 Characterization
 Effluent Toxicity
  The effluent was intermittently acutely
toxic  to  aquatic organisms (fish  and
invertebrates) in toxicity tests. Behavioral
monitoring of fish continuously exposed
to the plant effluent was used to identify
periods of effluent toxicity.
  Increases in fish locomotor and respir-
atory activity correlate with fish  mortality
in  bioassays of  grab  samples  Some
possible causes of observed toxicity were
thought  to be related to  elevated total
residual  chlorine  or  carbon  dioxide
concentrations resulting from changes in
wastewater  treatment in response to
changes in influent conditions
  It  is  recommended  that any future
 bioassays of WLSSD  effluent, or the
effluent from other treatment plants, be
complemented with chemical analyses ol
total chlorine, pH (immediate and after
extended   aeration),  carbon   dioxide,
alkalinity,   and hardness.  If  possible,
these  tests  should  be  coupled with
sensitive  aquatic organism behavioral
monitoring to identify episodic periods ol
toxicity.


Effluent Characterization
  A comparative qualitative analysis was
made of the WLSSD effluent and influent,
and a similar analysis was made of the
effluent from the largest single contribu-
tor of industrial type organics (a pulp and
paper industry) to the WLSSD influent
The isolation and concentrations in com-
posite samples were done  in threes  tc
reflect  the  acidic,  neutral,  and  basic
functionalities  m   the  components
analyzed using mass spectroscopy. The
mass of data is presently being incorpora-
ted into a three x three matrix (3 analyses
and 3 sample sites) based on functional-
ity. When completed, an interpretation ol
the meaning and significance of the data
will be  made.
  Because  chlorophenols   originating
from WLSSD had been previously tracec
within the bay and into Lake Superior, E
gas  chromatography with  electror
capture detection  procedure  aimed  a
sensitivity and a second procedure with
liquid chromatography with  a  variable
wavelength that would aid the identifica
tion of  chlorophenols  in  comple)
mixtures were developed.
  A  detailed   report  containing  the
methods used in effluent characteriza-
tion  and  raw data,  and chlorophenol
analysis  procedures are available  on
request.
Conclusions
  1.  The water quality of the St.  Louis
     Harbor has improved. Much of the
     improvement can be attributed tc
     the  onset  of the operation of the
     present WLSSD  wastewater
     treatment plant.


  2.  There was  only a slight impact or
     the benthic invertebrate community
     from the WLSSD outfall.
  3.  Survey data indicate  that  phyto-
     plankton and zooplankton were no(
     demonstrably  impacted  by   the
     WLSSD effluent.

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  4. The WLSSD plant is currently treat-
     ing its waste to a higher degree than
     the  1  mg/L phosphorus limit. The
     concentration in the main channel
     opposite the plant has decreased by
     a factor of three since  1973.

  5. The WLSSD discharge was  occa-
     sionally acutely toxic. It appears that
     some toxic discharges are related to
     changes in treatment processes and
     plant  operations  in  response  to
     special  waste  treatment   needs
     resulting in high residual chlorineor
     carbon dioxide concentrations in the
     effluent. Data indicate that at times
     the  mixtures of the WLSSD plant
     effluent and bay would be acutely
     toxic in the immediate vicinity of the
     discharge  pipe but not impact the
     rest of the bay because of a high
     dilution ratio.

  6. The  primary  objectives  of this
     research project were not attainable
     at this site because persistent toxic
     pollutants were  not found in  the
     WLSSD effluent and no persistent
     open water pollutant problems were
     apparent.

Bibliography
  Devore,  P.   1983.   An   Annotated
Bibliography of Environmental Research
Conducted  Within  the St  Louis  River
Estuary   1903-1982. [Order  No  NTIS
PB83-261 -693] (EPA-600/S3-83-092).
This report is intended as a tool for people
to locate specific types of  studies con-
ducted within St. Louis  Bay and was an
attempt to compile and review  all  the
physical, biological, and chemical studies
related to the bay.
R.  B.  Cook, J. A meet, J. R. Hargis, and R. Caple are with the University of
  Minnesota, Duluth, MN 55812; D. J. Call, L T. Brook. C.Northcott, and D. E.
  Hammermeister are with the University of Wisconsin, Superior, Wl 54880; the
  EPA authors A.  R. Carlson, N.  A. Thomas (also the EPA Project Officers, see
  below),  7. H. Roush,  and R.  A.  Drummond are  with the  Environmental
  Research Labortory, Duluth, MN 55804.
The complete report, entitled "Chemical and Biological Studies Related to the
  Water Quality of St. Louis Bay of Lake Superior," (Order No. PB 84-195 379;
  Cost: $14.50, subject to change) will be available only from:
        National Technical Information Service
        5285 Port Royal Road
        Springfield, VA 22161
        Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
        Environmental Research Laboratory
        U.S. Environmental Protection Agency
        6201 Congdon Blvd.
        Duluth, MN 55804
                                    U S GOVERNMENT PRINTING OFFICE, 1984 — 759-015/7734

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